\r\n\tThe human microbiota consists of a wide variety of bacteria, viruses, fungi, and other single-celled animals that live in the body while microbiome is the name given to all of the genes inside these microbial cells. Recently, there has been renewed interest in the role played by microbiota and microbiome in both human health and human disease. A correct equilibrium between the human host and their microorganisms is important for an appropriate physiological function. \r\n\tMicroorganisms have evolved alongside humans and form an integral part of life, carrying out a range of vital functions. They are implicated in both health and disease, and research has found links between bacterial populations, whether normal or disturbed, and the following diseases: asthma, cancer, diabetes, obesity, heart disease and, neurological and neurodegenerative diseases. \r\n\tThe chapters of this book aim to present outstanding research on biochemical, genetics, clinical, molecular and behavioral fields about microbiota-gut-brain axis with emphasis in how neuropeptides such as brain derived factor (BDNF), substance P, calcitonin gene-related peptide and neuropeptide Y (NPY), vasoactive intestinal polypeptide, somatostatin and corticotropin-releasing factor are also likely to play a role in the bidirectional gut-brain communication. In this capacity they may influence the activity of the gastrointestinal microbiota and its interaction with the gut-brain axis. \r\n\tIt will be shown evidence that neuropeptides represents a challenge in understanding the complex interactions between gut and brain. Although their precise role in the microbiota-gut-brain axis has not yet been defined, neuropeptides play an important role in this respect. For instance, a growing field of work is implicating the microbiota-microbiome in a variety of psychological processes and neuropsychiatric disorders. These include mood and anxiety disorders, neurodevelopmental disorders such as autism spectrum disorder and schizophrenia, and even neurodegenerative disorders such as Alzheimer’s and Parkinson’s diseases. These brain disturbances have been linked to molecular and biochemical alterations in the course of neurodevelopment so, the research in this area has established different approaches (nutritional, immunological, energy homeostasis), to find the role played by the gut microbiota-microbiome in the etiology of the aforementioned brain disorders.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"2c441b6a49e0eba12af16fcb6ad8b887",bookSignature:"Dr. Sandra Morales-Mulia",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/8940.jpg",keywords:"Gut-Microbiota, Neurodevelopment, Synaptic plasticity, Neurogenesis, Neuroimmune system, Neuropeptide Y, Brain-derived neurotrophic factor (BDNF), Peptide YY, Cholecystokinin (CCK), Corticotropin-releasing factor (CRF), Substance P, Neuropeptide Y (NPY), Oxytocin",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 24th 2019",dateEndSecondStepPublish:"June 14th 2019",dateEndThirdStepPublish:"August 13th 2019",dateEndFourthStepPublish:"November 1st 2019",dateEndFifthStepPublish:"December 31st 2019",remainingDaysToSecondStep:"2 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"287114",title:"Dr.",name:"Sandra",middleName:null,surname:"Morales-Mulia",slug:"sandra-morales-mulia",fullName:"Sandra Morales-Mulia",profilePictureURL:"https://mts.intechopen.com/storage/users/287114/images/system/287114.jpeg",biography:"EDUCATION AND DEGREES \n1988-1991. National Autonomous University of Mexico (UNAM). School of Sciences. B. S. in Biology. \n1995-1997. National Autonomous University of Mexico (UNAM). Cell Physiology Institute. Master in Basic Biomedical Sciences Research\n1998-2000. National Autonomous University of Mexico (UNAM). Cell Physiology Institute. PhD in Biomedical Sciences (Neuroscience) \n2002-2004. Postdoctoral Fellow. Laboratory of Cell Biology: Mitosis, Ciliogenesis, Intracellular Transport and Motor Protein Functions. University of California, Davis- Dept. of Molecular & Cellular Biology, One Shields Ave. Davis, CA 95616. \n2005-2008. Postdoctoral Fellow. Laboratory of Neuropharmacology. National Institute of Psychiatry “Ramón de La Fuente Muñiz”. Calzada México-Xochimilco #101, Col. San Lorenzo Huipulco, CP 14370 México City, México. \n2009-present. Teaching Professor in Biochemistry. Bachelor in Biology Program. School of Sciences. National Autonomous University of Mexico (UNAM). Av. Insurgentes Sur 3000, Circuito Exterior. Ciudad Universitaria, Mexico D.F. C.P. 04510.\n2006-present. Consultant and Assessor Researcher. \nLaboratory of Psychiatric and Neurodegenerative Diseases. National Institute of Genomic Medicine (INMEGEN-SAP). Periferico Sur 4809, Arenal Tepepan, 14610 México City, México.\nLaboratory of Molecular Basis of Addictions. National Institute of Psychiatry RFM, Mexico City, Mexico.",institutionString:"National Autonomous University of Mexico",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"National Autonomous University of Mexico",institutionURL:null,country:{name:"Mexico"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"18",title:"Neuroscience",slug:"life-sciences-neuroscience"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"301331",firstName:"Mia",lastName:"Vulovic",middleName:null,title:"Mrs.",imageUrl:"https://mts.intechopen.com/storage/users/301331/images/8498_n.jpg",email:"mia.v@intechopen.com",biography:"As an Author Service Manager, my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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\n
1. Introduction
\n
Over the past centuries, CO2 has become the main carbon resource due to the decreases of limited resources such as coal, oil, and natural gas [1]. However, the CO2 concentration in the atmosphere has consequently increased from ~280 ppm (preindustrial) to ~390 ppm in 2010 at a rate of ca. 1% per year [2], which arguably contributes to the “greenhouse effect,” and increases the global temperatures and climate change. CO2 emissions are still existing threat to humans; it is high time that effective measures should be taken to decrease the emission of CO2.
\n
Hence, the carbon capture and sequestration (CCS) system is considered to be an efficient method for CO2 utilization [3, 4]. Nevertheless, the hydrogenation reaction is the most important chemical conversions of CO2; moreover, which offers a good opportunity for sustainable development in the energy and environmental sectors. Indeed, the reaction process not only reduces the CO2 amount in the atmosphere but also produces fuels and valuable chemicals [5].
\n
As a promising fuel energy, methane, a simple hydrocarbon, has a wide range of applications in the industry and civil use, which also used to produce some downstream products, such as ethyne, hydrogen, and ammonia [6, 7]; therefore, the strategy of CO2 methanation is significantly meaningful. Undeniably, the resources of fossil fuels are diminishing and fuel prices have undergone strong fluctuation in recent years. Therefore, developing alternative fuels from nonfossil fuel sources and processes are highly desirable. The products from CO2 hydrogenation, such as methane, hydrocarbons, methanol, and dimethyl ether, are excellent fuels in internal combustion engines, and are easily stored and transported, but the literature studies showed that the CO2 conversion to methanol and dimethyl ether is still very low (~20%) and it is difficult to achieve higher conversion of CO2 [8, 9]. CO2 methanation is a simple reaction, generating methane under atmospheric pressure with several advantages over other chemicals. Although the conversion was still very low, the CH4 formation from CO2 at low temperature has become an important breakthrough in the utilization of CO2 [10].
\n
CO2 methanation is a significant catalytic hydrogenation process, as is shown in Eq. (1).
\n
CO2+4H2→CH4+2H2O,ΔH298K=-252.9KJ·mol-1E1
\n
The methanation of CO2 has a wide range of applications including the production of syngas and the formation of compressed natural gas [1]. A prototype CO2 recycling plant to supply clean energy preventing global warming has been built in 1996 using these key materials and has been operating successfully [11]. Without doubt, CO2 methanation is the key pathway for CO2 recycling, which requires a catalyst to achieve acceptable rates and selectivities. And extensive studies have been conducted on metal-based catalytic systems in the hydrogenation of CO2 to methane.
\n
Noble metals (e.g., Ru, Rh, Pd) supported on oxide supports (e.g., TiO2, Al2O3, CeO2) were the most effective catalysts for CO2 methanation under relatively mild operating conditions [12–14]; however, the high cost of the catalysts limited their practical applications [15]. Therefore, to obtain a feasible and cost-effective catalytic process, nonnoble metal catalysts (e.g., Ni, Co) were focused by many scholars [16, 17]. This review attempts to present the catalytic reactivity and reaction mechanism over the catalysts, particularly over the heterogeneous catalysts with an emphasis on the effects of supports and the second metal additives, as well as an overview regarding the challenges and opportunities for future research in the field.
\n
\n
\n
2. Catalysts for CO2 methanation
\n
\n
2.1. Noble metal catalysts for low-temperature methanation of CO2
\n
The most widely used catalysts for the CO2 methanation are noble metals, such as Rh, Ru, and Pd, and Ni-based catalysts. The noble metals are highly active toward CO2 methanation at lower temperature and more resistant to the carbon formation than other transition metals; however, they are expensive. In particular, the noble metals also used to promote the Ni catalysts to enhance their catalytic activities. The noble metal catalytic systems for the synthesis of methane by CO2 hydrogenation are summarized in Table 1.
Summarization of activities of CO2 methanation on noble metal catalysts.
\n
\n
2.1.1. Role of the support on catalyst activity
\n
CO2 methanation has been studied over a series of supported Ru and Rh catalysts, which were very active for CO2 hydrogenation [13, 14, 20, 21]. The supports, including Al2O3, TiO2, and CeO2 for these active metals, have also been investigated. To clarify the influences of the supports on the catalytic behavior of ruthenium, a FT-IR study is used to obtain more insight into the reaction mechanism [21]. Based on the FT-IR spectra of CO and CO2 adsorbed on the catalysts, the improvement in the CO2 methanation activity was related to a higher positive polarization of ruthenium on the zeolite, which led to a weaker Ru−CO bond on the H-ZSM-5-supported sample with a corresponding increase of the hydrogen surface coverage, which favors the transformation of the intermediate CO to methane, and which indicated that Ru/ZSM-5 exhibits more CH4 selectivity than Ru/SiO2 [21].
\n
The Ru dispersion was significantly influenced by the crystal phase structure of the TiO2 supports [19]. Rutile-type TiO2 (r-TiO2) was a much better support than anatase-TiO2 (a-TiO2) in stabilizing of RuO2 due to the interfacial lattice matching, resulting in a higher reactivity and stability in CO2 methanation. Owing to the highly dispersed Ru catalyst with a narrow size distribution, r-TiO2 was a promising support [12]. There was a strong interaction between RuO2 and r-TiO2 during the calcination process, which prohibited the aggregation of RuO2 in the presence of the Ru–O–Ti bond. As represented in Figure 1, upon calcination at 300°C, the Ru/r-TiO2 exhibited a much higher activity and thermal stability in CO2 methanation than Ru/a-TiO2. Moreover, the reaction rate of the Ru/r-TiO2 was 2.4 times higher than that of the Ru/a-TiO2, which mainly originated from the different particle sizes of ruthenium [12].
\n
Figure 1.
(a) The effects of reaction temperature on the CO2 conversion over the Ru catalysts and (b) the specific rates of CO2 conversion calculated at 225°C. The feed gas was 18 vol.% CO2+ 72 vol.% H2+ 10 vol.% N2, and the catalyst was each 0.040 g of Ru/TiO2 diluted with 0.400 g of SiO2, the total space velocity was 75,000 mL·gcat−1·h−1 [12].
\n
The Ru/TiO2 catalysts were prepared via a spray reaction (SPR) [20, 22], and the catalytic CO2 hydrogenation activities of the SPR fine particles were much higher than those of impregnation catalysts [20]. The high activity of the SPR catalysts was attributed to the occurrence of new active sites at the metal-support perimeters without any strong metal-support interaction phenomenon. In addition, highly dispersed Ru nanoparticle-loaded TiO2 was prepared using a “dry” modification method [18], which markedly enhances the performance of low-temperature methanation, achieving a 100% yield at 160°C. In addition, the methanation reaction over Ru/TiO2 proceeded at temperatures as low as room temperature with a reaction rate of 0.04 mmol·min−1·g−1.
\n\n
Although Ru catalysts deposited on different supports, such as alumina, titanium, or silica, have been extensively studied, and the effect of the support on the catalytic properties of small Ru particles in CO2 hydrogenation has not been fully recognized. Different supports (low and high surface area graphitized carbons, magnesia, alumina and a magnesium-aluminum spinel) were used in CO2 methanation, and alumina was found to be the most advantageous material [23]. The catalytic properties of very small ruthenium particles are strongly affected by metal-support interactions. In the case of Ru/C, the carbon support partly covers the metal surface, lowering the number of active sites (site blocking). A sequence of the surface-based activities (TOF): Ru/Al2O3 > Ru/MgAl2O4 > Ru/MgO > Ru/C is almost identical to that of electron-deficiencies of the metal, determined by the Lewis acidities of the supports [23].
\n
\n
\n
2.1.2. Effect of metal loading
\n
The most likely effects caused by increasing the loading amount are the growth of the particle size, e.g., the mean particle size of surface Rh species increased with the metal loading amount, which affected the reactivity [24]. From the study over Rh/γ-Al2O3, varying Rh amounts show Rh particle sizes of 3.6–15.4 nm, and a 100% methane selectivity was observed over the entire temperature range and Rh amounts, and the turnover frequency for CH4 formation depended on the Rh particle size. Larger Rh particles exhibited a catalytic activity of up to four times higher than the smaller particles at 135–150°C, whereas at higher temperatures (200°C) the turnover frequencies are similar for all particle sizes [13].
\n
The Rh loading amount can significantly change the product selectivity of CO2 hydrogenation over Rh/SiO2 [25], and the main products transformed from CO2 to CH4 with the loading amount of Rh, as shown in Figure 2. To the 1 wt% Rh/SiO2 catalyst, the concentration of surface Rh particles was low, and the Rh species were surrounded by the hydroxyl groups of SiO2. For the 10 wt% Rh/SiO2, 5.8 times more surface Rh particles than that of 1 wt% Rh/SiO2 were found with accordingly less surface hydroxyl groups of SiO2 existed around Rh particles [25]. In the Ru/Al2O3 catalysts with a Ru amount of 0.1–5.0%, the CH4 selectivity in CO2 methanation increased with the increase in the Ru loading amount [26]. In the 0.1% Ru/Al2O3 catalyst, Ru is mostly present in the atomic dispersion, and the agglomeration of small metal particles (and atoms) in the 3D clusters was observed, indicating a decrease in CH4 selectivity.
\n
Figure 2.
Effect of Rh loading on the distribution of CH4 and CO [25]. Reaction conditions: temperature = 473 K, pressure = 5 MPa, H2/CO2 ratio = 3, flow rate = 100 cm3 min−1.
\n
\n
\n
2.1.3. Effect of second metal
\n
Actually, when the alkaline salts were added to Ru/Al2O3 catalysts, a synergetic effect can be detected, including the electron donation of an alkaline promoter modified the local electron density of the Ru metal, the formation of alkaline chlorides to neutralize the residual chlorine ions, and the removal of the depositional inactive carbon, which was formed on the catalyst surface during CO2 hydrogenation [22]. Tests of the Ba- and K-containing Rh/Al2O3 and the pure Rh/Al2O3 in 300–700°C revealed remarkable differences in the catalytic behavior (Figure 3). The Ba-containing and especially the pure Rh/Al2O3 catalyst showed high selectivity to CH4 below 500°C with a maximum CH4 yield of 60% at 400°C; however, at higher temperatures, the CO formation became significant. K-containing Rh/Al2O3 converted CO2 only to CO in 300–700°C and no CH4 was found. A vastly different adsorption behavior of the Ba- and K-containing catalysts and a significant influence of these additives on the Rh(0)/Rh(I) ratio were revealed [27].
\n
Figure 3.
Comparison of selectivity and yield to CH4 (A and C, respectively) and CO (B and D) is shown as a function of temperature for Ba-containing (circles) and K-containing (squares) Rh/Al2O3 catalysts, as well as for pure Rh/Al2O3 (triangles) [27].
\n
\n
\n
\n
2.2. Recent advances in Ni-based catalysts
\n
\n
2.2.1. Effect of supports
\n
\n
2.2.1.1. Enhancement of catalytic performance
\n
Choosing a suitable support is mostly according to its properties to activate CO2 and the interaction between the metal and supports, which is a key parameter for the methanation reaction [28]. The structure and properties of the support do affect the dispersity of active metals and the stability, which enhance the activity of catalysts.
\n
Currently, various materials are used as the supports for nickel catalysts, such as γ-Al2O3 [29–31], SiO2 [32, 33], CexZr1−xO2 [33–36], and TiO2 [37]. Because the support has a significant influence on the morphology of the active phase, adsorption, and catalytic properties [38], Ni was supported on the mesostructured silica nanoparticles (MSNs), MCM-41, HY zeolite, SiO2, and γ-Al2O3. And the CO2 methanation activity followed in the order of Ni/MSN > Ni/MCM-41 > Ni/HY > Ni/SiO2> Ni/γ-Al2O3 [32]. The high activity of Ni/MSN is due to the presence of both intraparticle and interparticle porosities, which led to a high concentration of basic sites. In addition, the defect sites or oxygen vacancies in MSNs were responsible for the formation of surface carbon species, while Ni sites dissociated hydrogen to form atomic hydrogen.
\n
An encouraging result was found in the CO methanation reaction over the zeolite supports, and the same results also found in the Ru/Y and Ru/Al2O3 catalysts [39], as well as the supporting Pd on the zeolites, and the catalytic activity on the supporter was in the order of HY > HZSM-5 > NaZSM-5 > NaY > SiO2 [40]. Similarly, when CO2 hydrogenation to methane was carried out over nickel species supported on a HNaUSY zeolite, interesting CO2 conversions and CH4 selectivities were achieved. CO2 conversion increased with the Ni content from 2 to 14%, due to the higher amount of Ni0 species after reduction [41]. Nickel particles were grafted onto SBA-15, and a chemical bond was formed between Ni and Si by O, and no bulk nickel oxides existed in the Ni-grafted SBA-15 [42]. Therefore, the Ni-grafted SBA-15 suited CO2 methanation, resulting in the higher CO2 conversion (TOF of 19.4 s−1) and methane selectivity (92%) than a NiO dispersed SBA-15. The status of catalytic systems for the synthesis of methane by CO2 hydrogenation is summarized in Table 2.
Summary of various Ni catalysts for CO2 methanation.
\n
\n
\n
2.2.1.2. Nickel dispersion
\n
As a highly active catalyst for CO2 methanation, a highly uniform dispersed active species over the support is required; therefore, a high specific surface area support is needed. In general, the support usually plays a very important role in the interaction between the Ni and the support. The nickel compounds on different support surfaces result in different “metal-support effects” [30], which implies that catalysts would exhibit different performance toward activity and selectivity for a given process.
\n
Ni/Al2O3 with a high specific surface area showed an excellent controllability on the specific surface area of catalysts with the increase in the Ni amount, and increased the reducibility of the catalyst. However, a further increase in the Ni amount would cause a decrease in CO2 conversion due to the bigger crystallite size and lower surface area of the catalyst [29, 30]. Indeed, the CO2 conversion and CH4 yield are strongly dependent on the Ni amount and the calcination temperature. Compared with the no pretreatment catalysts, the prereduced 16% Ni catalyst obtained 100% CH4 selectivity with no CO detected [47]. With a higher calcination temperature, the metal nickel is in the form of NiAl2O4, which is an inactive phase for methanation [47, 48]. The existential state of Ni is usually affected by the support. Cubic metallic Ni particles are found mostly without carbon whiskers, and fast methanation occurs at the expense of the CO intermediate on the corners of nanoparticles interacting with Al2O3 [43].
\n\n
The Ni-based catalyst prepared by coprecipitation is active for CO2 methanation as well. Coprecipitated Ni/Al2O3 catalysts are found to be efficient promoters for CO2 methanation, and Al2O3 is active for CO2 adsorption [49]. A Ni-Al hydrotalcite-derived catalyst (Ni-Al2O3-HT) was prepared by a coprecipitation method with a narrow Ni particle-size distribution and an average particle size of 4.0 nm, a large number of Ni nanoparticles were surrounded by amorphous alumina [31]. As for the Ni amount up to 78 wt%, the average crystalline size of Ni was only 4 nm with a narrow distribution in the range of 3–9 nm. Compared with the 78 wt% Ni/Al2O3 catalyst using an impregnation method, the Ni-Al hydrotalcite-derived catalyst exhibited a much higher Ni dispersion than its impregnated counterpart, indicating that Ni-Al hydrotalcite is an ideal precursor for preparation of a well-dispersed Ni catalyst.
\n
Recently, a surface defect-promoted Ni nanocatalyst with a high dispersion and high particle density embedded on a hierarchical Al2O3 matrix exhibits excellent activity and stability simultaneously for CO2 methanation. The abundant surface vacancy clusters serve as the active sites, accounting for the significantly enhanced low-temperature activity of the supported Ni nanoparticles [43]. Ni/H−Al2O3(400) clearly possesses a significantly enhanced low-temperature activity for CO2 methanation. The CO2 conversion exceeded 90% at 265°C and reached the maximal value of 99% at 300°C (Figure 4A). The methane production rate increased along with the Ni surface area, indicating a strong correlation between the activity and the Ni surface area. The TOF value as a function of Ni dispersion for the three samples (Figure 4B) shows a linear correlation, indicative of a structure sensitive reaction. And the TOF values of the three catalysts toward CO2 methanation decrease in the following order: Ni/H−Al2O3(400) > Ni/H−Al2O3(500) > Ni/Al2O3 [43].
\n
The different Ni loading amount over the Ni/TiO2 catalyst strongly affects catalytic CO2 methanation. When the Ni loading amount was increased to 10 wt%, the selectivity switched to favor the CH4 formation. Ni nanoparticles (NPs) immobilized on a TiO2 support were synthesized using a deposition-precipitation method followed by a calcination-reduction process, and the CO2 conversion and CH4 selectivity achieved 96 and 99% with a Ni loading of 15 wt% at 260°C [37]. Due to the good dispersion of Ni NPs with large unsaturation facilitates a high exposure of active sites, the formation of surface-dissociated hydrogen and the subsequent hydrogenation removal of surface nickel carbonyl species was accelerated, accounting for the resulting enhanced low-temperature catalytic performance [37].
\n
Figure 4.
(A) Profiles of CO2 conversion vs. temperature for CO2 methanation in the presence of (a) Ni/H–Al2O3(400), (b) Ni/H–Al2O3(500), and (c) Ni/Al2O3 (reacted at 200–410°C and 2400 mL gcat−1·h−1(WHSV)). (B) The relationship between the TOF value and the Ni dispersion (reacted at 220°C, 9600 mL gcat−1·h−1(WHSV), and <10% CO2 conversion) [43].
\n\n
In the past few years, CeO2–ZrO2 solid solution (CexZr1−xO2), an active oxygen material, has been commonly used as a support for automotive three-way catalysts because of its high oxygen storage capacity (OSC), which is important in many reactions [50, 51], and it also used as the support for CO2 methanation. The Ni-based catalysts on CexZr1−xO2 are greatly efficient in terms of activity and stability, which can be attributed to their high oxygen storage capacities and high Ni dispersion [34–36]. In CO2 methanation, the Ni2+ ion incorporation into the Ni–CexZr1−xO2(Ni–CZ) catalyst significantly enhances the specific catalytic activity of the CZ catalyst [44], and the global catalytic activities of CO2 methanation on CZ catalysts depended on the surface for available metallic nickel, the composition of the support, and its modification by Ni2+ doping. In addition, the CexZr1−xO2 catalyst can be synthesized by a simple hydration process, which achieved the goal of Ce and Ni enriched on the surface [34]. Meanwhile, a new NH3 reduction method for the preparation of Ni−Ce0.12Zr0.88O2 lead to a higher active metal reducibility, smaller Ni0 crystallite size, and higher metal dispersion compared to the H2-reduction method with 100% CO and 97% CO2 conversions and ≥ 98% CH4 selectivity at 250°C [36]. For NH3-treated samples, the metal dispersion is found to decrease with the increase in Ni amounts due to the formation of bulk Ni particles. However, all H2-treated samples showed a larger NiO particle size and a lower metal dispersion than the NH3-treated samples might owing to the H2-reduced sample exhibits an aggregation of smaller particles and/or metal sintering [36].
\n
Nowadays, metal-organic frameworks (MOFs) have attracted much interest as catalysts and/or supporting materials for active metals or complexes in heterogeneous catalysts [52, 53], e.g., a highly active catalyst Ni/MOF-5 showed unexpected activity at low temperature for CO2 methanation [46]. For 10Ni/MOF-5, a very high specific surface area of 2961 m−2·g−1 and a large pore volume of 1.037 cm−3·g−1 led to a high dispersion of Ni of 41.8%, and the highly uniform dispersion of Ni in the framework of MOF-5 facilitates a high exposure of active sites, resulting the enhancement of the CO2 conversion to 75.09% and CH4 selectivity to 100% at 320°C. To further confirm the high dispersion of Ni on the MOF-5 support, the Ni dispersion on MOF-5 and SiO2 was measured by the H2 chemisorption. The Ni dispersion on the 10Ni/MOF-5 catalyst was 41.8% as well as that on 10Ni/SiO2 was 33.7%, as shown in Figure 5, which indicated that Ni was more highly dispersed on MOF-5 [46]. In conclusion, the Ni loading amount is dependent on the type of support used, and the Ni loading amount on the support will determine its crystallite size and dispersion on the surface of the support.
\n
Figure 5.
The relation of Ni dispersion and support [36, 37, 43, 46].
\n
\n
\n
2.2.1.3. Catalyst stability
\n
The stability of a catalyst is closely related to the structural destruction, coking, and metal sintering during CO2 methanation [28, 54]. The long-term catalytic stability and thermal stability of Ni/H−Al2O3 was investigated, the CO2 conversion decreases slowly in the first 180 h and then remains almost constant with a total decrease of 7% after 252 h. No obvious aggregation or sintering of Ni nanoparticles was observed for the Ni/H−Al2O3 catalyst after 252 h upon streaming [43]. Moreover, the control of thermal sintering is critical for maintaining the activity, which requires a stable support and an effective method to prevent particle migration and coalescence [55]. The embedding of Ni nanoparticles onto the Al2O3 matrix enhances the metal-support interaction, and prevents the sintering and/or the aggregation of the active nickel species, which shows that the Ni species was embedded in the hierarchical matrix by an in situ reduction approach, and the Ni species exhibit a high dispersion degree and high stability, guaranteeing their high activity during the long-term use.
\n\n
The Ni/MOF-5 catalyst also shows the catalytic activity during 100 h of CO2 methanation over 10Ni/MOF-5 at 280°C (Figure 6). The CO2 conversion remained above 47.2% and CH4 selectivity was almost 100% during the 80 h reaction. Obviously, the 10Ni/MOF-5 catalyst was quite stable [46]. However, on CexZr1−xO2 support, the Ce-rich sample (5NiC4Z) showed the better stability from the CO2 conversions (72.21–62.18%), whereas the CO2 conversions were 51.63–36.42% and 37.64–23.19% over 5NiCZ and 5NiCZ4, respectively [34]. The higher reducibility of the Ce-rich supported highly-dispersed Ni catalyst was considered to be the important factors to ensure its long-term stability [34].
As shown in Figure 7, the stability of different Ni supported catalysts was studied, and the rate formation of CH4 of Ni/MCM-41, Ni/HY, Ni/SiO2, and Ni/γ-Al2O3 catalysts decreases slightly with time on stream increases; however, the rate formation of CH4 on the Ni/MSN catalyst shows no obvious decrease [32]. In particular, the Ni/MCM-41 shows a minimum percent decrease of the CH4 formation rate of 3.4%, whereas the Ni/HY, Ni/SiO2, and Ni/γ-Al2O3 is 9.0, 10.6 and 26.6%, respectively. The presence of coke deposition on the active sites is known for the catalyst deactivation; however, no coke content was observed on the Ni/MSN catalyst from the TGA result and the highest coke content was observed on the Ni/Al2O3 catalyst (9.1%), indicating that the Ni/MSN catalyst did not show any sign of deactivation for the methanation reaction up to 200 h of time-on-stream. Therefore, the Ni/MSN catalyst is resistant toward coke formation and presented good stabilities under the reaction conditions [32].
\n
Figure 7.
Long-term stability test of Ni catalysts for the CO2 methanation reaction at a temperature of 573 K, GHSV = 50,000 mL·g−1·h−1 and H2/CO2= 4:1 [32].
\n
\n
\n
\n
2.2.2. Effect of the second metal
\n
\n
2.2.2.1. Enhancement of catalytic performance
\n
Ni-based catalysts are vulnerable to sintering and coking, which may lead to their deactivation. Hence, many efforts have been made to enhance the catalytic activity, including selection of appropriate supports and addition of catalytic promoters such as Ce, Zr, La, Mg, V, and Co [45, 56, 57]. The most noticeable effect due to the promotion with these metals is a considerable increase both in the CO2 conversion and CH4 selectivity under steady conditions.
\n\n
The catalytic performance of nickel-based catalysts supported on mesoporous nanocrystalline γ-Al2O3 promoted with CeO2, MnO2, ZrO2, or La2O3 was investigated, and the Ce promoter considerably increases the CO2 conversion in the methanation reaction (Table 3). The addition of the Ce promoter to Ni increased the dissociation and CO2 hydrogenation, and weakened the C=O bond of CO2 adsorbed on the Ni active sites. Compared with the unpromoted Ni/Al2O3 catalyst, the addition of Ce strengthen the interaction between Ce and Ni, resulting in better activity of the Ce–Ni/Al2O3 catalyst [58]. Doping the Ni-zeolites catalysts with 3–15% of Ce would be much more enhanced the catalytic performance than the unpromoted catalysts [41]. Actually, the presence of CeO2 after reduction might promote CO2 activation into CO, the final catalyst properties being due to the synergetic effect between the metal active sites and the promoter.
\n
\n
\n
\n
\n\n
\n
Catalysts
\n
CO2 conversion (%)
\n
CH4 selectivity (%)
\n
\n\n\n
\n
20Ni/Al2O3
\n
77.2
\n
100
\n
\n
\n
2Ce-20Ni/Al2O3
\n
80.3
\n
100
\n
\n
\n
2Mn-20Ni/Al2O3
\n
78
\n
100
\n
\n
\n
2La-20Ni/Al2O3
\n
75.4
\n
97.6
\n
\n
\n
2Zr-20Ni/Al2O3
\n
74.4
\n
99.1
\n
\n\n
Table 3.
Catalytic evaluation of the Ni/Al2O3 catalyst with different promoters [56].
\n
Reaction conditions: H2/CO2 molar ratio = 3.5, GHSV = 9000 mL·gcat−1·h−1 and 350°C.
\n
Some active metals, such as Co, Cu, and Fe, are also used to control the catalytic performance over the supported Ni catalyst, which behave an active aspect as the second metal. Compared with Co and Cu, iron is a suitable second metal for the Ni/ZrO2 catalyst for low-temperature CO2 methanation [59], which might be due to its strong electron-donating ability, and Fe2+ can promote the reduction of nickel and zirconia. Interestingly, similar results are verified and evaluated the catalytic performance of mesoporous nickel-alumina xerogel catalysts (denote as NiAX) with different second metal (M = Fe, Zr, Ni, Y, and Mg) in a fixed bed reactor (Table 4) [45]. However, the oxidized Co is more active toward the methane formation at low temperatures [59, 60], and the Co addition can remarkably change the catalytic performance when active CexZr1−xO2 are used as a support for the Ni catalysts [61]. In addition, a homogeneous alloy of Co and Ni can be formed after H2 reduction and remain after use for reaction in Co-Ni bimetallic catalysts, which increase the metal dispersion in the catalyst, indicating a certain amount of Co addition can considerably improve the catalytic performance [61, 62].
\n
\n
\n
\n
\n
\n\n
\n
Catalysts
\n
CO2 conversion (%)
\n
CH4 selectivity (%)
\n
CH4 yield (%)
\n
\n\n\n
\n
35Ni5FeAX
\n
63.4
\n
99.5
\n
63.1
\n
\n
\n
35Ni5ZrAX
\n
61.6
\n
99.1
\n
61.0
\n
\n
\n
35Ni5NiAX
\n
61.1
\n
99.2
\n
60.6
\n
\n
\n
35Ni5YAX
\n
58.4
\n
99.5
\n
58.1
\n
\n
\n
35Ni5MgAX
\n
54.2
\n
99.5
\n
53.9
\n
\n\n
Table 4.
Catalytic performance of 35Ni5MAX (M = Fe, Zr, Ni, Y, and Mg) catalysts for methane production from carbon dioxide and hydrogen obtained at 220°C after a 10 h-catalytic reaction [45].
\n
\n
\n
2.2.2.2. Nickel reducibility
\n
In general, the promotion of methanation catalysts with addition of second metals would enhance the nickel reducibility [63, 64]. The improvements in the Co reducibility may occur without any effect on the Co dispersion for the Ni-Ce/USY catalysts [41]. While the effect of promotion with Ce on the Ni reducibility is particularly pronounced with the alumina-supported Ni catalysts [63]. Compared to the unpromoted Ni/Al2O3, the lower reduction temperature of NiO in Ni-CeO2/Al2O3 samples implies that addition of CeO2 decreased the reduction temperature by altering the interaction between Ni and Al2O3, and improved the catalyst reducibility [16, 63, 64]. CNTs-supported catalysts exhibited better catalytic performance than the traditional Al2O3-supported catalysts [16], which attributed to the outstanding reduction properties of the CNTs-supported catalysts, which provided much more active sites for CO2 methanation. As shown in H2-TPR analysis (Figure 8), the accession of Ce could effectively promote the reduction of the nickel oxides, the high reduction peak temperature, corresponding to the highly dispersed nickel oxides in intimate contact with the exterior walls of the CNTs, decreased from 480 to 460°C for the 12Ni/CNT and 12Ni4.5Ce/CNT [16], which suggested easily reducible nickel species on the surface of the 12Ni4.5Ce/CNT catalyst, which may due to the interaction change between the metal oxides and CNTs by the addition of cerium.
\n
Figure 8.
H2-TPR profiles of the catalysts. (a) 12Ni/CNT, (b) 12Ni4.5Ce/CNT, (c) 12Ni/Al2O3, (d) 12Ni4.5Ce/Al2O3 [16].
\n
Recently, a new kind of γ-Al2O3−ZrO2−TiO2−CeO2 composite oxide supported Ni-based catalysts was synthesized for CO2 methanation [65]. The optimal catalytic activity of the composite oxide supported Ni-based catalysts was achieved because of the improvements in the reducibility. According to the H2-TPR profile for all the catalysts, the high temperature peak (weakly interacted with Al2O3, or called Ni rich phase) shifts downward for the composite oxide-supported Ni-based catalysts, suggesting a weaker interaction between NiO and the composite support. Furthermore, the reduction of the Ni rich phase would benefit the formation of large-sized Ni particles, which are active at low temperatures [66]. Therefore, increasing the fraction of Ni rich phase, i.e., NiO, the active species for the methanation reaction, would result in an increase in the CO2 conversion at lower temperatures. Moreover, the H2 consumed amount increased on the composite oxides support, confirming a higher reducibility of NiO on the composite oxides due to the weaker metal-support interaction [65].
\n
\n
\n
\n
\n
2.3. Cobalt-based catalysts for low-temperature methanation of CO2
\n
Generally, the Co-based Fischer-Tropsch catalysts exhibit a superior catalytic performance with respect to low-temperature CO2 methanation [17, 67, 68]. A higher CH4 selectivity was observed in the Fischer-Tropsch synthesis when the Co catalysts were not completely reduced or when the catalysts contain smaller Co3O4 particles [67]. When taking the coke oven gas as feed gas and using a nanosized Co3O4 catalyst, CO was easily adsorbed onto the smaller nanosized Co3O4 surface and react with H2, and the temperature at which CO completely converted to CH4 was much lower than that using nanosized Co3O4 with large particles [67].
\n\n
In addition, the Ru-doped Co3O4 catalyst with a relatively rough surface shows a lower light-off temperature than that of a Co catalyst [68]. The relatively rough surface morphology of Ru-doped Co3O4 probably results from the larger ionic radius of Ru3+, which affects the dissolution-recrystallization process. Therefore, the final surface morphology of nanorods was disrupted with the addition crystalline defects. The correlation between the surface chemistry and the catalytic performances suggests that doping a noble metal to an oxide of an earth-abundant metal followed by reduction could create a chemically stable, cost-effective catalyst with a bimetallic surface, which has an equivalent or much better catalytic performance [68]. Usually, the catalytic activity affected by the catalyst composition and structure, e.g., when used the mesoporous Co/KIT-6 and Co/meso-SiO2 in CO2 methanation, the highly ordered bicontinuous mesoporous structure of the Co/KIT-6 catalyst exhibits higher methane selectivity than the Co/meso-SiO2 catalyst, and the CO2 conversion exceeds 48.9%, and the methane selectivity can be retained at 100% at 280°C [17].
\n
\n
\n
\n
3. Reaction mechanisms
\n
According to the previous research, the reaction mechanism was difficult to establish mainly because of the different opinions on the intermediate and the methane formation process. Two feasible reaction mechanisms were proposed for CO2 methanation in the past decades. The first one involves the CO2 convert to CO prior to methanation, and the subsequent reaction follows the same mechanism as CO methanation [69]. Similar to the mechanism of CO2 hydrogenation to CH3OH, someone considered CO was an intermediate [32], and the CO hydrogenation to methane also been focused [70, 71]. The other mechanism involves the direct CO2 hydrogenation to methane without forming CO as an intermediate [72]. However, the mechanism depends on different catalysis systems, which are still under investigation.
\n
H2+2*→2H*E2
\n
CO2+*→CO2*E3
\n
CO2*+*→CO*+O*E4
\n
CO*+*→C*+O*E5
\n
C*+H*→CH*E6
\n
CH*+3H*→CH4+*E7
\n
O*+H*→OH*E8
\n
OH*+H*→H2O*→H2O+*E9
\n
The atomic hydrogen dissociated from Ni sites in the MSN may facilitate the formation of methane, as shown in Figure 9. The oxygen vacancies will be formed when H2 react with the surface oxygen along with the water generation, which activate additional CO2 to fill the vacancies and produce CO. During the CO2 methanation reaction, CO was also suggested as the alternative product, which was an intermediate, as shown in Eqs. (2)–(9) [32]. Therefore, the higher CH4 selectivity can be explained by the enhanced supply of adsorbed hydrogen to the activated adsorbed CO intermediate, which was the rate-determining step [73]. However, some researchers considered that the main mechanism for CO2 methanation does not require CO as the reaction intermediate [28, 74], which can be explained by the importance of weak basic sites the adsorption of CO2 [28].
\n\n
Density functional theory is helpful in understanding the mechanistic aspects of the reactions. Different mechanisms of CO2 methanation on Ni(111) surfaces were investigated, and the energy barrier of 237.4 kJ mol−1 is acquired for the dissociation of CO into C and O species, which support that CO2 is converted to CO, subsequently to carbon before hydrogenation [75].
\n
As mentioned, the CO2 adsorption is a crucial step for methanation. Indeed, CO2 dissociation is the rate-limiting step. CO2 dissociation over Rh-based catalysts is influenced by the CO coverage on the surface and the strength of the bond Rh−CO, and the hydrogen adsorption at the surface is competed with CO2 adsorption. Due to the preferential adsorption of CO2 and the accumulation of CO on the surface, hydrogen coverage on the rhodium catalyst is very small [76]. However, CO2 adsorption on the medium basic sites of Ni/Ce0.5Zr0.5O2 results in monodentate carbonates, and monodentate formate derived from monodentate carbonate on medium basic sites, which could be hydrogenated more quickly than bidentate formate derived from hydrogen carbonate. The medium basic sites were proposed to promote the formation of monodentate formate species, thus to enhance the activity [77].
\n
Figure 9.
A probable mechanism for Ni/MSN whereby spillover of atomic hydrogen from Ni interacts with C(a) species and sequentially hydrogenates carbon until the product methane desorbs [32].
\n\n
In addition, at 383 K, a reaction mechanism was proposed for the carbon dioxide methanation reaction on 2% Ru/TiO2, which investigate the precursor existence for the adsorbed CO and reaction intermediate, and the side-product, formate was also found adsorbing on the support [78], which suggested the surface intermediate corresponding to the adsorbed formate on the metal-support interface, and the measured formate infrared bands are corresponding to the diffused formate species from the interface to the support. A pathway involving hydrogen carbonate is also presented for the formation of the interfacial formate, because the species is formed on the support during the reaction, and the transient response is consistent with the response of a CO precursor. The reaction mechanism that could account for all of these observations is presented in Figure 10 [78].
\n\n
To make a better understanding of the adsorption of possible intermediates, the reaction mechanism and factors determining the product selectivity, DFT calculations were considered to be a suitable method to investigate the hydrogenation process of CO2 and CO on the Ru(0001) surface [79]. For CO2 hydrogenation, the HCOO intermediate are firstly formed from the adsorbed CO2 hydrogenation, and subsequently produces an adsorbed CHO and O species. The active C and CH species then undergo stepwise hydrogenation to CH2, CH3 and CH4, or the CHx species, and further transforms to longer carbon chains. From the calculation results, CH3 hydrogenation is considered to be the rate determining step in the sequence of C hydrogenation on the Ru(0001) surface, and the lowest barrier channel of C–C coupling occurs via the CH + CH reaction [79]. In addition, the study based on DFT calculations on a Ru nanoparticle supported on the TiO2 catalyst further confirms the stronger electron transfer from the Ru cluster to the TiO2(101) facet than to TiO2(001); the Ru species supported on the (101) plane possesses a relatively lower activation energy for the CO dissociation, resulting in the highly catalytic activity toward CO2 methanation reaction [80].
\n
Figure 10.
Reaction mechanism of CO2 methanation [78].
\n\n
Finally, the detailed mechanism was proposed for CO2 methanation over metal-based MSNs [81]. As shown in Figure 11, CO2 and H2 were adsorbed and dissociated on the metal active sites to form CO, O, and H, followed by the migration of these atoms to the MSN surface. Subsequently, the CO dissociated from the active sites interacted with the MSN oxide surfaces to form the carbonyl, including bridged and linear carbonyl, and the H atom in the reaction facilitated the formation of bidentate formate. And the above three species were responsible for the methane formation, among them, the main route for the methane formation was due to the bidentate formate species, and the MSN support served as the sites for carbonyl species, which act as a precursor to methane formation [81].
\n
Figure 11.
Plausible mechanism of CO2 methanation on M/MSN [81].
\n
\n
\n
4. Conclusions and perspectives
\n
CO2 has been promoted to an important carbon resource for conversion and utilization, and CO2 hydrogenation is a feasible and powerful process, especially for methanation. However, CO2 is chemically stable and thermodynamically unfavorable. To eliminate the limitations on the conversion and selectivity, various technical directions and specific research approaches on rational design of catalysts and exploration of reaction mechanisms have been presented.
\n
Noble metal catalysts such as Ru, Rh and Pd are efficient for the formation of methane under relatively mild operating conditions, but the high cost as well as their limited availability restricts their practical applications. Therefore, researchers have paid increasing attention on the immobilization of homogenous catalysts to combine the efficient activity with the properties of separation and recyclability. Ni- and Co-based catalysts are, of course, more practical for industrial applications compared to noble metal catalysts. The catalysts with larger surface areas and higher metal dispersion can usually possess higher activity and selectivity, and longer stability in the hydrogenation of CO2. However, the Ni-based catalysts are more resistless to carbon formation compared with noble metal catalysts. Thus, one strategy has to be proposed for pursuing high-performance catalysts with abilities of low-temperature methanation and resisting carbon formation. In addition, understanding the fundamental mechanisms of CO2 methanation and explore its relationship with catalyst active site structures using both theoretical calculations (molecular/electronic level modeling) and experimental approaches to tailor new catalyst structures are considerably needed.
\n
\n
Acknowledgments
\n
This work was supported by the National Natural Science Foundation of China (21366004, 21425627) and the Guangxi Natural Science Foundation (2015GXNSFDA139005).
\n
\n',keywords:"catalytic hydrogenation, carbon dioxide, methanation, heterogeneous catalysis, noble metal catalyst, Ni-based catalyst, Co-based catalyst",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/52449.pdf",chapterXML:"https://mts.intechopen.com/source/xml/52449.xml",downloadPdfUrl:"/chapter/pdf-download/52449",previewPdfUrl:"/chapter/pdf-preview/52449",totalDownloads:2246,totalViews:686,totalCrossrefCites:3,totalDimensionsCites:6,hasAltmetrics:0,dateSubmitted:"April 11th 2016",dateReviewed:"August 29th 2016",datePrePublished:null,datePublished:"January 25th 2017",dateFinished:null,readingETA:"0",abstract:"With the accelerating industrialization, urbanization process, and continuously upgrading of consumption structures, the CO2 from combustion of coal, oil, natural gas, and other hydrocarbon fuels is unbelievably increased over the past decade. As an important carbon resource, CO2 gained more and more attention because of its converting properties to lower hydrocarbon, such as methane, methanol, and formic acid. Among them, CO2 methanation is considered to be an extremely efficient method due to its high CO2 conversion and CH4 selectivity. However, the CO2 methanation process requires high reaction temperatures (300–400°C), which limits the theoretical yield of methane. Thus, it is desirable to find a new strategy for the efficient conversion of CO2 to methane at relatively low reaction temperature, and the key issue is using the catalysts in the process. The advances in the noble metal catalysts, Ni-based catalysts, and Co-based catalysts, for catalytic hydrogenation CO2 to methane are reviewed in this paper, and the effects of the supports and the addition of second metal on CO2 methanation as well as the reaction mechanisms are focused.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/52449",risUrl:"/chapter/ris/52449",book:{slug:"new-advances-in-hydrogenation-processes-fundamentals-and-applications"},signatures:"Zuzeng Qin, Yuwen Zhou, Yuexiu Jiang, Zili Liu and Hongbing Ji",authors:[{id:"5795",title:"Dr.",name:"Hongbing",middleName:null,surname:"Ji",fullName:"Hongbing Ji",slug:"hongbing-ji",email:"jihb@mail.sysu.edu.cn",position:null,institution:{name:"Sun Yat-sen University",institutionURL:null,country:{name:"China"}}},{id:"188601",title:"Prof.",name:"Zuzeng",middleName:null,surname:"Qin",fullName:"Zuzeng Qin",slug:"zuzeng-qin",email:"qinzuzeng@gmail.com",position:null,institution:{name:"Guangxi University",institutionURL:null,country:{name:"China"}}},{id:"194474",title:"Mr.",name:"Yuwen",middleName:null,surname:"Zhou",fullName:"Yuwen Zhou",slug:"yuwen-zhou",email:"zhouyuwenmm@163.com",position:null,institution:null},{id:"194475",title:"Prof.",name:"Zili",middleName:null,surname:"Liu",fullName:"Zili Liu",slug:"zili-liu",email:"gzdxlzl@gmail.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Catalysts for CO2 methanation",level:"1"},{id:"sec_2_2",title:"2.1. Noble metal catalysts for low-temperature methanation of CO2",level:"2"},{id:"sec_2_3",title:"2.1.1. Role of the support on catalyst activity",level:"3"},{id:"sec_3_3",title:"2.1.2. Effect of metal loading",level:"3"},{id:"sec_4_3",title:"2.1.3. Effect of second metal",level:"3"},{id:"sec_6_2",title:"2.2. Recent advances in Ni-based catalysts",level:"2"},{id:"sec_6_3",title:"Table 2.",level:"3"},{id:"sec_6_4",title:"Table 2.",level:"4"},{id:"sec_7_4",title:"2.2.1.2. Nickel dispersion",level:"4"},{id:"sec_8_4",title:"2.2.1.3. Catalyst stability",level:"4"},{id:"sec_10_3",title:"Table 3.",level:"3"},{id:"sec_10_4",title:"Table 3.",level:"4"},{id:"sec_11_4",title:"2.2.2.2. Nickel reducibility",level:"4"},{id:"sec_14_2",title:"2.3. Cobalt-based catalysts for low-temperature methanation of CO2",level:"2"},{id:"sec_16",title:"3. Reaction mechanisms",level:"1"},{id:"sec_17",title:"4. Conclusions and perspectives",level:"1"},{id:"sec_18",title:"Acknowledgments",level:"1"}],chapterReferences:[{id:"B1",body:'\nWang W, Wang S, Ma X, Gong J. Recent advances in catalytic hydrogenation of carbon dioxide. Chem Soc Rev. 2011; 40: 3703–3727. doi: 10.1039/C1CS15008A\n'},{id:"B2",body:'\nXiaoding X, Moulijn J A. Mitigation of CO2 by chemical conversion: plausible chemical reactions and promising products. Energy Fuels. 1996; 10: 305–325. doi: 10.1021/ef9501511\n'},{id:"B3",body:'\nPerry R J, O’Brien M J. Amino disiloxanes for CO2 capture. Energy Fuels. 2011; 25: 1906–1918. doi: 10.1021/ef101564h\n'},{id:"B4",body:'\nWang J, Huang L, Yang R, Zhang Z, Wu J, Gao Y, Wang Q, O\'Hare D, Zhong Z. Recent advances in solid sorbents for CO2 capture and new development trends. Energy Environ Sci. 2014; 7: 3478–3518. doi: 10.1039/c4ee01647e\n'},{id:"B5",body:'\nJessop P G, Joo F, Tai C C. 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School of Chemistry and Chemical Engineering, Guangxi University, Nanning, China
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou, China
School of Chemistry and Chemical Engineering, Guangxi University, Nanning, China
School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, China
'}],corrections:null},book:{id:"5426",title:"New Advances in Hydrogenation Processes",subtitle:"Fundamentals and Applications",fullTitle:"New Advances in Hydrogenation Processes - Fundamentals and Applications",slug:"new-advances-in-hydrogenation-processes-fundamentals-and-applications",publishedDate:"January 25th 2017",bookSignature:"Maryam Takht Ravanchi",coverURL:"https://cdn.intechopen.com/books/images_new/5426.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"2416",title:"Dr.",name:"Maryam",middleName:null,surname:"Takht Ravanchi",slug:"maryam-takht-ravanchi",fullName:"Maryam Takht Ravanchi"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},chapters:[{id:"52501",title:"Palladium‐Based Catalysts‐Supported onto End‐Functionalized Poly(lactide) for C–C Double and Triple Bond Hydrogenation Reactions",slug:"palladium-based-catalysts-supported-onto-end-functionalized-poly-lactide-for-c-c-double-and-triple-b",totalDownloads:1114,totalCrossrefCites:0,signatures:"Marco Frediani, Werner Oberhauser, Luca Rosi, Elisa Passaglia and\nMattia Bartoli",authors:[{id:"53209",title:"Dr.",name:"Marco",middleName:null,surname:"Frediani",fullName:"Marco Frediani",slug:"marco-frediani"},{id:"53215",title:"Dr.",name:"Luca",middleName:null,surname:"Rosi",fullName:"Luca Rosi",slug:"luca-rosi"},{id:"188999",title:"Dr.",name:"Mattia",middleName:null,surname:"Bartoli",fullName:"Mattia Bartoli",slug:"mattia-bartoli"},{id:"189810",title:"Dr.",name:"Werner",middleName:null,surname:"Oberhauser",fullName:"Werner Oberhauser",slug:"werner-oberhauser"},{id:"194561",title:"Dr.",name:"Elisa",middleName:null,surname:"Passaglia",fullName:"Elisa Passaglia",slug:"elisa-passaglia"}]},{id:"52126",title:"Alkyne Selective Hydrogenation with Mono- and Bimetallic- Anchored Catalysts",slug:"alkyne-selective-hydrogenation-with-mono-and-bimetallic-anchored-catalysts",totalDownloads:1304,totalCrossrefCites:0,signatures:"Cecilia Lederhos, Carolina Betti, Domingo Liprandi, Edgardo\nCagnola and Mónica Quiroga",authors:[{id:"148671",title:"Dr.",name:"Cecilia",middleName:"R.",surname:"Lederhos",fullName:"Cecilia Lederhos",slug:"cecilia-lederhos"},{id:"154325",title:"Prof.",name:"Edgardo",middleName:null,surname:"Cagnola",fullName:"Edgardo Cagnola",slug:"edgardo-cagnola"},{id:"193998",title:"Dr.",name:"Carolina",middleName:null,surname:"Betti",fullName:"Carolina Betti",slug:"carolina-betti"},{id:"193999",title:"MSc.",name:"Domingo",middleName:null,surname:"Liprandi",fullName:"Domingo Liprandi",slug:"domingo-liprandi"},{id:"194000",title:"Dr.",name:"Monica",middleName:null,surname:"Quiroga",fullName:"Monica Quiroga",slug:"monica-quiroga"}]},{id:"52401",title:"Asymmetric Transfer Hydrogenation of C=O and C=N Bonds Catalyzed by [Ru(η6 arene)(diamine)] Complexes: A Multilateral Study",slug:"asymmetric-transfer-hydrogenation-of-c-o-and-c-n-bonds-catalyzed-by-ru-6-arene-diamine-complexes-a-m",totalDownloads:1204,totalCrossrefCites:0,signatures:"Ondřej Matuška, Martin Kindl and Petr Kačer",authors:[{id:"190932",title:"Associate Prof.",name:"Petr",middleName:null,surname:"Kačer",fullName:"Petr Kačer",slug:"petr-kacer"},{id:"194576",title:"MSc.",name:"Ondřej",middleName:null,surname:"Matuška",fullName:"Ondřej Matuška",slug:"ondrej-matuska"},{id:"194577",title:"MSc.",name:"Martin",middleName:null,surname:"Kindl",fullName:"Martin Kindl",slug:"martin-kindl"}]},{id:"52449",title:"Recent Advances in Heterogeneous Catalytic Hydrogenation of CO2 to Methane",slug:"recent-advances-in-heterogeneous-catalytic-hydrogenation-of-co2-to-methane",totalDownloads:2246,totalCrossrefCites:3,signatures:"Zuzeng Qin, Yuwen Zhou, Yuexiu Jiang, Zili Liu and Hongbing Ji",authors:[{id:"5795",title:"Dr.",name:"Hongbing",middleName:null,surname:"Ji",fullName:"Hongbing Ji",slug:"hongbing-ji"},{id:"188601",title:"Prof.",name:"Zuzeng",middleName:null,surname:"Qin",fullName:"Zuzeng Qin",slug:"zuzeng-qin"},{id:"194474",title:"Mr.",name:"Yuwen",middleName:null,surname:"Zhou",fullName:"Yuwen Zhou",slug:"yuwen-zhou"},{id:"194475",title:"Prof.",name:"Zili",middleName:null,surname:"Liu",fullName:"Zili Liu",slug:"zili-liu"}]},{id:"52322",title:"Hydrogenation of Polycrystalline Silicon Thin‐Film Transistors",slug:"hydrogenation-of-polycrystalline-silicon-thin-film-transistors",totalDownloads:1083,totalCrossrefCites:0,signatures:"Akito Hara and Kuninori Kitahara",authors:[{id:"188567",title:"Prof.",name:"Akito",middleName:null,surname:"Hara",fullName:"Akito Hara",slug:"akito-hara"},{id:"194496",title:"Prof.",name:"Kuninori",middleName:null,surname:"Kitahara",fullName:"Kuninori Kitahara",slug:"kuninori-kitahara"}]},{id:"53512",title:"Catalytic Hydrogenation of Benzoic Acid",slug:"catalytic-hydrogenation-of-benzoic-acid",totalDownloads:1512,totalCrossrefCites:0,signatures:"Sunil B. 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Russell, Jennifer R. Baker, Peter J. 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1. Introduction
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In the 1960s, major milestones were achieved in in vitro maturation (IVM) of human oocytes, and in vitro fertilization (IVF) of IVM oocytes was also established. Therefore, modern assisted reproductive technologies (ARTs) are based on IVM. Currently, the clinical application of IVM may be extended to treat patients with polycystic ovary syndrome (PCOS), ovarian hyperresponsiveness, and hyporesponsiveness, as well as to preserve the fertility of cancer patients [1]. In 2013, the practice committees of the American Society for Reproductive Medicine (ASRM) and the Society for Assisted Reproductive Technology (SART) stated that the clinical pregnancy rate of IVM was still lower than that of conventional IVF, and hence IVM could not yet be considered the first treatment choice for all cases of female infertility [2].
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The current standard protocol for ovulation induction in clinical practice involves intense stimulation with nonphysiological doses of gonadotropins to obtain an average of 10–15 or even dozens of mature oocytes per woman. Although the regimen of high-dose gonadotropin treatment may enable the retrieval of a larger number of oocytes, this approach can exert several short- and long-term adverse effects, including the risk of ovarian hyperstimulation syndrome (OHSS). At present, with the improvement in the IVF efficiency and culture systems, a natural cycle or mild stimulation may be more suitable for women receiving IVF treatments. A previous study showed that natural cycle or mild stimulation IVF is more effective than conventional stimulation protocols in patients with a low functional ovarian reserve [3]. In contrast to the standard stimulation protocol, the mild stimulation protocol is a safer and more rational regimen that helps reduce the hormone dosage, lower treatment risks, and retrieve a small number of high-quality oocytes. Despite these theoretical advantages, the mild stimulation protocol has yet to become a mainstream treatment modality in the United States. With the development of IVM technology, a modified protocol able to increase the success rates of natural cycle or mild stimulation IVF has been established. In this protocol, in addition to the retrieval of mature oocytes in naturally or mildly stimulated cycles, immature oocytes from small follicles are also retrieved for IVM, thereby increasing the total number of retrieved oocytes in a single treatment cycle and the clinical pregnancy rate. Data from previous clinical studies has shown that the combined use of natural cycle or mild stimulation IVF with IVM can expand the applicable scope of IVM technology to the treatment of various types of female infertility and has resulted in satisfactory clinical pregnancy rates and live birth rates [4, 5].
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2. Mechanism of oocyte maturation
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Cyclic adenosine monophosphate (cAMP) plays an important role in regulating the maturation of oocytes. The mural granulosa cells (MGC) located on the follicular wall contain natriuretic peptide precursor C (NPPC), while the cumulus cells around oocytes express natriuretic peptide receptor 2 (NPR2). Oocyte-derived paracrine factors can promote the activation of NPR2 in cumulus cells, while the NPPC in mural granulosa cells can bind to NPR2 receptors in cumulus cells to produce cyclic guanosine monophosphate (cGMP), which then enters into oocytes through gap junctions to inhibit the activity of phosphodiesterase (PDE3A), thereby maintaining a high level of cAMP in oocytes and the arrest of oocytes in the meiosis cycle. The activation of PDE3A by luteinizing hormone (LH) downregulates the level of cAMP in oocytes and induces the maturation of oocytes, thereby relieving the immature oocytes in the germinal vesicle (GV) stage or first meiotic metaphase (MII) from cell cycle arrest, so that they can complete the first meiosis and enter the second MII to develop into mature oocytes [6]. Zhang et al. [7] reported that estradiol can promote and maintain the expression of NPR2 in cumulus cells and participate in NPPC-mediated meiotic arrest of oocytes in vitro. These studies have opened up a new field of molecular mechanistic research on resuming the meiosis of oocytes, providing a theoretical basis for revealing the molecular mechanisms underlying the maturation of oocytes.
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Studies have found that small molecule ribonucleotides (microRNAs) are also important for oocyte maturation. A certain number of dynamic and stable microRNAs were found in both mature oocytes and early-stage embryos, presumably contributing to the maturation of oocytes. Kim et al. [8, 9] reported that microRNAs may affect oocyte maturation by altering the gene expression and function of cumulus cells through cumulus cell interaction and paracrine secretion. Let-7 is one of the most abundant microRNAs in the ovary. Upregulation of Let-7c can increase the rate of oocyte maturation, suggesting that Let-7c may be involved in the information exchange between oocytes and surrounding mural granulosa cells. In addition, maturation-promoting factor (MPF), cytostatic factor (CSF), oocyte maturation inhibitor (OMI), and mitogen-activated protein kinase (MAPK) are involved in oocyte maturation and division [7]. The mechanisms underlying oocyte maturation awaits further studies.
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3. Definition of oocyte IVM
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The biological definition of oocyte IVM is to remove immature oocytes in the GV stage from antral follicles and culture them in a suitable culture system, so that these immature oocytes can mature to MII stage in vitro. However, the clinical definition of IVM technology for immature human oocytes is completely different from its biological definition. The differences include the different sources of immature oocytes, the different protocols used to induce ovulation, and the different time of oocyte retrieval. These factors may lead to the situation where the immature oocytes retrieved clinically are not in the GV stage. The use of human chorionic gonadotropin (hCG) to induce ovulation prior to clinical retrieval of oocytes may lead to the initiation of endogenous oocyte maturation, and hence some of the retrieved immature oocytes may have undergone germinal vesicle breakdown (GVBD) or entered the MI stage. Although immature oocytes in the MI stage have initiated the process of in vivo maturation, they still need to participate in the procedure of in vitro culture and maturation. Therefore, the definition of clinical IVM treatment should include the in vitro culture of immature oocytes in the GV and MI stages.
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A recent point of view proposed to give the clinical definition of IVM of immature oocytes based on the diameter of follicles when the oocytes are retrieved [10]. However, this definition is not completely scientific, since the meiotic state of oocytes cannot be completely determined according to the size of follicles during the stimulation cycle [11, 12]. In addition, for immature oocytes collected from different clinical sources, their maturation rate and the rates to potentially develop into embryos and achieve live birth are different. Therefore, for clinical definition and research of IVM, attention should be paid to the effect of different sources of immature oocytes on the efficiency of IVM.
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4. Factors affecting the in vitro maturation of oocytes
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4.1 Effect of culture time on in vitro maturation of oocytes
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Maturation of oocytes includes the nuclear and cytoplasmic maturation of oocytes. Nuclear maturation refers to the rupture of the germinal vesicle, separation of homologous chromosomes, appearance of the perivitelline space, and discharge of the first polar body. Cytoplasmic maturation refers to the completion of protein phosphorylation and dephosphorylation as well as the rearrangement of organelles in oocytes. Only the oocytes whose nucleus and cytoplasm are matured simultaneously can have adequate fertility and the potential for embryo development. Studies have found that most oocytes cultured in vitro can reach maturity within 24–48 h. The length of in vitro culture can affect the developmental potential of the embryo. The rate of nuclear maturation in oocytes cultured for 48 h in vitro is significantly higher than that for 24 h, but the rate of cytoplasmic maturation in oocytes cultured for 48 h is not significantly different from that for 24 h. Excessive culture time leads to the aging of oocytes and an increased level of associated genetic risks. When the culture time is too short, the maturation of cytoplasm and nucleus is not synchronized and will affect the subsequent development potential of the embryo. Wrenzycki et al. [13] found that oocytes only possess the ability to mature in the final stage of development. Therefore, adequate extension of IVM time can promote the necessary process of oocyte maturation, increase the rate of nuclear maturation in immature oocytes, and significantly improve in vitro developmental potential of oocytes and the rate of high-quality embryos.
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4.2 Effects of hormones on in vitro maturation of oocytes
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Gonadotropin can promote the expansion of cumulus cells and stimulate the maturation of the nucleus and cytoplasm of oocytes, thus facilitating the formation of embryos and blastocysts in the cleavage stage and playing an important role in follicular development [14]. The addition of follicle-stimulating hormone to the culture medium for oocyte maturation can promote the cytoplasmic maturation of oocytes. Some scholars believe that the effect of follicle-stimulating hormone is related to its concentration. When the concentration is 5 g/mL, a relatively high cleavage rate (79.1%) and blastocyst rate (16.1%) can be obtained [15]. The addition of LH or human chorionic gonadotropin to the IVM culture medium may promote protein synthesis, enhance oocyte metabolism, and facilitate oocyte maturation. The concentration of estradiol (E2) in the human body increases with an increasing volume of follicles. In addition, estradiol is involved in maintaining the meiotic arrest of oocytes and can promote the cytoplasmic maturation of oocytes. During in vitro culture of oocytes, nuclear maturation is faster than cytoplasmic maturation. Therefore, the addition of E2 to the culture medium helps synchronize the development of the nucleus and cytoplasm in oocytes.
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4.3 Effect of antioxidant addition on in vitro maturation of oocytes
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As a hydrophobic activator, forskolin (FSK) can increase the activity of adenylate cyclase in mammalian cells and the level of intracellular cAMP. By adding FSK to an IVM culture medium, Ezoe et al. [16] significantly improved the developmental capacity of oocytes in the GV stage. By adding FSK to the culture medium, Zeng et al. [17] promoted the synchronization of nuclear and cytoplasmic maturation and increased the rates of maturation, cleavage, and high-quality embryos. During IVM, the presence of oxidative stress may block oocyte maturation, lead to abnormal gene expression, and impair the cytoplasmic and nuclear development of oocytes, thereby resulting in the failure to obtain high-quality oocytes and decreasing the fertility and developmental capacity. The addition of antioxidants to the culture medium can reduce the damage caused by oxidative stress. By adding a-lipoic acid to the culture medium, Zavareh et al. [18] reduced the content of active oxygen, increased the total antioxidation capacity, and promoted the nuclear and cytoplasmic maturation of oocytes in vitro. The results of Mokhber et al. [19, 20] showed that an appropriate concentration of a natural antioxidant, crocin (100 g/mL), and aqueous extract of saffron (40 g/mL) can increase the concentration of glutathione (GSH), protect oocytes, and significantly increase IVM rate and fertility rate.
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4.4 Effect of co-culture with mural granulosa cells on in vitro maturation of oocytes
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Together with cumulus cells and follicular fluid, MGC form an in vivo environment for oocyte maturation. Co-culture with MGC can increase the rate of nuclear and cytoplasmic maturation of immature oocytes. Studies have shown that co-culture with parietal MGC can improve the nuclear maturation of naked oocytes, slow down the nuclear maturation of naked oocytes, increase the content of glutathione in naked oocytes, reduce the activity of glucose-6-phosphate dehydrogenase in naked oocytes, increase the rate of cytoplasmic maturation, and facilitate the simultaneous development of the nucleus and cytoplasm of oocytes [21]. Although immature oocytes detached of MGC can still mature, they cannot undergo normal fertilization and development because the cytoplasm is not synchronously matured [22]. The addition of a certain amount of MGC to the culture medium can delay the nuclear maturation of oocytes, so that the maturation of the nucleus and cytoplasm becomes more synchronized. However, there is currently no uniform standard for the amount of MGC addition. Choi et al. [23] significantly increased the development potential of embryos by co-culturing the oocyte-corona-cumulus complex with naked oocytes at a 1:5 ratio.
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4.5 Effect of co-culture with oviductal epithelial cells on in vitro maturation of oocytes
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Some scholars have pointed out that the maturation of oocytes is completed in the fallopian tube, and hence some components of the fallopian tube may affect the maturation process of oocytes. Human tubal fluid (HTF) has been used to culture oocytes. Shirazi et al. [24] co-cultured ovine oocytes with oviductal epithelial cells (OECs) and conducted IVF, resulting in higher cleavage and blastocyst rates.
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4.6 Effect of co-culture with mesenchymal stem cells on in vitro maturation of oocytes
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In addition to the potential of self-renewal and multidirectional differentiation, mesenchymal stem cells (MSCs) can also secrete a variety of cytokines and growth factors, and some biologically active factors can enhance the in vitro maturation of oocytes and subsequent developmental potential of embryos. By adding MSCs to a culture medium, Ling et al. [25] significantly increased the maturation rate and rate of blastocyst formation of immature murine oocytes. It can be seen that the co-culture system with MSCs can promote the simultaneous development of the nucleus and cytoplasm of murine oocytes.
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5. Sources of immature oocytes
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5.1 Oocyte retrieval from cesarean section or gynecological surgery
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Immature oocytes retrieved from the ovarian cortex during cesarean section can be cultured in vitro to achieve maturation, fertilization, and healthy progeny. The mature oocytes cultured in this way are expected to be used as the source of oocytes to preserve female fertility [26]. At present, few studies have investigated the approach to obtain immature oocytes during cesarean section for in vitro culture, and hence more studies are needed to prove the safety and effectiveness of immature oocytes obtained from cesarean section.
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In addition to cesarean section, immature oocytes can also be obtained via gynecological surgery in the follicular phase or luteal phase. The number of retrieved oocytes is mainly related to the age, pathological status, and stage of the menstrual cycle of the patient. Clinical studies have confirmed that oocyte retrieval carried out at different stages of the menstrual cycle does not affect the rate of in vitro maturation and the rate of fertilization of oocytes, suggesting that IVM technique can be used to preserve fertility in cancer patients during the follicular phase or luteal phase [27]. Therefore, for cancer patients who lack sufficient time for treatment and are unable to use hormone to induce ovulation, immature oocytes can be retrieved before chemotherapy to carry out IVM and vitrification to maximize the preservation of fertility.
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5.2 PCOS patients
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A large number of antral follicles are present in the ovary of infertile women with anovulatory PCOS. These antral follicles are more sensitive to gonadotropins, and hence the risk of OHSS is increased when hormones are used to induce ovulation. Therefore, for PCOS patients, immature oocytes can be retrieved from antral follicle for in vitro maturation [28]. The use of hCG at 36 h before oocyte retrieval in PCOS patients can promote the resumption of meiosis of immature oocytes and their in vitro maturation, improving the rate of pregnancy and clinical outcomes [29]. The use of small doses of gonadotropin before the retrieval of immature oocytes from PCOS patients is also beneficial to improve the maturation potential of oocytes, increasing the rate of embryo implantation and clinical pregnancy. In addition, IVM techniques can also be considered for some PCOS patients with no or low response to hormones [30].
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5.3 Women with normal ovaries and menstrual cycles
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Based on the advantages of low hormone dosage, low cost, and simple treatment process, IVM has been gradually applied to the treatment of infertile women with normal ovaries and regular menstrual cycles. However, it remains controversial as whether the use of hCG is required in the IVM treatment of this type of patient prior to oocyte retrieval. It should be noted that the hCG trigger exerts different effects on normal ovaries and PCOS patients. In the IVM treatment cycle of PCOS patients, dominant follicles are barely visible in the ovary, but MI-stage oocytes can be retrieved from small follicles after hCG-induced ovulation. However, after the hCG trigger is used in the normal ovary during the follicular phase, most oocytes retrieved from small follicles are oocytes in the GV stage. There is currently no evidence suggesting that the hCG trigger exerts a significant effect on the pregnancy rate, live birth rate, or abortion rate in the IVM of immature oocytes obtained from normal ovaries [31]. However, the accuracy of these findings is limited by the small number of samples. Therefore, a well-designed, randomized, and controlled clinical trial is needed to further confirm the optimal dosage and timing of hCG administration.
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6. IVM culture system
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6.1 Improvement of IVM media
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The in vitro maturation of oocytes is mainly affected by culture conditions. At present, the common media used for the IVM of immature human oocytes include TCM-199 medium, Ham’s F10 medium, and Chang’s medium. In addition, serum, gonadotropin [follicle-stimulating hormone and luteinizing hormone], growth factors, and steroids can be added in a basal medium to produce a complex medium. At present, commercial IVM media have been widely used. However, no breakthrough has been made in the research on improving the quality of oocytes by improving the IVM medium. In recent years, research and application of antioxidants and growth-promoting factors have promoted the advancement of this technology to some extent. In addition, using cell cycle regulators or inhibitors of mitotic spindle formation, the synchronization of nuclear and cytoplasmic maturation of immature oocytes can be achieved by inhibiting GVBD, thereby increasing the blastocyst rate and live birth rate in animal models [32]. However, the safety and efficacy of this method in human oocytes should be further verified.
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6.2 Optimization of IVM culture environment and process
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The culture environment, equipment, and related operations in the IVM system may affect the in vitro maturation and embryo development of immature oocytes. Therefore, the optimization of the embryo culture environment and process of in vitro operation will help to maintain the potential of embryonic development [33, 34]. The three-dimensional culture system can support the development of follicles by using biological materials to maintain cell-to-cell information exchange. In addition, mature oocytes can be obtained by using a three-dimensional culture system in the in vitro culture of anterior follicles of nonhuman primates [35], although no reports are available regarding the use of a three-dimensional culture system in the in vitro culture of immature human oocytes. A past study has used microreactors to form three-dimensional bioreactors to support the growth of different types of cells [36]. Consisting of a drop of liquid encapsulated by hydrophobic powder particles, this system can provide a suitable microenvironment for in vitro maturation of oocytes. In addition, the development of microfluidic technology will exert an important impact in the field of human gametes and preimplantation embryo development and will have potential applications in the field of ART. This technology enables the creation of microfluidic models mimicking the “menstrual cycle of women” [37]. These models include interconnected 3D models of different tissues, such as 3D models of the ovaries, fallopian tubes, uterus, cervix, and vagina, in the female reproductive system and the endocrine cycle between various organ modules. The mechanical and biochemical properties of microfluidic systems still require intensive research before these systems can be applied to clinical applications in areas such as IVM of immature human oocytes.
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7. Clinical application and safety of IVM
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At present, the in vitro maturation rate of immature human oocytes can reach 70%, but the developmental potential of mature oocytes obtained in vitro is still lower than that of mature oocytes obtained in vivo. In addition, the rate of blastocyst development and the rate of implantation are relatively low after the fertilization of IVM oocytes. The main reason of such discrepancy may be related to non-synchronized nuclear and cytoplasmic maturation during IVM. With the further development in the basic and clinical research of IVM, the in-depth study on the mechanisms of oocyte maturation and mastery of key factors involved in oocyte maturation will contribute to the improvement and optimization of clinical IVM technology.
\n
The results of current research showed that human oocytes matured in vivo or in vitro display no significant differences in terms of their spindle morphology, organelle distribution, cortical particle distribution, and mitochondrial morphology [38, 39]. By observing embryos dynamically using time-lapse videos, it was confirmed that oocytes matured in vivo or in vitro showed no significant differences in terms of the morphological dynamics observed during the early development of embryos derived from these oocytes [40]. Another study has also shown that the oocytes matured in vitro and in vivo are different in terms of their organelle function, distribution, and gene expression [41]. The different experimental conclusions mentioned above may be caused by different sources and quality of oocytes used in these studies. Therefore, attention should be paid to clarify the IVM efficiency of oocytes retrieved from different sources, so as to reasonably evaluate the safety of IVM. In terms of epigenetics, a study has reported that IVM exerts no significant effect on the methylation level of maternal imprinted genes, such as LIT1, SNRPN, PEG3, and GTL2, in human oocytes [42]. After an imprinted gene examination was carried out for infant chorionic cells and cord blood obtained from IVM and a standard stimulation protocol, no significant difference was observed between the two methods [43, 44]. Currently, the follow-up of IVM-aided pregnancies shows that the IVM technique does not increase the risk of pregnancy, the rate of maternal complications, and the rate of neonatal abnormalities [45, 46]. However, due to a small sample size and the lack of in-depth study on epigenetics, the clinical application and safety of IVM still require investigations of large sample sizes to reach a definitive conclusion regarding the safety of IVM in terms of epigenetics.
\n
At present, more than 5000 IVM babies have been born worldwide, and the rate of clinical pregnancy among PCOS patients undergoing IVM treatment can reach about 35–40% [47]. IVM has been extended from the basic research to the treatment of patients with PCOS, ovarian hyperresponsiveness and hyporesponsiveness, as well as cancer patients to preserve the fertility. Therefore, IVM has a prospect of broad applications.
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8. Conclusion
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At present, the application scope of IVM technology can be extended to patients with various causes of infertility. In addition, the IVM technology is associated with acceptable pregnancy and live birth rates. Although IVM has been used as an effective treatment and achieved significant outcomes with thousands of healthy IVM babies having been delivered, IVM is still considered as an experimental technique by the society. With the development of IVM technology, the combination of natural cycle IVF with the IVM of immature oocytes can be used as an attractive regimen to promote IVM treatment. More infertile women can benefit from such approaches if the treatment process is simplified by mild stimulation, especially when the difficulty to obtain immature oocytes is reduced. Therefore, the combination of mild stimulation IVF and IVM treatment can become a viable alternative to current standard treatments. With the accumulation of more experience and results, it will be further demonstrated that the combination of mild stimulation IVF and IVM is not only a viable alternative to current standard treatments but may also become a potential option of first-line treatment.
\n
\n\n',keywords:"in vitro maturation (IVM), assisted reproductive technologies (ARTs), cytoplasmic maturation, antral follicles, granulosa cells",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/67832.pdf",chapterXML:"https://mts.intechopen.com/source/xml/67832.xml",downloadPdfUrl:"/chapter/pdf-download/67832",previewPdfUrl:"/chapter/pdf-preview/67832",totalDownloads:614,totalViews:3,totalCrossrefCites:0,dateSubmitted:"January 9th 2019",dateReviewed:"June 6th 2019",datePrePublished:"June 28th 2019",datePublished:"August 28th 2019",dateFinished:null,readingETA:"0",abstract:"In vitro maturation (IVM) is a technique used to induce immature oocytes collected in different periods of embryonic growth. The rates vary for immature oocytes collected from different clinical sources to potentially develop into embryos and achieve live birth. As an effective treatment method, IVM can be used to treat patients with polycystic ovary syndrome (PCOS), ovarian hyperresponsiveness, and hyporesponsiveness, as well as to preserve the fertility of cancer patients. This technology has been used worldwide for the birth of thousands of healthy babies. The improvement in clinical IVM technology mainly focuses on the IVM medium and the optimization of the culture environment and operation process. At present, with the improvement in the in vitro fertilization (IVF) efficiency and culture systems, a natural cycle or mild stimulation may be more suitable for women receiving IVF treatments. A new treatment option was proposed to combine natural cycle/mild stimulation IVF with IVM. In particular, the combination of mild stimulation IVF and IVM is not only expected to become a viable alternative to current standard treatments but may also become a potential option of first-line treatment.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/67832",risUrl:"/chapter/ris/67832",signatures:"Xiaolin La, Jing Zhao and Zhihui Wang",book:{id:"6977",title:"Embryology",subtitle:"Theory and Practice",fullTitle:"Embryology - Theory and Practice",slug:"embryology-theory-and-practice",publishedDate:"August 28th 2019",bookSignature:"Bin Wu and Huai L. Feng",coverURL:"https://cdn.intechopen.com/books/images_new/6977.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"108807",title:"Ph.D.",name:"Bin",middleName:null,surname:"Wu",slug:"bin-wu",fullName:"Bin Wu"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:[{id:"291066",title:"Dr.",name:"Xiaolin",middleName:null,surname:"La",fullName:"Xiaolin La",slug:"xiaolin-la",email:"909232905@qq.com",position:null,institution:null},{id:"291067",title:"Dr.",name:"Jing",middleName:null,surname:"Zhao",fullName:"Jing Zhao",slug:"jing-zhao",email:"littlemili@126.com",position:null,institution:null},{id:"308602",title:"Dr.",name:"Zhihui",middleName:null,surname:"Wang",fullName:"Zhihui Wang",slug:"zhihui-wang",email:"309145859@qq.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Mechanism of oocyte maturation",level:"1"},{id:"sec_3",title:"3. Definition of oocyte IVM",level:"1"},{id:"sec_4",title:"4. Factors affecting the in vitro maturation of oocytes",level:"1"},{id:"sec_4_2",title:"4.1 Effect of culture time on in vitro maturation of oocytes",level:"2"},{id:"sec_5_2",title:"4.2 Effects of hormones on in vitro maturation of oocytes",level:"2"},{id:"sec_6_2",title:"4.3 Effect of antioxidant addition on in vitro maturation of oocytes",level:"2"},{id:"sec_7_2",title:"4.4 Effect of co-culture with mural granulosa cells on in vitro maturation of oocytes",level:"2"},{id:"sec_8_2",title:"4.5 Effect of co-culture with oviductal epithelial cells on in vitro maturation of oocytes",level:"2"},{id:"sec_9_2",title:"4.6 Effect of co-culture with mesenchymal stem cells on in vitro maturation of oocytes",level:"2"},{id:"sec_11",title:"5. Sources of immature oocytes",level:"1"},{id:"sec_11_2",title:"5.1 Oocyte retrieval from cesarean section or gynecological surgery",level:"2"},{id:"sec_12_2",title:"5.2 PCOS patients",level:"2"},{id:"sec_13_2",title:"5.3 Women with normal ovaries and menstrual cycles",level:"2"},{id:"sec_15",title:"6. IVM culture system",level:"1"},{id:"sec_15_2",title:"6.1 Improvement of IVM media",level:"2"},{id:"sec_16_2",title:"6.2 Optimization of IVM culture environment and process",level:"2"},{id:"sec_18",title:"7. Clinical application and safety of IVM",level:"1"},{id:"sec_19",title:"8. Conclusion",level:"1"}],chapterReferences:[{id:"B1",body:'Sauerbrun-Cutler MT, Vega M, Keltz M. et al., In vitro maturation and its role in clinical assisted reproductive technology. Obstetrical & Gynecological Survey. 2015;70(1):45-57\n'},{id:"B2",body:'Practice Committees of the American Society for Reproductive Medicine and the Society for Assisted Reproductive Technology. 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Developmental competence of vitrified-warmed bovine oocytes at the germinal-vesicle stage is improved by cyclic adenosine monophosphate modulators during in vitro maturation. PLoS One. 2015;10(5):e0126801\n'},{id:"B17",body:'Zeng H, Ren Z, Guzman L, et al. Heparin and cAMP modulators interact during pre-in vitro maturation to affect mouse and human oocyte meiosis and developmental competence. Human Reproduction. 2013;28(6):1536-1545\n'},{id:"B18",body:'Zavareh S, Karimi I, Salehnia M, et al. Effect of in vitro maturation technique and alpha lipoic acid supplementation on oocyte maturation rate: Focus on oxidative status of oocytes. International Journal of Fertility and Sterility. 2016;9(4):442-451\n'},{id:"B19",body:'Mokhber Maleki E, Eimani H, Bigdeli MR, et al. Effects of crocin supplementation during in vitro maturation of mouse oocytes on glutathione synthesis and cytoplasmic maturation. International Journal of Fertility and Sterility. 2016;10(1):53-61\n'},{id:"B20",body:'Mokhber Maleki E, Eimani H, Bigdeli MR, et al. A comparative study of saffron aqueous extract and its active ingredient, crocin on the in vitro maturation, in vitro fertilization, and in vitro culture of mouse oocytes. Taiwanese Journal of Obstetrics & Gynecology. 2014;53(1):21-25\n'},{id:"B21",body:'Casillas F, Ducolomb Y, Lemus AE, et al. Porcine embryo production following in vitro fertilization and intracytoplasmic sperm injection from vitrified immature oocytes matured with a granulosa cell co-culture system. Cryobiology. 2015;71(2):299-305\n'},{id:"B22",body:'Abdel-Ghani MA, Shimizu T, Asano T, et al. In vitro maturation of canine oocytes co-cultured with bovine and canine granulosa cell monolayers. Theriogenology. 2012;77(2):347-355\n'},{id:"B23",body:'Choi BH, Bang JI, Jin JI, et al. Coculturing cumulus oocyte complexes with denuded oocytes alters zona pellucida ultrastructure in in vitro matured bovine oocytes. Theriogenology. 2013;80(9):1117-1123\n'},{id:"B24",body:'Shirazi A, Motaghi E. The in vitro fertilization of ovine oocytes in the presence of oviductal cells and its effect on the expression of zygote arrest 1 (Zar 1) and subsequent embryonic development. Journal of Reproduction & Infertility. 2013;14(1):8-16\n'},{id:"B25",body:'Ling B, Feng D-q, Zhou Y, et al. Effect of conditioned medium of mesenchymal stem cells on the in vitro maturation and subsequent development of mouse oocyte. Brazilian Journal of Medical and Biological Research. 2008;41(11):978-985\n'},{id:"B26",body:'Duarte Alcoba D, Gonsales Valrio E, Conzatti M, et al. Selection of developmentally competent human oocytes aspirated during cesarean section. The Journal of Maternal-Fetal & Neonatal Medicine. 2018;31(6):735-739\n'},{id:"B27",body:'Maman E, Meirow D, Brengauz M, et al. Luteal phase oocyte retrieval and in vitro maturation is an optional procedure for urgent fertility preservation. Fertility and Sterility. 2011;95(1):64-67\n'},{id:"B28",body:'Siristatidis C, Sergentanis TN, Vogiatzi P, et al. In vitro maturation in women with vs. without polycystic ovarian syndrome: A systematic review and meta-analysis. PLoS One. 2015;10(8):e0134696\n'},{id:"B29",body:'Reavey J, Vincent K, Child T, et al. Human chorionic gonadotrophin priming for fertility treatment with in vitro maturation. Cochrane Database of Systematic Reviews. 2016;11:CD008720\n'},{id:"B30",body:'Choavaratana R, Thanaboonyawat I, Laokirkkiat P, et al. Outcomes of follicle-stimulating hormone priming and nonpriming in in vitro maturation of oocytes in infertile women with polycystic ovarian syndrome: A single-blinded randomized study. Gynecologic and Obstetric Investigation. 2015;79(3):153-159\n'},{id:"B31",body:'Fadini R, Dal Canto MB, Mignini Renzini M, et al. Effect of different gonadotrophin priming on IVM of oocytes from women with normal ovaries: A prospective randomized study. Reproductive Biomedicine Online. 2009;19(3):343-351\n'},{id:"B32",body:'Gilchrist RB. Recent insights into oocyte-follicle cell interactions provide opportunities for the development of new approaches to in vitro maturation. Reproduction, Fertility, and Development. 2011;23(1):23-31\n'},{id:"B33",body:'Swain JE. Optimal human embryo culture. Seminars in Reproductive Medicine. 2015;33(2):103-117\n'},{id:"B34",body:'Swain JE, Carrell D, Cobo A, et al. Optimizing the culture environment and embryo manipulation to help maintain embryo developmental potential. Fertility and Sterility. 2016;105(3):571-587\n'},{id:"B35",body:'Smith GD, Takayama S. Application of microfluidic technologies to human assisted reproduction. Molecular Human Reproduction. 2017;23(4):257-268\n'},{id:"B36",body:'Xiao S, Coppeta JR, Rogers HB, et al. A microfluidic culture model of the human reproductive tract and 28-day menstrual cycle. Nature Communications. 2017;8:14584\n'},{id:"B37",body:'Ledda S, Idda A, Kelly J, et al. A novel technique for in vitro maturation of sheep oocytes in a liquid marble microbioreactor. Journal of Assisted Reproduction and Genetics. 2016;33(4):513-518\n'},{id:"B38",body:'Omidi M, Khalili MA, Ashourzadeh S, et al. Zona pellucida birefringence and meiotic spindle visualisation of human oocytes are not influenced by IVM technology. Reproduction, Fertility, and Development. 2014;26(3):407-413\n'},{id:"B39",body:'Coticchio G, Dal Canto M, Fadini R, et al. Ultrastructure of human oocytes after in vitro maturation. Molecular Human Reproduction. 2016;22(2):110-118\n'},{id:"B40",body:'Dal Canto M, Novara PV, Coticchio G, et al. Morphokinetics of embryos developed from oocytes matured in vitro. Journal of Assisted Reproduction and Genetics. 2016;33(2):247-253\n'},{id:"B41",body:'Walls ML, Hart R, Keelan JA, et al. Structural and morphologic differences in human oocytes after in vitro maturation compared with standard in vitro fertilization. Fertility and Sterility. 2016;106(6):1392-1398\n'},{id:"B42",body:'Kuhtz J, Romero S, De Vos M, et al. Human in vitro oocyte maturation is not associated with increased imprinting error rates at LIT1, SNRPN, PEG3 and GTL2. Human Reproduction. 2014;29(9):1995-2005\n'},{id:"B43",body:'Yoshida H, Abe H, Arima T. Quality evaluation of IVM embryo and imprinting genes of IVM babies. Journal of Assisted Reproduction and Genetics. 2013;30(2):221-225\n'},{id:"B44",body:'Pliushch G, Schneider E, Schneider T, et al. In vitro maturation of oocytes is not associated with altered deoxyribonucleic acid methylation patterns in children from in vitro fertilization or intracytoplasmic sperm injection. Fertility and Sterility. 2015;103(3):720.e1-727.e1\n'},{id:"B45",body:'Chian RC, Xu CL, Huang JY, et al. Obstetric outcomes and congenital abnormalities in infants conceived with oocytes matured in vitro. Facts, Views & Vision in ObGyn. 2014;6(1):15-18\n'},{id:"B46",body:'Fadini R, Mignini Renzini M, Guarnieri T, et al. Comparison of the obstetric and perinatal outcomes of children conceived from in vitro or in vivo matured oocytes in in vitro maturation treatments with births from conventional ICSI cycles. Human Reproduction. 2012;27(12):3601-3608\n'},{id:"B47",body:'Chian RC, Uzelac PS, Nargund G. In vitro maturation of human immature oocytes for fertility preservation. Fertility and Sterility. 2013;99(5):1173-1181\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Xiaolin La",address:"909232905@qq.com",affiliation:'
First Affiliated Hospital of Xinjiang Medical University, Xinjiang, China
First Affiliated Hospital of Xinjiang Medical University, Xinjiang, China
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The company was founded in Vienna in 2004 by Alex Lazinica and Vedran Kordic, two PhD students researching robotics. While completing our PhDs, we found it difficult to access the research we needed. So, we decided to create a new Open Access publisher. A better one, where researchers like us could find the information they needed easily. The result is IntechOpen, an Open Access publisher that puts the academic needs of the researchers before the business interests of publishers.
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We started by publishing journals and books from the fields of science we were most familiar with - AI, robotics, manufacturing and operations research. Through our growing network of institutions and authors, we soon expanded into related fields like environmental engineering, nanotechnology, computer science, renewable energy and electrical engineering, Today, we are the world’s largest Open Access publisher of scientific research, with over 4,200 books and 54,000 scientific works including peer-reviewed content from more than 116,000 scientists spanning 161 countries. Our authors range from globally-renowned Nobel Prize winners to up-and-coming researchers at the cutting edge of scientific discovery.
\\n\\n
In the same year that IntechOpen was founded, we launched what was at the time the first ever Open Access, peer-reviewed journal in its field: the International Journal of Advanced Robotic Systems (IJARS).
\\n\\n
The IntechOpen timeline
\\n\\n
2004
\\n\\n
\\n\\t
Intech Open is founded in Vienna, Austria, by Alex Lazinica and Vedran Kordic, two PhD students, and their first Open Access journals and books are published.
\\n\\t
Alex and Vedran launch the first Open Access, peer-reviewed robotics journal and IntechOpen’s flagship publication, the International Journal of Advanced Robotic Systems (IJARS).
\\n
\\n\\n
2005
\\n\\n
\\n\\t
IntechOpen publishes its first Open Access book: Cutting Edge Robotics.
\\n
\\n\\n
2006
\\n\\n
\\n\\t
IntechOpen publishes a special issue of IJARS, featuring contributions from NASA scientists regarding the Mars Exploration Rover missions.
\\n
\\n\\n
2008
\\n\\n
\\n\\t
Downloads milestone: 200,000 downloads reached
\\n
\\n\\n
2009
\\n\\n
\\n\\t
Publishing milestone: the first 100 Open Access STM books are published
\\n
\\n\\n
2010
\\n\\n
\\n\\t
Downloads milestone: one million downloads reached
\\n\\t
IntechOpen expands its book publishing into a new field: medicine.
\\n
\\n\\n
2011
\\n\\n
\\n\\t
Publishing milestone: More than five million downloads reached
\\n\\t
IntechOpen publishes 1996 Nobel Prize in Chemistry winner Harold W. Kroto’s “Strategies to Successfully Cross-Link Carbon Nanotubes”. Find it here.
\\n\\t
IntechOpen and TBI collaborate on a project to explore the changing needs of researchers and the evolving ways that they discover, publish and exchange information. The result is the survey “Author Attitudes Towards Open Access Publishing: A Market Research Program”.
\\n\\t
IntechOpen hosts SHOW - Share Open Access Worldwide; a series of lectures, debates, round-tables and events to bring people together in discussion of open source principles, intellectual property, content licensing innovations, remixed and shared culture and free knowledge.
\\n
\\n\\n
2012
\\n\\n
\\n\\t
Publishing milestone: 10 million downloads reached
\\n\\t
IntechOpen holds Interact2012, a free series of workshops held by figureheads of the scientific community including Professor Hiroshi Ishiguro, director of the Intelligent Robotics Laboratory, who took the audience through some of the most impressive human-robot interactions observed in his lab.
\\n
\\n\\n
2013
\\n\\n
\\n\\t
IntechOpen joins the Committee on Publication Ethics (COPE) as part of a commitment to guaranteeing the highest standards of publishing.
\\n
\\n\\n
2014
\\n\\n
\\n\\t
IntechOpen turns 10, with more than 30 million downloads to date.
\\n\\t
IntechOpen appoints its first Regional Representatives - members of the team situated around the world dedicated to increasing the visibility of our authors’ published work within their local scientific communities.
\\n
\\n\\n
2015
\\n\\n
\\n\\t
Downloads milestone: More than 70 million downloads reached, more than doubling since the previous year.
\\n\\t
Publishing milestone: IntechOpen publishes its 2,500th book and 40,000th Open Access chapter, reaching 20,000 citations in Thomson Reuters ISI Web of Science.
\\n\\t
40 IntechOpen authors are included in the top one per cent of the world’s most-cited researchers.
\\n\\t
Thomson Reuters’ ISI Web of Science Book Citation Index begins indexing IntechOpen’s books in its database.
\\n
\\n\\n
2016
\\n\\n
\\n\\t
IntechOpen is identified as a world leader in Simba Information’s Open Access Book Publishing 2016-2020 report and forecast. IntechOpen came in as the world’s largest Open Access book publisher by title count.
\\n
\\n\\n
2017
\\n\\n
\\n\\t
Downloads milestone: IntechOpen reaches more than 100 million downloads
\\n\\t
Publishing milestone: IntechOpen publishes its 3,000th Open Access book, making it the largest Open Access book collection in the world
We started by publishing journals and books from the fields of science we were most familiar with - AI, robotics, manufacturing and operations research. Through our growing network of institutions and authors, we soon expanded into related fields like environmental engineering, nanotechnology, computer science, renewable energy and electrical engineering, Today, we are the world’s largest Open Access publisher of scientific research, with over 4,200 books and 54,000 scientific works including peer-reviewed content from more than 116,000 scientists spanning 161 countries. Our authors range from globally-renowned Nobel Prize winners to up-and-coming researchers at the cutting edge of scientific discovery.
\n\n
In the same year that IntechOpen was founded, we launched what was at the time the first ever Open Access, peer-reviewed journal in its field: the International Journal of Advanced Robotic Systems (IJARS).
\n\n
The IntechOpen timeline
\n\n
2004
\n\n
\n\t
Intech Open is founded in Vienna, Austria, by Alex Lazinica and Vedran Kordic, two PhD students, and their first Open Access journals and books are published.
\n\t
Alex and Vedran launch the first Open Access, peer-reviewed robotics journal and IntechOpen’s flagship publication, the International Journal of Advanced Robotic Systems (IJARS).
\n
\n\n
2005
\n\n
\n\t
IntechOpen publishes its first Open Access book: Cutting Edge Robotics.
\n
\n\n
2006
\n\n
\n\t
IntechOpen publishes a special issue of IJARS, featuring contributions from NASA scientists regarding the Mars Exploration Rover missions.
\n
\n\n
2008
\n\n
\n\t
Downloads milestone: 200,000 downloads reached
\n
\n\n
2009
\n\n
\n\t
Publishing milestone: the first 100 Open Access STM books are published
\n
\n\n
2010
\n\n
\n\t
Downloads milestone: one million downloads reached
\n\t
IntechOpen expands its book publishing into a new field: medicine.
\n
\n\n
2011
\n\n
\n\t
Publishing milestone: More than five million downloads reached
\n\t
IntechOpen publishes 1996 Nobel Prize in Chemistry winner Harold W. Kroto’s “Strategies to Successfully Cross-Link Carbon Nanotubes”. Find it here.
\n\t
IntechOpen and TBI collaborate on a project to explore the changing needs of researchers and the evolving ways that they discover, publish and exchange information. The result is the survey “Author Attitudes Towards Open Access Publishing: A Market Research Program”.
\n\t
IntechOpen hosts SHOW - Share Open Access Worldwide; a series of lectures, debates, round-tables and events to bring people together in discussion of open source principles, intellectual property, content licensing innovations, remixed and shared culture and free knowledge.
\n
\n\n
2012
\n\n
\n\t
Publishing milestone: 10 million downloads reached
\n\t
IntechOpen holds Interact2012, a free series of workshops held by figureheads of the scientific community including Professor Hiroshi Ishiguro, director of the Intelligent Robotics Laboratory, who took the audience through some of the most impressive human-robot interactions observed in his lab.
\n
\n\n
2013
\n\n
\n\t
IntechOpen joins the Committee on Publication Ethics (COPE) as part of a commitment to guaranteeing the highest standards of publishing.
\n
\n\n
2014
\n\n
\n\t
IntechOpen turns 10, with more than 30 million downloads to date.
\n\t
IntechOpen appoints its first Regional Representatives - members of the team situated around the world dedicated to increasing the visibility of our authors’ published work within their local scientific communities.
\n
\n\n
2015
\n\n
\n\t
Downloads milestone: More than 70 million downloads reached, more than doubling since the previous year.
\n\t
Publishing milestone: IntechOpen publishes its 2,500th book and 40,000th Open Access chapter, reaching 20,000 citations in Thomson Reuters ISI Web of Science.
\n\t
40 IntechOpen authors are included in the top one per cent of the world’s most-cited researchers.
\n\t
Thomson Reuters’ ISI Web of Science Book Citation Index begins indexing IntechOpen’s books in its database.
\n
\n\n
2016
\n\n
\n\t
IntechOpen is identified as a world leader in Simba Information’s Open Access Book Publishing 2016-2020 report and forecast. IntechOpen came in as the world’s largest Open Access book publisher by title count.
\n
\n\n
2017
\n\n
\n\t
Downloads milestone: IntechOpen reaches more than 100 million downloads
\n\t
Publishing milestone: IntechOpen publishes its 3,000th Open Access book, making it the largest Open Access book collection in the world
\n
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