The physiochemical properties of the perovskite-type catalysts (taken from ref.17, reproduced by permission of The Royal Society of Chemistry).
\r\n\t
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Ismail",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10013.jpg",keywords:"Thermodynamics, Heat Transfer Analyses, Geothermal Power Generation, Economics, Geothermal Systems, Geothermal Heat Pump, Green Energy Buildings, Exploration Methods, Geologic Fundamentals, Geotechnical, Geothermal System Materials, Sustainability",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"October 29th 2020",dateEndSecondStepPublish:"November 26th 2020",dateEndThirdStepPublish:"January 25th 2021",dateEndFourthStepPublish:"April 15th 2021",dateEndFifthStepPublish:"June 14th 2021",remainingDaysToSecondStep:"2 months",secondStepPassed:!0,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"Leading research investigator in a collaborative project (2007-2010) with Goldcorp-Musselwhite Canada Ltd. and Engineering of Lakehead University, owner of a Ph.D. degree in Mechanical Engineering from McMaster University, Hamilton, Ontario, Canada and postdoctoral researcher (2004 to 2005) at McMaster University.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"62122",title:"Dr.",name:"Basel",middleName:"I.",surname:"Ismail",slug:"basel-ismail",fullName:"Basel Ismail",profilePictureURL:"https://mts.intechopen.com/storage/users/62122/images/system/62122.jpg",biography:"Dr. B. Ismail is currently an Associate Professor and Chairman of the Department of Mechanical Engineering, Lakehead University, Thunder Bay, Ontario, Canada. In 2004, Prof. Ismail earned his Ph.D. degree in Mechanical Engineering from McMaster University, Hamilton, Ontario, Canada. From 2004 to 2005, he worked as a Postdoctoral researcher at McMaster University. His specialty is in engineering heat transfer, engineering thermodynamics, and energy conversion and storage engineering. Dr. Ismail’s research activities are theoretical and applied in nature. Currently, his research areas of interest are focused on green engineering technologies related to alternative and renewable energy systems for power generation, heating and cooling. Dr. Ismail was the leading research investigator in a collaborative project (2007-2010) with Goldcorp-Musselwhite Canada Ltd. and Engineering of Lakehead University. This innovative project was state-of-the-art in geothermal heat pump technology applied in Northwestern Ontario, Canada. Dr. Ismail has published many technical reports and articles related to his research areas in reputable International Journals and Conferences. During his research activities, Dr. Ismail has supervised and trained many graduate students and senior undergraduate students in Mechanical Engineering with projects and theses related to innovative renewable and alternative energy engineering, and technologies.",institutionString:"Lakehead University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"3",institution:{name:"Lakehead University",institutionURL:null,country:{name:"Canada"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"11",title:"Engineering",slug:"engineering"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"184402",firstName:"Romina",lastName:"Rovan",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/184402/images/4747_n.jpg",email:"romina.r@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"5084",title:"Advances in Geothermal Energy",subtitle:null,isOpenForSubmission:!1,hash:"d4647f1f9dae170acf327283d55abbf1",slug:"advances-in-geothermal-energy",bookSignature:"Basel I. Ismail",coverURL:"https://cdn.intechopen.com/books/images_new/5084.jpg",editedByType:"Edited by",editors:[{id:"62122",title:"Dr.",name:"Basel",surname:"Ismail",slug:"basel-ismail",fullName:"Basel Ismail"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"5602",title:"Renewable Hydropower Technologies",subtitle:null,isOpenForSubmission:!1,hash:"15ea891d96b6c9f2d3f28d5a21c09203",slug:"renewable-hydropower-technologies",bookSignature:"Basel I. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"49475",title:"Copper-based Perovskite Design and Its Performance in CO2 Hydrogenation to Methanol",doi:"10.5772/61520",slug:"copper-based-perovskite-design-and-its-performance-in-co2-hydrogenation-to-methanol",body:'Perovskite-type oxides have received significant attention because of their important electric, magnetic, ferromagnetic, pyroelectric, and piezoelectric properties [1,2]. Recently, much attention has been paid to perovskite-type oxides as catalysts due to their high activity and thermal stability. For a typical ABO3 perovskite, A-site is a larger rare earth and/or alkaline earth cation and B-site is a smaller transition metal cation. In such structure, the A-site keeps the structure and the B-site provides the catalytic activity site. B-site cations could be reduced to well-dispersed metallic species supported on the A-site cations oxide, which leads to ideal catalyst precursors for many reactions that involve metal as active sites [3,4]. Besides, perovskite-type A2BO4 mixed oxides with the K2NiF4 structure, consisting of alternating layers of ABO3 perovskite and AO rock salt, have also been studied [5], which exhibit variable oxygen stoichiometry. The replacement of A-site and/or B-site cations by other metal cations often results in the formation of crystal microstrain and adjustable activity [6].
CO2 is the main greenhouse gas, and various strategies have been implemented to reduce its concentration [7-10]. An important CO2 utilization is the hydrogenation to methanol, which is considered as the most valuable product since it can be used as solvent, alternative fuel, and raw material, and it can be converted to olefins, aromatics, or gasoline derived from traditional petrochemical processes [11,12].
The synthesis of methanol over Cu/ZnO-type catalysts has been studied for many years. However, several important problems still remain open, such as the working oxidation of copper and the reaction mechanism [13-15]. In addition, the low activity and stability of catalysts, which are partly attributed to Cu sintering accelerated by the presence of the by-product, water vapor, create major barriers for practical application [16]. It is found that the catalysts with higher Cu dispersion, easier reduction property, and better adsorption properties for relative gases could achieve better catalytic performance for methanol synthesis [16].
Few work on the application of Cu-based perovskite-type oxides for CO2 hydrogenation has been investigated. In the present work, three series of perovskite-type-based catalysts were prepared and tested for CO2 hydrogenation to methanol, and the relationship between physical–chemical property and catalytic performance was discussed.
The perovskite-type oxides were prepared by sol-gel method using citric acid as complexing agent. The precursor salts were La(NO3)3. nH2O; Mn(NO3)2, 50% solution; Cu(NO3)2. 3H2O; Mg(NO3)2. 6H2O; Y(NO3)3. 6H2O; Zn(NO3)2. 6H2O; Ce(NO3)3. 6H2O; ZrO(NO3)2.2H2O. Adequate amounts of the precursor salts along with citric acid were dissolved in deionized water at a molar ratio of 2:1 (metal cations: citric acid). The solution was heated to 353 K to remove the water, and then the temperature was increased to 423 K until ignition. The resulting powder was finally calcined under air at 673 K for 2 h and then at 1073 K for 4 h. The three series of catalysts were: (1) For doped La–M-Mn–Cu–O based (M= Mg, Y, Zn, Ce) perovskite materials, the ratio for La, M, Mn, Cu is 0.8: 0.2: 0.5: 0.5. The La–Mn–Cu–O catalyst and Mg, Y, Zn, Ce doping catalysts were then denoted as P, Mg–P, Y–P, Zn–P, and Ce–P, respectively. (2) A series of La–M-Cu–Zn–O (M= Ce, Mg, Zr, Y) based perovskite-type catalysts, i.e., LaCu0.7Zn0.3Ox, La0.8Ce0.2Cu0.7Zn0.3Ox, La0.8Mg0.2Cu0.7Zn0.3Ox, La0.8Zr0.2Cu0.7Zn0.3Ox and La0.8Y0.2Cu0.7Zn0.3Ox samples were prepared, of which the subscripts were the nominal composition. The catalysts were then denoted as LCZ-173, LCCZ-8273, LMCZ-8273, LZCZ-8273 and LYCZ-8273, respectively. (3) The LaZn0.4Cu0.6Oy, LaMn0.1Zn0.3Cu0.6Oy, LaMn0.2Zn0.2Cu0.6Oy, LaMn0.3Zn0.1Cu0.6Oy, and LaMn0.4 Cu0.6Oy samples were prepared, of which the subscripts were the nominal composition. The catalysts were denoted as LZC-046, LMZC-136, LMZC-226, LMZC-316, and LMC-406, respectively.
As shown in Figure 1a [17], for the La–M-Mn–Cu–O (M = Mg, Y, Zn, Ce) based perovskite precursors, the LaMnO3 (JCPDS # 75-0440) are the main phase. The diffraction peak at about 2θ=32.5° shift towards higher values when the fourth elements were doped. Small peaks at 2θ=35.6°and 38.9°assigned to CuO (JCPDS # 89-5899) appear in the doped samples but not in the P sample. In all diffraction patterns, no phase that ascribes to Mg, Y, or Zn is observed, while a new phase ascribed to CeO2 is found for the sample of Ce–P, which demonstrates that it is difficult for all the Ce to enter the perovskite lattice, which agrees with the conclusion by Weng et al. [18].
For all reduced samples (Figure 1b), LaMnO3 phase is still the main phase, which reveals that the reduction process does not destroy the perovskite structure. Meanwhile, the CuO phase disappears and the Cu phase emerges.
XRD patterns of the calcined (a) and reduced (b) perovskite-type catalysts: (□) LaMnO3; (●) CuO; (♦) CeO2; (*) Cu (taken from ref.17, reproduced by permission of The Royal Society of Chemistry).
The physicochemical properties of the calcined perovskite-type catalysts are summarized in Table 1 [17]. Low specific surface area for perovskite-type oxides is common. For this series samples, the largest one is only 11.3 m2 g-1 for Y–P and the lowest one is only 4.1 m2 g-1 for the Zn–P. The exposed Cu surface area and the Cu dispersion measured by N2O adsorption technique are also low, which even cannot be measured for both P and Ce–P. Y–P possesses the largest Cu surface area and the Cu dispersion by comparison. The lower copper surface area may not be favorable for the conversion of CO2 to methanol [19]. The ICP results show that the experimental lanthanum amount is lower than the theoretical value, and other element amounts are similar to the nominal values.
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tSBET\n\t\t\t\t\n\t\t\t\t \n\t\t\t\t(m2 g-1)\n\t\t\t | \n\t\t\t\n\t\t\t\tDispersion\n\t\t\t\t \n\t\t\t\t(%)a\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tSCu\n\t\t\t\t\n\t\t\t\t \n\t\t\t\t(m2 g-1)\n\t\t\t | \n\t\t\t\n\t\t\t\tElemental composition\n\t\t\t\t \n\t\t\t\t(ICP-OES)b\n\t\t\t\t\n\t\t\t | \n\t\t
P Mg-P Y-P Zn-P Ce-P | \n\t\t\t6.5 5.4 11.3 4.1 7.2 | \n\t\t\t- 0.9 3.8 0.7 - | \n\t\t\t- 1.2 4.6 0.9 - | \n\t\t\tLa0.84Mn0.51Cu0.50\n\t\t\t\t La0.67Mg0.22Mn0.49Cu0.50\n\t\t\t\t La0.67Y0.23Mn0.47Cu0.50\n\t\t\t\t La0.67 Zn0.18Mn0.50Cu0.50\n\t\t\t\t La0.68 Ce0.19Mn0.49Cu0.50\n\t\t\t | \n\t\t
The physiochemical properties of the perovskite-type catalysts (taken from ref.17, reproduced by permission of The Royal Society of Chemistry).
a Calculated from N2O dissociative adsorption.
b Subscripts came from ICP results.
The XPS results presented in Table 2 [17] show that lanthanum ions of the reduced perovskite-type catalysts are present in the trivalent form because the La3d5/2 peak is close to the value of pure lanthana at 834.4 eV [20]. However, the BE of La3d5/2 of P sample is higher than the other samples, which implies the increasing of the electron cloud density around La ions for the doped samples. It may due to the fourth elements affect the transfer of the electrons of La to O, since O has the highest electronegativity value among all elements [21]. For O1s, the binding energy at around 528.9–529.1 eV is assigned to the lattice oxygen (O2-) [21,22] and the binding energy at around 530.8–533.0 eV is ascribed to the adsorbed oxygen species (Oad) in the surface, which contains hydroxyl (OH-), carbonate species (CO32-), and molecular water. The binding energy decreases after the fourth element except Ce adding, which indicates that there are more electrons around oxygen. It is likely that the fourth components transfer the electronic to the oxygen. The presence of surface adsorbed oxygen species suggests the formation of oxygen vacancies in the defected oxides [23], which is favorable for the activation of the catalyst. The Oad/O2- ratio is increased for the doped samples, which implies the improvement of catalysis activity. The binding energy values of Mn2p3/2 for the perovskite-type catalysts are located at 641.3 eV–642.2 eV. The peak positons of level of MnO, Mn2O3, and MnO2 are 640.6, 641.9, and 642.2 eV, respectively. The values are very similar, and the mean oxidation state of Mn ions at the surface layers is extremely difficult to detect by XPS, as reported in other studies [24,25]. However, the previous reports suggested that the BE difference between Mn2p3/2 and O1s emissions increases with about 0.6–0.7 eV for the change of the oxidation state between Mn3+ and Mn4+. As shown in Table 2, the BE difference is in the range of 112.3–113.0 eV, i.e., increasing with 0.7 eV, which means a change of the Mn4+/Mn3+ ratio for the perovskite-type catalysts [26,27].
Since the binding energy of the Cu2p3/2 band in the metal (932.6 eV) and in Cu+ (932.4 eV) is almost same, they can be distinguished by different kinetic energy of the Auger Cu LMM line position in Cu0 (918.6 eV), Cu+ (916.7 eV), or in Cu2+ (917.9 eV) [19,28]. The Auger electron spectroscopies of Cu LMM of reduced samples are shown in Figure 2 [17]. The profiles are convoluted into two peaks. It can be seen that the majority of the copper species exist as Cu+ for all samples, which is in accordance with the report of Jia et al. [29]. The weak Cu0 peak could be the explanation for the immeasurable of exposed Cu0 for P and Ce–P (Table 1).
The binding energy of the fourth components shows that they exist in Mg-O binding [29], Zn-O binding [23], Y 3+, and Ce4+, respectively.
Samples | \n\t\t\tLa3d5/2(eV) | \n\t\t\tMn2p3/2 (eV) | \n\t\t\tO1s (eV) | \n\t\t\tOad/O2-\n\t\t\t | \n\t\t
P | \n\t\t\t835.1 | \n\t\t\t642.2 | \n\t\t\t529.2 (50.5%) | \n\t\t\t1.02 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | 531.7 (49.5%) | \n\t\t\t\n\t\t |
Mg-P | \n\t\t\t834.0 | \n\t\t\t642.0 | \n\t\t\t529.1 (51.5%) | \n\t\t\t1.06 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | 531.5 (48.5%) | \n\t\t\t\n\t\t |
Y-P | \n\t\t\t834.4 | \n\t\t\t641.3 | \n\t\t\t529.0 (54.0%) | \n\t\t\t1.18 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | 531.4 (46.0%) | \n\t\t\t\n\t\t |
Zn-P | \n\t\t\t834.1 | \n\t\t\t641.5 | \n\t\t\t529.1 (51.2%) | \n\t\t\t1.05 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | 531.5 (48.8%) | \n\t\t\t\n\t\t |
Ce-P | \n\t\t\t834.3 | \n\t\t\t641.8 | \n\t\t\t529.2 (51.9%) | \n\t\t\t1.08 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | 532.2 (48.1%) | \n\t\t\t\n\t\t |
The binding energy of La, Mn, O, and the ratio of different oxygen species (taken from ref. 17, reproduced by permission of The Royal Society of Chemistry).
Cu LMM Auger electron spectroscopy of (a) P; (b) Mg–P; (c) Y–P; (d) Zn–P; (e) Ce–P samples after reduction (taken from ref. 17, reproduced by permission of The Royal Society of Chemistry).
The H2 desorption over the prereduced materials on the unit surface area below 523 K (test temperature) increases apparently with the addition of the fourth element, as shown in Table 3 [17].
Two CO2 desorption peaks are observed for all samples (Figure 3), which are denoted as peak α and peak β [17]. The peak α at around 400 K could be assigned to weak basic sites and the peak β at around 600 K could be assigned to strong basic sites. With the introduction of the fourth components, the peak α shifts to higher temperature, while the peak β shifts to lower temperature, which indicate the increase of the weak basic sites’ strength but the decrease of the strong basic sites’ strength. The strength for the weak basic sites of the catalysts increases in the order of: P < Ce–P < Y–P < Mg–P < Zn–P. The amount of the basic sites is also changed with the fourth element doping. The quantitative analysis for the CO2-TPD based on the relative area of the profiles is listed in Table 3, in which the P sample is assigned as 1.00. Both the weak basic sites and the strong basic sites increase due to the alkalinity of Mg for Mg–P. For Y–P, the amount of total basic sites and strong basic sites improved remarkably with the amount of weak basic sites’ decreasing. Moreover, the amount of the weak basic sites increases, but the amount of the strong basic sites and total basic sites decrease for Zn–P and Ce–P samples.
CO2-TPD curves of the catalysts (taken from ref. 17, reproduced by permission of The Royal Society of Chemistry).
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tH2 desorption below\n\t\t\t\t \n\t\t\t\t523 K on per unit area\n\t\t\t\t \n\t\t\t\t( μmol g-1m-2)\n\t\t\t | \n\t\t\t\n\t\t\t\tAdsoption type and distribution based in CO2-TPD dataa\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t | |||||
\n\t\t\t | \n\t\t\t\tPeak α\n\t\t\t | \n\t\t\t\n\t\t\t\tPeak β\n\t\t\t | \n\t\t\t\n\t\t\t\tTotal\n\t\t\t | \n\t\t|||||
P Mg-P Y-P Zn-P Ce-P | \n\t\t\t1.34 3.50 3.56 5.93 3.47 | \n\t\t\t1.00 (383 ) 1.30 (396) 0.87 (387) 1.56 (401) 1.22 (385) | \n\t\t\t1.00 (614) 1.06 (583) 1.67 (595) 0.85(596) 0.69(581) | \n\t\t\t1.00 1.11 1.53 0.97 0.78 | \n\t\t
The H2-TPD and CO2-TPD data (taken from ref. 17, reproduced by permission of The Royal Society of Chemistry).
a The amount of basicity of P is assigned as 1.00 to compare with other samples and the values in parentheses are the desorption temperature (K).
The catalytic performances of the catalysts for CO2 hydrogenation to methanol are summarized in Table 4 [17]. Both the CO2 conversion and methanol selectivity are improved when the fourth element is added. With the introduction of Zn, the activity increased greatly, which might be due to the fact that the active site is Cuδ+–O–Zn2+ [31,32]. However, the activity improvement is slight for Ce-P. The relationship between the CO2 conversion and the amount of H2 desorption on unit surface area below 523 K (Table 3) is shown in Figure 4 [17]. It can be seen that the more the H2 that is desorbed on the unit area, the more the CO2 that is converted. Lower CO2 conversion may result from lower copper content as well as lower surface area of copper in the system. The results of Figure 5 [17] show that the trend of the weak basic sites’ strength and methanol selectivity is similar, which indicates their dependency.
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tCO2 conversion\n\t\t\t\t \n\t\t\t\t(%)\n\t\t\t | \n\t\t\t\n\t\t\t\tSelectivity (C-mol%)\n\t\t\t | \n\t\t\t\n\t\t | |
\n\t\t\t\tCH3OH\n\t\t\t | \n\t\t\t\n\t\t\t\tCO\n\t\t\t | \n\t\t\t\n\t\t\t\tCH4\n\t\t\t\t\n\t\t\t | \n\t\t||
P Mg-P Y-P Zn-P Ce-P | \n\t\t\t1.8 2.8 4.6 6.1 2.0 | \n\t\t\t0.7 23.7 14.5 51.0 5.0 | \n\t\t\t93.4 68.1 82.6 46.4 85.9 | \n\t\t\t5.9 6.5 2.9 2.7 9.2 | \n\t\t
The performance for methanol synthesis from CO2 hydrogenation over the reduced catalysts (taken from ref. 17, reproduced by permission of The Royal Society of Chemistry).
Reaction conditions: n(H2)/n(CO2)=3:1, T=523 K, P=5.0 MPa, GHSV=4000 h-1.
Relationship between the CO2 conversion and the amount of H2 desorbed on unit surface area below 523 K (taken from ref. 17, reproduced by permission of The Royal Society of Chemistry).
Relationship between the selectivity for methanol and the strength of the weak basic sites of the catalysts (taken from ref.17, reproduced by permission of The Royal Society of Chemistry).
Figure 6 [33] shows that the orthorhombic perovskite structure (A2BO4) with high degree of crystallinity of the La2CuO4 (JCPDS # 82-2142) is the main phase and two small peaks at 2θ=35.6˚ and 38.9˚ ascribed to the CuO phase (JCPDS # 89-5899) present in all samples. The weak peak at 2θ=36.3˚ attributed to the ZnO phase (JCPDS # 80-0075) appears in all samples except LMCZ-8273, which implies that Mg seems to have a special effect on the structure. The phase of Ce7O12 and La2Zr2O7 appear in the sample of LCCZ-8273 and LZCZ-8273, respectively, while there are no new phases containing Mg and Y appearing in the sample of LMCZ-8273 and LYCZ-8273.
XRD patterns of the perovskite-type catalysts: (□)La2CuO4; (*)CuO; (♦)La2Zr2O7; (●)ZnO; (∇)Ce7O12 (taken from ref. 33, reproduced by permission of Elsevier B.V.)
The crystallographic parameters of the prepared materials were calculated by employing least-squares refinement, assuming an orthorhombic crystal system for the samples, and the results are listed in Table 5 [33]. A certain degree of changes of the lattice parameters occured after the fourth component was introduced. The lattice parameters a, b, and c were lower than those of LCZ-173, which can be attributed to the shrinkage of the La2CuO4 due to the introduction of the fourth elements. The mean grain size of La2CuO4 calculated by the Scherrer equation shows that the particles size of the La2CuO4 decreased remarkably for LCCZ-8273, LZCZ-8273, and LMCZ-8273, but slightly for LYCZ-8273. The physicochemical properties of the calcined catalysts are summarized in Table 6 [33]. The BET surface area for all calcined samples are rather low (SBET < 3 m2 g-1), which is common for perovskite-type of materials [4]. It can be seen that the highest specific surface area is just only 2.3 m2 g-1 for LZCZ-8273. Moreover, the tendency of the exposed Cu surface area and the Cu dispersion measured by N2O adsorption is the same for the materials. The LZCZ-8273 shows the highest Cu surface area (SCu) and the best dispersion of copper (DCu). The physicochemical properties of LYCZ-8273 are similar to that of the LCZ-173, which indicates that the influence of the Y doping is negligible.
\n\t\t\t\t | \n\t\t
The lattice parameters of the perovskite-type catalysts (taken from ref. 33, reproduced by permission of Elsevier B.V.).
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tSBET (m2g-1)\n\t\t\t | \n\t\t\t\n\t\t\t\tDispersiona (%)\n\t\t\t | \n\t\t\t\n\t\t\t\tSCu (m2g-1)\n\t\t\t | \n\t\t
LCZ-173 | \n\t\t\t0.7 | \n\t\t\t5.3 | \n\t\t\t3.4 | \n\t\t
LCCZ-8273 | \n\t\t\t1.3 | \n\t\t\t8.5 | \n\t\t\t5.9 | \n\t\t
LMCZ-8273 | \n\t\t\t1.2 | \n\t\t\t8.5 | \n\t\t\t6.2 | \n\t\t
LZCZ-8273 | \n\t\t\t2.3 | \n\t\t\t8.6 | \n\t\t\t6.5 | \n\t\t
LYCZ-8273 | \n\t\t\t0.7 | \n\t\t\t4.5 | \n\t\t\t3.2 | \n\t\t
The physiochemical properties of the perovskite-type catalysts (taken from ref. 33, reproduced by permission of Elsevier B.V.).
a Calculated from N2O dissociative adsorption.
The reduced perovskite-type catalysts are analyzed by XPS, and the binding energies (BE) of La3d5/2 and Zn2p3/2 are presented in Table 7 [33]. According to the literature, La3d5/2 features in perovskite structure are located at 837.5 and 834.3 eV [20,34] which are close to the values of pure lanthana at 837.8 and 834.4 eV, indicating that lanthanum ions are present in the trivalent form. A slight shift in the La3d5/2 binding energy is observed upon introduction of the fourth elements and the values are in the range of 837.86–838.01 eV and 834.06–834.36 eV, respectively. Small differences may relate to the changes in crystal structure and/or electronic structure. In addition, small changes are also observed for the binding energy of Zn at around 1021.7 eV for different samples. The Auger electron spectroscopies of Cu LMM of reduced samples are shown in Figure 7 [33]. A broad peak appears in the range of 915.0 eV–920.0 eV for all samples, and it is hard to distinguish the Cu+, Cu2+, and Cu0 apparently. However, the peaks at around 918.6 eV attributed to Cu0 are distinct for all samples. A new peak appears at around 911.2–914.3 eV, lower than that of Cu+, which is defined as peak α, implying that a special Cu species Cuα+ exists in the perovskite system. The presence of Cu+ may accelerate the reduction of CO2 to CO (RWGS) [34],while the Cuα+ (not Cu2+, Cu+, Cu0) plays an important role for the methanol synthesis from CO2/H2 [31,35].
The X-ray photoelectron spectroscopies of the fourth elements in the reduced samples suggest that both Ce3+ and Ce4+ exist in the LCCZ-8273 and the +4 oxidation state is predominant. The result agrees with the XRD analysis. The Zr in the LZCZ-8273 sample exists in the phase of La2Zr2O7.
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tBinding energy (eV)\n\t\t\t | \n\t\t\t\n\t\t |
\n\t\t\t\tLa 3d5/2\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tZn 2p3/2\n\t\t\t\t\n\t\t\t | \n\t\t|
LCZ-173 LCCZ-8273 LMCZ-8273 LZCZ-8273 LYCZ-8273 | \n\t\t\t837.89 834.15 837.92 834.06 837.87 834.36 838.01 834.26 837.86 834.23 | \n\t\t\t1021.67 1021.71 1021.34 1021.78 1021.69 | \n\t\t
XPS parameters of the perovskite-type catalysts (taken from ref. 33, reproduced by permission of Elsevier B.V.).
Cu LMM Auger electron spectroscopy of (a) LCZ-173; (b) LCCZ-8273; (c) LMCZ8273; (d) LZCZ-8273; (e) LYCZ-8273 samples after reduce (taken from ref. 33, reproduced by permission of Elsevier B.V.).
The catalytic performance for La-M-Cu-Zn-O (M = Ce, Mg, Zr, Y) catalysts are listed in Table 8 [33]. The LMCZ-8273 shows the highest CO2 conversion and the maximum yield of methanol despite the lowest selectivity among all the samples. The LMCZ 8273 shows the highest methanol selectivity and the LCCZ-8273 shows moderate CO2 conversion and methanol selectivity. The lowest CO2 conversion and less improvement for methanol selectivity are observed for LYCZ-8273. The varying of the CO2 conversion had the same tendency as the surface area of copper (Figure 8 [33]), indicating more surface copper existing in the catalysts may lead to higher activity, i.e., Cu0 is the active site for CO2 hydrogenation to methanol [10,16,19,22,35]. It is noteworthy that all catalysts show promising CH3OH selectivity, especially for LMCZ-8273. The order of the selectivity to CH3OH is as follows: LMCZ-8273 > LCCZ-8273 > LYCZ-8273 > LCZ173 > LZCZ-8273. The relationship between CH3OH selectivity and the Cuα+ Auger peaks is shown in Figure 9 [33]. It can be seen that Cuα+ had a strong effect on the selectivity for methanol: the lower the binding energy of the peak α, the higher is the CH3OH selectivity. Cu+ is favorable for the reduction of CO2 to CO (RWGS), so it can be derived that the farther away from 916.6 eV (the binding energy of Cu+ in Cu LMM) for the peak α, the higher the CH3OH selectivity that can be obtained. As discussed above, doping of Mg leads to the proper oxide state of copper, which results in the best selectivity for methanol. For LCCZ-8273 and LYCZ-8273, Ce and Y substitute La in the A-site with the same charge (+3) and similar ionic radius, which produces more defects in the perovskite structure that causes the special oxide state for copper species. With the special structure of La2CuO4 perovskite, the high dispersed copper species can be realized and stronger physical and electric interaction between the copper and other metal oxides can be obtained, which may lead to the formation and stabilization of the copper species with special valence [23]. However, for the LZCZ-8273, the formation of lanthanum zirconium pyrochlore has little influence on the perovskite structure but a great influence on the content of La2CuO4 perovskite, which may lead to the lowest selectivity of methanol. The turnover frequency (TOF), which represents the number of CO2 molecules hydrogenated in a unit site per second (s-1), is calculated from the exposed copper surface area for the perovskite-type catalysts (Table 8 [33]). The TOF values of the perovskite-type catalysts were very high compared with other catalytic systems [22,35], indicating the better efficiency for copper atoms on perovskite-type catalysts.
\n\t\t\t\t | \n\t\t
Catalytic performance for methanol synthesis from CO2 hydrogenation over the reduced catalysts (taken from ref. 33, reproduced by permission of Elsevier B.V.).
Reaction conditions: n(H2)/n(CO2)=3:1, T=523 K, P=5.0 MPa, GHSV=3600 h-1.
Relationship between copper surface area and CO2 conversion (taken from ref. 33, reproduced by permission of Elsevier B.V.).
Relationship between methanol selectivity and the binding energy of Cuα+ (taken from ref. 33, reproduced by permission of Elsevier B.V.).
The XRD patterns of the fresh and reduced perovskites are presented in Figure 10a and b, respectively [36]. La2CuO4 perovskite-like structure can be observed for all fresh samples. LaMnO3 phase emerges and the La2CuO4 phase transfers from tetragonal (JPCDS 81-2450) to orthorhombic (JPCDS 81-0872) as the manganese is introduced, which indicates that the manganese introduction distorts the structure of the La2CuO4. With the increasing of the manganese amount, the intensity of the La2CuO4 phase decreases while that of the LaMnO3 phase increases, which implies that the formation of LaMnO3 is easier than that of La2CuO4. This phenomenon reveals that the structure of LaMnO3 is more stable than La2CuO4. Small peaks for both CuO and ZnO can also be observed except LMC-046, which indicates the perovskite structure has certain tolerance for the involved elements for this perovskite-type system. Moreover, the peak intensity of the separated CuO decreases when the value of Mn/Zn decreases, which means the formation of LaMnO3 can lead to the separation of copper from the La2CuO4 perovskite structure. For the reduced sample (Figure 10b), the La2CuO4 perovskite structure disappears and the metallic copper and La2O3 is observed, which indicates that the ‘‘metal-on-oxide’’ can be attained. The appearance of La0.974Mn0.974O3 phase reveals that the reduction progress can result in defects rather than destruction for the Mn-based perovskite.
X-ray patterns of the fresh (a) and reduced (b) catalysts: (o) tetragonal La2CuO4; (□) orthorhombic La2CuO4; (▽) CuO; (♦) ZnO; (♣) LaMnO3; (♥) La2O3; (∙) La0.974Mn0.974O3; (*) Cu (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
The crystallographic parameters of the prepared materials were calculated by employing least-squares refinement and the results are listed in Table 9 [36]. It can be found that the axes are elongated for the four element samples, which means that doping may strut the perovskite structure. The size of La2CuO4 crystallites becomes smaller with the introduction of manganese. The LaMnO3 phase changes from cubic to orthorhombic structure as zinc is introduced. Moreover, the LMZC-136 and LZC-046 possess the smallest LaMnO3 and the largest La2CuO4 crystallites among all the samples, which implies that the abundant zinc species can improve the formation of small LaMnO3 and large La2CuO4 crystallites. The change of lattice parameters of the samples implies that interaction between the involved elements might be different.
The BET specific surface area along with the exposed surface copper area and the copper dispersion measured by N2O adsorption are summarized in Table 10 [36]. The specific surface area for all samples is low, which is common for perovskite-type materials [37]. LMC-406 possesses the largest specific surface area (SBET), the exposed surface copper area (SCu) as well as the copper dispersion (DCu), while the LZC-046 sample shows the lowest SCu and DCu, which indicate that the existence of LaMnO3 perovskite structure is favorable for increasing the surface copper area due to the extension of the space structure for the samples with manganese (Table 9).
\n\t\t\t\t | \n\t\t
The lattice parameters of the perovskite-type samples (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tSBET (m2 g-1)\n\t\t\t | \n\t\t\t\n\t\t\t\tDispersiona (%)\n\t\t\t | \n\t\t\t\n\t\t\t\tSCu (m2 g-1)\n\t\t\t | \n\t\t
LZC-046 LMZC-136 LMZC-226 LMZC-316 LMC-406 | \n\t\t\t2.4 1.1 1.4 1.2 2.5 | \n\t\t\t1.9 2.3 2.6 2.7 4.2 | \n\t\t\t2.3 2.7 2.8 3.0 4.5 | \n\t\t
The physiochemical properties of the perovskite-type catalysts (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
a Calculated from N2O dissociative adsorption.
The XPS results of the reduced perovskite-type catalysts are listed in Table 11 [36]. The values of La3d5/2 binding energy (BE) are located in the range of 834.2–834.6 eV, demonstrating that La ions are in the trivalent form for all samples. Small changes of Zn (around 1021.7 eV) and Mn (around 642.0 eV) BE may relate to the small distortions in electronic structure and/or crystal structure. For the O1s patterns, the peak at around 528.2–529.3 eV can be attributed to the oxygen ions in the crystal lattice (O2-) and the peak at around 531.1–531.5 eV can be assigned to the adsorbed oxygen species (Oad) derived from the defects or oxygen vacancies in the structure [38]. The O1s BE shifts to lower value with the decreasing of the Mn/Zn ratio, which suggests the increasing of electron cloud density around O element. The value of Oad/O2- is max for the LZC-046, which decreases for the Mn containing samples, indicating that the LaMnO3 could reduce the structural defects.
For this series catalyst, the binding energies of Cu2p3/2 are lower than that for the copper oxide (933.0 eV) apparently, indicating that the Cu atoms are not in the simple copper oxides form. Figure 11 [36] shows the Auger electron spectroscopies of Cu LMM for the reduced samples. A broad peak can be observed, which can then be deconvoluted into three peaks. The peak at around 916.5 and 919.0 eV matched with kinetic binding energy of Cu+ and Cu0 within the error limit, respectively. However, a new peak at around 911.2–913.2 eV is observed which may be ascribed to the Cuα+. According to literatures and our works, Cuα+ can be appeared in perovskite-type system.
\n\t\t\t\tSamples\n\t\t\t | \n\t\t\t\n\t\t\t\tBinding energy (eV)\n\t\t\t | \n\t\t|||||
\n\t\t\t\tLa3d5/2\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tCu2p3/2\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tMn2p3/2\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tZn2p3/2\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tO1s\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\tOad/O2-\n\t\t\t\t\n\t\t\t | \n\t\t|
LZC-046 | \n\t\t\t834.6 | \n\t\t\t932.2 | \n\t\t\t- | \n\t\t\t1021.4 | \n\t\t\t528.2 | \n\t\t\t1.33 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | 531.1 | \n\t\t\t\n\t\t |
LMZC-136 | \n\t\t\t834.3 | \n\t\t\t932.4 | \n\t\t\t642.0 | \n\t\t\t1021.8 | \n\t\t\t528.7 | \n\t\t\t1.29 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | 531.3 | \n\t\t\t\n\t\t |
LMZC-226 | \n\t\t\t834.2 | \n\t\t\t932.5 | \n\t\t\t641.9 | \n\t\t\t1021.6 | \n\t\t\t528.8 | \n\t\t\t1.25 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | 531.3 | \n\t\t\t\n\t\t |
LMZC-316 | \n\t\t\t834.3 | \n\t\t\t932.7 | \n\t\t\t642.0 | \n\t\t\t1021.6 | \n\t\t\t529.2 | \n\t\t\t1.18 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | 531.4 | \n\t\t\t\n\t\t |
LMC-406 | \n\t\t\t834.5 | \n\t\t\t932.6 | \n\t\t\t642.0 | \n\t\t\t- | \n\t\t\t529.3 | \n\t\t\t1.13 | \n\t\t
\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t\t | 531.5 | \n\t\t\t\n\t\t |
XPS data of the perovskite-type catalysts (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
Cu LMM Auger electron spectroscopy of the reduced perovskite-type catalysts (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
The performance of the La–Mn–Zn–Cu–O based perovskite catalysts for methanol synthesis from CO2 hydrogenation is shown in Table 12 [36]. The LMC-406 shows the worst performance despite the largest surface area and exposed copper surface area. The LZC- 046, which also contains three metal elements, but Zn instead of Mn, shows a moderate catalytic performance. It is well-known that the site of Cu+-O-Zn2+ favors the adsorption of hydrogen that can transport to the bulk copper species via spillover [20,39]. So the lack of the site of Cu+-O-Zn2+ may be the reason for the poor catalytic performance of LMC-406. Moreover, the TOFCu value increases sharply upon Zn introduction, which verifies that the copper sites are not the only active sites for the reaction [40]. With more reducible copper species and high TOFCu values, the four-component samples show a good catalytic performance. The ratio of both Cuα+ and Cu0 species to the total copper species (calculated from the Auger spectroscopy (Figure 11)) shows the same change tendency with the CO2 conversion (Figure 12) [36], indicating that both Cuα+ and Cu0 species could be the active sites for the conversion of CO2. In addition, with the change of the ratio for Mn/Zn, the synergy between copper and the other components might vary, and then the reduction state of copper species (Cuα+ and Cu0) changes. The four-component samples with two kinds of perovskites show better methanol selectivity, which implies that the strong synergy for different elements and different perovskite phases are significant for the improvement of the catalytic performance. In addition, it is also found that the lower the BE of the Cuα+, the higher is the CH3OH selectivity (Figure 13) [36].
\n\t\t\t\t | \n\t\t
The catalytic performance for methanol synthesis from CO2 hydrogenation over the reduced catalysts (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
a The ratio value was calculated from the Auger spectroscopy (Figure 11).
Reaction conditions: n(H2)/n(CO2) = 3:1, T = 543 K, P = 5.0 MPa, GHSV = 3800 h-1.
Relationship between CO2 conversion and ratio value of (Cuα++Cu0)/CuTotal (taken from ref.36, reproduced by permission of Springer Science+Business Media).
Relationship between methanol selectivity and binding energy of Cuα+ (taken from ref. 36, reproduced by permission of Springer Science+Business Media).
Three series of catalysts derived from perovskite-type precursors were prepared by sol-gel method, which were applied in the CO2 hydrogenation to methanol. The conclusions are as follows:
The perovskite-type ABO3, A2BO4, and ABO3+A2BO4 can be purposive obtained in our work. Cu-based perovskite-type catalyst shows good methanol selectivity in CO2 hydrogenation to methanol.
For La–M–Mn–Cu–O (M = Mg, Y, Zn, Ce) catalysts, the introduction of the fourth elements leads to the separation of copper from the LaMnO3 perovskite lattice and thus produces more oxygen vacancies. Because of the increasing of defects, temperature adsorption properties are improved for the doped samples. The CO2 conversion is related to the amount of absorbed H2 on the unit area under 523 K, and the methanol selectivity corresponds to the strength of the weak basic sites. The catalytic performance enhanced considerably for Zn–P based on this, which also implies that Zn is important to the CO2 hydrogenation to methanol.
La2CuO4 (A2BO4) perovskite structure is obtained for the La–M–Cu–Zn–O (M = Ce, Mg, Zr, Y) samples. With the addition of Ce, Mg, and Zr, good properties can be obtained: smaller particle size, higher Cu dispersion, larger amount of hydrogen desorption at low temperature, higher concentration of basic sites, and so on. The excellent methanol selectivity originates from the special copper valence that presents in the perovskite structure after reduction, and the CO2 conversion is in correlation with the surface area of metallic copper.
Both La2CuO4 and LaMnO3 perovskite structure can be observed in the LaMn0.4-xZnxCu0.6Oy (x = 0, 0.1, 0.2, 0.3, 0.4) catalysts. The ‘‘metal-on-oxide’’ can be realized after reduction. With decreasing of Mn/Zn, more oxygen defects were formed. The perovskites exhibited better methanol selectivity due to the appearance of Cuα+ derived from the abundant defects of perovskite structure and the strong interaction between different elements. Moderate LaMnO3 can balance the defects in the structure, and then lead to the perfect Cuα+, which is important for the methanol selectivity.
This work was financially supported by the Key Science and Technology Program of Shanxi Province, China (MD2014-10), the National Key Technology Research and Development Program of the Ministry of Science and Technology (2013BAC11B00), and the Natural Science Foundation of China (21343012).
At the beginning of the space age, all satellites were “small.” Sputnik 1 was the first artificial Earth satellite (Figure 1a) [1]. It was launched by the Soviet Union from Baikonur Cosmodrome on October 4, 1957, into an elliptical low Earth orbit (LEO) with an inclination of 65°. Sputnik 1 was a 58-cm-diameter metal sphere, weighing approximately 84 kg, with four radio antennas transmitting at 20.005 and 40.002 MHz. Tracking and studying Sputnik 1 signals from Earth provided valuable information on upper atmosphere density, and the propagation of radio signals provided information on the ionosphere. Sputnik did not have solar panels, so the mission ended after 3 weeks when batteries died.
Pictures of (a) sputnik 1 [4], (b) explorer 1 [5], and (c) vanguard 1 [6].
Explorer 1 was the first US satellite (Figure 1b) [2], and the third one after Sputnik 1 and 2. It was launched from Cape Canaveral, Florida, on January 31, 1958. Explorer 1 was 205 cm tall and 15 cm in diameter, weighing nearly 14 kg. It was the first spacecraft to detect the Van Allen radiation belts. Explorer 1 did not have solar panels either, so after 4 months the mission ended when batteries were exhausted.
Vanguard 1 was the fourth artificial Earth satellite (Figure 1c) [3]. It was launched by the USA from Cape Canaveral on March 17, 1958, into a 654 by 3969 km elliptical orbit with an inclination of 34.25°. Vanguard 1 was a 16.5-cm-diameter aluminum sphere, weighing just 1.47 kg, and it was the first satellite with six solar cells powering two beacons at 108 and 108.03 MHz, which were used to measure the total electron content.
During the first two decades of the space age, each satellite had its own design. They were the art pieces of the space craftsmen. Standard spacecraft busses were practically unknown until the end of the 1970s. In the early 1980s, microsatellites emerged and adopted a radically different design approach to reduce costs, focusing on available and existing technologies and using properly qualified commercial off-the-shelf (COTS) components.
For many years, satellite mass increased as illustrated in Table 1. However, except for some military, astronomy, and specific communication applications, it seems that the era of massive satellites is over.
Spacecraft | Agency application | Mass | Duration |
---|---|---|---|
KH-11 Kennen (a.k.a. CRYSTAL, EECS, 1010) [7] | US NRO/optical imaging | 19,600 kg | 1976–present |
Proton [8] | USSR/astronomy | 17,000 kg | 1965–1969 |
Compton Gamma Ray Obs. [9] | US NASA/astronomy | 16,329 kg | 1991–2000 |
Lacrosse [10] | US NRO/SAR | 14,500–16,000 kg | 1988–2005 |
Hubble Space Telescope [11] | US NASA/astronomy | 11,110 kg | 1990–present |
ENVISAT [12] | ESA/Earth observation | 8211 kg | 2002–2012 |
Telstar 19 V [13] | Canada/communications | 7075 kg | 2018–present |
Heaviest spacecrafts (excluding space stations and manned orbiters).
The “small satellite mission philosophy” represents a design-to-cost approach, with strict cost and schedule constraints, often combined with a single mission objective in order to reduce complexity. Figure 2 from [14] summarizes the standardized definition of satellites according to their weight: picosatellites (0.1–1 kg), nanosatellites (1–10 kg), microsatellites (10–100 kg), and mini-satellites or small/medium satellites (100–1000 kg).
Satellite classification [14].
In the field of Earth observation (EO), this has led to smaller target-focused missions which, with reduced spacecraft and launch costs (shared rides), are enabling massive (>100) satellite constellations of nano- and microsatellites with reduced revisit times, unthinkable just a few years ago.
In the field of satellite communications, there are plans as well to deploy massive constellations of LEO satellites to provide worldwide Internet coverage, IoT services, and machine-to-machine (M2M) communications.
It is anticipated that enhanced inter-satellite communication capabilities (LEO-ground, LEO-LEO, LEO-MEO, and LEO-GEO) will also improve the performance of EO systems [15]. All this is leading to the evolution of the space segment from monolithic to distributed and federated satellite systems [16], aiming at establishing win-win collaborations between satellites to improve their mission performance by using the unused onboard resources.
The so-called CubeSat standard was conceived in 1999 by Profs. Jordi Puig-Suari of California Polytechnic State University (CalPoly) and Bob Twiggs of Stanford University to allow graduate students to conceive, design, implement, test, and operate in space a complete spacecraft in a “reasonable” amount of time (i.e., the duration of their studies). CubeSats are small satellite multiples of 1 U (1 U: 10 cm × 10 cm × 11.35 cm, weighing less than 1.33 kg), including all the basic subsystems as large satellites but using COTS components. The CubeSat “standard” only defines the mechanical external interfaces, i.e., those referring to the orbital deployer. Originally, it was never meant to be a standard, however, because of its simplicity, it soon became a “de facto” standard. As Prof. Twiggs said in an interview to Spaceflight Now in 2014: “It all started as a university education program satellite. It was kind of funny. I didn’t think that people would criticize it as much as they did, but we got a lot of feedback (…). Another thing that was kind of funny we had no interest from NASA or any of the military organizations. It just wasn’t anything they were interested in, so it was all funded without any funding from those aerospace organizations.” The first six CubeSats were launched on a Russian Eurockot on June 30th, 2003. Then, after more than a decade in which the concept silently matured in university labs, space agencies got interested and showed that CubeSat-based mission reliability could be improved by proper engineering. In 2013, it all took off on the commercial Earth Observation sector with the first launches from two companies that are now running 100+ CubeSats constellations for optical imaging or weather prediction, with very low revisit times. Today, many of the initial CubeSat limitations (most notably size, available power, and down-link bandwidth) are being overcome, and the same revolution is starting to take place in the fields of telecommunications, and astronomical scientific missions.
The current CubeSat Design Specification defines the envelopes for 1 U, 1.5 U, 2 U, 3 U and 3 U+, and 6 U form factors (see, e.g., CubeSat Design Specification Rev. 13 or 6 U CubeSat Design Specification in [17], Figure 3), and the standardization of 12 U and 16 U is in progress, although some companies have produced standards up to 27 U [18]. On the other side, smaller picosatellites, the so-called PocketQubes, about 1/8 the size of a CubeSat, have also been standardized [19].
CubeSat form factors from 1 U to 12 U [20].
Probably, what has had the most significant impact in the popularization of the CubeSat standard has been the capability to separate the interface between the spacecraft and the poly-picosatellite orbital deployer (P-POD) and between the dispenser and the rocket itself. There are two different classes of PODs. The first type is the classical one with four rails in the corners [17], and the second one is with tables [18]. Note however that modern deployers from ISIS and NanoRacks allow larger deployables, wider solar panels, and thinner rails as compared to original P-POD, e.g., increased extruded height up to 9 mm and up to 2 kg per 1 U.
As of June 2019, 64 countries have launched nanosatellites or CubeSats. The total number of nanosatellites launched is 1186, from which 1088 are CubeSats. Most of them (273) have been launched from the International Space Station at ~400 km orbital height with an inclination of 51.6° and the rest at low Earth orbits (LEO) typically at 500 km sun-synchronous orbit (SSO) with an inclination of 97.5° (217 CubeSats) and 580 km height with 97.8° inclination (80 CubeSats). So far, only two (MarCO-1 and MarCO-2) have performed interplanetary missions.
Figure 4 shows the number of nanosatellites launched per year (a) and organization, either companies, universities, space agencies, etc., or (b) form factor from picosats, 0.25 up to 16 U.
The number of nanosatellites launched per year and (a) organization or (b) form factor [21].
As it can be appreciated, until 2013 most CubeSats were launched by universities and research institutes, and most of them were 1 U or 2 U. However, in 2013 the first 3 U CubeSats from the Planet Labs Inc. [22] and Spire Global Inc. [23] were launched. That was the beginning of today’s revolution in EO, and—as of June 10, 2019—these two companies had launched the largest commercial constellations ever with 355 and 103 CubeSats, respectively. The following ones have launched at most seven CubeSats. Therefore, 3 U CubeSats are dominating the scene, and they will over the next decade, followed by far by the 1 U, 2 U, and 6 U form factors (Figure 5). However, it is expected that the next wave of growth will be based on 6 U and 12 U CubeSats, which offer the right balance between very capable payloads and limited manufacturing and launch costs.
The number of CubeSats by form factor [21].
Table 2 (extracted from the database in [21]) shows the main companies that have launched CubeSats, the number of launched and planned CubeSats, the year of the first launch, the form factor, the application field, and some technical details. The rows marked in light blue correspond to EO optical imaging, in light green to EO passive microwaves applications, in dark green to EO active microwaves applications, and in light orange typically to IoT and M2M communications. In the next sections, we will focus on the EO applications but keeping in mind that future advances in satellite communication networks will also improve the performance of EO systems and enable new ones as well as distributed ones (e.g., large synthetic apertures).
Organization | Launched/planned size | First launch | Form factor | Field | Technical and comments |
---|---|---|---|---|---|
Planet Labs | 355/150 | 2013 | 3 U | Earth observation | 29 MP sensor taking images with 3.7 m ground resolution and swath of 24.6 km × 16.4 km from 475 km altitude |
Spire | 103/150 | 2013 | 3 U | Weather, AIS, ADS-B, earthquake | Measure change in GPS signal after passing atmosphere to calculate precise profiles for temperature, pressure, and humidity. Investigating earthquake (ELF) detection |
AprizeSat | 12/12 | 2002 | Microsat | IoT/M2M | Low-cost satellite data services for monitoring the fuel level and oil and gas pipelines and mobile tracking of shipping containers, railcars, and trailers |
GeoOptics | 7/N/A | 2017 | 6 U | Weather | Using GPS radio occultation for weather data |
Swarm Technologies | 7/150 | 2018 | 0.25 U, 1 U | IoT/M2M | World’s smallest two-way communication satellites |
Commsat | 7/72 | 2018 | Microsat, 6 U, 3 U | IoT/M2M, AIS | Ladybeetle 1 is 100 kg and 3 CubeSats of 6 U and 3 of 3 U. Plans 4 more in 2019 and complete 72 satellites in 2022 |
Astro Digital | 6/25 | 2014 | 6 U, 16 U | Earth observation | 6 U has 22 m resolution in RGB and NIR. 16 U has 2.5 m resolution in RGB, red edge, and NIR with 70 MP sensor |
Fleet Space | 4/100 | 2018 | 3 U, 12 U, 1.5 U | IoT/M2M | Main constellation potentially with 12 U CubeSats |
Sky and Space Global | 3/200 | 2017 | 8 U, 6 U, 3 U | IoT/M2M | Communication service (voice, data, and M2M). Plans to use inter-satellite links |
NanoAvionics | 2/72 | 2017 | 6 U, 12 U | IoT/M2M | Global IoT constellation-as-a-service system aimed at IoT/M2M communication providers |
Helios Wire | 2/30 | 2017 | 6 U, 16 U | IoT/M2M | Uses 30 MHz of S-band spectrum to receive tiny data packages from billions of sensors |
Kepler Communications | 2/140 | 2018 | 3 U, 6 U | IoT/M2M, Internet | IoT/M2M data communication network. Monthly fee based on the data amount. Hope to achieve rates of 1–40 Mbps |
Analytical Space | 1/N/A | 2018 | 6 U | IoT/M2M, orbital data relay, optical comms. | In-orbit relays receiving radio and downlink to ground with laser communication enabling more data downlink from satellites |
Hiber | 2/48 | 2018 | 6 U | IoT/M2M | Sends small packets of data (140 characters, accompanied by time stamp, identifier, and location) |
Guodian Gaoke | 2/38 | 2018 | 6 U | IoT/M2M | Reliable and economical satellite IoT services and industry solutions for our customers |
Astrocast | 2/80 | 2018 | 3 U | IoT/M2M | Targeting L-band. Inter-satellite links. NanoSpace propulsion. Further 80 satellites in orbit by 2022 |
AISTech | 2/150 | 2018 | 2 U, 6 U | IoT/M2M, ADS-B, AIS, IR imaging | Two-way comms., thermal imaging to detect forest fires, aviation tracking (ADS-B) |
ICEYE | 2/18 | 2018 | Microsat | SAR | 21-launch agreement with Vector Space Systems. 10-platform agreement with York Space Systems |
Harris Corp. | 1/12 | 2018 | 6 U | Weather | Immediate access to 3D wind data sets from Harris-owned HyperCubes |
SIRION | 1/N/A | 2018 | CubeSat | IoT/M2M | IoT/M2M constellation. Partnered closely with Helios Wire. Sharing spectrum and satellites |
Reaktor Space | 1/36 | 2018 | 6 U, 2 U | Earth observation, hyperspectral | Hyperspectral constellation for smart agriculture with 100’s of spectral bands and 20 m resolution |
Myriota | 1/50 | 2018 | CubeSat | IoT/M2M | Run unique, patented software which provides reliable, direct-to-satellite Internet of Things (IoT) connectivity |
LaserFleet | 1/192 | 2018 | CubeSat | Internet, optical comms. | Provide reliable 1 Gbps communication rates to aircraft at altitude. Higher effective data rate at a lower cost than the best-in-class Ku/Ka/V |
ADASpace | 1/192 | 2018 | Microsat CubeSat | Earth observation | Establish a global, minute-level updated Earth image data network consisting of 192 satellites |
Orbital Micro Systems | 1/40 | 2019 | 3 U | Weather | Weather constellation utilizes microwave technology to capture temperature and moisture measurements, refreshed and delivered every 15 minutes |
Lacuna Space | 1/32 | 2019 | 3 U, 6 U | IoT/M2M | IoT/M2M constellation. Selected Open Cosmos to build 3 U demonstrator |
The main existing and planned CubeSats and microsat commercial constellations.
Blue for constellations for optical EO, light green for passive microwave EO, dark green for active microwave EO, and orange for IoT and M2M communications.
The interested reader is encouraged to consult [21] for the most updated information as these numbers can change rapidly. Note that the number of CubeSats that can be launched in a single rocket can be very high. The current record is held by the Indian rocket PSLV-C37 that, on February 15, 2017, launched Cartosat-2D and 103 CubeSats, from which 88 are from the Planet Labs Inc. and 8 are from the Spire Global Inc. The interested reader is invited to see the deployment of these satellites from the onboard camera at [24].
As illustrated in Table 2, by 2010 the maturity achieved by CubeSats and dispensers/launchers, on one side, and by some EO technologies (high-resolution multispectral imagery and GNSS-RO), on the other side, made possible that a number of companies developed applications based on commercial constellations. Today, thanks to an intense technology R&D, the situation is completely different.
The reasons for this have been threefold. On one side, due to their small size, it has been difficult to include deployable solar panels so as to increase the electrical power generated, and, on the other side, it has been difficult to include large antenna reflectors and to transmit enough RF power so as to have a satisfactory space-to-Earth link budget. The third reason was the poor pointing accuracy that now has significantly improved thanks to miniaturized star trackers and reaction wheels. So far, these reasons have kept active optical (LIDAR) and active microwave sensors (RADAR) away from CubeSats, although it has to be stated that synthetic aperture radars (SAR) have been recently boarded in microsatellite platforms successfully (ICEYE, Table 2).
For spaceborne EO applications, frequency bands are restricted to those in which the atmosphere exhibits a high transmissivity, that is, the microwave and millimeter-wave parts of the radio spectrum and the long-wave infrared (LWIR), near infrared (NIR), and visible (VIS) parts of the spectrum, as illustrated in Figure 6.
Electromagnetic spectrum with different bands indicated [25].
For astronomical observations, ground-based observations are also limited to Earth’s atmospheric windows in the radio and optical parts of the spectrum (Figure 6). Therefore, to explore the remaining parts of the EM spectrum, space-based observatories are required.
In any case, either for EO or astronomical observations, the lower cost of individual CubeSat-based missions allows having more units, which reduces the revisit time at a given cost. This offers a number of new science opportunities [26]:
Earth science:
Multipoint high temporal resolution of Earth processes
Mitigation of data gaps
Continuous monitoring
Astrophysics:
Space telescopes allow access to energies across the whole electromagnetic spectrum avoiding large gaps in the radio, far IR, and the entire high-energy range (UV to γ-rays).
Feasibility to conduct time domain programs, which are very challenging with flagship missions such as the Hubble Space Telescope and James Webb Space Telescope.
Heliophysics, e.g., measurement of plasma processes in the magnetosphere-ionosphere system.
Planetary science: in situ investigation of planetary surfaces or atmospheres.
Astronomy and astrophysics: low-frequency radio science and the search for extrasolar planets.
Biological and physical sciences, e.g., survival and adaptation of organisms to space
Since the CubeSat standard was proposed in 1999, it took about a decade for NASA to start the Educational Launch of Nanosatellites (ELaNa) initiative in 2010. Partnerships were established with universities in the USA to design and launch CubeSats through NASA’s CubeSat Launch Initiative (CSLI). Since then, 85 CubeSat missions have flown on 25 ELaNa calls, and 34 more CubeSats are manifested in 4 more calls. While it provides NASA with valuable opportunities to test emerging technologies that may be useful in future space missions, university students get involved in all phases of the mission, from the instrument and satellite design to its launch and monitoring.
As early as 2012, NASA’s Science Mission Directorate (SMD) technology programs began to accommodate the use of CubeSats for validation of new science instruments and strategically promoted the use of small spacecraft to advance its science portfolio.
On one side, the Earth Science Technology Office (ESTO), which is responsible for identifying and developing technologies in support of future Earth Science Division missions, manages three major observation technology programs that solicit new awards on a 2–3-year selection cycle, as shown in Table 3 [27].
Earth science program | Approx. funding | Description |
---|---|---|
Instrument Incubator (IIP) | $28 M/year | Nurtures the development and assessment of innovative remote sensing concepts in ground, aircraft, or engineering model demonstrations (early to mid-stage development) |
Advanced Components (ACT) | $5 M/year | Enables the research, development, and demonstration of component- and subsystem-level technologies to reduce the risk, cost, size, mass, and development time of missions and infrastructure |
In-Space Validation of Earth Science Technologies (InVEST) | $5 M/year | Advances the readiness of existing Earth science-related technology and reduces risks to future missions through space flight validation using CubeSats |
Earth science technology programs relevant to small satellites [27].
And on the other side, following the outcomes of [28] in 2014, the Planetary Science Division (PSD) has also made significant strides toward accommodating small satellites for exploration of the solar system and for astrophysics research. Table 4 [27] summarizes the three main planetary science technology programs.
Planetary science program | Approx. funding | Description |
---|---|---|
Planetary Instrument Concepts for the Advancement of Solar System Observations (PICASSO) | $4 M/year | Supports the development of spacecraft-based instrument components and systems that show promise for future planetary missions. The program supports early-stage technologies |
Maturation of Instruments for Solar System Exploration (MatISSE) | $6 M/year | Supports the advanced development of spacecraft-based instruments that may be proposed for future planetary missions that are at the middle stages of technology readiness |
Development and Advancement of Lunar Instruments (DALI) | $5 M/year | Supports the development of science instruments for small lunar landers and orbital assets that are at the middle stages of technology readiness |
Planetary science technology programs relevant to small satellites [27].
The result of these continued investments is summarized in Table 5, where a number of EO techniques that were infeasible in 2012 [29] were all feasible 5 years later [30], many of them demonstrated by CubeSat missions, some of them commercial, and some even operational constellations. CubeSat-based astronomy missions will be discussed later.
Technology | 2012 technology review by Selva and Krejci | 2017 technology review by Freeman et al. | Justification |
---|---|---|---|
Atmospheric chemistry instruments | Problematic | Feasible | PICASSO, IR sounders |
Atmospheric temperature and humidity sounders | Feasible | Feasible | — |
Cloud profile and rain radars | Infeasible | Feasible | JPL RainCube demo |
Earth radiation budget radiometers | Feasible | Feasible | SERB, RAVAN |
Gravity instruments | Feasible | Feasible | No demo mission |
Hi-res optical imagers | Infeasible | Feasible | Planet Labs. |
Imaging microwave radars | Infeasible | Problematic | Ka-Band 12 U design |
Imaging multispectral radiometers (Vis/IR) | Problematic | Feasible | AstroDigital |
Imaging multispectral radiometers (μW) | Problematic | Feasible | TEMPEST |
Lidars | Infeasible | Problematic | DIAL laser occultation |
Lightning imagers | Feasible | Feasible | — |
Magnetic field | Feasible | Feasible | InSPIRE |
Multiple direction/polarization radiometers | Problematic | Feasible | HARP Polarimeter |
Ocean color instruments | Feasible | Feasible | SeaHawk |
Precision orbit | Feasible | Feasible | CanX-4 and CanX-5 |
Radar altimeters | Infeasible | Feasible | Bistatic LEO-GEO/MEO |
Scatterometers | Infeasible | Feasible | CYGNSS (GNSS-R) |
Figure 7 illustrates some of these NASA CubeSat-based EO missions. They follow the 3 U or 6 U form factor and include deployable solar panels for higher electrical power generation capabilities. RainCube (Figure 7c) also includes a 0.5-m-diameter deployable Ka band that stows in 1.5 U. This antenna has a gain of 42.6 dBi, and it was optimized for the radar frequency of 35.75 GHz. References are provided for more information on the cited missions.
Artist’s view of (a) TEMPEST [31], (b) RAVAN [32], and (c) RainCube missions [33].
On the educational side, the ESA launched in February 2008 the first Call for CubeSat Proposals to universities in ESA member and cooperating states. Seven student-built CubeSats were launched onboard the Vega maiden flight on February 13, 2012. Since then, 12 more CubeSats have been enrolled in the first and second editions of the “Fly Your Satellite!” program.
Since 2013, the ESA has invested more than 16 M€ as part of the General Support Technology Program (GSTP) FLY Element [34], in 12 CubeSat IOD missions [35, 36]. As part of ESA’s Systems Department Project Office of the Systems Department, Directorate of Technical and Engineering Quality, in April 2019, the CubeSat Systems Unit was created.
Artist’s view of (a) GOMX-3 [35] and (b) GOMX-4 [36] nanosatellites in space (credits GomSpace) and (c) FSSCat mission [38, 39].
In addition to the work conducted by this unit, there are a number of other CubeSat-related initiatives in ESA:
The Directorate of Telecommunications and Integrated Applications is developing a pioneer series of CubeSat missions, to test novel telecommunication technologies.
The Directorate of Operations has OPS-SAT [37] ready to fly, an IOD test-bed for innovative mission control software.
The Directorate of Human and Robotic Exploration is considering a CubeSat mission to test out a key capability for Mars sample return optical detection and navigation to a sample container from the orbit.
The Science Directorate is also adapting some CubeSat technologies for operation in the deep space environment as well as studying the potential use of CubeSats in support of planetary science missions.
The Directorate of Earth Observation will fly FSSCat [38, 39], a double 6 U CubeSat mission for tandem observation of the polar regions and for soil moisture mapping using the FMPL-3 (UPC, ES), a combined L-band microwave radiometer and GNSS-Reflectometer using a software-defined radio, and HyperScout-2 (Cosine, NL), a VNIR and TIR hyperspectral imager enhanced with artificial intelligence for cloud detection (PhiSat-1).
The first ESA CubeSat projects are listed in Table 6. In addition to these missions, numerous studies have focused on the applications of CubeSat missions and miniaturized payloads, including remote sensing with cooperative nanosatellites, asteroid impact missions, lunar CubeSats, astrobiology/astrochemistry experiment CubeSats, asteroid observer missions, etc.
Organization | Mission | Launch | Form factor | Field | Technical and comments |
---|---|---|---|---|---|
GomSpace (DK) | GOMX-3 | 2015 | 3 U | Tech demo | ADS-B, GEO Satcom signal monitoring, X-band transmitter (Figure 8a) |
GomSpace (DK) | GOMX-4B | 2018 | 2 × 6 U | Tech demo Earth observation | Inter-satellite link and propulsion while in tandem with GOMX-4A (GomSpace, Ministry of Defense, DK), star tracker HyperScout compact hyperspectral VNIR imager (Cosine, NL) (Figure 8b) |
VKI (BE) | Qarman | 2019 | 3 U | Tech demo | Demonstrates reentry technologies, novel heatshield materials, new passive aerodynamic drag stabilization system, and telemetry transmission during reentry via data relay satellites in low Earth orbit |
RMI (BE) KU Leuven (BE) | SIMBA | 2019 | 3 U | Earth observation | Total solar irradiance and Earth radiation budget |
BIRA-IASB (BE) VTT (FI) Clyde Space (UK) | PICASSO | 2019 | 3 U | Atmosphere and ionosphere | Stratospheric ozone distribution, mesospheric temperature profile, and ionospheric electron density |
C3S and MTA EK (HU) ICL (UK) Astronika (PO) | RadCube | 2019 | 3 U | Tech demo Space weather | 3 U platform In situ space radiation and magnetic field in LEO |
RUAG (AU) TU Graz (AU) Seibersdorf Labor GmbH (AU) | PRETTY | — | 3 U | Earth observation | GNSS-R at low grazing angles, radiation dosimeter |
ESA | OPS-SAT | 2019 | 3 U | Tech demo | Experimentation with onboard and ground software by offering a safe and reconfigurable environment |
UPC (ES) Golbriak (EE) Deimos Eng (PT) Tyvak Intl. (IT) Cosine (NL) | FSSCat | 2019 | 2 × 6 U | Tech demo Earth observation | RF and O-ISL, federated satellite experiment 3Cat-5/A: Microwave radiometer and GNSS-R (UPC, ES) 3Cat-5/B: HyperScout-2 VNIR + TIR hyperspectral imager (Cosine, NL) (Figure 8c) |
The first ESA CubeSat-based missions.
In blue from the CubeSat Systems Unit, Directorate of Technical and Engineering Quality; in orange from the Directorate of Operations; and in green from the Directorate of Earth Observation (2017 ESA S^3 Challenge, Copernicus Masters Competition).
As highlighted in Sections 1.3 and 2.1, the majority of the CubeSats orbiting today are devoted to Earth observation, notably from two commercial companies, followed by communications. In the coming years, these two categories will still dominate. Although the largest increase will occur in communication satellites, the growth in scientific (non-EO) missions will not be negligible (from 10 to 20%, Figure 9) considering that the predicted number of satellites to be launched is going to multiply by more than a factor of 3 (see Figure 4).
Satellite application trends (1–50 kg): (a) 2014–2018 and (b) 2019–2023 (adapted from [14]).
In particular, until 2017 there were only 5 astronomy missions, and in the field interplanetary missions, until 2018 only 14 nano−/microsatellites had been launched to destinations outside the LEO. Beyond-the-Earth orbit is the domain of civil agencies who, for the sake of reliability, have been historically reluctant to invest in small satellites. However, things may be changing, since only in 2018 four nano−/microsatellites made their way beyond the Earth orbit, which is more than those in the previous 5 years all together, and 35 more are expected to be launched in the coming 5 years. Naturally, most of them target the moon, but a non-negligible fraction will be devoted to interplanetary missions (Figure 10).
CubeSats launched beyond the earth orbit: 14 from 2003 to 2018 and 35 planed from 2019 to 2023 (adapted from [14]).
As in other fields, at the beginning all the astronomy or heliophysics missions were conducted by universities, and it was not until 2017 that the first NASA JPL mission (ASTERIA) was launched. Achieving state-of-the-art astronomy with CubeSats has become possible due to advances in precision pointing, communications technology, and deployables, among others (Tables 5.1 and 5.2 of [40]). Table 7, distilled from [21], shows the main astronomy and beyond-the-Earth past and planned missions. It also shows that the majority of these missions are based on the 6 U form factor, which is the smallest one capable to accommodate all the advanced attitude determination and control systems (ADCS), larger deployable solar panels and antennas, as well as telescope optics. It is also remarkable that so far there are no funded CubeSat missions in the far IR because the thermal stability and detector cooling require cryo-coolers for CubeSats that have yet to be developed for astrophysics due to power and space limitations [41].
Organization | Mission | Launch | Form factor | Technical and comments |
---|---|---|---|---|
Morehead State University Kentucky Space | CXBN | 2012 | 2 U |
|
University of Colorado | CSSWE | 2012 | 3 U |
|
Austria Canada Poland | BRITE | 2013 2014 | 8 U (2 × 2 × 2) |
|
University of Colorado at Boulder | MinXSS | 2015 | 3 U |
|
JPL (USA) MIT (USA) | ASTERIA | 2017 | 6 U |
|
ERC, CNRS, ESEP Lab, PSL Université Paris, Fondation MERAC, CNES, CCERES and Obs. de Paris – LESIA | PicSat | 2018 | 3 U |
|
University of Iowa | HaloSat | 2018 | 6 U |
|
Spacety (China) | Tongchuan-1 | 2018 | 6 U |
|
University of Colorado Boulder | MinXSS-2 | 2018 | 3 U |
|
University of Colorado | CSIM | 2018 | 6 U |
|
DARPA | SHFT-1 | 2018 | 3 U |
|
NASA | MarCO-1/MarCO-2 | 2018 | 6 U |
|
University of Hawaii at Manoa | NEUTRON-1 | 2019* | 3 U |
|
Boston University | CuPID | 2019* | 6 U |
|
University of Colorado Boulder | CUTE | 2020 | 6 U |
|
Isaware (FI) | XFM Cube | 2020 | 3 U |
|
Lockheed Martin | LunIR | 2020 | 6 U |
|
Arizona State University | LunaH-Map | 2020 | 6 U |
|
NASA JPL | Lunar Flashlight | 2020 | 6 U |
|
Morehead State University | Lunar IceCube | 2020 | 6 U |
|
Arizona State University (USA) | SPARCS | 2021 | 6 U |
|
NASA’s Goddard Space Flight Center | BurstCube | 2021 | 6 U |
|
ESA Luxembourg Space Agency (LU) GomSpace (DK) | M-ARGO | 2023 | 12 U |
|
ESA | HERA CUBESAT | N/A | 2x6 U |
|
Non-comprehensive list of astronomy and beyond-the-earth CubeSat-based missions.
It is worth noting that the large number of CubeSats to be launched to the Moon in 2020 corresponds to the Artemis-1 mission (Figure 11), formerly known as Exploration Mission-1. The first mission for NASA’s Orion rocket and the European Service Module will send the spacecraft beyond the moon and back. Thirteen low-cost CubeSat missions were competitively selected as secondary payloads on the Artemis-1 test flight, all of them having the 6 U form factor. The selected CubeSats are Lunar Flashlight, Lunar South Pole, Near-Earth Asteroid Scout, BioSentinel (carrying the first living creatures into deep space since 1972), SkyFire, Lunar IceCube, CubeSat for Solar Particles (CuSP), Lunar Polar Hydrogen Mapper (LunaH-Map), EQUULEUS, OMOTENASHI, ArgoMoon, Cislunar Explorers, Earth Escape Explorer (CU-E3), and Team Miles.
Overview of the mission plan for Artemis-1: CubeSats will be deployed at steps A, B, C, and D [https://www.nasa.gov/image-feature/artemis-1-map].
Talking about interplanetary missions, on May 5, 2018, NASA launched a stationary lander called InSight to Mars. InSight landed on Mars on November 26, 2018. Riding along with InSight were two CubeSats—the first of this kind of spacecraft ever to fly to deep space [42]. Both MarCO-A and MarCO-B succeeded in a flyby of Mars, relaying data to Earth from InSight as it landed on Mars. Figure 12 shows an artist view of the MarCOs with the reflectarray used for communication purposes.
Artist view of MarCO-A and MarCO-B [42].
In addition to the “classical” astronomy, lunar and Martian missions cited above, CubeSats are nowadays finding their way to other bodies of the solar system, and there are proposals [43] to send them to Venus (CUVE mission), Deimos and Phobos asteroids (PRISM and PROME missions), comets (PrOVE mission), or Jupiter (ExCSITE mission, [44]). Figure 13 from [44] illustrates the LEO and beyond-LEO CubeSat exploration initiatives.
Solar system exploration with CubeSats and nanosats [44].
Since its conception in 1999, CubeSats have produced a “disruptive innovation”: from simple applications at the bottom of a market (mostly educational), they have relentlessly moved up, eventually displacing established medium-size competing satellites. However, CubeSats cannot displace all the large space missions as physics laws cannot be changed, i.e., large apertures and focal lengths are required to collect faint signals and achieve large angular resolution. However, CubeSats are finding their own niche in many Earth observation, astronomical, and communications applications where short revisit times or even continuous monitoring is required.
Early CubeSats typically had short lifetimes once in orbit (a few months), but with increased ground testing and added redundancies, lifetimes have grown significantly, up to 4–5 years in some cases.
Despite all these outstanding improvements, in order to exploit the full potential of CubeSats, many technologies still need to be developed. Table 8 summarizes the enabling technologies required for different science applications, indicating in red the most challenging technologies and applications, notably increased communications performance, reliability, thermal stability, and calibration accuracy, to form constellations or formation flying satellite topologies to create large interferometers and distributed apertures.
Science discipline | Enabling technology | Example application |
---|---|---|
Solar and space physics | Propulsion | |
Sub-arcsecond attitude control | High-resolution solar imaging | |
Missions beyond low Earth orbit | ||
Miniature field and plasma sensors | In situ measurements of upper atmosphere plasmas | |
Earth science | Propulsion | |
Miniaturized sensors | Stable, repeatable, and | |
Planetary science | Propulsion | Orbit insertion |
Direct/indirect to Earth communications | ||
Radiation-tolerant electronics | ||
Deployables | Deployable solar panel enhanced power generation | |
Deployable mirrors and antennas | ||
Astronomy and astrophysics | Propulsion | |
Sub-arcsecond attitude control | High-resolution imaging | |
High data rate | ||
Deployables | Increased aperture and thermal control | |
Miniaturized sensors | UV and X-ray imaging | |
Physical and biological | Thermal control |
CubeSat-enabling technologies and potential applications for each science discipline (adapted from [40]).
In the field of Earth observation, future developments in nanosat sensors will likely occur:
In the field of passive microwave sensors:
Miniature microwave and millimeter-wave radiometers for weather applications, such as the MiniRad which is onboard the Global Environmental Monitoring System (GEMS) constellation from Orbital Micro Systems [45], or
GNSS-R instruments with real-time processing for target detection/identification [46] or—as larger downlink bandwidths are available—with raw data acquisition and on-ground processing to optimize the processing according to the target, as planned in FMPL-3, the evolution of the FMPL-2 on board FSSCat [38, 39].
In the field of passive VNIR/TIR hyperspectral imagers, imagers will include a larger number of bands but will include advanced image compression algorithms to minimize the amount of information to be downloaded and will incorporate artificial intelligence to download only the information extracted instead of the raw data.
Also, both their calibration will have to be refined so as to improve the quality of the scientific data.
Due to power and antenna size requirements, active microwave sensors (e.g., radar altimeters and SARs) will likely remain in domain of mini- and microsats (< 100 kg, e.g., ICEYE constellation [47]), and it is unlikely that active optical sensor technology (i.e., lidars) develops in small satellites in the midterm.
In the field of astronomy, and in particular heliophysics, NASA has also been taking the lead. In 2017 NASA selected nine proposals under its Heliophysics Small Explorers Program [48]: (1) the Mechanisms of Energetic Mass Ejection Explorer (MEME-X), (2) the Focusing Optics X-ray Solar Imager (FOXSI), (3) the Multi-Slit Solar Explorer (MUSE), (4) the Tandem Reconnection and Cusp Electrodynamics Reconnaissance Satellites (TRACERS), (5) the Polarimeter to Unify the Corona and Heliosphere (PUNCH), (6) the Atmospheric Waves Experiment (AWE), (7) the US Contributions to the THOR mission (THOR-US), (8) the Coronal Spectrographic Imager in the Extreme ultraviolet (COSIE), and (9) the Sun Radio Interferometer Space Experiment (SunRISE) mission concept, which is a space-based sparse array, composed of formation flying of six SmallSats designed to localize the radio emission associated with coronal mass ejections (CMEs) from the sun [49].
More recently, in August 2019, NASA selected two proposals to demonstrate SmallSat technologies to study interplanetary space [50]: (1) Science-Enabling Technologies for Heliophysics (SETH) will demonstrate two technologies, an optical communications technology and experiment to detect solar energetic neutral atoms as well as an array of waves and other particles that erupt from our sun, and (2) Solar Cruiser, which will deploy a nearly 18,000 square foot solar sail and a coronagraph instrument that would enable simultaneous measurements of the sun’s magnetic field structure and velocity of coronal mass ejections or CMEs.
As a final thought, quoting Prof. Puig-Suari, “Before cubesats, we were so conservative nobody was willing to try anything out of the ordinary. When we did, we discovered some of the things everybody said would not work, did work. The fundamental change was that there was a mechanism to go try to those things. Some will work and some will not, but it allows us to try them and that was very infrequent before cubesats arrived. That was really important. That was the big change.” And this is just the beginning of a new way to do Earth observation, astronomy, and satellite communications much more, in a different and more efficient way than it was done in the past decades. What will the future bring? Nobody knows, but certainly the future is being shaped today with these novel technologies, and only our imagination will set the limits.
This work has been supported by an ICREA Acadèmia award from the Generalitat de Catalunya to Prof. A. Camps. The author wants to express his gratitude to Profs. A. Golkar (Skoltech, Moscow, Russia) and H. Park (Universitat Politècnica de Catalunya, Barcelona, Spain) for the revision of this chapter and useful comments.
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