Open access peer-reviewed chapter

Catalytic Applications of Metal-Organic Frameworks

Written By

Sandra Loera-Serna and Elba Ortiz

Submitted: 16 May 2015 Reviewed: 28 October 2015 Published: 03 February 2016

DOI: 10.5772/61865

From the Edited Volume

Advanced Catalytic Materials - Photocatalysis and Other Current Trends

Edited by Luis Enrique Norena and Jin-An Wang

Chapter metrics overview

4,160 Chapter Downloads

View Full Metrics

Abstract

In recent years, metal organic frameworks (MOF) have received considerable interest due to their physicochemical properties, such as structures’ flexibility, high surface area, tunable pore size, and topologies, among others, which have lead to promising applications, particularly in the area of catalysis. In this chapter, we present the most important results of research conducted with MOF in catalytic applications; mainly in the design of its structure, synthesis, characterization, and possible limitations.

Keywords

  • Metal-organic frameworks
  • Heterogeneous catalysis
  • Porous materials

1. Introduction

MOFs and the related researches have become more and more important not only in chemistry but also in general science and technology. MOFs are a class of porous materials composed of metal-containing nodes connected by organic linkers through strong chemical bonds. The union of these two building units produces different coordination modes, depending on the symmetry of the linker and the coordination number of the metal center. The flexibility or rigidity of the added linker can allow the articulation of the clusters into a highly crystalline three-dimensional framework, which can exhibit higher surface area and pore volume than most porous zeolites [1]. Depending on the architecture of the obtained MOFs, they can be synthesized with high purity and also, they can be engineered to have a high skeletal density but constructed from relatively light elements. Therefore, most of the important related work is aimed at designing compounds possessing very large pores and high surface areas in order to load these materials with atoms, molecules, or even biomolecules. Due to these loading possibilities, wide applications of MOFs have emerged in different fields, such as in catalysis [24], guest adsorption (molecular recognition) [5], drug delivery [6, 7], gas storage [813], optical applications [1416], composites [17], water treatment [18, 19], and sensor technologies [20], among others [2126].

Some materials as metals in solution (transition metal complexes or metal salts) have been used in catalysis with excellent results. These materials are able to catalyze a variety of organic reactions, in many cases, reaching high yields and regenerating the material after the reaction. However, in many cases the metals are hardly recovered and/or decompose during the reaction due to the conditions. To achieve control these limitations, researchers have developed methods using porous materials as carriers, to achieve well-isolated, uniform single sites that don’t interact between them, preventing the decomposition [2, 27]. Active sites on MOFs are located at the metal nodes on the crystalline structure; when the reaction occurs, the framework protects their active sites and increases the efficiency and resistance of catalyst [28].

Given the variety of metallic nodes and organic linkers, it is possible to control the synthesis of MOFs to design them with modular properties, functionalized with specific sites or specific assets to catalyze organic reactions. In this chapter, we present the main results of research with MOFs in the field of catalysis, with special focus on design, relationship between structure and activity, formation of active sites and limitations of these materials.

Advertisement

2. Design of MOFs

2.1. Crystal engineering of MOF

The term of metal organic framework was introduced by Yaghi in 1995 [29, 30], however, such structures were known until 1964 when Bailar first reported them [31]. The resurgence of the structures has been accompanied by the application of these materials in various areas, including: catalysis [24], guest adsorption (molecular recognition) [5], drug delivery [6, 7], gas storage [813], optical applications [1416], composites [17], water treatment [18, 19] and sensor technologies [20], among others [2126].

The structural characteristics of the MOFs are mainly determined by the nature of the metal center and the organic linker, yet, during the synthesis of these materials, solvents and/or counterions are typically used [32] and they also play an important role. The counterions change the environment of the metal ion and may generate overlaps with the structure resulting in weak interactions with the MOF. Meanwhile, solvent molecules with the MOF generally crystallize during synthesis, modifying the pore size.

Generally, the transition metal ions used can generate a wide range of structures. The properties of these metals, including the oxidation state and coordination number (typically varies from 2 to 7), produce a linear, trigonal, square planar, tetrahedral, trigonal pyramidal, trigonalbipyramidal, octahedral, and pentagonal bipyramidal geometries as well as some other distorted forms [32]. The lanthanoidions, whose coordination number varies between 7 and 10, have polyhedral geometries and can generate MOFs with particular topologies [33].

In the formation of MOFs, the organic linkers must meet certain requirements to form coordination bonds, mainly being multidentate having at least two donor atoms (N-, O- or S-) and being neutral or anionic. The structure of MOF is also affected by the shape, length, and functional groups present in the organic linker. The linkers commonly used in the MOFs synthesis are piperazine [34], 4,4′-bipyridine [3437] (neutral ligands), and polycarboxylates (anionic ligands). Polycarboxylates may be di- [3843], tri- [38, 4043], tetra- [44, 45], or hexacarboxylates [46, 47].

The binding of a linker to the metal center may generate a one-dimensional (1D), two-dimensional (2D) or three-dimensional (3D) arrangement, which depends on the metal center (Figure 1) [48]. In a 1D network, two ligand molecules are coordinated to the metal center to generate a chain, while in a 2D network, three or four molecules of the organic linker are coordinated to generate a plane, and it grows in two dimensions. In a 3D MOF, the metal center, with high coordination number, joins three more linker molecules, along the three spatial dimensions, generating a three-dimensional structure with pores and cavities defined.

Figure 1.

Basic building units of one-, two-, and three-dimensional MOFs [48].

Figure 2 shows examples of MOF with different dimensionalities. The helix (1D) is constituted by distorted tetrahedrons mercury (II), formed by the union of two nitrogen atoms (from two different linkers) and two terminal bromine atoms [49].

The 2D structures with grid shape are generally synthesized with a molar ratio between the ligand and the metal center of 1:2. An example of such structures is shown in Figure 3, the MOF is constituted by cobalt metal centers and ligands N-(3-pyridyl) nicotinamide [50]. The metal ions are coordinated with four molecules of ligand, which result in a two-dimensional flat-shaped structure.

Figure 2.

Examples of MOF structures 1D, 2D, and 3D.

The three-dimensional MOFs are formed by the interaction of one-dimensional chains in all three directions. Connectivity of the construction nodes depends on the metal center, and the formed structures are usually tetrahedral or octahedral. An example of such structures, wherein the metal is cadmium center and has an octahedral coordination, is given in Figure 3. The bidentate linker forms connections, where the four terminals of each linker involves oxygen atoms. The three-dimensional growth of the framework generates cavities; generally occupied by solvent molecules [51].

2.2. Synthesis of MOF

The physicochemical characteristics of MOFs can be modulated and it is clear that all these properties can be modified in the material from the synthesis process. The solvothermal synthesis is the most common way of obtaining MOFs. However, other recently studied methods of synthesis, which may cause significant changes in the MOF’s properties, include (i) mechanochemical, (ii) electrochemistry, (iii) assisted synthesis (by ultrasound or microwave), and (iv) subcritical water.

2.2.1. Solvothermal synthesis

The solvothermal synthesis comprises the reaction of the metal salt and the organic ligand in the presence of organic solvents or solvent mixtures typically involving formamide [5255], alcohols [56, 57], or pyrrolidones [58]. The reaction temperature is usually considerably less than 523 K, but depends on the boiling point of the solvent used, for example, in the case of methanol, the synthesis temperature is 338 K. Upon heating, the blends in sealed containers such as teflon or glass pressure tubes produced compounds incorporating solvent molecules in the pores of the material. These organic solvents are often toxic, carcinogenic, and/or dangerous to the environment. For example, dimethylformamide (DMF), one of the most commonly used solvents in the synthesis of MOFs is contaminant, mutagenic, and toxic [59]. Additionally, DMF decomposes when heated at high temperatures for long periods and therefore cannot be reused [60].

The concern about the use of these organic solvents has increased due to their negative impact on the environment [61]. Therefore, the replacement of polluting solvents in the synthesis of MOFs with solvents that do not pose a risk to the environment has been established as a primary objective, committing to the principles of Green Chemistry [62]. When the solvent is water, the main problem encountered during synthesis is the low or nonsolubility of the reactants and organic ligands, which generally prevents the formation of coordination polymer.

Other important parameters in the solvothermal synthesis are: temperature, concentration of reactants (which can be varied over a wide range) and the pH of the solution.

One of the advantages of this synthesis are the yields ranging from 60% to 95%; however, removing solvent molecules occluded in the pores of the MOF is not a simple process, the solids must be washed several times, which can take several days and considerably reduce performance.

2.2.2. Mechanochemical synthesis

The mechanochemical synthesis is named due to the chemical reaction that occurs as a consequence of mechanical energy supplied to the system [63]. In the mechanical grinding process, several phenomena occur, such as

  1. Fragmentation of grains

  2. Generation of new surfaces

  3. Formation of dislocations and defects in the crystal structure

  4. Polymorphic phase transformation material, and

  5. Chemical reactions (decomposition, ion exchange, oxidation-reduction, complexation, etc.).

In the synthesis of MOFs, the metal salt and the organic linker are ground together in the absence of solvents. In 2002, Belcher et al. [64] reported the synthesis of a 1D copper coordination polymer, using mechanochemical synthesis (Figure 3).

Figure 3.

Basic unit of construction of coordination polymer [Cu(O2C-Me)2]2(μ-dpp) dpp = 2,3-bis(2-pyridyl)pyrazine. Gray, red, white, violet, and orange spheres correspond to atoms of C, H, N, O and Cu, respectively.

In other recent studies [65], MOFs were synthesized using 12 metal salts and 5 organic linkers to obtain 60 different solids. As a result, 38 microcrystalline MOFs were identified using X-ray diffraction techniques. Their structure patterns are found on the CSD database (Cambridge Structure Database), including microporous MOFs [Cu(INA)2]n (INA = isonicotinate) and Cu3(BTC)2.

2.2.3. Electrochemical synthesis

Electrochemical synthesis of MOFs was reported by BASF in 2005 [66], in order to eliminate the use of anions such as nitrate, perchlorate, and chloride, which act as counterions or as impurities in the network. In this synthesis method, the metal salts are replaced by metal ions produced from the anodic dissolution in the reaction medium. The dissolution also contained organic linkers; in cathodes, metal deposition occurred. In particular, for the synthesis of Cu3(BTC)2, copper metal bars that function as electrodes (anode and cathode) were employed in the electrochemical cell with organic linker (BTC = benzene-1,3,5-tricaboxylic), dissolved in methanol [67], with an applied voltage between 12 and 19 V and a current of 1.3 A for 150 min. The result was the oxidation of the copper bar acting as the anode to form Cu2+, which reacts with the organic linker. Furthermore, in cathode, water reduction took place to produce hydrogen. At the end of the reaction, a greenish-blue precipitate was formed, which was filtered and dried to obtain Cu3(BTC)2. Using these synthesis pathways, materials can be produced with high purity and ease of being industrially scalable.

Other studies on the electrochemical synthesis of MOFs are presented in Table 1.

MOF Type of synthesis Reference
Zn and Cu-carboxylates Systematic study of Zn, Cu, Co and Mg as anode 1,2,3-H3BTC, 1,2,5-H3BTC, H2BCD y H2BCD-(OH)2 [66]
Zn-Imidazolates Synthesis of Zn(MeIm)2 and Zn(BIm)2 [68]
Cu3(BTC)2 Synthesis and y growth of galvanic displacement layered [67]

Table 1.

MOFs synthesized electrochemically.

H3BTC = benzene-1,3,5-tricarboxilic acid; H2BCD = terephtalic acid; MeIm = 2-methyl-1H-imidazole; BIm = benzimidazole.


2.2.4. Microwave or ultrasound-assisted synthesis

Synthesis assisted by ultrasound or microwave is an alternative to the solvothermal synthesis. In microwave-assisted synthesis, the reaction mixture is subjected to nonionizing radiation, which does not change the electronic structure of the material. The energy supplied to the material by electromagnetic waves through interactions of molecular type offers a number of advantages, such as a uniform controlled heating as well as a great speed with which energy is generated [69]. The characteristic frequency of this radiation is between 300 MHz and 300 GHz (wavelengths between 0.01 and 1 m). This synthetic method has been applied to organic molecules [70] and inorganic materials [71].

Generally, the microwave synthesis is carried out in minutes and offers a better method to control the morphology of the material and the selectivity of the phases. For example, MOF-5 (Figure 4) was synthesized using microwave at 368 K for 9 min, with a yield of 27% [72], while using the solvothermal synthesis, a yield of 60% was achieved after 7 days.

Table 2 shows the conditions of microwave-assisted synthesis of MOFs.

MOF Time (min) Temperature (K)
IRMOF1, IRMOF2, IRMOF3 0.42
(EMIm)2[Ni3(TMA)2(OAc)2](EMIm)2[Co3(TMA)2(OAc)2] 50 473
[Ni20(C5H6O4)20 (H2O)8 ]·40H2O 1 423–493
MIL(Cr)-101 1–40 483
[Cu2(pyz)2 (SO4)(H2O)2]n 20, 360 453
[Cu2(oba)2 (DMF)2]·5.25(DMF) 1–150 433
[Mn3(BTC)2 (H2O)]6 10 393
[Cd(H3IDC)(bbi)0.5] 20
MOF-5 9–60 368–408
[Cu3(BTC)2(H2O)3] [Cu2(OH)(BTC)(H2O)]·2nH2O 60 413
[Cu(H2BTC)2 (H2O)2]·3H2 O 10 443
[Zn2(NDC)2(DPNI)] 60 393
[Co3(NDC)3(DMF)4] y [Mn3(NDC)3(DMF)4] 30 383

Table 2.

Conditions of microwave-assisted synthesis of MOFs [73].

EMIm = 1-ethyl-3-methylimidazolium; TMA = trimesate; pyz = pyrazine; oba = 4,4′-oxydibenzoic acid; BTC = benzene-1,3,5-tricarboxilic; H3IDC = 4,5-imidazoledicarboxylic acid; bbi = 1,1′-(1,4-butanediyl)bis(imidazole); NDC = 2,7-naphthalene dicarboxylate; DPNI = N,N di(4-pyridyl)-1,4,8-naphthalenetetracarboxydiimide.


Ultrasound-assisted synthesis is another route for obtaining materials, where you can get MOFs with small crystal size in a short reaction time. In this synthesis, the reaction mixture is subjected to ultrasound (part of the spectrum of the sound whose frequency is approximately 19 kHz) to generate high temperatures (above 5000 K) and pressures at specific locations within the mixture. Such increases in temperature and pressure are due to the phenomenon of "cavitation", which involves the creation, expansion, and destruction of small bubbles that appear when the reaction mixture is treated with ultrasound [74]. In this case, acoustic radiation mechanical energy is converted into thermal energy. Among the MOFs synthesized by this method are MOF-5, MOF-177, Cu3BTC2, Zn-2,2′bipiridina-5,5′dicaboxilato, Zn3(BTC)2 12H2O [Zn (1,4-bencendicarboxilato) (H2O)]n [75].

2.2.5. Synthesis of MOFs using near supercritical water conditions

Motivated by the resolution of the problem that exists with the use of solvents (1.3.1), Schröder and Poliakoff [76] developed a new methodology for the synthesis of MOFs, building for its acronym high-temperature water (HTW). Due to these properties, the HTW has been studied as a means of organic reactions [77, 78], destruction of contaminants [79] and formation of nanoparticles [80, 81]. Water properties change dramatically as it approaches its critical point (647 K, 220 bar) [82]. For example, the dielectric constant decreases to values of typical nonpolar solvents, and therefore, organic compounds, such as organic ligands of MOFs, can be dissolved.

Water can potentially be reused after the reaction has been completed and, if necessary, ion exchange may be employed in order to remove any traces of unreacted organic ligand and metal ions. HTW presents some technical difficulties due to the high pressures and accelerated corrosion of the reactors. However, Schröder and Poliakoff [76], in 2012, first reported the possibility of using HTW (573 K) as solvent for the synthesis of a MOF with high performance. The new MOF, {[Zn2(L)] (H2O)3}; (L = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene) (Figure 4), is synthesized using only water as reaction medium at 573 K and 80 bar.

Figure 4.

View of the crystal structure of the structure {[Zn2(L)] (H2O)3}. Green, red, black and gray represent Zn atoms, O, C, and H, respectively [76].

2.3. Characterization and evaluation methods of MOFs

The different methods of synthesis of MOFs can generate homogeneous solids that allow carrying out processes of heterogeneous catalysis. Once the reaction finished, it is desirable that the physicochemical characteristics of material prevail. There are different characterization techniques for determining the homogeneity of the material, structural characteristics, and stability of the MOF. Analytical methods that are useful and applicable are listed below. However, others characterizations may exist which are also useful in the evaluation of MOFs, such as heterogeneous catalysis.

Powder X-ray diffraction (XRD) is used in determining the crystallographic MOFs by comparing the diffractogram of MOF before and after the catalytic process. In certain processes, the stability of the structure is also determined. Additionally, it is possible to determine the purity of the catalyst and some crystallographic parameters as red parameter, size of lattice, and crystal size.

Fourier transform infrared spectroscopy (FTIR) provides information about functional groups present in the network of the MOF. It is possible to make a comparison to determine the changes once the network has carried out the catalytic reaction.

Nuclear magnetic resonance (NMR) is a widely used technique in the characterization of products, by-products, and intermediates of the catalysed reaction. It is possible to determine the chemical environment inside the catalyst using probe molecules.

Nitrogen physisorption. The texture parameters such as surface area, pore volume, and average pore size are determined by this technique. The shape of the isotherm provides information about the homogeneity of the solid.

Ultraviolet-visible diffuse reflectance spectrum provides information about the environment metal coordination before and after carrying out a catalysed reaction.

Thermogravimetric analysis (TGA) is useful to determine the thermal stability of the MOF. In some processes, it is necessary to conduct a heat treatment prior to the catalysed reaction and treatment parameters are determined by TGA. It is possible to obtain a model which is highly suitable for the process reaction desired.

Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are able to show the morphology, defects, grain boundaries, mixtures of crystalline phases, and grain size, among others. In some solids, even the crystallinity and porosity can be determined by these techniques.

Energy-dispersive X-ray (EDX) is used to determine the elemental materials analysis. The MOF is studied before and after the catalytic process for identifying the presence of new elements and their percentage.

Gas absorption analyser can be used to analyze the adsorption capacity for MOF for a particular gas or vapour.

Gas/liquid chromatography-mass spectrometry (GC/LC-MS) is a powerful technique to analyse the catalytic reaction and determine the amount and type of products.

Raman spectroscopy is widely used in the characterization of noncrystalline or low-crystalline catalysts. Comparing the spectra before and after the reaction provides information about the incorporation of new components into the MOF network.

Temperature-programmed reduction (TPR) is used in determining redox reaction parameters. The catalytic activity in redox conditions can be determined by this technique.

Advertisement

3. MOF’s structure using catalytic reaction

The active sites of MOFs can be designed depending on the type of catalytic process. The Rosseinsky group reported the methanolysis of rac-propylene oxide and expected to yield 2-methoxy-1-propanol and 1-methoxy-2-propanol reaction. They used the postsynthesis modification of a porous homochiral Ni(L-asp)bipy 0.5, 1 (L-asp = L-aspartate, bipy = 4,4-dipyridyl), leading to a functional Brønsted acidic material. These compounds are amino acids (L- or D-aspartate) together with dipyridyls as struts. The coordination chemistry is such that the amine group of the aspartate cannot be protonated by added HCl, but one of the aspartate carboxylates can. Thus, the framework-incorporated amino acid can exist in a form that is not accessible for the free amino acid. While the nickel-based compounds are marginally porous, on account of tiny channel dimensions, the copper versions are clearly porous [83].

The results showed that the carboxylic acids behave as Brønsted acidic catalysts, facilitating (in the copper cases) the ring-opening methanolysis of a small, cavity-accessible epoxide at up to 65% yield. These researchers pointed out that the superior homogeneous catalysts existed, but emphasized that the catalyst formed here is unique to the MOF environment, thus representing an interesting proof of concept [84].

Lewis acid solids are commonly used in selective oxidation. An example of this type of catalysts is trinuclear networks containing Cu2+, which have shown a high activity and selectivity for the peroxidative oxidation process of cyclohexane into the corresponding alcohols and ketones (MeCN/H2O/HNO3 media) [85]. The structure of such MOFs is composed of the secondary building unit of {Cu33-OH)(μ-pyrazole)} with tetracoordinate metal centers in axial positions of easy access.

Other structures with these types of catalytic sites on the Cu3(BTC)2 coordinated network are made of copper links. It is feasible to prepare this MOF with modulated amounts of physisorbed (molecules placed into the channels) or chemisorbed (molecules occupying CuX coordination sites) water molecules with high surface area straight from the reaction vessel without any postsynthetic steps [8]. Different reaction models have been tested in this MOF including: citronellal cyclization [86], benzaldehydecyanosilylation [87], rearrangement of ethylene acetal of 2-bromopropiophenone, isomerization of alpha-pinene oxide [86], among others [28].

Another example of MOF with high concentration of Lewis acidic sites is Mn3[(Mn4Cl)3(BTT)8(CH3OH)10]2; H3BTT = 1,3,5-benzene-tristetrazol-5-yl. Mn2+ ions that are exposed on the surface of the framework might serve as potent Lewis acids, and catalyze the cyanosilylation of aromatic aldehydes and ketones, as well as the more demanding Mukaiyama-aldol reaction. Moreover, in each case, a pronounced size-selectivity effect consistent with the pore dimensions is observed [88].

Different types of MOF have been used in catalytic process as base catalysis, Brønsted acid catalysis, Lewis acid catalysis, C–C bond formation and polymerization, enantio selective catalysis, and catalysis by organometallic complex supported on MOFs, among others. Table 3 summarizes the MOF structures used in some catalytic processes reported so far. The most common ions catalysis are: Ag+, Al3+, Bi3+, Ce4+, Cr3+, Co2+, Cu2+, Fe3+, Mn2+, Mg2+, Pd2+, Sc3+, V4+, Zn2+, and Zr4+.

MOF Catalysed reaction Reference
Al2(bdc)3(MIL-53(Al)) Reduction of carbon–carbon multiple bonds [89]
[Ag3(tpha)2] 3BF4
(Ag-tpha)
1,3-Dipolar cycloaddition [90]
Bi(btb) Hydroxymethylation of 2-methylfuran [91]
Ce-mdip1 Cyanosilylation of aldehydes [92]
Cd(4-btapa)2(NO3)2 Knoevenagel condensation [93]
[Cd(bpy)2](NO3)2 Cyanosilylation of aldehyde [94]
Cd3Cl6L13 Alkylation of aldehyde [95]
Co(BPB) Oxidation of olefin [96]
Co2(dhbdc)( H2O)
(Co-MOF-74)
Cycloaddition of CO2 and epoxides [97]
[Co(DMA)6]3[(Co4Cl)3 - (btt)8(H2O)12]2(Co-btt) Ring opening of epoxides; oxidation of hydrocarbons [98]
Cr3X(H2O)2O(bdc)3
X = F, OH, (MIL101(Cr))
Knoevenagel condensation;
Heck coupling;
Cyanosilylation of aldehydes
Oxidation of hydrocarbons
Oxidation of sulfides Cycloaddition of CO2 and epoxides
[99103]
[PW11TiO40]5-@[Cr3F(H2O)2O(bdc)3], and [PW11CoO39]5-@[Cr3F(H2O)2O(bdc)3] Oxidation of olefin [104]
Cu(2-pymo)2] and [Co(PhIM)2 Aerobic oxidation of olefin [105]
Cu(bpy)( H2O)2(BF4)2(bpy) Ring-opening of epoxide [106]
Cu(D-asp)bpe0.5and Cu(L-asp)bpe0.5] Methanolysis of epoxide [83]
Cu(L2)2(H2O)2, Cu(L3)2(H2O)(Py)2, Cu(L3)3(H2O)Cl and Co(sal)( H2O)(Py)3 Epoxidation of olefin [107]
Cu(SO4)(pbbm) and (Cu(Ac)2(pbbm))CH3OH Oxidative self-coupling [108]
Cu3(btc)2 Isomerization; cyclization; rearrangement Oxidation of polyphenol Cyanosilylation of aldehyde [86, 87, 109113]
Cu2(papa)2Cl2 Biginelli reaction; 1,2-additionof a,b-unsaturated ketones [115]
Cu3(pdtc)(pvba)2(H2O)3 Henry reaction [115]
Cu(2-pymo)2 Click reaction
Three-component couplings of amines, aldehydes and alkynes
[116, 117]
Cu(tcba)(DMA) Epoxidation of olefins [118]
Cu2(bpdc)2(bpy) Cross-dehydrogenative coupling reaction [119]
Cu2I2(bttp4) Three-component coupling of azides, alkynes, and amines [120, 121]
Cu-MOF-SiF6and Cu-MOF-NO3 Oxidation of benzylic compounds [122]
CuPhos-Br and CuPhos-Cl and CuPhos-PF6 Ketalization reaction [123]
Fe3F(H2O)2O(btc)2
(MIL-100(Fe))
Friedel–Crafts benzylation Oxidation of hydrocarbons Ring-opening of epoxides Claisen Schmidt condensation Oxidation of thiophenol to diphenyldisulfide
Isomerization of a-pinene oxide
[124129
In(OH)(hippb) Acetalization of aldehyde [130]
In2(OH)3(bdc)1.5 Reduction of nitroaromatic; oxidation of sulfide [131]
Mg3(pdc1)(OH)3(H2O)2 Aldol condensation reactions [132]
Mg(pdc2)( H2O) Aldol condensation reactions [133]
Mn(porphyrin)@[In48(HImDC)96] Oxidation of alkane [134]
Ln(OH)(1,5-NDS) H2O Epoxidation of olefin [135]
(Mn(TpCPP)Mn1.5)(C3H7NO)5 C3H7NO Epoxidation of olefin; oxidation of alkane [136]
[Mn3((Mn4Cl)3BTT8(CH3OH)10)]2 Cyanosilylation of aldehyde; Mukaiyama-aldol [88]
Mn2(pvia)2(H2O)2 Alcohol oxidation [137]
(Na20(Ni8L412)(H2O)28)( H2O)13(CH3OH)2 Oxidation to CO2 [138]
Sc3(OH)( H2O)2O(btc)2
(MIL-100(Sc))
Intermolecular carbonyl ene reaction; Michael addition reaction; ketimine and aldimine formation [139]
Pd(2-pymo)2 Oxidation of alcohol; Suzuki–Miyaura coupling; hydrogenation of olefin [140142]
Tb[V6O13{(OCH2)3C(NH2CH2C6H4-4- CO2)}{(OCH2)3C-(NHCH2C6H4-4-CO2)}2]4- Oxidation of sulfide [143]
VIVO(bdc) (MIL-47(V)) Oxidation of hydrocarbons [144, 145]
Zn2(bpdc)2L5 Epoxidation of olefins [146]
Zn2(Py2(PhF5)2PorZn)(TCPB) Intermolecular transfer of acyl [147]
[Zn3(m3-O)(O2CR)6(H2O)3]n+ Transesterification [148]
Zn4O(bdc)3] and [Zn4O(ndc)3 Friedel–Crafts alkylation [149]
[(Zn4O)(bdc-NH2)3]Vsal0.4 Oxidation of olefin [150]
Zn2(bdc)(L-lac)(dmf) Oxidation of thioethers [151]
Zn3(chirbtb-1)2 Mukaiyama aldol reaction [152]
Zn3(chirbtb-2)2 Mukaiyama aldol reaction [152]
Zn(Meim)2(ZIF-8) Cycloaddition of CO2 and epoxides [153]
Zr6O4(OH)4(bdc)6
(UiO-66)
Aldol condensation reactions Cyclization of citronellal [154156]]

Table 3.

MOF structure used for catalytic reaction.

Ac = acetyl; bdc = 1,4-benzenedicarboxylate; BPB = 1,4-bis(4´-pyrazolyl)benzene; bpdb = 1,4-bis(3,5-dimethyl-1H-pyrazol-4-yl)benzene; bpdc = biphenyldicarboxylate; bpe = trans-1,2-bis(4-pyridyl)ethylene); bpy = 4,4´-bipyridine; btc = benzene-1,3,5-tricarboxylate; btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]; btb = 5 -(4-carboxyphenyl)-[1,1′:3′,1″-terphenyl]-4,4′-dicarboxylate; btt = 1,3,5-benzenetris(tetrazol-5-yl); bttp4 = benzene-1,3,5-triyl triisonicotinate; ChirBTB-1 = 5′-(4-carboxy-3-((S)-4-isopropyl-2-oxooxazolidin-3-yl)phenyl)-3-((S)-4-isopropyl-2-oxooxazolidin-3-yl)-3′-(3-isopropyl-5-oxooxazolidin-4-yl)-[1,1′:3′,1″-terphenyl]-4,4″-dicarboxylate;ChirBTB-2 = 3,3″-bis((S)-4-benzyl-2-oxooxazolidin-3-yl)-5′-(3-(3-benzyl-5-oxooxazolidin-4-yl)-4-carboxyphenyl)-[1,1′:3′,1″-terphenyl]-4,4″-icarboxylic; D-asp = D-aspartate; bdc = benzene-1,4-dicarboxylate; dhbdc = 2,5-dihydroxyisophthalic; ImDC = 4,5-imidazole dicarboxylate; ippb = 4,4′-(hexafluoroisopropyl-idene)bis(benzoate); L1 = (R)-6,6′-dichloro-2,2-dihydroxy-1,1′-binaphthyl-4,4′-bipyridine; L2 = (4-formylphenoxy)acetic acid; L3 = 2-[2-[[(2-aminoethyl)imino]methyl]phenoxy]acetic acid; L4 = 4,5-imidazoledicarboxylic acid; L5 = (R,R)-(-)-1,2-cyclohexanediamino-N,N-bis(3-tert-butyl-5-(4-pyridyl)salicylidene)MnIIICl; L-lac = L-lactic acid; mdip = 5,50 -methylenediisophthalic; meim = 2-methyl-1H-imidazole;nds = naphthalenedisulfonic acid; papa = (S)-3-hydroxy-2-((pyridin-4-ylmethyl)amino)propanoic;pbbm = 1,1′-(1,5-pentanediyl)bis(1H-benzimidazole); pdc-1 = pyrazole-3,5-dicarboxylate; pdc-2= pyridine-2,5-dicarboxylate; PhIM = phenyl imidazolate; ptdc = pyridine-2,3,5,6-tetracarboxylic; pymo = 2-hydroxypyrimidinolate; Py2(PhF5)2Por = 5,15-dipyridyl-1′,2′-bis(pentafluorophenyl)porphyrin; pvia= (E)-5-(2-(pyridin-4yl)vinyl)isophthalic; pvba = (E)-4-(2-(pyridin-4-yl)vinyl)benzoic; sal = salicylidene moiety; tcba = 4,′4″,′4″″-nitrilotris([1,10-biphenyl]-4-carboxylic); TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene; TpCPP = tetra-(p-carboxyphenyl)porphyrin; tpha = tris(4-((E)-1-(2-(pyridin-2-yl)hydrazono)ethyl)phenyl)amine.


Advertisement

4. Limitation of MOF structures

MOFs are excellent candidates for certain catalytic processes because: (1) they can be designed on a rational basis according to specific requirements; (2) their well-defined structure allows the assessment of structure–activity relationships; (3) the uniform catalytic sites; and (4) the intrinsic nature of their pores.

However, the synthesis of MOF requires a series of steps to allow an activation network free of solvent molecules and to expose the active sites, which can often require coordinating solvents that may be toxic, carcinogenic, and/or dangerous to the environment [59]. In some processes, the structure collapses, and activation prevents further use in catalysis.

Furthermore, when washed with solvent, they typically require energy, which increases the time synthesis process and drastically affects the efficiency. For example, with MOF-5 synthesized using solvothermal processes, a yield of 60% was achieved after 7 days [72].

The use of coordinating solvents during the synthesis of MOF such as dimethylformamide (DMF) or diethylformamide (DEF) may interfere with the availability of molecules to interact with the active sites. DMF and DEF decompose when heated at high temperatures for long periods and therefore cannot be reused [60]. The study of local defects is also crucial since catalytic processes can be favoured with the appearance of the same or conversely the process is catalysed not by excess thereof.

The MOF’s purity can be affected by the formation of other crystalline compounds or the presence of reagents in the network. However, characterization of MOFs’ purity and homogeneity can seldom be found in scientific papers about catalysis.

The thermal and chemical stability of MOFs is also a limitation for use in some catalytic process. The zirconium MOF reported by Hafizovic Cavka et al. [157], which has a thermal resistance above 500°C, resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure, whereas other MOFs have a lower thermal and chemical stability.

References

  1. 1. Janiak C, Vieth J K, MOFs, MILs and more: concepts, properties and applications for porous coordination netkorks (PCNs). New J. Chem. 2010;34:2366–2388. DOI: 10.1039/C0NJ00275E
  2. 2. Farrusseng D, Aguado S, Pinel C, Metal-organic frameworks: opportunities for catalysis. Angew. Chem. Int. Ed. 2009;48:7502–7513.DOI: 10.1002/anie.200806063
  3. 3. Lui J, Chen L, Cui H, Zhang J, Zhang L, Su C, Application of metal-organic frameworks in heterogeneous supramolecular catalysis. Chem. Soc. Rev. 2014;43:6011–6061. DOI: 10.1039/c4cs00094c
  4. 4. Gascon J, Corma A, Kaptejin F, Llabrés F X, Metal organic framework catalysis; Quo vadis? ACS Catal. 2014;4:361–378. DOI: 10.1021/cs400959k
  5. 5. Chen L, Xiang S C, Qian G D, Metal−organic frameworks with functional pores for recognition of small molecules. Acc. Chem. Res., 2010;43:1115–1124. DOI: 10.1021/ar100023y
  6. 6. Horcajada P, Chalati T, Serre C, Gillet B, Sebrie C, Baati T, Eubank J F, Heurtaux D, Clayette P, Kreuz C, Chang J S, Hwang Y K, Marsaud V, Bories P N, Cynober L, Gil S, Férey G, Couvreur P, Gref R, Porous metal–organic-framework nanoscalecarriers as a potential platform for drug delivery and imaging. Nature Mater. 2010;9:172–178. DOI: 10.1038/NMAT2608
  7. 7. Sun C Y, Qin C, Wang C G, Su Z M, Wang S, Wang X L, Yang G S, Shao K Z, Lan Y Q, Wang E B, Chiral nanoporous metal-organic frameworks with high porosity as materials for drug delivery. Advanced Mater. 2011;23:5629–5632. DOI: 0.1002/adma.201102538
  8. 8. Loera-Serna S, López L, Flores J, López-Simeon R, Beltrán H I, An alkaline one-pot metathesis reaction to give a [Cu3(BTC)2] MOF at r.t., with free Cu coordination sites and enhanced hydrogen uptake properties. RSC Advances. 2013;3:10962–10972. DOI: 10.1039/c3ra40726h
  9. 9. Rowsell L C, Spencer E C, Eckert J; Howard J A K, Yaghi O M, Gas adsorption sites in a large-pore metal-organic framework. Science, 2005;309:1350–1354. DOI: 10.1126/science.1113247
  10. 10. Llewellyn P L, Maurin G, Devic T, Loera-Serna S, Rosenbach N, Serre C, Bourrelly S, Horcajada P, Filinchuk Y, Férey G, Prediction of the conditions for breathing of metal organic framework materials using a combination of X-ray powder diffraction, microcalorimetry, and molecular simulation. J. Am. Chem. Soc. 2008;130:12808–12814. DOI: 10.1021/ja803899q
  11. 11. Llewellyn P L, Horcajada P, Maurin G, Devic T, Rosenbach N, Bourrelly S, Serre C, Loera-Serna S, Vincent D, Filinchuk Y, Férey G, Complex adsorption of short linear alkanes in flexible metal-organic-frameworks MIL-53(Fe). J. Am. Chem. Soc. 2009;131:13002–13008. DOI: 10.1021/ja902740r
  12. 12. Trung T K, Trens P, Tanchoux N, Bourrelly S, Llewellyn P L, Loera-Serna S, Serre C, Loiseau T, Fajula F, Férey G, Hydrocarbon adsorption in the flexible metal organic frameworks MIL-53(Al, Cr). J. Am. Chem. Soc. 2008;130:16926–16932.DOI: 10.1021/ja8039579
  13. 13. Li J R, Kuppler R J, Zhou H C, Selective gas adsorption and separation in metal-organic frameworks. Chem. Soc. Rev. 2009;38:1477–1504. DOI: 10.1039/B802426J
  14. 14. Hu Z, Deibert B J, Li J, Luminiscent metal-organic frameworks for chemical sensing and explosive detection. Chem Soc. Rev. 2014;43:5815–5840. DOI: 10.1039/c4cs00010b
  15. 15. Gandara F, Snejko N, Andres A D, Fernandez J R, Gomez-Sal J C, Gutierrez-Puebla E, Monge A, Stable organic radical stacked by in situ coordination to rare earth cations in MOF materials, RSC Advances, 2012;2:949–955. DOI: 10.1039/C1RA00447F
  16. 16. Yan D, Tang Y, Lin H, Wang D, Tunable two-color luminescence and host–guest energy transfer of fluorescent chromophores encapsulated in metal-organic frameworks. Scientific Reports. 2014;4:4337:1–7.DOI: 10.1038/srep04337
  17. 17. Zhu Q L, Xu Q, Metal-organic frameworks composites. Chem. Soc. Rev. 2014;43:5468–6176. DOI: 10.1039/c3cs60472a
  18. 18. AdeyemoA A, Adeoye I O, Bello O S, Metal organic frameworks as adsorbents for dye adsorption: overview, prospects and future challenges. Toxicological Env. Chem. 2012;94:1846–1863. DOI: 10.1080/02772248.2012.744023
  19. 19. Hu J, Dai W, Yan X, Comparison study on the adsorption performance of methylene blue and congo red on Cu-BTC. Desalination Water Treat. 2014:1–9. DOI: 10.1080/19443994.2014.988654
  20. 20. Yang W, Feng J, Song S, Zhang H, Microwave-assisted modular fabrication of nanoscale luminescent metal-organic framework for molecular sensing. Chem. Phys. Chem. 2012;13:2734–2738.DOI: 10.1002/cphc.201200265
  21. 21. Barea E, Montoro C, Navarro J A R, Toxic gas removal—metal–organic frameworks for the capture and degradation of toxic gases and vapours. Chem. Soc. Rev. 2014;43:5419–5430. DOI: 10.1039/c3cs60475f
  22. 22. Zhang C F, Qiu L G, Ke F, Zhu Y J, Yuan Y P, Xua G S, Jianga X, A novel magnetic recyclable photocatalyst based on a core–shell metal–organic framework Fe3O4@MIL-100(Fe) for the decolorization of methylene blue dye. J. Mater. Chem. A. 2013;1:14329–14334. DOI: 10.1039/c3ta13030d
  23. 23. Bourrelly S, Moulin B, Rivera A, Maurin G, Devautour-Vinot S, Serre C, Devic T, Horcajada P, Vimont A, Clet G, Daturi M, Lavalley J C, Denoyel R, Llewellyn P, Férey G, Loera-Serna S, Explanation of the adsorption of polar vapors in the highly flexible metal organic framework MIL-53(Cr). J. Am. Chem. Soc. 2010;132:9488–9498. DOI: 10.1021/ja1023282
  24. 24. Loera-Serna S, Oliver-Tolentino M A, López-Núñez M L, Santana-Cruz A, Guzmán-Vargas A, Cabrera-Sierra R, Beltrán H I, Flores J, Electrochemical behavior of [Cu3(BTC)2] metal–organic framework: The effect of the method of synthesis. J. Alloys Comp. 2012;540:113–120. DOI: 10.1016/j.jallcom.2012.06.030
  25. 25. Van de Voorde B, Bueken B, Denayer J, De Vos D, Adsorptive separation on metal–organic frameworks in the liquid phase. Chem. Soc. Rev. 2014;43:5766–5788. DOI: 10.1039/c4cs00006d
  26. 26. Falcaro P, Ricco R, Doherty C M, Liang K, Hill A J, Styles M J, MOF positioning technology and device fabrication. Chem. Soc. Rev. 2014;43:5513–5560. DOI: 10.1039/c4cs00089g
  27. 27. Bianchini C, Cole-Hamilton D J, van Leeuwe P W N M, Heterogenized homogeneous catalysts for fine chemicals production. Catalysis by Metal Complex 2010. Ed. Springer. DOI: 10.1007/978-90-481-3696-4
  28. 28. Luz I, Llabrés F X, Corma A, Bridging homogneous and heterogeneous catalysis with MOFs: “Clik” reactions with Cu-MOF catalysis. J. Cat. 2010;276:134–140. DOI: 10.1016/j.cat.2010.09.010
  29. 29. Yaghi O M, Li G, Li H, Selective binding and removal of guests in a microporous metal–organic framework. Nature, 1995;378:703–706. DOI: 10.1038/378703a0
  30. 30. Yaghi O M, Li H, Hydrothermal synthesis of a metal-organic framework containing large rectangular channels. J. Am. Chem. Soc., 1995;117:10401–10402. DOI: 10.1021/ja00146a033
  31. 31. Archer R D, Preparative inorganic reactions. Volume 1. J. Am. Chem. Soc. 1965;87:1151–1152. DOI: 10.1021/ja01083a051
  32. 32. Seo J, Sakamoto H, Matsuda R, Kitagawa S, Chemistry of porous coordination polymers having multimodal nanospace and their multimodal functionality J. Nanosci. Nanotechnol. 2010;10:3–20. DOI: http://dx.doi.org/10.1166/jnn.2010.1494
  33. 33. Blake A J, Champness N R, Hubberstey P, Li W S, Withersby M A, Schröder M, Inorganic crystal engineering using self-assembly of tailored building-blocks. Coord. Chem. Rev. 1999;183:117–138. DOI: 10.1016/S0010-8545(98)00173-8
  34. 34. Lu J, Paliwala T, Lim S C, Yu C, Niu T Y, Jacobson A J, Coordination polymers of Co(NCS)2 with pyrazine and 4,4′-bipyridine:  Syntheses and structures. Inorg. Chem. 1997;36:923–929.DOI: 10.1021/ic961158g
  35. 35. Zaworotko M J, Superstructural diversity in two dimensions: crystal engineering of laminated solids. Chem. Commun. 2001;1:1–9.DOI: 10.1039/B007127G
  36. 36. Kitagawa S, Kondo M, Functional micropore chemistry of crystalline metal complex-assembled compounds. Bull. Chem. Soc. Jpn. 1998;71:1739–1753. DOI: 10.1246/bcsj.71.1739
  37. 37. Moulton B, Zaworotko M J, From molecules to crystal engineering:  Supramolecular isomerism and polymorphism in network solids. Chem. Rev. 2001;101:1629–1658.DOI: 10.1021/cr9900432
  38. 38. Eddaoudi M, Moler D B, Li H L, Chen B L, Reineke T M, O'Keeffe M, Yaghi O M, Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks. Acc. Chem. Res. 2001;34:319–330. DOI: 10.1021/ar000034b
  39. 39. Burrows A D, Harrington R W, Mahon M F, Price C E, The influence of hydrogen bonding on the structure of zinc co-ordination polymers. J. Chem. Soc. Dalton Trans. 2000;21:3845–3854. DOI: 10.1039/B003210G
  40. 40. Choi H J, Lee T S, Suh M P, Selective binding of open frameworks assembled from nickel(II) macrocyclic complexes with organic and inorganic guests. J. Incl. Phenom. Macrocycl. Chem. 2001;41:155–162. DOI: 10.1023/A:1014436406651
  41. 41. Gutschke S O H, Price D J, Powell A K, Wood P T, Hydrothermal synthesis, structure, and magnetism of [Co2(OH){1,2,3-(O2C)3C6H3}(H2O)]⋅H2O and [Co2(OH){1,2,3-(O2C)3C6H3}]: magnetic Δ-chains with mixed cobalt geometries. Angew. Chem. Int. Edit. 2001;40:1920–1923. DOI: 10.1002/1521-3773(20010518)40:10<1920::AID-ANIE1920>3.0.CO;2-2
  42. 42. Prior T J, Rosseinsky M J, Crystal engineering of a 3-D coordination polymer from 2-D building blocks. Chem. Commun. 2001;5:495–496.DOI: 10.1039/B009455M
  43. 43. Yaghi O M, Li H L, Groy T L, Construction of porous solids from hydrogen-bonded metal complexes of 1,3,5-benzenetricarboxylic acid. J. Am. Chem. Soc. 1996;118:9096–9101. DOI: 10.1021/ja960746q
  44. 44. Lin X, Jia J H, Zhao X B, Thomas K M, Blake A J, Walker G S, Champness N R, Hubberstey P, Schröder M, High H2 adsorption by coordination‐framework materials. Angew. Chem.-Int. Edit. 2006;45:7358–7364. DOI: 10.1002/anie.200601991
  45. 45. Yang S, Lin X, Blake A J, Thomas K M, Hubberstey P, Champness N R, Schröder M, Enhancement of H2 adsorption in Li+-exchanged co-ordination framework materials. Chem. Commun. 2008;46:6108–6110. DOI: 10.1039/B814155J
  46. 46. Yan Y, Lin X, Yang S, Blake A J, Dailly A, Champness N R, Hubberstey P, Schröder M, Exceptionally high H2 storage by a metal–organic polyhedral framework. Chem. Commun. 2009;9:1025–1027. DOI: 10.1039/B900013E
  47. 47. Yan Y, Telepeni I, Yang S, Lin X, Kockelmann W, Dailly A, Blake A J, Lewis W, Walker G S, Allan D R, Barnett S A, Champness N R, Schröder M, Metal−organic polyhedral frameworks: high H2 adsorption capacities and neutron powder diffraction studies. J. Am. Chem. Soc. 2010;132:4092–4094. DOI: 10.1021/ja1001407
  48. 48. James S L, Metal-organic frameworks. Chem. Soc. Rev. 2003;32:276–288. DOI: 10.1039/B200393G
  49. 49. Cheng J Y, Dong Y B, Huang R Q, Smith M D, Synthesis and characterization of new coordination polymers generated from oxadiazole-containing ligands and IIB metal ions. Inorg. Chim. Acta, 2005;358:891-898. DOI: 10.1016/j.ica.2004.10.034
  50. 50. Uemura K, Kitagawa S, Kondo M, Fukui K, Kitaura R, Chang H C, Mizutani T, Novel flexible frameworks of porous cobalt(II) coordination polymers that show selective guest adsorption based on the switching of hydrogen-bond pairs of amide groups. Chem. Eur. J. 2002;8:3586–3600. DOI: 10.1002/1521-3765(20020816)8:16<3586::AID-CHEM3586>3.0.CO;2-K
  51. 51. Chen Z F, Xiong R G, Abrahams B F, You X Z, Che C M, An unprecedented six-fold anion-type chiral diamondoid-like eight-coordinate Cd(II) coordination polymer with a second-order nonlinear optical effect. J. Chem. Soc. Dalton Trans. 2001;17:2453–2454. DOI: 10.1039/B105130J
  52. 52. Kim J, Chen B, Reineke T M, Li H, Eddaoudi M, Moler D B, O’Keeffe M, Yaghi O M, Assembly of metal−organic frameworks from large organic and inorganic secondary building units:  new examples and simplifying principles for complex structure. J. Am. Chem. Soc. 2001;123:8239–8247. DOI: 10.1021/ja010825o
  53. 53. Farha O K, Malliakas C D, Kanatzidis M G, Hupp J T, Control over catenation in metal−organic frameworks via rational design of the organic building Block.J. Am. Chem. Soc. 2010;132:950–952. DOI: 10.1021/ja909519e
  54. 54. Sun D, Ma S, Ke Y, Collins D J, Zhou H C, An interweaving MOF with high hydrogen uptake. J. Am. Chem. Soc. 2006;128:3896–3897. DOI: 10.1021/ja058777l
  55. 55. Li J R, Yakovenko A A, Lu W, Timmons D J, Zhuang W, Yuan D, Zhou H C, Ligand bridging-angle-driven assembly of molecular architectures based on quadruply bonded Mo−Mo dimers. J. Am. Chem. Soc. 2010;132:17599–17610. DOI: 10.1021/ja1080794
  56. 56. Hartmann M, Kunz S, Himsl D, Tangermann O, Adsorptive separation of isobutene and isobutane on Cu3(BTC)2.Langmuir. 2008;24:8634–8642. DOI: 10.1021/la8008656
  57. 57. Guo H, Zhu G, Hewitt I J, Qiu S, “Twin copper source” growth of metal−organic framework membrane: Cu3(BTC)2 with high permeability and selectivity for recycling H2. J. Am. Chem. Soc. 2009;131:1646–1647. DOI: 10.1021/ja8074874
  58. 58. Son W J, Kim J, Kim J, Ahn S, Sonochemical synthesis of MOF-5. Chem. Commun. 2008; 6336–6338. DOI: 10.1039/B814740J
  59. 59. Pohanish R P, Sittig's (2008) Handbook of Toxic and Hazardous Chemicals and Carcinogens, 5th ed., William Andrew Publishing. ISBN: 978-1-4377-7869-4
  60. 60. Muzart J, N,N-dimethylformamide: much more than a solvent. Tetrahedron. 2009;65:8313–8323. DOI: 10.1016/j.tet.2009.06.091
  61. 61. Tateyama Y, Ohki Y, Suzuki Y, OuchiA, The crystal and molecular structure of diaquadihydroxotetrakis(m-nitrobenzenesulfonato)discandium(III) in a linear polymeric form, [Sc2(OH)2(O2NC6H4SO3)4(H2O)2]n. Bull. Chem. Soc. Jap. 1998;61:2214–2216. DOI: 10.1246/bcsj.61.2214
  62. 62. Anastas P T, Warner J C, Green Chemistry: Theory and Practice, Oxford University Press, 1998. ISBN: 9780198506980
  63. 63. Fernández-Bertran J F, Mechanochemistry: an overview. Pure Appl. Chem. 1999;71:581–586. DOI: 10.1351/pac199971040581
  64. 64. Belcher W J, Longstaff C A, Neckenig M R, Steed J W, Channel-containing 1D coordination polymers based on a linear dimetallic spacer. Chem. Comm. 2002;15:1602–1603. DOI: 10.1039/B202652J
  65. 65. Pichon A, James S L, Conditions—insights and trends. Cryst. Chem. Comm. 2008;10:1839–1847. DOI: 10.1039/B810857A
  66. 66. Mueller U, Puetter H, Hesse M, Wessel H, Method for electrochemical production of a crystalline porous metal organic skeleton material. Patent; 2005. WO 2005/049892 A1.
  67. 67. Mueller U, Schubert M, Teich F, Puetter H, Shierle-Arndt K, Pastré J, Metal–organic frameworks—prospective industrial applications. J. Mater. Chem. 2006;16:626–636. DOI: 10.1039/B511962F
  68. 68. Richter I, Schubert M, Muller U, Porous metal organic framework based on pyrroles and pyridinones. Patent;2007. WO 2007/131955 A1.
  69. 69. Hill J, Marchant R, Applied. Modelling microwave heating. Mathematical Modern. 1996;20:3–15. DOI: 10.1016/0307-904X(95)00107-U
  70. 70. Larhed M, Moberg C, HallbergA, Microwave-accelerated homogeneous catalysis in organic chemistry. Acc. Chem. Res. 2002;35:717–727. DOI: 10.1021/ar010074v
  71. 71. Jhung S H, Yoon J W, Hwang J S, Cheetham A K, Chang J S, Facile synthesis of nanoporous nickel phosphates without organic templates under microwave irradiation. Chem. Mater. 2005;17:4455–4460. DOI: 10.1021/cm047708n
  72. 72. Choi J Y, Kim J, Jhung S H, Kim H K, Chang J S, Chae H K, Microwave synthesis of a porous metal-organic framework, zinc terephthalate MOF-5. Bull. Korean Chem. Soc. 2006;27:1523–1524. DOI: 10.5012/bkcs.2006.27.10.1523
  73. 73. Klinowski J, Almeida Paz F A, Silva P Rocha J, Microwave-assisted synthesis of metal–organic frameworks. Dalton Trans. 2011;40:321–330. DOI: 10.1039/C0DT00708K
  74. 74. Suslick K S, Hammerton D A, Cline R E, Sonochemical hot spot. J. Am. Chem. Soc. 1986;108:5641–5642. DOI: 10.1021/ja00278a055
  75. 75. Meek S T, Greathouse J A, Allendorf M D, Metal-organic frameworks: A rapidly growing class of versatile nanoporous materials. Adv. Mater. 2011;23:249–267.DOI: 10.1002/adma.201002854
  76. 76. Ibarra I A, Bayliss P A, Pérez E, Yang S, Blake A J, Nowell H, Allan D R, Poliakoff M, Schröder M, Near-critical water, a cleaner solvent for the synthesis of a metal–organic framework. Green Chem. 2012;14:117–122. DOI: 10.1039/C1GC15726D
  77. 77. Savage P E, Organic chemical reactions in supercritical water. Chem. Rev. 1999;99:603–621. DOI: 10.1021/cr9700989
  78. 78. Fraga-Dubreuil J, Poliakoff M, Organic reactions in high-temperature and supercritical water. Pure Appl. Chem. 2006;78:1971–1982. DOI: 10.1351/pac200678111971
  79. 79. Brunner G, Near and supercritical water. Part II: Oxidative processes. J. Supercrit. Fluids. 2009;47:382–390. DOI: 10.1016/j.supflu.2008.09.001
  80. 80. Aymonier C, Loppinet-Serani A, Reveron H, Garrabos Y, Cansell F, Review of supercritical fluids in inorganic materials science. J. Supercrit. Fluids, 2006;38:242–251. DOI: 10.1016/j.supflu.2006.03.019
  81. 81. Cabañas A, Poliakoff M, The continuous hydrothermal synthesis of nano-particulate ferrites in near critical and supercritical water. J. Mater. Chem. 2001;11:1408–1416. DOI: 10.1039/B009428P
  82. 82. Weingartner H, Franck E U, Supercritical water as a solvent. Angew. Chem. Int. Ed. 2005;44:2672–2692. DOI: 10.1002/anie.200462468
  83. 83. Ingleson M J, Perez Barrio J, Bacsa J, Dickinson C, Park H, Rosseinsky M J, Generation of a solid Brønsted acid site in a chiral framework. Chem. Commun. 2008;11:1287–1289. DOI: 10.1039/b718443c
  84. 84. Lee J Y, Farha O K, Roberts J, Scheidt K A, Nguyen S T, Hupp J T, Metal–organic framework materials as catalysts. Chem. Soc. Rev. 2009;38:1450–1459. DOI: 10.1039/b807080f
  85. 85. Nicola C D, Karabach Y Y, Kirollov A M, Monar M, Pandolfo L, Pettinari C, Pombeiro A J L, Supramolecular assemblies of trinuclear triangular copper(II) secondary building units through hydrogen bonds. Generation of different metal−organic frameworks, valuable catalysts for peroxidative oxidation of alkanes. Inorg. Chem. 2007;46:221–230. DOI: 10.1021/ic061595n
  86. 86. Alaerts L, Seguin E, Poelman H, Thibault-Starzyk F, Jacobs P A, De Vos D E, Probing the Lewis acidity and catalytic activity of the metal–organic framework [Cu3(BTC)2] (BTC = benzene-1,3,5-tricarboxylate). Chem. Eur. J. 2006;12:7353–7363. DOI: 10.1002/chem.200600220
  87. 87. Schlichte K, Kratzke T, Kaskel S, Improved synthesis, thermal stability and catalytic properties of the metal-organic framework compound Cu3(BTC)2 Micro. Meso. Mater. 2004;73:81–88. DOI: 10.1016/j.micromeso.2003.12.027
  88. 88. Horike S, Dinca M, Tamaki K, Long J R, Size-selective Lewis acid catalysis in a microporous metal-organic framework with exposed Mn2+ coordination sites. J. Am. Chem. Soc. 2008;130:5854–5855. DOI: 0.1021/ja800669j
  89. 89. Dhakshinamoorthy A, Alvaro M, García H, Metal-organic frameworks (MOFs) as heterogeneous catalysts for the chemoselective reduction of carbon-carbon multiple bonds with hydrazine. Adv. Synth. Catal. 2009;351:2271–2276. DOI: 10.1002/adsc.200900362
  90. 90. Jing X, He C, Dong D, Yang L, Duan C, Angew. Homochiral crystallization of metal–organic silver frameworks: Asymmetric [3+2] cycloaddition of an azomethineylide. Chem., Int. Ed. 2012;51:10127–10131. DOI: 10.1002/anie.201204530
  91. 91. Feyand M, Mugnaioli E, Vermoortele F, Bueken B, Dieterich J M, Reimer T, Kolb U, de Vos D, Stock N, Automated diffraction tomography for the structure elucidation of twinned, sub-micrometer crystals of a highly porous, catalytically active bismuth metal–organic framework. Angew. Chem., Int. Ed. 2012;51:10373–10376. DOI: 10.1002/anie.201204963
  92. 92. Dang D, Wu P, He C, Xie Z, Duan C, Homochiral metal−organic frameworks for heterogeneous asymmetric catalysis, J. Am. Chem. Soc. 2010;132:14321–14323. DOI: 10.1021/ja101208s
  93. 93. Hasegawa S, Horike S, Matsuda R, Furukawa S, Mochizuki K, Kinoshita Y, Kitagawa S, Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand:  Selective sorption and catalysis. J. Am. Chem. Soc. 2007;129:2607–2614. DOI: 10.1021/ja067374y
  94. 94. Fujita M, Kwon Y J, Washizu S, Ogura K, Preparation, clathration ability, and catalysis of a two-dimensional square network material composed of cadmium(II) and 4,4′-bipyridine. J. Am. Chem. Soc. 1994;116:1151–1152. DOI: 10.1021/ja00082a055
  95. 95. Wu C D, Hu A, Zhang L, Lin W, A homochiral porous metal−organic framework for highly enantioselective heterogeneous asymmetric catalysis. J. Am. Chem. Soc. 2005;127:8940–8941. DOI: 10.1021/ja052431t
  96. 96. Tonigold M, Lu Y, Mavrandonakis A, Puls A, Staudt R, Mollmer J, Sauer J, Volkmer D, Pyrazolate-based cobalt(II)-containing metal–organic frameworks in heterogeneous catalytic oxidation reactions: elucidating the role of entatic states for biomimetic oxidation processes. Chem. Eur. J. 2011;17:8671–8695. DOI: 10.1002/chem.201003173
  97. 97. Cho H-Y, Yang D A, Kim J, Jeong S Y, Ahn W S, CO2 adsorption and catalytic application of Co-MOF-74 synthesized by microwave heating. Catal. Today. 2012;185:35–40. DOI: 10.1016/j.cattod.2011.08.019
  98. 98. Biswas S, Maes M, Dhakshinamoorthy A, Feyand M, De Vos D E, Garcia H, Stock N, Fuel purification, Lewis acid and aerobic oxidation catalysis performed by a microporous Co-BTT (BTT3− = 1,3,5-benzenetristetrazolate) framework having coordinatively unsaturated sites. J. Mater. Chem. 2012;22:10200–10209. DOI: 10.1039/C2JM15592C
  99. 99. Henschel A, Gedrich K, Kraehnert R, Kaskel S, Catalytic properties of MIL-101. Chem. Commun. 2008;4192–4194. DOI: 10.1039/B718371B
  100. 100. Kim J, Bhattacharjee S, Jeong K E, Jeong S Y, Ahn W S, Selective oxidation of tetralin over a chromium terephthalate metal organic framework, MIL-101. Chem. Commun. 2009;3904–3906. DOI: 10.1039/B902699A
  101. 101. Hwang Y K, Hong D Y, Chang J S, Seo H, Yoon M, Kim J, Jhung S H, Serre C, F érey G, Selective sulfoxidation of aryl sulfides by coordinatively unsaturated metal centers in chromium carboxylate MIL-101. Appl. Catal., A, 2009;358:249–253. DOI: 10.1016/j.apcata.2009.02.018
  102. 102. Maksimchuk N V, Kovalenko K A, Fedin V P, Kholdeeva O A, Heterogeneous selective oxidation of alkenes to α,β-unsaturated ketones over coordination polymer MIL-101. Adv. Synth. Catal. 2010;352:2943–2948. DOI: 10.1002/adsc.201000516
  103. 103. Zalomaeva O V, Chibiryaev A M, Kovalenko K A, Kholdeeva O A, Balzhinimaev B S, Fedin V P, Cyclic carbonates synthesis from epoxides and CO2 over metal–organic framework Cr-MIL-101. J. Catal. 2013;298:179–185. DOI: 10.1016/j.jcat.2012.11.029
  104. 104. Maksimchuk N V, Timofeeva M N, Melgunov M S, Shmakov A N, Chesalov A Y, Dybtsev D N, Fedin V P, Kholdeeva O A, Heterogeneous selective oxidation catalysts based on coordination polymer MIL-101 and transition metal-substituted polyoxometalates. J. Catal. 2008;257:315–323. DOI: 10.1016/j.jcat.2008.05.014
  105. 105. Llabrés i Xamena F X, Casanova O, Galiasso Tailleur R, Garcia H, Corma A, Metal organic frameworks (MOFs) as catalysts: A combination of Cu2+ and Co2+ MOFs as an efficient catalyst for tetralin oxidation. J. Catal. 2008;255:220–227. DOI: 10.1016/j.jcat.2008.02.011
  106. 106. Jiang D, Mallat T, Krumeich F, Baiker A, Copper-based metal-organic framework for the facile ring-opening of epoxides. J. Catal. 2008;257:390–395. DOI: 10.1016/j.jcat.2008.05.021
  107. 107. Pramanik A, Abbina S, Das G, Molecular, supramolecular structure and catalytic activity of transition metal complexes of phenoxy acetic acid derivatives. Polyhedron, 2007;26:5225–5234. DOI: 10.1016/j.poly.2007.07.033
  108. 108. Xiao B, Hou H, Fan Y, Catalytic applications of CuII-containing MOFs based on N-heterocyclic ligand in the oxidative coupling of 2,6-dimethylphenol. J. Organomet. Chem. 2007;692:2014–2020. DOI: 10.1016/j.jorganchem.2007.01.010
  109. 109. Chui S S Y, Lo S M F, Charmant J P H, Orpen A G, Williams I D, A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]N Science. 1999;283:1148–1150. DOI: 10.1126/science.283.5405.1148
  110. 110. Corma A, Iglesias M, Llabrés i Xamena F X, Sanchez F, Cu and Au metal–organic frameworks bridge the gap between homogeneous and heterogeneous catalysts for alkene cyclopropanation reactions. Chem. Eur. J. 2010;16:9789–9795. DOI: 10.1002/chem.201000278
  111. 111. Pérez-Mayoral E, Cejka J, [Cu3(BTC)2]: A metal–organic framework catalyst for the Friedländer reaction. Chem. Cat. Chem. 2011;3:157–159. DOI: 10.1002/cctc.201000201
  112. 112. Pérez-Mayoral E, Musilova Z, Gil B, Marszalek B, Polozij M, Nachtigall P, Cejka J, Synthesis of quinolines via Friedländer reaction catalyzed by CuBTC metal–organic-framework. Dalton Trans. 2012;41:4036–4044. DOI: 10.1039/C2DT11978A
  113. 113. Opanasenko M, Shamzhy M, Cejka J, Solid acid catalysts for coumarin synthesis by the Pechmann reaction: MOFs versus zeolites. Chem. Cat. Chem. 2013;5:1024–1031. DOI: 10.1002/cctc.201200232
  114. 114. Wang M, Xie M H, Wu C D, Wang Y G, From one to three: a serine derivate manipulated homochiral metal-organic framework. Chem. Commun. 2009, 2396–2398. DOI: 10.1039/B823323C
  115. 115. Shi L X, Wu, C D, A nanoporous metal–organic framework with accessible Cu2+ sites for the catalytic Henry reaction. Chem. Commun. 2011;47:2928–2930. DOI: 10.1039/C0CC05074A
  116. 116. Luz I, Llabrés i Xamena F X, Corma A, Bridging homogeneous and heterogeneous catalysis with MOFs: “Click” reactions with Cu-MOF catalysts. J. Catal. 2010;276:134–140. DOI: 10.1016/j.jcat.2010.09.010
  117. 117. Luz I, Llabrés i Xamena F X, Corma A, Bridging homogeneous and heterogeneous catalysis with MOFs: Cu-MOFs as solid catalysts for three-component coupling and cyclization reactions for the synthesis of propargylamines, indoles and imidazopyridines. J. Catal. 2012;285:285–291. DOI: 10.1016/j.jcat.2011.10.001
  118. 118. Shi D, Ren Y, Jiang H, Cai B, Lu J, Synthesis, structures, and properties of two three-dimensional metal–organic frameworks, based on concurrent ligand extension. Inorg. Chem. 2012;51:6498–6506. DOI: 10.1021/ic202624e
  119. 119. Phan N T S, Vu P H L, Nguyen T T, Expanding applications of copper-based metal–organic frameworks in catalysis: oxidative C–O coupling by direct C–H activation of ethers over Cu2(BPDC)2(BPY) as an efficient heterogeneous catalyst. J. Catal.2013;306:38–46. DOI: 10.1016/j.jcat.2013.06.006
  120. 120. Yang T, Cui H, Zhang C, Zhang L, Su C Y, Porous metal–organic framework catalyzing the three-component coupling of sulfonyl azide, alkyne, and amine. Inorg. Chem. 2013;52:9053–9059. DOI: 10.1021/ic4012229
  121. 121. Yang T, Cui H, Zhang C, Zhang L, Su C Y, From homogeneous to heterogeneous catalysis of the three-component coupling of oxysulfonyl azides, alkynes, and amines. Chem. Cat. Chem. 2013;5:3131–3138. DOI: 10.1002/cctc.201300241
  122. 122. Wang S, Li L, Zhang J, Yuan X, Su C Y, Anion-tuned sorption and catalytic properties of a soft metal–organic solid with polycatenated frameworks. J. Mater. Chem. 2011;21:7098–7104. DOI: 10.1039/C1JM10394F
  123. 123. Tan X, Li L, Zhang J, Han X, Jiang L, Li F, Su C Y, Three-dimensional phosphine metal–organic frameworks assembled from Cu(I) and pyridyl diphosphine. Chem. Mater. 2012;24:480–485. DOI: 10.1021/cm202608f
  124. 124. Horcajada P, Surble S, Serre C, Hong D Y, Seo Y K, Chang J S, Greneche J M, Margiolaki I, Férey G, Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores. Chem. Commun. 2007;2820–2822. DOI: 10.1039/B704325B
  125. 125. Dhakshinamoorthy A, Alvaro M, Garcia H, Metal organic frameworks as efficient heterogeneous catalysts for the oxidation of benzylic compounds with t-butylhydroperoxide. J. Catal. 2009;267:1–4. DOI: 10.1016/j.jcat.2009.08.001
  126. 126. Dhakshinamoorthy, A, Alvaro M, Garcia H, Claisen–Schmidt condensation catalyzed by metal-organic frameworks. Adv. Synth. Catal. 2010;352:711–717. DOI: 10.1002/adsc.200900747
  127. 127. Dhakshinamoorthy A, Alvaro M, Garcia H, Aerobic oxidation of thiols to disulfides using iron metal–organic frameworks as solid redox catalysts. Chem. Commun. 2010;46:6476–6478. DOI: 10.1039/C0CC02210A
  128. 128. Dhakshinamoorthy A, Alvaro M, Garcia H, Metal–organic frameworks as efficient heterogeneous catalysts for the regioselective ring opening of epoxides. Chem. – Eur. J. 2010;16:8530–8536. DOI: 10.1002/chem.201000588
  129. 129. Dhakshinamoorthy A, Alvaro M, Chevreau H, Horcajada P, Devic T, Serre C, Garcia H, Iron(III) metal–organic frameworks as solid Lewis acids for the isomerization of α-pinene oxide. Catal. Sci. Technol. 2012;2:324–330. DOI: 10.1039/C2CY00376G
  130. 130. Gándara F, Gomez-Lor B, Gutiérrez-Puebla E, Iglesias M, Monge M A, Proserpio D M, Snejko N, An indium layered MOF as recyclable Lewis acid catalyst. Chem. Mater. 2008;20:72–76. DOI: 10.1021/cm071079a
  131. 131. Gomez-Lor B, Gutierrez-Puebla E, Iglesias M, Monge M A, Ruiz-Valero C, Snejko N, In2(OH)3(BDC)1.5 (BDC = 1,4-Benzendicarboxylate):  an In(III) supramolecular 3D framework with catalytic activity. Inorg. Chem. 2002;41:2429–2432. DOI: 10.1021/ic0111482
  132. 132. Sen R, Saha D, Koner S, Controlled construction of metal-organic frameworks: hydrothermal synthesis, X-ray structure, and heterogeneous catalytic study. Chem. Eur. J. 2012;18:5979–5986. DOI: 10.1002/chem.201102953
  133. 133. Saha D, Sen R, Maity T, Koner S, Porous magnesium carboxylate framework: synthesis, X-ray crystal structure, gas adsorption property and heterogeneous catalytic aldol condensation reaction. Dalton Trans. 2012;41:7399–7408. DOI: 10.1039/c2dt00057a
  134. 134. Alkordi M H, Liu Y, Larsen R W, Eubank J F, Eddaoudi M, Zeolite-like metal-organic frameworks (ZMOFs) as platforms for applications: On metalloporphyrin-based catalysts. J. Am. Chem. Soc. 2008;130:12639–12641. DOI: 10.1021/ja804703w
  135. 135. Gándara F, García-Cortés A, Cascales C, Gómez-Lor B, Gutiérrez-Puebla E, Iglesias M, Monge A, Snejko N, Rare earth arenedisulfonate metal−organic frameworks:  An approach toward polyhedral diversity and variety of functional compounds. Inorg. Chem. 2007;46:3475–3484. DOI: 10.1021/ic0617689
  136. 136. Suslick K S, Bhyrappa P, Chou J H, Kosal M E, Nakagaki S, Smithenry D W, Wilson S R, Microporous porphyrin solids. Acc. Chem. Res. 2005;38:283–291. DOI: 10.1021/ar040173j
  137. 137. Xie M H, Yang X L, Wu C D, From 2D to 3D: A single-crystal-to-single-crystal photochemical framework transformation and phenylmethanol oxidation catalytic activity. Chem. Eur. J. 2011;17:11424–11427. DOI: 10.1002/chem.201101321
  138. 138. Zou R Q, Sakurai H Xu Q, Preparation, adsorption properties, and catalytic activity of 3D porous metal–organic frameworks composed of cubic building blocks and alkali-metal ions. Angew. Chem., Int. Ed. 2006;45:2542–2546. DOI: 10.1002/anie.200503923
  139. 139. Mitchell L, Gonzalez-Santiago B, Mowat J P S, Gunn M E, Williamson P, Acerbi N, Clarke M L, Wright P A, Remarkable Lewis acid catalytic performance of the scandium trimesate metal organic framework MIL-100(Sc) for C–C and C[double bond, length as m-dash]N bond-forming reactions. Catal. Sci. Technol. 2013;3:606–617. DOI: 10.1039/C2CY20577G
  140. 140. Llabrés i Xamena F, Abad A, Corma A, Garcia H, MOFs as catalysts: activity, reusability and shape-selectivity of a Pd-containing MOF. J. Catal. 2007;250:294–298. DOI: 10.1016/j.jcat.2007.06.004
  141. 141. Opelt S, Krug V, Sonntag J, Hunger M Klemm E, Investigations on stability and reusability of [Pd(2-pymo)2]n as hydrogenation catalyst. Micropor. Mesopor. Mater. 2012;147:327–333. DOI: 10.1016/j.micromeso.2011.07.003
  142. 142. Schuster S, Klemm E, Bauer M, Chem. Eur. J. 2012;18:15831–15837.
  143. 143. Han J W, Hill C L, A coordination network that catalyzes O2-based oxidations. J. Am. Chem. Soc. 2007;129:15094–15095. DOI: 10.1021/ja069319v
  144. 144. Leus K, Muylaert I, Vandichel M, Marin G B, Waroquier M, Van Speybroeck V, Van der Voort P, The remarkable catalytic activity of the saturated metal organic framework V-MIL-47 in the cyclohexene oxidation. Chem. Commun. 2010;46:5085–5087. DOI: 10.1039/C0CC01506G
  145. 145. Leus K, Vandichel M, Liu Y Y, Muylaert I, Musschoot J, Pyl S, Vrielinck H, Callens F, Marin G Detavernier B C, Wiper P V, Khimyak Y Z, Waroquier M, Van Speybroeck V, Van Der Voort P, The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene. J. Catal. 2012;285:196–207. DOI: 10.1016/j.jcat.2011.09.014
  146. 146. Cho S H, Ma B, Nguyen S T, Hupp J T Albrecht-Schmitt T E, A metal–organic framework material that functions as an enantioselective catalyst for olefin epoxidation. Chem. Commun. 2006;2563–2565. DOI: 10.1039/B600408C
  147. 147. Shultz A M, Farha O K, Hupp J T, Nguyen S T, A catalytically active, permanently microporous MOF with metalloporphyrin struts. J. Am. Chem. Soc. 2009, 131, DOI: 10.1021/ja900203f.
  148. 148. Seo J S, Whang D, Lee H, Jun S I, Oh J, Jeon Y J, Kim K, A homochiral metal–organic porous material for enantioselective separation and catalysis. Nature. 2000;404:982–986. DOI: 10.1038/35010088
  149. 149. Ravon U, Domine M E, Gaudillere C, Desmartin-Chomel A, Farrusseng D, MOFs as acid catalysts with shape selectivity properties. New J. Chem. 2008;32:937–940. DOI: 10.1039/B803953B
  150. 150. Ingleson M J, Barrio J P, Guilbaud J B, Khimyak Y Z, Rosseinsky M J, Framework functionalisation triggers metal complex binding. Chem. Commun. 2008;2680–2682. DOI: 10.1039/B718367D
  151. 151. Dybtsev D N, Nuzhdin A L, Chun H, Bryliakov K P, Talsi E P, Fedin V P, Kim K, A homochiral metal–organic material with permanent porosity, enantioselective sorption properties, and catalytic activity. Angew. Chem. Int. Ed. 2006;45:916–920. DOI: 10.1002/anie.200503023
  152. 152. Gedrich K, Heitbaum M, Notzon A, Senkovska I, Frohlich R, Getzschmann J, Mueller U, Glorius F, Kaskel S, A family of chiral metal–organic frameworks. Chem. Eur. J. 2011;17:2099–2106. DOI: 10.1002/chem.201002568
  153. 153. Miralda C M, Macias E E, Zhu M, Ratnasamy P, Carreon M A, Zeolitic imidazole framework-8 catalysts in the conversion of CO2 to chloropropene carbonate. ACS Catal. 2012;2:180–183. DOI: 10.1021/cs200638h
  154. 154. Vermoortele F, Ameloot R, Vimont A, Serre C, De Vos D, An amino-modified Zr-terephthalate metal–organic framework as an acid–base catalyst for cross-aldol condensation. Chem. Commun. 2011;47:1521–1523. DOI: 10.1039/C0CC03038D
  155. 155. Vermoortele F, Vandichel M, Van de Voorde B, Ameloot R, Waroquier M, Van Speybroeck V, De Vos D E, Electronic effects of linker substitution on Lewis acid catalysis with metal–organic frameworks. Angew. Chem. Int. Ed. 2012;51:4887–4890. DOI: 10.1002/anie.201108565
  156. 156. Vermoortele F, Bueken B, Le Bars G, Van de Voorde B, Vandichel M, Houthoofd K, Vimont A, Daturi M, Waroquier M, Van Speybroeck V, Kirschhock C, De Vos D E, Synthesis modulation as a tool to increase the catalytic activity of metal–organic frameworks: the unique case of UiO-66(Zr). J. Am. Chem. Soc. 2013;135:11465–11468. DOI: 10.1021/ja405078u
  157. 157. Hafizovic Cavka J, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S, Petter Lillerud K, A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 2008;13850–13851. DOI: 10.1021/ja8057953

Written By

Sandra Loera-Serna and Elba Ortiz

Submitted: 16 May 2015 Reviewed: 28 October 2015 Published: 03 February 2016