10.1007/s40089-018-0255-1

Synthesis and catalytic applications of metal–organic frameworks: a review on recent literature

  1. Department of Chemistry, Mar Athanasius College, Kothamangalam, 686666, IN
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Published in Issue 2018-12-05

How to Cite

Remya, V. R., & Kurian, M. (2018). Synthesis and catalytic applications of metal–organic frameworks: a review on recent literature. International Nano Letters, 9(1 (March 2019). https://doi.org/10.1007/s40089-018-0255-1

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Abstract

Abstract Metal–organic frameworks (MOFs) are an emerging class of porous materials created by the assembly of inorganic connectors and organic linkers. They have potential applications in fields such as gas storage as well as separation, sensing, catalysis, and drug delivery due to its properties such as flexibility, porosity, high surface area and functionality. Among the various synthetic approaches for the preparation of MOFs, solvothermal and microwave-assisted methods are of particular importance, and hence have been used frequently. They have been recently used as heterogeneous catalysts in Friedel–Crafts reactions, condensations reactions, oxidations, coupling reactions, etc. However, owing to the low thermal stability and moisture sensitivity, their catalytic applications are limited. This short review covers recent developments in the synthetic methods employed for the preparation of MOFs as well as their catalytic applications.

Keywords

  • Metal–organic framework,
  • Synthesis techniques,
  • Stability,
  • Heterogeneous catalyst

References

  1. Dey et al. (2014) Crystalline metal-organic frameworks (MOFs): synthesis, structure and functions (pp. 3-10)
  2. Lee et al. (2013) Synthesis of metal organic frameworks: a mini review (pp. 1667-1680) https://doi.org/10.1007/s11814-013-0140-6
  3. Czaja et al. (2009) Industrial applications of metal-organic frameworks (pp. 1284-1293) https://doi.org/10.1039/b804680h
  4. Ferey (2009) Some suggested perspectives for multifunctional hybrid porous solids (pp. 4400-4415) https://doi.org/10.1039/b817360p
  5. Kuppler et al. (2009) Potential applications of metal-organic frameworks (pp. 3042-3066) https://doi.org/10.1016/j.ccr.2009.05.019
  6. Kitagawa et al. (2004) Functional porous coordination polymers (pp. 2334-2375) https://doi.org/10.1002/anie.200300610
  7. Isaeva and Kustov (2010) The application of metal-organic frameworks in catalysis (Review) (pp. 167-180) https://doi.org/10.1134/S0965544110030011
  8. Farrusseng et al. (2009) Metal-organic frameworks: opportunities for catalysis (pp. 7502-7513) https://doi.org/10.1002/anie.200806063
  9. Murinzi et al. (2017) Synthesis and characterization of a cobalt-2,6-pyridinedicarboxylate MOF with potential application in electrochemical sensing (pp. 188-196) https://doi.org/10.1016/j.poly.2017.08.030
  10. Wang et al. (2009) Metal–organic frameworks based on the pyridine-2,3-dicarboxylate and a flexible bispyridyl ligand: syntheses, structures, and photoluminescence (pp. 292-297) https://doi.org/10.1039/B809557D
  11. Pan et al. (2018) A new three-dimensional zinc-based metal-organic framework as a fluorescent sensor for detection of cadmium ion and nitrobenzene (pp. 418-426) https://doi.org/10.1016/j.jcis.2017.11.034
  12. Li et al. (2017) A porous Cu(II) metal-organic framework: synthesis, crystal structure and gas adsorption properties (pp. 20-22) https://doi.org/10.1016/j.molstruc.2017.04.068
  13. Du and Zou (2016) A novel microporous zinc(II) metal-organic framework with highly selectivity adsorption of CO2 over CH4 (pp. 20-23) https://doi.org/10.1016/j.inoche.2016.04.015
  14. Tzitzios et al. (2017) Solvothermal synthesis, nanostructural characterization and gas cryo-adsorption studies in a metal–organic framework (IRMOF-1) material (pp. 23899-23907) https://doi.org/10.1016/j.ijhydene.2017.04.059
  15. Li et al. (2017) Synthesis, characterization, crystal structure of magnesium compound based 3, 3′, 5, 5′-azobenzentetracarboxylic acid and application as high-performance heterogeneous catalyst for cyanosilylation (pp. 607-614) https://doi.org/10.1016/j.molstruc.2016.12.005
  16. Klimakow et al. (2012) Characterization of mechanochemically synthesized MOFs (pp. 113-118) https://doi.org/10.1016/j.micromeso.2011.11.039
  17. Fernandez-Bertran (1999) Mechanochemistry: an overview (pp. 581-586) https://doi.org/10.1351/pac199971040581
  18. Chen et al. (2017) Highly efficient mechanochemical synthesis of an indium based metal-organic framework with excellent water stability (pp. 539-544) https://doi.org/10.1016/j.ces.2016.11.009
  19. Singh et al. (2017) Solvent-free mechanochemical synthesis and magnetic properties of rare-earth based metal-organic frameworks (pp. 118-122) https://doi.org/10.1016/j.jallcom.2016.11.220
  20. Yang et al. (2011) Study of mechanochemical synthesis in the formation of the metal–organic framework Cu3(BTC)2 for hydrogen storage (pp. 37-45) https://doi.org/10.1016/j.micromeso.2011.02.003
  21. Joaristi et al. (2012) Electrochemical synthesis of some archetypical Zn2+, Cu2+, and Al3+ metal organic frameworks (pp. 3489-3498) https://doi.org/10.1021/cg300552w
  22. Li et al. (2014) Electrochemical preparation of metal–organic framework films for fast detection of nitro explosives (pp. 19473-19478) https://doi.org/10.1039/C4TA04203D
  23. Campagnol et al. (2013) High pressure, high temperature electrochemical synthesis of metal–organic frameworks: films of MIL-100 (Fe) and HKUST-1 in different morphologies (pp. 5827-5830) https://doi.org/10.1039/c3ta10419b
  24. Sun and Zhou (2015) Recent progress in the synthesis of metal–organic frameworks Sci https://doi.org/10.1088/1468-6996/16/5/054202
  25. Khan and Jhung (2015) Synthesis of metal-organic frameworks (MOFs) with microwave or ultrasound: rapid reaction, phase-selectivity, and size reduction (pp. 11-23) https://doi.org/10.1016/j.ccr.2014.10.008
  26. Zhu et al. (2017) Microwave assisted synthesis of reduced graphene oxide incorporated MOF-derived ZnO composites for photocatalytic application (pp. 5-8) https://doi.org/10.1016/j.catcom.2016.09.024
  27. Zhu et al. (2015) Microwave-assisted synthesis of Ag-doped MOFs-like organotitanium polymer with high activity in visible-light driven photocatalytic NO oxidization (pp. 46-51) https://doi.org/10.1016/j.apcatb.2015.02.003
  28. da Silva et al. (2016) Synthesis of Zn-BTC metal organic framework assisted by a home microwave oven and their unusual morphologies (pp. 231-234) https://doi.org/10.1016/j.matlet.2016.06.015
  29. Khan and Jhung (2015) Synthesis of metal-organic frameworks (MOFs) with microwave or ultrasound: rapid reaction, phase-selectivity, and size reduction (pp. 11-23) https://doi.org/10.1016/j.ccr.2014.10.008
  30. Vakili et al. (2018) Microwave-assisted synthesis of zirconium-based metal organic frameworks (MOFs): optimization and gas adsorption (pp. 45-53) https://doi.org/10.1016/j.micromeso.2017.10.028
  31. McKinstry et al. (2017) Scalable continuous production of high quality HKUST-1 via conventional and microwave heating (pp. 570-577) https://doi.org/10.1016/j.cej.2017.05.169
  32. Schlesinger et al. (2010) Evaluation of synthetic methods for microporous metal–organic frameworks exemplified by the competitive formation of [Cu2(btc)3(H2O)3] and [Cu2(btc)(OH)(H2O)] (pp. 121-127) https://doi.org/10.1016/j.micromeso.2010.02.008
  33. Masoomi et al. (2016) High adsorption capacity of two Zn-based metal-organic frameworks by ultrasound assisted synthesis (pp. 54-60) https://doi.org/10.1016/j.ultsonch.2016.04.013
  34. Li et al. (2009) Ultrasonic synthesis of the microporous metal–organic framework Cu3(BTC)2 at ambient temperature and pressure: an efficient and environmentally friendly method (pp. 78-80) https://doi.org/10.1016/j.matlet.2008.09.010
  35. Razavi et al. (2017) Ultrasonic assisted synthesis of a tetrazine functionalized MOF and its application in colorimetric detection of phenylhydrazine (pp. 502-508) https://doi.org/10.1016/j.ultsonch.2017.02.011
  36. Armstrong et al. (2017) Particle size studies to reveal crystallization mechanisms of the metal organic framework HKUST-1 during sonochemical synthesis (pp. 365-370) https://doi.org/10.1016/j.ultsonch.2016.06.011
  37. Masoomi et al. (2017) Porosity and dye adsorption enhancement by ultrasonic synthesized Cd(II) based metal-organic framework (pp. 244-250) https://doi.org/10.1016/j.ultsonch.2017.01.018
  38. Lestari et al. (2018) Green and facile synthesis of MOF and nano MOF containing zinc(II) and benzene 1,3,5-tri carboxylate and its study in ibuprofen slow-release (pp. 141-146) https://doi.org/10.1016/j.matchemphys.2017.10.034
  39. Bosch et al. (2014) Increasing the stability of metal–organic frameworks https://doi.org/10.1155/2014/182327
  40. Chevreau et al. (2013) Mixed-linker hybrid superpolyhedra for the production of a series of large-pore Iron(III) carboxylate metal-organic frameworks (pp. 5056-5060) https://doi.org/10.1002/anie.201300057
  41. Devic and Serre (2014) High valence 3p and transition metal based MOFs (pp. 6097-6115) https://doi.org/10.1039/C4CS00081A
  42. Mondloch (2013) Vapor-phase metalation by atomic layer deposition in a metal-organic framework (pp. 10294-10297) https://doi.org/10.1021/ja4050828
  43. Fu (2012) An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction (pp. 3364-3367) https://doi.org/10.1002/anie.201108357
  44. ul Qadir et al. (2015) Structural stability of metal organic frameworks in aqueous media—controlling factors and methods to improve hydrostability and hydrothermal cyclic stability (pp. 61-90) https://doi.org/10.1016/j.micromeso.2014.09.034
  45. Li et al. (2014) Mechanical tunability via hydrogen bonding in metal–organic frameworks with the perovskite architecture (pp. 7801-7804) https://doi.org/10.1021/ja500618z
  46. Yang et al. (2011) Methyl modified MOF-5: a water stable hydrogen storage material (pp. 5244-5246) https://doi.org/10.1039/c1cc11054c
  47. Serre (2012) Superhydrophobicity in highly fluorinated porous metal-organic frameworks (pp. 6048-6050) https://doi.org/10.1002/anie.201201440
  48. Howarth et al. (2016) Chemical, thermal and mechanical stabilities of metal–organic framework (pp. 1-15) https://doi.org/10.1038/natrevmats.2015.18
  49. Zhang and Su (2014) Applications of metal–organic frameworks in heterogeneous supramolecular catalysis (pp. 6011-6061) https://doi.org/10.1039/C4CS00094C
  50. Hu et al. (2018) Taking organic reactions over metal-organic frameworks as heterogeneous catalysis (pp. 111-127) https://doi.org/10.1016/j.micromeso.2017.07.057
  51. Zhu et al. (2018) A readily available urea based MOF that act as a highly active heterogeneous catalyst for Friedel–Crafts reaction of indoles and nitrostryenes (pp. 123-127) https://doi.org/10.1016/j.catcom.2017.10.010
  52. Calleja et al. (2014) Copper-based MOF-74 material as effective acid catalyst in Friedel–Crafts acylation of anisole (pp. 130-137) https://doi.org/10.1016/j.cattod.2013.11.062
  53. Anbu and Dhakshinamoorthy (2017) Cu3(BTC)2 as a viable heterogeneous solid catalyst for Friedel–Crafts alkylation of indoles with nitroalkenes (pp. 282-289) https://doi.org/10.1016/j.jcis.2017.01.091
  54. Phan et al. (2010) MOF-5 as an efficient heterogeneous catalyst for Friedel–Crafts alkylation reactions (pp. 246-253) https://doi.org/10.1016/j.apcata.2010.04.053
  55. Nguyen et al. (2011) Towards applications of metal–organic frameworks in catalysis: Friedel–Crafts acylation reaction over IRMOF-8 as an efficient heterogeneous catalyst (pp. 28-35) https://doi.org/10.1016/j.molcata.2011.08.011
  56. Gascon et al. (2009) Amino-based metal-organic frameworks as stable, highly active basic catalysts (pp. 75-87) https://doi.org/10.1016/j.jcat.2008.11.010
  57. Hartmann and Fischer (2012) Amino-functionalized basic catalysts with MIL-101 structure (pp. 38-43) https://doi.org/10.1016/j.micromeso.2012.06.044
  58. Yang et al. (2014) Amino-functionalized Zr(IV) metal–organic framework as bifunctional acid–base catalyst for Knoevenagel condensation (pp. 198-205) https://doi.org/10.1016/j.molcata.2014.04.002
  59. Llabrés i Xamena et al. (2012) An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions (pp. 112-117) https://doi.org/10.1016/j.micromeso.2011.12.058
  60. Martínez et al. (2017) Catalytic advantages of NH2-modified MIL-53(Al) materials for Knoevenagel condensation reaction (pp. 43-50) https://doi.org/10.1016/j.micromeso.2017.03.011
  61. Saha et al. (2012) Heterogeneous catalysis over a barium carboxylate framework compound: synthesis, X-ray crystal structure and aldol condensation reaction (pp. 63-70) https://doi.org/10.1016/j.poly.2012.05.043
  62. Pathan et al. (2011) Metal-organic framework Cu3(BTC)2(H2O)3 catalyzed Aldol synthesis of pyrimidine-chalcone hybrids (pp. 1170-1176) https://doi.org/10.1016/j.catcom.2011.03.040
  63. Kikhtyanin et al. (2015) Toward understanding of the role of Lewis acidity in aldol condensation of acetone and furfural using MOF and zeolite catalysts (pp. 158-162) https://doi.org/10.1016/j.cattod.2014.08.016
  64. Anbu and Dhakshinamoorthy (2017) Cu3(BTC)2 catalyzed oxidation of silane to silanol using TBHP or water as oxidants (pp. 145-153) https://doi.org/10.1016/j.apcata.2017.07.028
  65. Kholdeeva et al. (2014) Hydrocarbon oxidation over Fe- and Cr-containing metal-organic frameworks MIL-100 and MIL-101–a comparative study (pp. 54-61) https://doi.org/10.1016/j.cattod.2014.01.010
  66. Skobelev et al. (2013) Solvent-free allylic oxidation of alkenes with O2 mediated by Fe- and Cr-MIL-101 (pp. 61-69) https://doi.org/10.1016/j.jcat.2012.11.003
  67. Torbina et al. (2016) Propylene glycol oxidation with tert-butyl hydroperoxide over Cr-containing metal-organic frameworks MIL-101 and MIL-100 (pp. 97-103) https://doi.org/10.1016/j.cattod.2016.04.008
  68. Phan et al. (2013) Ullmann-type coupling reaction using metal-organic framework MOF-199 as an efficient recyclable solid catalyst (pp. 69-77) https://doi.org/10.1016/j.apcata.2013.02.005
  69. Chen et al. (2015) Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions (pp. 122-128) https://doi.org/10.1016/j.cattod.2014.03.074
  70. Nguyen et al. (2016) Direct C–N coupling of azoles with ethers via oxidative C–H activation under metal–organic framework catalysis (pp. 136-145) https://doi.org/10.1016/j.jiec.2016.08.025
  71. Anbu and Dhakshinamoorthy (2017) Cu3(BTC)2 catalyzed dehydrogenative coupling of dimethylphenylsilane with phenol and homocoupling of dimethylphenylsilane to disiloxane (pp. 430-435) https://doi.org/10.1016/j.jcis.2016.11.081
  72. Brown et al. (2015) Heterogeneous heck coupling in multivariate metal–organic frameworks for enhanced selectivity (pp. 105-107) https://doi.org/10.1016/j.catcom.2015.03.005
  73. Luz et al. (2012) 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 (pp. 285-291) https://doi.org/10.1016/j.jcat.2011.10.001
  74. Dang et al. (2016) Synthesis of indolizines through aldehyde–amine–alkyne couplings using metal-organic framework Cu-MOF-74 as an efficient heterogeneous catalyst (pp. 167-176) https://doi.org/10.1016/j.jcat.2016.02.013
  75. Zhang et al. (2013) Catalytic palladium nanoparticles supported on nanoscale MOFs: a highly active catalyst for Suzuki–Miyaura cross-coupling reaction (pp. 9237-9244) https://doi.org/10.1016/j.tet.2013.08.059
  76. Neogi et al. (2009) Knoevenagel condensation and cyanosilylation reactions catalyzed by a MOF containing coordinatively unsaturated Zn(II) centers (pp. 1-4) https://doi.org/10.1016/j.molcata.2008.10.008
  77. Bhunia et al. (2016) A homochiral vanadium-salen based cadmium bpdc MOF with permanent porosity as an asymmetric catalyst in solvent-free cyanosilylation (pp. 1401-1404) https://doi.org/10.1039/C5CC09459C
  78. Babu et al. (2017) Inverse relationship of dimensionality and catalytic activity in CO2 transformation: a systematic investigation by comparing multidimensional metal–organic frameworks (pp. 15961-15969) https://doi.org/10.1039/C7TA04004K
  79. Babu et al. (2016) Rapid, microwave-assisted synthesis of cubic, three-dimensional, highly porous MOF-205 for room temperature CO2 fixation via cyclic carbonate synthesis (pp. 33723-33731) https://doi.org/10.1021/acsami.6b12458
  80. Kurian and Sugunan (2006) Tertiary butylation of phenol over iron pillared montmorillonites (pp. 417-421) https://doi.org/10.1016/j.catcom.2005.12.005
  81. Kurian and Sugunan (2005) Selective benzylation of benzene over alumina pillared clays (pp. 1772-1781)
  82. Kurian and Sugunan (2004) Selective benzylation of o-xylene over transition metal doped montmorillonites https://doi.org/10.1023/B:REAC.0000016517.85282.be
  83. Kurian and Sugunan (2003) Liquid phase benzylation of o-xylene over pillared clays
  84. Nguyen et al. (2017) A highly active copper-based metal–organic framework catalyst for a Friedel-Crafts alkylation in the under ultrasound irradiation https://doi.org/10.1016/j.arabjc.2017.11.009
  85. Ullah et al. (2018) 12-Tungstophosphoric acid niched in Zr-based metal-organic framework: a stable and efficient catalyst for Friedel-Crafts acylation 61(4) (pp. 402-411) https://doi.org/10.1007/s11426-017-9182-0
  86. Rao and Mandal (2017) Friedel–Crafts alkylation of indoles with ntroalkenes through hydrogen-bond-donating metal–organic framework 9(7) (pp. 1172-1176) https://doi.org/10.1002/cctc.201601583
  87. Rahmani and Rahmani (2018) Al-Based MIL-53 metal organic framework (MOF) as the new catalyst for Friedel–Crafts alkylation of benzene 57(1) (pp. 169-178) https://doi.org/10.1021/acs.iecr.7b04206
  88. Jiang et al. (2015) Metal-organic framework MIL-53(Al): synthesis, catalytic performance for the Friedel–Crafts acylation, and reaction mechanism 58(10) (pp. 1544-1552) https://doi.org/10.1007/s11426-015-5359-0
  89. Calleja et al. (2014) Copper-based MOF-74 material as effective acid catalyst in Friedel–Crafts acylation of anisole 21(227) (pp. 130-137) https://doi.org/10.1016/j.cattod.2013.11.062
  90. Doan et al. (2016) Friedel-Crafts benzoylation of arenes: an efficient combination of Zr-MOF and microwave irradiation in catalytic Lewis acid Friedel-Crafts benzoylation 45(18) (pp. 7875-7880) https://doi.org/10.1039/C6DT00827E
  91. Jiang et al. (2016) Preparation of magnetically recyclable MIL-53(Al)@SiO2@Fe3O4 catalysts and their catalytic performance for Friedel–Crafts acylation reaction (pp. 83-90) https://doi.org/10.1016/j.cattod.2015.10.003
  92. Farzaneh and Mortazavi (2017) Zn metal organic framework as a heterogeneous catalyst for the alkylation of toluene with benzyl bromide 120(1) (pp. 333-344) https://doi.org/10.1007/s11144-016-1077-7
  93. Khalil et al. (2017) Introduction of an effective and economical heterogeneous ruthenium catalyst for regioselective ring-opening of epoxides and the Friedel–Crafts alkylation reaction of indoles and pyrroles 14(3) (pp. 207-217) https://doi.org/10.2174/1570178614666170117152437
  94. Chung et al. (2014) Friedel–Crafts acylation of p-xylene over sulfonated zirconium terephthalates (pp. 817-824) https://doi.org/10.1007/s10562-014-1242-4
  95. Zhu et al. (2016) Micro-Cu4I4-MOF: reversible iodine adsorption and catalytic properties for tandem reaction of Friedel-Crafts alkylation of indoles with acetals https://doi.org/10.1039/C6CC07027B
  96. Rostamnia et al. (2016) Pd-grafted open metal site copper-benzene-1,4-dicarboxylate metal organic frameworks (Cu-BDC MOF’s) as promising interfacial catalysts for sustainable Suzuki coupling (pp. 310-317) https://doi.org/10.1016/j.jcis.2016.02.021
  97. Zhang et al. (2016) Robust metal-organic framework containing benzoselenadiazole for highly efficient aerobic cross-dehydrogenative coupling reactions under visible light 55(3) (pp. 1005-1007) https://doi.org/10.1021/acs.inorgchem.5b02626
  98. Chen and Jiang (2016) Porphyrinic metal–organic framework catalyzed heck-reaction: fluorescence “turn-on” sensing of Cu(II) ion 28(18) (pp. 6698-6704) https://doi.org/10.1021/acs.chemmater.6b03030
  99. Kardanpour et al. (2014) Highly dispersed palladium nanoparticles supported on amino functionalized metal-organic frameworks as an efficient and reusable catalyst for Suzuki cross-coupling reaction (pp. 127-133) https://doi.org/10.1016/j.jorganchem.2014.03.012
  100. Rostamnia and Morsali (2014) Basic isoreticular nanoporous metal–organic framework for Biginelli and Hantzsch coupling: IRMOF-3 as a green and recoverable heterogeneous catalyst in solvent-free conditions (pp. 54487-54493) https://doi.org/10.1039/C4RA10065D
  101. Zhang et al. (2015) Palladium nanoparticle supported on metal–organic framework derived N-decorated nanoporous carbon as an efficient catalyst for the Suzuki coupling reaction (pp. 21-25) https://doi.org/10.1016/j.catcom.2014.12.004
  102. Qiu et al. (2014) Solventless oxidative coupling of amines to imines by using transition-metal-free metal–organic frameworks 7(6) (pp. 1684-1688) https://doi.org/10.1002/cssc.201301340
  103. Wang et al. (2015) A porous metal–organic framework as active catalyst for multiple C–N/C–C bond formation reactions (pp. 13-15) https://doi.org/10.1016/j.inoche.2015.08.010
  104. Yang et al. (2014) A stable microporous mixed-metal metal–organic framework with highly active Cu2+ sites for efficient cross-dehydrogenative coupling reactions 20(5) (pp. 1447-1452) https://doi.org/10.1002/chem.201303615
  105. Horike et al. (2008) Size-selective lewis acid catalysis in a microporous metal-organic framework with exposed Mn2+ coordination sites (pp. 5854-5855) https://doi.org/10.1021/ja800669j
  106. Schlichte et al. (2004) Improved synthesis, thermal stability and catalytic properties of the metal-organic framework compound Cu3(BTC)2 73(1–2) (pp. 81-88) https://doi.org/10.1016/j.micromeso.2003.12.027
  107. Gao et al. (2014) Crystal engineering of an nbo topology metal-organic framework for chemical fixation of CO2 under ambient conditions (pp. 2615-2619) https://doi.org/10.1002/anie.201309778
  108. Li et al. (2016) A triazole-containing metal-organic framework as a highly effective and substrate size-dependent catalyst for CO2 conversion 138(7) (pp. 2142-2145) https://doi.org/10.1021/jacs.5b13335
  109. De et al. (2016) A versatile CuII metal–organic framework exhibiting high gas storage capacity with selectivity for CO2: conversion of CO2 to cyclic carbonate and other catalytic abilities 22(10) (pp. 3387-3396) https://doi.org/10.1002/chem.201504747
  110. Cho et al. (2006) A metal–organic framework material that functions as an enantioselective catalyst for olefin epoxidation (pp. 2563-2565) https://doi.org/10.1039/B600408C
  111. Alaerts et al. (2006) Probing the lewis acidity and catalytic activity of the metal–organic framework [Cu3(btc)2] (BTC = Benzene-1,3,5-tricarboxylate) 12(28) (pp. 7271-7531) https://doi.org/10.1002/chem.200600220
  112. Sun et al. (2009) Highly stable crystalline catalysts based on a microporous metal–organic framework and polyoxometalates 131(5) (pp. 1883-1888) https://doi.org/10.1021/ja807357r
  113. Wu et al. (2005) A homochiral porous metal–organic framework for highly enantioselective heterogeneous asymmetric catalysis 127(25) (pp. 8940-8941) https://doi.org/10.1021/ja052431t
  114. Vermoortele et al. (2011) An amino-modified Zr-terephthalate metal–organic framework as an acid–base catalyst for cross-aldol condensation 47(5) (pp. 1521-1523) https://doi.org/10.1039/C0CC03038D
  115. Feng et al. (2012) Mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts (pp. 10307-10310) https://doi.org/10.1002/anie.201204475
  116. Pérez-Mayoral and Čejka (2011) [Cu3(BTC)2]: a metal-organic framework catalyst for the friedländer reaction 3(1) (pp. 157-159) https://doi.org/10.1002/cctc.201000201
  117. Song et al. (2011) [Cu3(C9H3O6)2]4 [{(CH3)4N}4CuPW11O39H] a multiunit catalyst with synergistic stability and reactivity: a polyoxometalate metal organic framework for aerobic decontamination (pp. 16839-16846) https://doi.org/10.1021/ja203695h
  118. Comito et al. (2016) Zn5Cl4(BTDD)3-single-site heterogeneous catalysts for olefin polymerization enabled by cation exchange in a metal-organic framework (pp. 10232-10237) https://doi.org/10.1021/jacs.6b05200
  119. Manna et al. (2014) Fe- and Co-functionalized MOFs (sal-M-MOF, M = Fe, Co)-salicylaldimine-based metal–organic framework enabling highly active olefin hydrogenation with iron and cobalt catalysts (pp. 13182-13185) https://doi.org/10.1021/ja507947d
  120. Lin et al. (2015) Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water 349(6253) (pp. 1208-1213) https://doi.org/10.1126/science.aac8343
  121. Liu et al. (2015) Selective photooxidation of a mustard-gas simulant catalyzed by a porphyrinic metal-organic framework 54(31) (pp. 9001-9005) https://doi.org/10.1002/anie.201503741
  122. Liu et al. (2015) Dual-function metal-organic framework as a versatile catalyst for detoxifying chemical warfare agent simulants 9(12) (pp. 12358-12364) https://doi.org/10.1021/acsnano.5b05660
  123. López-Maya et al. (2015) Textile/metal–organic-framework composites as self-detoxifying filters for chemical-warfare agents 54(23) (pp. 6790-6794) https://doi.org/10.1002/anie.201502094
  124. Hod et al. (2015) A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution https://doi.org/10.1038/ncomms9304
  125. Reinares-Fisac et al. (2016) A mesoporous indium metal-organic framework: remarkable advances in catalytic activity for strecker reaction of ketones 138(29) (pp. 9089-9092) https://doi.org/10.1021/jacs.6b05706
  126. Gonzalez et al. (2015) Single-crystal-to-single-crystal metalation of a metal–organic framework: a route toward structurally well-defined catalysts (pp. 2995-3005) https://doi.org/10.1021/acs.inorgchem.5b00096
  127. Klet et al. (2015) Single-site organozirconium catalyst embedded in a metal-organic framework 137(50) (pp. 15680-15683) https://doi.org/10.1021/jacs.5b11350
  128. Beyzavi et al. (2015) A hafnium-based metal-organic framework as a nature-inspired tandem reaction catalyst 137(42) (pp. 13624-13631) https://doi.org/10.1021/jacs.5b08440
  129. Nasalevich et al. (2014) Co@NH2-MIL-125(Ti): cobaloxime-derived metal– organic framework-based composite for light driven H2 production https://doi.org/10.1039/c4ee02853h
  130. Jiao et al. (2016) Metal–organic framework-based CoP/reduced graphene oxide: high-performance bifunctional electrocatalyst for overall water splitting (pp. 1690-1695) https://doi.org/10.1039/C5SC04425A
  131. Zhao et al. (2014) Core-shell palladium nanoparticle@metal–organic frameworks as multifunctional catalysts for cascade reactions 136(5) (pp. 1738-1741) https://doi.org/10.1021/ja411468e
  132. Chen et al. (2015) Tiny Pd@Co core-shell nanoparticles confined inside a metal-organic framework for highly efficient catalysis 11(1) (pp. 71-76) https://doi.org/10.1002/smll.201401875
  133. Qi et al. (2015) Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols 21(4) (pp. 1589-1597) https://doi.org/10.1002/chem.201405685
  134. Noh et al. (2016) An exceptionally stable metal-organic framework supported molybdenum(VI) oxide catalyst for cyclohexene epoxidation 138(44) (pp. 14720-14726) https://doi.org/10.1021/jacs.6b08898
  135. Mo et al. (2014) Li MOF—a homochiral metal-organic framework as an effective asymmetric catalyst for cyanohydrin synthesis 136(5) (pp. 1746-1749) https://doi.org/10.1021/ja411887c
  136. Manna et al. (2016) Metal-organic framework nodes support single-site magnesium-alkyl catalysts for hydroboration and hydroamination reactions 138(24) (pp. 7488-7749) https://doi.org/10.1021/jacs.6b03689
  137. Hu et al. (2016) Metal–organic-framework-engaged formation of Co nanoparticle-embedded carbon@Co9S8 double-shelled nanocages for efficient oxygen reduction (pp. 107-111) https://doi.org/10.1039/C5EE02903A
  138. Xia et al. (2016) A metal–organic framework-derived bifunctional oxygen electrocatalyst https://doi.org/10.1038/nenergy.2015.6
  139. Li et al. (2016) Sintering-resistant single-site nickel catalyst supported by metal-organic framework 138(6) (pp. 1977-1982) https://doi.org/10.1021/jacs.5b12515
  140. Hod et al. (2015) Fe-porphyrin-based metal-organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2 5(11) (pp. 6302-6309) https://doi.org/10.1021/acscatal.5b01767
  141. Yang et al. (2016) Pd nanocubes@ZIF-8: integration of plasmon-driven photothermal conversion with a metal-organic framework for efficient and selective catalysis 55(11) (pp. 3685-3689) https://doi.org/10.1002/anie.201510655
  142. Beyzavi et al. (2014) A hafnium-based metal-organic framework as an efficient and multifunctional catalyst for facile CO2 fixation and regioselective and enantioretentive epoxide activation 136(45) (pp. 15861-15864) https://doi.org/10.1021/ja508626n
  143. Li et al. (2015) MIL-101-Cr-SO3H·Al(III) MOF-metal–organic framework based upon the synergy of a brønsted acid framework and lewis acid centers as a highly efficient heterogeneous catalyst for fixed-bed reactions (pp. 4243-4248) https://doi.org/10.1021/jacs.5b01352
  144. Fei et al. (2015) Photocatalytic CO2 reduction to formate using a Mn(I) molecular catalyst in a robust metal-organic framework 54(14) (pp. 6821-6828) https://doi.org/10.1021/acs.inorgchem.5b00752
  145. Sawano et al. (2015) Chiral, and porous BINAP-based metal-organic frameworks for highly enantioselective cyclization reactions 137(38) (pp. 12241-12248) https://doi.org/10.1021/jacs.5b09225