The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion

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The carbon dioxide challenge is one of the most pressing problems facing our planet. Each stage in the carbon cycle — capture, regeneration and conversion — has its own materials requirements. Recent work on metal–organic frameworks (MOFs) demonstrated the potential and effectiveness of these materials in addressing this challenge. In this Review, we identify the specific structural and chemical properties of MOFs that have led to the highest capture capacities, the most efficient separations and regeneration processes, and the most effective catalytic conversions. The interior of MOFs can be designed to have coordinatively unsaturated metal sites, specific heteroatoms, covalent functionalization, other building unit interactions, hydrophobicity, porosity, defects and embedded nanoscale metal catalysts with a level of precision that is crucial for the development of higher-performance MOFs. To realize a total solution, it is necessary to use the precision of MOF chemistry to build more complex materials to address selectivity, capacity and conversion together in one material.

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Figure 1: Chronology of key achievements made in the field of MOFs and CO2.
Figure 2: Important structural design features of effective MOF adsorbents for selective CO2 capture.
Figure 3: IRMOF-74-III with alkylamine functionality for the chemisorption of CO2 in the presence of water.
Figure 4: Selectivity versus CO2 permeability compared to the Robeson upper bound curves for pure polymeric, mixed-matrix and pure MOF membranes.
Figure 5: Strategies for improving photochemical CO2 reduction.
Figure 6: Electrocatalytic reduction of CO2 to CO by a Co-porphyrin-containing MOF.
Figure 7: Proposed mechanism for the catalytic cycloaddition of propylene oxide with CO2 by Hf-NU-1000 to form a cyclic carbonate.


  1. 1

    Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013).

  2. 2

    Sumida, K. et al. Carbon dioxide capture in metal-organic frameworks. Chem. Rev. 112, 724–781 (2012).

  3. 3

    Li, J.-R. et al. Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks. Coord. Chem. Rev. 255, 1791–1823 (2011).

  4. 4

    Jiang, J., Zhao, Y. & Yaghi, O. M. Covalent chemistry beyond molecules. J. Am. Chem. Soc. 138, 3255–3265 (2016).

  5. 5

    Furukawa, H., Muller, U. & Yaghi, O. M. “Heterogeneity within order” in metal-organic frameworks. Angew. Chem. Int. Ed. 54, 3417–3430 (2015).

  6. 6

    Millward, A. R. & Yaghi, O. M. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature. J. Am. Chem. Soc. 127, 17998–17999 (2005).

  7. 7

    Britt, D., Furukawa, H., Wang, B., Glover, T. G. & Yaghi, O. M. Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites. Proc. Natl Acad. Sci. USA 106, 20637–20640 (2009). This publication describes the first breakthrough experiment using MOFs, which is an important method for evaluating CO2 capture under dynamic conditions.

  8. 8

    Mason, J. A. et al. Application of a high-throughput analyzer in evaluating solid adsorbents for post-combustion carbon capture via multicomponent adsorption of CO2, N2, and H2O. J. Am. Chem. Soc. 137, 4787–4803 (2015).

  9. 9

    Bao, Z., Yu, L., Ren, Q., Lu, X. & Deng, S. Adsorption of CO2 and CH4 on a magnesium-based metal organic framework. J. Colloid Interface Sci. 353, 549–556 (2011).

  10. 10

    Caskey, S. R., Wong-Foy, A. G. & Matzger, A. J. Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. J. Am. Chem. Soc. 130, 10870–10871 (2008).

  11. 11

    Märcz, M., Johnsen, R. E., Dietzel, P. D. C. & Fjellvåg, H. The iron member of the CPO-27 coordination polymer series: synthesis, characterization, and intriguing redox properties. Microporous Mesoporous Mater. 157, 62–74 (2012).

  12. 12

    Yazaydin, A. O. et al. Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach. J. Am. Chem. Soc. 131, 18198–18199 (2009).

  13. 13

    Wang, L. J. et al. Synthesis and characterization of metal-organic framework-74 containing 2, 4, 6, 8, and 10 different metals. Inorg. Chem. 53, 5881–5883 (2014).

  14. 14

    Queen, W. L. et al. Comprehensive study of carbon dioxide adsorption in the metal-organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn). Chem. Sci. 5, 4569–4581 (2014).

  15. 15

    Kizzie, A. C., Wong-Foy, A. G. & Matzger, A. J. Effect of humidity on the performance of microporous coordination polymers as adsorbents for CO2 capture. Langmuir 27, 6368–6373 (2011).

  16. 16

    Si, X. et al. High and selective CO2 uptake, H2 storage and methanol sensing on the amine-decorated 12-connected MOF CAU-1. Energy Environ. Sci. 4, 4522–4527 (2011).

  17. 17

    Cui, P. et al. Multipoint interactions enhanced CO2 uptake: a zeolite-like zinc-tetrazole framework with 24-nuclear zinc cages. J. Am. Chem. Soc. 134, 18892–18895 (2012).

  18. 18

    An, J., Geib, S. J. & Rosi, N. L. High and selective CO2 uptake in a cobalt adeninate metal-organic framework exhibiting pyrimidine- and amino-decorated pores. J. Am. Chem. Soc. 132, 38–39 (2010).

  19. 19

    Meyers, A. L. & Prausnitz, J. M. Thermodynamics of mixed-gas adsorption. AlChE J. 11, 121–127 (1965).

  20. 20

    Hwang, Y. K. et al. Amine grafting on coordinatively unsaturated metal centers of MOFs: consequences for catalysis and metal encapsulation. Angew. Chem. Int. Ed. 47, 4144–4148 (2008). This paper reported the initial strategy of grafting alkylamines onto MOF structures, thus paving the way for realizing chemisorptive MOF materials.

  21. 21

    Demessence, A., D’Alessandro, D. M., Foo, M. L. & Long, J. R. Strong CO2 binding in a water-stable, triazolate-bridged metal-organic framework functionalized with ethylenediamine. J. Am. Chem. Soc. 131, 8784–8786 (2009).

  22. 22

    McDonald, T. M., D’Alessandro, D. M., Krishna, R. & Long, J. R. Enhanced carbon dioxide capture upon incorporation of N,N′-dimethylethylenediamine in the metal-organic framework CuBTTri. Chem. Sci. 2, 2022–2028 (2011).

  23. 23

    McDonald, T. M. et al. Capture of carbon dioxide from air and flue gas in the alkylamine-appended metal-organic framework mmen-Mg2(dobpdc). J. Am. Chem. Soc. 134, 7056–7065 (2012).

  24. 24

    Fracaroli, A. M. et al. Metal-organic frameworks with precisely designed interior for carbon dioxide capture in the presence of water. J. Am. Chem. Soc. 136, 8863–8866 (2014).

  25. 25

    Xiong, Y. et al. Amide and N-oxide functionalization of T-shaped ligands aford isoreticular MOFs with giant enhancements in CO2 separation. Chem. Commun. 50, 14631–14634 (2014).

  26. 26

    Safarifard, V. et al. Influence of the amide groups in the CO2/N2 selectivity of a series of isoreticular, interpenetrated metal-organic frameworks. Cryst. Growth Des. 16, 6016–6023 (2016).

  27. 27

    Benson, O. et al. Amides do not always work: observation of guest binding in an amide-functionalized porous metal-organic framework. J. Am. Chem. Soc. 138, 14828–14831 (2016).

  28. 28

    Burd, S. D. et al. Highly selective carbon dioxide uptake by [Cu(bpy-n)2(SiF6)] (bpy-1 = 4,4′-bipyridine; bpy-2 = 1,2-bis(4-pyridyl)ethene). J. Am. Chem. Soc. 134, 3663–3666 (2012).

  29. 29

    Nugent, P. et al. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495, 80–84 (2013).

  30. 30

    Liao, P. Q. et al. Monodentate hydroxide as a super strong yet reversible active site for CO2 capture from high-humidity flue gas. Energy Environ. Sci. 8, 1011–1016 (2015).

  31. 31

    Nguyen, N. T. T. et al. Selective capture of carbon dioxide under humid conditions by hydrophobic chabazite-type zeolitic imidazolate frameworks. Angew. Chem. Int. Ed. 53, 10645–10648 (2014). This report details the synthesis of hydrophobic ZIFs for selective capture of CO2 in the presence of water.

  32. 32

    Ding, N. et al. Partitioning MOF-5 into confined and hydrophobic compartments for carbon capture under humid conditions. J. Am. Chem. Soc. 138, 10100–10103 (2016).

  33. 33

    Zhang, Z. et al. Polymer-metal-organic frameworks (polyMOFs) as water tolerant materials for selective carbon dioxide separations. J. Am. Chem. Soc. 138, 920–925 (2016).

  34. 34

    Liu, B. et al. Significant enhancement of gas uptake capacity and selectivity via the judicious increase of open metal sites and Lewis basic sites within two polyhedron-based metal–organic frameworks. Chem. Commun. 52, 3223–3226 (2016).

  35. 35

    Forrest, K. A., Pham, T., McLaughlin, K., Hogan, A. & Space, B. Insights into an intriguing gas sorption mechanism in a polar MOF with open metal sites and narrow channels. Chem. Commun. 50, 7283–7286 (2014).

  36. 36

    Li, B. et al. Enhanced binding affinity, remarkable selectivity, and high capacity of CO2 by dual functionalization of a rht-type metal-organic framework. Angew. Chem. Int. Ed. 51, 1412–1415 (2012).

  37. 37

    Kim, J. et al. Control of catenation in CuTATB-n metal–organic frameworks by sonochemical synthesis and its effect on CO2 adsorption. J. Mater. Chem. 21, 3070–3076 (2011).

  38. 38

    Zheng, B., Bai, J., Duan, J., Wojtas, L. & Zaworotko, M. J. Enhanced CO2 binding affinity of a high-uptake rht -type metal-organic framework decorated with acylamide groups. J. Am. Chem. Soc. 133, 758–751 (2011).

  39. 39

    Lu, Y. et al. Porous pcu-type Zn(II) framework material with high adsorption selectivity for CO2 over N2 . J. Mol. Struct. 1107, 66–69 (2016).

  40. 40

    Law, J., Watkins, S. & Alexander, D. In-flight carbon dioxide exposures and related symptoms: associate, susceptibility, and operational implications (NASA, 2010).

  41. 41

    Dallbauman, L. A. & Finn, J. E. in Adsorption and its Applications in Industry and Environmental Protection: Applications in Environmental Protections, Part B Vol. 120 (ed. Dabrowski, A. ) 455–471 (Elsevier, 1999).

  42. 42

    Bhatt, P. M. et al. A fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture using physisorption. J. Am. Chem. Soc. 138, 9301–9307 (2016). This contribution describes the first MOF applied towards the capture of a trace amount of CO2 in confined spaces.

  43. 43

    Cavenati, S., Grande, C. A. & Rodrigues, A. E. Removal of carbon dioxide from natural gas by vacuum pressure swing adsorption. Energy Fuels 20, 2648–2659 (2006).

  44. 44

    Ferey, G. et al. Why hybrid porous solids capture greenhouse gases? Chem. Soc. Rev. 40, 550–562 (2011).

  45. 45

    Li, J. R., Sculley, J. & Zhou, H.-C. Metal-organic frameworks for separations. Chem. Rev. 112, 869–832 (2012).

  46. 46

    Xiong, S. et al. A new tetrazolate zeolite-like framework for highly selective CO2/CH4 and CO2/N2 separation. Chem. Commun. 50, 12101–12104 (2014).

  47. 47

    Nguyen, N. T. T. et al. Mixed-metal zeolitic imidazolate frameworks and their selective capture of wet carbon dioxide over methane. Inorg. Chem. 55, 6201–6207 (2016).

  48. 48

    Chen, K.-J. et al. Tuning pore size in square-lattice coordination networks for size-selective sieving of CO2 . Angew. Chem. Int. Ed. 55, 10268–10272 (2016).

  49. 49

    Chen, Z. et al. Significantly enhanced CO2/CH4 separation selectivity within a 3D prototype metal-organic framework functionalized with OH groups on pore surfaces at room temperature. Eur. J. Inorg. Chem. 2011, 2227–2231 (2011).

  50. 50

    Bae, Y.-S. et al. Separation of CO2 from CH4 using mixed-ligand metal-organic frameworks. Langmuir 24, 8592–8598 (2008).

  51. 51

    Hamon, L. et al. Comparative study of hydrogen sulfide adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal-organic frameworks at room temperature. J. Am. Chem. Soc. 131, 8775–8777 (2009).

  52. 52

    Hamon, L. et al. Molecular insight into the adsorption of H2S in the flexible MIL-53(Cr) and rigid MIL-47(V) MOFs: Infrared spectroscopy combined to molecular simulations. J. Phys. Chem. C 115, 2047–2056 (2011).

  53. 53

    Belmabkhout, Y. et al. Metal-organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S. J. Mater. Chem. A 5, 3293–3303 (2017).

  54. 54

    Vellingiri, K., Deep, A. & Kim, K.-H. Metal-organic frameworks as a potential platform for selective treatment of gaseous sulfur compounds. ACS Appl. Mater. Interfaces 8, 29835–29857 (2016).

  55. 55

    Gedrich, K. et al. A highly porous metal-organic framework with open nickel sites. Angew. Chem. Int. Ed. 49, 8489–8492 (2010).

  56. 56

    Alezi, D. et al. MOF crystal chemistry paving the way to gas storage needs: aluminum-based soc-MOF for CH4, O2, and CO2 storage. J. Am. Chem. Soc. 137, 13308–13318 (2015).

  57. 57

    Yuan, D., Zhao, D., Sun, D. & Zhou, H. C. An isoreticular series of metal-organic frameworks with dendritic hexacarboxylate ligands and exceptionally high gas-uptake capacity. Angew. Chem. Int. Ed. 49, 5357–5361 (2010).

  58. 58

    Xue, M. et al. New prototype isoreticular metal-organic framework Zn4O(FMA)3 for gas storage. Inorg. Chem. 48, 4649–4651 (2009).

  59. 59

    Farha, O. K. et al. De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities. Nat. Chem. 2, 944–948 (2010).

  60. 60

    Dietzel, P. D. C., Besikiotis, V. & Blom, R. Application of metal–organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide. J. Mater. Chem. 19, 7362–7370 (2009).

  61. 61

    Llewellyn, P. L. et al. High uptakes of CO2 and CH4 in mesoporous metal-organic frameworks MIL-100 and MIL-101. Langmuir 24, 7245–7250 (2008).

  62. 62

    Furukawa, H. et al. Ultrahigh porosity in metal-organic frameworks. Science 329, 424–428 (2010). This report details the synthesis of ultra-highly porous MOFs, using the principles of reticular chemistry, which resulted in record-breaking CO2 uptake properties.

  63. 63

    Mason, J. A., Sumida, K., Herm, Z. R., Krishna, R. & Long, J. R. Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption. Energy Environ. Sci. 4, 3030–3040 (2011). This publication demonstrated the feasibility of regenerating MOFs through temperature swing adsorption processes.

  64. 64

    Olajire, A. A. CO2 capture and separation technologies for end-of-pipe applications — a review. Energy 35, 2610–2628 (2010).

  65. 65

    Yu, C.-H., Huang, C.-H. & Tan, C.-S. A review of CO2 capture by absorption and adsorption. Aerosol Air Qual. Res. 12, 745–769 (2012).

  66. 66

    Sircar, S. & Golden, T. C. Purification of hydrogen by pressure swing adsorption. Sep. Sci. Technol. 35, 667–687 (2000).

  67. 67

    Herm, Z. R., Swisher, J. A., Smit, B., Krishna, R. & Long, J. R. Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture. J. Am. Chem. Soc. 133, 5664–5667 (2011).

  68. 68

    Ferreira, A. F. P., Ribeiro, A. M., Kulaç, S. & Rodrigues, A. E. Methane purification by adsorptive processes on MIL-53(Al). Chem. Eng. Sci. 124, 79–95 (2015).

  69. 69

    Serra-Crespo, P. et al. Preliminary design of a vacuum pressure swing adsorption process for natural gas upgrading based on amino-functionalized MIL-53. Chem. Eng. Technol. 38, 1183–1194 (2015).

  70. 70

    Berger, A. H. & Bhown, A. S. Comparing physisorption and chemisorption solid sorbents for use separating CO2 from flue gas using temperature swing adsorption. Energy Procedia 4, 562–567 (2011).

  71. 71

    McDonald, T. M. et al. Cooperative insertion of CO2 in diamine-appended metal-organic frameworks. Nature 519, 303–308 (2015). This work highlights an alternative CO2 capture mechanism for an alkylamine-appended MOF to the established aqueous monoethanolamine system, indicating solid-state systems may operate differently despite both being chemisorptive processes.

  72. 72

    Ye, S. et al. Post-combustion CO2 capture with the HKUST-1 and MIL-101(Cr) metal-organic frameworks: adsorption, separation and regeneration investigations. Microporous Mesoporous Mater. 179, 191–197 (2013).

  73. 73

    Dasgupta, S. et al. CO2 recovery from mixtures with nitrogen in a vacuum swing adsorber using metal-organic framework adsorbent: a comparative study. Int. J. Greenh. Gas Control 7, 225–229 (2012).

  74. 74

    Andersen, A. et al. On the development of vacuum swing adsorption (VSA) technology for post-combustion CO2 capture. Energy Procedia 37, 33–39 (2013).

  75. 75

    Zhang, Y., Sunarso, J., Liu, S. M. & Wang, R. Current status and development of membranes for CO2/CH4 separation: A review. Int. J. Greenhouse Gas Control 12, 84–107 (2013).

  76. 76

    Robeson, L. M. Correlation of separation factor versus permeability for polymeric membranes. J. Membr. Sci. 62, 165–185 (1991).

  77. 77

    Rui, Z., James, J. B., Kasik, A. & Lin, Y. S. Metal-organic framework membrane process for high purity CO2 production. AlChE J. 62, 3836–3841 (2016).

  78. 78

    Robeson, L. M. The upper bound revisited. J. Membr. Sci. 320, 390–400 (2008).

  79. 79

    Koros, W. J. & Mahajan, R. Pushing the limits on possibilities for large scale gas separation: which strategies? J. Membr. Sci. 181, 141 (2001).

  80. 80

    Venna, S. R. & Carreon, M. A. Metal-organic framework membranes for carbon dioxide separation. Chem. Eng. Sci. 124, 3–19 (2015).

  81. 81

    Hermes, S., Schroder, F., Chelmowski, R., Woll, C. & Fischer, R. A. Selective nucleation and growth of metal-organic open framework thin films on patterned COOH/CF3-terminated self-assembled monolayers on Au(111). J. Am. Chem. Soc. 127, 13744–13745 (2005). This contribution details the growth of the first pure MOF membrane, which serves as the basis for later developments in using MOF membranes for gas separations.

  82. 82

    Liu, Y. et al. Synthesis of continuous MOF-5 membranes on porous α-alumina substrates. Microporous Mesoporous Mater. 118, 296–301 (2009).

  83. 83

    Qiu, S., Xue, M. & Zhu, G. Metal-organic framework membranes: from synthesis to separation application. Chem. Soc. Rev. 43, 6116–6140 (2014).

  84. 84

    Liu, Y. et al. Remarkable enhanced gas separation by partial self-conversion of a laminated membrane to metal-organic frameworks. Angew. Chem. Int. Ed. 54, 3028–3032 (2015).

  85. 85

    Peng, Y. et al. Metal-organic framework nanosheets as building blocks for molecular sieving membranes. Science 346, 1356–1359 (2014).

  86. 86

    Liu, Y., Zeng, G., Pan, Y. & Lai, Z. Synthesis of highly c -oriented ZIF-69 membranes by secondary growth and their gas permeation properties. J. Membr. Sci. 379, 46–51 (2011).

  87. 87

    Liu, Y., Hu, E. P., Khan, E. A. & Lai, Z. Synthesis and characterization of ZIF-69 membranes and separation for CO2/CO mixture. J. Membr. Sci. 353, 36–40 (2010).

  88. 88

    An, J., Fiorella, R., Geib, S. J. & Rosi, N. L. Synthesis, structure, assembly, and modulation of the CO2 adsorption properties of a zinc-adeninate macrocyle. J. Am. Chem. Soc. 131, 8401–8403 (2009).

  89. 89

    Bohrman, J. A. & Carreon, M. A. Synthesis and CO2/CH4 separation performance of bio-MOF-1 membranes. Chem. Commun. 48, 5130–5132 (2012).

  90. 90

    Xie, Z., Li, T., Rosi, N. L. & Carreon, M. A. Alumina-supported cobalt-adeninate MOF membranes for CO2/CH4 separation. J. Mater. Chem. A 2, 1239–1241 (2014).

  91. 91

    Al-Maythalony, B. A. et al. Quest for anionic MOF membranes: continuous sod-ZMOF membrane with CO2 adsorption-driven selectivity. J. Am. Chem. Soc. 137, 1754–1757 (2015).

  92. 92

    Bétard, A. et al. Fabrication of a CO2-selective membrane by stepwise liquid-phase deposition of an alkylether functionalized pillared-layered metal-organic framework [Cu2L2P]n on a macroporous support. Microporous Mesoporous Mater. 150, 76–82 (2012).

  93. 93

    Huang, A., Liu, Q., Wang, N. & Caro, J. Organosilica functionalized zeolitic imidazolate framework ZIF-90 membrane for CO2/CH4 separation. Microporous Mesoporous Mater. 192, 18–22 (2014).

  94. 94

    Zhao, Z., Ma, X., Kasik, A., Li, Z. & Lin, Y. S. Gas separation properties of metal organic framework (MOF-5) membranes. Ind. Eng. Chem. Res. 52, 1102–1108 (2013).

  95. 95

    Yin, H. et al. A highly permeable and selective amino-functionalized MOF CAU-1 membrane for CO2-N2 separation. Chem. Commun. 50, 3699–3701 (2014).

  96. 96

    Yehia, H., Pisklak, T. J., Ferraris, J. P., Balkus, K. J. & Musselman, I. H. Methane facilitated transport using copper(II) biphenyl dicarboxylate-triethylenediamine poly(3-acetoxyethylthiophene) mixed matrix membranes. Polym. Preprints 45, 35–36 (2004).

  97. 97

    Bae, T.-H. & Long, J. R. CO2/N2 separation with mixed-matrix membranes containing Mg2(dobdc) nanocrystals. Energy Environ. Sci. 6, 3565–3569 (2013).

  98. 98

    Bae, T.-H. et al. A high-performance gas-separation membrane containing submicrometer-sized metal-organic framework crystals. Angew. Chem. Int. Ed. 49, 9863–9866 (2010).

  99. 99

    Seoane, B. et al. Metal-organic framework based mixed matrix membranes: a solution for highly efficient CO2 capture? Chem. Soc. Rev. 44, 2421–2454 (2015).

  100. 100

    Duan, C., Ji, X., Liu, D., Cao, Y. & Yuan, Q. Post-treatment effect on gas separation property of mixed matrix membranes containing metal organic frameworks. J. Membr. Sci. 466, 92–102 (2014).

  101. 101

    Al-Maythalony, B. et al. Tuning the interplay between selectivity and permeability of ZIF-7 mixed matrix membranes. ACS Appl. Mater. Interfaces (2017). This contribution details a post-synthetic modification strategy to fine-tune the permselectivity of spongy mixed matrix membranes.

  102. 102

    Wang, Z., Wang, D., Zhang, S., Hu, L. & Jin, J. Interfacial design of mixed matrix membranes for improved gas separation performance. Adv. Mater. 28, 3399–3405 (2016).

  103. 103

    Zhang, C. et al. Highly scalable ZIF-based mixed-matrix hollow fiber membranes for advanced hydrocarbon separations. AIChE J. 60, 2625–2635 (2014).

  104. 104

    Wang, C., Xie, Z., DeKrafft, K. E. & Lin, W. Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. J. Am. Chem. Soc. 133, 13445–13454 (2011).

  105. 105

    Choi, K. et al. Plasmon-enhanced photocatalytic CO2 conversion within metal-organic frameworks under visible light. J. Am. Chem. Soc. 139, 356–362 (2017). This publication details the use of a ‘heterogeneity within order’ strategy for constructing a highly active photocatalytic MOF used for CO2 conversion to CO.

  106. 106

    Fu, Y. et al. An amine-functionalized titantium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction. Angew. Chem. Int. Ed. 51, 3364–3367 (2012).

  107. 107

    Wang, D., Huang, R., Liu, W., Sun, D. & Li, Z. Fe-based MOFs for photocatalytic CO2 reduction: role of coordination unsaturated sites and dual excitation pathways. ACS Catal. 4, 4254–4260 (2014).

  108. 108

    Sun, D. et al. Construction of a supported Ru complex on bifunctional MOF-253 for photocatalytic CO2 reduction under visible light. Chem. Commun. 51, 2645–2648 (2015).

  109. 109

    Zhang, S. et al. Hierarchical metal–organic framework nanoflowers for effective CO2 transformation driven by visible light. J. Mater. Chem. A 3, 15764–15768 (2015).

  110. 110

    Zhang, S., Li, L., Zhao, S., Sun, Z. & Luo, J. Construction of interpenetrated ruthenium metal−organic frameworks as stable photocatalysts for CO2 reduction. Inorg. Chem. 54, 8375–8379 (2015).

  111. 111

    Wu, P. et al. Photoactive metal−organic framework and its film for light-driven hydrogen production and carbon dioxide reduction. Inorg. Chem. 55, 8153–8159 (2016).

  112. 112

    Li, L. et al. Effective visible-light driven CO2 photoreduction via a promising bifunctional iridium coordination polymer. Chem. Sci. 5, 3808–3813 (2014).

  113. 113

    Wang, S., Yao, W., Lin, J., Ding, Z. & Wang, X. Cobalt imidazolate metal-organic frameworks photosplit CO2 under mild reaction conditions. Angew. Chem. Int. Ed. 53, 1034–1038 (2014).

  114. 114

    Fei, H., Sampson, M. D., Lee, Y., Kubiak, C. P. & Cohen, S. M. Photocatalytic CO2 reduction to formate using a Mn(I) molecular catalyst in a robust metal-organic framework. Inorg. Chem. 54, 6821–6828 (2015).

  115. 115

    Sun, D. et al. Studies on photocatalytic CO2 reduction over NH2-UiO-66(Zr) and its derivatives: towards a better understanding of photocatalysis on metal-organic frameworks. Chem. Eur. J. 19, 14279–14285 (2013).

  116. 116

    Lee, Y., Kim, S., Kang, J. K. & Cohen, S. M. Photocatalytic CO2 reduction by a mixed metal (Zr/Ti), mixed ligand metal-organic framework under visible light irradiation. Chem. Commun. 51, 5735–5738 (2015).

  117. 117

    Sun, D., Liu, W., Qiu, M., Zhang, Y. & Li, Z. Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal-organic frameworks (MOFs). Chem. Commun. 51, 2056–2059 (2015).

  118. 118

    Chen, D., Xing, H., Wang, C. & Su, Z. Highly efficient visible-light-driven CO2 reduction to formate by a new anthracene-based zirconium MOF via dual catalytic routes. J. Mater. Chem. A 4, 2657–2662 (2016).

  119. 119

    Liu, Y. et al. Chemical adsorption enhanced CO2 capture and photoreduction over a copper porphyrin based metal-organic framework. ACS Appl. Mater. Interfaces 5, 7654–7658 (2013).

  120. 120

    Khaletskaya, K. et al. Fabrication of gold/titania photocatalyst for CO2 reduction based on pyrolytic conversion of the metal-organic framework NH2-MI-125(Ti) loaded with gold nanoparticles. Chem. Mater. 27, 7248–7257 (2015).

  121. 121

    Li, R. et al. Integration of an inorganic semiconductor with a metal-organic framework: a platform for enhanced gaseous photocatalytic reactions. Adv. Mater. 26, 4783–4788 (2014).

  122. 122

    Li, W. in Advances in CO2 Conversion and Utilization (ed. Hu, Y. H. ) 55–76 (American Chemical Society, 2010).

  123. 123

    Hinogami, R. et al. Electrochemical reduction of carbon dioxide using a copper rubeanate metal-organic framework. ECS Electrochem. Lett. 1, H17–H19 (2012).

  124. 124

    Senthil Kumar, R., Senthil Kumar, S. & Anbu Kulandainathan, M. Highly selective eletrochemical reduction of carbon dioxide using Cu-based metal-organic framework as an electrocatalyst. Electrochem. Commun. 25, 70–73 (2012).

  125. 125

    Kornienko, N. et al. Metal-organic frameworks for electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 137, 14129–14135 (2015).

  126. 126

    Hod, I. et al. Fe-porphyrin-based metal-organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2 . ACS Catal. 5, 6302–6309 (2015). This electrocatalytic system makes use of a highly active molecular catalyst as the linker for MOF synthesis. The resulting thin films lead to maximal mass and charge transport for CO2 reduction.

  127. 127

    Rungtaweevoranit, B. et al. Copper nanocrystals encapsulated in Zr-based metal-organic frameworks for highly selective CO2 hydrogenation to methanol. Nano Lett. 16, 7645–7649 (2016). This contribution is the first report of a MOF used for hydrogenation of CO2 to a liquid fuel.

  128. 128

    An, B. et al. Confinement of ultrasmall Cu/ZnOx nanoparticles in metal-organic frameworks for selective methanol synthesis from catalytic hydrogenation of CO2 . J. Am. Chem. Soc. 139, 3834–3840 (2017).

  129. 129

    Aresta, M., Dibenedetto, A. & Angelini, A. Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. Technological use of CO2 . Chem. Rev. 114, 1709–1742 (2014).

  130. 130

    Sakakura, T., Choi, J.-C. & Yasuda, H. Transformation of carbon dioxide. Chem. Rev. 107, 2365–2387 (2007).

  131. 131

    Beyzavi, M. H. et al. Metal-organic framework-based catalysts: chemical fixation of CO2 with epoxides leading to cyclic organic carbonates. Front. Energy Res. 2, 63 (2015).

  132. 132

    He, H., Perman, J. A., Zhu, G. & Ma, S. Metal-organic frameworks for CO2 chemical transformations. Small 12, 6309–6324 (2016).

  133. 133

    Song, J. et al. MOF-5/n-Bu4Br: an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions. Green Chem. 11, 1031–1036 (2009).

  134. 134

    Rayon, U. et al. Engineering of coordination polymers for shape selective alkylation of large aromatics and the role of defects. Microporous Mesoporous Mater. 129, 319–329 (2010).

  135. 135

    Miralda, C. M., Macias, E. E., Zhu, M., Ratnasamy, P. & Carreon, M. A. Zeolitic imidazolate framework-8 catalysts in the conversion of CO2 to chloropropene carbonate. ACS Catal. 2, 180–183 (2012).

  136. 136

    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 185, 35–40 (2012).

  137. 137

    Guillerm, V. et al. Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal-organic frameworks. Nat. Chem. 6, 673–680 (2014).

  138. 138

    Kleist, W., Jutz, F., Maciejewski, M. & Baiker, A. Mixed-linker metal-organic frameworks as catalysts for the synthesis of propylene carbonate from propylene oxide and CO2 . Eur. J. Inorg. Chem. 2009, 3552–3561 (2009).

  139. 139

    Li, P.-Z. et al. A triazole-containing metal-organic framework as a highly effective and substrate size-dependent catalyst for CO2 conversion. J. Am. Chem. Soc. 138, 2142–2145 (2016).

  140. 140

    Jiang, Z.-R., Wang, H., Hu, Y., Lu, J. & Jiang, H.-L. Polar group and defect engineering in a metal-organic framework: synergistic promotion of carbon dioxide sorption and conversion. ChemSusChem 8, 878–885 (2015).

  141. 141

    Senkovska, I. et al. New highly porous aluminium based metal-organic frameworks: Al(OH)(ndc) (ndc = 2,6-naphthalene dicarboxylate) and Al(OH)(bpdc) (bpdc = 4,4′-biphenyl dicarboxylate) Microporous Mesoporous Mater. 122, 93–98 (2009).

  142. 142

    Bloch, E. D. et al. Metal insertion in a microporous metal-organic framework lined with 2,2′-bipyridine. J. Am. Chem. Soc. 132, 14382–14384 (2010).

  143. 143

    Gao, W.-Y. et al. Crystal engineering of an nbo topology metal-organic framework for chemical fixation of CO2 under ambient conditions. Angew. Chem. Int. Ed. 53, 2615–2619 (2014).

  144. 144

    Darensbourg, D. J., Chung, W.-C., Wang, K. & Zhou, H.-C. Sequestering CO2 for short-term storage in MOFs: copolymer synthesis with oxiranes. ACS Catal. 4, 1511–1515 (2014).

  145. 145

    González-Zamora, E. & Ibarra, I. A. CO2 capture under humid conditions in metal-organic frameworks. Mater. Chem. Front. (2017).

  146. 146

    Drisdell, W. S. et al. Probing the mechanism of CO2 capture in diamine-appended metal-organic frameworks using measured and simulated X-ray spectroscopy. Phys. Chem. Chem. Phys. 17, 21448–21457 (2015).

  147. 147

    Queen, W. L. et al. Site-specific CO2 adsorption and zero thermal expansion in an isotropic pore network. J. Phys. Chem. C 115, 24915–24919 (2011).

  148. 148

    Lee, J. S. et al. Understanding small-molecule interactions in metal-organic frameworks: coupling experiment with theory. Adv. Mater. 27, 5785–5796 (2015).

  149. 149

    Schoedel, A., Ji, Z. & Yaghi, O. M. The role of metal-organic frameworks in a carbon-neutral energy cycle. Nat. Energy 1, 16034 (2016).

  150. 150

    Hassan Beyzavi, M. et al. A hafnium-based metal-organic framework as an efficient and multifunctional catalyst for facile CO2 fixation and regioselective and enantioretentive epoxide activation. J. Am. Chem. Soc. 136, 15861–15864 (2014).

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Work related to this topic is funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Energy Frontier Research Center (DE-SC0001015) for adsorption and S. Aramco Carbon Capture and Utilization Chair Program at King Fahd University of Petroleum and Minerals for industrial considerations. The authors acknowledge collaborations with and support of S. Aramco (Project No. ORCP2390). Finally, the authors are grateful to K. Choi for helpful discussions.

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Correspondence to Omar M. Yaghi.

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Trickett, C., Helal, A., Al-Maythalony, B. et al. The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion. Nat Rev Mater 2, 17045 (2017) doi:10.1038/natrevmats.2017.45

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