Review Article

The role of metal–organic frameworks in a carbon-neutral energy cycle

  • Nature Energy 1, Article number: 16034 (2016)
  • doi:10.1038/nenergy.2016.34
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Abstract

Reducing society's reliance on fossil fuels presents one of the most pressing energy and environmental challenges facing our planet. Hydrogen, methane and carbon dioxide, which are some of the smallest and simplest molecules known, may lie at the centre of solving this problem through realization of a carbon-neutral energy cycle. Potentially, this could be achieved through the deployment of hydrogen as the fuel of the long term, methane as a transitional fuel, and carbon dioxide capture and sequestration as the urgent response to ongoing climate change. Here we detail strategies and technologies developed to overcome the difficulties encountered in the capture, storage, delivery and conversion of these gas molecules. In particular, we focus on metal–organic frameworks in which metal oxide ‘hubs’ are linked with organic ‘struts’ to make materials of ultrahigh porosity, which provide a basis for addressing this challenge through materials design on the molecular level.

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References

  1. 1.

    BP Statistical Review of World Energy June 2015 (BP, 2015);

  2. 2.

    CO2 Emissions (World Bank, 2015);

  3. 3.

    America's Energy Future: Technology and Transformation: Summary Edition (National Academies Press, 2009); This report provides information on potentials barriers costs and impact of energy supply and technologies.

  4. 4.

    et al. China's Energy and Carbon Emissions Outlook to 2050 (China Energy Group, Lawrence Berkeley National Laboratory, 2011);

  5. 5.

    Lighting the Way: Toward a Sustainable Energy Future (InterAcademy Council, 2007);

  6. 6.

    Basic Research Needs for Carbon Capture: Beyond 2020 (US Department of Energy, 2010);

  7. 7.

    The Impact of Increased Use of Hydrogen on Petroleum Consumption and Carbon Dioxide Emissions (Energy Information Administration, 2008);

  8. 8.

    Basic Research Needs for the Hydrogen Economy (US Department of Energy, 2004);

  9. 9.

    An Overview of Hydrogen Production and Storage Systems with Renewable Hydrogen Case Studies (Clean Energy States Alliance, 2011);

  10. 10.

    & Hydrogen-storage materials for mobile applications. Nature 414, 353–358 (2001).

  11. 11.

    Hydrogen Storage (US Department of Energy, 2015);

  12. 12.

    Target Explanation Document: Onboard Hydrogen Storage for Light-Duty Fuel Cell Vehicles (USDRIVE, 2015);

  13. 13.

    Mercedes-Benz F125 concept: Mercedes' dream of a 2025 S-class takes flight. Car and Driver (21 October 2015);

  14. 14.

    et al. Ford/BASF-SE/UM Activities in Support of the Hydrogen Storage Engineering Center of Excellence (HSECoE, 2015);

  15. 15.

    et al. Enhancing H2 uptake by “close-packing” alignment of open copper sites in metal–organic frameworks. Angew. Chem. Int. Ed. 47, 7263–7266 (2008).

  16. 16.

    , , & Hydrogen storage in metal–organic frameworks. Chem. Rev. 112, 782–835 (2012).

  17. 17.

    & Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal−organic frameworks. J. Am. Chem. Soc. 128, 1304–1315 (2006).

  18. 18.

    & Strategies for hydrogen storage in metal–organic frameworks. Angew. Chem. Int. Ed. 44, 4670–4679 (2005). This paper highlights different strategies for hydrogen storage in MOFs being used today and has led to room temperature uptake of 2–3 wt% and 6 wt% at 77 K.

  19. 19.

    , , , & Post-synthesis alkoxide formation within metal−organic framework materials: a strategy for incorporating highly coordinatively unsaturated metal ions. J. Am. Chem. Soc. 131, 3866–3868 (2009).

  20. 20.

    & Significantly enhanced hydrogen storage in metal−organic frameworks via spillover. J. Am. Chem. Soc. 128, 726–727 (2006).

  21. 21.

    et al. A route to high surface area, porosity and inclusion of large molecules in crystals. Nature 427, 523–527 (2004). This contribution details a strategy and interpretation for using exposed six-membered rings to make ultrahigh-porosity MOFs.

  22. 22.

    , & Independent verification of the saturation hydrogen uptake in MOF-177 and establishment of a benchmark for hydrogen adsorption in metal–organic frameworks. J. Mater. Chem. 17, 3197–3204 (2007).

  23. 23.

    , & Polycatenation, polythreading and polyknotting in coordination network chemistry. Coord. Chem. Rev. 246, 247–289 (2003).

  24. 24.

    et al. Ultrahigh porosity in metal–organic frameworks. Science 329, 424–428 (2010).

  25. 25.

    et al. A new metal–organic framework with ultra-high surface area. Chem. Commun. 50, 3450–3452 (2014).

  26. 26.

    et al. Porous metal−organic polyhedra:25 Å cuboctahedron constructed from 12 Cu2(CO2)4 paddle-wheel building blocks. J. Am. Chem. Soc. 123, 4368–4369 (2001).

  27. 27.

    , , & Nanoballs: nanoscale faceted polyhedra with large windows and cavities. Chem. Commun. 9, 863–864 (2001).

  28. 28.

    et al. Supermolecular building blocks (SBBs) for the design and synthesis of highly porous metal–organic frameworks. J. Am. Chem. Soc. 130, 1833–1835 (2008). This contribution provided the foundation for a large class of isoreticular MOFs with high H2 adsorption.

  29. 29.

    et al. Metal−organic polyhedral frameworks: high H2 adsorption capacities and neutron powder diffraction studies. J. Am. Chem. Soc. 132, 4092–4094 (2010).

  30. 30.

    , , & 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).

  31. 31.

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

  32. 32.

    et al. Designing higher surface area metal–organic frameworks: are triple bonds better than phenyls?. J. Am. Chem. Soc. 134, 9860–9863 (2012).

  33. 33.

    et al. Metal–organic framework materials with ultrahigh surface areas: is the sky the limit?. J. Am. Chem. Soc. 134, 15016–15021 (2012). This paper reports a MOF that currently holds the world record with respect to BET surface area.

  34. 34.

    & Programmed pore architectures in modular quaternary metal–organic frameworks. J. Am. Chem. Soc. 135, 17731–17734 (2013).

  35. 35.

    , , , & A family of porous lonsdaleite-e networks obtained through pillaring of decorated kagomé lattice sheets. J. Am. Chem. Soc. 135, 14016–14019 (2013).

  36. 36.

    et al. The asc trinodal platform: two-step assembly of triangular, tetrahedral, and trigonal-prismatic molecular building blocks. Angew. Chem. Int. Ed. 52, 2902–2905 (2013).

  37. 37.

    , & Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal–organic frameworks. J. Phys. Chem. B 110, 9565–9570 (2006).

  38. 38.

    & Understanding hydrogen adsorption in metal–organic frameworks with open metal sites: a computational study. J. Phys. Chem. B 110, 655–658 (2006).

  39. 39.

    , & Selective gas adsorption in a magnesium-based metal–organic framework. Chem. Commun. 36, 5436–5438 (2009).

  40. 40.

    & Optimal isosteric heat of adsorption for hydrogen storage and delivery using metal–organic frameworks. Micropor. Mesopor. Mater. 132, 300–303 (2010).

  41. 41.

    , , & Review on processing of metal–organic framework (MOF) materials towards system integration for hydrogen storage. Int. J. Energy Res. 39, 607–620 (2015).

  42. 42.

    MOVE Program Overview (ARPA-E, 2012);

  43. 43.

    et al. Methane storage in metal–organic frameworks: current records, surprise findings, and challenges. J. Am. Chem. Soc. 135, 11887–11894 (2013).

  44. 44.

    et al. The materials genome in action: identifying the performance limits for methane storage. Energy Environ. Sci. 8, 1190–1199 (2015).

  45. 45.

    et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002). This publication describes use of the isoreticular principle in making MOFs and designing their interior for methane storage.

  46. 46.

    , , & Design and synthesis of an exceptionally stable and highly porous metal–organic framework. Nature 402, 276–279 (1999). This contribution revealed the first MOF with porosity and surface area exceeding previous records and featuring a robust architecture.

  47. 47.

    , , & A new, methane adsorbent, porous coordination polymer [{CuSiF6(4,4′-bipyridine)2}n]. Angew. Chem. Int. Ed. 39, 2081–2084 (2000).

  48. 48.

    , , , & A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n. Science 283, 1148–1150 (1999).

  49. 49.

    , , & High methane storage capacity in aluminum metal–organic frameworks. J. Am. Chem. Soc. 136, 5271–5274 (2014). This paper shows that the availability of polyphenylene units as terminal ligands in MOFs provides for ultrahigh methane delivery.

  50. 50.

    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).

  51. 51.

    et al. Gram-scale, high-yield synthesis of a robust metal–organic framework for storing methane and other gases. Energy Environ. Sci. 6, 1158–1163 (2013).

  52. 52.

    , & High-capacity methane storage in metal−organic frameworks M2(dhtp): the important role of open metal sites. J. Am. Chem. Soc. 131, 4995–5000 (2009).

  53. 53.

    et al. Large-scale screening of hypothetical metal–organic frameworks. Nature Chem. 4, 83–89 (2012).

  54. 54.

    et al. High-resolution carbon dioxide concentration record 650,000–800,000 years before present. Nature 453, 379–382 (2008).

  55. 55.

    Atmospheric CO2 Data (Scripps Institution of Oceanography, 2015);

  56. 56.

    Stabilization Wedges and the Polygame (2013);

  57. 57.

    & Stabilization wedges: solving the climate problem for the next 50 years with current technologies. Science 305, 968–972 (2004).

  58. 58.

    CO2 capture and storage: are we ready? Energy Environ. Sci. 2, 449–458 (2009).

  59. 59.

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

  60. 60.

    , & Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. J. Am. Chem. Soc. 130, 10870–10871 (2008).

  61. 61.

    et al. Rod packings and metal−organic frameworks constructed from rod-shaped secondary building units. J. Am. Chem. Soc. 127, 1504–1518 (2005).

  62. 62.

    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).

  63. 63.

    et al. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495, 80–84 (2013). This publication shows a crystal engineering strategy to control pore funtionality and size in MOFs for CO2 separation in the presence of water.

  64. 64.

    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).

  65. 65.

    & Photochemical removal of mercury from flue gas. Ind. Eng. Chem. Res. 41, 5470–5476 (2002).

  66. 66.

    , , , & From the cover: 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).

  67. 67.

    , , , & Progress in adsorption-based CO2 capture by metal–organic frameworks. Chem. Soc. Rev. 41, 2308–2322 (2012).

  68. 68.

    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). This paper demonstrates a method for covalently functionalizing the interior of MOFs to capture CO2 in the presence of water.

  69. 69.

    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).

  70. 70.

    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).

  71. 71.

    et al. Direct observation and quantification of CO2 binding within an amine-functionalized nanoporous solid. Science 330, 650–653 (2010).

  72. 72.

    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).

  73. 73.

    et al. Cooperative insertion of CO2 in diamine-appended metal–organic frameworks. Nature 519, 303–308 (2015).

  74. 74.

    et al. Large-pore apertures in a series of metal–organic frameworks. Science 336, 1018–1023 (2012).

  75. 75.

    et al. Microporous metal–organic framework with potential for carbon dioxide capture at ambient conditions. Nature Commun. 3, 954 (2012).

  76. 76.

    et al. Porous materials with pre-designed single-molecule traps for CO2 selective adsorption. Nature Commun. 4, 1538 (2013).

  77. 77.

    , , , & Evaluating metal–organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption. Energy Environ. Sci. 4, 3030–3040 (2011).

  78. 78.

    & Comparative molecular simulation study of CO2/N2 and CH4/N2 Separation in zeolites and metal−organic frameworks. Langmuir 25, 5918–5926 (2009).

  79. 79.

    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).

  80. 80.

    & Towards rapid computational screening of metal–organic frameworks for carbon dioxide capture: calculation of framework charges via charge equilibration. Chem. Eng. J. 171, 775–781 (2011).

  81. 81.

    & The interaction of water with MOF-5 simulated by molecular dynamics. J. Am. Chem. Soc. 128, 10678–10679 (2006).

  82. 82.

    et al. Multiple functional groups of varying ratios in metal–organic frameworks. Science 327, 846–850 (2010).

  83. 83.

    , & “Heterogeneity within order” in metal–organic frameworks. Angew. Chem. Int. Ed. 54, 3417–3430 (2015).

  84. 84.

    , & Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques. J. Am. Chem. Soc. 131, 16589–16605 (2009).

  85. 85.

    et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).

  86. 86.

    & Storage of hydrogen, methane, and carbon dioxide in highly porous covalent organic frameworks for clean energy applications. J. Am. Chem. Soc. 131, 8875–8883 (2009).

  87. 87.

    & Metal–organic frameworks for artificial photosynthesis and photocatalysis. Chem. Soc. Rev. 43, 5982–5993 (2014).

  88. 88.

    , , & Photocatalytic CO2 reduction in metal–organic frameworks: a mini review. J. Mol. Struct. 1083, 127–136 (2015).

  89. 89.

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

  90. 90.

    , , & Doping metal–organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. J. Am. Chem. Soc. 133, 13445–13454 (2011).

  91. 91.

    et al. Construction of ultrastable porphyrin Zr metal–organic frameworks through linker elimination. J. Am. Chem. Soc. 135, 17105–17110 (2013).

  92. 92.

    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).

  93. 93.

    et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).

  94. 94.

    , , , & A highly porous metal–organic framework: structural transformations of a guest-free MOF depending on activation method and temperature. Chem. Eur. J. 17, 7251–7260 (2011).

  95. 95.

    et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).

  96. 96.

    et al. Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal−organic carboxylate frameworks. Acc. Chem. Res. 34, 319–330 (2001).

  97. 97.

    , , & The chemistry and applications of metal–organic frameworks. Science 341, 1230444 (2013).

  98. 98.

    , & Selective binding and removal of guests in a microporous metal–organic framework. Nature 378, 703–706 (1995).

  99. 99.

    Amine scrubbing for CO2 capture. Science 325, 1652–1654 (2009).

  100. 100.

    Carbon capture and storage: how green can black be?. Science 325, 1647–1652 (2009).

  101. 101.

    , , & Adsorption of CO2 on molecular sieves and activated carbon. Energy Fuels 15, 279–284 (2001).

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Acknowledgements

Funding of MOF research in the Yaghi group is supported by BASF SE (Ludwigshafen, Germany), US Department of Defense, Defense Threat Reduction Agency (HDTRA 1-12-1-0053), US Department of Energy, Office of Science, Office of Basic Energy Sciences, Energy Frontier Research Center grant (DE-SC0001015), and King Abdulaziz City of Science and Technology (KACST). A.S. gratefully acknowledges the German Research Foundation (DFG, SCHO 1639/1-1) for financial support. The authors would like to thank A. Fracaroli for help with collating data on carbon dioxide capture in the presence of water, L. Ding (Delft University of Technology) for producing Fig. 1 graphics, and Ahmad S. Alshammari for helpful discussions.

Author information

Affiliations

  1. Department of Chemistry, University of California, Berkeley, California 94720, USA.

    • Alexander Schoedel
    • , Zhe Ji
    •  & Omar M. Yaghi
  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.

    • Alexander Schoedel
    • , Zhe Ji
    •  & Omar M. Yaghi
  3. Kavli Energy Nanoscience Institute, University of California, Berkeley, California 94720, USA.

    • Alexander Schoedel
    • , Zhe Ji
    •  & Omar M. Yaghi
  4. King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia.

    • Omar M. Yaghi

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Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Omar M. Yaghi.

Supplementary information

Excel files

  1. 1.

    Supplementary Data 1

    Table of metal–organic frameworks showing Brunauer–Emmett–Teller surface area versus CO2 uptake at 298 K and 1 bar.