Solar-light-driven reduction of CO2-to-CH4 is a complex process involving multiple elementary reactions and various by-products. Achieving high CH4 activity and selectivity therefore remain a significant challenge. Here we show a bioinspired photocatalyst with flexible dual-metal-site pairs (DMSPs), which exhibit dynamic self-adaptive behaviour to fit mutative C1 intermediates, achieving CO2-to-CH4 photoreduction. The Cu and Ni DMSPs in their respective single-site forms under flexible microenvironment are incorporated into a metal-organic framework (MOF) to afford MOF-808-CuNi. This dramatically boosts CH4 selectivity up to 99.4% (electron basis) and 97.5% (product basis), and results in a high production rate of 158.7 μmol g−1 h−1 with a sacrificial reagent. Density functional theory calculations reveal that the flexible self-adaptive DMSPs can stabilize various C1 intermediates in multistep elementary reactions, leading to highly selective CO2-to-CH4 process. This work demonstrates that efficient and selective heterogeneous catalytic processes can be achieved by stabilizing reaction intermediates via the self-adaptive DMSP mechanism.
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McDonald, T. M. et al. Cooperative insertion of CO2 in diamine-appended metal-organic frameworks. Nature 519, 303–308 (2015).
Leung, J. J. et al. Solar-driven reduction of aqueous CO2 with a cobalt bis(terpyridine)-based photocathode. Nat. Catal. 2, 354–365 (2019).
Rao, H., Schmidt, L. C., Bonin, J. & Robert, M. Visible-light-driven methane formation from CO2 with a molecular iron catalyst. Nature 548, 74–77 (2017).
Wu, Y. A. et al. Facet-dependent active sites of a single Cu2O particle photocatalyst for CO2 reduction to methanol. Nat. Energy 4, 957–968 (2019).
Ding, M., Flaig, R. W., Jiang, H. L. & Yaghi, O. M. Carbon capture and conversion using metal-organic frameworks and MOF-based materials. Chem. Soc. Rev. 48, 2783–2828 (2019).
Appel, A. M. et al. Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation. Chem. Rev. 113, 6621–6658 (2013).
Liu, X., Inagaki, S. & Gong, J. Heterogeneous molecular systems for photocatalytic CO2 reduction with water oxidation. Angew. Chem. Int. Ed. 55, 14924–14950 (2016).
Ji, Y. & Luo, Y. Theoretical study on the mechanism of photoreduction of CO2 to CH4 on the anatase TiO2(101) surface. ACS Catal. 6, 2018–2025 (2016).
Fu, Y. 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).
Li, D., Kassymova, M., Cai, X., Zang, S.-Q. & Jiang, H.-L. Photocatalytic CO2 reduction over metal-organic framework-based materials. Coord. Chem. Rev. 412, 213262 (2020).
White, J. L. et al. Light-driven heterogeneous reduction of carbon dioxide: photocatalysts and photoelectrodes. Chem. Rev. 115, 12888–12935 (2015).
Wang, L. et al. Surface strategies for catalytic CO2 reduction: from two-dimensional materials to nanoclusters to single atoms. Chem. Soc. Rev. 48, 5310–5349 (2019).
Li, X., Yu, J., Jaroniec, M. & Chen, X. Cocatalysts for selective photoreduction of CO2 into solar fuels. Chem. Rev. 119, 3962–4179 (2019).
Corma, A. & Garcia, H. Photocatalytic reduction of CO2 for fuel production: possibilities and challenges. J. Catal. 308, 168–175 (2013).
Varghese, O. K., Paulose, M., LaTempa, T. J. & Grimes, C. A. High-rate solar photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels. Nano Lett. 9, 731–737 (2009).
Guo, Z. et al. Selectivity control of CO versus HCOO− production in the visible-light-driven catalytic reduction of CO2 with two cooperative metal sites. Nat. Catal. 2, 801–808 (2019).
Wang, Y. et al. Visible-light driven overall conversion of CO2 and H2O to CH4 and O2 on 3D-SiC@2D-MoS2 heterostructure. J. Am. Chem. Soc. 140, 14595–14598 (2018).
Li, X. et al. Selective visible-light-driven photocatalytic CO2 reduction to CH4 mediated by atomically thin CuIn5S8 layers. Nat. Energy 4, 690–699 (2019).
Long, R. et al. Isolation of Cu atoms in Pd lattice: forming highly selective sites for photocatalytic conversion of CO2 to CH4. J. Am. Chem. Soc. 139, 4486–4492 (2017).
Zhao, Y. et al. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation. Proc. Natl Acad. Sci. USA 115, 2902–2907 (2018).
Wang, J.-W., Zhong, D.-C. & Lu, T.-B. Artificial photosynthesis: catalytic water oxidation and CO2 reduction by dinuclear non-noble-metal molecular catalysts. Coord. Chem. Rev. 377, 225–236 (2018).
Jiao, J. et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2. Nat. Chem. 11, 222–228 (2019).
Li, H. et al. Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation. Nat. Nanotechnol. 13, 411–417 (2018).
Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013).
Zhou, H. C. & Kitagawa, S. Metal-organic frameworks (MOFs). Chem. Soc. Rev. 43, 5415–5418 (2014).
Li, B. et al. Emerging multifunctional metal-organic framework materials. Adv. Mater. 28, 8819–8860 (2016).
Li, G., Zhao, S., Zhang, Y. & Tang, Z. Metal-organic frameworks encapsulating active nanoparticles as emerging composites for catalysis: recent progress and perspectives. Adv. Mater. 30, e1800702 (2018).
Islamoglu, T. et al. Postsynthetic tuning of metal-organic frameworks for targeted applications. Acc. Chem. Res. 50, 805–813 (2017).
Jiao, L., Wang, J. & Jiang, H.-L. Microenvironment modulation in metal-organic framework-based catalysis. Acc. Mater. Res. 2, 327–339 (2021).
Medford, A. J. et al. From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis. J. Catal. 328, 36–42 (2015).
Guo, X. et al. Tackling the activity and selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via atomically dispersed biatom catalysts. J. Am. Chem. Soc. 142, 5709–5721 (2020).
Benkovic, S. J. & Hammes-Schiffer, S. A perspective on enzyme catalysis. Science 301, 1196–1202 (2003).
Baek, J. et al. Bioinspired metal-organic framework catalysts for selective methane oxidation to methanol. J. Am. Chem. Soc. 140, 18208–18216 (2018).
Kuhn, H. J., Braslavsky, S. E. & Schmidt, R. Chemical actinometry (IUPAC Technical Report). Pure Appl. Chem. 76, 2105–2146 (2004).
Zhang, H. et al. Efficient visible-light-driven carbon dioxide reduction by a single-atom implanted metal-organic framework. Angew. Chem. Int. Ed. 55, 14310–14314 (2016).
Yang, F. et al. Tuning internal strain in metal–organic frameworks via vapor phase infiltration for CO2 reduction. Angew. Chem. Int. Ed. 132, 4602–4610 (2020).
Qin, J.-S. et al. Creating well-defined hexabenzocoronene in zirconium metal–organic framework by postsynthetic annulation. J. Am. Chem. Soc. 141, 2054–2060 (2019).
Mahmoud, M. E., Audi, H., Assoud, A., Ghaddar, T. H. & Hmadeh, M. Metal-organic framework photocatalyst incorporating bis(4′-(4-carboxyphenyl)-terpyridine)ruthenium(ii) for visible-light-driven carbon dioxide reduction. J. Am. Chem. Soc. 141, 7115–7121 (2019).
An, B. et al. Molecular iridium complexes in metal–organic frameworks catalyze CO2 hydrogenation via concerted proton and hydride transfer. J. Am. Chem. Soc. 139, 17747–17750 (2017).
Xu, H.-Q. et al. Visible-light photoreduction of CO2 in a metal–organic framework: boosting electron–hole separation via electron trap states. J. Am. Chem. Soc. 137, 13440–13443 (2015).
Chen, X. et al. MOFs conferred with transient metal centers for enhanced photocatalytic activity. Angew. Chem. Int. Ed. 59, 17182–17186 (2020).
Hartmann, M., Azuma, N. & Kevan, L. Electron spin resonance and electron spin echo modulation study of Ni(i) in silicoaluminophosphate type 5: adsorbate interactions and evidence for the framework incorporation of Ni(i). J. Phys. Chem. 99, 10988–10994 (1995).
Li, N. et al. Toward high-value hydrocarbon generation by photocatalytic reduction of CO2 in water vapor. ACS Catal. 9, 5590–5602 (2019).
Neatu, S., Macia-Agullo, J. A., Concepcion, P. & Garcia, H. Gold-copper nanoalloys supported on TiO2 as photocatalysts for CO2 reduction by water. J. Am. Chem. Soc. 136, 15969–15976 (2014).
Yates, J. T. & Cavanagh, R. R. Search for chemisorbed HCO: the interaction of formaldehyde, glyoxal, and atomic hydrogen + CO with Rh. J. Catal. 74, 97–109 (1982).
Koshland, D. E. Jr. & Neet, K. E. The catalytic and regulatory properties of enzymes. Annu. Rev. Biochem. 37, 359–410 (1968).
Peng, Y. et al. A versatile MOF-based trap for heavy metal ion capture and dispersion. Nat. Commun. 9, 187 (2018).
Furukawa, H. et al. Water adsorption in porous metal-organic frameworks and related materials. J. Am. Chem. Soc. 136, 4369–4381 (2014).
Jrad, A., Abu Tarboush, B. J., Hmadeh, M. & Ahmad, M. Tuning acidity in zirconium-based metal organic frameworks catalysts for enhanced production of butyl butyrate. Appl. Catal. A Gen. 570, 31–41 (2019).
VandeVondele, J. et al. Quickstep: fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput. Phys. Commun. 167, 103–128 (2005).
Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).
Nie, X., Esopi, M. R., Janik, M. J. & Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: the role of the kinetics of elementary steps. Angew. Chem. Int. Ed. 125, 2519–2522 (2013).
Krack, M. & Parrinello, M. All-electron ab-initio molecular dynamics. Phys. Chem. Chem. Phys. 2, 2105–2112 (2000).
Capdevila-Cortada, M. & Lopez, N. Entropic contributions enhance polarity compensation for CeO2(100) surfaces. Nat. Mater. 16, 328–334 (2017).
Clayborne, A., Chun, H. J., Rankin, R. B. & Greeley, J. Elucidation of pathways for NO electroreduction on Pt(111) from first principles. Angew. Chem. Int. Ed. 127, 8373–8376 (2015).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B. 108, 17886–17892 (2004).
Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J. & Nørskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3, 1311–1315 (2010).
Ling, C., Niu, X., Li, Q., Du, A. & Wang, J. Metal-free single atom catalyst for N2 fixation driven by visible light. J. Am. Chem. Soc. 140, 14161–14168 (2018).
Mills, G., Jdnsson, H. & Schenter, G. K. Reversible work transition state theory: application to dissociative adsorption of hydrogen. Surf. Sci. 324, 305–337 (1995).
Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
This work was financially supported by the National Key Projects for Fundamental Research and Development of China (grant no. 2016YFB0600901 C.Z.), National Natural Science Foundation of China (grant nos. 22038010 to C.Z., 21978212 to H.H., 21725101 to H.L.J., 22161142001 to H.L.J., 91961119 to D.M. and 21521001 to H.L.J.) and the Science and Technology Plans of Tianjin (grant nos. 18PTSYJC00180 C.Z. and 19PTSYJC00020 H.H.). We thank the 1W1B station for X-ray absorption fine structure measurements at BSRF and Testing Centre of Tiangong University for providing some analytical tests.
The authors declare no competing interests.
Peer review information Nature Catalysis thanks Julien Bonin, Mohamad Hmadeh and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Figs. 1–46, Tables 1–15 and Notes 1–12.
Video 1 AIMD simulations.
Data 1 Atomic coordinates of the initial and final configurations of the trajectories in AIMD simulations.
Data 2 Coordinates for electronic structure.
TEM observations and structural characterization of MOF-808-CuNi.
Photocatalytic CO2 reduction performance.
Charge transfer in CO2 photoreduction over MOF-808-CuNi.
Detection of the reaction mechanism for the photoreduction of CO2 to CH4.
Self-adaptive Cu and Ni sites for the selective photoreduction of CO2 to CH4.
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Li, J., Huang, H., Xue, W. et al. Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4. Nat Catal 4, 719–729 (2021). https://doi.org/10.1038/s41929-021-00665-3
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