Cooperative copper centres in a metal–organic framework for selective conversion of CO2 to ethanol

Abstract

Selective conversion of CO2 to ethanol is of great interest but presents a significant challenge in forming a C–C bond while keeping a C–O bond intact throughout the process. Here, we report cooperative CuI sites on a Zr12 cluster of a metal–organic framework (MOF) for selective hydrogenation of CO2 to ethanol. With the assistance of an alkali cation, the spatially proximate Zr12-supported CuI centres activate hydrogen via bimetallic oxidative addition and promote C–C coupling to produce ethanol. The Cs+-modified MOF catalyst, in 10 hours, produces ethanol with >99% selectivity and a turnover number (based on all Cu atoms) of 4,080 in supercritical CO2, with 30 MPa of CO2 and 5 MPa of H2 at 85 °C, or a turnover number of 490 at 2 MPa of CO2/H2 (1/3) and 100 °C. Our work highlights the potential of using MOFs as a tunable platform to design earth-abundant metal catalysts for CO2 conversion.

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Fig. 1: Schematic showing Cu supported on ZrO2 and Zr12-SBU in a MOF for CO2 hydrogenation.
Fig. 2: Synthesis and structures of Zr12-bpdc and Zr12-bpdc-CuLi catalysts.
Fig. 3: Characterization of alkali metal-modified Zr12-bpdc-Cu catalysts.
Fig. 4: Catalytic performance in CO2 hydrogenation.
Fig. 5: Isotope labelling experiments.
Fig. 6: Proposed mechanism of methanol and ethanol synthesis from CO2 hydrogenation over Zr12-bpdc-Cu catalysts.

Data availability

All the data that support the findings of this study are available within the paper and its Supplementary Information files, or from the corresponding author on reasonable request.

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Acknowledgements

The authors thank C. Wang and Z. Lin for advice on isotopic mass-spectrometric analysis, K. Cheng and J. Lei (from Xiamen HanDe Engineering Co.) for experimental and equipment help, P. Ji for XAFS data collection and Q. Li for 3Li NMR tests. The authors acknowledge funding support from the Ministry of Science and Technology of China (2016YFA0200702) and the National Natural Science Foundation of China (21671162, 21471126 and 21721001). XAS analysis was performed at Beamline 10-BM of the Advanced Photon Source (APS), Argonne National Laboratory (ANL). Use of the APS, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under contract no. DE-AC02-06CH11357.

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B.A., C.W. and W.L. conceived and designed the project. B.A., Z.L., Y.S. and J.Z. carried out the synthesis of the materials, characterized the materials and analysed the data. B.A. performed the high-throughput catalysis with the help of L.Z., while Z.L. performed the theoretical calculations. B.A. and Z.L. performed the experiments investigating the catalytic cycle, under the supervision of C.W. All authors discussed the results and commented on the manuscript. B.A., Z.L., C.W. and W.L. wrote the manuscript.

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Correspondence to Cheng Wang.

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Supplementary methods, Supplementary Figs. 1–58, Supplementary Tables 1–11, Supplementary Notes 1-3, Supplementary references

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An, B., Li, Z., Song, Y. et al. Cooperative copper centres in a metal–organic framework for selective conversion of CO2 to ethanol. Nat Catal 2, 709–717 (2019). https://doi.org/10.1038/s41929-019-0308-5

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