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A triple tandem reaction for the upcycling of products from poorly selective CO2 photoreduction systems

Nature Synthesis volume 3, pages 406–418 (2024)Cite this article

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Abstract

Low-selective CO2 photoreduction systems are often overlooked in research, because the resulting mixed products are difficult to use in further reactions. In particular, the reutilization of gaseous hybrid products (such as CO and H2), which are often mixed with incompletely converted CO2, is difficult. Here we design and construct two highly active cluster-based catalysts, Ni5W10 and Ni6W10, which can be utilized in an efficient triple tandem reaction composed of low-selective CO2 photoreduction, alkyne semi-hydrogenation and carbonylation reactions. The triple tandem system can sequentially convert the H2 and CO mixture into high-value olefins and carbonyls, with an atomic utilization efficiency of up to 94%. In situ one-pot coupling of low-selective CO2 photoreduction with alkyne semi-hydrogenation promotes the overall photoconversion efficiency (up to 1,425.0 μmol g−1 h−1), CO selectivity (from 50.8% to 80.0%) and alkyne-to-olefin transformation (conversion >86.0%, selectivity ~100.0%). Subsequently, the purified CO can be converted to different types of carbonylated product (CO conversion between 51% and 99%).

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Fig. 1: Schematic of triple tandem.
Fig. 2: Assembly of cluster-based crystal structures.
Fig. 3: One-pot coupling of the semi-hydrogenation of alkynes and photocatalytic CO2RR.
Fig. 4: Mechanism of hydrogenation reaction at different catalytic sites.
Fig. 5: Mechanistic analysis for triple tandem reaction.
Fig. 6: Triple tandem reactions to convert CO2 reduction products.

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Data availability

The data that support the findings of this study are available within the paper and its supplementary information files. The X-ray crystallographic coordinates for structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers CCDC 2215238 (Ni5W10) and 2215237 (Ni6W10). These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (No. 22225109 to Y.-Q.L., 22271104 to J.L., 22201082 to L.Z. and 92061101 to J.L.); the Excellent Youth Foundation of Jiangsu Scientific Committee (BK20211593 to J.L.); and the GuangDong Basic and Applied Basic Research Foundation (No. 2021A1515110429 to L.Z.).

Author information

Authors and Affiliations

  1. School of Chemistry, South China Normal University, Guangzhou, People’s Republic of China

    Yuan-Sheng Xia, Lei Zhang, Long-Zhang Dong, Jiang Liu & Ya-Qian Lan

  2. Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, People’s Republic of China

    Jia-Ni Lu, Xin-Hui Zhao, Jiang Liu & Ya-Qian Lan

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Contributions

Y.-S.X., L.Z. and J.-N.L. contributed equally to this work. Y.-Q.L., J.L. and Y.-S.X. conceived and designed the idea. L.Z. and Y.-S.X. synthesized the Ni cluster-based catalysts. Y.-S.X. and X.-H.Z. conducted the characterizations and designed the tandem catalytic reaction experiments. Y.-S.X., L.Z. and L.-Z.D. assisted with dealing with the data of SCXRD. Y.-Q.L., J.L., J.-N.L. and Y.-S.X. discussed the result and prepared the manuscript. All the authors reviewed and contributed to this paper.

Corresponding authors

Correspondence to Jiang Liu or Ya-Qian Lan.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–61, Tables 1–12 and Notes 1–31, and NMR spectra.

Supplementary Data 1

Crystallographic data for Ni5W10, CCDC 2215238.

Supplementary Data 2

Crystallographic data for Ni6W10, CCDC 2215237.

Supplementary Data 3

DFT modelling of adsorption of different alkyne substrates on Ni6W10 for Supplementary Fig. 56.

Source data

Source Data Fig. 3

One-pot tandem reaction data.

Source Data Table 1

Semi-hydrogenation reaction data.

Source Data Fig. 4

Computational calculations.

Source Data Fig. 6

Triple tandem reaction data.

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Xia, YS., Zhang, L., Lu, JN. et al. A triple tandem reaction for the upcycling of products from poorly selective CO2 photoreduction systems. Nat. Synth 3, 406–418 (2024). https://doi.org/10.1038/s44160-023-00458-5

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