Article

Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation

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Abstract

Hydrogenation of CO2 into fuels and useful chemicals could help to reduce reliance on fossil fuels. Although great progress has been made over the past decades to improve the activity of catalysts for CO2 hydrogenation, more efficient catalysts, especially those based on non-noble metals, are desired. Here we incorporate N atoms into Co nanosheets to boost the catalytic activity toward CO2 hydrogenation. For the hydrogenation of CO2, Co4N nanosheets exhibited a turnover frequency of 25.6 h−1 in a slurry reactor under 32 bar pressure at 150 °C, which was 64 times that of Co nanosheets. The activation energy for Co4N nanosheets was 43.3 kJ mol−1, less than half of that for Co nanosheets. Mechanistic studies revealed that Co4N nanosheets were reconstructed into Co4NH x , wherein the amido-hydrogen atoms directly interacted with the CO2 to form HCOO* intermediates. In addition, the adsorbed H2O* activated amido-hydrogen atoms via the interaction of hydrogen bonds.

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Acknowledgements

This work was supported by the Collaborative Innovation Center of Suzhou Nano Science and Technology, MOST of China (2014CB932700), NSFC (21573206 and 51371164), Key Research Program of Frontier Sciences of the CAS (QYZDB-SSW-SLH017), Anhui Provincial Key Scientific and Technological Project (1704a0902013), and Fundamental Research Funds for the Central Universities.

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Author notes

  1. Liangbing Wang, Wenbo Zhang and Xusheng Zheng contributed equally to this work.

Affiliations

  1. Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, 230026, China

    • Liangbing Wang
    • , Wenbo Zhang
    • , Xusheng Zheng
    • , Yizhen Chen
    • , Wenlong Wu
    • , Jianxiang Qiu
    • , Xiangchen Zhao
    • , Xiao Zhao
    • , Yizhou Dai
    •  & Jie Zeng

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Contributions

L.W., W.Z. and X. Zheng equally contributed to this work. L.W. and J.Z. designed the studies and wrote the paper. L.W., W.Z., and Y.C. synthesized catalysts. L.W., W.Z., W.W. and J.Q. performed catalytic tests. L.W., Xiangchen Zhao, Xiao Zhao and Y.D. conducted in situ DRIFT, XRD, solid-state D-NMR and isotope measurements. L.W. and Xus.Z. conducted quasi in situ XPS measurements. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jie Zeng.

Electronic supplementary material

  1. Supplementary Information

    Supplementary Figures 1–28, Supplementary Tables 1 and 2