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

Nature Energy volume 2, pages 869–876 (2017)Cite this article

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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.

Hydrogenation of CO2 into fuels such as methane, methanol and gasoline as well as useful chemicals could help to reduce the reliance on fossil fuels. The chemical transformation of CO2 has been achieved in industry by using heterogeneous Cu/ZnO/Al2O3 catalysts, which require high pressure (50–100 bar) and elevated temperature (200–300 °C) because of the chemical inertness of CO2 (refs 1,2,3,4). During the past decades, a vast variety of strategies have been developed to boost the catalytic activity toward CO2 hydrogenation5,6,7,8. A typical strategy to improve the catalytic performance in CO2 hydrogenation is based on the modification of surface electronic properties such as negative charge density, d-band centre and electronic polarization by engineering the arrangement and composition of surface atoms9,10,11,12,13,14. For instance, the accumulation of negative charges on the active sites induced by fabricating sharp tips and alloying with non-noble metal in Pt3Co octapods promoted the activation of CO2 and accordingly enhanced the catalytic activity for CO2 hydrogenation9. Besides, shifting up the d-band centre in RhW nanosheets strengthened the adsorption of CO2, contributing to the enhanced activity for CO2 hydrogenation10. Moreover, the electronic polarization at the interface between Au and a CeO x /TiO2 substrate was reported to generate active centres for CO2 adsorption11. In addition, constructing highly active metal/oxide interfaces such as Cu/CeO x and Cu/ZnO interfaces has been emerging to increase the activity for CO2 hydrogenation15,16,17,18,19,20,21. Furthermore, a descriptor-based analysis using theoretical calculations also offered an effective method to scrutinize optimal catalysts22,23. Although great progress has been achieved in improving the catalytic activity, highly efficient catalysts, especially for non-noble metal catalysts, for CO2 hydrogenation are still urgently desired.

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Fig. 1: Structural characterization of Co4N nanosheets.
Fig. 2: Catalytic performance of Co4N in the hydrogenation of CO2.
Fig. 3: The formation of Co4NH x from Co4N under H2 atmosphere.
Fig. 4: Mechanistic studies of the catalytic activity of Co4N nanosheets in CO2 hydrogenation.

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

Authors and 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.

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Correspondence to Jie Zeng.

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Wang, L., Zhang, W., Zheng, X. et al. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation. Nat Energy 2, 869–876 (2017). https://doi.org/10.1038/s41560-017-0015-x

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