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Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products

Author

Listed:
  • Yong Zhang

    (Nankai University)

  • Feifei Chen

    (Nankai University)

  • Xinyi Yang

    (Nankai University)

  • Yiran Guo

    (Nankai University)

  • Xinghua Zhang

    (Hebei University of Technology)

  • Hong Dong

    (Nankai University)

  • Weihua Wang

    (Nankai University)

  • Feng Lu

    (Nankai University)

  • Zunming Lu

    (Hebei University of Technology)

  • Hui Liu

    (Tianjin University)

  • Hui Liu

    (Nankai University)

  • Yao Xiao

    (Wenzhou University)

  • Yahui Cheng

    (Nankai University)

Abstract

In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore the correlations between electronic structures and CO2RR performances. For these catalysts, the electronic metal-support interaction (EMSI) induced by charge transfer between Cu sites and supports subtly modulates the Cu electronic structure to form different highest occupied-orbital. The highest occupied 3dyz orbital of Al2O3-CuSAC enhances the adsorption strength of CO and weakens C-O bonds through 3dyz-π* electron back-donation. This reduces the energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. The highest occupied 3dz2 orbital of TiO2-CuSAC accelerates the H2O activation, and lowers the reaction energy for forming CH4. This over activated H2O, in turn, intensifies competing hydrogen evolution reaction (HER), which hinders the high-selectivity production of CH4 on TiO2-CuSAC. CeO2-CuSAC with highest occupied 3dx2-y2 orbital promotes CO2 activation and its localized electronic state inhibits C-C coupling. The moderate water activity of CeO2-CuSAC facilitates *CO deep hydrogenation without excessively activating HER. Hence, CeO2-CuSAC exhibits the highest CH4 Faradaic efficiency of 70.3% at 400 mA cm−2.

Suggested Citation

  • Yong Zhang & Feifei Chen & Xinyi Yang & Yiran Guo & Xinghua Zhang & Hong Dong & Weihua Wang & Feng Lu & Zunming Lu & Hui Liu & Hui Liu & Yao Xiao & Yahui Cheng, 2025. "Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products," Nature Communications, Nature, vol. 16(1), pages 1-12, December.
  • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57307-6
    DOI: 10.1038/s41467-025-57307-6
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