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<p>In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al<sub>2</sub>O<sub>3</sub>-Cu<sub>SAC</sub>, CeO<sub>2</sub>-Cu<sub>SAC</sub>, and TiO<sub>2</sub>-Cu<sub>SAC</sub>) are used as theoretical models to explore the correlations between electronic structures and CO<sub>2</sub>RR 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 3<i>d</i><sub><i>yz</i></sub> orbital of Al<sub>2</sub>O<sub>3</sub>-Cu<sub>SAC</sub> enhances the adsorption strength of CO and weakens C-O bonds through 3<i>d</i><sub><i>yz</i></sub>-π* electron back-donation. This reduces the energy barrier for C-C coupling, thereby promoting multicarbon formation on Al<sub>2</sub>O<sub>3</sub>-Cu<sub>SAC</sub>. The highest occupied 3<i>d</i><sub><i>z2</i></sub> orbital of TiO<sub>2</sub>-Cu<sub>SAC</sub> accelerates the H<sub>2</sub>O activation, and lowers the reaction energy for forming CH<sub>4</sub>. This over activated H<sub>2</sub>O, in turn, intensifies competing hydrogen evolution reaction (HER), which hinders the high-selectivity production of CH<sub>4</sub> on TiO<sub>2</sub>-Cu<sub>SAC</sub>. CeO<sub>2</sub>-Cu<sub>SAC</sub> with highest occupied 3<i>d</i><sub><i>x2-y2</i></sub> orbital promotes CO<sub>2</sub> activation and its localized electronic state inhibits C-C coupling. The moderate water activity of CeO<sub>2</sub>-Cu<sub>SAC</sub> facilitates *CO deep hydrogenation without excessively activating HER. Hence, CeO<sub>2</sub>-Cu<sub>SAC</sub> exhibits the highest CH<sub>4</sub> Faradaic efficiency of 70.3% at 400 mA cm<sup>−2</sup>.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年2月25日

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  • 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

摘要

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.