Ni‐Electrocatalytic CO 2 Reduction Toward Ethanol

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Abstract
The electroreduction of CO 2 offers a sustainable route to generate synthetic fuels. Cu‐based catalysts have been developed to produce value‐added C 2+ alcohols; however, the limited understanding of complex C−C coupling and reaction pathway hinders the development of efficient CO 2 ‐to‐C 2+ alcohols catalysts. Herein, a Cu‐free, highly mesoporous NiO catalyst, derived from the microphase separation of a block copolymer, is reported, which achieves selective CO 2 reduction toward ethanol with a Faradaic efficiency of 75.2% at −0.6 V versus RHE. The dense mesopores create a favorable local reaction environment with CO 2 ‐rich and H 2 O‐deficient interfaces, suppressing hydrogen evolution and maximizing catalytic activity of NiO for CO 2 reduction. Importantly, the C 1 ‐feeding experiments, in situ spectroscopy, and theoretical calculations consistently show that the direct coupling of *CO 2 and *COOH is responsible for C−C bond formation on NiO, and subsequent reduction of *CO 2 ‐COOH to ethanol is energetically facile through the *COCOH and *OC 2 H 5 pathway. The unconventional C−C coupling mechanism on NiO, in contrast to the *CO dimerization on Cu, is triggered by strong CO 2 adsorption on the polarized Ni 2+ ‐O 2− sites. The work not only demonstrates a highly selective Cu‐free Ni‐based alternative for CO 2 ‐to‐C 2+ alcohols transformation but also provides a new perspective on C−C coupling toward C 2+ synthesis.
Funding Information
  • National Natural Science Foundation of China (22309146)
  • National Natural Science Foundation of China (2207119)
  • National Natural Science Foundation of China (52272238)
  • Key Research and Development Projects of Shaanxi Province (2024GX‐YBXM‐418)
  • Key Research and Development Projects of Shaanxi Province (2023‐YBGY‐425)
  • Natural Science Foundation of Shaanxi Province (2022‐JM‐097)
  • Natural Science Foundation of Chongqing Municipality (CSTB2023NSCQ‐MSX0429)

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