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<p>Despite utilization of state-of-the-art Cu-based catalysts, achieving high selectivity and stability in multicarbon (C<sub>2+</sub>) compounds production through electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) remains a critical and challenging objective. Here we employ lattice chlorine-doped Cu<sub>2</sub>O nanocubes (Cl<sub>d</sub>-Cu<sub>2</sub>O NCs) with well-defined {100} facets as a model catalyst to demonstrate that halogen doping can serve as a versatile and effective strategy for modulating surface charge distribution, thereby enhancing asymmetric C–C coupling toward high-selectivity C<sub>2+</sub> products in CO<sub>2</sub>RR. Compared to Cl-free Cu<sub>2</sub>O NCs, Cl<sub>d</sub>-Cu<sub>2</sub>O NCs exhibit a greatly enhanced C<sub>2+</sub> Faraday efficiency, i.e., ∼85% at −1.1 V (versus the reversible hydrogen electrode). Additionally, the Cl<sub>d</sub>-Cu<sub>2</sub>O NCs demonstrate significantly enhanced long-term durability, attributed to better preservation of the cubic morphology and more stable <i>Cu</i><sup><i>δ</i>+</sup> states. <i>In-situ</i> electrochemical studies reveal that Cl<sub>d</sub>-Cu<sub>2</sub>O NCs facilitate the formation of the key asymmetric *COH and *OCCOH intermediates, ultimately leading to higher C<sub>2+</sub> products. Density functional theory (DFT) calculations confirm that the introduced Cl-dopants disrupt the charge balance of the Cu<sub>2</sub>O(100) surface, enriching the Cl-adjacent Cu atoms with more electrons compared to those near O atoms. This unbalanced charge distribution significantly reduces the free energy of the rate-determining step for asymmetric C–C coupling from the *CO to *OCCOH on Cl-doped Cu<sub>2</sub>O (100) surface, requiring only 1.04 eV, in contrast to 1.50 eV on pristine Cu<sub>2</sub>O(100) surface. This study provides valuable insights into the surface charge modulation of Cu<sub>2</sub>O catalysts via halogen doping for enhancing asymmetric C–C coupling and C<sub>2+</sub> production in CO<sub>2</sub>RR.</p>

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Tailoring surface charge distribution via lattice Cl-doping on Cu2O nanocubes for high-selectivity CO2-to-C2+ electroreduction via asymmetric C–C coupling

  • 期刊论文

  • 发表日期：

    2025年8月26日

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  • Kai Kang,
  • Qiuxiang Wang,
  • Hongpu Huang,
  • Xinxin Zhuang,
  • Junlin Cai,
  • Tao Wang,
  • Xue Wang,
  • Zhaoxiong Xie,
  • Shuifen Xie

摘要

Despite utilization of state-of-the-art Cu-based catalysts, achieving high selectivity and stability in multicarbon (C2+) compounds production through electrocatalytic CO2 reduction reaction (CO2RR) remains a critical and challenging objective. Here we employ lattice chlorine-doped Cu2O nanocubes (Cld-Cu2O NCs) with well-defined {100} facets as a model catalyst to demonstrate that halogen doping can serve as a versatile and effective strategy for modulating surface charge distribution, thereby enhancing asymmetric C–C coupling toward high-selectivity C2+ products in CO2RR. Compared to Cl-free Cu2O NCs, Cld-Cu2O NCs exhibit a greatly enhanced C2+ Faraday efficiency, i.e., ∼85% at −1.1 V (versus the reversible hydrogen electrode). Additionally, the Cld-Cu2O NCs demonstrate significantly enhanced long-term durability, attributed to better preservation of the cubic morphology and more stable Cuδ+ states. In-situ electrochemical studies reveal that Cld-Cu2O NCs facilitate the formation of the key asymmetric *COH and *OCCOH intermediates, ultimately leading to higher C2+ products. Density functional theory (DFT) calculations confirm that the introduced Cl-dopants disrupt the charge balance of the Cu2O(100) surface, enriching the Cl-adjacent Cu atoms with more electrons compared to those near O atoms. This unbalanced charge distribution significantly reduces the free energy of the rate-determining step for asymmetric C–C coupling from the *CO to *OCCOH on Cl-doped Cu2O (100) surface, requiring only 1.04 eV, in contrast to 1.50 eV on pristine Cu2O(100) surface. This study provides valuable insights into the surface charge modulation of Cu2O catalysts via halogen doping for enhancing asymmetric C–C coupling and C2+ production in CO2RR.