Planar chlorination engineering induced symmetry-broken single-atom site catalyst for enhanced CO2 electroreduction
Breaking the geometric symmetry of traditional metal-N<sub>4</sub> sites and further boosting catalytic activity are significant but challenging. Herein, planar chlorination engineering is proposed for successfully converting the traditional Zn-N<sub>4</sub> site with low activity and selectivity for CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) into highly active Zn-N<sub>3</sub> site with broken symmetry. The optimal catalyst Zn-SA/CNCl-1000 displays a highest faradaic efficiency for CO (FE<sub>CO</sub>) around 97 ± 3% and good stability during 50 h test at high current density of 200 mA/cm<sup>2</sup> in zero-gap membrane electrode assembly (MEA) electrolyzer, with promising application in industrial catalysis. At -0.93 V vs. RHE, the partial current density of CO (J<sub>CO</sub>) and the turnover frequency (TOF) value catalyzed by Zn-SA/CNCl-1000 are 271.7 ± 1.4 mA/cm<sup>2</sup> and 29325 ± 151 h<sup>-1</sup>, as high as 29 times and 83 times those of Zn-SA/CN-1000 without planar chlorination engineering. The in-situ extended X-ray absorption fine structure (EXAFS) measurements and density functional theory (DFT) calculation reveal the adjacent C-Cl bond induces the self-reconstruction of Zn-N<sub>4</sub> site into the highly active Zn-N<sub>3</sub> sites with broken symmetry, strengthening the adsorption of <sup>*</sup>COOH intermediate, and thus remarkably improving CO<sub>2</sub>RR activity.
Authors
- Shengjie Wei (ORCID: https://orcid.org/0000-0002-7336-0985)
- Liqiang Mai (ORCID: https://orcid.org/0000-0003-4259-7725)
- Jiexin Zhu (ORCID: https://orcid.org/0000-0003-1629-240X)
- Shenghua Chen (ORCID: https://orcid.org/0000-0002-0898-5292)
- Ching‐Yu Chiang (ORCID: https://orcid.org/0000-0002-3640-0474)
- Xingbao Chen
- Lei Li (ORCID: https://orcid.org/0000-0003-1963-5033)
- Rongyan Yang
- Kevin Gu (ORCID: https://orcid.org/0000-0001-9613-2179)
Institutions
- University of Science and Technology of China (CN)
- Wuhan University of Technology (CN)
- Nankai University (CN)
- Beijing University of Technology (CN)
- National Synchrotron Radiation Research Center (TW)
- Hefei National Center for Physical Sciences at Nanoscale (CN)
- Xi'an Jiaotong University (CN)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-02-15
- DOI
- https://doi.org/10.1038/s41467-025-56271-5
- Citations
- 43
- Primary Topic
- CO2 Reduction Techniques and Catalysts
- Type
- article
- Field-Weighted Citation Impact
- 15.63
Funders
- National Natural Science Foundation of China
- China Postdoctoral Science Foundation
- Natural Science Foundation of Hubei Province
- University of Science and Technology of China
- National Synchrotron Radiation Research Center
- Natural Science Foundation of Anhui Province
- National Postdoctoral Program for Innovative Talents
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities
- Beijing Synchrotron Radiation Facility