Planar chlorination engineering induced symmetry-broken single-atom site catalyst for enhanced CO<sub>2</sub> electroreduction.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39952945.
- Also identified by DOI 10.1038/s41467-025-56271-5 and PMC identifier 11829013.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
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.