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Article Abstract

Metal single-atom catalysts (SACs) with near-100% metal utilization and flexible coordination environments are promising candidates for electrochemical chlorine evolution reaction (CER) to produce valuable Cl-a key raw material for plastics manufacturing, water treatment, and pharmaceuticals. However, it remains challenging to assess specific coordination environments for structure-activity relationships and monitor their dynamic structural evolution under catalytic reaction conditions. Herein, operando X-ray absorption fine structure (XAFS) revealed distinct dynamic structural evolution on the low-coordinated Pt site, compared to the conventional PtN site. Specifically, the low-coordinated Pt site transformed into an asymmetry PtNCl structure upon exposure to a Cl-containing solution, transiently evolved to PtNCl intermediate at low overpotentials, and reverted to PtNCl after CER. By overcoming the limitation of *Cl intermediate coverage on PtN SAC, the low-coordinated Pt SAC displayed superior CER performance to commercial RuO and PtN benchmarks. This work provides new insights into the rational design of coordination geometry in SACs for electrocatalysis.

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http://dx.doi.org/10.1002/anie.202513656DOI Listing

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