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While prior research focused on tuning the chelating atoms of Ni\u2010centered sites or [\n                    <jats:bold>\n                      NiS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] in metal\u2010organic frameworks (MOFs), how different metal centers affect the electronic structure and catalytic activity is often overlooked. Notably, reported [\n                    <jats:bold>\n                      NiS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] molecular analogues exhibits a Faradaic efficiency (FE) of less than 70% for the major carbon product and shows operational stability for only about 4 hours (say falling FE and current density beyond). In this study, MOFs are used to host [\n                    <jats:bold>\n                      MS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] units with varying central metals (M = Ni, Cu, Co, Fe) to assess how the metal center affects electrocatalytic CO\n                    <jats:sub>2<\/jats:sub>\n                    RR. Among the studied\n                    <jats:bold>\n                      MS\n                      <jats:sub>4<\/jats:sub>\n                      \u2010In\n                    <\/jats:bold>\n                    MOFs,\n                    <jats:bold>\n                      NiS\n                      <jats:sub>4<\/jats:sub>\n                      \u2010In\n                    <\/jats:bold>\n                    demonstrates the best performance, achieving a FE\n                    <jats:sub>CO<\/jats:sub>\n                    of 88.54% and operational stability greater than 6 hours\u2014significantly outlasting the \u2248200 seconds of the [\n                    <jats:bold>\n                      NiS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] molecule. This work underscores the importance of frameworks in stabilizing [\n                    <jats:bold>\n                      MS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] units and highlights [\n                    <jats:bold>\n                      MS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] as essential for CO\n                    <jats:sub>2<\/jats:sub>\n                    binding and reduction, with [\n                    <jats:bold>\n                      NiS\n                      <jats:sub>4<\/jats:sub>\n                    <\/jats:bold>\n                    ] exhibiting optimal catalytic performance due to its favorable electronic properties. This findings clarify how substituting the metal center within the framework enhances electronic structure and coordination, leading to improved electrocatalytic performance.\n                  <\/jats:p>","DOI":"10.1002\/smll.202503299","type":"journal-article","created":{"date-parts":[[2025,5,12]],"date-time":"2025-05-12T04:05:35Z","timestamp":1747022735000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Harnessing Coordination Microenvironment of Metal\u2010bis(dithiolene) Sites for Modulating Electrocatalytic CO\n                    <sub>2<\/sub>\n                    Reduction by Metal\u2010Organic Framework"],"prefix":"10.1002","volume":"21","author":[{"given":"Zhixin","family":"Jiang","sequence":"first","affiliation":[{"name":"School of Chemical Engineering and Light Industry Guangdong University of Technology  Guangzhou Guangdong 510006 P. R. 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