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Photocatalytic and electrocatalytic CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction reactions (CO\n                    <jats:sub>2<\/jats:sub>\n                    RRs) offer a promising route to valorize CO\n                    <jats:sub>2<\/jats:sub>\n                    into energy\u2010rich fuels and chemical feedstocks, yet the intrinsic thermodynamic and kinetic barriers necessitate catalysts that combine high activity, selectivity, and durability. Recent breakthroughs in materials chemistry have spotlighted two emerging material classes\u2014atomically precise metal nanoclusters (NCs) and extended reticular frameworks such as metal\u2013organic frameworks (MOFs) and covalent organic frameworks (COFs)\u2014as frontiers for next\u2010generation CO\n                    <jats:sub>2<\/jats:sub>\n                    RR catalysts. Both systems offer unparalleled opportunities to engineer active sites at the atomic and molecular levels, enabling precise modulation of local environments, electronic structures, and substrate interactions. This review brings these two materials paradigms under a common vision of precision\u2010controlled catalysis, highlighting how innovations in cluster size, framework topology, and chemical functionality dictate product selectivity and C\u2500C coupling behavior. We discuss emerging mechanistic insights, synthetic strategies, and structure\u2013function relationships and outline challenges in conductivity, stability, and scalability. Finally, we propose integrated design principles to guide the development of hybrid platforms for efficient and selective CO\n                    <jats:sub>2<\/jats:sub>\n                    valorization.\n                  <\/jats:p>","DOI":"10.1002\/anie.202515667","type":"journal-article","created":{"date-parts":[[2025,9,25]],"date-time":"2025-09-25T10:02:22Z","timestamp":1758794542000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Materials Innovation and the Changing Face of Photocatalytic and Electrocatalytic Carbon Dioxide Reduction Research: From Metal Nanoclusters to Extended Frameworks"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5253-3341","authenticated-orcid":false,"given":"Tsukasa","family":"Irie","sequence":"first","affiliation":[{"name":"Institute of Multidisciplinary Research for Advanced Materials Tohoku University  2\u20101\u20101 Katahira Aoba\u2010ku 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