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Understanding the fundamental features of CO\n                    <jats:sub>2<\/jats:sub>\n                    activation and hydrogenation at the molecular level is essential for carbon utilization and sustainable chemical production in the current climate crisis. This review explores the recent advances in understanding the design of catalysts with desired active sites, including single\u2010atom, dual\u2010atom, interface, defects\/vacancies and promoters\/dopants. We focused on the design of various catalytic systems to enhance their catalytic performances by stabilizing active metal in a catalyst, identifying the unique structure of active species, and engineering coordination environments of active sites. Mechanistic insights provided by advanced operando and in\u2005situ spectroscopies were also discussed. 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