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Herein, rhenium (Re) is atomically dispersed in In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> to fabricate a 2Re\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> photocatalyst. In sacrificial\u2010agent\u2010free photoreduction of CO<jats:sub>2<\/jats:sub> with H<jats:sub>2<\/jats:sub>O, 2Re\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> shows a long\u2010term stable efficiency which is enhanced by 3.5 times than that of pure In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> and is also higher than those on Au\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, Ag\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, Cu\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, Ir\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, Ru\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, Rh\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> and Pt\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> photocatalysts. Moreover, carbon\u2010based product of the photoreduction overturns from CO on pure In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> to CH<jats:sub>3<\/jats:sub>OH on 2Re\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>. Re promotes charge separation, H<jats:sub>2<\/jats:sub>O dissociation and CO<jats:sub>2<\/jats:sub> activation, thus enhancing photoreduction efficiency of CO<jats:sub>2<\/jats:sub> on 2Re\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>. During the photoreduction, CO is a key intermediate. CO prefers to desorption rather than hydrogenation on pure In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, as CO binds to pure In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> very weakly. Re strengthens the interaction of CO with 2Re\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> by 5.0 times, thus limiting CO desorption but enhancing CO hydrogenation to CH<jats:sub>3<\/jats:sub>OH. This could be the origin for photoreduction product overturn from CO on pure In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> to CH<jats:sub>3<\/jats:sub>OH on 2Re\u2010In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>. The present work opens a new way to boost sacrificial\u2010agent\u2010free photoreduction of CO<jats:sub>2<\/jats:sub>.<\/jats:p>","DOI":"10.1002\/anie.202402369","type":"journal-article","created":{"date-parts":[[2024,3,6]],"date-time":"2024-03-06T16:33:41Z","timestamp":1709742821000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":73,"title":["Boosted Sacrificial\u2010Agent\u2010Free Selective Photoreduction of CO<sub>2<\/sub> to CH<sub>3<\/sub>OH by Rhenium Atomically Dispersed on Indium Oxide"],"prefix":"10.1002","volume":"63","author":[{"given":"Chenyang","family":"Shen","sequence":"first","affiliation":[{"name":"School of Chemical Engineering and Technology Tianjin University  Tianjin 300350 P. R. 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