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The CO<jats:sub>2<\/jats:sub>\/CoTIB (1.0\u2005mg)\/Ru(bpy)<jats:sub>3<\/jats:sub>Cl<jats:sub>2<\/jats:sub> (bpy=2,2\u2019\u2010bipyridine) (11.3\u2005mg)\/CH<jats:sub>3<\/jats:sub>CN (40\u2005mL)\/TEOA (10\u2005mL)\/H<jats:sub>2<\/jats:sub>O (400\u2005\u03bcL) system produced 76.9\u2005\u03bcmol of CO in 9\u2005h, corresponding to the efficiency of 9.4\u2005mmol\u2009g<jats:sup>\u22121<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup> (TOF: 7.3\u2005h<jats:sup>\u22121<\/jats:sup>) with a &gt;99% selectivity. Its catalytic activity is even higher than that of ZIF\u201067 based on TOF values. However, CoTIB is non\u2010porous and has a very poor CO<jats:sub>2<\/jats:sub> adsorption capacity and poor conductivity. Extensive photocatalytic experiments and energy\u2010level diagrams suggest that the reduction did not depend on the CO<jats:sub>2<\/jats:sub> adsorption by the cocatalyst, but can occur by the direct electron transfer from conduction\u2010band maximum (CBM) of the cocatalyst to the zwitterionic alkylcarbonate adduct formed by the reaction of TEOA and CO<jats:sub>2<\/jats:sub>. In addition, the process utilizes the short\u2010lived singlet state (<jats:sup>1<\/jats:sup>MLCT), not the long\u2010lived triplet state (<jats:sup>3<\/jats:sup>MLCT) of Ru(bpy)<jats:sub>3<\/jats:sub>Cl<jats:sub>2<\/jats:sub> to transfer electrons to the CBM of CoTIB. We found that the high efficiency of a cocatalyst, a photosensitizer, or a photocatalytic system depends on the matching of all related energy levels of the photosensitizer, the cocatalyst, CO<jats:sub>2<\/jats:sub>, and the sacrificial agent in the reaction system.<\/jats:p>","DOI":"10.1002\/asia.202300297","type":"journal-article","created":{"date-parts":[[2023,6,12]],"date-time":"2023-06-12T02:01:16Z","timestamp":1686535276000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Highly Efficient and Selective Visible\u2010light Photocatalytic CO<sub>2<\/sub> Reduction to CO Using a 2D Co(II)\u2010Imidazole MOF as Cocatalyst and Ru(bpy)<sub>3<\/sub>Cl<sub>2<\/sub> as Photosensitizer"],"prefix":"10.1002","volume":"18","author":[{"given":"Lin","family":"Wang","sequence":"first","affiliation":[{"name":"Jiangsu Key Laboratory of New Power Batteries Jiangsu Collaborative Innovation Center of Biomedical Functional 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