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Zirconia species are considered to be an essential support in Cu\u2010based catalysts due to their excellent properties for CO<jats:sub>2<\/jats:sub> adsorption and activation. However, the evolution of Zr species during the reaction and the effect of their structure on the reaction pathways remain unclear. Herein, single\u2010site Zr species in an amorphous SiO<jats:sub>2<\/jats:sub> matrix are created by enhancing the Zr\u2212Si interaction in Cu\/ZrO<jats:sub>2<\/jats:sub>\u2010SiO<jats:sub>2<\/jats:sub> catalysts. In situ X\u2010ray absorption spectroscopy (XAS) reveals that the coordination environment of single\u2010site Zr is sensitive to the atmosphere and reaction conditions. We demonstrate that the CO<jats:sub>2<\/jats:sub> adsorption occurs preferably on the interface of Cu and single\u2010site Zr rather than on ZrO<jats:sub>2<\/jats:sub> nanoparticles. Methanol synthesis in reverse water\u2010gas\u2010shift (RWGS)+CO\u2010hydro pathway is verified only over single\u2010dispersed Zr sites, whereas the ordinary formate pathway occurs on ZrO<jats:sub>2<\/jats:sub> nanoparticles. Thus, it expands a non\u2010competitive parallel pathway as a supplement to the dominant formate pathway, resulting in the enhancement of Cu activity sixfold and twofold based on Cu\/SiO<jats:sub>2<\/jats:sub> and Cu\/ZrO<jats:sub>2<\/jats:sub> catalysts, respectively. The establishment of this dual\u2010channel pathway by single\u2010site Zr species in this work opens new horizons for understanding the role of atomically dispersed oxides in catalysis science.<\/jats:p>","DOI":"10.1002\/anie.202312292","type":"journal-article","created":{"date-parts":[[2023,11,7]],"date-time":"2023-11-07T04:14:38Z","timestamp":1699330478000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":62,"title":["Unlocking a Dual\u2010Channel Pathway in CO<sub>2<\/sub> Hydrogenation to Methanol over Single\u2010Site Zirconium on Amorphous Silica"],"prefix":"10.1002","volume":"63","author":[{"given":"Meng","family":"Yang","sequence":"first","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Zhongshan Road 457 116023 Dalian China"},{"name":"University of Chinese Academy of Sciences  100049 Beijing 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