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Although comparable catalytic performances have been observed for metal carbides in several types of reactions, precise control of reaction pathways on them remains a formidable challenge, partially due to strong adsorption of reactants or intermediates. In this study, we show that bimolecular dehydrogenation of methanol to methyl formate and H<jats:sub>2<\/jats:sub> is kinetically favored on bare <jats:italic>\u03b1<\/jats:italic>\u2010MoC catalysts, while monomolecular dehydrogenation to CO and H<jats:sub>2<\/jats:sub> becomes the dominant pathway when <jats:italic>\u03b1<\/jats:italic>\u2010MoC is decorated with crowding atomic Ni species. Under optimal conditions, excellent selectivities of the target products (&gt;90\u2009%) were achieved in both cases, with unprecedented production rates of methyl formate and H<jats:sub>2<\/jats:sub> for the former and latter mechanisms, respectively. Kinetic, spectroscopic, and computational assessments were integrated to clarify the mechanism driving this remarkable selectivity inversion. Isolated Ni sites bound to <jats:italic>\u03b1<\/jats:italic>\u2010MoC exhibit superior dehydrogenation activity, which promotes complete cleavage of C\u2212H bonds in methanol\u2010derived intermediates rather than the C\u2212O coupling between them. Our study offers an effective approach to modulating the selectivity of carbide\u2010based catalysts in alcohol dehydrogenation towards different target products.<\/jats:p>","DOI":"10.1002\/anie.202423682","type":"journal-article","created":{"date-parts":[[2024,12,30]],"date-time":"2024-12-30T11:30:12Z","timestamp":1735558212000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Inverting Methanol Dehydrogenation Selectivity by Crowding Atomic Ni Species over <i>\u03b1<\/i>\u2010MoC Catalysts"],"prefix":"10.1002","volume":"64","author":[{"given":"Yuzhen","family":"Ge","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences, N ew Corner-Stone Science Laboratory College of Chemistry and Molecular Engineering Peking University  Beijing 100871 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