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More effort should be paid to understand the complicated correlation between the nature of supports and hydrogenation involving hydrogen spillover. Herein, we report the development of the hydrogenation system of hexagonal boron nitride (h\u2010BN)\u2010supported Pd nanoparticles for the hydrogenation of aldehydes\/ketones to alcohols with hydrogen spillover. Nitrogen vacancies in h\u2010BN determine the feasibility of hydrogen spillover from Pd to h\u2010BN. The hydrogenation of aldehydes\/ketones with hydrogen spillover from Pd proceeds on nitrogen vacancies on h\u2010BN. The weak adsorption of alcohols to h\u2010BN inhibits the deep hydrogenation of aldehydes\/ketones, thus leading to high catalytic selectivity to alcohols. Moreover, the hydrogen spillover\u2010based hydrogenation mechanism makes the catalyst system exhibit a high tolerance to CO poisoning.<\/jats:p>","DOI":"10.1002\/anie.202217191","type":"journal-article","created":{"date-parts":[[2022,12,27]],"date-time":"2022-12-27T10:05:14Z","timestamp":1672135514000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":53,"title":["Heterogeneous Hydrogenation with Hydrogen Spillover Enabled by Nitrogen Vacancies on Boron Nitride\u2010Supported Pd Nanoparticles"],"prefix":"10.1002","volume":"62","author":[{"given":"Yazhou","family":"Zhang","sequence":"first","affiliation":[{"name":"State Key Laboratory for Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials National &amp; Local Joint Engineering Research Center of Preparation Technology of Nanomaterials College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 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