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The hydrogen spillover effect. A misunderstanding story

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CATALYSIS REVIEWS-SCIENCE AND ENGINEERING
卷 64, 期 1, 页码 87-125

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TAYLOR & FRANCIS INC
DOI: 10.1080/01614940.2020.1787771

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Hydrogen spillover; hydroxyls; nonreducible oxides; supported metal catalysts; hydroconversion reactions; hydrogen storage

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The controversial hydrogen spillover effect on metal catalysts supported on non-reducible oxides is caused by a misunderstanding of pioneer works. Hydroxyl groups on the oxide surface play a crucial role in the formation and reactivity of hydrogen spillover. The spillover process involves H/OH pairs that diffuse over the support through a thermodynamically neutral mechanism, contrary to the commonly believed hopping process.
The hydrogen spillover effect (HSPE) on metal catalysts supported on non-reducible oxides is still controversial. Our investigation shows that the controversy comes from a misunderstanding about statements of pioneer works. Papers accepting or rejecting the HSPE and based on these statements were found both not pertinent. Factually, the oxide surface OH groups play an important role in the formation, extent, and reactivity of hydrogen spillover. We propose that hydrogen spillover would consist in H/OH pairs, produced by an interfacial dehydroxylation then diffusing over the support by a thermodynamically neutral H/OH exchange mechanism and not by an H atom hopping process, as generally believed. The hydrogen atoms of the H/OH pairs may be consumed chemically or desorb as H-2, giving rise to & x25a1;/O(2-)pairs (where & x25a1; denotes an oxygen vacancy) which, in turn, may further dissociate H-2, renewing the H/OH active sites. H/OH and & x25a1;/O(2)constitute conjugated pairs in the hydrogen spillover effect.

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