Catalytic transfer hydrogenolysis, using liquid H‐donors in the absence of pressurized H2 under mild temperatures, is regarded as the most important technology to substitute traditional hydrogenation processes in industry. Despite decade development with several breakthroughs in catalyst design, the reaction mechanism involved in H2 generation and subsequent hydrogenolysis reactions is still under debate. In this review, transfer hydrogenolysis of glycerol, as a representative example, on metallic catalysts is revised critically with respect to surface reaction mechanism and catalyst design. The detailed reaction pathways for propanol, methanol, formic acid and ethanol for H2 generation have been discussed systematically. In particular, reaction mechanism for catalytic C−H cleavage, H spillover/transfer and C−O cleavage reaction steps will be critically revised with experimental and theoretical results in literature. Insights into reaction pathways, mechanism and H2 transfer efficiency and structure‐performance relation for Pd, Cu and Ni catalysts will be provided for future development of catalyst manufacture and process development. The outcome of this work is useful for successful implementation of bio‐refinery.
Catalytic
dehydrogenation–oxidation of bio-oxygenates to
carboxylic acids and green H2 has been considered a key
technology for biorefineries. Composition, size, and morphology are
critical parameters for solid catalysts. However, the synergism of
surface/lattice oxygen in inexpensive metal oxide catalysts is largely
unexplored in this area. In this work, a systematic study on the surface/lattice
oxygen synergism of crystallized CuO catalysts has been performed
using glycerol dehydrogenation as an example. The key finding is that
surface oxygen contributes to enhanced C–H bond activation,
while lattice oxygen is key for tandem dehydrogenation–oxidation
reactions. Thus, the crystallized CuO catalysts display a 2-fold enhancement
in activity and 7-fold improvement in the durability of CuO catalysts,
leading to almost 93% reduction of Cu leaching with negligible deactivation.
The methodology discussed in this work will provide insights into
the rational design of cost-effective CuO materials for other important
aqueous dehydrogenation reactions in the chemical industry.
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