Abstract
Acceptorless dehydrogenation into carbonyls and molecular hydrogen is an attractive strategy to valorize (biobased) alcohols. Using 2-octanol dehydrogenation as benchmark reaction in a continuous reactor, a library of metal-supported catalysts is tested to validate the predictive level of catalytic activity for combined DFT and micro-kinetic modeling. Based on a series of transition metals, scaling relations are determined as a function of two descriptors, i.e. the surface binding energies of atomic carbon and oxygen. Then, a volcano-shape relation based on both descriptors is derived, paving the way to further optimization of active catalysts. Evaluation of 294 diluted alloys but also a series of carbides and nitrides with the volcano map identified 12 promising candidates with potentially improved activity for alcohol dehydrogenation, which provides useful guidance for experimental catalyst design. Further screening identifies β-Mo2N and γ-Mo2N exposing mostly (001) and (100) facets as potential candidates for alcohol dehydrogenation.
Highlights
Acceptorless dehydrogenation into carbonyls and molecular hydrogen is an attractive strategy to valorize alcohols
Acceptorless dehydrogenation reactions are less thermodynamically favored than oxidation reactions[10], they limit the risk of over-oxidation to the carboxylic acid[11]
Successful catalysts for acceptorless alcohol dehydrogenation into carbonyl compounds rely on Ru11,15 Ir16–18 and Os19 complexes
Summary
Acceptorless dehydrogenation into carbonyls and molecular hydrogen is an attractive strategy to valorize (biobased) alcohols. Validation of theoretically predicted activity trend by experimental 2-octanol dehydrogenation: Evaluating directly the agreement between micro-kinetic modeling and experimental results will provide validation of the theoretically identified activity trends of metals for CH3OH dehydrogenation shown, which is essential for rational catalyst screening.
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