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Issue 9, 2014
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A mechanism of gas-phase alcohol oxidation at the interface of Au nanoparticles and a MgCuCr2O4 spinel support

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Abstract

The catalytic oxidation of bio-ethanol to acetaldehyde entails a promising route for valorization of biomass into many important chemicals that are currently mainly being produced from fossil-based ethylene feedstock. We employ here DFT calculations to understand the unprecedented synergy between gold clusters and a MgCuCr2O4 spinel support, which shows excellent catalytic performance for the oxidation of ethanol to acetaldehyde (space-time yield of 311 gacetaldehyde ggold−1 h−1 at 250 °C). The investigations support a mechanism involving catalytic reactions at the gold–support interface. Dissociative adsorption of ethanol is facilitated by cooperative action of a gold atom at the metal cluster–support interface and a basic oxygen atom of the support. The most difficult step is the recombinative desorption of water from the surface. The oxygen vacancy formation energy is found to be a good performance descriptor for ethanol oxidation of Au/MgMeCr2O4 (Me = Cu, Ni, Co) catalysts. The high selectivity towards acetaldehyde stems from the facile desorption of acetaldehyde as compared to the cleavage of the remaining α-C–H bond in the product. The opposite holds for methanol oxidation, explaining why experimentally we observe complete methanol oxidation over Au/MgCuCr2O4 under conditions where ethanol is selectively converted to acetaldehyde.

Graphical abstract: A mechanism of gas-phase alcohol oxidation at the interface of Au nanoparticles and a MgCuCr2O4 spinel support

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Publication details

The article was received on 11 Apr 2014, accepted on 22 May 2014 and first published on 23 May 2014


Article type: Paper
DOI: 10.1039/C4CY00462K
Catal. Sci. Technol., 2014,4, 2997-3003
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    A mechanism of gas-phase alcohol oxidation at the interface of Au nanoparticles and a MgCuCr2O4 spinel support

    W. Song, P. Liu and E. J. M. Hensen, Catal. Sci. Technol., 2014, 4, 2997
    DOI: 10.1039/C4CY00462K

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