Ethanol conversion on cyclic (MO3)3 (M = Mo, W) clusters

Zhenjun Li; Zongtang Fang; Matthew S. Kelley; Bruce D. Kay; Roger Rousseau; Zdenek Dohnalek; David A. Dixon

doi:10.1021/jp500255f

Ethanol conversion on cyclic (MO₃)₃ (M = Mo, W) clusters

Zhenjun Li, Zongtang Fang, Matthew S. Kelley, Bruce D. Kay, Roger Rousseau, Zdenek Dohnalek, David A. Dixon

Research output: Contribution to journal › Article › peer-review

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Abstract

The reactions of ethanol (CH₃CH₂OD) over cyclic (MO₃)₃ (M = Mo, W) clusters were studied experimentally and computationally. The cyclic clusters were prepared by sublimation of MoO₃ and WO₃ powders in a vacuum. To evaluate the cluster activity in dehydration, dehydrogenation, and condensation reactions, they were suspended in an ethanol matrix on an inert substrate, graphene monolayer on Pt(111). The reaction products formed upon heating were followed and quantified using temperature-programmed desorption. The experimental results were corroborated using coupled cluster CCSD(T) calculations at DFT optimized geometries that provide quantitative molecular-scale information on the reaction mechanisms. The dehydration and dehydrogenation of ethanol probe both the Lewis/Brønsted acid/base and redox properties of the metal centers. The overall conversion of the alcohol is governed by the Lewis acidity of the metal center, and product selectivities, as determined by the relative weights of dehydrogenation and dehydration, are governed by the reducibility of the metal center.

Original language	English
Pages (from-to)	4869-4877
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	118
Issue number	9
DOIs	https://doi.org/10.1021/jp500255f
State	Published - Mar 6 2014
Externally published	Yes

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title = "Ethanol conversion on cyclic (MO3)3 (M = Mo, W) clusters",

abstract = "The reactions of ethanol (CH3CH2OD) over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally and computationally. The cyclic clusters were prepared by sublimation of MoO3 and WO3 powders in a vacuum. To evaluate the cluster activity in dehydration, dehydrogenation, and condensation reactions, they were suspended in an ethanol matrix on an inert substrate, graphene monolayer on Pt(111). The reaction products formed upon heating were followed and quantified using temperature-programmed desorption. The experimental results were corroborated using coupled cluster CCSD(T) calculations at DFT optimized geometries that provide quantitative molecular-scale information on the reaction mechanisms. The dehydration and dehydrogenation of ethanol probe both the Lewis/Br{\o}nsted acid/base and redox properties of the metal centers. The overall conversion of the alcohol is governed by the Lewis acidity of the metal center, and product selectivities, as determined by the relative weights of dehydrogenation and dehydration, are governed by the reducibility of the metal center.",

author = "Zhenjun Li and Zongtang Fang and Kelley, {Matthew S.} and Kay, {Bruce D.} and Roger Rousseau and Zdenek Dohnalek and Dixon, {David A.}",

year = "2014",

month = mar,

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doi = "10.1021/jp500255f",

language = "English",

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TY - JOUR

T1 - Ethanol conversion on cyclic (MO3)3 (M = Mo, W) clusters

AU - Li, Zhenjun

AU - Fang, Zongtang

AU - Kelley, Matthew S.

AU - Kay, Bruce D.

AU - Rousseau, Roger

AU - Dohnalek, Zdenek

AU - Dixon, David A.

PY - 2014/3/6

Y1 - 2014/3/6

N2 - The reactions of ethanol (CH3CH2OD) over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally and computationally. The cyclic clusters were prepared by sublimation of MoO3 and WO3 powders in a vacuum. To evaluate the cluster activity in dehydration, dehydrogenation, and condensation reactions, they were suspended in an ethanol matrix on an inert substrate, graphene monolayer on Pt(111). The reaction products formed upon heating were followed and quantified using temperature-programmed desorption. The experimental results were corroborated using coupled cluster CCSD(T) calculations at DFT optimized geometries that provide quantitative molecular-scale information on the reaction mechanisms. The dehydration and dehydrogenation of ethanol probe both the Lewis/Brønsted acid/base and redox properties of the metal centers. The overall conversion of the alcohol is governed by the Lewis acidity of the metal center, and product selectivities, as determined by the relative weights of dehydrogenation and dehydration, are governed by the reducibility of the metal center.

AB - The reactions of ethanol (CH3CH2OD) over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally and computationally. The cyclic clusters were prepared by sublimation of MoO3 and WO3 powders in a vacuum. To evaluate the cluster activity in dehydration, dehydrogenation, and condensation reactions, they were suspended in an ethanol matrix on an inert substrate, graphene monolayer on Pt(111). The reaction products formed upon heating were followed and quantified using temperature-programmed desorption. The experimental results were corroborated using coupled cluster CCSD(T) calculations at DFT optimized geometries that provide quantitative molecular-scale information on the reaction mechanisms. The dehydration and dehydrogenation of ethanol probe both the Lewis/Brønsted acid/base and redox properties of the metal centers. The overall conversion of the alcohol is governed by the Lewis acidity of the metal center, and product selectivities, as determined by the relative weights of dehydrogenation and dehydration, are governed by the reducibility of the metal center.

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JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 9

ER -

Ethanol conversion on cyclic (MO₃)₃ (M = Mo, W) clusters

Abstract

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