Bifunctional Synergy in CO Hydrogenation to Methanol with Supported Cu

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Abstract

Abstract: Future energy storage could be distributed at local plants and involve production of methanol from reaction of sustainably derived hydrogen with CO or CO2 from locally available carbon sources. Such decentralized production would benefit from milder operating conditions than found in the current large-scale industrial process. We propose that a route via CO hydrogenation deserves consideration for this purpose, as it will be free of water, which is unavoidable from CO2-containing gas and strongly inhibiting to the methanol synthesis at lower temperatures. On pure Cu the rate of methanol synthesis from CO is an order of magnitude lower than the rate from CO2, but active CO hydrogenation catalysts can emerge from a bifunctional mechanism in catalysts that combine copper with a basic oxide. Mechanistic studies are consistent with the bifunctional Cu/support synergy arising from a mechanism, where basic oxide sites activate CO as formates at the metal/oxide interface followed by metal assisted hydrogenation of the interfacial formates. Active catalysts for CO hydrogenation are strongly inhibited by CO2, which forms carbonates that block the basic oxide sites and thereby prevent the synergistic pathway from CO.
Original languageEnglish
JournalCatalysis Letters
Number of pages7
ISSN1011-372X
DOIs
Publication statusAccepted/In press - 2019

Cite this

@article{32fe6f49469c471f800e5215e5fc370f,
title = "Bifunctional Synergy in CO Hydrogenation to Methanol with Supported Cu",
abstract = "Abstract: Future energy storage could be distributed at local plants and involve production of methanol from reaction of sustainably derived hydrogen with CO or CO2 from locally available carbon sources. Such decentralized production would benefit from milder operating conditions than found in the current large-scale industrial process. We propose that a route via CO hydrogenation deserves consideration for this purpose, as it will be free of water, which is unavoidable from CO2-containing gas and strongly inhibiting to the methanol synthesis at lower temperatures. On pure Cu the rate of methanol synthesis from CO is an order of magnitude lower than the rate from CO2, but active CO hydrogenation catalysts can emerge from a bifunctional mechanism in catalysts that combine copper with a basic oxide. Mechanistic studies are consistent with the bifunctional Cu/support synergy arising from a mechanism, where basic oxide sites activate CO as formates at the metal/oxide interface followed by metal assisted hydrogenation of the interfacial formates. Active catalysts for CO hydrogenation are strongly inhibited by CO2, which forms carbonates that block the basic oxide sites and thereby prevent the synergistic pathway from CO.",
author = "Nielsen, {Niels Dyreborg} and Joachim Thrane and Jensen, {Anker Degn} and Christensen, {Jakob Munkholt}",
year = "2019",
doi = "10.1007/s10562-019-03036-7",
language = "English",
journal = "Catalysis Letters",
issn = "1011-372X",
publisher = "Springer New York",

}

TY - JOUR

T1 - Bifunctional Synergy in CO Hydrogenation to Methanol with Supported Cu

AU - Nielsen, Niels Dyreborg

AU - Thrane, Joachim

AU - Jensen, Anker Degn

AU - Christensen, Jakob Munkholt

PY - 2019

Y1 - 2019

N2 - Abstract: Future energy storage could be distributed at local plants and involve production of methanol from reaction of sustainably derived hydrogen with CO or CO2 from locally available carbon sources. Such decentralized production would benefit from milder operating conditions than found in the current large-scale industrial process. We propose that a route via CO hydrogenation deserves consideration for this purpose, as it will be free of water, which is unavoidable from CO2-containing gas and strongly inhibiting to the methanol synthesis at lower temperatures. On pure Cu the rate of methanol synthesis from CO is an order of magnitude lower than the rate from CO2, but active CO hydrogenation catalysts can emerge from a bifunctional mechanism in catalysts that combine copper with a basic oxide. Mechanistic studies are consistent with the bifunctional Cu/support synergy arising from a mechanism, where basic oxide sites activate CO as formates at the metal/oxide interface followed by metal assisted hydrogenation of the interfacial formates. Active catalysts for CO hydrogenation are strongly inhibited by CO2, which forms carbonates that block the basic oxide sites and thereby prevent the synergistic pathway from CO.

AB - Abstract: Future energy storage could be distributed at local plants and involve production of methanol from reaction of sustainably derived hydrogen with CO or CO2 from locally available carbon sources. Such decentralized production would benefit from milder operating conditions than found in the current large-scale industrial process. We propose that a route via CO hydrogenation deserves consideration for this purpose, as it will be free of water, which is unavoidable from CO2-containing gas and strongly inhibiting to the methanol synthesis at lower temperatures. On pure Cu the rate of methanol synthesis from CO is an order of magnitude lower than the rate from CO2, but active CO hydrogenation catalysts can emerge from a bifunctional mechanism in catalysts that combine copper with a basic oxide. Mechanistic studies are consistent with the bifunctional Cu/support synergy arising from a mechanism, where basic oxide sites activate CO as formates at the metal/oxide interface followed by metal assisted hydrogenation of the interfacial formates. Active catalysts for CO hydrogenation are strongly inhibited by CO2, which forms carbonates that block the basic oxide sites and thereby prevent the synergistic pathway from CO.

U2 - 10.1007/s10562-019-03036-7

DO - 10.1007/s10562-019-03036-7

M3 - Journal article

JO - Catalysis Letters

JF - Catalysis Letters

SN - 1011-372X

ER -