The direct synthesis of hydrogen peroxide over Au and Pd nanoparticles: A DFT study

Nishtha Agarwal; Liam Thomas; Ali Nasrallah; Mala A. Sainna; Simon J. Freakley; Jennifer K. Edwards; C. Richard A. Catlow; Graham J. Hutchings; Stuart H. Taylor; David J. Willock

doi:10.1016/j.cattod.2020.09.001

The direct synthesis of hydrogen peroxide over Au and Pd nanoparticles: A DFT study

Nishtha Agarwal, Liam Thomas, Ali Nasrallah, Mala A. Sainna, Simon J. Freakley, Jennifer K. Edwards, C. Richard A. Catlow, Graham J. Hutchings, Stuart H. Taylor, David J. Willock

Cardiff University

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Abstract

Catalysts consisting of Au, Pd and their alloys have been shown to be active oxidation catalysts. These materials can use dioxygen or hydrogen peroxide as the oxidant with CO and activated organic molecules using O₂(g) while more challenging cases, such as methane to partial oxygenates, relying on H₂O₂. Although H₂O₂ is a green oxidant, the incorporation of dioxygen greatly reduces overall cost and so there is an incentive to find new ways to reduce the reliance on H₂O₂. In this study we use DFT calculations to discuss the direct synthesis of H₂O₂ from H₂(g) and O₂(g) and use this understanding to identify the important surface species derived from dioxygen. We cover the adsorption of oxygen, hydrogen and water to model Au and Pd nanoclusters and the oxidation of the metals, since reduction of any oxides formed will consume H₂. We then turn to the production of a surface hydroperoxy species; the first step in the synthesis of H₂O₂. This can occur via hydrogenation of O₂(ads) with H₂(ads) or via protonation of O₂(ads) by solvent water. Both routes are found to be energetically reasonable, but the latter is likely to be favoured under experimental conditions.

Original language	English
Pages (from-to)	76-85
Number of pages	10
Journal	Catalysis Today
Volume	381
Early online date	10 Sept 2020
DOIs	https://doi.org/10.1016/j.cattod.2020.09.001
Publication status	Published - 1 Dec 2021

Bibliographical note

Funding Information:
We would like to thank the Engineering and Physical Sciences Reasearh Council (EPSRC) for funding this work (Grant reference codes: EP/P033695/1 and EP/L027240/1). via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) and the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194). Information on the data underpinning the results presented here, including how to access them, can be found in the Cardiff University data catalogue at http://doi.org/10.17035/d.2020.0116559060.

Funding Information:
We would like to thank the Engineering and Physical Sciences Reasearh Council (EPSRC) for funding this work (Grant reference codes: EP/P033695/1 and EP/L027240/1 ). via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC ( EP/L000202 , EP/R029431 ), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) and the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC ( EP/P020194 ). Information on the data underpinning the results presented here, including how to access them, can be found in the Cardiff University data catalogue at http://doi.org/10.17035/d.2020.0116559060 .

Publisher Copyright:
© 2020

Funding

We would like to thank the Engineering and Physical Sciences Reasearh Council (EPSRC) for funding this work (Grant reference codes: EP/P033695/1 and EP/L027240/1 ). via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC ( EP/L000202 , EP/R029431 ), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) and the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC ( EP/P020194 ). Information on the data underpinning the results presented here, including how to access them, can be found in the Cardiff University data catalogue at http://doi.org/10.17035/d.2020.0116559060 .

Keywords

Catalysis
DFT calculations
Hydrogenperoxide
Nanoparticles
Oxidation
Reaction scheme

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1016/j.cattod.2020.09.001

Brazil_Catal_Today_16July2020.PDFAccepted author manuscript, 981 KBLicence: CC BY-NC-ND

Cite this

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title = "The direct synthesis of hydrogen peroxide over Au and Pd nanoparticles: A DFT study",

abstract = "Catalysts consisting of Au, Pd and their alloys have been shown to be active oxidation catalysts. These materials can use dioxygen or hydrogen peroxide as the oxidant with CO and activated organic molecules using O2(g) while more challenging cases, such as methane to partial oxygenates, relying on H2O2. Although H2O2 is a green oxidant, the incorporation of dioxygen greatly reduces overall cost and so there is an incentive to find new ways to reduce the reliance on H2O2. In this study we use DFT calculations to discuss the direct synthesis of H2O2 from H2(g) and O2(g) and use this understanding to identify the important surface species derived from dioxygen. We cover the adsorption of oxygen, hydrogen and water to model Au and Pd nanoclusters and the oxidation of the metals, since reduction of any oxides formed will consume H2. We then turn to the production of a surface hydroperoxy species; the first step in the synthesis of H2O2. This can occur via hydrogenation of O2(ads) with H2(ads) or via protonation of O2(ads) by solvent water. Both routes are found to be energetically reasonable, but the latter is likely to be favoured under experimental conditions.",

keywords = "Catalysis, DFT calculations, Hydrogenperoxide, Nanoparticles, Oxidation, Reaction scheme",

author = "Nishtha Agarwal and Liam Thomas and Ali Nasrallah and Sainna, {Mala A.} and Freakley, {Simon J.} and Edwards, {Jennifer K.} and Catlow, {C. Richard A.} and Hutchings, {Graham J.} and Taylor, {Stuart H.} and Willock, {David J.}",

note = "Funding Information: We would like to thank the Engineering and Physical Sciences Reasearh Council (EPSRC) for funding this work (Grant reference codes: EP/P033695/1 and EP/L027240/1). via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) and the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194). Information on the data underpinning the results presented here, including how to access them, can be found in the Cardiff University data catalogue at http://doi.org/10.17035/d.2020.0116559060. Funding Information: We would like to thank the Engineering and Physical Sciences Reasearh Council (EPSRC) for funding this work (Grant reference codes: EP/P033695/1 and EP/L027240/1 ). via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC ( EP/L000202 , EP/R029431 ), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) and the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC ( EP/P020194 ). Information on the data underpinning the results presented here, including how to access them, can be found in the Cardiff University data catalogue at http://doi.org/10.17035/d.2020.0116559060 . Publisher Copyright: {\textcopyright} 2020",

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AU - Thomas, Liam

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AU - Freakley, Simon J.

AU - Edwards, Jennifer K.

AU - Catlow, C. Richard A.

AU - Hutchings, Graham J.

AU - Taylor, Stuart H.

AU - Willock, David J.

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AB - Catalysts consisting of Au, Pd and their alloys have been shown to be active oxidation catalysts. These materials can use dioxygen or hydrogen peroxide as the oxidant with CO and activated organic molecules using O2(g) while more challenging cases, such as methane to partial oxygenates, relying on H2O2. Although H2O2 is a green oxidant, the incorporation of dioxygen greatly reduces overall cost and so there is an incentive to find new ways to reduce the reliance on H2O2. In this study we use DFT calculations to discuss the direct synthesis of H2O2 from H2(g) and O2(g) and use this understanding to identify the important surface species derived from dioxygen. We cover the adsorption of oxygen, hydrogen and water to model Au and Pd nanoclusters and the oxidation of the metals, since reduction of any oxides formed will consume H2. We then turn to the production of a surface hydroperoxy species; the first step in the synthesis of H2O2. This can occur via hydrogenation of O2(ads) with H2(ads) or via protonation of O2(ads) by solvent water. Both routes are found to be energetically reasonable, but the latter is likely to be favoured under experimental conditions.

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The direct synthesis of hydrogen peroxide over Au and Pd nanoparticles: A DFT study

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

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