A DFT study of molecular adsorption on titania-supported AuRh nanoalloys

Ilker Demiroglu; Ziyou Li; Laurent Piccolo; Roy L. Johnston

doi:10.1016/j.comptc.2017.02.012

A DFT study of molecular adsorption on titania-supported AuRh nanoalloys

Ilker Demiroglu, Ziyou Li, Laurent Piccolo, Roy L. Johnston^*

^*Corresponding author for this work

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

12 Citations (Scopus)

215 Downloads (Pure)

Abstract

AuRh/TiO₂ nanocatalysts have proved their efficiency in several catalytic reactions. In this work, density functional theory calculations are performed to investigate the effect of the TiO₂ support on the structures of fcc 38-atom and 79-atom AuRh nanoalloys and their adsorption properties towards the reactant molecules CO and O₂. d-band centre analysis shows that the d-band model captures the trends better for both larger and supported alloy clusters due to reduced mechanical effects. Calculations reveal metal-to-support electron transfer, depending mainly on which metal atoms lie at the interface with the support. The adsorption strengths of CO and O₂ molecules on experimentally-relevant Janus segregated structures are slightly lower than on pure Rh clusters, which may reduce poisoning effects, while maintaining the high reactivity of Rh. In addition, higher adsorption energies are predicted for the less stable Au_coreRh_shell structure, which may lead to adsorption-induced restructuring under reaction conditions.

Original language	English
Pages (from-to)	142–151
Number of pages	10
Journal	Computational and Theoretical Chemistry
Volume	1107
Early online date	17 Feb 2017
DOIs	https://doi.org/10.1016/j.comptc.2017.02.012
Publication status	Published - May 2017

Keywords

Adsorption properties
Alloying effects
Au-Rh
D-band centre
Nanoalloys
Support effects

ASJC Scopus subject areas

Biochemistry
Condensed Matter Physics
Physical and Theoretical Chemistry

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10.1016/j.comptc.2017.02.012Licence: Creative Commons: Attribution (CC BY)

Demiroglu_et_al_DFT_molecular_adsorption_Computational_Theoretical_ChemistryFinal published version, 3.58 MBLicence: Creative Commons: Attribution (CC BY)

TOUCAN: Towards an Understanding of Catalysis on Nanialloys
Johnston, R.
Engineering & Physical Science Research Council
1/09/12 → 31/05/18
Project: Research Councils

Cite this

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title = "A DFT study of molecular adsorption on titania-supported AuRh nanoalloys",

abstract = "AuRh/TiO2 nanocatalysts have proved their efficiency in several catalytic reactions. In this work, density functional theory calculations are performed to investigate the effect of the TiO2 support on the structures of fcc 38-atom and 79-atom AuRh nanoalloys and their adsorption properties towards the reactant molecules CO and O2. d-band centre analysis shows that the d-band model captures the trends better for both larger and supported alloy clusters due to reduced mechanical effects. Calculations reveal metal-to-support electron transfer, depending mainly on which metal atoms lie at the interface with the support. The adsorption strengths of CO and O2 molecules on experimentally-relevant Janus segregated structures are slightly lower than on pure Rh clusters, which may reduce poisoning effects, while maintaining the high reactivity of Rh. In addition, higher adsorption energies are predicted for the less stable AucoreRhshell structure, which may lead to adsorption-induced restructuring under reaction conditions.",

keywords = "Adsorption properties, Alloying effects, Au-Rh, D-band centre, Nanoalloys, Support effects",

author = "Ilker Demiroglu and Ziyou Li and Laurent Piccolo and Johnston, {Roy L.}",

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volume = "1107",

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journal = "Computational and Theoretical Chemistry",

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T1 - A DFT study of molecular adsorption on titania-supported AuRh nanoalloys

AU - Demiroglu, Ilker

AU - Li, Ziyou

AU - Piccolo, Laurent

AU - Johnston, Roy L.

PY - 2017/5

Y1 - 2017/5

N2 - AuRh/TiO2 nanocatalysts have proved their efficiency in several catalytic reactions. In this work, density functional theory calculations are performed to investigate the effect of the TiO2 support on the structures of fcc 38-atom and 79-atom AuRh nanoalloys and their adsorption properties towards the reactant molecules CO and O2. d-band centre analysis shows that the d-band model captures the trends better for both larger and supported alloy clusters due to reduced mechanical effects. Calculations reveal metal-to-support electron transfer, depending mainly on which metal atoms lie at the interface with the support. The adsorption strengths of CO and O2 molecules on experimentally-relevant Janus segregated structures are slightly lower than on pure Rh clusters, which may reduce poisoning effects, while maintaining the high reactivity of Rh. In addition, higher adsorption energies are predicted for the less stable AucoreRhshell structure, which may lead to adsorption-induced restructuring under reaction conditions.

AB - AuRh/TiO2 nanocatalysts have proved their efficiency in several catalytic reactions. In this work, density functional theory calculations are performed to investigate the effect of the TiO2 support on the structures of fcc 38-atom and 79-atom AuRh nanoalloys and their adsorption properties towards the reactant molecules CO and O2. d-band centre analysis shows that the d-band model captures the trends better for both larger and supported alloy clusters due to reduced mechanical effects. Calculations reveal metal-to-support electron transfer, depending mainly on which metal atoms lie at the interface with the support. The adsorption strengths of CO and O2 molecules on experimentally-relevant Janus segregated structures are slightly lower than on pure Rh clusters, which may reduce poisoning effects, while maintaining the high reactivity of Rh. In addition, higher adsorption energies are predicted for the less stable AucoreRhshell structure, which may lead to adsorption-induced restructuring under reaction conditions.

KW - Adsorption properties

KW - Alloying effects

KW - Au-Rh

KW - D-band centre

KW - Nanoalloys

KW - Support effects

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EP - 151

JO - Computational and Theoretical Chemistry

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A DFT study of molecular adsorption on titania-supported AuRh nanoalloys

Abstract

Keywords

ASJC Scopus subject areas

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Projects

TOUCAN: Towards an Understanding of Catalysis on Nanialloys

Cite this