The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.
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14 August 2024
Research Article|
August 12 2024
Surface chlorination of IrO2(110) by HCl
Connor Pope;
Connor Pope
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Project administration, Resources, Supervision, Writing – original draft)
1
Department of Chemical Engineering, University of Florida
, Gainesville, Florida 32611, USA
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Jungwon Yun;
Jungwon Yun
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Project administration, Resources, Supervision, Writing – original draft)
2
William G. Lowrie Chemical and Biomolecular Engineering, The Ohio State University
, Columbus, Ohio 43210, USA
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Rishikishore Reddy;
Rishikishore Reddy
(Data curation, Formal analysis, Investigation, Methodology)
1
Department of Chemical Engineering, University of Florida
, Gainesville, Florida 32611, USA
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Jovenal Jamir;
Jovenal Jamir
(Conceptualization, Data curation, Formal analysis, Investigation, Writing – original draft)
1
Department of Chemical Engineering, University of Florida
, Gainesville, Florida 32611, USA
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Dongjoon Kim;
Dongjoon Kim
(Data curation, Formal analysis, Investigation)
2
William G. Lowrie Chemical and Biomolecular Engineering, The Ohio State University
, Columbus, Ohio 43210, USA
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Minkyu Kim
;
Minkyu Kim
(Data curation, Formal analysis, Investigation, Methodology)
3
School of Chemical Engineering, Yeungnam University
, 280 Daehak-Ro, Gyeongsan 38541, Republic of Korea
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Aravind Asthagiri
;
Aravind Asthagiri
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Project administration, Resources, Supervision, Writing – original draft)
2
William G. Lowrie Chemical and Biomolecular Engineering, The Ohio State University
, Columbus, Ohio 43210, USA
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Jason F. Weaver
Jason F. Weaver
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Project administration, Resources, Supervision, Writing – original draft)
1
Department of Chemical Engineering, University of Florida
, Gainesville, Florida 32611, USA
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 064704 (2024)
Article history
Received:
June 19 2024
Accepted:
July 29 2024
Citation
Connor Pope, Jungwon Yun, Rishikishore Reddy, Jovenal Jamir, Dongjoon Kim, Minkyu Kim, Aravind Asthagiri, Jason F. Weaver; Surface chlorination of IrO2(110) by HCl. J. Chem. Phys. 14 August 2024; 161 (6): 064704. https://doi.org/10.1063/5.0224164
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