Selective Electrified Propylene-to-Propylene Glycol Oxidation on Activated Rh-Doped Pd.

Huang, JE; Chen, Y; Ou, P; Ding, X; Yan, Y; Dorakhan, R; Lum, Y; Li, X-Y; Bai, Y; Wu, C; Fan, M; Lee, MG; Miao, RK; Liu, Y; O'Brien, C; Zhang, J; Tian, C; Liang, Y; Xu, Y; Luo, M; Sinton, D; Sargent, EH

Selective Electrified Propylene-to-Propylene Glycol Oxidation on Activated Rh-Doped Pd.

Huang, JE Chen, Y Ou, P Ding, X Yan, Y Dorakhan, R Lum, Y Li, X-Y Bai, Y Wu, C Fan, M Lee, MG Miao, RK Liu, Y O'Brien, C Zhang, J

Tian, C Liang, Y Xu, Y Luo, M Sinton, D Sargent, EH

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Publisher:: AMER CHEMICAL SOC
Publication Type:: Journal Article
Citation:: J Am Chem Soc, 2024, 146, (12), pp. 8641-8649
Issue Date:: 2024-03-27

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Field	Value	Language
dc.contributor.author	Huang, JE
dc.contributor.author	Chen, Y
dc.contributor.author	Ou, P
dc.contributor.author	Ding, X
dc.contributor.author	Yan, Y
dc.contributor.author	Dorakhan, R
dc.contributor.author	Lum, Y
dc.contributor.author	Li, X-Y
dc.contributor.author	Bai, Y
dc.contributor.author	Wu, C
dc.contributor.author	Fan, M
dc.contributor.author	Lee, MG
dc.contributor.author	Miao, RK
dc.contributor.author	Liu, Y
dc.contributor.author	O'Brien, C
dc.contributor.author	Zhang, J https://orcid.org/0000-0001-5476-0134
dc.contributor.author	Tian, C
dc.contributor.author	Liang, Y
dc.contributor.author	Xu, Y
dc.contributor.author	Luo, M
dc.contributor.author	Sinton, D
dc.contributor.author	Sargent, EH
dc.date.accessioned	2025-01-16T04:35:37Z
dc.date.available	2025-01-16T04:35:37Z
dc.date.issued	2024-03-27
dc.identifier.citation	J Am Chem Soc, 2024, 146, (12), pp. 8641-8649
dc.identifier.issn	0002-7863
dc.identifier.issn	1520-5126
dc.identifier.uri	http://hdl.handle.net/10453/183778
dc.description.abstract	Renewable-energy-powered electrosynthesis has the potential to contribute to decarbonizing the production of propylene glycol, a chemical that is used currently in the manufacture of polyesters and antifreeze and has a high carbon intensity. Unfortunately, to date, the electrooxidation of propylene under ambient conditions has suffered from a wide product distribution, leading to a low faradic efficiency toward the desired propylene glycol. We undertook mechanistic investigations and found that the reconstruction of Pd to PdO occurs, followed by hydroxide formation under anodic bias. The formation of this metastable hydroxide layer arrests the progressive dissolution of Pd in a locally acidic environment, increases the activity, and steers the reaction pathway toward propylene glycol. Rh-doped Pd further improves propylene glycol selectivity. Density functional theory (DFT) suggests that the Rh dopant lowers the energy associated with the production of the final intermediate in propylene glycol formation and renders the desorption step spontaneous, a concept consistent with experimental studies. We report a 75% faradic efficiency toward propylene glycol maintained over 100 h of operation.
dc.format	Print-Electronic
dc.language	eng
dc.publisher	AMER CHEMICAL SOC
dc.relation.ispartof	J Am Chem Soc
dc.relation.isbasedon	10.1021/jacs.4c00312
dc.rights	info:eu-repo/semantics/closedAccess
dc.subject	03 Chemical Sciences
dc.subject.classification	General Chemistry
dc.subject.classification	34 Chemical sciences
dc.subject.classification	40 Engineering
dc.title	Selective Electrified Propylene-to-Propylene Glycol Oxidation on Activated Rh-Doped Pd.
dc.type	Journal Article
utslib.citation.volume	146
utslib.location.activity	United States
utslib.for	03 Chemical Sciences
pubs.organisational-group	University of Technology Sydney
pubs.organisational-group	University of Technology Sydney/Faculty of Science
pubs.organisational-group	University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	closed_access	*
dc.date.updated	2025-01-16T04:35:35Z
pubs.issue	12
pubs.publication-status	Published
pubs.volume	146
utslib.citation.issue	12

Abstract:

Renewable-energy-powered electrosynthesis has the potential to contribute to decarbonizing the production of propylene glycol, a chemical that is used currently in the manufacture of polyesters and antifreeze and has a high carbon intensity. Unfortunately, to date, the electrooxidation of propylene under ambient conditions has suffered from a wide product distribution, leading to a low faradic efficiency toward the desired propylene glycol. We undertook mechanistic investigations and found that the reconstruction of Pd to PdO occurs, followed by hydroxide formation under anodic bias. The formation of this metastable hydroxide layer arrests the progressive dissolution of Pd in a locally acidic environment, increases the activity, and steers the reaction pathway toward propylene glycol. Rh-doped Pd further improves propylene glycol selectivity. Density functional theory (DFT) suggests that the Rh dopant lowers the energy associated with the production of the final intermediate in propylene glycol formation and renders the desorption step spontaneous, a concept consistent with experimental studies. We report a 75% faradic efficiency toward propylene glycol maintained over 100 h of operation.

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http://hdl.handle.net/10453/183778