Compressive Strain Reduces the Hydrogen Evolution and Oxidation Reaction Activity of Platinum in Alkaline Solution
Abstract
It is unclear why the hydrogen evolution and oxidation reactions (HER/HOR) of platinum (Pt) is much slower in base than in acid. Neither is clear why the sluggish HER/HOR of Pt in base can be improved by mixing Pt with some transition metals. Herein, we constructed dealloyed carbon-supported Pt-Cu nanoclusters (D-PtCu3/C) with a core-shell Cu@Pt structure wherein the Pt-Cu alloying core is surrounded by Pt shells as a model HER/HOR catalyst to interpret these puzzles. Combined microscopy and in situ x-ray absorption spectroscopy verified the Cu@Pt structure in association with compressive-strain in the D-PtCu3/C during the HER/HOR. The superior oxygen reduction reaction activity of the D-PtCu3/C to that of Pt/C in both acid and alkaline solutions confirmed that the compressive-strain weakens the Pt-O binding energy (EPt-O) of the D-PtCu3/C. Meanwhile, the D-PtCu3/C exhibited inferior HER/HOR activity and positive shift of the sharp hydrogen adsorption/desorption peaks towards higher potential in comparison with Pt/C in alkaline solution. These results together verified that the compressive-strain reduces the HER/HOR activity of Pt by weakening EPt-O. This conclusion indicates that the HER/HOR kinetics of Pt in base is mainly limited by the overly weak EPt-O rather than overly stronger Pt-H binding energy.
- Authors:
-
[1];
[2];
[3];
[2];
[2]
- Northeastern Univ., Boston, MA (United States). Dept. of Chemical Engineering
- Northeastern Univ., Boston, MA (United States). Dept. of Chemistry and Chemical Biology
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1808665
- Report Number(s):
- BNL-221816-2021-JAAM
Journal ID: ISSN 2155-5435
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 13; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; HER/HOR; platinum catalyst; core−shell structure; XAS; interface
Citation Formats
Jiao, Li, Liu, Ershuai, Hwang, Sooyeon, Mukerjee, Sanjeev, and Jia, Qingying. Compressive Strain Reduces the Hydrogen Evolution and Oxidation Reaction Activity of Platinum in Alkaline Solution. United States: N. p., 2021.
Web. doi:10.1021/acscatal.1c01723.
Jiao, Li, Liu, Ershuai, Hwang, Sooyeon, Mukerjee, Sanjeev, & Jia, Qingying. Compressive Strain Reduces the Hydrogen Evolution and Oxidation Reaction Activity of Platinum in Alkaline Solution. United States. https://doi.org/10.1021/acscatal.1c01723
Jiao, Li, Liu, Ershuai, Hwang, Sooyeon, Mukerjee, Sanjeev, and Jia, Qingying. Fri .
"Compressive Strain Reduces the Hydrogen Evolution and Oxidation Reaction Activity of Platinum in Alkaline Solution". United States. https://doi.org/10.1021/acscatal.1c01723. https://www.osti.gov/servlets/purl/1808665.
@article{osti_1808665,
title = {Compressive Strain Reduces the Hydrogen Evolution and Oxidation Reaction Activity of Platinum in Alkaline Solution},
author = {Jiao, Li and Liu, Ershuai and Hwang, Sooyeon and Mukerjee, Sanjeev and Jia, Qingying},
abstractNote = {It is unclear why the hydrogen evolution and oxidation reactions (HER/HOR) of platinum (Pt) is much slower in base than in acid. Neither is clear why the sluggish HER/HOR of Pt in base can be improved by mixing Pt with some transition metals. Herein, we constructed dealloyed carbon-supported Pt-Cu nanoclusters (D-PtCu3/C) with a core-shell Cu@Pt structure wherein the Pt-Cu alloying core is surrounded by Pt shells as a model HER/HOR catalyst to interpret these puzzles. Combined microscopy and in situ x-ray absorption spectroscopy verified the Cu@Pt structure in association with compressive-strain in the D-PtCu3/C during the HER/HOR. The superior oxygen reduction reaction activity of the D-PtCu3/C to that of Pt/C in both acid and alkaline solutions confirmed that the compressive-strain weakens the Pt-O binding energy (EPt-O) of the D-PtCu3/C. Meanwhile, the D-PtCu3/C exhibited inferior HER/HOR activity and positive shift of the sharp hydrogen adsorption/desorption peaks towards higher potential in comparison with Pt/C in alkaline solution. These results together verified that the compressive-strain reduces the HER/HOR activity of Pt by weakening EPt-O. This conclusion indicates that the HER/HOR kinetics of Pt in base is mainly limited by the overly weak EPt-O rather than overly stronger Pt-H binding energy.},
doi = {10.1021/acscatal.1c01723},
journal = {ACS Catalysis},
number = 13,
volume = 11,
place = {United States},
year = {Fri Jun 18 00:00:00 EDT 2021},
month = {Fri Jun 18 00:00:00 EDT 2021}
}
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