Platinum single-atom catalyst with self-adjustable valence state for large-current-density acidic water oxidation

Su Hui; Soldatov Mikhail A.; Roldugin Victor; Liu Qinghua

doi:10.1016/j.esci.2021.12.007

Volume 2 Issue 1

Jan. 2022

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Su Hui, Soldatov Mikhail A., Roldugin Victor, Liu Qinghua. Platinum single-atom catalyst with self-adjustable valence state for large-current-density acidic water oxidation[J]. eScience, 2022, 2(1): 102-109. doi: 10.1016/j.esci.2021.12.007

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Su Hui, Soldatov Mikhail A., Roldugin Victor, Liu Qinghua. Platinum single-atom catalyst with self-adjustable valence state for large-current-density acidic water oxidation[J]. eScience, 2022, 2(1): 102-109. doi: 10.1016/j.esci.2021.12.007

Citation:

Su Hui, Soldatov Mikhail A., Roldugin Victor, Liu Qinghua. Platinum single-atom catalyst with self-adjustable valence state for large-current-density acidic water oxidation[J]. eScience, 2022, 2(1): 102-109. doi: 10.1016/j.esci.2021.12.007

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Platinum single-atom catalyst with self-adjustable valence state for large-current-density acidic water oxidation

doi: 10.1016/j.esci.2021.12.007

a.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, Anhui, PR China
b.
The Smart Materials Research Institute, Southern Federal University, 344090, Sladkova 178/24, Rostov-on-Don, Russia

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Corresponding author: Qinghua Liu qhliu@ustc.edu.cn
Received Date: 2021-10-11
Revised Date: 2021-11-28
Accepted Date: 2021-12-24

Available Online: 2021-12-28

Abstract

Abstract

The design of active acidic oxygen evolution reaction (OER) catalysts is of paramount importance to achieve efficient large-current-density industrial hydrogen fuel production via water electrolysis. Herein, we develop a Pt-based catalyst with high electrochemical activity for the OER in acidic conditions under a large current. We achieve this by modulating the electronic structure of Pt into a high-valence, electron-accessible Pt₁^(2.4+δ)+ (δ = 0–0.7) state during the reaction. This electron-accessible Pt₁^(2.4+δ)+ single-site catalyst can effectively maintain a large OER current density of 120 mA cm⁻² for more than 12 h in 0.5 M H₂SO₄ at a low overpotential of 405 mV, and it shows a high mass activity of ∼3350 A g_metal⁻¹ at 10 mA cm⁻² current density and 232 mV overpotential. Using in situ synchrotron radiation infrared and X-ray absorption spectroscopies, we directly observe in an experiment that a key (∗O)–Pt₁–C₂N₂ intermediate is produced by the potential-driven structural optimization of square pyramidal Pt₁–C₂N₂ moieties; this highly favors the dissociation of H₂O over Pt₁^(2.4+δ)+ sites and prevents over-oxidation and dissolution of the active sites.
- Oxygen evolution reaction,
- Acidic electrolyte,
- In situ characterization

● The Pt₁–C₂N₂ SAC maintains 120 mA/cm² at overpotential of 405 mV and delivers a high mass activity of 3350 A g⁻¹ at 232 mV.
● A self-modulating valence state of Pt₁^{(2.4+δ)+ (δ = 0–0.7)} sites is for effective accessibility of oxo-containing species.
● In situ techniques directly detected a self-modulating Pt^(2.4+δ)+ site to produce the ∗O for an efficient 4e⁻ OER process.
● The Pt₁–C₂N₂ moieties were strongly interfacial chemically coupled in the 3D conductive carbon substrate for improved stability.

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