Targeted construction of high-performance single-atom platinum-based electrocatalysts for hydrogen evolution reaction

doi:10.1016/S1872-2067(24)60199-3

Chinese Journal of Catalysis ›› 2025, Vol. 69: 259-270.DOI: 10.1016/S1872-2067(24)60199-3

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Targeted construction of high-performance single-atom platinum-based electrocatalysts for hydrogen evolution reaction

Jing Liu^a^,^b^,¹^,^*(), Xiandi Ma^c^,¹, Jeonghan Roh^b^,¹, Dongwon Shin^b, Ara Cho^d, Jeong Woo Han^d, Jianping Long^a, Zhen Zhou^c^,^e^,^f, Menggai Jiao^c^,^*(), Kug-Seung Lee^g^,^*(), EunAe Cho^b^,^*()

^aCollege of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, China
^bDepartment of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-Ro, Yuseong-Gu, Daejeon 34141, Korea
^cInterdisciplinary Research Center for Sustainable Energy Science and Engineering (IRC4SE), School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^dDepartment of Chemical Engineering, Pohang University of Science and Technology, Pohang, Gyeongbuk 37673, Korea
^eSchool of Materials Science and Engineering, Institute of New Energy Material Chemistry, Renewable Energy Conversion and Storage Center, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300350, China
^fLongmen Laboratory, Luoyang 471023, Henan, China
^gBeamline Division, Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang, Gyeongbuk 37673, Korea

Received:2024-10-31 Accepted:2024-11-13 Online:2025-02-18 Published:2025-02-10
Contact: *E-mail: jingliu@cdut.edu.cn (J. Liu), mgjiao@zzu.edu.cn (M. Jiao), lks3006@postech.ac.kr (K.-S. Lee), eacho@kaist.ac.kr (E. Cho).
About author:First author contact:
¹Contributed equally to this work.
Supported by:
National Research Foundation of Korea (NRF) grant funded by Korea Government (MSIT)(NRF-2019M3D1A1079306);National Research Foundation of Korea (NRF) grant funded by Korea Government (MSIT)(NRF-2021R1A2C1011415);Sichuan Natural Science Foundation(2023NSFSC1079);Key Research Projects of Higher Education Institutions of Henan Province(24A530009);Frontier Exploration Projects of Longmen Laboratory(LMQYTSKT021)

Abstract

Abstract:

Exploring platinum single-atom electrocatalysts (SACs) is of great significance for effectively catalyzing the hydrogen evolution reaction in order to maximize the utilization of metal atoms. Herein, ruthenium clusters with several atoms (Ru_x) supported on nitrogen-doped, cost-efficient Black Pearls 2000 (Ru_xNBP), were synthesized as initial materials via a simple hydrothermal method. Then, [PtCl₄]^2‒ ion was reductively deposited on Ru_xNBP to obtain a Pt SAC (Pt₁/Ru_xNBP). Electrochemical measurements demonstrate the excellent HER performance of Pt₁/Ru_xNBP with a 5.7-fold increase in mass activity compared to the commercial Pt/C at 20 mV. Moreover, the cell voltage of the proton exchange membrane electrolyzer with Pt₁/Ru_xNBP is 20 mV lower compared to that with commercial Pt/C at 1.0 A cm^‒2. Physical characterization and density functional theory calculations revealed that the preserved Pt-Cl bond of [PtCl₄]^2‒ and the Ru_xNBP support co-regulate the 5dstate of isolated Pt atoms and enhance the catalytic HER capacity of Pt₁/Ru_xNBP.

Key words: Platinum, Single-atom eletrocatalyst, Ruthenium cluster, Hydrogen evolution reaction, Density functional theory

Jing Liu, Xiandi Ma, Jeonghan Roh, Dongwon Shin, Ara Cho, Jeong Woo Han, Jianping Long, Zhen Zhou, Menggai Jiao, Kug-Seung Lee, EunAe Cho. Targeted construction of high-performance single-atom platinum-based electrocatalysts for hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2025, 69: 259-270.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60199-3

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Figures/Tables 6

Fig. 1. Flow chart of the sample preparation method.

Fig. 2. HAADF-STEM images of Pt1/RuxNBP with low (a) and high (b) magnification. (c) The corresponding intensity profile of Pt1/RuxNBP marked with yellow box in Fig. 1(b). (d) Elemental mapping of Pt1/RuxNBP.

Fig. 3. (a) XPS survey of Pt1/BP, Pt1/NBP, Pt/NBP, Pt/RuxNBP, and Pt1/RuxNBP. (b) High-resolution XPS spectra of N 1s for Pt1/RuxNBP. (c) The proportion (at.%) of NPd, NIm, M-N, NAm, and NPy in NBP, RuxNBP, Pt/NBP, Pt/RuxNBP, Pt1/RuxNBP, and Pt1/NBP, respectively. (d) High-resolution XPS spectra of Cl 2p for Pt1/BP, Pt/NBP, Pt1/NBP, Pt/RuxNBP, Pt1/RuxNBP, and Commercial K2PtCl4. (e) High-resolution XPS spectra of Ru 3p for RuxNBP, Pt/RuxNBP, and Pt1/RuxNBP. (f) High-resolution XPS spectra of Pt 4f for Pt(acac)2, Pt/NBP, Pt/RuxNBP, K2PtCl4, Pt1/BP, Pt1/NBP, and Pt1/RuxNBP.

Fig. 4. The Ru K-edge XANES (a) and k2-weighted FT EXAFS spectra (b) of Ru foil, Rux/NBP, Pt/RuxNBP, Pt1/RuxNBP, and RuO2. The Pt L3-edge XANES (c) and k2-weighted FT EXAFS spectra (d) of Pt foil, Pt/NBP, Pt/RuxNBP, Pt1/NBP, Pt1/RuxNBP, and PtO2.

Fig. 5. Electrochemical characterization of different catalysts. (a) The polarization curves for RuxNBP, Pt/NBP, Pt/RuxNBP, Pt1/BP, Pt1/NBP, Pt1/RuxNBP and the commercial Pt/C in 0.1 mol L?1 HClO4 solution with a scan rate of 1 mV s?1 and rotation speed of 2500 r min?1. (b) The HER mass activity of the corresponding electrocatalysts at an overpotential of 20 mV. (c) Tafel Plots of RuxNBP, Pt/NBP, Pt/RuxNBP, Pt1/BP, Pt1/NBP, Pt1/RuxNBP and the commercial Pt/C for HER. The polarization curves of Pt1/RuxNBP (d) and commercial Pt/C (e) at initial and after 10000 cycles. (f) Current-voltage relationships measured using 5 cm2 single electrolysis cell at 80 °C and atmospheric pressure of gases; cathodic catalyst: Pt1/RuxNBP (0.040 mgPt+Ru cm?2) and commercial Pt/C (0.031mgPt cm?2); anodic catalyst: commercial IrO2 (1 mgIrO2 cm?2); Nafion?-212 membrane.

Fig. 6. (a) The optimized configurations (top and side views) of two types of Pt1 sites in Pt1/RuxNBP, which include Pt1/RuxNBP-i with the Pt1 site positions near the Ru2 unit and Pt1/RuxNBP-ii with the Pt1 site locates far away from the Ru2 unit. The brown, blue, red, green, cyan, dark blue, and white spheres represent C, N, O, Cl, Pt, and Ru atoms, respectively. (b) The free energies diagram of the HER on the models involving Pt1-based active sites in the corresponding catalyst and Pt(111).

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Targeted construction of high-performance single-atom platinum-based electrocatalysts for hydrogen evolution reaction

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