Activity origin of single/double-atom catalyst for hydrogen evolution reaction

doi:10.19799/j.cnki.2095-4239.2021.0393

Abstract

Abstract:

Electrocatalytic hydrogen evolution reaction (HER) is a promising hydrogen energy conversion method. To develop high-performance and low-cost hydrogen evolution electrocatalysts, single- and double-atom catalysts (SACs, DACs) with transition metals (e.g., Fe, Ni, and Co) as the active center and nitrogen-doped graphene (N-graphene) as the substrate are selected for HER utilizing density functional theory calculations. The selected catalytic materials exhibit exceptional stability against sintering. We then chose H adsorption energy as the descriptor for analyzing the HER activity, and the results demonstrate that the CoN₄ site exhibits excellent HER activity over other candidates. In contrast, NiN₄ and Ni₂N₆ sites display inferior HER activity. In addition, the electronic structures of the catalysts are systematically discussed to uncover the origin of catalytic activity. This work reveals that DACs have poor HER activity compared to SACs and DACs, while the SACs (e.g., CoN₄, FeN₃, and FeN₄) show low overpotential in HER. Therefore, the SACs can substitute commercial precious metals catalysts (Pt/C) for HER catalysts.

Key words: hydrogen evolution reaction, single-atom catalyst, electrocatalyst, density functional theory

CLC Number:

TM 911

Shishi ZHANG, Yanyang QIN, Yaqiong SU. Activity origin of single/double-atom catalyst for hydrogen evolution reaction[J]. Energy Storage Science and Technology, 2021, 10(6): 2008-2012.

Figures/Tables 6

Fig. 1

Table 1

Fig. 2

Fig. 3

Fig. 4

Fig. 5

References 16

1	ZHANG H B, LIU G G, SHI L, et al. Single-atom catalysts: Emerging multifunctional materials in heterogeneous catalysis[J]. Advanced Energy Materials, 2018, 8(1): 1701343.
2	YANG S, KIM J, TAK Y J, et al. Single-atom catalyst of platinum supported on titanium nitride for selective electrochemical reactions[J]. Angewandte Chemie International Edition, 2016, 55(6): 2058-2062.
3	XU H, WANG D, YANG P, et al. A theoretical study of atomically dispersed MN₄/C (M=Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction[J]. Physical Chemistry Chemical Physics, 2020, 22(48): 28297-28303.
4	ZHAO J, CHEN Z. Single Mo atom supported on defective boron nitride monolayer as an efficient electrocatalyst for nitrogen fixation: A computational study[J]. Journal of the American Chemical Society, 2017, 139(36): 12480-12487.
5	WANG D W, LI Q, HAN C, et al. Single-atom ruthenium based catalyst for enhanced hydrogen evolution[J]. Applied Catalysis B: Environmental, 2019, 249: 91-97.
6	LIU X H, ZHENG L R, HAN C X, et al. Identifying the activity origin of a cobalt single-atom catalyst for hydrogen evolution using supervised learning[J]. Advanced Functional Materials, 2021, 31(18): 2100547.
7	CHEN Y J, JI S F, CHEN C, et al. Single-atom catalysts: Synthetic strategies and electrochemical applications[J]. Joule, 2018, 2(7): 1242-1264.
8	CHENG N, STAMBULA S, WANG D, et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction[J]. Nature Communications, 2016, 7: 13638.
9	LEI C J, WANG Y, HOU Y, et al. Efficient alkaline hydrogen evolution on atomically dispersed Ni-Nx Species anchored porous carbon with embedded Ni nanoparticles by accelerating water dissociation kinetics[J]. Energy & Environmental Science, 2019, 12(1): 149-156.
10	CHEN Z W, YAN J M, JIANG Q. Single or double: Which is the altar of atomic catalysts for nitrogen reduction reaction?[J]. Small Methods, 2019, 3(6): 1800291.
11	ZHANG N, ZHOU T P, GE J K, et al. High-density planar-like Fe₂N₆ structure catalyzes efficient oxygen reduction[J]. Matter, 2020, 3(2): 509-521.
12	ROSSMEISL J, LOGADOTTIR A, NØRSKOV J K. Electrolysis of water on (oxidized) metal surfaces[J]. Chemical Physics, 2005, 319(1/2/3): 178-184.
13	LI Y C, LIU X F, ZHENG L R, et al. Preparation of Fe-N-C catalysts with FeNx (x=1, 3, 4) active sites and comparison of their activities for the oxygen reduction reaction and performances in proton exchange membrane fuel cells[J]. Journal of Materials Chemistry A, 2019, 7(45): 26147-26153.
14	LAURSEN A B, KEGNÆS S, DAHL S, et al. Molybdenum sulfides—Efficient and viable materials for electro-and photoelectrocatalytic hydrogen evolution[J]. Energy & Environmental Science, 2012, 5(2): 5577-5591.
15	NØRSKOV J K, BLIGAARD T, LOGADOTTIR A, et al. Trends in the exchange current for hydrogen evolution[J]. Journal of the Electrochemical Society, 2005, 152(3): J23.
16	FEI H, DONG J, ARELLANO-JIMÉNEZ M J, et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation[J]. Nature Communications, 2015, 6: 8668.

Item	FeN₃	FeN₄	CoN₄	NiN₄	Fe₂N₆	Co₂N₆	Ni₂N₆
TM—N/?	1.92	1.89	1.87	1.87	1.79/1.95	1.78/1.94	1.83/1.87
E_b/eV	-4.91	-7.59	-7.42	-4.64	-14.41	-13.90	-12.89

[1]	WANG Peican, WAN Lei, XU Ziang, XU Qin, PANG Maobin, CHEN Jinxun, WANG Baoguo. Interface engineering of self-supported electrode for electrochemical water splitting [J]. Energy Storage Science and Technology, 2022, 11(6): 1934-1946.
[2]	Jianxin CHEN, Nan SHENG, Chunyu ZHU, Zhonghao RAO. Study on nickel-based nanoparticles supported by biomass carbon for electrocatalytic hydrogen evolution [J]. Energy Storage Science and Technology, 2022, 11(5): 1350-1357.
[3]	Yezhou HU, Shuang WANG, Tao SHEN, Ye ZHU, Deli WANG. Recent progress in confined noble-metal electrocatalysts for oxygen reduction reaction [J]. Energy Storage Science and Technology, 2022, 11(4): 1264-1277.
[4]	Peiping YU, Liang XU, Bingyun MA, Qintao SUN, Hao YANG, Yue LIU, Tao CHENG. Multiscale simulation of a solid electrolyte interphase [J]. Energy Storage Science and Technology, 2022, 11(3): 921-928.
[5]	Shenzhi ZHANG, Likai WANG, Yinggang SUN, Heng LÜ, Ziyin YANG, Leilei LI, Zhongfang LI. Construction of two dimensional carbon-supported Au₄Pd₂ catalysts and their electrocatalytic performances [J]. Energy Storage Science and Technology, 2021, 10(6): 2028-2038.
[6]	Wenwu ZOU, Guoxing JIANG, Li DU. Recent advances in covalent organic frameworks （COFs） for electrocatalysis of oxygen electrodes [J]. Energy Storage Science and Technology, 2021, 10(6): 1891-1905.
[7]	Yuexia LI, Quanbing LIU. Application of MXene-based nanomaterials in electrocatalysis for oxygen reduction reaction [J]. Energy Storage Science and Technology, 2021, 10(6): 1918-1930.
[8]	Ziyue ZHU, Dongju FU, Jianjun CHEN, Bianrong ZENG. Research progress of non-precious metal bifunctional cathode electrocatalysts for zinc-air batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1489-1496.
[9]	CHEN Xiang, LEI Kaixiang, SUN Hongming, CHENG Fangyi, CHEN Jun. Spinel-type transition metal oxide electrocatalysts for metal-air batteries [J]. Energy Storage Science and Technology, 2017, 6(5): 904-923.
[10]	XU Ke, WANG Baoguo. A review of air electrodes for zinc air batteries [J]. Energy Storage Science and Technology, 2017, 6(5): 924-940.
[11]	HUANG Jie, LING Shigang, WANG Xuelong, JIANG Liwei, HU Yongsheng, XIAO Ruijuan, LI Hong. Fundamental scientific aspects of lithium ion batteries(ⅩⅣ)—Calculation methods [J]. Energy Storage Science and Technology, 2015, 4(2): 215-230.