高导电性和催化活性的Janus-TiNbCO2析氢反应催化材料

doi:10.13208/j.electrochem.201109

摘要/Abstract

摘要：

探寻具有高导电性和高催化活性的析氢反应（HER）催化材料一直是可持续能源发展研究中的热点。Ti₂C具有表面活性位点多和优良的力学稳定性、导电性等,已成为潜在的制氢催化剂。然而,终端O修饰Ti₂C表面,会降低该材料的导电性,进而限制了电子在价带与导带间的输运。本研究通过Nb掺杂,构建双电层Janus-TiNbCO₂,并借助VASP软件研究了Janus-TiNbCO₂的能带结构、HER性能和HER反应路径过渡态。结果表明,Janus-TiNb-CO₂为导体材料,其在应力、氧空位缺陷和H*覆盖度的影响下,均表现出极优异的催化活性,计算获得的最优ΔG_H*值为0.02 eV。H*在Janus-TiNbCO₂上可能以Heyrovsky路径进行反应,该路径的迁移能势垒为0.23 eV。Janus-TiNbCO₂是一种具有HER应用前景的催化材料。

关键词: MXene, Janus-TiNbCO₂, 能带, 析氢反应

Abstract:

Exploring the potential hydrogen evolution reaction (HER) catalysts with the high activity and high conductivity has always been a hot spot in the research of renewable energy development. Ti₂C, as one of the 2D-MXene, has excellent properties relating to many active sites, mechanical stability, conductivity, etc., and has become a potential HER catalyst. However, the modification of the surface of Ti₂C by terminal O will reduce the conductivity, thereby limiting the transport of electrons between the valence band and the conduction band. In this study, an electric double layer Janus-TiNbCO₂ was constructed by Nb doping. The band property, HER activity and HER reaction path of Janus-TiNbCO₂ are studied by the first-principles calculations. The results show that Nb doping increases the distance between Ti and O atoms, which increases the lattice parameters of Janus-TiNbCO₂ comparing with that of Ti₂CO₂ structure. The Janus-TiNbCO₂ structure is stable by calculating the thermodynamic stability at 500 K using AIMD method. The band gap of Ti₂CO₂ is approximate 0.9 eV. After Nb doping, the orbital hybridization between Nd-3d and O-2p affects the electronic rearrangement of Ti-3d, leading that Janus-TiNbCO₂ has the metal band structure. In Janus-TiNbCO₂, both Ti and Nb surfaces adsorb H* by O site, where the ΔG_H*(@Ti) = -0.55 eV,ΔG_H*(@Nb) = 0.02 eV, showing Ti and Nb surfaces have different catalytic activities. Comparing with graphenes, e.g., h-B₂O, Pt, and g-C₃N₄, Janus-TiNbCO₂ has better catalytic activity. The charge distribution of Janus-TiNbCO₂ near the Fermi level was analyzed by HSE-06 function. The result reveals that O atoms on the Ti surface exhibit charge unsaturation at the Fermi level, while those on Nb surface strong saturation. Moreover, the effects of H* coverage and strains(+2% ~ +4%) on the catalyst activity of Janus-TiNbCO₂ are studied. When the H* coverage is low, the optimal ΔG_H* of Nb surface is approximate 0.02 eV, while Ti surface has an excellent catalytic activity at high H* coverages (θ = 7/9, ΔG_H* = -0.06 eV). Under the strain action, the H* coverage on surface is not affected. However, strains will reduce the HER activity of Nb surface, and increase the HER activity of Ti surface. Furthermore, oxygen defect is a stable point defect in Janus-TiNbCO₂. Oxygen defect will increase the HER activity of Ti surface and decrease the HER activity of Nb surface. Comparing to the Tafel pathway, the Heyrovsky is a more suitable pathway for the HER, in which the migration barrier of Heyrovsky is 0.23 eV for H* on Nb surface. Janus-TiNbCO₂ can be used as a potential HER catalyst.

Key words: MXene, Janus-TiNbCO₂, band, hydrogen evolution reaction

徐黎黎, 任冬燕, 赵骁锋, 易勇. 高导电性和催化活性的Janus-TiNbCO₂析氢反应催化材料[J]. 电化学（中英文）, 2021, 27(5): 570-578.

Li-Li Xu, Dong-Yan Ren, Xiao-Feng Zhao, Yong Yi. Janus-TiNbCO₂ for Hydrogen Evolution Reaction with High Conductivity and Catalytic Activity[J]. Journal of Electrochemistry, 2021, 27(5): 570-578.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.201109

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I5/570

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参考文献 26

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Site	θ	-4%	-2%	+2%	+4%
@Ti	1/9	-0.508	-0.507	-0.509	-0.510
	2/9	-0.432	-0.431	-0.431	-0.430
	3/9	-0.340	-0.339	-0.338	-0.337
	4/9	-0.281	-0.280	-0.278	-0.270
	5/9	-0.196	-0.195	-0.193	-0.192
	6/9	-0.131	-0.130	-0.127	-0.126
	7/9	-0.060	-0.059	-0.056	-0.055
	8/9	0.028	0.032	0.035	0.034
	9/9	0.097	0.099	0.102	0.104
@Nb	1/9	0.075	0.069	0.068	0.063
@Nb	2/9	0.191	0.190	0.186	0.174

Janus-TiNbCO₂	Adsorption site	ΔE_H*/eV	ΔG_H*/eV
@Ti	Vacancy	-0.52	-0.27
@Ti	O atom	-0.59	-0.34
@Nb	Vacancy	-0.08	0.17
@Nb	O atom	-0.99	-0.75

高导电性和催化活性的Janus-TiNbCO₂析氢反应催化材料

Janus-TiNbCO₂ for Hydrogen Evolution Reaction with High Conductivity and Catalytic Activity

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