Rational Design of Cost-Effective Metal-Doped ZrO2 for Oxygen Evolution Reaction

doi:10.1007/s40820-024-01403-7

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Abstract

The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction (OER) due to the “stable-or-active” dilemma. Zirconium dioxide (ZrO₂), a versatile and low-cost material that can be stable under OER operating conditions, exhibits inherently poor OER activity from experimental observations. Herein, we doped a series of metal elements to regulate the ZrO₂ catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions. Microkinetic modeling as a function of the OER activity descriptor (G_O*-G_HO*) displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO₂ surface, among which Fe and Rh (in the form of single-atom dopant) reach the volcano peak (i.e. the optimal activity of OER under the potential of interest), indicating excellent OER performance. Free energy diagram calculations, density of states, and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO₂, leading to low OER overpotential, high conductivity, and good stability. Considering cost-effectiveness, single-atom Fe doped ZrO₂ emerged as the most promising catalyst for OER. This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.

Key words： Oxygen evolution reaction Metal oxide Electrocatalysis Surface Pourbaix analysis Doping

Received: 14 December 2023 Published: 25 April 2024

Corresponding Authors: Hao Li, Zhiyuan Zeng

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	Yuefeng Zhang
	Tianyi Wang
	Liang Mei
	Ruijie Yang
	Weiwei Guo
	Hao Li
	Zhiyuan Zeng

Cite this article:

Yuefeng Zhang,Tianyi Wang,Liang Mei, et al. Rational Design of Cost-Effective Metal-Doped ZrO₂ for Oxygen Evolution Reaction[J]. Nano-Micro Letters, 2024, 16(1): 180-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01403-7 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/180

Fig. 1 a Proposed strategy for screening metals capable of enhancing the OER activity of ZrO2 via doping. b Calculated surface energies of the three low-index slabs of monoclinic ZrO2. More details can be found in Fig. S1

Fig. 2 a Optimized configuration of ZrO2 with top and side views. The purple and red spheres represent Zr and O, respectively. b Calculated surface Pourbaix diagram of the ZrO2 surface. c Formation energy values of different single-metal atoms doped ZrO2. d The feasible metals for doping on the surface of ZrO2.

$\varepsilon_{d}$ on elevated metal doped ZrO₂. e A heatmap represents the magnitude of values as a color. Values (unit eV) were obtained by G_O*-G_HO* = 1.5, and darker colors correspond to lower values implying higher activity.">

Fig. 3 a Kinetic OER activity volcano model as a function of GO*-GHO* at 5 μ A cm−2 (black line). b Scaling relation between EO* and EHO* on feasible metals doped ZrO2. The linear scaling relations of EHO* vs. c EHOO* and d $\varepsilon_{d}$ on elevated metal doped ZrO2. e A heatmap represents the magnitude of values as a color. Values (unit eV) were obtained by GO*-GHO* = 1.5, and darker colors correspond to lower values implying higher activity.

Fig. 4 Gibbs Free energy diagram of OER on a ZrO2, b Ti-ZrO2, c Pt-ZrO2, d Fe-ZrO2, and e Rh-ZrO2. f Adsorption energy values of O* (pink line) and HO* (blue line) on five varied substrates. The inset is the charge density difference of HO*, and the isosurface value was set to 0.001 e Å−3

Fig. 5 Crystal orbital Hamilton population (COHP) analysis of the interactions between a Rh-O in O*, b Zr-O in O*, c Fe-O in O*, d Rh-O in HO*, f Zr-O in HO*, and e Fe-O in HO*

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