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

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 (ZrO 2 ), 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 ZrO 2 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 ZrO 2 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 ZrO 2 , leading to low OER overpotential, high conductivity, and good stability. Considering cost-effectiveness, single-atom Fe doped ZrO 2 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.