Mo掺杂α-MnO2电催化析氧反应的理论研究

doi:10.15541/jim20210280

摘要/Abstract

摘要：

析氧反应(Oxygen Evolution Reaction, OER)在解决能源短缺和环境问题中扮演了重要角色, 但需要巨大的过电位克服缓慢的动力学势垒, 因此开发高效电催化剂成为不可或缺的一步。本工作应用密度泛函理论研究了α-MnO₂(001)和Mo掺杂α-MnO₂(001)的电催化析氧反应性能, 根据反应路径计算了吉布斯自由能、态密度和差分电荷密度。研究结果表明Mo掺杂可以有效调节α-MnO₂(001)面的电子结构, 改善中间物和催化剂之间的脱吸附能力, 为OER提供更多的电子。吉布斯自由能结果表明Mo掺杂α-MnO₂(001)体系中*OOH生成O₂是发生OER的决速步骤, Mo掺杂降低了过电位, 产生的过电位为1.01 V, 表现出良好的析氧催化性能。

关键词: 析氧反应, 密度泛函理论, 吉布斯自由能, 催化活性

Abstract:

Oxygen evolution reaction (OER) plays an important role in solving energy shortage and environmental problems, but it requires a huge overpotential to overcome the slow kinetic barriers, so the development of high- efficiency electrocatalysts has become an indispensable step. In this work, the performance of α-MnO₂(001) and Mo doped α-MnO₂(001) electrocatalytic oxygen evolution reaction were studied by using density functional theory. Gibbs free energy, density of states and differential charge density were calculated according to the reaction path. The research results show that Mo doping can effectively modulate the electronic structure of α-MnO₂(001) surface, improve desorption and adsorption capacity between intermediates and the catalyst, and provide more electrons for OER. Gibbs free energy calculation results indicate that the formation of O₂ from *OOH is the rate-determining step for OER in the Mo doped α-MnO₂(001) system. Mo doping reduces the overpotential to 1.01 V, which presents a good catalytic performance for oxygen evolution.

Key words: oxygen evolution reaction, density functional theory, Gibbs free energy, catalytic activity

中图分类号:

TQ151

王鹏, 靳遵龙, 陈宁光, 刘勇豪. Mo掺杂α-MnO₂电催化析氧反应的理论研究[J]. 无机材料学报, 2022, 37(5): 541-546.

WANG Peng, JIN Zunlong, CHEN Ningguang, LIU Yonghao. Theoretical Investigation of Mo Doped α-MnO₂ Electrocatalytic Oxygen Evolution Reaction[J]. Journal of Inorganic Materials, 2022, 37(5): 541-546.

图/表 5

图1 (a) α-MnO2(001)和(b) Mo掺杂α-MnO2(001)优化结构的俯视图

Fig. 1 Top view of optimized structures for (a) α-MnO2(001) and (b)Mo doped α-MnO2(001)

图2 α-MnO2和Mo掺杂α-MnO2的OER自由能图

Fig. 2 OER free energy diagrams of α-MnO2 and Mo doped α-MnO2

图3 α-MnO2吸附不同中间物的态密度图

Fig. 3 DOS of α-MnO2 adsorbing different intermediates (a) Undoped; (b)*OH; (c)*O; (d)*OOH Colorful figures are available on website

图4 Mo掺杂α-MnO2吸附不同中间物的态密度图

Fig. 4 DOS of Mo-doped α-MnO2 adsorbing different intermediates (a) Undoped; (b)*OH; (c)*O; (d)*OOH Colorful figures are available on website

图5 (a) α-MnO2和(b) Mo掺杂α-MnO2吸附不同中间物的差分电荷密度图

Fig. 5 Charge density difference of (a) α-MnO2 and (b) Mo doped α-MnO2 adsorbing different intermediates Blue area refers consuming charge; Yellow area refers assembling charge

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Mo掺杂α-MnO₂电催化析氧反应的理论研究

Theoretical Investigation of Mo Doped α-MnO₂ Electrocatalytic Oxygen Evolution Reaction

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