Band Gap Narrowing in a High-Entropy Spinel Oxide Semiconductor for Enhanced Oxygen Evolution Catalysis

Rowan R Katzbaer; Francisco Marques Dos Santos Vieira; Ismaila Dabo; Zhiqiang Mao; Raymond E Schaak

doi:10.1021/jacs.2c12887

Band Gap Narrowing in a High-Entropy Spinel Oxide Semiconductor for Enhanced Oxygen Evolution Catalysis

J Am Chem Soc. 2023 Mar 29;145(12):6753-6761. doi: 10.1021/jacs.2c12887. Epub 2023 Mar 15.

Authors

Rowan R Katzbaer¹, Francisco Marques Dos Santos Vieira², Ismaila Dabo², Zhiqiang Mao^{1

3}, Raymond E Schaak^{1

4

5}

Affiliations

¹ Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
² Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
³ Department of Physics, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
⁴ Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
⁵ Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.

PMID: 36920866
DOI: 10.1021/jacs.2c12887

Abstract

High-entropy oxides (HEOs), which contain five or more metal cations that are generally thought to be randomly mixed in a crystalline oxide lattice, can exhibit unique and enhanced properties, including improved catalytic performance, due to synergistic effects. Here, we show that band gap narrowing emerges in a high-entropy aluminate spinel oxide, (Fe_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2)Al₂O₄ (A⁵Al₂O₄). The 0.9 eV band gap of A⁵Al₂O₄ is narrower than the band gaps of all parent spinel oxides. First-principles calculations for multicomponent AAl₂O₄ spinels indicate that the band gap narrowing arises from the broadening of the energy distribution of the 3d states due to variations in the electronegativities and crystal field splitting across the 3d transition-metal series. As a catalyst for the oxygen evolution reaction in an alkaline electrolyte, A⁵Al₂O₄ reaches a current density of 10 mA/cm² at an overpotential of 400 mV, outperforming all of the single-metal end members at an applied potential of 1.7 V vs RHE. Catalyst deactivation occurs after 5 h at 10 mA/cm² and is attributed, based on elemental analysis and grazing-incidence X-ray diffraction, to the formation of a passivating layer that blocks the high-entropy oxide surface. This result helps to validate that the HEO is the active catalyst. The observation of band gap narrowing in A⁵Al₂O₄ expands the scope of synergistic properties exhibited by high-entropy materials and offers insight into the question of how the electronic structure of multicomponent oxide materials can be engineered via a high-entropy approach to achieve enhanced catalytic properties.