What's behind their various activities? Discerning the importance of surface terminations in Ag3PO4 semiconductor from DFT calculations

Abstract

The surface energy and band gap of inorganic semiconductors are essential properties for a wide variety of applications in materials science, and studying morphologies holds significant importance. However, it is challenging to find a correlation between them at the atomic scale when these materials are multifunctional. This motivates the development of predictive computational models that can optimize these materials based on these quantities. Present findings shed light on the structure and electronic properties of (100), (110), and (111) surfaces of Ag3PO4 by using density functional theory calculations. By introducing two concepts, namely, polyhedron energy and polyhedron band gap, we provide compelling evidence for the effects of surface termination of Ag3PO4 photocatalyst. We compare our predictions to experimental crystal habits, and our results not only allow us to explain their evolution for obtaining a given morphology but also offer a coherent explanation, based on atomic-scale insights, for the discrepancies of morphology-photocatalytic activity relationship of Ag3PO4 in the recent literature. Overall, this work opens a novel avenue for first-principles calculations of morphology and provides a roadmap for the design of more effective inorganic semiconductors with desirable physicochemical properties for potential applications.