Electron bipolarons at the DMASnBr3 –water interface: Effect on the photocatalytic hydrogen production
Journal article, 2024
In this article, we report on advanced molecular dynamics simulations of the atomistic DMASnBr3–water interface, which, coupled with a grand-canonical formulation of adsorbates and defects, elucidate the surface chemistry and reactivity of this novel water-stable perovskite and highlight the role of small electron bipolarons in photocatalytic hydrogen production. We find that the extremely acidic nature of the surface Br atoms does not allow for significant adsorption of protons at the interface under charge-neutral conditions. However, when electrons are accumulated on the surface, the formation of a small electron bipolaron in the form of a Sn-Sn dimer provides the required electron localization to drive adsorption of H, which is assimilated on surface Sn atoms as hydride. Finally, we estimate a favourable alignment between the bipolaron energy level and the H+/H2 redox level, which suggests the occurrence of a feasible route for hydrogen evolution, bypassing the common reaction mechanism.
Small electron bipolarons
Ab initio molecular dynamics
Energy levels alignment
Photocatalysis
Water-stable metal halide perovskites
pH-dependent surface chemistry
Author
Damiano Ricciarelli
Istituto Per La Microelettronica E Microsistemi, Catania
Consiglo Nazionale Delle Richerche
E. Mosconi
Consiglo Nazionale Delle Richerche
Julia Wiktor
Chalmers, Physics, Condensed Matter and Materials Theory
Lorenzo Malavasi
Universita degli studi di Pavia
Francesco Ambrosio
University of Basilicata
Consiglo Nazionale Delle Richerche
F. De Angelis
Sungkyunkwan University
University of Perugia
Consiglo Nazionale Delle Richerche
King Saud University College of Science
International Journal of Hydrogen Energy
0360-3199 (ISSN)
Vol. 58 863-871Atomistic Design of Photoabsorbing Materials
Swedish Research Council (VR) (2019-03993), 2020-01-01 -- 2023-12-31.
Subject Categories
Physical Chemistry
Materials Chemistry
DOI
10.1016/j.ijhydene.2024.01.268