Imaging Anisotropic Proton Intercalation in Photochromic MoO 3

Protonation represents a fundamental chemical process with promising applications in the fields of energy, environment, and memory devices. Probing the protonation mechanism, however, presents a formidable challenge owing to the elusiveness of intercalated protons. In this work, we utilize the atomic and electronic structure changes associated with protonation to directly image the proton intercalation pathways in α-MoO induced by UV illumination. We reveal the anisotropic intercalation behavior which is initiated by photocatalyzed water dissociation preferentially at the (001) edges and then propagates along the axis, transforming α-MoO into H MoO to realize photochromism. This photochromic process can be reversed via heating in air, leading to anisotropic proton deintercalation, also preferentially along the axis. The observed anisotropic behavior can be attributed to the intrinsically low energy barriers for both proton migration along the axis and water dissociation/formation at (001) edges.