Redefining Atomically Dispersed Catalyst Stability via Entropy

Abstract Atomically dispersed catalysts (ADCs) have drawn considerable attention in recent years for their promising activity in heterogeneous catalysis. Conventional catalyst sintering theory largely ignores the entropy effect and suggests that ADCs are normally thermodynamically unstable due to their high surface free energies, which becomes an obstacle for practical applications. Here, we present a generalized thermodynamic framework to demonstrate how the previously ignored entropy effect induces the self-redispersion of supported NPs. Through machine-learning-assisted molecular dynamics simulations, in situ Cs-corrected environmental scanning transmission electron microscopy, and synchrotron-based ambient-pressure X-ray photoelectron spectroscopy experiments, we reveal an entropy-driven phenomenon: the supported NPs redisperse into untrapped ADCs upon heating and reversibly sinter upon cooling in three systems (Pd-CeO2, Cu-TiO2, Ag-TiO2), contrary to the traditional understanding that “high temperature promotes sintering”. We further establish the entropy-driven catalyst redispersion theory, analogous to two-dimensional dissolution, where thermodynamically stable ADCs are ubiquitous up to their saturation concentration. It redefines the basic understanding of sintering, dispersion, and coexistence behavior between NPs and ADCs, thereby offering multiple strategies for obtaining thermodynamically stable ADCs.