Defect engineering within clusters to enhance cluster–support interaction boosts catalytic performance

Abstract

Supported cluster catalysts effectively optimize mass transfer and electron transfer efficiency, synergistically boosting catalytic performance. However, the regular morphology of clusters hinders adsorption on the support. Therefore, strengthening the metal–support surface interaction remains a critical challenge requiring urgent solutions. In this study, we constructed the Au₄₀ cluster by modifying the Au₄₄ cluster with phosphine, and the resulting Au₄₀ cluster exhibits features similar to those of the parent Au₄₄ cluster, albeit with three gold atoms missing from its core as defects. Furthermore, we loaded the two clusters onto various support materials to evaluate the interaction strength between the clusters and their supports. The results of experiments as well as DFT calculations showed that the defects enhanced the interaction between the Au₄₀ clusters and their supports. Using the hydrogenation of 4-nitrophenol as a model, the catalytic activity of supported catalysts was investigated. The catalytic activity of the Au₄₀ system was much higher than that of the Au₄₄ system, with a catalytic time ratio of approximately 1 : 4. This work reveals that constructing surface defects on clusters serves as an effective method to enhance the interaction between clusters and supports, providing a novel approach for developing cluster-based heterogeneous catalysts.