Understanding the fundamental mechanisms for charge transfer in supported catalysts is of great importance for heterogeneous catalysis. Several experimental and theoretical results suggest that charge flow through metal-support interfaces leads to the catalytic enhancement that is often observed in mixed catalysts. Therefore, it is crucial to directly probe this charge flow in metal-support catalysts during catalytic reactions. In this review, we consider the main aspects of research studying the processes that create and allow interfacial transfer of highly excited(hot) charge carriers in supported catalysts, and discuss the effect of this charge transfer on catalytic activity. We show a close connection between the phenomena of hot electron creation and chemical energy dissipation that accompanies catalytic reactions at both the gas/solid and liquid/solid interfaces. The intensity of hot electron flow is well correlated with the turnover rates of corresponding reactions, which opens up the possibility for developing new operando methodologies for studying chemical processes on catalytic surfaces.
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