Is electron ping-pong limiting the catalytic hydrogen evolution activity in covalent photosensitizer–polyoxometalate dyads?

Understanding the limitations of catalytic processes enables the design of optimized catalysts. Here, femtosecond transient absorption spectroelectrochemistry is used to explore the photophysics of polyoxometalate-based covalent photosensitizer-hydrogen evolution catalyst dyads. The study shows that the presence of light-driven forward and backward electron transfer, i.e. "electron ping-pong", is a limiting factor for charge accumulation on the polyoxometalate. Based on this insight, chemical means of optimizing catalyst performance are proposed.