Abstract
Advances in the rational design of semiconductor-electrocatalyst photoelectrodes provide robust driving forces for improving energy conversion and quantitative analysis, while a deep understanding of elementary processes remains underwhelming due to the multistage interfaces involved in semiconductor/electrocatalyst/electrolyte. To address this bottleneck, we have constructed carbon-supported nickel single atoms (Ni SA@C) as an original electron transport layer with catalytic sites of Ni-N(4) and Ni-N(2)O(2). This approach illustrates the combined effect of photogenerated electron extraction and the surface electron escape ability of the electrocatalyst layer in the photocathode system. Theoretical and experimental studies reveal that Ni-N(4)@C, with excellent oxygen reduction reaction catalytic activity, is more beneficial for alleviating surface charge accumulation and facilitating electrode-electrolyte interfacial electron-injection efficiency under a similar built-in electric field. This instructive method enables us to engineer the microenvironment of the charge transport layer for steering the interfacial charge extract and reaction kinetics, providing a great prospect for atomic scale materials to enhance photoelectrochemical performance.