Advances demonstrate that the incorporation of phosphorous into the network of nitrogen, sulfur, or fluorine‐doped carbon materials can remarkably enhance their oxygen and hydrogen evolution activities. However, the electrocatalytic behaviors of pristine phosphorous single‐doped carbon catalysts toward the oxygen and hydrogen evolution reactions (OER and HER) are rarely investigated and their corresponding active species are not yet explored. To clearly ascertain the effects of phosphorous doping on the OER and HER and identify the active sites, herein, phosphorous unitary‐doped graphite layers with different phosphorous species distributions are prepared and the correlations between the oxygen or hydrogen evolution activity and different phosphorous species are investigated, respectively. Results indicate that phosphorous single‐doped graphite layers show a superior oxygen evolution activity to most of the reported OER catalysts and the commercial IrO2 in alkaline medium, and comparable hydrogen evolution activity to most reported carbon catalysts in acidic medium. Moreover, the relevancies unveil that the COP species are the main OER active species, and the defects derived from the decomposition of C3P = O species are the main active sites for HER, as evidenced by density functional theory calculations, showing a new perspective for the design of more effective phosphorous‐containing water‐splitting catalysts.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.