High-Performance Photoelectrochemical Water Oxidation with Phosphorus-Doped and Metal Phosphide Cocatalyst-Modified g-C N Formation Through Gas Treatment.

Graphitic carbon nitride (g-C N ) has been widely explored as a photocatalyst for water splitting. The anodic water oxidation reaction (WOR) remains a major obstacle for such processes, with issues such as low surface area of g-C N , poor light absorption, and low charge-transfer efficiency. In this work, such longtime concerns have been partially addressed with band gap and surface engineering of nanostructured graphitic carbon nitride (g-C N ). Specifically, surface area and charge-transfer efficiency are significantly enhanced through architecting g-C N on nanorod TiO to avoid aggregation of layered g-C N . Moreover, a simple phosphide gas treatment of TiO /g-C N configuration not only narrows the band gap of g-C N by 0.57 eV shifting it into visible range but also generates in situ a metal phosphide (M=Fe, Cu) water oxidation cocatalyst. This TiO /g-C N /FeP configuration significantly improves charge separation and transfer capability. As a result, our non-noble-metal photoelectrochemical system yields outstanding visible light (>420 nm) photocurrent: approximately 0.3 mA cm at 1.23 V and 1.1 mA cm at 2.0 V versus RHE, which is the highest for a g-C N -based photoanode. It is expected that the TiO /g-C N /FeP configuration synthesized by a simple phosphide gas treatment will provide new insight for producing robust g-C N for water oxidation.