Organic Surface Passivation on Rh@CeO2 Cocatalysts for Photocatalytic Overall Water Splitting

• Published in: Angewandte Chemie International Edition p. e202513029
• Main Authors: Xu, Teng, Shi, Jinfeng, Peng, Kang-Shun, Hsu, Yung-Hsi, Liu, Yu-Chun, Wang, Sibo, Zhang, Hansong, Wang, Yongjie, Zhang, Guigang, Hung, Sung-Fu, Liu, Kunlong, Wang, Xinchen
• Format: Journal Article
• Language: English
• Published: 12.08.2025
• ISSN: 1521-3773; 1521-3773
• DOI: 10.1002/anie.202513029

Decorating Rh cocatalysts with Cr2O3 overlayers can enhance the performance of photocatalytic overall water splitting (POWS). However, there is a general concern on the dissolution of Cr2O3, calling for the development of environment-friendly metal oxides. Here, we employ phenylphosphonic acid (PPOA) as a model surface modifier to decorate the model Rh@CeO2 cocatalysts and demonstrate the critical role of organic surface passivation in H2 evolution catalysis. We identify a "surface passivation effect" in photocatalysis, wherein the PPOA modification on CeO2 overlayers not only suppress the adsorption and activation of oxygen but exhibit strong resistance to hydrogen reduction during POWS. This dual functionality effectively suppresses the reverse reactions by blocking the redox cycle of exposed Rh sites and defective CeO2 overlayers, resulting in significantly enhanced photocatalytic activity and stability. Importantly, this strategy is not limited to Rh@CeO2-PPOA systems; it also improves POWS performance in systems where other reducible oxides-organophosphonic acids structure are used as passivation layers on other noble metal cocatalysts. These findings provide fundamental insights into the universal principles of surface passivation in photocatalysis and offer a practical framework for regulating the reverse reactions and provide guidance for optimizing POWS through targeted surface organic modification.Decorating Rh cocatalysts with Cr2O3 overlayers can enhance the performance of photocatalytic overall water splitting (POWS). However, there is a general concern on the dissolution of Cr2O3, calling for the development of environment-friendly metal oxides. Here, we employ phenylphosphonic acid (PPOA) as a model surface modifier to decorate the model Rh@CeO2 cocatalysts and demonstrate the critical role of organic surface passivation in H2 evolution catalysis. We identify a "surface passivation effect" in photocatalysis, wherein the PPOA modification on CeO2 overlayers not only suppress the adsorption and activation of oxygen but exhibit strong resistance to hydrogen reduction during POWS. This dual functionality effectively suppresses the reverse reactions by blocking the redox cycle of exposed Rh sites and defective CeO2 overlayers, resulting in significantly enhanced photocatalytic activity and stability. Importantly, this strategy is not limited to Rh@CeO2-PPOA systems; it also improves POWS performance in systems where other reducible oxides-organophosphonic acids structure are used as passivation layers on other noble metal cocatalysts. These findings provide fundamental insights into the universal principles of surface passivation in photocatalysis and offer a practical framework for regulating the reverse reactions and provide guidance for optimizing POWS through targeted surface organic modification.