A Protocol for Unveiling the Nature of Photocatalytic Hydrogen Evolution Reactions: True Water Splitting or Sacrificial Reagent Acceptorless Dehydrogenation?

• Published in: Angewandte Chemie Vol. 136; no. 52
• Main Authors: Peng, Yong, Rabeah, Jabor, Junge, Henrik, Beller, Matthias
• Format: Journal Article
• Language: English; German
• Published: Weinheim Wiley Subscription Services, Inc 20.12.2024
• Subjects: Alcohols; Amines; C-C coupling; Dehydrogenation; Fuel production; Hydrogen evolution Hydrogen source; Hydrogen evolution reactions; Hydrogen production; Photocatalysis; Protons; Reagents; Redox potential; Sacrificial reagents; Solar energy; Splitting; Sustainable production; Tetrahydofuran; Thiols; Water splitting
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202408626

Photocatalytic water splitting for hydrogen evolution is a highly topical subject in academic research and a promising approach for sustainable fuel production from solar energy. Due to the mismatched energy diagram of the photosensitizer (especially semiconductor‐based materials where band‐edge engineering is not trivial) and the redox potential of the half‐reactions of water splitting, photocatalytic H2 generation from water splitting is usually accelerated by the addition of hole scavengers, i.e. sacrificial reagents such as alcohols, amines, and thiols. However, the source of the protons of the evolved H2 is often neglected, and it is questionable whether such systems are really water splitting. Here, we discuss recent reports on sacrificial reagent‐assisted photocatalytic water splitting and present our recent findings, which showcase that the sacrificial reagent in the investigated photocatalytic water splitting systems inherently undergoes acceptorless dehydrogenation, with H2O serving as the proton shuttle, the amount of which doesn't change during the course of the reaction. The proton source for photocatalytic H2 evolution in the presence of sacrificial reagents (SRs) is comprehensively investigated. Water is found to act as a proton shuttle as its amount remains constant during the course of the reaction. The results also demonstrate the importance of identifying the products of the often‐complicated oxidation processes, as the potential value‐added oxidation products might be even more interesting than the hydrogen produced.