Photocatalytic Hydrogen Production Coupled with Selective Benzylamine Oxidation over MOF Composites

• Published in: Angewandte Chemie International Edition Vol. 57; no. 19; pp. 5379 - 5383
• Main Authors: Liu, Hang, Xu, Caiyun, Li, Dandan, Jiang, Hai‐Long
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 04.05.2018
• Edition: International ed. in English
• Subjects: amine oxidative coupling; Catalytic activity; charge separation; Composite materials; Hydrogen production; Metal-organic frameworks; Oxidation; Photocatalysis; Photoexcitation; Protons; Separation; Triazine; Water splitting; amine oxidative coupling; charge separation; photocatalysis; hydrogen production; metal-organic frameworks
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201800320

Photocatalytic water splitting requires separation of the mixed H2 and O2 products and is often hampered by the sluggish O2‐producing half reaction. An approach is now reported to address these issues by coupling the H2‐producing half reaction with value‐added benzylamine oxidation reaction using metal–organic framework (MOF) composites. Upon MOF photoexcitation, the electrons rapidly reduce the protons to generate H2 and the holes promote considerable benzylamine oxidation to N‐benzylbenzaldimine with high selectivity. Further experimental characterizations and theoretical calculation reveal that the highly conjugated s‐triazine strut in the MOF structure is crucial to the efficient charge separation and excellent photocatalytic activity. A metal–organic framework (MOF) composite (Pt/PCN‐777) has been prepared to achieve efficient proton reduction and selective benzylamine oxidation simultaneously under light irradiation. The enlarged π‐conjugation in the MOF ligand has been demonstrated to be crucial for improving the separation of charge carriers and thus greatly enhanced catalytic efficiency.