Morphology and Size-Dependent Visible-Light-Driven Photocatalytic Hydrogen Evolution of Porphyrin Assemblies

Photocatalytic water splitting to form hydrogen can effectively alleviate energy and environmental problems attracting wide attention. However, the current photocatalysts have low photocatalytic efficiencies due to the narrow absorption spectrum, which is far from the actual application requirements. Herein, we use the as-prepared zinc porphyrin self-assemblies to visible-light-drive photocatalytic hydrogen evolution with Pt as the cocatalyst and ascorbic acid (AA) as the sacrificial agent. The results exhibit morphology-dependent performance and hexagonal stacks achieved optimal H-2 evolution rate (47.1 mmol/h/g), then followed by nanodiscs, nanorod and tetragonal stacks, meanwhile the nanorods with different aspect ratios show size-dependent properties. The UV-vis absorption and photoluminescence spectra and the shortening of decay time of the corresponding ZnTPyP aggregates reveal that the well-defined self-assembled porphyrin networks are J-aggregation and boost efficient energy transfer with respect to monomer. Such porphyrin self-assemblies are standing for one of the most promising photosensitizers in photocatalysis field and provide an important reference for designing the next generation of hydrogen production.