Efficient Visible Light Photocatalytic Hydrogen Evolution by Boosting the Interfacial Electron Transfer in Mesoporous...

Photocatalytic water splitting for hydrogen generation is an appealing means of sustainable solar energy storage. In the past few years, mesoporous semiconductors have been at the forefront of investigations in low-cost chemical fuel production and energy conversion technologies. Mesoporosity combined with the tunable electronic properties of semiconducting nanocrystals offers the desired large accessible surface and electronic connectivity throughout the framework, thus enhancing photocatalytic activity. In this work, we present the construction of rationally designed 3D mesoporous networks of Co₂P-modified CdIn₂S₄ nanoscale crystals (ca. 5-6 nm in size) through an effective soft-templating synthetic route and demonstrate their impressive performance for visible-light-irradiated catalytic hydrogen production. Spectroscopic characterizations combined with electrochemical studies unravel the multipathway electron transfer dynamics across the interface of Co₂P/CdIn₂S₄ Mott-Schottky nanoheterojunctions and shed light on their impact on the photocatalytic hydrogen evolution chemistry. The strong Mott-Schottky interaction occurring at the heterointerface can regulate the charge transport toward greatly improved hydrogen evolution performance. The hybrid catalyst with 10 wt % Co₂P content unveils a H₂ evolution rate of 20.9 mmol g_cat ^-1 h^-1 under visible light irradiation with an apparent quantum efficiency (AQE) up to 56.1% at 420 nm, which is among the highest reported activities. The understanding of interfacial charge-transfer mechanism could provide valuable insights into the rational development of highly efficient catalysts for clean energy applications.