Enhancing the Photoelectrochemical Hydrogen Evolution Reaction through Nanoscrolling of Two-Dimensional Material...

The clean production of hydrogen from water using sunlight has emerged as a sustainable alternative toward large-scale energy generation and storage. However, designing photoactive semiconductors that are suitable for both light harvesting and water splitting is a pivotal challenge. Atomically thin transition metal dichalcogenides (TMD) are considered as promising photocatalysts because of their wide range of available electronic properties and compositional variability. However, trade-offs between carrier transport efficiency, light absorption, and electrochemical reactivity have limited their prospects. We here combine two approaches that synergistically enhance the efficiency of photocarrier generation and electrocatalytic efficiency of two-dimensional (2D) TMDs. The arrangement of monolayer WS₂ and MoS₂ into a heterojunction and subsequent nanostructuring into a nanoscroll (NS) yields significant modifications of fundamental properties from its constituents. Spectroscopic characterization and ab initio simulation demonstrate the beneficial effects of straining and wall interactions on the band structure of such a heterojunction-NS that enhance the electrochemical reaction rate by an order of magnitude compared to planar heterojunctions. Phototrapping in this NS further increases the light-matter interaction and yields superior photocatalytic performance compared to previously reported 2D material catalysts and is comparable to noble-metal catalyst systems in the photoelectrochemical hydrogen evolution reaction (PEC-HER) process. Our approach highlights the potential of morphologically varied TMD-based catalysts for PEC-HER.