Radiolytic Water Splitting Sensitized by Nanoscale Metal–Organic Frameworks

High-energy radiation that is compatible with renewable energy sources enables direct H2 production from water for fuels; however, the challenge is to convert it as efficiently as possible, and the existing strategies have limited success. Herein, we report the use of Zr/Hf-based nanoscale UiO-66 metal-organic frameworks as highly effective and stable radiation sensitizers for purified and natural water splitting under γ-ray irradiation. Scavenging and pulse radiolysis experiments with Monte Carlo simulations show that the combination of 3D arrays of ultrasmall metal-oxo clusters and high porosity affords unprecedented effective scattering between secondary electrons and confined water, generating increased precursors of solvated electrons and excited states of water, which are the main species responsible for H2 production enhancement. The use of a small quantity (<80 mmol/L) of UiO-66-Hf-OH can achieve a γ-rays-to-hydrogen conversion efficiency exceeding 10% that significantly outperforms Zr-/Hf-oxide nanoparticles and the existing radiolytic H2 promoters. Our work highlights the feasibility and merit of MOF-assisted radiolytic water splitting and promises a competitive method for creating a green H2 economy.