MOCHAs: An Emerging Class of Materials for Photocatalytic H 2 Production.

Production of green hydrogen (H 2 ) is a sustainable process able to address the current energy crisis without contributing to long-term greenhouse gas emissions. Many Ag-based catalysts have shown promise for light-driven H 2 generation, however, pure Ag-in its bulk or nanostructured forms-suffers from slow electron transfer kinetics and unfavorable Ag─H bond strength. It is demonstrated that the complexation of Ag with various chalcogenides can be used as a tool to optimize these parameters and reach improved photocatalytic performance. In this work, metal-organic-chalcogenolate assemblies (MOCHAs) are introduced as effective catalysts for light-driven hydrogen evolution reaction (HER) and investigate their performance and structural stability by examining a series of AgXPh (X = S, Se, and Te) compounds. Two catalyst-support sensitization strategies are explored: by designing MOCHA/TiO 2 composites and by employing a common Ru-based photosensitizer. It is demonstrated that the heterogeneous approach yields stable HER performance but involves a catalyst transformation at the initial stage of the photocatalytic process. In contrast to this, the visible-light-driven MOCHA-dye dyad shows similar HER activity while also ensuring the structural integrity of the MOCHAs. The work shows the potential of MOCHAs in constructing photosystems for catalytic H 2 production and provides a direct comparison between known AgXPh compounds.