Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites

Abstract Thiomolybdates are molecular molybdenum‐sulfide clusters formed from Mo centers and sulfur‐based ligands. For decades, they have attracted the interest of synthetic chemists due to their unique structures and their relevance in biological systems, e.g., as reactive sites in enzymes. More recently, thiomolybdates are explored from the catalytic point of view and applied as homogeneous and molecular mimics of heterogeneous molybdenum sulfide catalysts. This review summarizes prominent examples of thiomolybdate‐based electro‐ and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. Active sites of thiomolybdates relevant for the hydrogen evolution reaction are examined, aiming to shed light on the link between cluster structure and performance. The shift from solution‐phase to surface‐supported thiomolybdates is discussed with a focus on applications in electrocatalysis and photocatalysis. The outlook highlights current trends and emerging areas of thiomolybdate research, ending with a summary of challenges and key takeaway messages based on the state‐of‐the‐art research.