Abstract. The conversion of inert, energy-poor chemical pollutants into energy-rich chemical fuels represents an attractive solution for the generation of a secure and sustainable energy economy. To date, activation of these substrates is performed industrially via heterogeneous catalysis, often conducted at extreme temperatures and pressures, requiring dedicated facilities. A prominent class of materials invoked in small molecule activation are reducible metal chalcogenides. These materials are composed of metal centers capable of fluctuating between multiple oxidation states. Toward the elucidation of design criteria for new materials, my research group is investigating the synthesis and reactivity of atomically precise transition metal chalcogenide clusters. My talk will discuss a new project in my laboratory, focused on the use of thiomolybdate clusters as models for the catalytic reactivity of the surface of MoS2. Our initial results demonstrate that a cobalt-doped assembly Cp*3CoMo2S4 (Cp* = 1,2,3,4,5-pentamethylcyclopentadienide) serves as a structural and functional model for the basal plane of Co-doped MoS2. Cp*3CoMo2S4 is an electrocatalyst for proton reduction in dimethylformamide. Compared with its homometallic congener (Cp*3Mo3S4), cobalt incorporation improves activity by lowering the overpotential for proton reduction, consistent with the contrasting catalytic performance of MoS2 and its Co-doped derivative. Isolation of the reduced form of Cp*3CoMo2S4 and subsequent reactivity studies provide insight into the reaction pathway. Current work is focused on the synthesis of externally heterometal-doped derivatives of this cluster and evaluation of their electronic structure and reactivity toward proton reduction. By studying these molecular models, we aim to elucidate the effects of heterometal doping and its site-specific influence, enabling a deeper mechanistic understanding of proton reduction through the isolation of key intermediates.
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