The ability to efficiently and cost-effectively convert solar energy into molecular hydrogen through water splitting is necessary for meeting rising energy demands and to mitigate the adverse effects of carbon-based fuels on the environment. Hydrogenase enzymes catalyze reversible HER from water with remarkably high turnover frequencies at low overpotentials. Practical electrochemical and photoelectrochemical energy devices require the immobilization of stable and active hydrogen evolving catalysts onto electrodes and photocathodes materials, which remains a significant challenge. Heterogenization of molecular catalysts has emerged as a viable immobilization strategy, which combines the advantageous properties of homogeneous and heterogeneous catalysis. We have recently reported the immobilization of metal dithiolene units into extended frameworks as a method of heterogenizing molecular catalysts. These systems have been shown to retain their molecular nature while displaying enhanced stability, activity, and durability in acidic aqueous media in comparison to their molecular analogues. We have expanded this methodology to the formation of a variety of metal chalcogenide coordination polymers and explored their electrochemical H2 evolving activity. Through simple modifications of the ligand scaffold and/or metal center, we have systematically investigated the ability to tune important catalytic parameters of the coordination polymers such as overpotential and stability under exposure to prolonged reductive and acidic conditions.

H<sub>2</sub> Evolution by metal chalcogenide coordination polymers, highly active molecular models of [NiFe] hydrogenases

253rd National Meeting (2017)

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H2 Evolution by metal chalcogenide coordination polymers, highly active molecular models of [NiFe] hydrogenases

H₂ Evolution by metal chalcogenide coordination polymers, highly active molecular models of [NiFe] hydrogenases