Controlling Hydrogen Evolution and CO2 Reduction at Transition Metal Hydrides

Fuel-forming reactions such as the hydrogen evolution reaction (HER) and CO2 reduction (CO2R) are vital to transitioning to a carbon-neutral economy. The equivalent oxidation reactions are also important for efficient utilization in fuel cells. Metal hydride intermediates are common in these catalytic and electrocatalytic processes. Guiding metal hydride reactivity is important for achieving selective, kinetically fast, and low overpotential redox reactions. Our work has focused on understanding kinetic and thermodynamic aspects for controlling these reactive hydride species in an effort to design more selective electrocatalysts that operate at low overpotentials. Key to our research approach is understanding the free energy changes and rate of discrete steps of catalysis through the synthesis of proposed intermediates to independently investigate catalytic steps. Hydricity, the free energy of hydride dissociation, and how these values change with metal and ligand environment have informed catalyst design in the past few decades. We describe here how we have advanced upon these earlier studies.In our early studies we sought to understand solvent-dependent changes in hydricity for transition metal hydrides and how they impact the free energy for reduction of CO2 to formate (HCO2 -). Additionally, we described how hydricity values can be applied to optimize HER and CO2R catalysis. This framework provides general guidelines for achieving selective CO2 reduction to formate without concomitant generation of H2. Kinetic information on steps in the proposed catalytic cycle of HER and CO2R catalysts were evaluated to identify potential rate-determining steps. As a second approach to achieve selective reduction for CO2, we explored two catalyst design strategies to kinetically inhibit HER using electrostatic (charged) and steric interactions. Hydricity values and other considerations for minimizing the free energy of proposed catalytic steps were also used to design an electrocatalyst for the interconversion between CO2 and HCO2 - at low overpotentials. Further, we discuss our efforts to translate the CO2 hydrogenation activity of homogeneous catalysts to electrocatalysis.All of these catalytic systems operate with classical metal hydrides, where the electrons and proton are colocated on the metal center. However, classical metal hydrides all require very reducing potentials to generate sufficiently strong hydride donors for CO2 reduction. An analysis of metal hydride hydricity and reduction potentials shows that the strong correlation between reduction potential and hydricity is a general trend because the former is also highly correlated to pK a. However, formate dehydrogenase (FDH) generates a competent hydride donor at more mild potentials through bidirectional hydride transfer, where the proton and electrons of the hydride are not colocated. This bioinspired approach points to a promising new strategy for generating strong hydride donors at milder potentials and will surely open new avenues for using hydricity as a guide for addressing new and existing problems in catalysis.