Predictive energetic tuning of C-Nucleophiles for the electrochemical capture of carbon dioxide.

This work maps the thermodynamics of electrochemically generated C-nucleophiles for reactive capture of CO. We identify a linear relationship between the pK, the reduction potential of a protonated nucleophile ( ), and the nucleophile's free energy of CO binding ( ). Through synergistic experiments and computations, this study establishes a three-parameter correlation described by the equation for a series of twelve imidazol(in)ium/N-heterocyclic carbene pairs with an of 0.

Surface Hydrides on FeP Electrocatalyst Reduce CO at Low Overpotential: Steering Selectivity to Ethylene Glycol.

Development of efficient electrocatalysts for the CO reduction reaction (CORR) to multicarbon products has been constrained by high overpotentials and poor selectivity. Here, we introduce iron phosphide (FeP) as an earth-abundant catalyst for the CORR to mainly C-C products with a total CORR Faradaic efficiency of 53% at 0 V vs RHE. Carbon product selectivity is tuned in favor of ethylene glycol formation with increasing negative bias at the expense of C-C products.

Diazaphospholenes as reducing agents: a thermodynamic and electrochemical DFT study.

Diazaphospholenes have emerged as a promising class of metal-free hydride donors and have been implemented as molecular catalysts in several reduction reactions. Recent studies have also verified their radical reactivity as hydrogen atom donors. Experimental quantification of the hydricities and electrochemical properties of this unique class of hydrides has been limited by their sensitivity towards oxidation in open air and moist environments.