RESUMEN
This work maps the thermodynamics of electrochemically generated C-nucleophiles for reactive capture of CO2. We identify a linear relationship between the pKa, the reduction potential of a protonated nucleophile (E red ), and the nucleophile's free energy of CO2 binding ( Δ G b i n d ). Through synergistic experiments and computations, this study establishes a three-parameter correlation described by the equation Δ G b i n d = - 0.78 p K a + 4.28 E r e d + 20.95 for a series of twelve imidazol(in)ium/N-heterocyclic carbene pairs with an R 2 of 0.92. The correlation allows us to predict the Δ G b i n d of C-nucleophiles to CO2 using reduction potentials or pKas of imidazol(in)ium cations. The carbenes in this study were found to exhibit a wide range CO2 binding strengths, from strongly CO2 binding to nonspontaneous. This observation suggests that the Δ G b i n d of imidazol(in)ium-based carbenes is tunable to a desired strength by appropriate structural changes. This work sets the stage for systematic energetic tuning of electrochemically enabled reactive separations.
RESUMEN
Development of efficient electrocatalysts for the CO2 reduction reaction (CO2RR) to multicarbon products has been constrained by high overpotentials and poor selectivity. Here, we introduce iron phosphide (Fe2P) as an earth-abundant catalyst for the CO2RR to mainly C2-C4 products with a total CO2RR 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 C3-C4 products. Both Grand Canonical-DFT (GC-DFT) calculations and experiments reveal that *formate, not *CO, is the initial intermediate formed from surface phosphino-hydrides and that the latter form ionic hydrides at both surface phosphorus atoms (H@Ps) and P-reconstructed Fe3 hollow sites (H@P*). Binding of these surface hydrides weakens with negative bias (reactivity increases), which accounts for both the shift to C2 products over higher C-C coupling products and the increase in the H2 evolution reaction (HER) rate. GC-DFT predicts that phosphino-hydrides convert *formate to *formaldehyde, the key intermediate for C-C coupling, whereas hydrogen atoms on Fe generate tightly bound *CO via sequential PCET reactions to H2O. GC-DFT predicts the peak in CO2RR current density near -0.1 V is due to a local maximum in the binding affinity of *formate and *formaldehyde at this bias, which together with the more labile C2 product affinity, accounts for the shift to ethylene glycol and away from C3-C4 products. Consistent with these predictions, addition of exogenous CO is shown to block all carbon product formation and lower the HER rate. These results demonstrate that the formation of ionic hydrides and their binding affinity, as modulated by the applied potential, controls the carbon product distribution. This knowledge provides new insight into the influence of hydride speciation and applied bias on the chemical reaction mechanism of CO2RR that is relevant to all transition metal phosphides.
RESUMEN
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. Here, we implement quantum chemical density functional theory calculations to analyze the electrochemical catalytic cycle of diazaphospholenes in acetonitrile. We report computed hydricities, reduction potentials, pKa values, and bond dissociation free energies (BDFEs) for 64 P-based hydridic catalysts generated by functionalizing 8 main structures with 8 different electron donating/withdrawing groups. Our results demonstrate that a wide range of hydricities (29-66 kcal mol-1) and BDFEs (58-81 kcal mol-1) are attainable by functionalizing diazaphospholenes. Compared to the more common carbon-based hydrides, diazaphospholenes are predicted to require less negative reduction potentials to electrochemically regenerate hydrides with an equivalent hydridic strength, indicating their higher energy efficiency in the tradeoff between thermodynamic ability and reduction potential. We show that the tradeoff between the reducing ability and the energetic cost of regeneration can be optimized by varying the BDFE and the reorganization energy associated with hydride transfer (λHT), where lower BDFE and λHT correspond to more efficient catalysts. Aromatic phosphorus hydrides with predicted BDFEs of â¼62 kcal mol-1 and λHT's of â¼20 kcal mol-1 are found to require less negative reduction potentials than dihydropyridines and benzimidazoles with predicted BDFEs of â¼68 and â¼84 kcal mol-1 and λHT's of â¼40 and â¼50 kcal mol-1, respectively.
