Activity-Drop of Hydrogen Evolution Reaction in LiNO 3 Based "Hydronium-in-Salt" Acidic Electrolytes on Platinum Enables Electrochemical Nitrate Reduction.

The electrochemical nitrate reduction reaction (NO ₃ ^- RR) involves multiple hydrogenation and deoxygenation steps, which compete with the hydrogen evolution reaction (HER). Therefore, NO ₃ ^- RR driven in acidic media is challenging in spite of advantageous fast hydrogen transfers in its elementary steps. The findings presented in this article first demonstrate that the NO ₃ ^- RR is significantly activated even in acidic lithium nitrate solutions at LiNO ₃ concentrations exceeding 6 m on a Pt electrode (the highly effective catalyst for HER) by the formation of a "hydronium-in-salt" electrolyte (HISE), a new type of aqueous high concentration salt electrolyte. The observed enhancement of NO ₃ ^- RR while the suppression of HER-activity in the LiNO ₃ based HISE was verified by scanning electrochemical microscopy, electrochemical impedance spectroscopy, UV-vis/IR spectroscopy, and molecular dynamics simulations. The formation of a HISE in acidic LiNO ₃ solutions contrasts with that of a "water-in-salt" electrolyte in LiTFSI with the same concentration. The mechanism of NO ₃ ^- RR activation in a HISE suggests facilitated proton-coupled electron transfers (PCETs) from H ₃ O ⁺ to NO ₃ ^- and subsequent reactive intermediates owing to the proximity between the two ions induced by the unique solvation structure blended with all ions together (Li ⁺ + NO ₃ ^- + H ₃ O ⁺ ). In contrast, all the ions are separately hydrated at low concentrations of LiNO ₃ electrolytes. On the other hand, PCET from H ₂ O to NO ₃ ^- in a high concentration LiNO ₃ electrolyte (e.g., 9 m) is not kinetically preferred, probably owing to the slow dissociation kinetics of H ₂ O, and therefore, H ₂ O reduction is not suppressed by the NO ₃ ^- RR.