Automating electroanalytic experimentation accelerates the discovery of concerted proton-electron transfer

Electroanalysis of reaction kinetic is a time-tested method for the mechanistic inquiry of proton-coupled electron transfer (PCET), yet the tedious manual nature of its experimental operation reduces the analytical tool’s research throughput and impedes its broader application. Here we report an automated, high-throughput electrochemical platform for reliable electroanalysis of PCET reactions, with [OsII(bpy)2(py)(H2O)]2+ as the model system. The automated system increases the research throughput by more than 10-fold and accelerates our discovery of concerted PCET pathway by facilitating a proposed adduct formation between the redox and phosphate as a proton donor/acceptor. Instead of spending at least 3 years of manual experimentation, automated electroanalysis completed the inquiry within 1,580 hours (66 days) by analyzing more than 43,800 voltammograms and quantifying about 730 kinetics rate constants. Automating electroanalysis accelerates discovery and optimization for a wide range of critical applications in energy conversion and storage.