Three-Dimensional Activity Volcano Plot under an External Electric Field

An external electric field (EEF) can impact a broad range of catalytic processes beyond redox systems. Computational design of catalysts under EEFs targeting specific operation conditions essentially requires accurate predictions of the response of a complex physicochemical system to collective parameters such as EEF strength/direction and temperature. Here, we develop a multiscale approach that progressively bridges finite-field density functional theory, chemical reaction network theory, microkinetic modeling, and machine learning-assisted high-throughput computations, which leads to the construction of a three-dimensional activity volcano plot under EEFs for thousands of metallic alloys. Taking steam reforming of methanol as an example, we discover a nontrivial collective effect of EEF and temperature on the conversion of methanol: a positive EEF can increase the conversion at high temperatures but strongly suppress the conversion at low temperatures, highlighting the necessity of multiscale modeling for catalyst design under EEFs.