Three-Dimensional Activity Volcano Plot under an External Electric Field

Abstract

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.

Mechanistic Studies of Stimulus–Response Integrated Catalysis of Single-Atom Alloys under Electric Fields for Electrochemical Nitrogen Reduction

“…Different from traditional metal catalysts, the newly developed single-atom alloys (SAAs), in which an active metal atom is doped in isolation into the surface of another host metal (e.g., the coinage metals), exhibit not only synergy effects as a bimetallic alloy but also high activity and selectivity as a single-atom catalyst and, accordingly, are expected to promote the adsorption and reduction of molecular N 2 . − Thermodynamically, the essence of a catalytic process is to adjust the adsorption behavior of intermediates for improved activity. Therefore, apart from an effective catalyst, external stimuli, e.g., mechanic force, light irradiation, and electric/magnetic fields, can also alter the characters of adsorbates and affect reaction mechanisms. − In particular, because of the tunable intensity and sensitive modulation on electronic properties, the oriented external electric field (OEEF) has been proven as an invisible but powerful game changer in chemical processes. − Very recently, pioneering experiments of the OEEF-catalyzed Diels–Alder reaction and OEEF-modulated electrochemical oxygen/hydrogen evolution reactions clearly showed the superior catalytic performance of OEEFs in both thermal and electrochemical reactions. − Accordingly, we expected that the electric field can effectively alter the adsorption of key intermediates and facilitate the reduction of N 2 .…”