Steering Catalytic Selectivity with Atomically Dispersed Metal Electrocatalysts for Renewable Energy Conversion and Commodity Chemical Production.

Abstract

Electrocatalysis is a key driver in promoting the paradigm shift from the current fossil-fuel-based hydrocarbon economy to a renewable-energy-driven hydrogen economy. The success of electrocatalysis hinges primarily on achieving high catalytic selectivity along with maximum activity and sustained longevity. Many electrochemical reactions proceed through multiple pathways, requiring highly selective catalysts.Atomically dispersed metal catalysts have emerged as a new frontier in heterogeneous catalysis. In addition to the widely perceived advantages of maximized active site utilization and substantially reduced metal content, they have shown different catalytic selectivities in some electrocatalytic reactions compared to the traditional nanoparticle (NP)-based catalysts. Although there have been significant advances in their synthesis, the highly energetic nature of a single atomic site has made the preparation of atomically dispersed metal catalysts rely on empiricism rather than rational design. Consequently, the structural comprehension of a single atomic site and the understanding of its unusual electrocatalytic selectivity remain largely elusive.In this Account, we describe our endeavors toward developing general synthetic approaches for atomically dispersed metal catalysts for the discovery of new selective and active electrocatalysts and to understand their catalytic nature. We introduce synthetic approaches to produce a wide range of nonprecious- and precious-metal-based atomically dispersed catalysts and control their coordination environments. Metallomacrocyclic-compound-driven top-down and metal salt/heteroatom layer-based bottom-up strategies, coupled with a SiO2-protective-layer-assisted method, have been developed that can effectively generate single atomic sites while mitigating the formation of metallic NPs. The low-temperature gas-phase ligand exchange method can reversibly tune the coordination structure of the atomically dispersed metal sites. We have used the prepared atomically dispersed metal catalysts as model systems to investigate their electrocatalytic reactivity for renewable energy conversion and commodity chemical production reactions, in which high selectivity is important. The reactions of our interest include the following: (i) the oxygen reduction reaction, where O2 is reduced to either H2O or H2O2 via the four-electron or two electron pathway, respectively; (ii) the CO2 reduction reaction, which should suppress the hydrogen evolution reaction; and (iii) the chlorine evolution reaction, which competes with the oxygen evolution reaction. The type of metal center to which the reactant is directly bound is found to be the most important in determining the selectivity, which originates from the dramatic changes in the binding energy of each metal center with the reactants. The coordination structure surrounding the metal center also has a significant effect on the selectivity; its control can modulate the oxidation state of the metal center, thereby altering the binding strength with the reactants.We envisage that future advances in the synthesis of atomically dispersed metal catalysts, combined with the growing power of computational, spectroscopic, and microscopic methods, will bring their synthesis to the level of rational design. Elaborately designed catalysts can overcome the current limits of catalytic selectivity, which will help establish the field of atomically dispersed metal catalysts as an important branch of catalysis.