Engineering organic polymers as emerging sustainable materials for powerful electrocatalysts

Abstract

Cost-effective and high-efficiency catalysts play a central role in various sustainable electrochemical energy conversion technologies that are being developed to generate clean energy while reducing carbon emissions, such as fuel cells, metal–air batteries, water electrolyzers, and carbon dioxide conversion. In this context, a recent climax in the exploitation of advanced earth-abundant catalysts has been witnessed for diverse electrochemical reactions involved in the above mentioned sustainable pathways. In particular, polymer catalysts have garnered considerable interest and achieved substantial progress very recently, mainly owing to their pyrolysis-free synthesis, highly tunable molecular composition and microarchitecture, readily adjustable electrical conductivity, and high stability. In this review, we present a timely and comprehensive overview of the latest advances in organic polymers as emerging materials for powerful electrocatalysts. First, we present the general principles for the design of polymer catalysts in terms of catalytic activity, electrical conductivity, mass transfer, and stability. Then, the state-of-the-art engineering strategies to tailor the polymer catalysts at both molecular (i.e., heteroatom and metal atom engineering) and macromolecular (i.e., chain, topology, and composition engineering) levels are introduced. Particular attention is paid to the insightful understanding of structure–performance correlations and electrocatalytic mechanisms. The fundamentals behind these critical electrochemical reactions, including the oxygen reduction reaction, hydrogen evolution reaction, CO₂ reduction reaction, oxygen evolution reaction, and hydrogen oxidation reaction, as well as breakthroughs in polymer catalysts, are outlined as well. Finally, we further discuss the current challenges and suggest new opportunities for the rational design of advanced polymer catalysts. By presenting the progress, engineering strategies, insightful understandings, challenges, and perspectives, we hope this review can provide valuable guidelines for the future development of polymer catalysts.