Shifting the electrocatalysis paradigm: from transition metals to main group elements-based systems

Abstract

Electrocatalysts are pivotal to renewable energy conversion and sustainable chemical synthesis, yet conventional noble metal catalysts suffer from scarcity and high cost, while transition metal catalysts are plagued by the Fenton effect, which degrades electrode structures, reduces reaction selectivity, and poses safety risks. To address these bottlenecks, main-group element-based electrocatalysts have emerged as promising alternatives, leveraging their high terrestrial abundance, tunable s/p orbital characteristics, and radical resistance. This review systematically summarizes the synthesis strategies, catalytic mechanisms, and performance breakthroughs of main-group metal electrocatalysts. Key synthesis methods including pyrolysis, aerogel, hydrothermal, template, combinatorial magnetron co-sputtering, and chemical vapor carbonization enable precise regulation of atomic dispersion and nanostructure, with pyrolysis and template methods achieving 3–5 times higher specific surface area via Al-N₄ and Mg-N₂ coordination without harsh acid etching. In terms of catalytic performance, main-group metal catalysts exhibit remarkable activity. Mechanistically, p-band center regulation optimizes intermediate adsorption energy, while s-block metals (Mg, Ca) inhibit ·OH formation via stable valence states and s-orbital properties, improving alkaline stability. Furthermore, integrating in-situ characterization with machine learning accelerates the shift from “trial-and-error" to rational design. Despite challenges in acidic stability, reaction selectivity regulation, and large-scale preparation cost, main-group metal electrocatalysts offer innovative solutions for advancing electrocatalytic systems, with promising extensions to CO₂ reduction and nitrogen fixation. This review provides critical insights into the design and development of high-performance, cost-effective electrocatalysts for sustainable energy applications.