Yangming Lin

Heterogeneous catalysis underpins modern chemical manufacturing and emerging energy technologies, yet rational catalyst design still hinges on identifying the elementary steps that control rate and selectivity. Kinetic isotope effects (KIEs), the changes in rate induced by isotopic substitution, provide a sensitive kinetic window into transition-state structure and isotope-sensitive motions along catalytic reaction coordinates. This review summarizes how experimentally measured KIEs have been used to interrogate mechanisms in thermocatalysis, electrocatalysis, and photocatalysis, with representative cases where isotope substitution helps differentiate parallel pathways, reveal kinetically relevant proton/electron-transfer steps, or diagnose condition-dependent shifts in kinetic bottlenecks. We further compare how KIE signatures differ across thermal, electrochemical, and photochemical environments and summarize best practices for robust experimental design, quantitative modeling, and corroborative mechanistic validation. Finally, we outline opportunities for integrating isotope-resolved operando spectroscopy, microkinetic modeling, first-principles calculations, and AI-assisted data mining to transform KIE analysis from qualitative mechanistic labeling into quantitative, mechanism-guided catalyst development.

Efficient in situ spectroscopy studies to reveal mechanistic insights into the electrocatalytic oxygen evolution reaction.

Hydrogen energy is crucial for global carbon neutrality, relying on efficient green hydrogen electrolysis and fuel cells. However, sluggish kinetics in key electrocatalytic reactions, that is, oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR), and dependence on scarce platinum‐group metals hinder their viability. Single‐atom catalysts offer high atom utilization but lack multi‐site synergy for complex reactions like OER and certain HER pathways. Atomically precise clusters enable multi‐electron processes but suffer from electrochemical instability. Integrated single‐atom and cluster catalysts (ISACCs) overcome these limitations by creating synergistic interfaces. This synergy significantly enhances activity, selectivity, and stability for core hydrogen reactions (HER, OER, ORR, HOR), reducing dependence on platinum‐group metals. This review begins with introducing ISACC design strategies, synthesis methods, and performance breakthroughs in these four critical reactions. Then we analyze the atom‐cluster enhancement mechanisms and finally discuss challenges and future directions, aiming to guide the development of efficient, stable, and low‐cost electrocatalysts and promote their practical application in hydrogen energy technologies.

This study uncovered the underlying impact mechanism of conjugation size in COFs on H ₂ O ₂ selectivity in H ₂ O ₂ electrosynthesis.

An efficient carbon-based catalyst is designed for enhancing the anodic carbon oxidation reaction (COR), replacing sluggish oxygen evolution to enable hydrogen production below the 1.23 V boundary potential of water electrolysis, realizing low energy consumption of 3.53 kW h m⁻³ H₂. Pyridinic-N optimizes hydroxy group adsorption on adjacent carbons, boosting the COR efficiency.

Borocarbonitride (BCN) materials, as emerging metal-free catalysts, have garnered considerable interest owing to their abundance; their impressive pH tolerance; and the tunable capability of their B, N-doped carbon network and band structures.