近日，哈尔滨工业大学杜春雨团队报道了活动场地结构的混沌是爬升2e^-ORR火山图顶点的阶梯。该项研究成果发表在2026年2月11日出版的《美国化学会志》上。

中性介质中的两电子氧还原反应为过氧化氢的高效合成提供了环境友好且具实用性的策略，然而电催化机理认知的匮乏与催化剂活性的不足严重制约其发展。

研究组提出基于原子熵波动的四配位钴单原子催化剂战略性设计原则——通过几何与电子双维度修饰，定量描述为描述符φ。该描述符能够精准捕捉局域熵波动对催化性能的影响，在钴单原子催化剂体系中有效建立氧还原活性与配位环境间的构效关系，进而阐明位于火山图顶点附近的CoN₃S高活性来源。基于理论预测合成的Co–N₃SC催化剂，在中性电解液中实现了低过电位下97%的过氧化氢电合成选择性。

更值得关注的是，Co–N₃SC展现出卓越的稳定性，在流动池器件中（110小时@0.18A）实现10.58克过氧化氢累计产量；固态电解质电解池中产率高达10.25 mol g_cat^-1 h^-1，成功实现高纯度过氧化脲的直接合成。该工作不仅为高活性高选择性两电子氧还原催化剂设计提供新范式，更深化了对配位环境-活性调控机制的理解，并为催化剂的实际应用验证建立了完整研究范本。

附：英文原文

Title: Chaos of Active Site Structure as a Ladder to Climbing the Apex of the 2e–ORR Volcano Plot

Author: Jiannan Du, Guokang Han, Xin Zhang, Dongyue Xin, Yuqi Yan, Xiaodan Wen, Hua Huo, Geping Yin, Yong Shuai, Chunyu Du

Issue&Volume: February 11, 2026

Abstract: Two-electron oxygen reduction reaction (2e–ORR) in neutral media offers an eco-friendly and practical strategy for efficient synthesis of hydrogen peroxide (H2O2), yet limited understanding of electrocatalytic mechanisms and poor catalyst activity hinder its development. We propose a strategic design principle for high-performance four-coordinated Co single-atom catalysts based on atomic entropy fluctuation by both geometric and electronic modifications, quantitatively described by the descriptor φ, which is able to capture the impact of local entropy fluctuations on catalytic performance. φ serves as an effective metric for elucidating the relationship between ORR activity and the coordination environment in Co single-atom catalyst systems, thereby elucidating the origin of the high activity of CoN3S, which lies close to the apex of the volcano peak. Based on the prediction, the as-synthesized Co–N3SC catalyst achieved a 97% selectivity for H2O2 electrosynthesis at low overpotentials in neutral electrolytes. Impressively, Co–N3SC exhibited remarkable stability and delivered a cumulative yield of 10.58 g of H2O2 in flow cell devices (110 h @0.18A). In a solid-state electrolyte electrolyzer, it achieved a production rate of 10.25 mol gcat–1 h–1, enabling the direct synthesis of high-purity urea peroxide. This work offers not only strategies for designing highly active and selective 2e–ORR catalysts but deep insights into coordination environment–activity regulation and validation of practical catalyst applications.

DOI: 10.1021/jacs.5c15908

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c15908