南京理工大学李健生团队近日研究了孔洞MXene上不对称配位钴单原子/团簇的超快Fenton样催化。该项研究成果发表在2025年6月24日出版的《德国应用化学》杂志上。

开发具有不对称配位构型的单原子催化剂（SACs）对于增强Fenton样反应中过氧单硫酸盐（PMS）的活化至关重要。然而，精确调节金属中心的电子结构和配位环境以进一步改善活化动力学仍然是一个关键挑战。研究组设计了不对称的CoN₁O₂单原子（SA）位点和Co纳米簇（NC），它们在高度石墨化的碳层中空间受限，并通过双配位微环境策略支撑在多孔MXene纳米片（CoSA NC/H20MX）上。CoSA NC/H20MX催化剂在去除双酚A（BPA）方面表现出卓越的性能，校正速率常数（k_value）为2750 min^-1 M^-1，总有机碳去除效率为78.2%。 

机理研究表明，BPA的去除主要是通过非自由基电子转移过程（ETP，~100%）进行的，这有助于BPA的快速聚合。密度泛函理论计算表明，Co-NCs协同增强了不对称CoN₁O₂-SAs位点吸附和激活PMS的能力，显著加速了界面电荷转移。此外，通过交联CoSA NC/H20MX和石墨烯制备的催化膜在单程模式下实现了100%的BPA去除，在24小时的连续操作中，水力停留时间仅为40毫秒。这项工作为设计通过ETP驱动的聚合途径去除污染物的高性能催化剂提供了新的见解。

附：英文原文

Title: Confining Asymmetrically Coordinated Cobalt Single-Atoms/Clusters on Holey MXene for Ultrafast Fenton-like Catalysis

Author: Xin Guo, Hao Zhang, Yunlong Wang, Yiyuan Yao, Chengming Xiao, Kechen Gu, Junwen Qi, Yujun Zhou, Yue Yang, Zhigao Zhu, Jiansheng Li

Issue&Volume: 2025-06-24

Abstract: Developing single-atom catalysts (SACs) with asymmetric coordination configurations is essential for enhancing peroxymonosulfate (PMS) activation in Fenton-like reactions. However, precisely regulating the electronic structure and coordination environment of metal centers to further improve activation kinetics remains a key challenge. Herein, we designed asymmetric CoN1O2 single-atoms (SAs) sites and Co nanoclusters (NCs) that were spatially confined in highly graphitized carbon layers and supported on holey MXene nanosheet (CoSA-NC/H20MX) via a dual-coordination microenvironment strategy. The CoSA-NC/H20MX catalyst demonstrated exceptional performance on bisphenol A (BPA) removal, achieving a corrected rate constant (kvalue) of 2750 min-1 M-1 and a total organic carbon removal efficiency of 78.2%. Mechanistic studies revealed that BPA removal was dominated by a non-radical electron transfer process (ETP, ~100%), which facilitated rapid polymerization of BPA. Density functional theory calculations demonstrated that Co NCs synergistically enhanced the ability of asymmetric CoN1O2 SAs sites to adsorb and activate PMS, significantly accelerating interfacial charge transfer. Furthermore, a catalytic membrane fabricated by crosslinking of CoSA-NC/H20MX and graphene achieved 100% BPA removal in single-pass mode with a hydraulic retention time of just 40 ms over 24 h of continuous operation. This work provides new insights into designing high-performance catalysts for pollutant removal via ETP-driven polymerization pathways.

DOI: 10.1002/anie.202511266

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202511266