High-spin configuration of asymmetric CoN1C2 coordination for boosting d-p orbital hybridization in Fenton-like reactions

IF 15.7 1区 化学 Q1 CHEMISTRY, APPLIED
Qian Bai , Juanjuan Qi , Rongzhe Zhang , Zhiyuan Chen , Zihao Wei , Zhiyi Sun , Ziwei Deng , Xudong Yang , Qiangwei Li , Wenxing Chen , Lidong Wang
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引用次数: 0

Abstract

Asymmetric single-atom catalysts (ASACs) have attracted much attention owing to their excellent catalytic properties. However, the relationship between asymmetric coordination and the spin states of metal sites remains unclear. Additionally, the modulation of reactive oxygen species in Fenton-like reactions remains challenging. Herein, a novel strategy is reported for the rational design of highly loaded Co ASACs (CoN1C2/C2N) immobilized on three-dimensional flower-like C2N using an in situ-generated carbon defect method. In particular, the asymmetrically tricoordinated CoN1C2/C2N exhibited excellent catalytic activity for sulfachloropyridazine degradation, with a turnover frequency of 36.8 min–1. Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration (t2g6eg1) to the high-spin configuration (t2g5eg2) owing to asymmetric coordination. The high-spin Co 3d orbital in CoN1C2/C2N possessed more unpaired electrons and therefore, had a strong ability to gain electrons from the O 2p orbitals of HSO5, boosting d-p orbital hybridization. More importantly, the spin-electron filling in the σ* orbital of high-spin Co 3d−O 2p accelerated the desorption of *SO5•−, which acted as a rate-limiting step in the reaction, thus facilitating more 1O2 generation. This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state, paving the way for advancements in environmental remediation and energy conversion applications.
非对称CoN1C2配位促进类芬顿反应中d-p轨道杂化的高自旋构型
不对称单原子催化剂因其优异的催化性能而受到广泛关注。然而,不对称配位与金属位的自旋态之间的关系尚不清楚。此外,芬顿类反应中活性氧的调节仍然具有挑战性。本文提出了一种基于原位碳缺陷法的高负载Co ASACs (CoN1C2/C2N)的合理设计策略。其中,不对称三配位的CoN1C2/C2N对磺胺氯吡啶的降解表现出优异的催化活性,其周转率为36.8 min-1。实验结果和理论计算表明,由于不对称配位,共活性位点的电子自旋态从低自旋组态(t2g6eg1)转移到高自旋组态(t2g5eg2)。CoN1C2/C2N中的高自旋Co 3d轨道拥有更多的未配对电子,因此从HSO5 -的O 2p轨道获得电子的能力强,促进了d-p轨道的杂化。更重要的是,高自旋Co 3d−O 2p的σ*轨道上的自旋电子填充加速了*SO5•−的解吸,这在反应中起着限制速率的作用,从而促进了更多的1O2生成。本研究为实用的ASACs提供了创新的合成途径,阐明了结构与自旋态之间的关键关系,为推进环境修复和能量转换应用铺平了道路。
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来源期刊
Chinese Journal of Catalysis
Chinese Journal of Catalysis 工程技术-工程:化工
CiteScore
25.80
自引率
10.30%
发文量
235
审稿时长
1.2 months
期刊介绍: The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.
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