Rational modulation of Fe single-atom electronic structure in a Fe-N2B4 configuration for preferential 1O2 generation in Fenton-like reactions

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2023-12-21 DOI:10.1016/j.apcatb.2023.123643

Yuhan Long , Zhenhua Cao , Weiran Wu , Wenhao Liu , Peizhen Yang , Xuesong Zhan , Rongzhi Chen , Dongfang Liu , Wenli Huang

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Abstract

The important role of optimizing the coordination environment of single-atom catalysts (SACs) for selective production of singlet oxygen (¹O₂) in Fenton-like reactions is revealed. Herein, we introduce electron-depletion boron atoms to manipulate the coordination number and atom types of Fe site simultaneously and construct a six-coordination Fe-N₂B₄ catalyst for peroxymonosulfte (PMS) activation. Particularly, it achieves 98.68% ¹O₂ generation selectivity superior to unregulated Fe-N₄ catalyst (64.57%), exhibiting an exceptional bisphenol A (BPA) degradation performance with a reaction rate constant of 0.249 min⁻¹. Experimental and theoretical results unveil that the tailored electronic structure of Fe not only enhances the adsorption selectivity of terminal oxygen atoms in PMS and alters the reaction pathway preference, but also facilitates the electron donation from PMS and lowers the energy barrier for ¹O₂ generation. This work provides a universal strategy for rational and precise modulation of SACs for specific reactive species conversion in environment remediation.

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合理调节 Fe-N2B4 构型中的 Fe 单原子电子结构，在类似芬顿的反应中优先生成 1O2

在类似芬顿的反应中，优化单原子催化剂（SACs）的配位环境对选择性产生单线态氧（1O2）的重要作用得到了揭示。在此，我们引入了耗电子硼原子，同时操纵铁位点的配位数和原子类型，构建了一种用于过一硫酸盐（PMS）活化的六配位 Fe-N2B4 催化剂。与未配位的 Fe-N4 催化剂（64.57%）相比，该催化剂的 1O2 生成选择性高达 98.68%，并以 0.249 min-1 的反应速率常数表现出优异的双酚 A（BPA）降解性能。实验和理论结果表明，量身定制的 Fe 电子结构不仅提高了 PMS 中末端氧原子的吸附选择性，改变了反应途径的偏好，而且有利于 PMS 的电子捐赠，降低了生成 1O2 的能垒。这项工作为合理、精确地调节 SACs 以实现环境修复中特定活性物种的转换提供了一种通用策略。

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来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.