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金属基活性位点及其在多相催化臭氧氧化过程中与 O 相互作用的综合评述:类型、调控与鉴定。

A comprehensive review on metal based active sites and their interaction with O during heterogeneous catalytic ozonation process: Types, regulation and authentication.

机构信息

School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China.

School of Environment, South China Normal University, Guangdong Provincial Engineering Technology Research Center for Drinking Water Safety, Guangdong Provincial Key Lab of Functional Materials for Environmental Protection, Guangzhou 510006, China.

出版信息

J Hazard Mater. 2023 Feb 5;443(Pt B):130302. doi: 10.1016/j.jhazmat.2022.130302. Epub 2022 Nov 2.

Abstract

Heterogeneous catalytic ozonation (HCO) was a promising water purification technology. Designing novel metal-based catalysts and exploring their structural-activity relationship continued to be a hot topic in HCO. Herein, we reviewed the recent development of metal-based catalysts (including monometallic and polymetallic catalysts) in HCO. Regulation of metal based active sites (surface hydroxyl groups, Lewis acid sites, metal redox cycle and surface defect) and their key roles in activating O were explored. Advantage and disadvantage of conventional characterization techniques on monitoring metal active sites were claimed. In situ electrochemical characterization and DFT simulation were recommended as supplement to reveal the metal active species. Though the ambiguous interfacial behaviors of O at these active sites, the existence of interfacial electron migration was beyond doubt. The reported metal-based catalysts mainly served as electron donator for O, which resulted in the accumulation of oxidized metal and reduced their activity. Design of polymetallic catalysts could accelerate the interfacial electron migration, but they still faced with the dilemma of sluggish Me/Me redox cycle. Alternative strategies like coupling active metal species with mesoporous silicon materials, regulating surface hydrophobic/hydrophilic properties, polaring surface electron distribution, coupling HCO process with photocatalysis and HO were proposed for future research.

摘要

多相催化臭氧化(HCO)是一种很有前途的水净化技术。设计新型金属基催化剂并探索其结构-活性关系,一直是 HCO 中的热门话题。本文综述了金属基催化剂(包括单金属和多金属催化剂)在 HCO 中的最新发展。探讨了金属基活性位(表面羟基、路易斯酸位、金属氧化还原循环和表面缺陷)的调控及其在激活 O 中的关键作用。还声称了常规表征技术在监测金属活性位方面的优势和劣势。建议使用原位电化学表征和 DFT 模拟作为补充,以揭示金属活性物种。尽管这些活性位上 O 的界面行为不明确,但界面电子迁移的存在是毫无疑问的。报道的金属基催化剂主要作为 O 的电子供体,导致氧化金属的积累并降低其活性。多金属催化剂的设计可以加速界面电子迁移,但它们仍面临着 Me/Me 氧化还原循环缓慢的困境。未来的研究可以提出一些替代策略,如将活性金属物种与介孔硅材料耦合、调节表面疏水性/亲水性、极化表面电子分布、将 HCO 过程与光催化和 HO 耦合等。

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