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双金属CuSnS对HO的增强激活:促进Cu (II)/Cu (I)氧化还原循环的新见解。

Enhanced activation of HO by bimetallic CuSnS: A new insight for Cu (II)/Cu (I) redox cycle promotion.

作者信息

Yang Qiao, Xia Chuanhai, Chen Shuai, Cao Xuezhi, Hao Jingcheng

机构信息

Key Laboratory of Colloid and Interface Chemistry (Shandong University), Ministry of Education, Jinan 250100, China.

School of Resources and Environmental Engineering & Institute for Advanced Study of Coastal Ecology, Ludong University, Yantai 264025, China.

出版信息

J Colloid Interface Sci. 2023 Jun 15;640:750-760. doi: 10.1016/j.jcis.2023.02.159. Epub 2023 Mar 3.

DOI:10.1016/j.jcis.2023.02.159
PMID:36898181
Abstract

HYPOTHESIS

Despite that the development of CuSnS (CTS) catalyst has attracted increasing interests, few study has reported to investigate its heterogeneous catalytic degradation of organic pollutants in a Fenton-like process. Furthermore, the influence of Sn components towards Cu (II)/Cu (I) redox cycling in CTS catalytic systems remains a fascinating research.

EXPERIMENTS

In this work, a series of CTS catalysts with controlled crystalline phases were prepared via a microwave-assisted pathway and applied in the HO activation for phenol degradation. The efficiency of phenol degradation in CTS-1/HO system (CTS-1: the molar ratio of Sn (copper acetate) and Cu (tin dichloride) is determined to be Sn:Cu = 1:1) was systematically investigated by controlling various reaction parameters including HO dosage, initial pH and reaction temperature. We discovered that CuSnS exhibited superior catalytic activity to the contrast monometallic Cu or Sn sulfides and Cu (I) acted as the dominant active sites. The higher Cu (I) proportions conduce to the higher catalytic activities of CTS catalysts. Quenching experiments and electron paramagnetic resonance (EPR) further proved that the activation of HO by CTS catalyst produces reactive oxygen species (ROS) and subsequently leads to degradation of the contaminants. A reasonable mechanism of enhanced HO activation in Fenton-like reaction of CTS/HO system was proposed for phenol degradation by investigating the roles of copper, tin and sulfur species.

FINDINGS

The developed CTS acted as a promising catalyst in Fenton-like oxidation progress for phenol degradation. Importantly, the copper and tin species contribute to a synergetic effect for the promotion of Cu (II)/Cu (I) redox cycle, which thus enhanced the activation of HO. Our work may offer new insight on the facilitation of Cu (II)/Cu (I) redox cycle in Cu-based Fenton-like catalytic systems.

摘要

假设

尽管CuSnS(CTS)催化剂的开发已引起越来越多的关注,但很少有研究报道在类芬顿过程中研究其对有机污染物的非均相催化降解。此外,Sn组分对CTS催化体系中Cu(II)/Cu(I)氧化还原循环的影响仍是一个引人入胜的研究课题。

实验

在本工作中,通过微波辅助途径制备了一系列具有可控晶相的CTS催化剂,并将其应用于HO活化以降解苯酚。通过控制包括HO用量、初始pH值和反应温度在内的各种反应参数,系统地研究了CTS-1/HO体系(CTS-1:Sn(醋酸铜)与Cu(二氯化锡)的摩尔比确定为Sn:Cu = 1:1)中苯酚的降解效率。我们发现,CuSnS对对比单金属Cu或Sn硫化物表现出优异的催化活性,且Cu(I)作为主要活性位点。较高的Cu(I)比例有助于CTS催化剂具有更高的催化活性。猝灭实验和电子顺磁共振(EPR)进一步证明,CTS催化剂对HO的活化产生了活性氧物种(ROS),随后导致污染物降解。通过研究铜、锡和硫物种的作用,提出了CTS/HO体系类芬顿反应中增强HO活化的合理机制,用于苯酚降解。

发现

所开发的CTS在类芬顿氧化过程中作为一种有前景的催化剂用于苯酚降解。重要的是,铜和锡物种对促进Cu(II)/Cu(I)氧化还原循环具有协同作用,从而增强了HO的活化。我们的工作可能为促进基于铜的类芬顿催化体系中Cu(II)/Cu(I)氧化还原循环提供新的见解。

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