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金属硼化物作为高效且持久类 Fenton 反应的助催化剂:金属和硼的双共催化中心。

Metal Borides as Excellent Co-Catalysts for Boosted and Long-Lasting Fenton-like Reaction: Dual Co-Catalytic Centers of Metal and Boron.

机构信息

State Key Laboratory of Hydraulics and Mountain River Engineering, College of Architecture and Environment, Sichuan University, Chengdu 610065, China.

Sino-German Centre for Water and Health Research, Sichuan University, Chengdu 610065, China.

出版信息

Environ Sci Technol. 2023 Aug 22;57(33):12534-12545. doi: 10.1021/acs.est.3c03212. Epub 2023 Aug 9.

DOI:10.1021/acs.est.3c03212
PMID:37555746
Abstract

The continuous electron supply for oxidant decomposition-induced reactive oxygen species (ROS) generation is the main contributor for the long-standing micropollutant oxidation in the iron-based advanced oxidation processes (AOPs). Herein, as a new class of co-catalysts, metal borides with dual active sites and preeminent conductive performance can effectively overcome the inherent drawback of Fenton-like reactions by steadily donating electrons to inactive Fe(III). Among the metal borides, tungsten boride (WB) exhibits a significant co-catalytic performance run ahead of common heterogeneous co-catalysts and exceptionally high stability. Based on qualitative and semi-quantitative tests, the hydroxyl radical, sulfate radical, and iron(IV)-oxo complex are all produced in the WB/Fe(III)/PDS system and Fe(IV)-induced methyl phenyl sulfoxide decomposition is up to 72%. Moreover, the production efficiency of ROS and relative proportions of radical and nonradical pathways change with various experimental conditions (dosages of PDS, WB, and solution pH) and water matrices. The rate-determining step of Fe(II) regeneration is greatly accelerated resulting from the synergetic effect between exposed metallic reactive sites and nonmetallic boron with reductive properties of WB. In addition, the self-dissolution of surface tungsten oxide and boron oxide leads to a renovated surface for sustainable Fe(III) reduction in long-term operations. Our discovery provides an efficient and sustainable strategy in the field of enhanced AOPs for water remediation.

摘要

连续供应电子以分解氧化剂产生的活性氧物质(ROS)是铁基高级氧化工艺(AOPs)中长时间氧化微量污染物的主要原因。在此,作为一类新的共催化剂,具有双活性位和卓越导电性能的金属硼化物可以通过稳定地向非活性 Fe(III)供电子来有效地克服类 Fenton 反应的固有缺陷。在金属硼化物中,二硼化钨(WB)表现出显著的共催化性能,明显优于常见的多相共催化剂,且具有极高的稳定性。通过定性和半定量测试,在 WB/Fe(III)/PDS 体系中生成了羟基自由基、硫酸根自由基和铁(IV)-氧络合物,Fe(IV)诱导的甲基苯基亚砜分解高达 72%。此外,ROS 的生成效率以及自由基和非自由基途径的相对比例会随各种实验条件(PDS、WB 和溶液 pH 值的剂量)和水基质而变化。由于暴露的金属反应性位点与具有还原性能的 WB 的非金属硼之间的协同作用,Fe(II)再生的速率决定步骤大大加快。此外,表面氧化钨和氧化硼的自溶解导致表面更新,从而在长期运行中可持续还原 Fe(III)。我们的发现为水修复领域的增强型 AOPs 提供了一种高效且可持续的策略。

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