Built-in electric field of Ag2Se thermoelectric effect activated persulfate for humic acid decomposition in water: Molecular transformation mechanism

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-04-23 DOI:10.1016/j.watres.2025.123717

Qiuling Ma , Xiangqian Tan , Miao Fang , Zhiyuan Ning , He Guo , Guodong Zhang , Jian Zhou , Tiecheng Wang

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Abstract

Water temperature fluctuations directly impact pollutant decomposition processes in wastewater. Thermoelectric effect is considered an alternative to utilize these temperature variations for pollution control. In this study, a system for persulfate (PS) activation by Ag₂Se thermoelectric catalyst under water temperature gradients (Ag₂Se/Δ_T/PS) was developed for humic acid (HA) degradation in water. The experimental results showed that the Ag₂Se/Δ_T/PS system achieved a 90.7 % HA removal efficiency, outperforming both PS/Δ_T (PS with temperature gradients) and Ag₂Se/Δ_T systems. Thermoelectric simulations indicated that Ag₂Se generated an electric field under temperature variations, with higher current density at surface pores where polarized charges efficiently activated PS. Density functional theory calculations revealed that the thermoelectric effect of Ag₂Se lowered the energy barriers for PS activation and ·SO₄⁻ generation. Different from ·OH-led decomposition of HA in the Ag₂Se/Δ_T system, ·SO₄⁻ and ·OH dominated HA decomposition in the Ag₂Se/Δ_T/PS system, and ¹O₂ also contributed this process. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed that oxidation, decarboxylation, and sulfidation were the primary pathways driving HA degradation, leading to decreases in CHO-containing compounds and formation of S-rich byproducts. These findings highlighted the potential of thermoelectric catalysts in advancing water treatment technologies.

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内置电场的Ag2Se热电效应激活过硫酸盐对水中腐植酸的分解：分子转化机理

水温波动直接影响废水中污染物的分解过程。热电效应被认为是利用这些温度变化来控制污染的一种替代方法。本研究开发了Ag2Se热电催化剂在水温梯度下活化过硫酸盐（PS）的体系（Ag₂Se/ΔT/PS），用于水中腐植酸（HA）的降解。实验结果表明，Ag2Se/ΔT/PS体系的HA去除率为90.7%，优于PS/ΔT（带温度梯度的PS）和Ag2Se/ΔT体系。热电模拟表明，Ag2Se在温度变化下产生电场，极化电荷有效激活PS，表面孔隙处电流密度更高。密度泛函数理论计算表明，Ag2Se的热电效应降低了PS激活和生成·SO4−的能量垒。与Ag₂Se/ΔT体系中以·OH为主的HA分解不同，Ag₂Se/ΔT/PS体系中以·SO4−和·OH为主的HA分解，¹O₂也参与了这一过程。傅里叶变换离子回旋共振质谱（FT-ICR MS）显示氧化、脱羧和硫化是HA降解的主要途径，导致含cho化合物减少，形成富s副产物。这些发现突出了热电催化剂在推进水处理技术方面的潜力。

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来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

期刊介绍： Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include: •Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management; •Urban hydrology including sewer systems, stormwater management, and green infrastructure; •Drinking water treatment and distribution; •Potable and non-potable water reuse; •Sanitation, public health, and risk assessment; •Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions; •Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment; •Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution; •Environmental restoration, linked to surface water, groundwater and groundwater remediation; •Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts; •Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle; •Socio-economic, policy, and regulations studies.