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在与碳量子点智能集成的Z型催化剂ZnO-CuInS-ZnS上对极深液体燃料中二苯并噻吩进行光催化氧化脱硫:性能、机理及稳定性

Photocatalysis oxidative desulfurization of dibenzothiophene in extremely deep liquid fuels on the Z-scheme catalyst ZnO-CuInS-ZnS intelligently integrated with carbon quantum dots: performance, mechanism, and stability.

作者信息

Nguyen Manh B

机构信息

Institute of Chemistry, Vietnam Academy of Science and Technology 18 Hoang Quoc Viet, Cau Giay Hanoi Vietnam

出版信息

RSC Adv. 2024 Aug 19;14(36):26123-26132. doi: 10.1039/d4ra04599h. eCollection 2024 Aug 16.

DOI:10.1039/d4ra04599h
PMID:39161443
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11331397/
Abstract

In this study, we improved the electrochemical and photocatalytic properties of the ZnO-CuInS-ZnS (ZCZ) material by integrating with carbon quantum dots (CQD) with particle sizes from 2 to 5 nm. The integration of ZnO-CuInS-ZnS with carbon quantum dots (ZnO-CuInS-ZnS/CQD:ZCZ-CQD) enhanced the visible light absorption, significantly reduced the electron-hole recombination rate, and facilitated the electron transfer and separation processes as confirmed by UV-visible diffuse reflectance spectroscopy (UV-vis DRS), photoluminescence (PL), and electrochemical impedance spectroscopy (EIS). The successful integration of ZCZ with carbon quantum dots was confirmed using X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM) methods. The ZCZ/CQD photocatalyst removed up to 98.32% of DBT after 120 minutes of reaction, maintained over 90% durability after 10 cycles, and retained its structure without any changes. The ZCZ photocatalyst integrated with CQD enhances faster dibenzothiophene (DBT) removal by 4.46, 3.24, 2.53, and 1.72 times compared to ZnO, CuInS, ZnS, and ZnO-CuInS-ZnS, respectively. Factors influencing the oxidation process of DBT including the mass of the photocatalyst, initial DBT concentration, stability, and reaction kinetics were studied. Through active species trapping experiments, this study demonstrated that the formation of ˙O and ˙OH radicals determines the reaction rate. The mechanism of photocatalysis on ZCZ-CQD materials and the intermediate products formed in the process of photocatalytic oxidative desulfurization of dibenzothiophene is proposed based on electrochemical measurements and GC-MS results.

摘要

在本研究中,我们通过与粒径为2至5纳米的碳量子点(CQD)复合,改善了ZnO-CuInS-ZnS(ZCZ)材料的电化学和光催化性能。ZnO-CuInS-ZnS与碳量子点复合(ZnO-CuInS-ZnS/CQD:ZCZ-CQD)增强了可见光吸收,显著降低了电子-空穴复合率,并促进了电子转移和分离过程,这通过紫外-可见漫反射光谱(UV-vis DRS)、光致发光(PL)和电化学阻抗谱(EIS)得到证实。使用X射线光电子能谱(XPS)、能量色散谱(EDS)和透射电子显微镜(TEM)方法证实了ZCZ与碳量子点的成功复合。ZCZ/CQD光催化剂在反应120分钟后去除了高达98.32%的二苯并噻吩(DBT),在10次循环后保持了超过90%的耐久性,并且其结构没有任何变化。与ZnO、CuInS、ZnS和ZnO-CuInS-ZnS相比,与CQD复合的ZCZ光催化剂分别将二苯并噻吩(DBT)的去除速度提高了4.46、3.24、2.53和1.72倍。研究了影响DBT氧化过程的因素,包括光催化剂的质量、初始DBT浓度、稳定性和反应动力学。通过活性物种捕获实验,本研究表明˙O和˙OH自由基的形成决定了反应速率。基于电化学测量和GC-MS结果,提出了ZCZ-CQD材料的光催化机理以及二苯并噻吩光催化氧化脱硫过程中形成的中间产物。

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