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Journal of Zhejiang University SCIENCE A

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Co₃O₄-ZnO/rGO catalyst preparation and rhodamine B degradation by sulfate radical photocatalysis

Author(s): Zhanmei ZHANG, Yi ZHANG, Xilin CHEN, Ziran HUANG, Zuqin ZOU, Huaili ZHENG
Affiliation(s): Key Laboratory of Hydraulic and Waterway Engineering of the Ministry of Education, School of River and Ocean Engineering, Chongqing Jiaotong University, Chongqing 400074, China; more
Corresponding email(s): zhanmei2003@126.com
Key Words: Co₃O₄-ZnO/rGO catalyst; Rhodamine B (RhB); Heterojunction; Photocatalysis; Peroxymonosulfate (PMS)

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Abstract: The development of a combined photocatalytic system with peroxymonosulfate (PMS) has great potential applications in the degradation and treatment of aqueous organic pollutants. Herein, a Co₃O₄-ZnO/rGO was prepared by a hydrothermal method using cobalt acetate, zinc acetate, and reduced graphene oxide (rGO) as the main raw materials. The physical and chemical characteristics of the obtained catalyst were analyzed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR). The photocatalytic features and capacities of the catalytic materials to activate PMS were investigated. Co₃O₄-ZnO/rGO exhibited stronger photocatalytic activity and ability to activate PMS than Co₃O₄/rGO or ZnO/rGO, and significantly improved the ability of PMS and photocatalysis to synergistically degrade rhodamine B (RhB), with a degradation rate of 90.40% within 40 min. The mechanism of RhB degradation was proposed based on characterization of materials, evaluation of RhB degradation efficiency, and analysis of the active species involved. The unique particle/sheet structure of Co₃O₄-ZnO/rGO provides a large number of active sites, and the formation of heterojunctions between Co₃O₄ and ZnO improves carrier separation and transport in the reaction system. Our study offers a reference for designing more effective heterojunction catalysts based on the combination of PMS and photocatalytic technology.

Co₃O₄-ZnO/rGO催化剂的制备及在硫酸盐自由基光催化降解罗丹明B的应用

作者：张占梅^1,2，张毅¹，陈熙琳¹，黄紫然¹，邹祖琴¹，郑怀礼³
机构：¹重庆交通大学，水利水运工程教育部重点实验室，中国重庆，400074；²国家内河航道整治工程技术研究中心，中国重庆，400074；³重庆大学，环境与生态学院，中国重庆，400044
目的：罗丹明B（RhB）作为一种合成染料被广泛应用在工业生产中，若不及时处理则会在自然界累积并对环境造成伤害。本文旨在制备出一种Co₃O₄-ZnO/rGO催化剂，并通过构建过硫酸盐光催化体系以实现RhB的降解。此外，本文还探究制备条件（水热时间、rGO掺杂量和煅烧温度等）对材料催化性能的影响，并提出可能的反应机理。
创新点：1.通过水热法制备Co₃O₄-ZnO/rGO，并探究其制备条件（水热时间、rGO掺杂量和煅烧温度等）对催化剂性能的影响；2.构建过硫酸盐光催化氧化体系实现了对RhB污染物的高效降解。
方法：1.通过实验分析，推导Co₃O₄-ZnO/rGO制备条件对其催化性能的影响；2.通过表征分析，对Co₃O₄-ZnO/rGO中各元素组成及表面形态进行分析；3.通过实验分析UV/Co₃O₄-ZnO/rGO/PMS对RhB的降解效率。4.通过反应前后表征对比及UV-Vis等手段探究催化氧化反应机制，并提出可能的反应机理。
结论：1.Co₃O₄-ZnO/rGO制备过程中rGO掺杂量及煅烧温度对催化性能的影响较大。2.所构建的UV/Co₃O₄-ZnO/rGO/PMS体系对RhB具有良好的去除效率；在主要自由基SO₄^??和?OH的作用下，RhB去除率在40min内可达90.40%。3.Co₃O₄-ZnO/rGO相比Co₃O₄/rGO及ZnO/rGO有更好的催化性能，这主要是因为Co₃O₄和ZnO之间异质结的生成促进了电子空穴对的重组。

关键词组：Co₃O₄-ZnO/rGO催化剂；罗丹明B；异质结；光催化；过硫酸盐

Reference

[1]AkbarzadehE, SoheiliHZ, HosseinifardM, et al., 2020. Preparation and characterization of novel Ag₃VO₄/Cu-MOF/rGO heterojunction for photocatalytic degradation of organic pollutants. Materials Research Bulletin, 121:110621.

[2]AlshaikhH, ShawkyA, MohamedRM, et al., 2021. Solution-based synthesis of Co₃O₄/ZnO p-n heterojunctions for rapid visible-light-driven oxidation of ciprofloxacin. Journal of Molecular Liquids, 334:116092.

[3]AnipsitakisGP, StathatosE, DionysiouDD, 2005. Heterogeneous activation of Oxone using Co₃O₄. The Journal of Physical Chemistry B, 109(27):13052-13055.

[4]CaoJ, YangZH, XiongWP, et al., 2020. Peroxymonosulfate activation of magnetic Co nanoparticles relative to an N-doped porous carbon under confinement: boosting stability and performance. Separation and Purification Technology, 250:117237.

[5]DongCJ, XiaoXC, ChenG, et al., 2015. Synthesis and photocatalytic degradation of methylene blue over p-n junction Co₃O₄/ZnO core/shell nanorods. Materials Chemistry and Physics, 155:1-8.

[6]El-MollaSA, AliLI, MahmoudHR, et al., 2017. Effect of preparation method, loading of Co₃O₄ and calcination temperature on the physicochemical and catalytic properties of Co₃O₄/ZnO nanomaterials. Materials Chemistry and Physics, 185:44-54.

[7]GautamS, AgrawalH, ThakurM, et al., 2020. Metal oxides and metal organic frameworks for the photocatalytic degradation: a review. Journal of Environmental Chemical Engineering, 8(3):103726.

[8]GhanbariF, MoradiM, 2017. Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: review. Chemical Engineering Journal, 310:41-62.

[9]GuoH, NiuHY, LiangC, et al., 2020. Few-layer graphitic carbon nitride nanosheet with controllable functionalization as an effective metal-free activator for peroxymonosulfate photocatalytic activation: role of the energy band bending. Chemical Engineering Journal, 401:126072.

[10]GuoJ, ShenCH, SunJ, et al., 2021. Highly efficient activation of peroxymonosulfate by Co₃O₄/Bi₂MoO₆ p-n heterostructure composites for the degradation of norfloxacin under visible light irradiation. Separation and Purification Technology, 259:118109.

[11]GuoY, DaiYX, ZhaoW, et al., 2018. Highly efficient photocatalytic degradation of naphthalene by Co₃O₄/Bi₂O₂CO₃ under visible light: a novel p–n heterojunction nanocomposite with nanocrystals/lotus-leaf-like nanosheets structure. Applied Catalysis B: Environmental, 237:273-287.

[12]HanCC, GeL, ChenCF, et al., 2014. Novel visible light induced Co₃O₄-g-C₃N₄ heterojunction photocatalysts for efficient degradation of methyl orange. Applied Catalysis B: Environmental, 147:546-553.

[13]HanWY, LiDG, ZhangMQ, et al., 2020. Photocatalytic activation of peroxymonosulfate by surface-tailored carbon quantum dots. Journal of Hazardous Materials, 395:122695.

[14]JinCY, KangJ, LiZL, et al., 2020a. Enhanced visible light photocatalytic degradation of tetracycline by MoS₂/Ag/g-C₃N₄ Z-scheme composites with peroxymonosulfate. Applied Surface Science, 514:146076.

[15]JinCY, WangM, LiZ, et al., 2020b. Two dimensional Co₃O₄/g-C₃N₄ Z-scheme heterojunction: mechanism insight into enhanced peroxymonosulfate-mediated visible light photocatalytic performance. Chemical Engineering Journal, 398:125569.

[16]LiF, DongB, 2019. Facile two-step synthesis of Ag nanoparticles dispersed on N, S co-doped RGO for highly efficient plasmonic photocatalytic water purification. Catalysis Communications, 119:42-45.

[17]LouYB, ZhangYK, ChengL, et al., 2018. A stable plasmonic Cu@Cu₂O/ZnO heterojunction for enhanced photocatalytic hydrogen generation. ChemSusChem, 11(9):‍1505-1511.

[18]MalefaneME, FeleniU, KuvaregaAT, 2020. Cobalt (II/III) oxide and tungsten (VI) oxide p-n heterojunction photocatalyst for photodegradation of diclofenac sodium under visible light. Journal of Environmental Chemical Engineering, 8:103560.

[19]RakibuddinM, AnanthakrishnanR, 2016. Effective photocatalytic dechlorination of 2,4-dichlorophenol by a novel graphene encapsulated ZnO/Co₃O₄ core–shell hybrid under visible light. Photochemical & Photobiological Sciences, 15(1):86-98.

[20]RashidJ, BarakatMA, MohamedRM, et al., 2014. Enhancement of photocatalytic activity of zinc/cobalt spinel oxides by doping with ZrO₂ for visible light photocatalytic degradation of 2-chlorophenol in wastewater. Journal of Photochemistry and Photobiology A: Chemistry, 284:1-7.

[21]RedaGM, FanHQ, TianHL, 2017. Room-temperature solid state synthesis of Co₃O₄/ZnO p‍–‍n heterostructure and its photocatalytic activity. Advanced Powder Technology, 28(3):953-963.

[22]RenJT, ZhengYL, YuanK, et al., 2020. Self-templated synthesis of Co₃O₄ hierarchical nanosheets from a metal–organic framework for efficient visible-light photocatalytic CO₂ reduction. Nanoscale, 12(2):755-762.

[23]RenWJ, GaoJK, LeiC, et al., 2018. Recyclable metal-organic framework/cellulose aerogels for activating peroxymonosulfate to degrade organic pollutants. Chemical Engineering Journal, 349:766-774.

[24]ShaoH, ZhaoX, WangY, et al., 2017. Synergetic activation of peroxymonosulfate by Co₃O₄ modified g-C₃N₄ for enhanced degradation of diclofenac sodium under visible light irradiation. Applied Catalysis B: Environmental, 218:810-818.

[25]ShenCH, WenXJ, FeiZH, et al., 2020. Visible-light-driven activation of peroxymonosulfate for accelerating ciprofloxacin degradation using CeO₂/Co₃O₄ p-n heterojunction photocatalysts. Chemical Engineering Journal, 391:123612.

[26]SuP, ZhangXJ, HaoXQ, et al., 2022. Co₃O₄ modified Mn_0.2Cd_0.8S with different shells forms p-n heterojunction to optimize energy/mass transfer for efficient photocatalytic hydrogen evolution. Separation and Purification Technology, 285:120318.

[27]TangCN, LiuEZ, WanJ, et al., 2016. Co₃O₄ nanoparticles decorated Ag₃PO₄ tetrapods as an efficient visible-light-driven heterojunction photocatalyst. Applied Catalysis B: Environmental, 181:707-715.

[28]ThakurK, KandasubramanianB, 2019. Graphene and graphene oxide-based composites for removal of organic pollutants: a review. Journal of Chemical & Engineering Data, 64(3):833-867.

[29]VelmuruganS, YangTCK, ChenSW, et al., 2021. Metal-organic frameworks derived ZnO-Co₃O₄ pn heterojunction photocatalyst for the photoelectrochemical detection of sulfadiazine. Journal of Environmental Chemical Engineering, 9(5):106169.

[30]WangM, ZhangY, JinCY, et al., 2019. Fabrication of novel ternary heterojunctions of Pd/g-C₃N₄/Bi₂MoO₆ hollow microspheres for enhanced visible-light photocatalytic performance toward organic pollutant degradation. Separation and Purification Technology, 211:1-9.

[31]XuP, WangP, WangQ, et al., 2021. Facile synthesis of Ag₂O/ZnO/rGO heterojunction with enhanced photocatalytic activity under simulated solar light: kinetics and mechanism. Journal of Hazardous Materials, 403:124011.

[32]YangJ, WangMY, ZhaoSS, et al., 2019. Petal-biotemplated synthesis of two-dimensional Co₃O₄ nanosheets as photocatalyst with enhanced photocatalytic activity. International Journal of Hydrogen Energy, 44(2):870-879.

[33]YangZH, CaoJ, ChenYP, et al., 2019. Mn-doped zirconium metal-organic framework as an effective adsorbent for removal of tetracycline and Cr(VI) from aqueous solution. Microporous and Mesoporous Materials, 277:277-285.

[34]ZhangJL, ZhaiCY, ZhaoW, et al., 2020. Insight into combining visible-light photocatalysis with transformation of dual metal ions for enhancing peroxymonosulfate activation over dibismuth copper oxide. Chemical Engineering Journal, 397:125310.

[35]ZhangJL, ZhaoW, LiZ, et al., 2021. Visible-light-assisted peroxymonosulfate activation over Fe(II)/V(IV) self-doped FeVO₄ nanobelts with enhanced sulfamethoxazole degradation: performance and mechanism. Chemical Engineering Journal, 403:126384.

[36]ZhangQS, XiaoY, LiYM, et al., 2020. Efficient photocatalytic overall water splitting by synergistically enhancing bulk charge separation and surface reaction kinetics in Co₃O₄–decorated ZnO@ZnS core-shell structures. Chemical Engineering Journal, 393:124681.

[37]ZouWX, DengB, HuXX, et al., 2018. Crystal-plane-dependent metal oxide-support interaction in CeO₂/g-C₃N₄ for photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 238:111-118.

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Co₃O₄-ZnO/rGO催化剂的制备及在硫酸盐自由基光催化降解罗丹明B的应用

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