缺陷氧化钼的制备及其可见光催化控藻机制研究

蔡婕; 徐源源; 文刚

PDF(3217 KB)

中国环境科学 ›› 2025, Vol. 45 ›› Issue (11) : 6343-6352.

环境生态

缺陷氧化钼的制备及其可见光催化控藻机制研究

蔡婕, 徐源源, 文刚

作者信息 +

Visible-light-active defective MoO₃ for photocatalytic algae inactivation: Preparation and mechanisms

CAI Jie, XU Yuan-yuan, WEN Gang

Author information +

文章历史 +

摘要

通过水热-热聚合法(未引入外源金属离子)制备MoO₃/MoO₃-_x光催化剂,采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和紫外-可见漫反射光谱(UV-Vis)等手段对其物理化学特性进行了表征,并系统探究其光催化除藻效果与作用机理.结果表明:0.2g/L MoO₃/MoO₃_-x光催化剂在可见光下照射6h后可去除近98.36%的叶绿素a;在较宽pH值范围内(4.0~11.0)表现出优异控藻效果,且在不同初始藻浓度下仍能保持稳定的除藻性能.猝灭实验证实光催化过程中形成的光生空穴(h⁺)、羟基自由基(·OH)和超氧自由基(·O₂^-)等活性物质是造成藻细胞失活的关键因素,据此明确了MoO₃/MoO₃_-x光催化除藻的核心作用机制.

Abstract

This study reveals the mechanism by which MoO₃/MoO_3-x photocatalyst inactivate algal cells. The photocatalysts were synthesized via hydrothermal and thermal polymerization methods without introducing foreign metal ions, and their physicochemical properties were characterized using XRD, XPS, SEM, and UV-Vis spectroscopy. The photocatalytic performance for algae removal was evaluated under visible light. Results demonstrated that 98.36% chlorophyll a was removed by 0.2g/L MoO₃/MoO_3-x within 6hours and the photocatalyst exhibited effective algal inhibition across a broad pH range (4.0~11.0). Additionally, the photocatalyst maintained stable performance at various initial algal concentrations. Quenching experiments confirmed that photogenerated holes (h⁺), hydroxyl radicals (·OH), and superoxide radicals (·O₂^-) were the primary reactive species responsible for algal cells inactivation. This result clarifies the core mechanism of MoO₃/MoO_3-x in photocatalytic algae removal.

导出引用

蔡婕, 徐源源, 文刚. 缺陷氧化钼的制备及其可见光催化控藻机制研究[J]. 中国环境科学. 2025, 45(11): 6343-6352

CAI Jie, XU Yuan-yuan, WEN Gang. Visible-light-active defective MoO₃ for photocatalytic algae inactivation: Preparation and mechanisms[J]. China Environmental Science. 2025, 45(11): 6343-6352

中图分类号： X131

参考文献

[1] Huisman J, Codd G A, Paerl H W, et al. Cyanobacterial blooms [J]. Nature Reviews Microbiology, 2018,16(8):471-483.
[2] D.M. Anderson, Approaches to monitoring, control and management of harmful algal blooms (HABs) [J]. Ocean & Coastal Management, 2009,52(7):342.
[3] 马子雅,严长安,李立新,等.微囊藻毒素的人群暴露健康危害与防控研究 [J]. 中国科学:生命科学, 2025,55(1):113-130. Ma Z Y, Yan C A, Li L X, et al. The adverse effects and mitigation strategies of microcystin exposure in humans: a critical review [J]. Science China: Life Sciences, 2025,55(1):113-130.
[4] Chen H M, Zhu Y Y, Zhang Y, et al. Cyanobacterial bloom expansion caused by typhoon disturbance in Lake Taihu China, Environmental Science and Pollution Research, 2020,27:42294-42303.
[5] S. Colas, B. Marie, E. Lance, et al. Overview on a harmful cyanobacterial neurotoxin from the environmental scale to the molecular target, Environmental Research, 2021,193:110590.
[6] J. Mao, X. An, Z. Gu, et al. Visualizing the interfacial charge transfer between photoactive microcystis aeruginosa and hydrogenated TiO₂, Environmental Science & Technology, 2020,54: 10323–10332.
[7] 杨留留,刘宏,陈厚望,等.漂浮型BiOCl_0.6I_0.4/GO光催化剂的制备及其除藻性能 [J]. 中国环境科学, 2021,41(10):4633-4644. Yang L L, Liu H, Chen H W, et al. Preparation of floating BiOCl_0.6I_0.4/GO photocatalyst and its algae removal performance [J]. China Environmental Science, 2021,41(10):4633-4644.
[8] Li T M, Zeng W, Zhang Y Y, et al．Nanobelt-assemblednest-like MoO₃ hierarchical structure: Hydrothermal synthesis and gas sensingproperties [J]. Materials Letters, 2015,160(12):476-479.
[9] 谷娜,赵扩林,高金龙,等.正交相氧化钼的制备及除藻效果研究 [J]. 现代化工, 2019,39(5):164-167. Gu N, Zhao K L, Gao J L, et al. Preparation of orthogonal phase molybdenum oxide and its effect in removing algae. Modern Chemical Industry, 2019,39(5):164-167.
[10] 张彤彤,杨红,马克伟,等.一维纳米h-MoO₃的制备及其光催化降解罗丹明B的研究 [J]. 广西大学学报(自然科学版), 2018,43:2438- 2444. Zhang T T, Yang H, Ma K W, et al. Preparation of one-dimensional nano-sized h-MoO₃ and its photocatalytic degradation of Rhodamine B [J]. Journal of Guangxi University (Nat. Sci. Ed.), 2018,43:2438– 2444.
[11] Wang M, Tan G Q, Wang Y, et al. Stable LSPR effect and full- spectrum photocatalytic water purification by g-C₃N₄_-x/MoO₃_-xwith passivated interface oxygen vacancies [J]. Journal of Alloys and Compounds, 2022,891:161928.
[12] Liang L W, Chang Q, Cai T T, et al. Combining carbon dots with WO₃_-x nanodots for utilizing the full spectrum of solar radiation in photocatalysis [J]. Chemical Engineering Journal, 2022,428:131-139.
[13] 陈九菊,李滨,姜伟.三氧化钼纳米颗粒的制备与性能分析 [J]. 黑龙江工程学院学报(自然科学版), 2009,23:66-68. Chen J J, Li B, Jiang W. Synthesis and performance characterization of MO₃ nanoparticles [J]. Journal of Heilongjiang Institute of Technology (Natural Science Edition), 2009,23:66-68.
[14] Lu W, Li H, Xue Z. Synthesis of h-MoO₃ nanorods and h-/α-MoO₃ composites and their photocatalytic performance [J]. Transactions of Nonferrous Metals Society of China, 2023,33(7):2155-2167.
[15] 张多多,刘小峰,邱建荣.基于等离激元纳米结构非线性响应的超快光开关及脉冲激光器 [J]. 物理学报, 2020,69(18):138-151. Zhang D D, Liu X F, Qiu J R. Ultrafast optical switches and pulsed lasers based on strong nonlinear optical response of plasmonic nanostructures [J]. Acta Phys. Sin., 2020,69(18):138-151.
[16] Li K, Wu W, Jiang Y, et al. Highly enhanced H₂ evolution of MoO₃/gC₃N₄ hybrid composites based on a direct Z-scheme photocatalytic system [J]. Inorganic Chemistry Frontiers, 2021,8(5): 1154-1165.
[17] 张泽迁.h-MoO₃的结构相变及其光催化性质的研究 [D]. 北京:中央民族大学, 2023. Zhang Z Q. Structural Phase Transitions and Photocatalytic Properties of h-MoO₃ [D]. Beijing: Minzu University of China, 2023.
[18] Song Y, Zhao Y, Huang Z, et al. Aqueous synthesis of molybdenum trioxide (h-MoO₃, α-MoO₃· H₂O and h-/α-MoO₃ composites) and their photochromic properties study [J]. Journal of alloys and compounds, 2017,693:1290-1296.
[19] Liu C, Ersan M S, Plewa M J, et al. Formation of regulated and unregulated disinfection byproducts during chlorination of algal organic matter extracted from freshwater and marine algae [J]. Water Research, 2018,142:313-324.
[20] Lu W, LI H, XUE Z. Synthesis of h-MoO₃ nanorods and h-/α-MoO₃ composites and their photocatalytic performance [J]. Transactions of Nonferrous Metals Society of China, 2023,33(7):2155-2167.
[21] Zheng F, Dong F, Lv Z, et al. A novel g-C₃N₄/tourmaline composites equipped with plasmonic MoO₃_-x to boost photocatalytic activity [J]. Colloid and Interface Science Communications, 2021,43:100434.
[22] Fang J, Ma J, Yang X, et al. Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosa [J]. Water Research, 2010,44(6):1934-1940.
[23] 舒敏,梁俊辉,陈达,等.基于水热合成法制备的MoO₃_-x纳米槽SERS基底的特性研究 [J]. 人工晶体学报, 2024,53(6):1061-1068. Shu M, Liang J H, Chen D, et al. Study on the characteristics of MoO₃_-x nanoslot SERS substrate prepared by hydrothermal method [J]. Journal of synthetic Crystals, 2024,53(6):1061-1068.
[24] F Rahman, Zavabeti A, Rahman M A, et al. Dual Selective Gas Sensing Characteristics of 2D α-MoO₃_-X via a Facile Transfer Process [J]. 2019.
[25] 张睿宸,杨汉培,高照,等.MoO₃_-x/BiOCl异质结光催化剂的制备及其可见光降解盐酸四环素的研究 [J]. 环境科技, 2020,33(1):1-6. Zhang R C, Yang H P, Gao Z, et al. MoO₃_-x/BiOCl heterojunction photocatalyst: preparation and visible-light photocatalytic performance in degradation of tetracycline hydrochloride [J]. Environmental Science and Technology, 2020,33(1):1-6.
[26] Etman A S, Abdelhamid H N, Yuan Y, et al. Facile water-based strategy for synthesizing MoO_3–x nanosheets: Efficient visible light photocatalysts for dye degradation [J]. ACS Omega, 2018,3(2):2193- 2201.
[27] Wang D, Ao Y, Wang P. Effective inactivation of Microcystis aeruginosa by a novel Z-scheme composite photocatalyst under visible light irradiation [J]. Science of the Total Environment, 2020, 746:141-149.
[28] 符晨峻.漂浮型改性金属有机框架光催化剂的制备及其除藻性能研究 [D]. 长春:中国科学院大学(中国科学院东北地理与农业生态研究所), 2024. Fu C J. Preparation of floating modified metal-organic framework photocatalyst and its algae removal performance [D]. Changchun: University of Chinese Academy of Sciences (Northeast Institute of Geography and Agroecology, Chinese Academy of Sciences), 2024.
[29] Fan G, Zhan J, Luo J, et al. Fabrication of heterostructured Ag/AgCl@g-C₃N₄@UIO-66(NH₂) nanocomposite for efficient photocatalytic inactivation of Microcystis aeruginosa under visible light [J]. Journal of Hazardous Materials, 2021,404:124062.
[30] Fan G, Zhou J, Zheng X, et al. Fast photocatalytic inactivation of Microcystis aeruginosa by metal-organic frameworks under visible light [J]. Chemosphere, 2020,239:124721.
[31] Yin K, Deng Y, Liu C, et al. Kinetics, pathways and toxicity evaluation of neonicotinoid insecticides degradation via UV/chlorine process [J]. Chemical Engineering Journal, 2018,346:298-306.
[32] 王铧,陈龙飞,陈广洲.铜绿微囊藻和微囊藻毒素的去除研究进展 [J]. 应用化工, 2022,51(11):3404-3408. Wang H, Chen L F, Chen G Z. Progress of removal of microcystis aeruginosa and microcystin [J]. Applied Chemistry Industry, 2022, 51(11):3404-3408.
[33] 詹佳钧.漂浮型g-C₃N₄@MOF纳米光催化剂的制备及光催化除藻效能与机理研究 [D]. 福州:福州大学, 2021. Zhan J J. Synthesis of a floating g-C₃N₄@MOF nano-photocatalyst and investigations on its photocatalytic inactivation effects and mechanisms on algae [D]. Fuzhou: Fuzhou University, 2021.
[34] Barapatre A, Aadil K R, Jha H. Synergistic antibacterial and antibiofilm activity of silver nanoparticles biosynthesized by lignin- degrading fungus [J]. Bioresources and Bioprocessing, 2016,3:1-13.
[35] Murray S A, Kohli G S, Farrell H, et al. A fish kill associated with a bloom of Amphidinium carterae in a coastal lagoon in Sydney, Australia [J]. Harmful Algae, 2015,49:19-28.
[36] Liu Y, Zhao Y, Sun Y, et al. A 4e-–2e-cascaded pathway for highly efficient production of H₂ and H₂O₂ from water photo-splitting at normal pressure [J]. Applied Catalysis B: Environmental, 2020,270: 118875.
[37] Bahmani F, Kazemi S H, Wu Y, et al. CuMnO₂-reduced graphene oxide nanocomposite as a free-standing electrode for high- performance supercapacitors [J]. Chemical Engineering Journal, 2019, 375:121966.
[38] 刘苏杰.CuInS₂对CdS光催化制氢性能的优化研究 [D]. 太原:太原理工大学, 2023. Liu S J. Study on CuInS₂ for optimizing the photocatalytic hydrogen production performance of CdS [D]. Taiyuan: University of Taiyuan, 2023.
[39] Liu Z, Zheng Y, Zhang S, et al. (1-x)Bi_0.5Na_0.5TiO₃_-xBiFeO₃ solid solutions with enhanced piezocatalytic dye degradation [J]. Separation and Purification Technology, 2022,290:120831.
[40] Song J, Wang X, Ma J, et al. Visible-light-driven in situ inactivation of Microcystis aeruginosa with the use of floating g-C₃N₄ heterojunction photocatalyst: Performance, mechanisms and implications. Applied Catalysis B: Environmental. 2018,226:83-92.
[41] Fan G D, You Y F, Wang B, et al. Inactivation of harmful cyanobacteria by Ag/AgCl@ZIF-8coating under visible light: Efficiency and its mechanisms [J]. Applied Catalysis B: Environmental, 2019,256:117866.
[42] Zhou Q, Yin H B, Wang A L, et al. Preparation of hollow B-SiO₂@TiO₂ composites and their photocatalytic performances for degradation of ammonia-nitrogen and green algae in aqueous solution [J]. Chinese Journal of Chemical Engineering, 2019,27(10):2535- 2543.
[43] Xu D, Li G, Dong Y, et al. Photocatalytic O₂ activation enhancement and algae inactivation mechanism of BiO₂_-x/Bi₃NbO₇ van der Waals heterojunction [J]. Applied Catalysis B: Environmental, 2022,312: 121402.