Preparation and visible light catalytic performance of CeO2/ZnO composite photocatalyst
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摘要: 采用微波超声法,以ZnO为基体原位生长CeO2晶体,得到CeO2/ZnO复合光催化剂。利用XRD、SEM、TEM、PL、UV-Vis DRS等方法对制备的材料进行表征,并通过可见光降解AF对样品的光催化性能进行评价。结果表明,ZnO为纳米片互相穿插形成的花形球状结构,其表面附着有纳米CeO2颗粒,分散性较好。ZnO和CeO2的摩尔比为20∶1的CeO2/ZnO复合光催化剂在可见光下表现出良好的光催化活性,光照90 min后对AF的光降解率达到96.44%,较纯相ZnO和CeO2有显著提高。CeO2/ZnO的稳定性较好,6次使用后对AF的光降解率仍达到93.53%。机制研究发现,·O2−是光催化降解AF过程中的主要活性物种。Abstract: CeO2/ZnO composite photocatalysts were prepared via in-situ precipitation of CeO2 nanoparticles on ZnO substrate by ultrasonic microwave method and were characterized by XRD, SEM, TEM, PL, UV-Vis DRS and other techniques. The photocatalytic properties of the samples were investigated by degrading acid fuchsin (AF). The results show that ZnO has flower-shaped spherical structure assembled by ZnO nanoflskes, and its surfaces are evenly attached with CeO2 nanoparticles. CeO2/ZnO composite photocatalyst showed good photocatalytic activity with visible light irradiation. When the molar ratio of ZnO and CeO2 was 20∶1, the photodegradation rate of AF reached 96.44% after 90 min of illumination, which was significantly higher than those of pure phase ZnO and CeO2. CeO2/ZnO indicated high stability, as the degradation rate retained 93.53% after repeated use of the same photocatalyst for 6 times. The photdegradation mechanism study shows that superoxide radical (·O2−) was the main active substance in photdegrading AF.
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Key words:
- ZnO /
- CeO2 /
- composite photocatalyst /
- photocatalytic activity /
- acid fuchsin
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表 1 样品成分配比
Table 1. Sample compositions
Sample n(Zn)∶n(Ce) ZnO/g Ce(NO3)3·6H2O/g CeO2/ZnO-1 10∶1 1.02 0.54 CeO2/ZnO-2 15∶1 1.53 CeO2/ZnO-3 20∶1 2.04 CeO2/ZnO-4 30∶1 3.05 CeO2/ZnO-5 50∶1 5.09 -
[1] 凡文. 石油和化工行业70年发展回顾[J]. 中国石油和化工经济分析, 2019(10):34-44.FAN Wen. 70 years of development review of the petroleum and chemical industry[J]. Economic Analysis of China Petroleum and Chemical Industry,2019(10):34-44(in Chinese). [2] 贾艳萍, 姜成, 郭泽辉, 等. 印染废水深度处理及回用研究进展[J]. 纺织学报, 2017, 38(8):172-180.JIA Yanping, JIANG Cheng, GUO Zehui, et al. Research progress on deep treatment and recycling of dye wastewater[J]. Journal of Textile Research,2017,38(8):172-180(in Chinese). [3] ZULAKHA Z, IMRAN A, SEONGJUN P, et al. Effect of different iron precursors on the synthesis and photocatalytic activity of Fe-TiO2 nanotubes under visible light[J]. Ceramics International,2020,46(3):3353-3366. doi: 10.1016/j.ceramint.2019.10.045 [4] MAEDA K, DOMEN K. Photocatalytic water splitting: Recent progress and future challenges[J]. Journal of Physical Chemistry Letters,2010,1(18):2655-2661. doi: 10.1021/jz1007966 [5] QU L, LANG J, WANG S, et al. Nanospherical composite of WO3 wrapped NaTaO3: Improved photodegradation of tetracycline under visible light irradiation[J]. Applied Surface Science,2016(388):412-419. [6] WANG Z, MAO F, HUANG X, et al. Orthogonal test design for preparation of TiO2/graphene composites and study on its photocatalytic activity[J]. Nanomaterials,2018,8(1):271-275. [7] WU Z, WANG L. Graphene oxide (GO) doping hexagonal flower-like ZnO as potential enhancer of photocatalytic ability[J]. Materials Letters,2019,234(1):287-290. [8] 刘成宝, 唐飞, 朱晨, 等. WO3-Ag/g-C3N4 Z型光催化材料的合成及其光催化性能[J]. 复合材料学报, 2021, 38(1): 209-220.LIU Chengbao, TANG Fei, ZHU Chen, et al. Preparation and photocatalytic properties of WO3 -Ag/ g-C3N4 Z-scheme photocatalyst[J]. Acta Materiae Compositae Sinica, 2021, 38(1): 209-220(in Chinese). [9] 崔舒. 氧化锌和二氧化钛材料的制备及其光催化、气敏性能研究[D]. 吉林: 吉林大学, 2019.CUI Shu. Fabrication, photocatalytic and gas sensing properties of ZnO and TiO2 materials[D]. Jilin: Jilin University, 2019(in Chinese). [10] ZHANG J, DENG S J, LIU S Y, et al. Preparation and photocatalytic activity of Nd doped ZnO nanoparticles[J]. Materials & Processing Report,2014,29(5):262-268. [11] 赵燕茹, 马建中, 刘俊莉. 可见光响应型ZnO基纳米复合光催化材料的研究进展[J]. 材料工程, 2017, 45(6):129-137.ZHAO Yanru, MA Jianzhong, LIU Junli. Research progress on visible-light responding ZnO-based nanocomposite photocatalyst[J]. Journal of Materials Engineering,2017,45(6):129-137(in Chinese). [12] HOSSEIN M C, REZA Z, DAVID M T, et al. Nanocrystalline ZnO-SnO2 mixed metal oxide powder: Microstructural study, optical properties, and photocatalytic activity[J]. Journal of Sol-Gel Science and Technology,2017,84(2):274-282. doi: 10.1007/s10971-017-4484-y [13] YAO H, YAO Q, WANG H, et al. Optoelectronic properties of MoS2/g-ZnO van der waals heterostructure investigated by first-principles calculations[J]. Journal of Electronic Materials,2020,49(8):4557-4562. doi: 10.1007/s11664-020-07997-z [14] CHEN C S, LIU X Y, FANG Q, et al. Self-assembly synthesis of CuO/ZnO hollow microspheres and their photocatalytic performance under natural sunlight[J]. Vacuum,2020,174:109198. doi: 10.1016/j.vacuum.2020.109198 [15] 冯雅楠, 甘俊珍, 陈星晖, 等. 形貌和粒度对纳米二氧化铈光催化降解盐基品红的研究[J]. 应用化工, 2019, 48(1):14-17. doi: 10.3969/j.issn.1671-3206.2019.01.004FENG Ya’nan, GAN Junzhen, CHEN Xinghui, et al. Study of morphology and particle size of nano-CeO2 on basic fuchsine photocatalytic degradation[J]. Applied Chemical Industry,2019,48(1):14-17(in Chinese). doi: 10.3969/j.issn.1671-3206.2019.01.004 [16] 陈子坚, 王石语, 吴限. 微波辅助法合成纳米CeO2/ZnO光催化剂及其光催化性能研究[J]. 化工新型材料, 2019, 47(7):190-193.CHEN Zijian, WANG Shiyu, WU Xian. Microwave assisted synthesis of nano CeO2/ZnO photocatalyst and its photocatalytic property[J]. New Chemical Materials,2019,47(7):190-193(in Chinese). [17] ZHANG W W, GUO H L, SUN H Q, et al. Hydrothermal synthesis and photoelectrochemical performance enhancement of TiO2/graphene composite in photo-generated cathodic protection[J]. Applied Surface Science,2016,382:128-134. doi: 10.1016/j.apsusc.2016.04.124 [18] 胡金娟, 马春雨, 王佳琳, 等. Ag-Ag2O/TiO2-g-C3N4纳米复合材料的制备及可见光催化性能[J]. 复合材料学报, 2020, 37(6):1401-1410.HU Jinjuan, MA Chunyu, WANG Jialin, et al. Preparation and photocatalytic properties of Ag-Ag2O/TiO2-g-C3N4 nanocomposites[J]. Acta Materiae Compositae Sinica,2020,37(6):1401-1410(in Chinese). [19] SHEN Y Z, ZHU Z D, WANG X G, et al. Synthesis of Z-scheme g-C3N4/Ag/Ag3PO4 composite for enhanced photocatalytic degradation of phenol and selective oxidation of gaseous isopropanol[J]. Materials Research Bulletin,2018,107:407-415. doi: 10.1016/j.materresbull.2018.08.017 [20] ZHU L Y, LI H, XIA P F, et al. Hierarchical ZnO decorated with CeO2 nanoparticles as the direct Z-scheme heterojunction for enhanced photocatalytic activity[J]. ACS Applied Materials & Interfaces,2018,10(46):39679-39687. [21] WAN S P, ZHONG Q, OU M, et al. Synthesis and characterization of direct Z-scheme Bi2MoO6/ZnIn2S4 composite photocatalyst with enhanced photocatalytic oxidation of NO under visible light[J]. Journal of Materials Science,2017,52:11453-11466. doi: 10.1007/s10853-017-1283-3