ZnO/g-C3N4复合光催化剂降解及产氢性能研究

摘要/Abstract

摘要： 本文采用热聚合法和水热法成功制备了ZnO/g-C₃N₄系列复合光催化剂,并对所制备样品的结构、形貌和光吸收性能等进行了表征和测试,通过在可见光照射下降解亚甲基蓝(MB)和光解水产氢评估了样品的光催化性能。实验结果表明,制备的ZnO/g-C₃N₄系列复合光催化剂性能均优于ZnO和g-C₃N₄样品。此外,当ZnO和g-C₃N₄的摩尔比为1:1时,所制备ZnO/g-C₃N₄复合样品的光催化性能最好。一方面,此样品仅在30 min后便达到了94.36%的降解率,其降解速率分别是ZnO和g-C₃N₄的5.6和6.7倍;另一方面,此样品6 h光解水产氢量为11.75 mmol,产氢速率是g-C₃N₄的7倍。研究表明,所制备的ZnO/g-C₃N₄系列复合光催化剂在降解污染物和光解水产氢方面均展现出了优异的性能。同时,本文还对ZnO/g-C₃N₄系列复合光催化剂的光催化降解和产氢机理进行了研究。

关键词: ZnO/g-C₃N₄复合光催化剂, 水热法, 光降解, 光解水产氢, 活性自由基

Abstract: In this paper, ZnO/g-C₃N₄ series composite photocatalysts were prepared by thermal polymerization and hydrothermal method. The structure, morphology and light absorption properties of the prepared samples were characterized and tested. The photocatalytic performance of these samples was evaluated by the photocatalytic degradation of methylene blue (MB) and the photolysis aquatic hydrogen under visible light irradiation. The experimental results indicate that the performances of the ZnO/g-C₃N₄ composite photocatalysts are superior to those of ZnO and g-C₃N₄. Moreover, when the molar ratio of ZnO and g-C₃N₄ is 1:1, the photocatalytic performance of the prepared ZnO/g-C₃N₄ composite samples is the best. On the one hand, the degradation rate of the 1:1 composite sample reaches 94.36% after only 30 min, and the degradation rate is 5.6 and 6.7 times that of ZnO and g-C₃N₄, respectively. On the other hand, the photolysis aquatic hydrogen of the 1:1 sample after 6 h is 11.75 mmol, and the photolysis aquatic hydrogen rate is 7 times that of g-C₃N₄. The results show that the ZnO/g-C₃N₄ composite photocatalyst has excellent performance in pollutant degradation and photolysis aquatic hydrogen. In addition, the photocatalytic degradation and photolysis aquatic hydrogen mechanism of ZnO/g-C₃N₄ series composite photocatalyst are also studied.

Key words: ZnO/g-C₃N₄ composite photocatalyst, hydrothermal method, photodegradation, photolysis aquatic hydrogen, active free radical

中图分类号:

张进峰, 富笑男, 郭叶飞, 刘瑞杰, 李媛媛. ZnO/g-C₃N₄复合光催化剂降解及产氢性能研究[J]. 人工晶体学报, 2023, 52(11): 2057-2067.

ZHANG Jinfeng, FU Xiaonan, GUO Yefei, LIU Ruijie, LI Yuanyuan. Degradation and Hydrogen Production Performance of ZnO/g-C₃N₄ Composite Photocatalyst[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(11): 2057-2067.

参考文献

[1] WU Q S, SIDDIQUE M S, YU W Z. Iron-nickel bimetallic metal-organic frameworks as bifunctional Fenton-like catalysts for enhanced adsorption and degradation of organic contaminants under visible light: kinetics and mechanistic studies[J]. Journal of Hazardous Materials, 2021, 401: 123261.
[2] LIU T, ZHOU H M, GRAHAM N, et al. 2D Kaolin ultrafiltration membrane with ultrahigh flux for water purification[J]. Water Research, 2019, 156: 425-433.
[3] MARUTHAPANDI M, LUONG J H T, GEDANKEN A. Kinetic, isotherm and mechanism studies of organic dye adsorption on poly(4, 4'-oxybisbenzenamine) and copolymer of poly(4, 4'-oxybisbenzenamine-pyrrole) macro-nanoparticles synthesized by multifunctional carbon dots[J]. New Journal of Chemistry, 2019, 43(4): 1926-1935.
[4] PIAI L, BLOKLAND M, VAN DER WAL A, et al. Biodegradation and adsorption of micropollutants by biological activated carbon from a drinking water production plant[J]. Journal of Hazardous Materials, 2020, 388: 122028.
[5] 全凤娇, 石彦彪, 孙红卫, 等. 卤氧化铋光催化去除环境污染物[J]. 华中师范大学学报(自然科学版), 2021, 55(6): 925-940+975.
QUAN F J, SHI Y B, SUN H W, et al. Photocatalytic removal of environmental pollutants by bismuth oxyhalide[J]. Journal of Central China Normal University (Natural Sciences), 2021, 55(6): 925-940+975 (in Chinese).
[6] OLA O, MAROTO-VALER M M. Review of material design and reactor engineering on TiO₂ photocatalysis for CO₂ reduction[J]. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2015, 24: 16-42.
[7] SAPKOTA K P, ISLAM M A, ABU HANIF M, et al. Hierarchical nanocauliflower chemical assembly composed of copper oxide and single-walled carbon nanotubes for enhanced photocatalytic dye degradation[J]. Nanomaterials, 2021, 11(3): 696.
[8] PI W B, HUMAYUN M, LI Y, et al. Properly aligned band structures in B-TiO₂/MIL53(Fe)/g-C₃N₄ ternary nanocomposite can drastically improve its photocatalytic activity for H₂ evolution: investigations based on the experimental results[J]. International Journal of Hydrogen Energy, 2021, 46(42): 21912-21923.
[9] MAHALA C, SHARMA M D, BASU M. ZnO nanosheets decorated with graphite-like carbon nitride quantum dots as photoanodes in photoelectrochemical water splitting[J]. ACS Applied Nano Materials, 2020, 3(2): 1999-2007.
[10] ZHANG Y C, SUN Y, LI M Z, et al. The application of a three-dimensional flower-like heterojunction containing zinc oxide nanoparticles and modified carbon nitride for enhanced photodegradation[J]. Journal of Alloys and Compounds, 2022, 890: 161744.
[11] AHMAD I. Comparative study of metal (Al, Mg, Ni, Cu and Ag) doped ZnO/g-C₃N₄ composites: efficient photocatalysts for the degradation of organic pollutants[J]. Separation and Purification Technology, 2020, 251: 117372.
[12] ZHANG C J, JIA M Y, XU Z Y, et al. Constructing 2D/2D N-ZnO/g-C₃N₄ S-scheme heterojunction: efficient photocatalytic performance for norfloxacin degradation[J]. Chemical Engineering Journal, 2022, 430: 132652.
[13] DHIMAN P, RANA G, KUMAR A, et al. ZnO-based heterostructures as photocatalysts for hydrogen generation and depollution: a review[J]. Environmental Chemistry Letters, 2022, 20(2): 1047-1081.
[14] 富笑男, 郭叶飞, 陈锦涛. 均匀沉淀法制备ZnO、Fe/ZnO光催化剂[J]. 功能材料, 2021, 52(3): 3170-3176.
FU X N, GUO Y F, CHEN J T. Synthesis of ZnO and Fe/ZnO photocatalyst with homogeneous precipitation method[J]. Journal of Functional Materials, 2021, 52(3): 3170-3176 (in Chinese).
[15] GUO Y, FU X, LIU R, et al. Efficient green photocatalyst of Ag/ZnO nanoparticles for methylene blue photodegradation[J]. Journal of Materials Science: Materials in Electronics, 2022, 33(5): 2716-28.
[16] ZHANG Z Y, SUN Y S, WANG Y L, et al. Synthesis and photocatalytic activity of g-C₃N₄/ZnO composite microspheres under visible light exposure[J]. Ceramics International, 2022, 48(3): 3293-3302.
[17] LI X, JIANG H P, MA C C, et al. Local surface plasma resonance effect enhanced Z-scheme ZnO/Au/g-C₃N₄ film photocatalyst for reduction of CO₂ to CO[J]. Applied Catalysis B: Environmental, 2021, 283: 119638.
[18] NI Y, WANG R, ZHANG W, et al. Graphitic carbon nitride (g-C₃N₄)-based nanostructured materials for photodynamic inactivation: synthesis, efficacy and mechanism [J]. Chemical Engineering Journal, 2021, 404.
[19] 严超, 周迅, 籍浩齐, 等. α-Fe₂O₃/g-C₃N₄复合材料的制备及光催化性能[J]. 化工新型材料, 2022, 50(9): 201-205.
YAN C, ZHOU X, JI H Q, et al. Preparation and photocatalytic properties of α- Fe₂O₃/g-C₃N₄ composites[J]. New Chemical Materials, 2022, 50(9): 201-205 (in Chinese).
[20] MOHAMMADZADEH KAKHKI R. Polymeric organic-inorganic C₃N₄/ZnO high-performance material for visible light photodegradation of organic pollutants[J]. Polymer Bulletin, 2022: 1-21.
[21] MULIK B B, BANKAR B D, MUNDE A V, et al. Electrocatalytic and catalytic CO₂ hydrogenation on ZnO/g-C₃N₄ hybrid nanoelectrodes[J]. Applied Surface Science, 2021, 538: 148120.
[22] DE JESUS MARTINS N, GOMES I C H, DA SILVA G T S T, et al. Facile preparation of ZnO: g-C₃N₄ heterostructures and their application in amiloride photodegradation and CO₂ photoreduction[J]. Journal of Alloys and Compounds, 2021, 856: 156798.
[23] LI B Y, ZHANG B N, ZHANG Y N, et al. Porous g-C₃N₄/TiO₂ S-scheme heterojunction photocatalyst for visible-light driven H₂-production and simultaneous wastewater purification[J]. International Journal of Hydrogen Energy, 2021, 46(64): 32413-32424.
[24] GENG X L, WANG L, ZHANG L, et al. H₂O₂ production and in situ sterilization over a ZnO/g-C₃N₄ heterojunction photocatalyst[J]. Chemical Engineering Journal, 2021, 420: 129722.
[25] SCHNEIDER J T, FIRAK D S, RIBEIRO R R, et al. Use of scavenger agents in heterogeneous photocatalysis: truths, half-truths, and misinterpretations[J]. Physical Chemistry Chemical Physics, 2020, 22(27): 15723-15733.
[26] MACHÍN A, FONTÁNEZ K, DUCONGE J, et al. Photocatalytic degradation of fluoroquinolone antibiotics in solution by Au@ZnO-rGO-gC₃N₄ composites[J]. Catalysts, 2022, 12(2): 166.
[27] LINGHU C, YANG M, YU H, et al. Synthesis of the wire-in-tube structure porous C₁₂H₁₂O₁₂S₃Tb₂@g-C₃N₄/ZnO luminescent composite in hydrothermal condition[J]. Journal of Alloys and Compounds, 2022, 900: 163397.
[28] AMIR Z, MUHAMMAD K, ZAHID H, et al. Extended visible light driven photocatalytic hydrogen generation by electron induction from g-C₃N₄ nanosheets to ZnO through the proper heterojunction[J]. Zeitschrift Für Physikalische Chemie, 2021, 236(1): 53-66.
[29] GAYATHRI M, SAKAR M, SATHEESHKUMAR E, et al. Insights into the mechanism of ZnO/g-C₃N₄ nanocomposites toward photocatalytic degradation of multiple organic dyes[J]. Journal of Materials Science: Materials in Electronics, 2022, 33(12): 9347-9357.
[30] PÉREZ-MOLINA Á, PASTRANA-MARTÍNEZ L M, PÉREZ-POYATOS L T, et al. One-pot thermal synthesis of g-C₃N₄/ZnO composites for the degradation of 5-fluoruracil cytostatic drug under UV-LED irradiation[J]. Nanomaterials, 2022, 12(3): 340.
[31] LEELAVATHI H, ABIRAMI N, MURALIDHARAN R, et al. Sunlight-assisted degradation of textile pollutants and phytotoxicity evaluation using mesoporous ZnO/g-C₃N₄ catalyst[J]. RSC Advances, 2021, 11(43): 26800-26812.
[32] CHIDHAMBARAM N, RAVICHANDRAN K. Fabrication of ZnO/g-C₃N₄ nanocomposites for enhanced visible light driven photocatalytic activity[J]. Materials Research Express, 2017, 4(7): 075037.
[33] GAYATHRI K, TEJA Y N, PRAKASH R M, et al. In situ-grown ZnO particles on g-C₃N₄ layers: a direct Z-scheme-driven photocatalyst for the degradation of dye and pharmaceutical pollutants under solar irradiation[J]. Journal of Materials Science: Materials in Electronics, 2022, 33(12): 9774-9784.
[34] ALHANASH A M, AL-NAMSHAH K S, MOHAMED S K, et al. One-pot synthesis of the visible light sensitive C-doped ZnO@g-C₃N₄ for high photocatalytic activity through Z-scheme mechanism[J]. Optik, 2019, 186: 34-40.
[35] ZHANG J Q, LI J, LIU X Y. Ternary nanocomposite ZnO-g-C₃N₄-Go for enhanced photocatalytic degradation of RhB[J]. Optical Materials, 2021, 119: 111351.
[36] VIJAYAKUMAR T P, BENOY M D, DURAIMURUGAN J, et al. Effect of g-C₃N₄ on structural, optical, and photocatalytic properties of hexagonal cylinder-like twinned ZnO microcrystals prepared by the hydrothermal method[J]. Journal of Materials Science: Materials in Electronics, 2021, 32(19): 24095-24106.
[37] NGULLIE R C, ALASWAD S O, BHUVANESWARI K, et al. Synthesis and characterization of efficient ZnO/g-C₃N₄ nanocomposites photocatalyst for photocatalytic degradation of methylene blue[J]. Coatings, 2020, 10(5): 500.
[38] MENG X, SHI L, CUI L, et al. Hydrothermal preparation of Mn_0.5Cd_0.5S/carbon nanotubes nanocomposite photocatalyst with improved H₂ production performance [J]. Materials Research Bulletin, 2021, 135.
[39] YU F C, LI Y M, LIU Z Y, et al. Preparation and photocatalytic properties of ZnO nanorods/g-C₃N₄ composite[J]. Applied Physics A, 2021, 127(11): 818.
[40] WANG J, SUN Y C, FU L J, et al. A defective g-C₃N₄/RGO/TiO₂ composite from hydrogen treatment for enhanced visible-light photocatalytic H₂ production[J]. Nanoscale, 2020, 12(43): 22030-22035.
[41] 陈美玲. 基于g-C₃N₄/ZnO纳米复合材料的制备及光催化性能研究[D]. 淮南: 安徽理工大学, 2019.
CHEN M L. Preparation and photocatalytic properties of g-C₃N₄/ZnO nanocomposites[D].Huainan: Anhui University of Science & Technology, 2019 (in Chinese).
[42] XUE M R, BAO X L, LI X Q, et al. A novel pathway toward efficient and stable C₃N₄-based photocatalyst for light driven H₂ evolution: the synergistic effect between Pt and CoWO₄[J]. International Journal of Hydrogen Energy, 2019, 44(52): 28113-28122.
[43] HAN X, AN L, HU Y, et al. Ti₃C₂ MXene-derived carbon-doped TiO₂ coupled with g-C₃N₄ as the visible-light photocatalysts for photocatalytic H₂ generation[J]. Applied Catalysis B: Environmental, 2020, 265: 118539.
[44] NIE Y C, YU F, WANG L C, et al. Photocatalytic degradation of organic pollutants coupled with simultaneous photocatalytic H₂ evolution over graphene quantum dots/Mn-N-TiO₂/g-C₃N₄ composite catalysts: performance and mechanism[J]. Applied Catalysis B: Environmental, 2018, 227: 312-321.
[45] WU W T, ZHANG J Q, FAN W Y, et al. Remedying defects in carbon nitride to improve both photooxidation and H₂ generation efficiencies[J]. ACS Catalysis, 2016, 6(5): 3365-3371.

ZnO/g-C₃N₄复合光催化剂降解及产氢性能研究

Degradation and Hydrogen Production Performance of ZnO/g-C₃N₄ Composite Photocatalyst

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