泡沫镍网负载TiO2/WO3薄膜对乙烯的光催化降解

doi:10.15541/jim20190234

无机材料学报 ›› 2020, Vol. 35 ›› Issue (5): 581-588.DOI: 10.15541/jim20190234

所属专题： 2020年环境材料论文精选(三)有机小分子去除

泡沫镍网负载TiO₂/WO₃薄膜对乙烯的光催化降解

季邦^1,²,赵文锋³,段洁利⁴,马立哲³,付兰慧¹,杨洲¹()

1.华南农业大学工程学院, 广州 510000
2.新加坡南洋理工大学材料科学与工程学院, 新加坡 639798
3.华南农业大学电子工程学院, 广州 510000
4.华南农业大学工程基础教学与训练中心, 广州 510000

收稿日期:2019-05-20 修回日期:2019-07-01 出版日期:2020-05-20 网络出版日期:2019-07-23
作者简介:季邦(1990-), 男, 博士研究生. E-mail: 369370030@qq.com<br/>JI Bang(1990-), male, PhD candidate. E-mail: 369370030@qq.com
基金资助:
现代农业产业技术体系建设专项资金(CARS-31);广东省科技计划项目(2018A050506076)

Synthesis of TiO₂/WO₃ on Nickel Foam for the Photocatalytic Degradation of Ethylene

JI Bang^1,²,ZHAO Wenfeng³,DUAN Jieli⁴,MA Lizhe³,FU Lanhui¹,YANG Zhou¹()

1.College of Engineering, South China Agricultural University, Guangzhou 510000, China
2.School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
3.College of Electronic Engineering, South China Agricultural University, Guangzhou 510000, China
4.Engineering Fundamental Teaching and Training Center, South China Agricultural University, Guangzhou 510000, China

Received:2019-05-20 Revised:2019-07-01 Published:2020-05-20 Online:2019-07-23
Supported by:
China Agriculture Research System(CARS-31);Science and Technology Planning Project of Guangdong Province(2018A050506076)

摘要/Abstract

摘要：

乙烯是果蔬采摘后腐烂变质的主要因素, 如何减少或去除果蔬贮藏过程中释放的乙烯, 是果蔬保鲜领域亟待解决的问题。本工作采用溶胶-凝胶法制备了一系列金属泡沫镍网负载TiO₂/WO₃薄膜催化剂, 采用不同手段对样品进行表征分析, 并以此薄膜为催化剂, 考察紫外光下乙烯催化降解性能。结果表明: TiO₂/WO₃成功负载在泡沫镍网表面。TiO₂与WO₃复合后形成了异质结, 抑制了电子-空穴对的复合, 样品的禁带宽度减小, 吸光度增强, 光催化性能提升。TiO₂/WO₃在紫外光下展现出良好的光催化活性和光催化稳定性, 当WO₃占TiO₂质量百分数为6%时, 光催化活性最高, 光催化乙烯速率常数为0.0332 min ^-1, 是TiO₂的9.48倍, 但是过量的WO₃会成为电子-空穴的复合中心, 降低光催化活性。研究还对紫外光下泡沫镍网负载TiO₂/WO₃薄膜的光催化降解乙烯机理进行了探讨。

关键词: 光催化降解, 泡沫镍网, 乙烯, WO₃, TiO₂

Abstract:

Ethylene is the main factor of postharvest spoilage of fruits and vegetables. Therefore, how to reduce or remove the ethylene released during the storage of fruits and vegetables is a problem to be solved. In this study, a series of nickel foam supported TiO₂/WO₃ were prepared by Sol-Gel method. The samples were characterized by different methods. The photocatalytic degradation activity of ethylene under ultraviolet light irradiation was investigated. The results show that TiO₂/WO₃ film is successfully supported on the nickel foam, and there formed heterojunction between TiO₂ and WO₃, which efficiently enhanced the separation and transfer rates of photogenerated electron and hole. The narrowed band-gap also leads to a red shift of optical absorbance and high photoactivity. The photocatalytic activity and stability of TiO₂/WO₃ were excellent under UV light irradiation. When the mass percentage of WO₃ is 6% of TiO₂, the photocatalytic ethylene degradation of the TiO₂/WO₃ composite film reaches maximum, and the degradation rate constant is almost 9.8 times as that of TiO₂. The mechanism of photocatalytic degradation of ethylene by TiO₂/WO₃ supported on nickel foam under ultraviolet light irradiation was also discussed.

Key words: photocatalytic degradation, nickel foam, ethylene, WO₃, TiO₂

中图分类号:

TQ031.7

季邦, 赵文锋, 段洁利, 马立哲, 付兰慧, 杨洲. 泡沫镍网负载TiO₂/WO₃薄膜对乙烯的光催化降解[J]. 无机材料学报, 2020, 35(5): 581-588.

JI Bang, ZHAO Wenfeng, DUAN Jieli, MA Lizhe, FU Lanhui, YANG Zhou. Synthesis of TiO₂/WO₃ on Nickel Foam for the Photocatalytic Degradation of Ethylene[J]. Journal of Inorganic Materials, 2020, 35(5): 581-588.

图/表 13

图1 光催化性能评价装置示意图

Fig. 1 Schematic drawing of Photocatalytic performance evaluation device

图2 样品的XRD图谱

Fig. 2 XRD patterns of samples

图3 泡沫镍网不同倍率的SEM照片(a~c), 样品TW-6的SEM(d)和HRTEM(e)照片及其元素面扫描分布(f~h)

Fig. 3 Different magnification SEM images of nickel foam(a-c), SEM (d) and HRTEM (e) images and EDS mapping (f-h) of sample TW-6 (a, b) Nickel foam before corrosion oxidation; (c) Nickel foam after corrosion oxidation

图4 所有样品的UV-Vis图谱

Fig. 4 UV-Vis spectra of all samples

图5 所有样品的Tauc曲线

Fig. 5 Tauc curves of all samples

图6 样品TW-6的XPS图谱

Fig. 6 XPS spectra of sample TW-6 (a) Full spectrum; High resolution spectra of (b) Ti2p; (c) O1s; (d) W4f

图7 所有样品的PL谱图

Fig. 7 Photoluminescence spectra of all samples

图8 所有样品紫外光下光催化降解乙烯的动力学拟合直线

Fig. 8 Kinetics curves of ethylene degradation over all samples under UV light irradiation

表1 光催化降解乙烯一级动力学参数

Table 1 First-order kinetic parameters of photocatalytic degradation of ethylene

Photocatalytic film	Regression equation	R²	Rate constant, K°/min^-1
Nickel foam	ln(C₀/C) = 0.0002t	0.9832	0.0002
TiO₂	ln(C₀/C) = 0.0035t	0.9785	0.0035
TW-2	ln(C₀/C) = 0.0055t	0.9942	0.0055
TW-4	ln(C₀/C) = 0.0069t	0.9905	0.0069
TW-6	ln(C₀/C) = 0.0332t	0.9803	0.0332
TW-8	ln(C₀/C) = 0.0075t	0.9744	0.0075

图9 所有样品对乙烯的光催化降解率

Fig. 9 Photocatalytic degradation rate of ethylene in all samples

图10 TW-6样品光催化降解乙烯稳定性测试

Fig. 10 Photocatalytic degradation of ethylene stability over TW-6 under UV light irradiation

图11 循环实验前后样品TW-6的XRD图谱

Fig. 11 XRD patterns of sample TW-6 before and after cycling experiment

图12 TiO2/WO3的光催化原理示意图

Fig. 12 Photocatalytic schematic of TiO2/WO3

参考文献 36

[1]	DAN M, HUANG M, LIAO F , et al. Identification of ethylene responsive mirnas and their targets from newly harvested banana fruits using high-throughput sequencing. Journal of Agricultural and Food Chemistry, 2018,66(40):10628-10639. DOI URL PMID
[2]	励建荣, 朱丹实 . 果蔬保鲜新技术研究进展. 食品与生物技术学报, 2012,31(4):337-347.
[3]	TAS C E, HENDESSI S, BAYSAL M , et al. Halloysite nanotubes/ polyethylene nanocomposites for active food packaging materials with ethylene scavenging and gas barrier properties. Food and Bioprocess Technology, 2017,10(4):789-798.
[4]	PIRSA S, CHAVOSHIZADEH S . Design of an optical sensor for ethylene based on nanofiber bacterial cellulose film and its application for determination of banana storage time. Polymers for Advanced Technologies, 2018,29(5):1385-1393.
[5]	SANWAL G G, PAYASI A . Garlic extract plus sodium metabisulphite enhances shelf life of ripe banana fruit. International Journal of Food Science & Technology, 2007,42(3):303-311.
[6]	ZHU X L, LIANG X Z, WANG P , et al. Porous Ag-ZnO microspheres as efficient photocatalyst for methane and ethylene oxidation: Insight into the role of Ag particles.Applied Surface Science, 2018,456:493-500.
[7]	CHA B J, SAQLAIN S, SEO H O , et al. Hydrophilic surface modification of TiO₂ to produce a highly sustainable photocatalyst for outdoor air purification. Applied Surface Science, 2019,479:31-38.
[8]	ZHANG Y J, HE P Y, YANG Y M , et al. Renewable conversion of slag to graphene geopolymer for H₂ production and wastewater treatment.Catalysis Today, 2019, doi: 10.1016/j.cattod.2019.02.003.
[9]	HE P Y, ZHANG Y J, CHEN H , et al. Development of an eco-eff1cient CaMoO₄/electroconductive geopolymer composite for recycling silicomanganese slag and degradation of dye wastewater. Journal of Cleaner Production, 2019,208:1476-1487.
[10]	MAKROPOULOU T, PANAGIOTOPOULOU P, VENIERI D . N-doped TiO₂ photocatalysts for bacterial inactivation in water. Journal of Chemical Technology & Biotechnology, 2018,93(9):2518-2526.
[11]	ZHANG H, LIN J, LI Z , et al. Organic dye doped graphitic carbon nitride with a tailored electronic structure for enhanced photocatalytic hydrogen production. Catalysis Science & Technology, 2019,9(2):502-508.
[12]	YANG Y, CUI Y, MIAO L , et al. Effects of treatment process and nano-additive on the microstructure and properties of Al₂O₃-TiO₂ nanocomposite powders used for plasma spraying. Powder Technology, 2018,338:304-312.
[13]	YAN Y, ZHOU X, LAN J , et al. Efficient photocatalytic disinfection of Escherichia coli by N-doped TiO₂ coated on coal fly ash cenospheres. Journal of Photochemistry and Photobiology A: Chemistry, 2018,367:355-364.
[14]	WANG X, XIANG Y, ZHOU B , et al. Enhanced photocatalytic performance of Ag/TiO₂ nanohybrid sensitized by black phosphorus nanosheets in visible and near-infrared light. Journal of Colloid and Interface Science, 2019,534:1-11. DOI URL PMID
[15]	DEB P, DHAR J C . Fast response UV photodetection using TiO₂ nanowire/graphene oxide thin-film heterostructure. IEEE Photonics Technology Letters, 2019,31(8):571-574.
[16]	PARK H, YOO S, KIM K . Synthesis of carbon-coated TiO₂ by underwater discharge with capillary carbon electrode. IEEE Transactions on Plasma Science, 2019,47(2):1482-1486.
[17]	MANIBALAN G, MURUGADOSS G, THANGAMUTHU R , et al. Facile synthesis of heterostructure CeO₂-TiO₂ nanocomposites for enhanced electrochemical sensor and solar cell applications.Journal of Alloys and Compounds, 2019, 773:449-461. DOI URL
[18]	SABZI M, MOUSAVI ANIJDAN S H . Microstructural analysis and optical properties evaluation of Sol-Gel heterostructured NiO-TiO₂ film used for solar panels. Ceramics International, 2019,45(3):3250-3255.
[19]	LI S, LIU Z, XIANG G , et al. Influence of calcination temperature on the photocatalytic performance of the hierarchical TiO₂ pinecone- like structure decorated with CdS nanoparticles. Ceramics International, 2019,45(1):767-776.
[20]	ZHANG Q, WU Y, LI L , et al. Sustainable approach for spent V₂O₅-WO₃/TiO₂ catalysts management: selective recovery of heavy metal vanadium and production of value-added WO₃-TiO₂ photocatalysts. ACS Sustainable Chemistry & Engineering, 2018,6(9):12502-12510.
[21]	YU YANG, TONG MING-XING, HE YU-LAN , et al. Preparation and visible-light photocatalytic performance of mesoporous hollow TiO₂/WO₃ spheres. Journal of Inorganic Materials, 2017,32(4):365-371.
[22]	ZHANG Y, WAN J, KE Y . A novel approach of preparing TiO₂ films at low temperature and its application in photocatalytic degradation of methyl orange. Journal of Hazardous Materials, 2010, 177(1/3):750-754. DOI URL PMID
[23]	JIA J, LI D, CHENG X , et al. Construction of graphite/TiO₂/ nickel foam photoelectrode and its enhanced photocatalytic activity. Applied Catalysis A: General, 2016,525:128-136.
[24]	HU H, XIAO W, YUAN J , et al. High photocatalytic activity and stability for decomposition of gaseous acetaldehyde on TiO₂/Al₂O₃ composite films coated on foam nickel substrates by Sol-Gel processes. Journal of Sol-Gel Science and Technology, 2008,45(1):1-8.
[25]	LI S, ZHANG G, ZHENG H , et al. Application of BiFeO₃-based on nickel foam composites with a highly efficient catalytic activity and easily recyclable in Fenton-like process under microwave irradiation. Journal of Power Sources, 2018,386:21-27.
[26]	PAL B, VIJAYAN B L, KRISHNAN S G , et al. Hydrothermal syntheses of tungsten doped TiO₂ and TiO₂/WO₃ composite using metal oxide precursors for charge storage applications. Journal of Alloys and Compounds, 2018,740:703-710.
[27]	DOHĿEVIĿ-MITROVIĿ Z, STOJADINOVIĿ S, LOZZI L , et al. WO₃/TiO₂ composite coatings: structural, optical and photocatalytic properties. Materials Research Bulletin, 2016,83:217-224. DOI URL
[28]	MENDOZA J A, LEE D H, KANG J . Photocatalytic removal of gaseous nitrogen oxides using WO₃/TiO₂ particles under visible light irradiation: effect of surface modification. Chemosphere, 2017,182:539-546. DOI URL PMID
[29]	KHAN H, RIGAMONTI M G, PATIENCE G S , et al. Spray dried TiO₂/WO₃ heterostructure for photocatalytic applications with residual activity in the dark. Applied Catalysis B: Environmental, 2018, 226:311-323.
[30]	WANG C, FU J, LONG M , et al. Facilitated photoinduced electron storage and two-electron reduction of oxygen by reduced graphene oxide in rGO/TiO₂/WO₃ composites. Electrochimica Acta, 2017,250:108-116.
[31]	ZHANG L, LI Y, WANG H , et al. Hierarchical nanostructure of WO₃ nanorods on TiO₂ nanofibers and the enhanced visible light photocatalytic activity for degradation of organic pollutants. CrystEngComm, 2013,15(31):5986-5993.
[32]	HUNGE Y M . Sunlight assisted photoelectrocatalytic degradation of benzoic acid using stratified WO₃/TiO₂ thin film. Ceramics International, 2017,43(13):10089-10096.
[33]	XIAO P Y, LOU J F, ZHANG H X , et al. Enhanced visible- light-driven photocatalysis from WS₂ quantum dots coupled to BiOCl nanosheets: synergistic effect and mechanism insight. Catalysis Science & Technology, 2018,8(1):201-209.
[34]	ZENG X, WANG Z, WANG G , et al. Highly dispersed TiO₂ nanocrystals and WO₃ nanorods on reduced graphene oxide: Z-scheme photocatalysis system for accelerated photocatalytic water disinfection. Applied Catalysis B: Environmental, 2017,218:163-173.
[35]	SONG X L, LI Y, WEI Z , et al. Synthesis of BiVO₄/P25 composites for the photocatalytic degradation of ethylene under visible light. Chemical Engineering Journal, 2017,314:443-452. DOI URL
[36]	LEE J Y, JO W . Heterojunction-based two-dimensional N-doped TiO₂/WO₃ composite architectures for photocatalytic treatment of hazardous organic vapor. Journal of Hazardous Materials, 2016,314:22-31. DOI URL PMID

泡沫镍网负载TiO₂/WO₃薄膜对乙烯的光催化降解

Synthesis of TiO₂/WO₃ on Nickel Foam for the Photocatalytic Degradation of Ethylene

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吐尔洪·木尼热, 赵红刚, 马玉花, 齐献慧, 李钰宸, 闫沉香, 李佳文, 陈平. 单晶WO₃/红磷S型异质结的构建及光催化活性研究[J]. 无机材料学报, 2023, 38(6): 701-707.
[2]	安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.
[3]	陈士昆, 王楚楚, 陈晔, 李莉, 潘路, 文桂林. 磁性Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ Z型异质结的制备及光催化降解性能[J]. 无机材料学报, 2022, 37(12): 1329-1336.
[4]	吕庆洋, 张玉亭, 顾学红. 超声辅助溶胶-凝胶法制备中空纤维TiO₂超滤膜[J]. 无机材料学报, 2022, 37(10): 1051-1057.
[5]	蔡苗, 陈子航, 曾实, 杜江慧, 熊娟. CuS纳米片修饰Bi₅O₇I复合材料用于光催化还原Cr(VI)水溶液[J]. 无机材料学报, 2021, 36(6): 665-672.
[6]	肖翔, 郭少柯, 丁成, 张志洁, 黄海瑞, 徐家跃. CsPbBr₃@TiO₂核壳结构纳米复合材料用作水稳高效可见光催化剂[J]. 无机材料学报, 2021, 36(5): 507-512.
[7]	席文, 李海波. TiO₂/Ti₃C₂T_x复合材料的制备及其杂化电容脱盐特性的研究[J]. 无机材料学报, 2021, 36(3): 283-291.
[8]	梁凤青, 温兆银. 固态锂电池用MOF/聚氧化乙烯复合聚合物电解质[J]. 无机材料学报, 2021, 36(3): 332-336.
[9]	熊金艳, 罗强, 赵凯, 张梦梦, 韩朝, 程刚. 界面电荷快速转移提升铜修饰氧化钨光催化性能[J]. 无机材料学报, 2021, 36(3): 325-331.
[10]	周开岭, 汪浩, 张倩倩, 刘晶冰, 严辉. WO₃电致变色薄膜离子传输动力过程及其循环稳定性[J]. 无机材料学报, 2021, 36(2): 152-160.
[11]	刘彩, 刘芳, 黄方, 王晓娟. 海藻基CDs-Cu-TiO₂复合材料的制备及其光催化性能[J]. 无机材料学报, 2021, 36(11): 1154-1162.
[12]	李翠霞, 孙会珍, 金海泽, 史晓, 李文生, 孔文慧. 3D多级孔rGO/TiO₂复合材料的构筑及其光催化性能研究[J]. 无机材料学报, 2021, 36(10): 1039-1046.
[13]	徐晶威,李政,王泽普,于涵,何祺,付念,丁帮福,郑树凯,闫小兵. 交错能带结构钕掺杂钒酸铋形貌与光催化性能调控[J]. 无机材料学报, 2020, 35(7): 789-795.
[14]	王苹,李心宇,时占领,李海涛. Ag与Ag₂O协同增强TiO₂光催化制氢性能的研究[J]. 无机材料学报, 2020, 35(7): 781-788.
[15]	方美蓉,秦利梅,贾晓博,李永生,牛德超,胡泽岚. 聚乙烯亚胺改性的双介孔氧化硅基因载体构建[J]. 无机材料学报, 2020, 35(2): 187-192.