二氧化钛/多孔碳纳米纤维复合材料的制备及其光催化性能

doi:10.13475/j.fzxb.20230403001

摘要/Abstract

摘要：

为实现纳米二氧化钛(TiO₂)的回收和重复使用,采用静电纺丝、高温煅烧和酸溶技术制备了多孔碳纳米纤维(PCNF),随后使用二次形核法将锐钛矿相TiO₂负载到其表面,得到具有光催化活性的TiO₂/PCNF复合材料。通过扫描电子显微镜、X射线衍射仪、X射线光电子能谱仪、紫外-可见漫反射光谱仪等表征了TiO₂/PCNF复合材料的形貌结构、成分和光吸收性能,并测试了其对降解亚甲基蓝(MB)溶液的光催化性能。结果显示:复合材料的比表面积高达331.9 m²/g,光照30 min后对MB溶液(5 mg/L)的去除率为98.6%,光照60 min 后对MB溶液的去除率可达99.6%,均高于同等TiO₂含量的对比组;重复使用5次后,其对MB溶液的去除率仍然保持在95.0%; PCNF是一种性能优异的光催化载体材料,它不仅能够实现对纳米TiO₂的固定和回收,而且能提高TiO₂的光催化性能。

关键词: 有机染料, 光降解, 二氧化钛, 静电纺丝, 碳纳米纤维, 亚甲基蓝, 二次形核法, 光催化性能, 废水处理

Abstract:

Objective With the widespread use of organic dyes, the residue of which have gradually become the main component of industrial wastewater and caused serious water pollution. As an environmentally friendly photocatalyst, titanium dioxide (TiO₂) nanoparticles have been used in dye degradation, wastewater treatment and other fields due to their high photocatalytic activity, large specific surface area and easy preparation, but they also have problems such as wide band gap and difficult separation and recovery. Therefore, it is urgent to find a suitable carrier material to achieve effective separation and recovery of TiO₂ without reducing its photocatalytic activity and stability.

Method Porous carbon nanofibers (PCNF) were prepared by electrospinning, high-temperature calcination, and acid dissolution. Then anatase TiO₂ was loaded onto its surface by secondary nucleation method to obtain photocatalytic TiO₂/PCNF composites. The morphology, structure, composition, and light absorption properties of TiO₂/PCNF nanocomposites were characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and UV-Vis diffuse reflection spectroscopy, and the photocatalytic properties of TiO₂/PCNF nanocomposites were tested by degradation methylene blue (MB) solution.

Results SEM results showed that TiO₂ nanoparticles were uniformly loaded on porous CNF surfaces, while it was difficult to be loaded on smooth CNF surfaces. This showed that the mesoporous surface of carbon nanofibers was the key to the loading of TiO₂. XRD results indicated that the three samples prepared, i.e., TiO₂, TiO₂/PCNF and TiO₂/CNF were of anatase phase TiO₂. Compared with rutile phase and titanite phase, anatase phase TiO₂ had better photocatalytic activity, so it was beneficial to improve the photocatalytic performance of TiO₂/PCNF. The full spectrum of XPS showed that Ti, O, C, F and N elements existed in TiO₂/PCNF composites, which further proved that TiO₂ had been successfully loaded onto the surface of porous carbon nanofibers. The UV-Vis DRS results showed that significant redshift could occur when TiO₂ was loaded onto both PCNF and CNF surfaces, which not only increased the utilization rate of visible light, but also reduced the band gap value. Brunauer-Emmett-Teller(BET)results suggested that the prepared TiO₂/PCNF composites had mesoporous structures, and the specific surface area was as high as 331.9 m²/g, providing abundant active sites for adsorption and surface reaction. The photocatalytic tests showed that the removal efficiency of TiO₂/PCNF composites was higher than that of the control group with the same TiO₂ content. After 30 min illumination of TiO₂/PCNF composite material, the removal rate of MB solution of 5 mg/L was 98.6%, and after 60 min illumination, the removal rate of MB solution could reach 99.6%. However, the removal rates of TiO₂ and TiO₂/CNF composites in the control group were only 93.3% and 73.2% for MB solution after 30 min illumination. After repeated use for 5 times, the removal rate of TiO₂/PCNF on MB solution remained at 95.0%. All these indicated that TiO₂/PCNF composites have excellent photocatalytic and reusable properties.

Conclusion The TiO₂/PCNF composite was successfully prepared by secondary nucleation method, and the composite had excellent photocatalytic and reusable properties. Compared with CNF, it was found that PCNF with mesoporous structure was more conducive to the loading of TiO₂. The improvement of photocatalytic performance of TiO₂/PCNF composites was mainly attributed to the following reasons. ①All the prepared TiO₂ were anatase phase, which has better photocatalytic activity than rutile phase and plate titanite phase. ②The TiO₂/PCNF composite increased the response range of TiO₂ to visible light, which was conducive to improve the utilization rate of TiO₂ for visible light. ③PCNF had excellent electrical conductivity, which was conducive to accelerating the separation of TiO₂ photogenerated electrons and holes. ④PCNF had a large specific surface area, which providing more active sites both for MB adsorption and surface reactions.

Key words: organic dye, photodegradation, titanium dioxide, electrospinning, carbon nanofiber, methylene blue, secondary nucleation method, photocatalytic performance, wastewater treatment

中图分类号:

TQ619.2

陆瑶瑶, 叶俊涛, 阮承祥, 娄瑾. 二氧化钛/多孔碳纳米纤维复合材料的制备及其光催化性能[J]. 纺织学报, 2024, 45(04): 67-75.

LU Yaoyao, YE Juntao, RUAN Chengxiang, LOU Jin. Preparation and photocatalytic performance of titanium dioxide/porous carbon nanofibers composite material[J]. Journal of Textile Research, 2024, 45(04): 67-75.

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http://www.fzxb.org.cn/CN/Y2024/V45/I04/67

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参考文献 28

[1]	MAO D, YUAN J, QU X, et al. Size tunable Bi₃O₄Br hierarchical hollow spheres assembled with {001}-facets exposed nanosheets for robust photocatalysis against phenolic pollutants[J]. Journal of Catalysis, 2019, 369: 209-221.
[2]	CHEN J, XIONG Y, DUAN M, et al. Insight into the synergistic effect of adsorption-photocatalysis for the removal of organic dye pollutants by Cr-doped ZnO[J]. Langmuir, 2019, 36(2):520-533.
[3]	ZHANG Q, YU L, YANG B, et al. Magnetic Fe₃O₄@Ru-doped TiO₂ nanocomposite as a recyclable photocatalyst for advanced photodegradation of methylene blue in simulated sunlight[J]. Chemical Physics Letters, 2021. DOI:10.1016/j.cplett.2021.138609.
[4]	HENG J, TANG K Y, MD R, et al. Solar-powered photodegradation of pollutant dyes using silver-embedded porous TiO₂ nanofibers[J]. Nanomaterials, 2021. DOI:10.3390/nano11040856.
[5]	杨丽, 王涛, 石现兵, 等. 改性聚丙烯腈纤维负载 MoS_x/TiO₂ 光催化材料制备及其降解染料性能[J]. 纺织学报, 2022, 43(9): 149-155.
	YANG Li, WANG Tao, SHI Xianbing, et al. Preparation of modified polyacrylonitrile fiber supported MoS_x/TiO₂ composite photocatalyst and its performance for dye degradation[J]. Journal of Textile Research, 2022, 43(9): 149-155.
[6]	ZHANG Q, YU L, XU C, et al. A novel method for facile preparation of recoverable Fe₃O₄@TiO₂ core-shell nanospheres and their advanced photocatalytic application[J]. Chemical Physics Letters, 2020. DOI:10.1016/j.cplett.2020.138073.
[7]	LI R, LI T, ZHOU Q. Impact of titanium dioxide(TiO₂) modification on its application to pollution treatment: a review[J]. Catalysts, 2020. DOI:10.3390/catal10070804.
[8]	YU D, BAI J, GU Y, et al. Solvothermal synthesis of TiO₂/CNFs heterostructures with photocatalytic activity[J]. Nano, 2015. DOI:10.1142/S1793292015500800.
[9]	DODOO-ARHIN D, BUABENG F P, MWABORA J M, et al. The effect of titanium dioxide synthesis technique and its photocatalytic degradation of organic dye pollutants[J]. Heliyon, 2018. DOI:10.1016/j.heliyon.2018.e00681.
[10]	李梦悦, 房国丽, 张刚, 等. TiO₂/AC复合材料的吸附性与光催化性能[J]. 河北大学学报(自然科学版), 2018, 38(5):480-489. doi: 10.3969/j.issn.1000-1565.2018.05.006
	LI Mengyue, FANG Guoli, ZHANG Gang, et al. Adsorption and photocatalytic performance of TiO₂/AC composites[J]. Journal of Hebei University (Natural Science Edition), 2018, 38(5):480-489.
[11]	XIAO F, GUO X, LI J, et al. Electrospinning preparation and dye adsorption capacity of TiO₂@carbon flexible fiber[J]. Ceramics International, 2019, 45(9): 11856-11860.
[12]	CHUNG W J, CHUN S Y, KIM S S, et al. Photocatalytic removal of tetracycline using TiO₂/Ge composite optimized by response surface methodo-logy (RSM)[J]. Journal of Industrial & Engineering Chemistry, 2016,36:320-325.
[13]	费锡智, 杨晶晶, 白仁碧. 光催化-膜分离耦合技术的水处理应用研究进展[J]. 水处理技术, 2014(12): 11-18.
	FEI Xizhi, YANG Jingjing, BAI Renbi. Research progress in application of photocatalysis membrane separation coupling technology in water treatment[J]. Water Treatment Technology, 2014(12):11-18.
[14]	MARINHO B A, DE SOUZA S M A G U, DE SOUZA A A U, et al. Electrospun TiO₂ nanofibers for water and wastewater treatment: a review[J]. Journal of Materials Science, 2021, 56:5428-5448.
[15]	ZHOU F L, GONG R H, PORAT I. Mass production of nanofibre assemblies by electrostatic spinning[J]. Polymer International, 2010, 58(4):331-342.
[16]	XUE J, WU T, DAI Y, et al. Electrospinning and electrospun nanofibers: methods, materials, and applications[J]. Chemical Reviews, 2019, 119(8):5298-5415. doi: 10.1021/acs.chemrev.8b00593 pmid: 30916938
[17]	CHANG G, ULLAH W, HU Y, et al. Functional carbon nanofibers with semi-embedded titanium oxide particles via electrospinning[J]. Macromolecular Rapid Communications, 2018. DOI:10.1002/marc.201800102.
[18]	BLANCO M, MONTESERIN C, ANGULO A, et al. TiO₂-doped electrospun nanofibrous membrane for photocatalytic water treatment[J]. Polymers, 2019. DOI:10.3390/polym11050747.
[19]	张梦媛, 黄庆林, 黄岩, 等. 静电纺聚四氟乙烯/二氧化钛光催化纳米纤维膜的制备及其应用[J]. 纺织学报, 2019, 40(9): 1-7.
	ZHANG Mengyuan, HUANG Qinglin, HUANG Yan, et al. Electrospun poly(tetrafluoroethylene)/TiO₂ photocatalytic nanofiber membrane and its applica-tion[J]. Journal of Textile Research, 2019, 40(9): 1-7.
[20]	钱怡帆, 周堂, 张礼颖, 等. 聚丙烯腈/醋酸纤维素/TiO₂复合纳米纤维膜的制备及其光催化降解性能[J]. 纺织学报, 2020, 41(5):8-14.
	QIAN Yifan, ZHOU Tang, ZHANG Liying, et al. Preparation of polyacrylonitrile/cellulose acetate/TiO₂ composite nanofiber membrane and its photocatalytic degradation performance[J]. Journal of Textile Research, 2020, 41(5):8-14.
[21]	AGHASILOO P, YOUSEFZADEH M, LATIFI M, et al. Highly porous TiO₂ nanofibers by humid-electrospinning with enhanced photocatalytic proper-ties[J]. Journal of alloys and compounds, 2019, 790:257-265.
[22]	XU S, HOU Z, CHUAI X, et al. Overview of secondary nucleation: from fundamentals to application[J]. Industrial & Engineering Chemistry Research, 2020, 59(41): 18335-18356.
[23]	于翔, 张效琳, 孟青青, 等. TiO₂/碳纳米纤维膜的制备与光催化性能[J]. 工业水处理, 2020, 40(12):96-99. doi: 10.11894/iwt.2020-0049
	YU Xiang, ZHANG Xiaolin, MENG Qingqing, et al. Preparation of TiO₂/carbon nanofibers membrane and its photocatalytic performance[J]. Industrial Water Treatment, 2020, 40(12):96-99. doi: 10.11894/iwt.2020-0049
[24]	BALTA Z, BILGINSIMSEK E, BEREK D. Solvothermal synthesis of WO₃/TiO₂/carbon fiber composite photocatalysts for enhanced performance under sunlight illumination[J]. Photochemistry and Photobiology, 2019, 95(6):1331-1338.
[25]	ETACHERI V, DI VALENTIN C, SCHNEIDER J, et al. Visible-light activation of TiO₂ photocatalysts: advances in theory and experiments[J]. Journal of Photochemistry & Photobiology C Photochemistry Reviews, 2015, 25:1-29.
[26]	HAN X, KUANG Q, JIN M, et al. Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties[J]. Journal of The American Chemical Society, 2009, 131(9):3152-3153. doi: 10.1021/ja8092373 pmid: 19216572
[27]	张天亮, 李军, 熊巍, 等. 碳酸钾活化一步法制备高比表活性炭及其电容性能的研究[J]. 无机盐工业, 2022, 54(4):159-164.
	ZHANG Tianliang, LI Jun, XIONG Wei, et al. Study on one-step preparation of activated carbon with high specific surface by K₂CO₃ activation and its capacitance performance[J]. Inorganic Chemicals Industry, 2022, 54(4):159-164.
[28]	RAZA N, RAZA W, GUL H, et al. Solar-light-active silver phosphate/titanium dioxide/silica heterostructures for photocatalytic removal of organic dye[J]. Journal of Cleaner Production, 2020. DOI:10.1016/j.jclepro.2020.120031.

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试样名称	孔径/ nm	孔体积/ (cm³·g^-1)	比表面积/ (m²·g^-1)
TiO₂	3.943	0.220	275.015
TiO₂/PCNF	1.382	0.106	331.940
TiO₂/CNF	13.171	0.216	58.418