Fe<sub>3</sub>O<sub>4</sub>-BiOBr/Graphene磁性气凝胶的构筑与Cr(VI)污水净化

铁伟伟; 邱帅彪; 王红霞; 袁双义; 董旭; 何伟伟

doi:10.13801/j.cnki.fhclxb.20230911.001

Fe₃O₄-BiOBr/Graphene磁性气凝胶的构筑与Cr(VI)污水净化

doi: 10.13801/j.cnki.fhclxb.20230911.001

许昌学院　化工与材料学院(表面微纳米材料研究所)，河南省微纳米能量储存与转换材料实验室，许昌 461000

基金项目: 河南省国家级大学生创新创业训练项目 (202110480014)；河南省高等学校青年骨干教师培养计划(2021GGJS145)；河南省高等学校重点科研项目(22A430036)

详细信息

通讯作者:
铁伟伟，博士，副教授，研究方向为纳米光电材料　E-mail: tieww929@163.com

中图分类号: O614.24+；TB333
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出版历程
- 收稿日期: 2023-06-13
- 修回日期: 2023-08-18
- 录用日期: 2023-08-29
- 网络出版日期: 2023-09-12
- 刊出日期: 2024-04-15

Construction of magnetic Fe₃O₄-BiOBr/Graphene aerogel and Cr(VI) wastewater purification

Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, College of Chemical and Materials Engineering, Xuchang University,Xuchang 461000, China

Funds: National Innovation and Entrepreneurship Training Program for College Students of Henan Province (202110480014); Youth Backbone Teacher Funding Project in Universities of Henan Province (2021GGJS145); Key Scientific Research Project in Universities of Henan Province (22A430036)

摘要

摘要: 为改善单一半导体粉体材料的光生电子-空穴分离和回收能力，基于功能协同效应，采用共沉淀法，将Fe³⁺/Fe²⁺盐在一定浓度的氨水作用下制备出纳米Fe₃O₄，并分散于含有溴化十六烷基三甲铵(CTAB)的正辛烷中，提供Br^–的同时，在室温下与水溶液中的硝酸铋和柠檬酸相互作用，利用非互溶体系，制备出Fe₃O₄-BiOBr；最后，将Fe₃O₄-BiOBr分散于含有赖氨酸的氧化石墨烯水溶液中，通过一步水热法合成Fe₃O₄-BiOBr协同修饰的磁性石墨烯气凝胶(Fe₃O₄-BiOBr/Graphene)。样品的晶体结构、形貌特征和催化活性通过XRD、Raman、XPS、SEM、TEM、UV-Vis光谱等综合测试技术进行了表征分析。Fe₃O₄-BiOBr/Graphene复合材料中的Fe₃O₄呈类球状，尺寸约10~25 nm，均匀镶嵌于BiOBr片层中间，并与石墨烯之间相互作用，整体呈现球-片-空洞构造。Fe₃O₄-BiOBr/Graphene复合材料显示出良好的可见光吸收性和Cr(VI)还原活性，30 min内可去除Cr(VI)至100%，高于单一组分的磁性Fe₃O₄，这可能与Fe₃O₄-BiOBr异质结构、石墨烯导电材料的引入及Fe₃O₄-BiOBr/Graphene三者之间良好的界面相互作用，有效地促进了光生电子与空穴的分离效率有关。
- 溴氧化铋 /
- 四氧化三铁 /
- 石墨烯气凝胶 /
- 六价铬 /
- 磁性回收 /
- 光催化还原
Abstract: In order to improve the photogenerated electron-hole separation and recycling ability of single semiconductor powder material, based on the functionally synergistic effect, magnetic graphene aerogel (Fe₃O₄-BiOBr/graphene) modified by Fe₃O₄-BiOBr had been facilely prepared by one-step hydrothermal process by dispersing Fe₃O₄-BiOBr composite in aqueous solution of graphene oxide containing lysine. The Fe₃O₄-BiOBr composite was synthesized in non-miscible solvent system under room-temperature, in which nano Fe₃O₄, firstly prepared by co-precipitation method using Fe³⁺/Fe²⁺ salt under the action of ammonia water with a certain concentration, was dispersed in n-octane containing hexadecyl trimethyl ammonium bromide (CTAB) for providing Br^–, interacting with an aqueous solution containing bismuth nitrate and citric acid adding drop by drop. The crystal structure, morphology and catalytic activity of the samples were characterized by XRD, Raman, XPS, SEM, TEM, and UV-Vis spectra. Fe₃O₄-BiOBr/graphene composites, in which spherical Fe₃O₄ with a size of 10-25 nm are evenly embedded in layered BiOBr flakes, and they interact with graphene, overall, have showed a sphere-sheet-cavity structure. Fe₃O₄-BiOBr/graphene composites have favorable visible light absorption efficiency and Cr(VI) photocatalytic activity. The photocatalytic activity of Cr(VI) could achieve about 100% within 30 min, which is higher than that of single magnetic Fe₃O₄. This phenomenon maybe origin from the introduction of Fe₃O₄-BiOBr heterostructure and conductive graphene as well as their good interfacial interaction within them, effectively promoting the separation efficiency of photogenerated electrons and holes between Fe₃O₄-BiOBr/graphene composite.
- BiOBr /
- Fe₃O₄ /
- graphene aerogel /
- Cr(VI) /
- magnetic recovery /
- photocatalytic reduction

HTML全文

图 1 Fe₃O₄-BiOBr/Graphene-1的宏观照片

Figure 1. Photographs of Fe₃O₄-BiOBr/Graphene-1

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图 2 Fe₃O₄ (a)、Fe₃O₄-BiOBr (b)和Fe₃O₄-BiOBr/Graphene-1 ((c), (d))的SEM图像

Figure 2. SEM images of Fe₃O₄ (a), Fe₃O₄-BiOBr (b) and Fe₃O₄-BiOBr/Graphene-1 ((c), (d))

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图 3 Fe₃O₄-BiOBr/Graphene-1的TEM图像

Figure 3. TEM image of Fe₃O₄-BiOBr/Graphene-1

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图 4 Fe₃O₄、BiOBr、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的XRD图谱

Figure 4. XRD patterns of Fe₃O₄, BiOBr, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 5 氧化石墨烯(GO)和Fe₃O₄-BiOBr/Graphene-1的拉曼图谱

Figure 5. Raman spectra of graphene oxide (GO) and Fe₃O₄-BiOBr/Graphene-1

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图 6 Fe₃O₄、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的XPS图谱(a)及Fe2p (b)和Bi4f (c)的XPS高分辨图谱

Figure 6. XPS spectra (a) and Fe2p (b), Bi4f (c) XPS high-resolution spectra of Fe₃O₄, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 7 Fe₃O₄、BiOBr、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的UV-Vis DRS光谱图

Figure 7. UV-Vis DRS spectra of Fe₃O₄, BiOBr, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 8 Fe₃O₄-BiOBr/Graphene系列样品在模拟太阳光照射下对Cr(VI)的光催化活性曲线

Figure 8. Photocatalytic activity curves of Cr(VI) in the presence of series of Fe₃O₄-BiOBr/Graphene samples under sunlight irradiation

C_t—Concentration of Cr(VI) at time t; C₀—Initial concentration of Cr(VI)

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图 9 Fe₃O₄-BiOBr/Graphene-1的电子顺磁共振(ESR)图谱

Figure 9. Electron spin resonance (ESR) spectra of Fe₃O₄-BiOBr/Graphene-1

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图 10 Fe₃O₄和Fe₃O₄-BiOBr/Graphene-1的磁滞回线图谱

Figure 10. Hysteresis loop spectra of Fe₃O₄ and Fe₃O₄-BiOBr/Graphene-1

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图 11 Fe₃O₄、BiOBr、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的瞬态光电流图谱

Figure 11. Photocurrent spectra of Fe₃O₄, BiOBr, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 12 模拟太阳光下Fe₃O₄-BiOBr/Graphene-1复合材料对污染物Cr(VI)的光催化还原示意图

Figure 12. Photocatalytic reduction mechanism of Fe₃O₄-BiOBr/Graphene-1 composite onto Cr(VI) under sunlight irradiation

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表 1 系列Fe₃O₄-BiOBr/Graphene气凝胶

Table 1. Series of Fe₃O₄-BiOBr/Graphene aerogel

Sample	Graphene oxide/(g·mL⁻¹)	Fe₃O₄-BiOBr/g
Fe₃O₄-BiOBr/Graphene-1	4.2	0.40
Fe₃O₄-BiOBr/Graphene-2	5.0	0.35
Fe₃O₄-BiOBr/Graphene-3	5.0	0.40
Fe₃O₄-BiOBr/Graphene-4	3.5	0.40

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表 2 Fe₃O₄-BiOBr/Graphene-1气凝胶的物理性能

Table 2. Physical properties of Fe₃O₄-BiOBr/Graphene-1 aerogel

Sample	BET surface area/(m²·g⁻¹)	Pore size/ nm (4 V/A by BET)	Pore volume / (cm³·g⁻¹)	Porosity/ %
Fe₃O₄-BiOBr/ Graphene-1	47.8902	17.14143	0.205227	85.5914
Note: BET—Brunauer-Emmett-Teller.

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参考文献(34)

[1]	XU D, HUANG Y, MA Q, et al. A 3D porous structured cellulose nanofibrils-based hydrogel with carbon dots-enhanced synergetic effects of adsorption and photocatalysis for effective Cr(VI) removal [J]. Chemical Engineering Journal, 2023, 456: 141104.
[2]	LI L X, GAO H J, LIU G R, et al. Synthesis of carnation flower-like Bi₂O₂CO₃ photocatalyst and its promising application for photoreduction of Cr(VI) [J]. Advanced Powder Technology, 2022, 33(3): 103481.
[3]	KE T L, GUO H G, ZHANG Y L, et al. Photoreduction of Cr(VI) in water using BiVO₄-Fe₃O₄ nano-photocatalyst under visible light irradiation[J]. Environmental Science and Pollution Research, 2017, 24(36): 28239-28247.
[4]	BASALEH A, ISMAIL A A, MOHAMED R M. Novel visible light heterojunction CdS/Gd₂O₃ nanocomposites photocatalysts for Cr(VI) photoreduction[J]. Journal of Alloys and Compounds, 2022, 927: 166988.
[5]	FENG Y B, JIANG X H, SUN L L, et al. Efficient degradation of tetracycline in actual water systems by 2D/1D g-C₃N₄-BiOBr Z-scheme heterostructure through a peroxymonosulfate-assisted photocatalytic process[J]. Journal of Alloys and Compounds, 2023, 938: 168698.
[6]	TIE W W, DU Z Y, YUE H W, et al. Self-assembly of carbon nanotube/graphitic-like flake-BiOBr nanocomposite with 1D/2D/3D heterojunctions for enhanced photocatalytic activity[J]. Journal of Colloid and Interface Science, 2020, 579: 862-871.
[7]	HUANG X, YAN X, XIA L, et al. A three-dimensional graphene/Fe₃O₄/carbon microtube of sandwich-type architecture with improved wave absorbing performance[J]. Scripta Materialia, 2016, 120: 107-111.
[8]	LI S, MA Q P, CHEN L, et al. Hydrochar-mediated photocatalyst Fe₃O₄-BiOBr@HC for highly efficient carbamazepine degradation under visible LED light irradiation[J]. Chemical Engineering Journal, 2022, 433: 134492.
[9]	XIE X, LIU Y G, DONG X X, et al. Synthesis and characterization of Fe₃O₄/BiOI n-p heterojunction magnetic photocatalysts [J]. Applied Surface Science, 2018, 455: 742-747.
[10]	LONG D, TU Y P, CHAI Y Q, et al. Photoelectrochemical assay based on SnO₂-BiOBr p-n heterojunction for ultrasensitive DNA detection[J]. Analytical Chemistry, 2021, 93(38): 12995-13000.
[11]	ZHU L Y, LI H, LIU Z R, et al. Synthesis of the 0D/3D CuO/ZnO heterojunction with enhanced photocatalytic activity[J]. Journal of Physical Chemistry C, 2018, 122(17): 9531-9539.
[12]	LIU X Y, YANG Z, ZHANG L. In-situ fabrication of 3D hierarchical flower-like β-Bi₂O₃@CoO Z-scheme heterojunction for visible-driven simultaneous degradation of multi-pollutants[J]. Journal of Hazardous Materials, 2021, 403: 123566.
[13]	XU H F, XU Z C, ZHOU J, et al. Hydrothermal fabrication of BiOBr/magnetic reduced graphene oxide composites with efficient visible light photocatalytic activity[J]. Ceramics International, 2019, 45(12): 15458-15465.
[14]	SUN Y M, WU W D, ZHOU H F. Lignosulfonate-controlled BiOBr/C hollow microsphere photocatalyst for efficient removal of tetracycline and Cr(VI) under visible light[J]. Chemical Engineering Journal, 2023, 453: 139819.
[15]	YU X, SHI J J, FENG L J, et al. A three-dimensional BiOBr/RGO heterostructural aerogel with enhanced and selective photocatalytic properties under visible light[J]. Applied Surface Science, 2017, 396: 1775-1782.
[16]	LIU J H, WEI X N, SUN W Q, et al. Fabrication of S-scheme CdS-g-C₃N₄-graphene aerogel heterojunction for enhanced visible light driven photocatalysis[J]. Environmental Research, 2021, 197: 111136.
[17]	AN W J, YANG T, WANG Y S, et al. Adsorption and in-situ photocatalytic Fenton multifield coupled degradation of organic pollutants and coking wastewater via FeBiOBr modification of three-dimensional graphene aerogel[J]. Applied Surface Science, 2023, 610: 155495.
[18]	智建辉, 师泽鹏, 孙小倩, 等. 杂化二氧化锰气凝胶的制备及其对氨气的吸附[J]. 中国环境科学, 2023, 43(7): 3368-3377. ZHI Jianhui, SHI Zepeng, SUN Xiaoqian, et al. Preparation of hybrid manganese dioxide aerogel and its application in ammonia adsorption[J]. China Environmental Science, 2023, 43(7): 3368-3377(in Chinese).
[19]	SHI Y Y, HU Y Y, WANG Y, et al. 3D N-doped graphene aerogel sponge-loaded CoS₂ co-catalytic Fenton system for ciprofloxacin degradation[J]. Journal of Cleaner Production, 2022, 380: 135008.
[20]	LI S, WANG Z W, ZHAO X T, et al. Insight into enhanced carbamazepine photodegradation over biochar-based magnetic photocatalyst Fe₃O₄-BiOBr/BC under visible LED light irradiation[J]. Chemical Engineering Journal, 2019, 360: 600-611.
[21]	XIE X Y, LI S, QI K M, et al. Photoinduced synthesis of green photocatalyst Fe₃O₄-BiOBr/CQDs derived from corncob biomass for carbamazepine degradation: The role of selectively more CQDs decoration and Z-scheme structure[J]. Chemical Engineering Journal, 2021, 420: 129705.
[22]	REN X Z, SUN Y H, XING H, et al. Magnetically separable Fe₃O₄@C-BiOBr heterojunction for the enhanced visible light-driven photocatalytic performance[J]. Journal of Nanoparticle Research, 2018, 20(10): 268.
[23]	MENG H N, ZHANG Z Z, ZHAO F X, et al. Orthogonal optimization design for preparation of Fe₃O₄ nanoparticles via chemical coprecipitation [J]. Applied Surface Science, 2013, 280: 679-685.
[24]	TIE W W, BHATTACHARYYA S S, HAN C C, et al. Green assembly of covalently linked BiOBr/graphene composites for efficient visible light degradation of dyes [J]. ACS Omega, 2022, 7(40): 35805-35813.
[25]	TIAN X K, WANG W W, TIAN N, et al. Cr(VI) reduction and immobilization by novel carbonaceous modified magnetic Fe₃O₄/halloysite nanohybrid[J]. Journal of Hazardous Materials, 2016, 309: 151-156.
[26]	禹凡, 郑涛, 汤涛, 等. 基于金属有机框架化合物的非织造复合材料制备及其对废水中六价铬的去除[J]. 纺织学报, 2022, 43(3): 139-145. YU Fan, ZHENG Tao, TANG Tao, et al. Preparation of nonwoven composites based on metal-organic frame compounds and removal of hexavalent chromium from wastewater[J]. Journal of Textile Research, 2022, 43(3): 139-145(in Chinese).
[27]	徐义邦, 樊孝俊, 龚娴. 二苯碳酰二肼分光光度法测定水中六价铬方法的改进[J]. 中国给水排水, 2015, 31(8): 106-108. XU Yibang, FAN Xiaojun, GONG Xian. Improvement of method for determination of chromium (VI) in water by 1, 5-diphenylcarbohydrazide spectrophotometry[J]. China Water & Wastewater, 2015, 31(8): 106-108(in Chinese).
[28]	LIU C, DONG X L, HAO Y C, et al. Efficient photocatalytic dye degradation over Er-doped BiOBr hollow microspheres wrapped with graphene nanosheets: Enhanced solar energy harvesting and charge separation[J]. RSC Advances, 2017, 7(36): 22415-22423.
[29]	CHEN T D, WANG J Q, WU X Z, et al. Ethanediamine induced self-assembly of long-range ordered GO/MXene composite aerogel and its piezoresistive sensing performances[J]. Applied Surface Science, 2021, 566: 150719.
[30]	CHEN Y, SUN F Q, HUANG Z J, et al. Photochemical fabrication of SnO₂ dense layers on reduced graphene oxide sheets for application in photocatalytic degradation of p-nitrophenol[J]. Applied Catalysis B: Environmental, 2017, 215: 8-17.
[31]	SONG N, FAN H Q, TIAN H L. Reduced graphene oxide/ZnO nanohybrids: Metallic Zn powder induced one-step synthesis for enhanced photocurrent and photocatalytic response[J]. Applied Surface Science, 2015, 353: 580-587.
[32]	YI X H, MA S Q, DU X D, et al. The facile fabrication of 2D/3D Z-scheme g-C₃N₄/UiO-66 heterojunction with enhanced photocatalytic Cr(VI) reduction performance under white light [J]. Chemical Engineering Journal, 2019, 375: 121944.
[33]	VALIZADEH B, NGUYEN T N, KAMPOURI S, et al. A novel integrated Cr(VI) adsorption-photoreduction system using MOF@polymer composite beads[J]. Journal of Materials Chemistry A, 2020, 8(19): 9629-9637.
[34]	BHATI A, ANAND S R, SAINI D, et al. Sunlight-induced photoreduction of Cr(VI) to Cr(III) in wastewater by nitrogen-phosphorus-doped carbon dots[J]. NPJ Clean Water, 2019, 2(1): 12. doi: 10.1038/s41545-019-0036-z