磁性纳米Fe3O4@TiO2可见光下光催化还原Cr(Ⅵ)

doi:10.11949/0438-1157.20190773

摘要/Abstract

摘要：

通过溶胶-凝胶法、水热法和煅烧法，成功制备出具有光催化活性的Fe₃O₄@TiO₂磁性纳米复合材料，将超顺磁性的Fe₃O₄与TiO₂复合，实现材料的快速回收与可见光响应能力的结合。进一步将Fe₃O₄@TiO₂磁性纳米复合材料应用于Cr(Ⅵ)的去除，实验结果表明，在可见光照射下Fe₃O₄@TiO₂对Cr(Ⅵ)的去除能力是P25的1.96倍。并深入探究了Fe₃O₄@TiO₂中TiO₂含量、Cr(Ⅵ)溶液的pH以及空穴去除剂对Fe₃O₄@TiO₂可见光下光催化还原Cr(Ⅵ)能力的影响，实验表明当Fe₃O₄@TiO₂中TiO₂含量为1.0 g/g，添加甲酸作为空穴去除剂并且溶液pH=2时Fe₃O₄@TiO₂对Cr(Ⅵ)的去除能力最佳，此条件下Cr(Ⅵ)的去除率达到99.85%，重复使用4次，催化能力依然保持较高水平。此外，Fe₃O₄@TiO₂对5~500 mg/L浓度范围内的Cr(Ⅵ)都具有良好的去除能力。Fe₃O₄@TiO₂磁性纳米复合材料对Cr(Ⅵ)具备优异的去除能力，具有良好的应用前景。

关键词: Fe₃O₄@TiO₂, 光催化, 六价铬去除, 磁性纳米粒子, 空穴去除剂

Abstract:

Fe₃O₄@TiO₂ magnetic nanocomposites with photocatalytic activity were successfully prepared by sol-gel, hydrothermal methods and calcination method. Combine superparamagnetism Fe₃O₄ and TiO₂, which can not only realize the rapid recovery of materials but also made the materials have visible light response capability. The Fe₃O₄@TiO₂ magnetic nanocomposites were further applied to the removal of Cr(Ⅵ). The results show that when Fe₃O₄@TiO₂ has a TiO₂ content of 1.0 g/g and the addition of formic acid as a hole remover and the solution pH=2, Fe₃O₄@TiO₂ has the best removal ability of Cr(Ⅵ). Under this condition, Cr(Ⅵ) removal rate reached 99.85%, and the catalytic performance remained high even used 4 times. In addition, Fe₃O₄@TiO₂ has good removal ability for Cr(Ⅵ) in the range of 5—500 mg/L. Fe₃O₄@TiO₂ has excellent removal ability for Cr(Ⅵ) magnetic nanocomposites and has a good application prospect.

Key words: Fe₃O₄@TiO₂, photocatalysis, removal of Cr(Ⅵ), magnetic nanoparticles, hole scavenger

中图分类号:

X 52

王子帅,王耀强,肖刚,苏海佳. 磁性纳米Fe₃O₄@TiO₂可见光下光催化还原Cr(Ⅵ)[J]. 化工学报, 2019, 70(10): 4062-4071.

Zishuai WANG,Yaoqiang WANG,Gang XIAO,Haijia SU. Photocatalytic reduction of Cr(Ⅵ) by magnetic nanomaterial Fe₃O₄@TiO₂ under visible light[J]. CIESC Journal, 2019, 70(10): 4062-4071.

图/表 11

表1 TiO2基光催化剂去除Cr(Ⅵ)能力比较

Table 1 Comparison of ability of TiO2 based photocatalystto remove Cr(Ⅵ)

Materials	Reaction time/h	Removal rate	Ref.
TiO₂@Au@CeO₂	5	79%	[19]
TiO₂/PS	2.5	nearly 100%	[20]
AuNPs/B-TiO₂/FTO glass	5	80%	[21]
CQDs-TiO_2- _x /rGO	1.3	80%	[22]
Ag@Fe₃O₄@SiO₂@TiO₂	4	nearly 100%	[23]
N-TiO₂/g-C₃N₄@diatomite	5	nearly 100%	[24]
C-SO₃H/CN-TiO₂	4	nearly 100%	[25]

图1 Fe3O4@TiO2中TiO2含量及不同材料对光催化还原Cr(Ⅵ)的影响

Fig.1 Effects of TiO2 amount in Fe3O4@TiO2 and different materials on photocatalytic reduction of Cr(Ⅵ)

图2 pH对Fe3O4@TiO2去除Cr(Ⅵ)的影响

Fig.2 Effect of pH on removal of Cr(Ⅵ) by Fe3O4@TiO2

图3 不同空穴去除剂对于Fe3O4@TiO2光催化还原Cr(Ⅵ)的影响及甲酸对Fe3O4@TiO2光催化还原Cr(Ⅵ)能力的提高

Fig.3 Effect of hole scavenger on reduction of Cr(Ⅵ) by Fe3O4@TiO2 and improvement of reduction of Cr(Ⅵ) by Fe3O4@TiO2

图4 Fe3O4@TiO2对不同浓度Cr(Ⅵ)的去除

Fig.4 Removal of different concentrations of Cr(Ⅵ) by Fe3O4@TiO2

图5 Fe3O4@TiO2的循环使用

Fig.5 Recycle use of Fe3O4@TiO2

图6 磁性纳米Fe3O4@TiO2的XRD谱图

Fig.6 XRD patterns of Fe3O4@TiO2

图7 Fe3O4@TiO2的TEM和SEM图

Fig.7 TEM and SEM images of Fe3O4@TiO2

图8 Fe3O4@TiO2与Cr(Ⅵ)发生反应之后的XPS谱图

Fig.8 XPS patterns of Fe3O4@TiO2 and after reaction with Cr(Ⅵ)

图9 Fe3O4@TiO2的UV-Vis图及相关分析

Fig.9 UV-Vis spectra of Fe3O4@TiO2 and related analysis

图10 Fe3O4@TiO2与P25的比表面积及孔径分析

Fig.10 Specific surface area and pore size distribution of Fe3O4@TiO2 and P25

参考文献 36

1	Challagulla S , Nagarjuna R , Ganesan R , et al . Acrylate-based polymerizable sol-gel synthesis of magnetically recoverable TiO₂ supported Fe₃O₄ for Cr(Ⅵ) photoreduction in aerobic atmosphere[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(3): 974-982.
2	Xu S C , Pan S S , Xu Y , et al . Efficient removal of Cr(Ⅵ) from wastewater under sunlight by Fe(Ⅱ)-doped TiO₂spherical shell[J]. Journal of Hazardous Materials, 2015, 283: 7-13.
3	Chen Z , Li Y , Guo M , et al . One-pot synthesis of Mn-doped TiO₂ grown on graphene and the mechanism for removal of Cr(Ⅵ) and Cr(Ⅲ)[J]. Journal of Hazardous Materials, 2016, 310: 188-198.
4	赵宇 . 重金属废水污染现状[J]. 江西化工, 2016, 2: 207-208.
	Zhao Y . Pollution status and hazard of heavy metal wastewater[J]. Jiangxi Chemical Industry, 2016, 2: 207-208.
5	Jin Z , Zhang Y X , Meng F L , et al . Facile synthesis of porous single crystalline ZnO nanoplates and their application in photocatalytic reduction of Cr(Ⅵ) in the presence of phenol[J]. Journal of Hazardous Materials, 2014, 276: 400-407.
6	Zhao X , Huang S , Liu Y , et al . In situ preparation of highly stable polyaniline/W₁₈O₄₉ hybrid nanocomposite as efficient visible light photocatalyst for aqueous Cr(Ⅵ) reduction[J]. Journal of Hazardous Materials, 2018, 353: 466-475.
7	Li S , Cai J , Wu X , et al . TiO₂@Pt@CeO₂ nanocomposite as a bifunctional catalyst for enhancing photo-reduction of Cr(Ⅵ) and photo-oxidation of benzyl alcohol[J]. Journal of Hazardous Materials, 2018, 346: 52-61.
8	Chen H , Shao Y , Xu Z , et al . Effective catalytic reduction of Cr(Ⅵ) over TiO₂ nanotube supported Pd catalysts[J]. Applied Catalysis B： Environmental, 2011, 105(3/4): 255-262.
9	Nanda B , Pradhan A C , Parida K M . Fabrication of mesoporous CuO/ZrO₂-MCM-41 nanocomposites for photocatalytic reduction of Cr(Ⅵ)[J]. Chemical Engineering Journal, 2017, 316: 1122-1135.
10	Liu J , Huang K , Xie K , et al . An ecological new approach for treating Cr(Ⅵ)-containing industrial wastewater: Photochemical reduction[J]. Water Research, 2016, 93: 187-194.
11	Wang Q , Shi X , Liu E , et al . Facile synthesis of AgI/BiOI-Bi₂O₃ multi-heterojunctions with high visible light activity for Cr(Ⅵ) reduction[J]. Journal of Hazardous Materials, 2016, 317: 8-16.
12	Fujishima A , Honda K . Electrochemical photolysis of water at a semiconductor electrode[J]. Nature, 1972, 238(5358): 37.
13	Chen C , Ma W , Zhao J . Semiconductor-mediated photodegradation of pollutants under visible-light irradiation[J]. Chemical Society Reviews, 2010, 39(11): 4206-4219.
14	于娜娜, 代岳, 陈珍, 等 . TiO₂光催化剂及其改性方法最新研究进展[J]. 化工中间体, 2011, 7(6): 16-20.
	Yu N N , Dai Y , Chen Z , et al . The latest review on modified methods of TiO₂ photocatalysis[J]. Chemical Intermediate, 2011, 7(6): 16-20.
15	Zhang G , Yong C Z , Nadagouda M , et al . Visible light-sensitized S, N and C co-doped polymorphic TiO₂, for photocatalytic destruction of microcystin-LR[J]. Applied Catalysis B: Environmental, 2014, 144(1): 614-621.
16	Cassaignon S , Colbeau-Justin C . Titanium dioxide in photocatalysis[M]// Durupthy O. Nanomaterials: A Danger or a Promise? London: Springer, 2013: 153-188.
17	张凤君, 刘卓婧, 刘兆煐, 等 . TiO₂光催化剂改性研究进展[J]. 科技导报, 2013, 31(17): 66-71.
	Zhang F J , Liu Z J , Liu Z Y , et al . Review on the modification of TiO₂ photocatalyst[J]. Science & Technology Review, 2013, 31(17): 66-71.
18	Liu X , Hu Q , Fang Z , et al . Magnetic chitosan nanocomposites: a useful recyclable tool for heavy metal ion removal[J]. Langmuir, 2008, 25(1): 3-8.
19	Cai J , Wu X , Li S , et al . Controllable location of Au nanoparticles as cocatalyst onto TiO₂@CeO₂ nanocomposite hollow spheres for enhancing photocatalytic activity[J]. Applied Catalysis B: Environmental, 2017, 201: 12-21.
20	Altin I , Sökmen M . Preparation of TiO₂-polystyrene photocatalyst from waste material and its usability for removal of various pollutants[J]. Applied Catalysis B: Environmental, 2014, 144: 694-701.
21	Kim W , Park J Y , Kim Y . Fabrication of branched-TiO₂ microrods on the FTO glass for photocatalytic reduction of Cr (Ⅵ) under visible-light irradiation[J]. Journal of Industrial and Engineering Chemistry, 2019, 73: 248-253.
22	Xu L , Yang L , Bai X , et al . Persulfate activation towards organic decomposition and Cr (Ⅵ) reduction achieved by a novel CQDs-TiO_2- _x /rGO nanocomposite[J]. Chemical Engineering Journal, 2019, 373: 238-250.
23	Su J , Zhang Y , Xu S , et al . Highly efficient and recyclable triple-shelled Ag@Fe₃O₄@SiO₂@TiO₂ photocatalysts for degradation of organic pollutants and reduction of hexavalent chromium ions[J]. Nanoscale, 2014, 6(10): 5181-5192.
24	Sun Q , Hu X , Zheng S , et al . Effect of calcination on structure and photocatalytic property of N-TiO₂/g-C₃N₄@ diatomite hybrid photocatalyst for improving reduction of Cr (Ⅵ)[J]. Environmental Pollution, 2019, 245: 53-62.
25	Huang Z , Li K , Yan L , et al . Fabrication of bio-based acidic nonmetals co-doped TiO₂ with core/shell structure and their unique photocatalytic performance for the rapid reduction of aqueous Cr (Ⅵ) under original pH and visible-light conditions[J]. Applied Catalysis A: General, 2019, 575: 142-151.
26	Mishra P M , Naik G K , Nayak A , et al . Facile synthesis of nano-structured magnetite in presence of natural surfactant for enhanced photocatalytic activity for water decomposition and Cr(Ⅵ) reduction[J]. Chemical Engineering Journal, 2016, 299: 227-235.
27	Zhao Y , Tao C , Xiao G , et al . Controlled synthesis and photocatalysis of sea urchin-like Fe₃O₄@ TiO₂@ Ag nanocomposites[J]. Nanoscale, 2016, 8(9): 5313-5326.
28	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(8): 106-108.
	Xu Y B , Fan J X , Gong X . Improvement of method for determination of chromium(Ⅵ) in water by 1, 5-diphenylcarbohydrazide spectrophotometry[J]. China Water＆Wastewater, 2015(8): 106-108.
29	Wang Y S , Shen J H , Horng J J . Chromate enhanced visible light driven TiO₂ photocatalytic mechanism on Acid Orange 7 photodegradation[J]. Journal of Hazardous Materials, 2014, 274: 420-427.
30	孙雪娇, 王思琦, 董佳, 等 . Ag/NH₂-MIL-125(Ti)的构建及可见光还原水中Cr(Ⅵ)[J]. 应用化学, 2019, (3): 314-323.
	Sun X J , Wang S Q , Dong J , et al . Construction of Ag /NH₂-MIL-125(Ti) catalyst for photo-driven reduction of aqueous Cr(Ⅵ) pollutant[J]. Chinese Journal of Applied Chemistry, 2019, (3): 314-323.
31	Das D P , Parida K , De B R . Photocatalytic reduction of hexavalent chromium in aqueous solution over titania pillared zirconium phosphate and titanium phosphate under solar radiation[J]. Journal of Molecular Catalysis A Chemical, 2006, 245(1/2): 217-224.
32	谢继阳, 王红琴, 彭程, 等 . 中空纳米材料功能化及在催化反应中的应用[J]. 化工进展, 2019, 38(8): 3730-3741.
	Xie J Y , Wang H Q , Peng C , et .al. Application of functionalization of hollow nanomaterials in catalytic reactions[J]. Chemical Industry and Engineering Progress, 2019, 38(8): 3730-3741.
33	Benjwal P , Kumar M , Chamoli P , et al . Enhanced photocatalytic degradation of methylene blue and adsorption of arsenic(Ⅲ) by reduced graphene oxide (rGO)-metal oxide (TiO₂/Fe₃O₄) based nanocomposites[J]. RSC Advances, 2015, 5: 73249-73260.
34	Roy S , Viswanath B , Hegde M S , et al . Low-temperature selective catalytic reduction of NO with NH₃ over Ti_0.9M_0.1O₂-δ (M = Cr, Mn, Fe, Co, Cu)[J]. Journal of Physical Chemistry C, 2008, 112(15): 6002-6012.
35	Yamashita T , Hayes P . Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials[J]. Applied Surface Science, 2008, 254(8): 2441-2449.
36	Zhu S R , Liu P F , Wu M K , et al . Enhanced photocatalytic performance of BiOBr/NH₂-MIL-125(Ti) composite for dye degradation under visible light[J]. Dalton Transactions, 2016, 45(43): 17521-17529.

[1]	肖川宝, 李林洋, 刘武锋, 钟年丙, 解泉华, 钟登杰, 常海星. 光催化与离子交换吸附耦合有效去除2，4，6-三氯苯酚[J]. 化工学报, 2023, 74(4): 1587-1597.
[2]	徐银, 蔡洁, 陈露, 彭宇, 刘夫珍, 张晖. 异相可见光催化耦合过硫酸盐活化技术在水污染控制中的研究进展[J]. 化工学报, 2023, 74(3): 995-1009.
[3]	王峰, 张顺鑫, 余方博, 刘亚, 郭烈锦. 光催化CO₂还原制碳氢燃料系统优化策略研究[J]. 化工学报, 2023, 74(1): 29-44.
[4]	张劢, 田瑶, 郭之旗, 王叶, 窦广进, 宋浩. 光催化-生物杂合系统设计优化用于燃料和化学品绿色合成[J]. 化工学报, 2022, 73(7): 2774-2789.
[5]	戴晓业, 安青松, 许云婷, 史琳. 废弃制冷剂降解方法研究现状及思考[J]. 化工学报, 2021, 72(S1): 1-6.
[6]	谢钦崟, 黄晓连, 李元, 李玲, 葛雪惠, 邱挺. TiO₂平板微反应器设计优化及光催化性能研究[J]. 化工学报, 2021, 72(7): 3626-3636.
[7]	党永强,李博妮,李可可,张建兰,冯香钰,张亚婷. 铁基催化剂光催化还原CO₂研究进展[J]. 化工学报, 2021, 72(10): 5016-5027.
[8]	任静, 谭玲, 赵宇飞, 宋宇飞. 超薄二维材料光/电催化CO₂还原的最新进展[J]. 化工学报, 2021, 72(1): 398-424.
[9]	张顾平, 王贝贝, 周舟, 陈冬赟, 路建美. 半导体材料在光催化低浓度氮氧化物的研究进展[J]. 化工学报, 2021, 72(1): 259-275.
[10]	贾勐, 张嘉宾, 冯亚青, 张宝. 金属-卟啉框架材料在光催化领域的应用[J]. 化工学报, 2020, 71(9): 4046-4057.
[11]	周柒, 丁红蕾, 郭得通, 潘卫国, 杜威. CO₂催化氢化制清洁能源的研究进展及趋势[J]. 化工学报, 2020, 71(8): 3428-3443.
[12]	胡京宇, 姚戎, 潘玉航, 朱超, 宋爽, 沈意. 可光助再生二氧化钛/层状双氢氧化物去除水体中有机染料[J]. 化工学报, 2020, 71(7): 3296-3303.
[13]	杨金曼, 朱兴旺, 周固礼, 许晖, 李华明. MOFs诱导中空Co₃O₄/CdIn₂S₄合成及光催化CO₂还原性能研究[J]. 化工学报, 2020, 71(6): 2780-2787.
[14]	刘帅,李学雷,李启朦,王彦娟,张健,封瑞江,胡绍争. 木棉纤维改性氮化碳光催化降解有机污染物[J]. 化工学报, 2020, 71(12): 5530-5540.
[15]	陈克龙, 黄建花. g-C₃N₄-CdS-NiS₂复合纳米管的制备及可见光催化分解水制氢[J]. 化工学报, 2020, 71(1): 397-408.

磁性纳米Fe₃O₄@TiO₂可见光下光催化还原Cr(Ⅵ)

Photocatalytic reduction of Cr(Ⅵ) by magnetic nanomaterial Fe₃O₄@TiO₂ under visible light

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价