硅藻土原位生长Nb2O5纳米棒及表面Cr(VI)吸附转化行为研究

doi:10.15541/jim20170308

摘要/Abstract

摘要：

以活化铌酸为铌源, 草酸铵为沉积剂, 十二烷基苯磺酸钠为模板剂, 采用水热法在硅藻土表面原位生长Nb₂O₅纳米棒。采用SEM、TEM、XRD、BET、FT-IR和XPS等分析方法对样品进行表征, 反应14 h后, Nb₂O₅纳米棒长度为500~700 nm, 直径为25~35 nm; 硅藻土原位生长Nb₂O₅纳米棒样品比表面积为157 m²/g。研究了样品对Cr(VI)的吸附与光还原行为, 可见光条件下对Cr(VI)吸附量可达220 mg/g; 紫外光条件下, 可将表面吸附的Cr(VI)转变为Cr(III), 样品经过5次循环使用后, 对Cr(VI)(100 mg/L)降解率仍能保持在93%左右。样品可对重金属污染废水中Cr(VI)进行吸附与毒性降解一体化去除。

关键词: 硅藻土, 氧化铌纳米棒, Cr(VI), 吸附, 毒性降解

Abstract:

Nb₂O₅ nanorods decorated diatomite were synthesized via a hydrothermal method by using niobic acid, ammonium oxalate and sodium dodecyl benzene sulfonate (SDBS). The as-prepared samples were characterized by SEM, TEM, XRD, BET, and FT-IR techniques. The Nb₂O₅nanorod was obtained with length of 500~700 nm and diameter of 25~35 nm. BET test showed that specific surface area of Nb₂O₅ nanorods decorated diatomite reached 157 m²/g which show a high adsorbance tendence. Under visible light irradiation, the adsorption capacity for Cr (VI) could be 220 mg/g. With the assistance of UV-light photoreduction, the maximum removal capacity for Cr (VI) could be 340 mg/g, and the absorbed Cr(VI) was transformed to Cr(III). After photodegradation for five times, the degradation rate of Cr(VI) (100 mg/L) were still at about 93%. Nb₂O₅ nanorods/diatomite could adsorb Cr(VI) from sewage effectively and in the meantime accomplish the toxicity degradation, showing a promising treatment of Cr(VI) containing waste water.

Key words: diatomite, Nb₂O₅nanorod, Cr(VI), adsorption, toxicity degradation

中图分类号:

TQ174

杜玉成, 王学凯, 侯瑞琴, 吴俊书, 张时豪, 祁超. 硅藻土原位生长Nb₂O₅纳米棒及表面Cr(VI)吸附转化行为研究[J]. 无机材料学报, 2018, 33(5): 557-564.

DU Yu-Cheng, WANG Xue-Kai, HOU Rui-Qin, WU Jun-Shu, ZHANG Shi-Hao, QI Chao. In-situ Growth of Nb₂O₅ Nanorods on Diatomite and Highly Effective Removal of Cr(VI)[J]. Journal of Inorganic Materials, 2018, 33(5): 557-564.

图/表 9

图1 硅藻土 (A), NS-1 (B), NS-2 (C), NS-3 (D)和NS-4 (E)~ (F)样品的SEM照片

Fig. 1 SEM images of (A) the Nb2O5/diatomite samples, (B) NS-1, (C) NS-2, (D) NS-3 and (E)-(F) NS-4

图2 样品NS-4的(A) TEM和(B) HRTEM照片, 图(A)中插图为SAED衍射花样

Fig. 2 (A) TEM image and (B) high resolution TEM images. Insert in (A) is the multiple electron diffraction rings in the SAED patterns of NS-4 sample

图3 硅藻土(A), 样品NS-1 (B), NS-2 (C), NS-3 (D)和NS-4 (E)的XRD图谱

Fig. 3 XRD patterns of diatomite (A), samples NS-1 (B), NS-2 (C), NS-3 (D), and NS-4(E)

图4 硅藻土、样品NS-2和NS-4氮气吸-脱附曲线(插图为样品孔径分布曲线)

Fig. 4 N2 adsorption-desorption isotherms of NS-2 and NS-4 samples with insert showing the pore-size distributions

图5 (A)溶液pH对Cr(Ⅵ)吸附性能影响和(B)可见光及紫外光条件下初始浓度对Cr(Ⅵ)吸附性能影响

Fig. 5 (A) Effect of the solution pH on the efficiency of Cr(VI) adsorption, and (B) effect of the initial Cr (Ⅵ) concentrations on the efficiency of Cr(Ⅵ) adsorption under UV and visible light irradiation

图6 (A)样品NS-4对Cr(Ⅵ)不同降解时间紫外吸收光谱图和(B)不同条件下Cr(VI)的光降解效率随时间变化图

Fig. 6 (A) Time-dependent ultraviolet-visible (UV) absorption spectrum of the Cr(Ⅵ) reduction by the sample NS-4 and (B) the time-dependent photoreduction rate under different conditions

图7 在pH=7时, NS-4样品光还原Cr(Ⅵ)的稳定性

Fig. 7 Stability of NS-4 sample for Cr (Ⅵ) photodegradation at pH=7

图8 硅藻土(a)和NS-4样品吸附Cr(Ⅵ)前(b)、后(c)的红外光谱图

Fig. 8 FT-IR spectra of (a) raw diatomite and NS-4 sample (b) before and (c) after Cr(Ⅵ) adsorption

图9 NS-4样品吸附前(a)、NS-4样品在紫外光照条件下吸附后(b)的(A)XPS全谱图, (B)Nb3d轨道谱图, (C)O1s轨道谱图和(D) Cr 2p轨道谱图

Fig. 9 (A) Full-scan XPS spectra, (B) Nb3d XPS spectra, and (C) O 1s XPS spectra of NS-4 (a) before and (b) after the photocatalytic reduction of Cr(Ⅵ), and (D) Cr2p XPS spectrum of NS-4 sample after the photocatalytic reduction of Cr(Ⅵ)

参考文献 24

[1]	METIN G, DUYGU V, AYSE M.Removal of trivalent chromium from water using low-cost natural diatomite.J. Hazard. Mater., 2008, 160(2/3): 318-323.
[2]	JIANG BO, XIN SHUAI-SHUAI, GAO LI,et al. Dramatically enhanced aerobic Cr(VI) reduction with scrap zero-valent aluminum induced by oxalate. Chemical Engineering Journal, 2016, 308: 588-596.
[3]	HANS R, SENANAYAKE G, DHARMASIRI L C S,et al. A preliminary batch study of sorption kinetics of Cr(VI) ions from aqueous solutions by a magnetic ion exchange (MIEX®;) resin and determination of film/pore diffusivity. Hydrometallurgy, 2016, 164: 208-218.
[4]	FU XIAO-FEI, YANG HAN-PEI, LU GUANG-HUA,et al. Improved performance of surface functionalized TiO2/activated carbon for adsorption-photocatalytic reduction of Cr(VI) in aqueous solution. Materials Science in Semiconductor Processing, 2015, 39: 362-370.
[5]	DINDA D, KUMAR S S.Sulfuric acid doped poly diaminopyridine/ graphene composite to remove high concentration of toxic Cr(VI). Journal of Hazardous Materials, 2015, 291: 93-101.
[6]	GUAN XIAO-HONG, DU JUAN-SHAN, MENG XIAO-GUANG,et al. Application of titanium dioxide in arsenic removal from water: a review. Journal of Hazardous Materials, 2012, 215-216(10): 1-16.
[7]	LI HUI, LI WEI, ZHANG YAN-JUN,et al. Chrysanthemum-like a-FeOOH microspheres produced by a simple green method and their outstanding ability in heavy metal ion removal . J. Mater. Chem., 2011, 21: 7878-7881.
[8]	MISHRA S, BHARAGAVA R N.Toxic and genotoxic effects of hexavalent chromium in environment and its bioremediation strategies. Journal of Environmental Science & Health Part C Environmental Carcinogenesis & Ecotoxicology Reviews, 2016, 34(1): 1-32.
[9]	YAO HUA, GUO LAN, JIANG BING-HUA,et al. Oxidative stress and chromium(VI) carcinogenesis. Journal of Environmental Pathology Toxicology & Oncology Official Organ of the International Society for Environmental Toxicology & Cancer, 2008, 27(2): 77-88.
[10]	WISE S S, HOLMES A L, SR J P W. Particulate and soluble hexavalent chromium are cytotoxic and genotoxic to human lung epithelial cells. Mutation Research/genetic Toxicology & Environmental Mutagenesis, 2006, 610(1/2): 2-7.
[11]	MYROSLAV SPRYNSKYY.The separation of uranium ions by natural and modified diatomite from aqueous solution. Hazard. Mater. , 2010, 181: 700-707.
[12]	LI CONG-JU, LI YONG-JIAN, WANG JIAO-NA,et al. PA6@FexOy nanofibrous membrane preparation and its strong Cr (VI)- removal performance. Chemical Engineering Journal, 2013, 220: 294-301.
[13]	LOPES O F, PARIS E C, RIBERIRO C.Synthesis of Nb2O5, nanoparticles through the oxidant peroxide method applied to organic pollutant photodegradation: a mechanistic study. Applied Catalysis B Environmental, 2014, 144(2): 800-808.
[14]	ZHAO YUN, ELEY CLIVE, HU JING-PING,et al. Shape- dependent acidity and photocatalytic activity of Nb2O5 nanocrystals with an active TT (001) surface. Angew. Chem. Int. Ed., 2012, 51(16): 3846-3849.
	ZHAO YUN, ELEY CLIVE, HU JING-PING,et al. Shape- dependent acidity and photocatalytic activity of Nb2O5 nanocrystals with an active TT (001) surface. Angew. Chem. Int. Ed., 2012, 51(16): 3846-3849.
[15]	GAO BAO-JIAO, JIANG PENG-FEI, AN FU-QIANG,et al. Studies on the surface modification of diatomite with polyethyleneimine and trapping effect of the modified diatomite for phenol. Applied Surface Science, 2005, 250(1-4): 273-279.
[16]	ONOZATO T, KATASE T, YAMAMOTO A,et al. Optoelectronic properties of valence-state-controlled amorphous niobium oxide. Journal of Physics Condensed Matter An Institute of Physics Journal, 2016, 28(25): 1-8.
[17]	HUO QI-SHENG, MARGOLESE DAVID I, CIESLA U LRIKE,et al. Organization of organic molecules with inorganic molecular species into nanocomposite biphase arrays. Chemistry of Materials, 1994, 6(8): 1176-1191.
[18]	YAN CHENG-LIN, XUE DONG-FENG.Formation of Nb2O5 nanotube arrays through phase transformation. Advanced Materials, 2010, 20(5): 1055-1058.
[19]	DU YU-CHENG, YAN JING, MENG QI,et al. Fabrication and excellent conductive performance of antimony-doped tin oxide- coated diatomite with porous structure. Materials Chemistry & Physics, 2012, 133(2/3): 907-912.
[20]	SHENG GUO-DONG, WANG SUO-WEI, HU JUN,et al. Adsorption of Pb(II) on diatomite as affected via aqueous solution chemistry and temperature. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2009, 339(1/2/3): 159-166.
[21]	KHRAISHEH M A, AL-GHOUTI M A, ALLEN S J,et al. Effect of OH and silanol groups in the removal of dyes from aqueous solution using diatomite. Water Research, 2005, 39(5): 922-932.
[22]	HADJAR H, HAMDI B, JABER M,et al. Elaboration and characterization of new mesoporous materials from diatomite and charcoal. Microporous and Mesoporous Materials, 2007, 107(3): 219-226.
[23]	CHENG YUE-HONG, JIANG HENG, GONG HONG,et al. Synthesis and characterization of niobic acid. Industrial Catalysis, 2011,19(1): 50-52.
[24]	JULIEN C M, MASSOT M.Spectroscopic studies of the structural transitions in positive electrodes for lithium batteries. Physical Chemistry Chemical Physics, 2002, 4(17): 4226-4235.

硅藻土原位生长Nb₂O₅纳米棒及表面Cr(VI)吸附转化行为研究

In-situ Growth of Nb₂O₅ Nanorods on Diatomite and Highly Effective Removal of Cr(VI)

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