季膦-磷钨酸室温离子液体的合成及光催化降解罗丹明B

doi:10.3724/SP.J.1095.2014.30339

摘要/Abstract

摘要： 以不同摩尔比的磷钨酸与烷基取代季膦盐为原料合成了一系列磷钨酸类离子液体，并使用DSC和IR对系列离子液体进行了表征。结果表明，[P(C14H29)(C6H13)3]-磷钨酸系列离子液体为室温离子液体，磷钨酸根保留了Keggin结构。进一步研究了在可见光照射下，以所制备的磷钨酸季膦盐离子液体为催化剂催化降解罗丹明B染液。以脱色率和COD来表征染料的降解效果，分别探讨了离子液体中阳离子碳链长度、催化剂用量、光照时间和罗丹明B的初始浓度等因素对光降解罗丹明B的影响。结果表明，其中[P(C14H29)(C6H13)3]3-PW12O40离子液体的催化效果最好，在催化剂用量为0.3 g时，3 h内50 mL 8.35×10-5 mol/L罗丹明B的降解率可达到95%以上，催化剂重复使用5次后，脱色率仍可达到97%以上。

关键词: 室温离子液体, 磷钨酸, 季膦盐, 罗丹明B, 光催化降解

Abstract: A series of ionic liquids was synthesized from phosphotungstic acid and alkyl substituted quaternary phosphonium salts with different molar ratios, and characterized by DSC and IR. The results show that [P(C14H29)(C6H13)3]-phosphotungstic series ionic liquids are liquid at room temperature. The degradation of Rhodamine-B(RhB) dye was successfully achieved by different phosphotungstic quaternary phosphonium ionic liquids under visible light irradiation. The degradation efficiency was characterized by decolorization and chemical oxygen demand(COD) of RhB. The influence of experimental parameters, such as the carbon chain length in the phosphonium ionic liquid, dosage of catalysts, irradiation time and the concentration of RhB solution on photo-catalyzed degradation of RhB were investigated. The results indicate that [P(C14H29)(C6H13)3]3[PW12O40] ionic liquid shows the best photo-catalytic degradation effect under visible light irradiation. The degradation rate can be up to 95% when the catalyst dosage is 0.3 g and concentration of RhB is 8.35×10-5 mol/L(50 mL) in 3 h. The decolorization of [P(C14H29)(C6H13)3]3-PW12O40 can reach 97% even used for 5 times.

Key words: room-temperature ionic liquid, phosphotungstic acid, quaternary phosphonium salts, Rhodamine-B, photocatalytic degradation

中图分类号:

O643
TQ139.1

刘玉婷, 陈彦安, 邢彦军. 季膦-磷钨酸室温离子液体的合成及光催化降解罗丹明B[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30339.

LIU Yuting1,2, CHEN Yanan2, XING Yanjun1,2*. Synthesis of Quaternary Phosphonium-Polyoxomatalate Room-temperature Ionic Liquids and Its Photocatalytic Degradation of Rhodamine-B[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30339.

参考文献

[1] Easton J R. Part I:the Problem of Colour, the Dye Maker′s View[M]//Cooper P. Colour in Dyehouse Effluent. Oxford:Alden Press,1995:9-21.

[2] Reife A, Betowski D, Freeman H S. Dyes and Pigments, Environmental Chemistry[M]//Meyers R A. Environmental Analysis and Remediation. New York:John Wiley & Sons,Inc;1998:1442-1465.

[3] Legrini O, Oliveros E, Braun A M. Photochemical Processes for Water Treatment[J]. Chem Rev,1993,93:671-698.

[4] Hoffmann M R,Martin S T,Choi W,et al. Environmental Applications of Semiconductor Photocatalysis[J]. Chem Rev,1995,95:69-96.

[5] Maldotti A,Molinari A,Amadelli R. Photocatalysis with Organized Systems for the Oxofunctionalization of Hydrocarbons by O2[J]. Chem Rev,2002,102:3811-3836.

[6] Emeline A V,Zhang X,Jin M,et al. Application of a “Black Body” like Reactor：for Measurements of Quantum Yields of Photochemical Reactions in Heterogeneous Systems[J]. Phys Chem B,2006,110:7409-7413.

[7] Okuhara T,Mizuno N,Misono M. Catalysis by Heteropoly Compounds-Recent Developments[J]. Appl Catal A:Gen,2001,222(1/2):63-77.

[8] LI Fumin,CHENG Ruonan,XING Yanjun. Effect of Phosphotungstate on Photocatalytic Degradation of Disperse Blue 130 under Visible Light[J]. Nanosci Nanotechnol,2011,8(2):20-27(in Chinese).

李富民,程若男,邢彦军. 可见光下磷钨酸盐光催化降解分散蓝130的研究[J]. 纳米科技,2011,8(2):20-27.

[9] Biboum R N,Njiki C P,Zhang G,et al. High Nuclearity Ni/Co Polyoxometalates and Colloidal TiO2 Assemblies as Efficient Multielectron Photocatalysts under Visible or Sunlight Irradiation[J]. J Mater Chem,2011,21:645-650.

[10] Liu W,Tan H,Chen W,et al. Ionothermal Synthesis and Characterization of Two New Heteropolytungstates with 1-Ethyl-3-methyl-imidazolium Bromide Ionic Liquid as Solvent[J]. J Coord Chem,2010,63(11):1833-1843.

[11] Xu L,Choi E Y,Kwon Y U. A New 3D Nickel(Ⅱ) Framework Composed of Large Rings:Ionothermal Synthesis and Crystal Structure[J]. J Solid State Chem,2008,181(11):3185-3188.

[12] Wasserscheid P,Keim W. Ionic Liquids-New “Solutions” for Transition Metal Catalysis[J]. Angew Chem Int Ed,2000,39(21):3772-3789.

[13] Wang H,Yan R,Li Z,et al. Fe-containing Magnetic Ionic Liquid as an Effective Catalyst for the Glycolysis of Poly(ethylene terephthalate)[J]. Catal Commun,2010,11:763 767.

[14] Rickert P G,Antonio M R,Firestone M A,et al. Tetraalkylphosphonium Polyoxometalates:Electroactive, Task-specific Ionic Liquids[J]. Dalton Trans,2007:529-531.

[15] Kozhevnikov I V. Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions[J]. Chem Rev,1998,98:171-198.

[16] Zhang W H,Leng Y,Zhu D R,et al. Phosphotungstic Acid Salt of Triphenyl(3-sulfopropyl)phosphonium:An Efficient and Reusable Solid Catalyst for Esterification[J]. Catal Comm,2009,11:151-154.

[17] Marmagne O,Coste C. Color Removal from Textile Plant Effluents[J]. Am Dyest Rep,1996,85(4):15-21.