Abstract
We report a novel cobalt tetraaminophthalocyanine (CoPc) functionalized nanomaterial by spacer-arm immobilization of CoPc onto cellulose nanofiber mats. The spacer-arm was attached through the reaction of tetraethylenepentamine with oxidized cellulose nanofiber mats. CoPc was then covalently immobilized onto the spacer-arm using glutaraldehyde. The functionalization processes on the nanofiber mats were monitored by attenuated total reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. This CoPc functionalized nanomaterial (CoPc-spacer-NM) was used for decoloration of reactive dye wastewater. Incorporation of the spacer-arm resulted in enhanced decoloration with respect to directly immobilized CoPc onto the cellulose nanofiber mats (CoPc-NM). Compared with CoPc-NM, CoPc-spacer-NM shows much higher adsorption capacity when conducted under acidic conditions, which enhances the catalytic oxidation rate of reactive dye when H2O2 was used as an oxidant. Reactive dye wastewater can also be efficiently decolorized by the CoPc-spacer-NM/H2O2 system under basic conditions, despite a relatively weak adsorption capacity. Electron paramagnetic resonance results suggested that the catalytic oxidation process involves the formation and reaction of hydroxyl radicals. Gas chromatography–mass spectrometry showed the main products of the catalytic oxidation of reactive red X-3B were biodegradable aliphatic acids, such as oxalic acid, malonic acid and maleic acid.
Similar content being viewed by others
Abbreviations
- CoPc-NM:
-
CoPc functionalized nanofiber mats
- CoPc-spacer-NM:
-
CoPc functionalized, spacer-arm attached cellulose nanofiber mats
- OC-NM:
-
Oxidized cellulose nanofiber mats
- TEPA-NM:
-
Tetraethylenepentamine attached nanofiber mats
- GA-NM:
-
Glutaraldehyde activated nanofiber mats
References
Achar BN, Fohlen GM, Parker JA, Keshavayya J (1987) Synthesis and structural studies of metal(Ii) 4,9,16,23-phthalocyanine tetraamines. Polyhedron 6:1463–1467
Arica MY, Bayramoglu G, Bicak N (2004) Characterisation of tyrosinase immobilised onto spacer-arm attached glycidyl methacrylate-based reactive microbeads. Process Biochem 39:2007–2017
Arica MY, Altintas B, Bayramoglu G (2009) Immobilization of laccase onto spacer-arm attached non-porous poly(GMA/EGDMA) beads: application for textile dye degradation. Bioresour Technol 100:665–669
Bayramoglu G, Yilmaz M, Arica MY (2004) Immobilization of a thermostable alpha-amylase onto reactive membranes: kinetics characterization and application to continuous starch hydrolysis. Food Chem 84:591–599
Chang ZJ, Fang Y, Zhang QH, Chen DJ (2009) “Click” chemistry for facile immobilization of iron phthalocyanines onto electrospun nanofiber surface. Chem Lett 38:1144–1145
Chen WX, Lu WY, Yao YY, Xu MH (2007) Highly efficient decomposition of organic dyes by aqueous-fiber phase transfer and in situ catalytic oxidation, using fiber-supported cobalt phthalocyanine. Environ Sci Technol 41:6240–6245
Chen WX, Lu WY, Li N, Yao YY (2009) The role of multiwalled carbon nanotubes in enhancing the catalytic activity of cobalt tetraaminophthalocyanine for oxidation of conjugated dyes. Carbon 47:3337–3345
Chen SL, Huang XJ, Xu ZK (2011) Functionalization of cellulose nanofiber mats with phthalocyanine for decoloration of reactive dye wastewater. Cellulose 18:1295–1303
Fernandez-Lorente G, Palomo JM, Cabrera Z, Guisan JM, Fernandez-Lafuente R (2007) Specificity enhancement towards hydrophobic substrates by immobilization of lipases by interfacial activation on hydrophobic supports. Enzyme Microb Technol 41:565–569
Heinze T, Liebert T (2001) Unconventional methods in cellulose functionalization. Prog Polym Sci 26:1689–1762
Iliev V, Alexiev V, Bilyarska L (1999) Effect of metal phthalocyanine complex aggregation on the catalytic and photocatalytic oxidation of sulfur containing compounds. J Mol Catal A-Chem 137:15–22
Jonoobi M, Harun J, Mathew AP, Hussein MZB, Oksman K (2010) Preparation of cellulose nanofibers with hydrophobic surface characteristics. Cellulose 17:299–307
Kluson P, Drobek M, Kalaji A, Zarubova S, Krysa J, Rakusan J (2008a) Singlet oxygen photogeneration efficiencies of a series of phthalocyanines in well-defined spectral regions. J Photochem Photobiol A-Chem 199:267–273
Kluson P, Drobek M, Krejcikova S, Krysa J, Kalaji A, Cajthaml T, Rakusan J (2008b) Molecular structure effects in photodegradation of phenol and its chlorinated derivatives with phthalocyanines. Appl Catal B-Environ 80:321–326
Kuznetsova N, Makarov D, Yuzhakova O, Strizhakov A, Roumbal Y, Ulanova L, Krasnovsky A, Kaliya O (2009) Photophysical properties and photodynamic activity of octacationic oxotitanium(IV) phthalocyanines. Photochem Photobiol Sci 8:1724–1733
Li D, Xia YN (2004) Electrospinning of nanofibers: reinventing the wheel? Adv Mater 16:1151–1170
Lin CP, Lee BS, Huang SH, Chiang YC, Chien YS, Mou CY (2008) Development of in vitro tooth staining model and usage of catalysts to elevate the effectiveness of tooth bleaching. Dent Mater 24:57–66
Ma ZW, Ramakrishna S (2008) Electrospun regenerated cellulose nanofiber affinity membrane functionalized with protein A/G for IgG purification. J Membr Sci 319:23–28
Mita DG, De Maio A, El-Masry MM, De Luca P, Grano V, Rossi S, Pagliuca N, Gaeta FS, Portaccio M (2003a) Influence of the spacer length on the activity of enzymes immobilised on nylon/poly GMA membranes part 2: non-isothermal conditions. J Mol Catal B-Enzym 21:253–265
Mita DG, De Maio A, El-Masry MM, Portaccio M, Diano N, Di Martino S, Mattei A, Bencivenga U (2003b) Influence of the spacer length on the activity of enzymes immobilised on nylon/polyGMA membranes part 1. Isothermal conditions. J Mol Catal B-Enzym 21:239–252
Mrowetz M, Selli E (2005) Enhanced photocatalytic formation of hydroxyl radicals on fluorinated TiO2. Phys Chem Chem Phys 7:1100–1102
OSullivan AC (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–207
Ozyilmaz G (2009) The effect of spacer arm on hydrolytic and synthetic activity of Candida rugosa lipase immobilized on silica gel. J Mol Catal B-Enzym 56:231–236
Ratnasamy P, Srinivas D (2009) Selective oxidations over zeolite- and mesoporous silica-based catalysts: Selected examples. Catal Today 141:3–11
Salem MA, Abdel-Halim ST, El-Sawy AEHM, Zaki AB (2009) Kinetics of degradation of allura red, ponceau 4R and carmosine dyes with potassium ferrioxalate complex in the presence of H(2)O(2). Chemosphere 76:1088–1093
Smith BA, Teel AL, Watts RJ (2004) Identification of the reactive oxygen species responsible for carbon tetrachloride degradation in modified Fenton’s systems. Environ Sci Technol 38:5465–5469
Sorokin AB, Kudrik EV (2011) Phthalocyanine metal complexes: versatile catalysts for selective oxidation and bleaching. Catal Today 159:37–46
Sorokin AB, Tuel A (1999) Heterogeneous oxidation of aromatic compounds catalyzed by metallophthalocyanine functionalized silicas. New J Chem 23:473–476
Sorokin A, Seris JL, Meunier B (1995) Efficient oxidative dechlorination and aromatic ring-cleavage of chlorinated phenols catalyzed by iron sulfophthalocyanine. Science 268:1163–1166
Sorokin A, DeSuzzoniDezard S, Poullain D, Noel JP, Meunier B (1996) CO2 as the ultimate degradation product in the H2O2 oxidation of 2,4,6-trichlorophenol catalyzed by iron tetrasulfophthalocyanine. J Am Chem Soc 118:7410–7411
Stillman MJ, Mack J (2001) Assignment of the optical spectra of metal phthalocyanines through spectral band deconvolution analysis and ZINDO calculations. Coord Chem Rev 219:993–1032
Sui MH, Liu J, Sheng L (2011) Mesoporous material supported manganese oxides (MnOx/MCM-41) catalytic ozonation of nitrobenzene in water. Appl Catal B-Environ 106:195–203
Tao X, Ma WH, Zhang TY, Zhao JC (2001) Efficient photooxidative degradation of organic compounds in the presence of iron tetrasulfophthalocyanine under visible light irradiation. Angew Chem Int Edit 40:3014–3016
Tao X, Ma WH, Zhang TY, Zhao JC (2002) A novel approach for the oxidative degradation of organic pollutants in aqueous solutions mediated by iron tetrasulfophthalocyanine under visible light radiation. Chem Eur J 8:1321–1326
Yamazaki I, Piette LH (1991) Epr spin-trapping study on the oxidizing species formed in the reaction of the ferrous ion with hydrogen-peroxide. J Am Chem Soc 113:7588–7593
Yang J, Dai J, Chen CC, Zhao JC (2009) Effects of hydroxyl radicals and oxygen species on the 4-chlorophenol degradation by photoelectrocatalytic reactions with TiO(2)-film electrodes. J Photochem Photobiol A-Chem 208:66–77
Zanjanchi MA, Ebrahimian A, Arvand M (2010) Sulphonated cobalt phthalocyanine-MCM-41: an active photocatalyst for degradation of 2,4-dichlorophenol. J Hazard Mater 175:992–1000
Acknowledgments
The authors are grateful to the financial support from the National Natural Science Foundation of China for Distinguished Young Scholars (Grant no. 50625309).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Chen, SL., Huang, XJ. & Xu, ZK. Effect of a spacer on phthalocyanine functionalized cellulose nanofiber mats for decolorizing reactive dye wastewater. Cellulose 19, 1351–1359 (2012). https://doi.org/10.1007/s10570-012-9701-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-012-9701-9