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Bacterial cellulose nanofibers decorated with phthalocyanine: Preparation, characterization and dye removal performance
Author's Accepted Manuscript
Bacterial cellulose nanofibers Decorated with phthalocyanine: Preparation, characterization and dye removal performance Shiliang Chen, Yijun Huang
www.elsevier.com/locate/matlet
PII: DOI: Reference:
S0167-577X(14)02202-2 http://dx.doi.org/10.1016/j.matlet.2014.12.036 MLBLUE18187
To appear in:
Materials Letters
Received date: 18 November 2014 Accepted date: 5 December 2014 Cite this article as: Shiliang Chen, Yijun Huang, Bacterial cellulose nanofibers Decorated with phthalocyanine: Preparation, characterization and dye removal performance, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2014.12.036 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Bacterial
cellulose
nanofibers
decorated
with
phthalocyanine:
preparation,
characterization and dye removal performance Shiliang Chen∗, Yijun Huang Department of Science and Technology, Qianjiang College, Hangzhou Normal University, Hangzhou 310012, China ABSTRACT: We report the preparation of a novel cobalt tetraaminophthalocyanine (CoPc) decorated bacterial cellulose (BC) nanocomposite by covalently immobilization of CoPc onto surface pre-oxidized bacterial cellulose nanofibers. The functionalization steps on the nanofibers were monitored by field emission scanning electron microscope (FESEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR/FT-IR), and X-ray photoelectron (XPS). The prepared CoPc decorated BC nanocomposite, CoPc@BC, was used as an efficient heterogeneous catalyst for the decoloration of recalcitrant rhodamine B (RhB) dye wastewater. We found that CoPc@BC has high decoloration capacity for RhB dye wastewater. With H2O2 as oxidant, more than 90% of RhB dye molecules can be removed in 180 min. Keywords:
Functional;
Bacterial
cellulose;
Nanocomposites;
Microstructure;
Decoloration
1. Introduction The production of cellulose fibers with nanoscale has gained increasing attention because these nanocelluloses combine prominent cellulose properties-such as hydrophilicity, renewability and tunable surface-with specific features of nanomaterials: very large surface-to-volume ratio and considerable modification possibility[1]. The preparation of nanocelluloses ranges from “top-down” methods with natural cellulose to ∗
Corresponding Author. Tel./fax: +86 571 28861372. E-mail address: [email protected] (S. Chen).
1
“bottom-up” methods with culture medium by certain bacteria[2-3]. The nanocelluloses biosynthesized by microorganisms is known as bacterial cellulose (BC). In terms of molecular formular, BC is identical to plant cellulose. The main remarkable features for BC includes high purity, high crystallinity, high degree of polymerization, and a three dimensional (3D) network. Potential application of BC has been exploited extensively, novel materials based on BC such as reinforcement nanocomposites[4], membrane[5], bio-inspired nanomaterial[6], and reaction template[7] are extensively reported. Due to their several attractive characteristics such as high aspect ratio, plenty of easily tunable hydroxyl groups and the web-like network with a distinct tunnel and pore structure, BC is a promising support for the immobilization of functional molecules. Organic and inorganic components can be immobilized onto BC with chemical and physical approaches to produce functional nanomaterials[8-10]. In particular, constructing efficient heterogeneous catalysts with BC as template is a field of extensive studies[11-12]. Various kinds of catalysts were immobilized onto BC for the treatment of wastewater effluents containing organic pollutants[13-14]. Metallophthalocyanine (MPc) has attracted considerable interest as an oxidation catalyst for its structural similarity to naturally occurring metalloporphyrin. In practical applications, it is often anchored to solid substrates as heterogeneous catalyst[15-17]. The microstructure of substrate has a great impact on its catalytic performance. Owing to the aforementioned outstanding characteristics, BC may be a promising candidate for MPc immobilization. Herein, we report the preparation and characterization of a new functional nanomaterial, CoPc decorated BC nanocomposite (CoPc@BC). Its catalytic effect for decoloration of recalcitrant rhodamine B (RhB) dye wastewater was also studied.
2
2. Experimental 2.1 Materials All chemicals purchased from Sinopharm Chemical Reagent Co. Ltd. (China) were of analytical grade and used as received. Bacterial cellulose (BC) sheet was prepared according to literature[18]. Cobalt tetraaminophthalocyanine (CoPc) was synthesized from 4-nitrophthalic acid, cobalt chloride hexahydrate and urea according to a method described previously[15, 19]. Water used in all experiments was de-ionized and ultrafiltrated to 18 MΩ with an ELGA LabWater system. An initial concentration of 10 µmol/L of RhB solution was prepared using this ultrafiltrated water. 2.2 Preparation For preparation of CoPc@BC, following steps were performed: 20 mg of BC was added to a 25 mmol/L NaIO4 solution and shaken for 7 h at 25 °C to generate aldehyde groups on the surface of BC. After thoroughly washed by ultrapure water and dried at 60 °C under vacuum, the resulted oxidized BC was then suspended in a 200 µmol/L CoPc solution. After reaction for 3 h at 25 °C, the product was washed with dimethylformamide (DMF) to remove residual CoPc and then rinsed three times with ultrapure water. 2.3 Characterization Surface morphologies of the nanofibers were examined by field emission scanning electron microscopy (FESEM, Serion, FEI, USA). Surface compositions of the nanofibers were verified by attenuated total reflection Fourier transform infrared spectra (ATR/FT-IR) and X-ray photoelectron spectrascopy (XPS). ATR/FT-IR spectra were acquired with a Vector 22 FTIR spectrometer (Brucker Optics, Switzerland) equipped with an ATR accessory (KRS-5 crystal, 45°). Each spectrum was taken by 32 scans at a
3
nominal resolution of 4 cm-1. XPS spectra were drawn on a PHI-5000C ESCA system (PerkinElmer, USA) with Al Kα radiation (1486.6 eV). 2.4 Decoloration Adsorption of RhB was carried out in a glass flask sealed in a water bath at 60 °C. 2 mg of CoPc@BC was added to 5 mL RhB solution (10 µmol/L). The catalytic oxidation was initiated by adding 8 mM H2O2 to a RhB solution containing CoPc@BC. At given time intervals, the samples were analyzed immediately on a UV-vis absorption spectrometer UV-2450 at the wavelength of maximum absorbance, 556 nm. The concentration change of RhB was expressed as the change of C/C0 value, where C0 is the initial concentration of the dye, and C is the residual concentration of the dye. 3. Results and discussion
--- Fig. 1 --The CoPc decorated BC nanocomposite, CoPc@BC, was prepared through covalently immobilization of CoPc onto the surface of BC after chemical oxidation with NaIO4. The optical and FESEM images of both BC and CoPc@BC are shown in Fig. 1. The color of as-prepared pure BC sheet is white as expected (Fig. 1a). After decorated
4
with CoPc, the dark green color appeared homogeneously on the entire sheet (Fig. 1c), indicating well distribution of CoPc on BC at macroscopic level. FESEM image of BC exhibits three dimensional nanofiber network architecture, the average diameter of nanofibers is approximately 10 nm (Fig. 1b). The shape of CoPc@BC (Fig. 1d) is still uniform compared with BC, indicating that BC has excellent stability during the surface oxidation and CoPc decoration. The progress of surface modification reactions were monitored by ATR/FT-IR. Fig. 2a represents the typical spectrum of biosynthesized BC, the strong absorption in the range of 3200-3500 cm-1 shows the presence of hydroxyl groups in the BC (as in case of natural cellulose). After oxidation, the appearance of a new characteristic peak at ∼1650 cm-1 indicates the successful formation of aldehyde groups on the surface of BC (Fig. 2b). The successful immobilization of CoPc on BC was verified by the expected appearance of the characteristic peak at ∼1610 cm-1 (υC=N of CoPc). In the meanwhile, the significant decrease of the peak at ∼1650 cm-1 corresponds to the successful reaction of aldehyde groups with CoPc (Fig. 2c).
--- Fig. 2 --The modification of BC involves the formation of aldehyde groups on its surface and
5
the decoration of the resulting product with CoPc. XPS was also used to analyze these reactions. Fig. 3 shows the XPS spectra from a wide scan for BC, oxidized BC and CoPc@BC, respectively. Compared with the XPS of oxidized BC (Fig. 3b), the spectrum of CoPc@BC shows a significant new signal at a binding energy (BE) of 402 eV, which is the characteristic peak of N 1s (Fig. 3c). In the meanwhile, two new peaks at binding energy of 793.9 and 779.1 eV were detected (Fig. 3, inset), which were assigned to the characteristic peaks of Co 2p1/2 and 2p3/2, respectively. This result provides further evidence for the decoration of CoPc on BC and the successful preparation of CoPc@BC.
--- Fig. 3 --The catalytic activity of the prepared nanocomposite, CoPc@BC, was evaluated on the basis of its decoloration performance to RhB dye wastewater. Almost no color change can be detected after 3 h with existence of H2O2 (Fig. 4a), indicating that RhB can hardly be degraded by H2O2. The concentration of RhB slightly decreased by 10% after 5 h with CoPc@BC presented as adsorbent. When both CoPc@BC and H2O2 were present, the RhB declined quickly and more than 90% of dye was degraded in 180 min (Fig. 4c), indicating that CoPc@BC/H2O2 is an effective reaction system for the
6
decoloration of recalcitrant RhB dye wastewater.
--- Fig. 4 --4. Conclusion In this study, CoPc decorated BC nanocomposite, CoPc@BC, was successfully prepared via covalently immobilization of CoPc onto surface pre-oxidized bacterial cellulose nanofibers. This nanocomposite has high catalytic activity on degradation of recalcitrant RhB dye wastewater. With H2O2 as oxidant, the decoloration ratio of RhB reached to 95% in 300 min. Acknowledgements The authors are grateful to the financial support from the National Natural Science Foundation of China (Grant no. 51103133). References [1] Huang Y, Zhu C, Yang J, Nie Y, Chen C, Sun D. Cellulose 2014;21:1-30. [2] Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, et al. Angew Chem Int Ed 2011;50:5438-66. [3] Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, et al. J Mater Sci 2010;45:1-33. [4] Wang JY, Jia HB, Zhang JJ, Ding LF, Huang Y, Sun DP, et al. J Mater Sci 2014;49:6093-101. [5] Ma H, Burger C, Hsiao BS, Chu B. Biomacromolecules 2012;13:180-6. [6] Capadona JR, Shanmuganathan K, Tyler DJ, Rowan SJ, Weder C. Science 2008;319:1370-4. [7] Abeer MM, Amin MCIM, Lazim AM, Pandey M, Martin C. Carbohydr Polym 2014;110:505-12.
7
[8] O-Rak K, Ummartyotin S, Sain M, Manuspiya H. Mater Lett 2013;107:247-50. [9] Wang M, Meng G, Huang Q, Qian Y. Environ Sci Technol 2012;46:367-73. [10] Martins NCT, Freire CSR, Pinto RJB, Fernandes SCM, Neto CP, Silvestre AJD, et al. Cellulose 2012;19:1425-36. [11] Huang Y, Wang T, Ji M, Yang J, Zhu C, Sun D. Mater Lett 2014;128:93-6. [12] Liu GG, He F, Li XQ, Wang SH, Li LJ, Zuo GF, et al. J Mater Chem 2011;21:10637-40. [13] Vyjayanthi JP, Suresh S. Water Environ Res 2010;82:601-9. [14] Yang J, Yu J, Fan J, Sun D, Tang W, Yang X. J Hazard Mater 2011;189:377-83. [15] Chen S, Huang X, Xu Z. Cellulose 2011;18:1295-303. [16] Zanjanchi MA, Ebrahimian A, Arvand M. J Hazard Mater 2010;175:992-1000. [17] Chen S, Huang X, Xu Z. Compos Sci Technol 2014;101:11-6. [18] Yang J, Sun D, Li J, Yang X, Yu J, Hao Q, et al. Electrochim Acta 2009;54:6300-5. [19] Achar B, Fohlen G, Parker J, Keshavayya J. Polyhedron 1987;6:1463-7.
Figure Captions: Fig. 1. Optical images of a: BC (1 cm×1 cm) and b: CoPc@BC (1 cm×1 cm); FESEM images of c: BC and d: CoPc@BC. Fig. 2. ATR/FT-IR spectra of a: BC, b: oxidized BC and c: CoPc@BC. Fig. 3. XPS spectra of a: BC, b: oxidized BC and c: CoPc@BC. The window included shows in detail the Co region. Fig. 4. Concentration changes of rhodamine B (initial concentration 10 µmol/L, pH=10, T=60 °C) with existence of a: H2O2 (8 mM), b: CoPc@BC (2 mg), and c: CoPc@BC (2 mg) & H2O2 (8 mM).
HIGHLIGHTS 1. A novel cobalt tetraaminophthalocyanine decorated bacterial cellulose nanocomposite (CoPc@BC) was designed and prepared. 2. The CoPc@BC has high catalytic decoloration capacity to recalcitrant rhodamine B dye wastewater. 3. Eco-friendly H2O2 was used as oxidant.
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Bacterial cellulose nanofibers Decorated with phthalocyanine: Preparation, characterization and dye removal performance Shiliang Chen, Yijun Huang
www.elsevier.com/locate/matlet
PII: DOI: Reference:
S0167-577X(14)02202-2 http://dx.doi.org/10.1016/j.matlet.2014.12.036 MLBLUE18187
To appear in:
Materials Letters
Received date: 18 November 2014 Accepted date: 5 December 2014 Cite this article as: Shiliang Chen, Yijun Huang, Bacterial cellulose nanofibers Decorated with phthalocyanine: Preparation, characterization and dye removal performance, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2014.12.036 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Bacterial
cellulose
nanofibers
decorated
with
phthalocyanine:
preparation,
characterization and dye removal performance Shiliang Chen∗, Yijun Huang Department of Science and Technology, Qianjiang College, Hangzhou Normal University, Hangzhou 310012, China ABSTRACT: We report the preparation of a novel cobalt tetraaminophthalocyanine (CoPc) decorated bacterial cellulose (BC) nanocomposite by covalently immobilization of CoPc onto surface pre-oxidized bacterial cellulose nanofibers. The functionalization steps on the nanofibers were monitored by field emission scanning electron microscope (FESEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR/FT-IR), and X-ray photoelectron (XPS). The prepared CoPc decorated BC nanocomposite, CoPc@BC, was used as an efficient heterogeneous catalyst for the decoloration of recalcitrant rhodamine B (RhB) dye wastewater. We found that CoPc@BC has high decoloration capacity for RhB dye wastewater. With H2O2 as oxidant, more than 90% of RhB dye molecules can be removed in 180 min. Keywords:
Functional;
Bacterial
cellulose;
Nanocomposites;
Microstructure;
Decoloration
1. Introduction The production of cellulose fibers with nanoscale has gained increasing attention because these nanocelluloses combine prominent cellulose properties-such as hydrophilicity, renewability and tunable surface-with specific features of nanomaterials: very large surface-to-volume ratio and considerable modification possibility[1]. The preparation of nanocelluloses ranges from “top-down” methods with natural cellulose to ∗
Corresponding Author. Tel./fax: +86 571 28861372. E-mail address: [email protected] (S. Chen).
1
“bottom-up” methods with culture medium by certain bacteria[2-3]. The nanocelluloses biosynthesized by microorganisms is known as bacterial cellulose (BC). In terms of molecular formular, BC is identical to plant cellulose. The main remarkable features for BC includes high purity, high crystallinity, high degree of polymerization, and a three dimensional (3D) network. Potential application of BC has been exploited extensively, novel materials based on BC such as reinforcement nanocomposites[4], membrane[5], bio-inspired nanomaterial[6], and reaction template[7] are extensively reported. Due to their several attractive characteristics such as high aspect ratio, plenty of easily tunable hydroxyl groups and the web-like network with a distinct tunnel and pore structure, BC is a promising support for the immobilization of functional molecules. Organic and inorganic components can be immobilized onto BC with chemical and physical approaches to produce functional nanomaterials[8-10]. In particular, constructing efficient heterogeneous catalysts with BC as template is a field of extensive studies[11-12]. Various kinds of catalysts were immobilized onto BC for the treatment of wastewater effluents containing organic pollutants[13-14]. Metallophthalocyanine (MPc) has attracted considerable interest as an oxidation catalyst for its structural similarity to naturally occurring metalloporphyrin. In practical applications, it is often anchored to solid substrates as heterogeneous catalyst[15-17]. The microstructure of substrate has a great impact on its catalytic performance. Owing to the aforementioned outstanding characteristics, BC may be a promising candidate for MPc immobilization. Herein, we report the preparation and characterization of a new functional nanomaterial, CoPc decorated BC nanocomposite (CoPc@BC). Its catalytic effect for decoloration of recalcitrant rhodamine B (RhB) dye wastewater was also studied.
2
2. Experimental 2.1 Materials All chemicals purchased from Sinopharm Chemical Reagent Co. Ltd. (China) were of analytical grade and used as received. Bacterial cellulose (BC) sheet was prepared according to literature[18]. Cobalt tetraaminophthalocyanine (CoPc) was synthesized from 4-nitrophthalic acid, cobalt chloride hexahydrate and urea according to a method described previously[15, 19]. Water used in all experiments was de-ionized and ultrafiltrated to 18 MΩ with an ELGA LabWater system. An initial concentration of 10 µmol/L of RhB solution was prepared using this ultrafiltrated water. 2.2 Preparation For preparation of CoPc@BC, following steps were performed: 20 mg of BC was added to a 25 mmol/L NaIO4 solution and shaken for 7 h at 25 °C to generate aldehyde groups on the surface of BC. After thoroughly washed by ultrapure water and dried at 60 °C under vacuum, the resulted oxidized BC was then suspended in a 200 µmol/L CoPc solution. After reaction for 3 h at 25 °C, the product was washed with dimethylformamide (DMF) to remove residual CoPc and then rinsed three times with ultrapure water. 2.3 Characterization Surface morphologies of the nanofibers were examined by field emission scanning electron microscopy (FESEM, Serion, FEI, USA). Surface compositions of the nanofibers were verified by attenuated total reflection Fourier transform infrared spectra (ATR/FT-IR) and X-ray photoelectron spectrascopy (XPS). ATR/FT-IR spectra were acquired with a Vector 22 FTIR spectrometer (Brucker Optics, Switzerland) equipped with an ATR accessory (KRS-5 crystal, 45°). Each spectrum was taken by 32 scans at a
3
nominal resolution of 4 cm-1. XPS spectra were drawn on a PHI-5000C ESCA system (PerkinElmer, USA) with Al Kα radiation (1486.6 eV). 2.4 Decoloration Adsorption of RhB was carried out in a glass flask sealed in a water bath at 60 °C. 2 mg of CoPc@BC was added to 5 mL RhB solution (10 µmol/L). The catalytic oxidation was initiated by adding 8 mM H2O2 to a RhB solution containing CoPc@BC. At given time intervals, the samples were analyzed immediately on a UV-vis absorption spectrometer UV-2450 at the wavelength of maximum absorbance, 556 nm. The concentration change of RhB was expressed as the change of C/C0 value, where C0 is the initial concentration of the dye, and C is the residual concentration of the dye. 3. Results and discussion
--- Fig. 1 --The CoPc decorated BC nanocomposite, CoPc@BC, was prepared through covalently immobilization of CoPc onto the surface of BC after chemical oxidation with NaIO4. The optical and FESEM images of both BC and CoPc@BC are shown in Fig. 1. The color of as-prepared pure BC sheet is white as expected (Fig. 1a). After decorated
4
with CoPc, the dark green color appeared homogeneously on the entire sheet (Fig. 1c), indicating well distribution of CoPc on BC at macroscopic level. FESEM image of BC exhibits three dimensional nanofiber network architecture, the average diameter of nanofibers is approximately 10 nm (Fig. 1b). The shape of CoPc@BC (Fig. 1d) is still uniform compared with BC, indicating that BC has excellent stability during the surface oxidation and CoPc decoration. The progress of surface modification reactions were monitored by ATR/FT-IR. Fig. 2a represents the typical spectrum of biosynthesized BC, the strong absorption in the range of 3200-3500 cm-1 shows the presence of hydroxyl groups in the BC (as in case of natural cellulose). After oxidation, the appearance of a new characteristic peak at ∼1650 cm-1 indicates the successful formation of aldehyde groups on the surface of BC (Fig. 2b). The successful immobilization of CoPc on BC was verified by the expected appearance of the characteristic peak at ∼1610 cm-1 (υC=N of CoPc). In the meanwhile, the significant decrease of the peak at ∼1650 cm-1 corresponds to the successful reaction of aldehyde groups with CoPc (Fig. 2c).
--- Fig. 2 --The modification of BC involves the formation of aldehyde groups on its surface and
5
the decoration of the resulting product with CoPc. XPS was also used to analyze these reactions. Fig. 3 shows the XPS spectra from a wide scan for BC, oxidized BC and CoPc@BC, respectively. Compared with the XPS of oxidized BC (Fig. 3b), the spectrum of CoPc@BC shows a significant new signal at a binding energy (BE) of 402 eV, which is the characteristic peak of N 1s (Fig. 3c). In the meanwhile, two new peaks at binding energy of 793.9 and 779.1 eV were detected (Fig. 3, inset), which were assigned to the characteristic peaks of Co 2p1/2 and 2p3/2, respectively. This result provides further evidence for the decoration of CoPc on BC and the successful preparation of CoPc@BC.
--- Fig. 3 --The catalytic activity of the prepared nanocomposite, CoPc@BC, was evaluated on the basis of its decoloration performance to RhB dye wastewater. Almost no color change can be detected after 3 h with existence of H2O2 (Fig. 4a), indicating that RhB can hardly be degraded by H2O2. The concentration of RhB slightly decreased by 10% after 5 h with CoPc@BC presented as adsorbent. When both CoPc@BC and H2O2 were present, the RhB declined quickly and more than 90% of dye was degraded in 180 min (Fig. 4c), indicating that CoPc@BC/H2O2 is an effective reaction system for the
6
decoloration of recalcitrant RhB dye wastewater.
--- Fig. 4 --4. Conclusion In this study, CoPc decorated BC nanocomposite, CoPc@BC, was successfully prepared via covalently immobilization of CoPc onto surface pre-oxidized bacterial cellulose nanofibers. This nanocomposite has high catalytic activity on degradation of recalcitrant RhB dye wastewater. With H2O2 as oxidant, the decoloration ratio of RhB reached to 95% in 300 min. Acknowledgements The authors are grateful to the financial support from the National Natural Science Foundation of China (Grant no. 51103133). References [1] Huang Y, Zhu C, Yang J, Nie Y, Chen C, Sun D. Cellulose 2014;21:1-30. [2] Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, et al. Angew Chem Int Ed 2011;50:5438-66. [3] Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, et al. J Mater Sci 2010;45:1-33. [4] Wang JY, Jia HB, Zhang JJ, Ding LF, Huang Y, Sun DP, et al. J Mater Sci 2014;49:6093-101. [5] Ma H, Burger C, Hsiao BS, Chu B. Biomacromolecules 2012;13:180-6. [6] Capadona JR, Shanmuganathan K, Tyler DJ, Rowan SJ, Weder C. Science 2008;319:1370-4. [7] Abeer MM, Amin MCIM, Lazim AM, Pandey M, Martin C. Carbohydr Polym 2014;110:505-12.
7
[8] O-Rak K, Ummartyotin S, Sain M, Manuspiya H. Mater Lett 2013;107:247-50. [9] Wang M, Meng G, Huang Q, Qian Y. Environ Sci Technol 2012;46:367-73. [10] Martins NCT, Freire CSR, Pinto RJB, Fernandes SCM, Neto CP, Silvestre AJD, et al. Cellulose 2012;19:1425-36. [11] Huang Y, Wang T, Ji M, Yang J, Zhu C, Sun D. Mater Lett 2014;128:93-6. [12] Liu GG, He F, Li XQ, Wang SH, Li LJ, Zuo GF, et al. J Mater Chem 2011;21:10637-40. [13] Vyjayanthi JP, Suresh S. Water Environ Res 2010;82:601-9. [14] Yang J, Yu J, Fan J, Sun D, Tang W, Yang X. J Hazard Mater 2011;189:377-83. [15] Chen S, Huang X, Xu Z. Cellulose 2011;18:1295-303. [16] Zanjanchi MA, Ebrahimian A, Arvand M. J Hazard Mater 2010;175:992-1000. [17] Chen S, Huang X, Xu Z. Compos Sci Technol 2014;101:11-6. [18] Yang J, Sun D, Li J, Yang X, Yu J, Hao Q, et al. Electrochim Acta 2009;54:6300-5. [19] Achar B, Fohlen G, Parker J, Keshavayya J. Polyhedron 1987;6:1463-7.
Figure Captions: Fig. 1. Optical images of a: BC (1 cm×1 cm) and b: CoPc@BC (1 cm×1 cm); FESEM images of c: BC and d: CoPc@BC. Fig. 2. ATR/FT-IR spectra of a: BC, b: oxidized BC and c: CoPc@BC. Fig. 3. XPS spectra of a: BC, b: oxidized BC and c: CoPc@BC. The window included shows in detail the Co region. Fig. 4. Concentration changes of rhodamine B (initial concentration 10 µmol/L, pH=10, T=60 °C) with existence of a: H2O2 (8 mM), b: CoPc@BC (2 mg), and c: CoPc@BC (2 mg) & H2O2 (8 mM).
HIGHLIGHTS 1. A novel cobalt tetraaminophthalocyanine decorated bacterial cellulose nanocomposite (CoPc@BC) was designed and prepared. 2. The CoPc@BC has high catalytic decoloration capacity to recalcitrant rhodamine B dye wastewater. 3. Eco-friendly H2O2 was used as oxidant.
8