J Nanostruct 11(1): 48-56, Winter 2021 RESEARCH PAPER Silver-nanoparticle Supported on Nanocrystalline Cellulose using Cetyltrimethylammonium Bromide: Synthesis and Catalytic Performance for Decolorization of Dyes Hannaneh Heidari*, Melika Karbalaee Department of Chemistry, Faculty of Physics and Chemsitry, Alzahra University, Tehran, Iran ARTICLE INFO ABSTRACT In this work, we reported that the ultrasonically synthesized Article History: nanocrystalline cellulose (NCC) from microcrystalline cellulose has the Received 16 September 2020 Accepted 28 December 2020 capacity for use as natural and green matrices for the synthesis of silver Published 01 January 2021 nanoparticles. Cationic surfactant cetyltrimethylammonium bromide (CTAB) was employed as a modifier and stabilizer for NCC. The structure Keywords: of as-synthesized composite (Ag/CTAB/NCC) was characterized by Cetyltrimethylammonium Fourier transform infrared spectroscopy (FT-IR); field emission scanning bromide electron microscopy (FE-SEM); Transmission electron microscopy (TEM); Dye Energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The Nanocomposite XRD pattern confirmed the single cubic phase of Ag nanoparticles with crystallite size about 30 nm. TEM study also verified that the average Nanocrystalline cellulose particle size of the spherical-shaped Ag NPs. catalytic activity of Ag/CTAB/ Silver nanoparticles NCC has been analyzed by performing the reduction of certain toxic azo methyl orange dye (MO) (by two methods) and aromatic nitro compound of 4- nitrophenol (4-NP) in shorter time. The reduction of MO to hydrazine derivatives and 4-NP to 4-aminophenol takes place with a pseudo-first- order rate constants. The reduction time regularly decreased and the rate of reduction (k) increases (3 fold) with increasing catalyst amount in method (2) (mmol NaBH4/mmol MO = 250 and 42 mg catalyst) compared to method (1) (mmol NaBH4/mmol MO = 400 and 5 mg catalyst). The results indicated that spherical AgNPs immobilized CTAB-adsorbed NCC showed better catalytic activity and shorter reduction time towards the removal of methyl orange (k = 14.2 × 10-3 s-1, t =150 s) and 4-nitrophenol (k = 5.4 × 10-3 s-1, t = 180 s) compared with previous works that could be introduces as an effective method for the catalytic treatment of wastewater. How to cite this article Heidari H., Karbalaee M. Silver-nanoparticle Supported on Nanocrystalline Cellulose using Cetyltrimethylammonium Bromide: Synthesis and Catalytic Performance for Decolorization of Dyes. J Nanostruct, 2021; 11(1): 48-56. DOI: 10.22052/ JNS.2021.01.006 INTRODUCTION Over the last decade, nanostructured particles, high surface area to volume ratio, small size, especially inorganic nanoparticles (NPs), have increased numbers of atoms at the edges, and received more attention in biomedical applications, the corners which are surrounded by fewer materials science, and engineering [1-6]. atoms and considered to be more reactive [7, Inorganic NPs, show special properties 8]. Among the inorganic NPs, silver as the most including tunable physicochemical characteristics, frequently used noble metal NPs has attracted * Corresponding Author Email: [email protected] considerable attention because of efficiency, cost This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. H. Heidari and M. Karbalaee / Catalytic activity of silver /nanocellulose viability and the potential in various applications sulphuric acid hydrolysis [7, 19]. However, in our such as catalysis and antimicrobials [2, 3, 9, 10]. study, NCC was prepared from microcrystalline However, metal NPs tend to aggregate that cellulose by a simple and facile mechanical method minimizes their surface area and reduce their using ultrasonication without acid hydrolysis as a catalytic performance. One of the potential common chemical process. It was used as green methods to overcome this problem is using support/carrier for silver nanoparticle by CTAB as hybrid inorganic-polymer nanocomposites. In this stabilizer. regard, environmentally benign natural polymers, Organic dyes were widely used and released like chitin, alginic acid, chitosan, and cellulose by many industries, which have been attracting [11-14] related to hydrophilicity and multiple serious public concern due to environmental functionalities, having the strong ability to chelate contamination [23, 24]. The anionic dye of metal ions could serve the purpose better. methyl orange due to intense color, toxicity, and NCC, as one of the natural biopolymers could carcinogenic effects is a pollutant compound when be obtained from different sources such as cotton released into the environment. 4-Nitrophenol is by using acid hydrolysis process as a common another toxic and chemically hazardous compound method [15]. However, other modified techniques due to solubility and stability in the ordinary and including mechanical processes compared to acid wastewater systems. Numerous methods were hydrolysis have been developed which are simple, used for the degradation of MO and 4-NP. Catalytic low cost, and environmentally friendly [16]. degradation of MO to hydrazine derivatives Generally, the deposition of metal NPs on and 4-NP to 4-Aminophenol (4-AP) by metal the surface of NCC can be readily achieved using nanoparticles is an important way without the a strong reducing agent like NaBH4. Recently, production of secondary toxic substances [25-30]. various methods were applied for surface Hence, developing an effective method for the functionalization of NCC by chemical bonding degradation of these dyes from the environment to control morphology and particle size of metal is still a challenge. Recently, we reported the nanoparticles using a surfactant [17]. Moreover, synthesis of Ag/NCC and its catalytic application in surfactant similar to other dispersants was utilized degradation of toxic dyes [16]. Here, NCC can be to prevent aggregation of NPs in the chemical improved by using the surfactant for the synthesis reduction process [18]. of NCC/CTAB/Ag nanocomposite. The formation of Cetyltrimethylammonium bromide (CTAB), a cellulose base nanocomposite was confirmed by cationic surfactant with multifunctional groups FTIR, FESEM, EDS, TEM and XRD characterization. (alkyl chain and quaternary ammonium group as This research reported an effective catalyst for hydrophobic tail and hydrophilic head) with the highly efficient reduction of organic pollutants abilities of reduction and/or coordination, has (MO and 4-NP) from environmental water within been used to stabilize inorganic NPs [18- 20]. few minutes. Zaid et al. synthesized functionalized iron oxide with mercaptopropionic acid (MPA-Fe3O4) MATERIALS AND METHODS nanoparticle and commercial nanocellulose All chemicals were purchased from Merck and crystalline functionalized cetyl trimethyl Acros chemical Companies and were used without ammonium bromide (NCC/CTAB) for DNA further purification. IR spectra were recorded from electrochemical biosensor. [21]. KBr disk using FT-IR Bruker Tensor 27 instrument. Manan et al. prepared commercial Fieldemission scanning electron microscopy (FE- nanocrystalline cellulose (NCC) with cationic SEM) with a FEI-Nanosem 450. Transmission surfactant of cetyltriammonium bromide (CTAB) electron microscopy (TEM) images have been and further decorated with 3-mercaptopropionic taken with a Philips, model EM 208s. The energy acid (3-MPA) capped CdS QDs as biosensor for dispersive spectroscopy (EDS) analysis was done phenol determination [22]. An et al. reported using a SAMx-analyzer. The X-ray diffraction NCC/CTAB/Ag nanocomposite as a catalyst for the patterns (XRD) were obtained using a Phillips reduction of 4-Nitrophenol. Yalcinkaya et al. have PW1730 X-ray diffractometer. The diffraction synthesized NCC/CTAB/Ag nanocomposites for use patterns were recorded using Cu-Kα radiation at in PLA films. NCC in all the above composites are 40 kV and 30 mA. The samples were scanned in prepared commercially or they are obtained by a 2θ range between 10 and 80. Ultraviolet–visible J Nanostruct 11(1): 48-56, Winter 2020 49 H. Heidari and M. Karbalaee / Catalytic activity of silver /nanocellulose Fig. 1. FT-IR spectra of a) NCC b) Ag/CTAB/NCC (UV–Vis) measurements were performed using dried composite as a catalyst. The color change of Lambda-25 UV–Vis spectrometer. the solution was observed and the absorbance of resulting solutions was monitored using UV–Vis Preparation of NCC spectrophotometer. The mixture of microcrystalline cellulose in Method 2: water (3 wt.%) put into ice/water bath and set in An aqueous suspension of 42 mg of the the ultrasonicator for 15 min at an output power dried composite was added into a mixed of 1200 W. The obtained colloidal suspension was aqueous solution containing methyl orange or 4- centrifuged, the supernatant was dried and stored nitrophenol (0.25 ml, 20 mM), sodium borohydride at 5 [16]. solution (0.25 ml, 5M), and 19.5 ml DI water under stirring at room temperature. Then, an aliquot of Preparation℃ of Ag /CTAB/ NCC nanocomposite the reaction mixture (0.5 mL) at the appropriate Synthesis of Ag nanocomposite was carried out intervals was filtered, the absorbance of the filtrate in a typical experiment with some modification, was recorded using a UV-Vis spectrophotometer in [9] in which NCC suspension was diluted into 0.2 the wavelength range of 250-550 nm. The reaction wt.% followed by sonification