Bioreduction (Ag+ to Ag0) and stabilization of silver nanocatalyst using hyaluronate biopolymer for azo-contaminated wastewater treatment

https://doi.org/10.1016/j.jallcom.2021.162502Get rights and content

Highlights

  • Hyaluronate has dual functions as reductant and stabilizer for nanosilver synthesis.

  • One-variable-at-a-time employed to control and optimize the nanosilver synthesis.

  • Synthesized nanosilvers were spherical, crystalline, and stable at room temperature.

  • Nanosilvers were highly efficient for the treatment of azo-contaminated pollutants.

Abstract

A facile and well-known eco-friendly strategy has been used to synthesize colloidal silver nanoparticles (AgNPs) and applied for the catalytic reduction of azo dyes. Herein, AgNPs were produced using silver nitrate (AgNO3) as a metal precursor and sodium hyaluronate (SH) as both reducing and stabilizing agents without the assistance of any other toxic reagents. The different characterizations were employed to investigate the morphology, crystallinity, surface plasmon resonance (SPR), particle size/distributions, and composition of particles. The investigation revealed that the AgNPs were mostly spherical/oval shape with an average size of 13.3 ± 4.7 nm, highly crystalline with a d-spacing of 0.233 – 0.257 nm, and coated with SH-macromolecules layer of cladding. In application of wastewater treatment, the AgNPs showed an excellent catalytic reduction (more than 99% rate of degradation) of two carcinogenic pollutants, i.e., reactive red 195 (RR195) and reactive yellow 145 (RY145) azo-dyes, with the support of sodium borohydride. The azo-dye catalysis has followed the model of pseudo-first-order kinetics reactions, with a kinetic constant (k) of 0.0948 min−1 (r2 = 0.9889) and 0.0222 min−1 (r2 = 0.9877) for RR195 and RY145, respectively. The present study not only provides a facile synthesis of AgNPs without toxic chemicals but also can be a potential candidate to meet the actual demand for textile wastewater treatment.

Introduction

The textile industry processes different natural and synthetic fibers with significant wet processing. One of the major steps is the coloration of yarns, fabrics, and garments, where the industry requires commercially available synthetic dyes. Only a few amounts of total applied dyes are absorbed/adsorbed by the textile materials, where most of them are discharged as effluent [1], [2]. Such synthetic dyes mainly contain toxic chemical groups, and they create environmental severity once they release into the river without treatment. Therefore, removing/treating the dyes from industrial wastewater has become a compulsory requirement before discharge from the textile industry [3]. Although some compliance textile industries use effluent treatment plants to remove such toxic dyes, other industries are not encouraged due to their high setup and operation costs [4]. Some industries directly discharge wastewater without treatment even after imposing more strict laws by the government of many countries and organizations [5]. However, when these dyes are mixed with the surface water, it creates severe collapses of the ecosystem in the water bodies [6]. It also prevents sunlight penetration into the aquatic environment and directly affects the living organism and their nutrition system [7]. The dyes are mostly non-degradable and structurally highly stable; as a result, they remain in the atmosphere as toxic compounds for a long time [8]. Therefore, a simple wastewater treatment strategy cannot remove these dyes and break down their complex structure [9], [10]. Many traditional techniques have been introduced in wastewater treatment, but they are costly and ineffective. For example, the adsorption process involves the simple transformation of pollutants from one stage to another, thereby generating secondary pollutants [11]. The coagulation/flocculation process consists of toxic chemicals, including ferric salts, alums, limes, etc., and thereby makes the technique non-ecofriendly and expensive [12]. Other methods, such as ultrafiltration [13], electrochemical/chemical treatment [14], biological aeration [15], etc., involve large-scale aromatics and heavy mechanical setup. These shortcomings make them unviable in real industrial wastewater treatment and their purification technology. Therefore, researchers are still working on realistic, effective, economic, and environmentally friendly techniques for dyes contaminated wastewater treatment.

In recent years, the use of metal nanocatalysts for dye degradation has created more attention due to their quick and efficient reduction ability [16]. More importantly, it does not produce any polycyclic compounds after the degradation of dyes. In this context, different metal and metal oxide nanoparticles have already been synthesized and applied [17], [18]. Among them, zero valent iron [19], [20], silver [16], [21], palladium [22], [23], gold [24], copper oxide [25], and zinc oxide [26], [27], [28] nanoparticles are most remarkable. There are several advantages for the efficient catalytic function of nanoparticles, which include the weaker bonds of reactant to the catalytic portions, a higher number of active metal atoms, and a higher specific surface area [29]. The applications of nanoparticles are not only included in the field of toxic dye reduction; it also broadly used biomedical, drug delivery, cosmetics, photochemical, light scattering, transistors, and so on [30]. Such features are mainly achieved by ultra-violet protection, antimicrobial, antiviral, antioxidant, biocompatibility, and stability [31]. In contrast, the aggregation/agglomeration tendency during and after the synthesis of nanoparticles limits the wider applications [32]. Therefore, different studies have been made to synthesize stable nanoparticles using various chemical and physical techniques [33]. Among them, the chemical reduction techniques are more convenient but require toxic reducing auxiliaries agents such as hydroquinone, alkaline solution, dimethylamine borane, ascorbic acid, etc. [34]. The photochemical synthesis process is also suitable, but control incidents of ultraviolet rays of various wavelengths are highly desired [35]. In this regard, bioreduction is the most convenient and safest option for preventing agglomerations and overcoming the aforementioned drawbacks. Generally, a support/template is required to reduce and stabilize nanoparticles in the bioreduction techniques [22]. Microbes could be a good example, but they required high precaution and handlings in their synthesis process [36]. The phytochemicals extracted from plant branches are another good option for such templates. Hence, phytochemicals obtained from plant latex (Euphorbia hirta, Plumeria rubra, Euphorbia tirucalli, Jatropha gossypifolia) [37], leaf (Vitex doniana, Mucuna pruriens) [38], callus (Helicteres angustifolia) [39], fruit (Solanum lycopersicum, Daucus carota L, Vitus sp, Actinidia chinensis) [40], [41], seed (Camellia sinensis, Paulinia cupana) [42], root (Panax ginseng) [43] and other sources (Anacardium occidentale, Caulerpa racemosa) [44], [45] were studied. Likewise, we have also previously shown the role of phytochemicals obtained from Ginkgo biloba [46], [47], Eucommia ulmoides [48], as a template for nanoparticle synthesis. But it has been found that an additional complicated step for the extraction of plant phytochemicals was required to prepare the desired template. In this viewpoint, commercially available natural carbohydrates/polysaccharides are superior candidates to avoid the hassle of plant phytochemicals extraction. Diverse functionality and structural flexibility (as contained abundant hydroxyl and carboxylic groups) of natural polysaccharides make them viable reagent for reducing and stabilizing the metal precursors. Therefore, various sources of natural polysaccharides including glucose, maltose, starch, agar, arabinose, pectin, etc. were studied to the evaluate the accessibility as template for the biosynthesis of AgNPs. Following the similar pattern, we have also previously shown the bioreduction and simultaneous stabilization of metal nanoparticles using chitosan [49], [50], [51], [52], alginate [53], [54], [55], [56], [57], [58], carrageen [59], [60], konjac [22], [24], [61], and cellulose [62], [63]. All reports found a high level of crystallinity, uniform particle size/shape with the narrow distribution, excellent stability, and multifunctional application such as catalytic reduction dyes and bacteria. Inspired by such tremendous findings, our current work utilizes the functionality of sodium hyaluronate (SH) as a reducer (Ag+ to Ag0) and simultaneously as a stabilizer of synthesized AgNPs.

The SH is a disaccharide polymer, sodium salt of hyaluronic acid, obtained from marine algae, and consists of glycosaminoglycan and disaccharide of Na-glucuronate-N-acetylglucosamine [64]. The SH has a broader application in the field of pharmaceuticals (creams for wound healing, intra-articular injection, intraocular viscoelastic injection, plastic surgery of skin injection), cosmetics (protection from burning and screen ulcers), and food industry (dietary control maintain the amount of carbohydrate) [65]. It can serve as a reductant of the metal cation and stabilizing agent for the synthesized metal and metal oxide nanoparticles. Since it is one of the disaccharides, demonstrates a negative surface charge and contains an enormous amount of hydroxyl/carboxyl groups. For that sake, several researchers have investigated the accessibility of SH as a reductant, stabilizer, and template for the reduction of metal cation. Accordingly, Han et al. reported a gold nanocluster preparation for the application of photodynamic tumor ablation [66]. El-Dakdouki et al. synthesized SH coated iron oxide nanoparticles for the imaging and monitoring drug delivery to the cancer cells [67]. Kemp et al. [68] reported a clean method of gold nanoparticles synthesis for effective anticoagulant and anti-inflammatory application. Hien et al. [69] used the γ-irradiation method to synthesize SH-coated gold nanoparticles for a potential application in biomedicine and cosmetics. The SH has also been used to synthesize zinc oxide nanoparticles to apply wound dressing [70] and anticancer activity [71]. However, no direct report on SH-macromolecules reduced-stabilized AgNPs synthesis using nontoxic chemicals for the treatment of azo-contaminated wastewater. Of course, some relevant reports on SH-mediate nanosilver but the ultimate protocols and applications were far from our study. For example, (a) Khachatryan et al. synthesized SH-matrix-embedded AgNPs for antibacterial application [72]; (b) Abdel-Mohsen et al. prepared AgNPs incorporated SH fibers employing multiple synthesis steps for wound dressing and healing purposes [73]; (c) Xia et al. reported SH mediated AgNPs synthesis by chemical reduction methods for a potential application in biosensing [33]; (d) Zhang et al. studied in-vivo imaging application using SH coated AgNPs [74]; (e) Li et al. are also synthesized AgNPs using Tween 80 assisted SH for targeted drug delivery at the cellular level [75]; (f) Deng et al. used cetyltrimethylammonium bromide with SH additive for the synthesis of silver nanowires [76]. Hence, it can be perceived that the SH-mediated AgNPs have not been synthesized yet for the azo-contaminated wastewater treatment.

In terms of environmentally friendliness and cytocompatibility of the final products, biosynthesis procedures have grown increasingly in current decades. Regrettably, the optimization of control factors for the nanoparticle yield synthesis receives minimal attention. In a typical approach for optimizing processing parameters, all factors are systematically examined in a specific range to produce predictable outputs (signals) for further evaluation. The Taguchi design of experiments may be a viable option in this case because of its benefit of reaching a corroborated formula with the least amount of raw materials and time [77]. Even though this approach can evaluate all factors together with very few trials, the signals can be subjected to statistical analysis, and it is possible while the outputs are numeric. Relying on this hypothesis, some reports [78], [79] showed the Taguchi design of experiments to synthesize silver and gold nanomaterials by optimizing crucial factors. Actually, these studies illustrate the optimization of absorption intensity (Abs.%) at the maximum wavelength (λmax) since it is one of the indirect indications of nanoparticles synthesis. In contrast, other reports [62], [80] have demonstrated the maximization of Abs. % at λmax is just not a single criterion for defining particle yield production. To comprehend the formulation defects, including nanoparticle agglomerations, several associated aspects such as blue/red-shift of peaks and broadness/sharpness of peaks should also be taken under consideration. In this case, the one-variable-at-a-time (OVAT) approach may be more fruitful since it examines both the altitude of the maximum absorption and other associated aspects together within a particular set of individual variables.

Herein, SH has been applied as a reductant of the metal cation reduction and stabilizing agent for synthesized AgNPs utilizing the concept of using nontoxic chemicals. The effects of reaction parameters such as concentration, pH, time, and temperature were systematically analyzed by an OVAT technique. After that, AgNPs synthesized at optimum conditions were characterized by series of tools to perceive their ultimate properties. Finally, their catalytic functions towards azo-contaminated wastewater treatment have been presented and discussed by means of the theory of pseudo-first-order kinetics.

Section snippets

Materials

A snowy white powder (110 mesh) of sodium hyaluronate (HA-EP 3.0, molecular weight, Mw = 799.6 g mol−1) was supplied by Bloomage Biotechnology Corporation Ltd., Jinan, China. The different chemicals such as, sodium borohydride (NaBH4; Mw = 37.83 g mol−1), silver nitrate (AgNO3; Mw = 169.87 g mol−1), and sodium hydroxide (NaOH; Mw = 39.997 g mol−1) were all purchased in analytical grade from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China. The two dye compounds, i.e., reactive yellow 145

Synthesis and optimization of AgNPs

The synthesis of AgNPs was achieved using SH as stabilizing and reducing agent. The novel nanoparticles showed a bright color in the colloidal solution due to localized surface plasmon resonance (LSPR) [16]. The step-by-step color change indicates the synthesis of AgNPs colloidal solution. Once the gray color aqueous solution of SH was mixed with the transparent solution of AgNO3, the mixture appeared yellowish-brown. As the reaction was continued, the color changed from yellowish-brown to

Conclusion

Herein, SH-macromolecules were used as a reducing and simultaneously as a stabilizing agent for synthesizing AgNPs without using nontoxic chemicals. A suitable reaction condition was systematically developed using an OVAT technique. The successful synthesis was confirmed by spectroscopical study and elemental analysis. Other characterizations evinced that the particles were nanosized with uniform distribution, mostly spherical shape, highly crystalline with clear lattice fringes, and

CRediT authorship contribution statement

We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors thank the kind support of this work from the Key Laboratory of Biomass Fibers & Eco-Dyeing and Finishing, Hubei Province (STRZ2020001 and STRZ2020011).

References (91)

  • Z. Fu et al.

    Facile synthesis of nano-particles attached spherical Ti-6Al-4V powder based on plasma spheroidization

    J. Alloy. Compd.

    (2021)
  • V. Kusnezh et al.

    Fabrication and photosensitivity of structures based on CdS: Au nano-particles nanocomposite

    J. Alloy. Compd.

    (2018)
  • Z. He et al.

    Polyvinylidene fluoride membrane functionalized with zero valent iron for highly efficient degradation of organic contaminants

    Sep. Purif. Technol.

    (2020)
  • T.N.J.I. Edison et al.

    Catalytic degradation of organic dyes using green synthesized N-doped carbon supported silver nanoparticles

    Fuel

    (2020)
  • J. Chen et al.

    Green synthesis of Konjac glucomannan templated palladium nanoparticles for catalytic reduction of azo compounds and hexavalent chromium

    Mater. Chem. Phys.

    (2021)
  • Z. Wang et al.

    Hyaluronate macromolecules reduced-stabilized colloidal palladium nanocatalyst for azo contaminated wastewater treatment

    Colloids Surf. A: Physicochem. Eng. Asp.

    (2021)
  • J. Chen et al.

    Gold/Konjac glucomannan bionanocomposites for catalytic degradation of mono-azo and di-azo dyes

    Inorg. Chem. Commun.

    (2020)
  • J. Singh et al.

    Biogenic synthesis of copper oxide nanoparticles using plant extract and its prodigious potential for photocatalytic degradation of dyes

    Environ. Res.

    (2019)
  • R. Atchudan et al.

    Facile synthesis of zinc oxide nanoparticles decorated graphene oxide composite via simple solvothermal route and their photocatalytic activity on methylene blue degradation

    J. Photochem. Photobiol. B: Biol.

    (2016)
  • R. Atchudan et al.

    Concurrent synthesis of nitrogen-doped carbon dots for cell imaging and ZnO@nitrogen-doped carbon sheets for photocatalytic degradation of methylene blue

    J. Photochem. Photobiol. A: Chem.

    (2018)
  • Z. Yuan et al.

    Simple synthesis of porous ZnO nanoplates hyper-doped with low concentration of Pt for efficient acetone sensing

    J. Alloy. Compd.

    (2021)
  • M.L. Eggersdorfer et al.

    Agglomerates and aggregates of nanoparticles made in the gas phase

    Adv. Powder Technol.

    (2014)
  • N. Xia et al.

    Green synthesis of silver nanoparticles by chemical reduction with hyaluronan

    Carbohydr. Polym.

    (2011)
  • X. Yang et al.

    Phytochemical characteristics of callus suspension culture of Helicteres angustifolia L. and its in vitro antioxidant, antidiabetic and immunomodulatory activities

    South Afr. J. Bot.

    (2019)
  • T.N.J.I. Edison et al.

    Reductive-degradation of carcinogenic azo dyes using Anacardium occidentale testa derived silver nanoparticles

    J. Photochem. Photobiol. B: Biol.

    (2016)
  • S. et al.

    Silver nanoparticles synthesized using Eucommia ulmoides bark and their antibacterial efficacy

    Mater. Lett.

    (2017)
  • K.M.F. Hasan et al.

    Coloration of aramid fabric via in-situ biosynthesis of silver nanoparticles with enhanced antibacterial effect

    Inorg. Chem. Commun.

    (2020)
  • K.M.F. Hasan et al.

    Colorful and antibacterial nylon fabric via in-situ biosynthesis of chitosan mediated nanosilver

    J. Mater. Res. Technol.

    (2020)
  • Y. Xiong et al.

    Bio-synthesized palladium nanoparticles using alginate for catalytic degradation of azo-dyes

    Chin. J. Chem. Eng.

    (2020)
  • X. Zhang et al.

    Sodium alginate fasten cellulose nanocrystal Ag@AgCl ternary nanocomposites for the synthesis of antibacterial hydrogels

    Compos. Commun.

    (2021)
  • H. Wan et al.

    Bioreduction (AuIII to Au0) and stabilization of gold nanocatalyst using Kappa carrageenan for degradation of azo dyes

    Int. J. Biol. Macromol.

    (2021)
  • H. Wan et al.

    Kappa carrageenan reduced-stabilized colloidal silver nanoparticles for the degradation of toxic azo compounds

    Colloids Surf. A: Physicochem. Eng. Asp.

    (2021)
  • J. Chen et al.

    Konjac glucomannan reduced-stabilized silver nanoparticles for mono-azo and di-azo contained wastewater treatment

    Inorg. Chim. Acta

    (2021)
  • G. Li et al.

    Green synthesis of palladium nanoparticles with carboxymethyl cellulose for degradation of azo-dyes

    Mater. Chem. Phys.

    (2017)
  • N.Q. Hien et al.

    Radiation synthesis and characterization of hyaluronan capped gold nanoparticles

    Carbohydr. Polym.

    (2012)
  • K.M. Rao et al.

    One-pot synthesis of ZnO nanobelt-like structures in hyaluronan hydrogels for wound dressing applications

    Carbohydr. Polym.

    (2019)
  • G. Khachatryan et al.

    Formation and properties of hyaluronan/nano Ag and hyaluronan-lecithin/nano Ag films

    Carbohydr. Polym.

    (2016)
  • A. Abdel-Mohsen et al.

    Green synthesis of hyaluronan fibers with silver nanoparticles

    Carbohydr. Polym.

    (2012)
  • H.-J. Li et al.

    Hyaluronan/Tween 80-assisted synthesis of silver nanoparticles for biological application

    J. Nanopart. Res.

    (2015)
  • M. Vijayakumar et al.

    Biosynthesis, characterisation and anti-bacterial effect of plant-mediated silver nanoparticles using Artemisia nilagirica

    Ind. Crop. Prod.

    (2013)
  • K. Priya et al.

    Chitosan-mediated synthesis of biogenic silver nanoparticles (AgNPs), nanoparticle characterisation and in vitro assessment of anticancer activity in human hepatocellular carcinoma HepG2 cells

    Int. J. Biol. Macromol.

    (2020)
  • R. Gengan et al.

    A549 lung cell line activity of biosynthesized silver nanoparticles using Albizia adianthifolia leaf

    Colloids Surf. B: Biointerfaces

    (2013)
  • K. Jyoti et al.

    Green synthesis of nanostructured silver particles and their catalytic application in dye degradation

    J. Genet. Eng. Biotechnol.

    (2016)
  • T.A. Khattab et al.

    Textile dyeing industry: environmental impacts and remediation

    Environ. Sci. Pollut. Res.

    (2020)
  • M.M. Islam et al.

    Study on different types of dyeing faults, causes and remedies of knit fabrics

    Int. J. Eng. Technol.

    (2015)
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