AgO/MgO/FeO@Si3N4 nanocomposite with robust adsorption capacity for tetracycline antibiotic removal from aqueous system

doi:10.1016/j.apt.2020.09.006

Advanced Powder Technology

Volume 31, Issue 10, October 2020, Pages 4310-4318

https://doi.org/10.1016/j.apt.2020.09.006 Get rights and content

Highlights

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AgO/MgO/FeO/Si₃N₄ synthesized by microwave irradiation method.
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Adsorption of tetracycline.
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Maximum adsorption capacity of 172.41 mg/g.
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Energy sites found to be energetically heterogeneous.

Abstract

Present study has been designed to govern the usage of nanocomposite of Si₃N₄ with trimetallic oxide nanoparticles of Ag, Mg and Fe (AgO/MgO/FeO@Si₃N₄) for the tetracycline (TC) removal from aqueous solution. Characterization techniques such as SEM, TEM, XRD, FTIR, XPS and BET were employed for analysing the successful fabrication of AgO/MgO/FeO@Si₃N₄ nanocomposite. Adsorption process has been found to be dependent upon the surface properties of AgO/MgO/FeO@Si₃N₄ nanocomposite (such as charge, functionality, etc), concentration of TC, solution pH and contact time. As determined from the isotherm studies, surface of AgO/MgO/FeO@Si₃N₄ nanocomposite has been found to be energetically heterogeneous in nature as the data fitted well to Freundlich isotherm. Maximum adsorption capacity of AgO/MgO/FeO@Si₃N₄ nanocomposite has been found to be 172.41 mg/g. Pseudo-second order kinetic model successfully explained the rate studies of TC adsorption. Also, reusability study of AgO/MgO/FeO@Si₃N₄ nanocomposite has also been carried out. In short, the present study could determine an effective way for the removal of toxic pollutants from the wastewater system.

Graphical abstract

Introduction

Water pollution due to antibiotics has been quite alarming due to their persistent and non- biodegradable nature. These are not completely absorbed by the human bodies due to which they are indirectly released into the water through urine or faeces. Herein, one of the most commonly utilized antibiotics, tetracycline (TC) has been considered as the model pollutant [1], [2]. TC has been known to exhibit antimicrobial activity against numerous pathogenic bacteria. Its presence in water not only suppresses the water quality but also arose the issues regarding water purification [3]. Also, prolonged exposure of TC to microorganisms could also result in their resistance against TC, thus its removal from the water system is of immense importance [4].

Purification of contaminated water can be achieved by using a variety of methods including coagulation, flocculation, photocatalysis [5], [6], [7], [8], [9], [10], membrane filtration [11], [12], ozonation, reverse osmosis, adsorption and ion exchange [13], [14], [15], [16], [17]. The remediation method is decided based on pollutants and in the present study, adsorption has been employed for the TC removal from aqueous solution. This technique offers major perks over other techniques such as its applicability at any concentration, lower cost of operation, design ease and no production of toxic by-products at the end of experiments [18], [19]. In the initial times, activated carbon was the best adsorbent for various pollutants but due to difficulty in its separation and regeneration led to the emergence of several new adsorbents. Numerous data has been published in the literature on TC adsorption such as Zhou and his co- workers synthesized ferroferric oxide nanoparticles assisted powdered activated carbon for the adsorption of TC molecules and found the chemisorption behavior [20]. Abadi et al., synthesized Fe- doped zeolite for TC adsorption and reported that the interactions were pH-dependent due to the amphoteric behavior of TC [21].

In the present study, a trimetallic nanocomposite of AgO/MgO/FeO@Si₃N₄ has been synthesized for the removal of TC from aqueous solution. Metal oxides are quite effective adsorbents for the removal of various pollutants from aqueous solutions [22]. Enough literature is available about the use of silver oxide, iron oxide and magnesium oxide as adsorbent [23], [24], [25]. These oxides exhibit better magnetic and chemical properties. In one of our previous study, we synthesized La/Cu/Zr trimetallic nanoparticles (TNPs) and utilized its catalytic activity for the removal of ampicillin from aqueous solution [26]. Some other reported work in this field includes the Sr_0.3Mg_0.7Fe₂O₄ nanocubes that were designed as a selective nanoadsorbent for congo red dye. Around 90% dye was adsorbed within just 30 min [27]. In other study, Fe⁰-based trimetallic system was designed for the elimination of aqueous diclofenac [28].

The trimetallic oxides were imprinted onto the matrix of silicon nitride (Si₃N₄). It offers high mechanical and thermal properties and also help in avoiding the leaching of dispersed metal oxides. It provides mechanical strength at high temperatures, ascertaining the stability under extreme conditions [29]. Main objectives of the present study were (i) to synthesize Si₃N₄; (ii) to synthesize AgO/MgO/FeO@Si₃N₄ nanocomposite; (iii) to characterize the synthesized composite by FTIR, SEM, XRD, TEM, XPS and BET; (iv) adsorption of TC from aqueous solution onto AgO/MgO/FeO@Si₃N₄ nanocomposite and (v) reusability of AgO/MgO/FeO@Si₃N₄ nanocomposite.

Section snippets

Chemicals

All the chemicals were of analytical grade and used as received. Trisodium citrate (Na₃C₆H₅O₇), silver nitrate (AgNO₃), magnesium nitrate (Mg(NO₃)₂), ferric nitrate (Fe(NO₃)₃), silica (SiO₂) and urea (NH₂CONH₂) were all purchased from Central Drug House Pvt. Ltd. (CDH), Solan, H.P., India. Tetracycline hydrochloride (C₂₂H₂₄N₂O₈. HCl) was obtained from Loba Chemie Pvt. Ltd., Solan H.P., India.

Synthesis of Si₃N₄ and AgO/MgO/FeO@Si₃N₄ nanocomposite

Si₃N₄ was prepared by pyrolysis as reported in our previous work [30] and the AgO/MgO/FeO@Si₃N₄

Synthesis of AgO/MgO/FeO@Si₃N₄ nanocomposite

The AgO/MgO/FeO@Si₃N₄ nanocomposite was prepared by the microwave reduction method. Trisodium citrate (Na₃C₆H₅O₇) was used as the reducing agent that shows its activity only at elevated temperature (~100 °C) which was accomplished by the microwave radiations. In addition to acting as a reducing agent, it also acts as a capping agent. Thus, it helps in reducing the further growth of formed nanoparticles and reduces the chances of agglomeration [39].

So, when metal nitrate solution mixed with

Conclusions

In summary, we synthesized AgO/MgO/FeO@Si₃N₄ nanocomposite by microwave reduction method. It was effectively utilized for the adsorption of TC molecules from aqueous solution. Various characterization techniques validated the successful formation of required nanocomposite and its surface properties are well presented. The pH of the solution was found to be major influencing parameter since TC behave differently in different pH solutions. Maximum adsorption capacity as obtained from Langmuir

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.

Acknowledgements

One of the authors (Mu. Naushad) acknowledges financial support from the Distinguished Scientist Fellowship Program (DSFP), King Saud University, Riyadh, Saudi Arabia. The authors are thankful to the Shoolni University, Solan, India for providing research facilities.

References (59)

P. Zhang et al.
Characteristics of tetracycline adsorption by cow manure biochar prepared at different pyrolysis temperatures
Bioresour. Technol.
(2019)
J. Niu et al.
Visible-light-mediated Sr-Bi₂O₃ photocatalysis of tetracycline: kinetics, mechanisms and toxicity assessment
Chemosphere
(2013)
A. Mehta et al.
Band gap tuning and surface modification of carbon dots for sustainable environmental remediation and photocatalytic hydrogen production – A review
J. Environ. Manage.
(2019)
C.V. Reddy et al.
Copper-doped ZrO₂ nanoparticles as high-performance catalysts for efficient removal of toxic organic pollutants and stable solar water oxidation
J. Environ. Manage.
(2020)
C.V. Reddy et al.
Metal-organic frameworks (MOFs)-based efficient heterogeneous photocatalysts: Synthesis, properties and its applications in photocatalytic hydrogen generation, CO2 reduction and photodegradation of organic dyes
Int. J. Hydrogen Energy
(2020)
R. Koutavarapu et al.
ZnO nanosheets-decorated Bi₂WO₆ nanolayers as efficient photocatalysts for the removal of toxic environmental pollutants and photoelectrochemical solar water oxidation
J. Environ. Manage.
(2020)
S.P. Dharupaneedi et al.
Membrane-based separation of potential emerging pollutants
Sep. Purif. Technol.
(2019)
T. Tavangar et al.
Textile waste, dyes/inorganic salts separation of cerium oxide-loaded loose nanofiltration polyethersulfone membranes
Chem. Eng. J.
(2020)
G. Sharma et al.
Adsorptive removal of noxious cadmium ions from aqueous medium using activated carbon/zirconium oxide composite: Isotherm and kinetic modelling
J. Mol. Liq.
(2020)
G. Sharma et al.
Pectin-crosslinked-guar gum/SPION nanocomposite hydrogel for adsorption of m-cresol and o-chlorophenol
Sustainable Chem. Pharm.
(2017)

G. Sharma et al.

Fabrication, characterization and antimicrobial activity of polyaniline Th(IV) tungstomolybdophosphate nanocomposite material: Efficient removal of toxic metal ions from water

Chem. Eng. J.

(2014)

W. Liu et al.

Gram-grade Cr (VI) adsorption on porous Fe@SiO₂ hierarchical microcapsules

J. Water Process Eng.

(2016)

C.V. Reddy et al.

Mn-doped ZrO₂ nanoparticles prepared by a template-free method for electrochemical energy storage and abatement of dye degradation

Ceram. Int.

(2019)

A. Dąbrowski et al.

Adsorption of phenolic compounds by activated carbon—a critical review

Chemosphere

(2005)

J. Zhou et al.

Adsorption behavior of tetracycline from aqueous solution on ferroferric oxide nanoparticles assisted powdered activated carbon

Chem. Eng. J.

(2020)

K.Y. Kumar et al.

Low-cost synthesis of metal oxide nanoparticles and their application in adsorption of commercial dye and heavy metal ion in aqueous solution

Powder Technol.

(2013)

A. Khaleel et al.

Nanocrystalline metal oxides as new adsorbents for air purification

Nanostruct. Mater.

(1999)

S. Dadfarnia et al.

Methyl red removal from water by iron based metal-organic frameworks loaded onto iron oxide nanoparticle adsorbent

Appl. Surf. Sci.

(2015)

G. Sharma et al.

Fabrication and characterization of trimetallic nano-photocatalyst for remediation of ampicillin antibiotic

J. Mol. Liq.

(2018)

R. Ravi et al.

Novel mesoporous trimetallic strontium magnesium ferrite (Sr_{0. 3}Mg_{0. 7}Fe₂O₄) nanocubes: A selective and recoverable magnetic nanoadsorbent for Congo red

J. Alloys Comp.

(2019)

A. Ghauch et al.

Fe0-based trimetallic systems for the removal of aqueous diclofenac: Mechanism and kinetics

Chem. Eng. J.

(2011)

G. Sharma et al.

Facile fabrication of Zr₂Ni₁Cu₇ trimetallic nano-alloy and its composite with Si₃N₄ for visible light assisted photodegradation of methylene blue

J. Mol. Liq.

(2018)

G. Sharma et al.

Guar gum-crosslinked-Soya lecithin nanohydrogel sheets as effective adsorbent for the removal of thiophanate methyl fungicide

Int. J. Biol. Macromol.

(2018)

M. Naushad et al.

Efficient removal of toxic phosphate anions from aqueous environment using pectin based quaternary amino anion exchanger

Int. J. Biol. Macromol.

(2018)

M. Ghasemi et al.

Adsorption of Pb(II) from aqueous solution using new adsorbents prepared from agricultural waste: Adsorption isotherm and kinetic studies

J. Ind. Eng. Chem.

(2014)

G. Sharma et al.

Honeycomb structured activated carbon synthesized from Pinus roxburghii cone as effective bioadsorbent for toxic malachite green dye

J. Water Process Eng.

(2019)

M.R. Awual et al.

Selective cesium removal from radioactive liquid waste by crown ether immobilized new class conjugate adsorbent

J. Hazard. Mater.

(2014)

H. Wadhwa et al.

Microwave assisted facile synthesis of reduced graphene oxide-silver (RGO-Ag) nanocomposite and their application as active SERS substrate

Mater. Chem. Phys.

(2017)

R. Farzana et al.

Sustainable synthesis of silicon nitride nanowires using waste carbon fibre reinforced polymer (CFRP)

J. Cleaner Prod.

(2018)

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Original Research PaperAgO/MgO/FeO@Si3N4 nanocomposite with robust adsorption capacity for tetracycline antibiotic removal from aqueous system

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals

Synthesis of Si3N4 and AgO/MgO/FeO@Si3N4 nanocomposite

Synthesis of AgO/MgO/FeO@Si3N4 nanocomposite

Conclusions

Declaration of Competing Interest

Acknowledgements

Bioresour. Technol.

Chemosphere

J. Environ. Manage.

J. Environ. Manage.

Int. J. Hydrogen Energy

J. Environ. Manage.

Sep. Purif. Technol.

Chem. Eng. J.

J. Mol. Liq.

Sustainable Chem. Pharm.

Chem. Eng. J.

J. Water Process Eng.

Ceram. Int.

Chemosphere

Chem. Eng. J.

Powder Technol.

Nanostruct. Mater.

Appl. Surf. Sci.

J. Mol. Liq.

J. Alloys Comp.

Chem. Eng. J.

J. Mol. Liq.

Int. J. Biol. Macromol.

Int. J. Biol. Macromol.

J. Ind. Eng. Chem.

J. Water Process Eng.

J. Hazard. Mater.

Mater. Chem. Phys.

J. Cleaner Prod.

Original Research Paper
AgO/MgO/FeO@Si₃N₄ nanocomposite with robust adsorption capacity for tetracycline antibiotic removal from aqueous system

Synthesis of Si₃N₄ and AgO/MgO/FeO@Si₃N₄ nanocomposite

Synthesis of AgO/MgO/FeO@Si₃N₄ nanocomposite