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Green synthesis and environmental application of Iron-based nanomaterials and

nanocomposite: A review

Piyal Mondal, A. Anweshan, Mihir Kumar Purkait

PII: S0045-6535(20)31703-3
DOI: https://doi.org/10.1016/j.chemosphere.2020.127509
Reference: CHEM 127509

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Received Date: 30 May 2020

Revised Date: 16 June 2020
Accepted Date: 19 June 2020

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 1 Green synthesis and environmental application of Iron-based nanomaterials and

2 nanocomposite: A review

3 Piyal Mondal, A. Anweshan, Mihir Kumar Purkait∗

5 Department of Chemical Engineering, Indian Institute of Technology Guwahati,

6 Guwahati - 781039, India

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∗
Corresponding author
Tel: + 91 - 361 - 2582262
Fax: +91 - 361 - 2582291
E. Mail: mihir@iitg.ernet.in

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18 Abstract

19 Green chemistry has been proven to be an efficient route for nanoparticle synthesis. Plant

20 extract based green synthesis of various nanoparticles is extensively studied since the last

21 decade. This paper “Green synthesis and environmental application of Iron-based

22 nanomaterials and nanocomposite: A review” unveils all the possible greener techniques for

23 the synthesis of iron-based nanoparticles and nanocomposites. The use of different plant

24 sources, microorganisms, and various biocompatible green reagents such as biopolymers,

25 cellulose, haemoglobin, and glucose for the synthesis of iron nanoparticles reported in the last

26 decade are summarized. The microwave method, along with hydrothermal synthesis due to

27 their lower energy consumption are also been referred to as a green route. Apart from

28 different plant parts, waste leaves and roots used for the synthesis of iron nanoparticles are

29 extensively briefed here. This review is thus compact in nature which covers all the broad

30 areas of green synthesis of iron nanoparticles (NPs) and iron-based nanocomposites. Detailed

31 discussion on environmental applications of the various green synthesized iron NPs and their

32 composites with performance efficiency is provided in this review article. The advantages of

33 bimetallic iron-based nanocomposites over iron NPs in various environmental applications

34 are discussed in detail. The hazards and toxic properties of green synthesized iron-based NPs

35 are compared with those obtained from chemical methods. The prospects and challenges

36 section of this article provides a vivid outlook of adapting such useful technique into a more

37 versatile process with certain inclusions which may encourage and provide a new direction to

38 future research.

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40

41 Keywords: Environmental application; Green synthesis; Iron nanoparticles; Iron

42 nanocomposites; Toxic effects.

2
43 1. Introduction

44 Nanotechnology is defined as the transformation of matter using physical, chemical, and

45 biological techniques and processes with or without incorporating other ingredients to

46 produce substances with specialized functionalities, enhanced characteristics and specific

47 attributes, which can be used in diverse field of applications (Goswami et al., 2012;

48 Taghizadeh 2013). A nanoparticle (NP) can be defined as a minuscule particle which has at

49 least one of its size/dimension, not more than 100 nm (Thakkar et al., 2010). The

50 nanoparticles thus produced are distinct from the bulk materials, as they exhibit unique

51 electrochemical, optical, and thermal properties, along with a substantially larger surface area

52 to volume ratio (Taghizadeh et al., 2013). These unique properties of the nanoparticles are

53 responsible for their popularity and widespread use in the field of agriculture, biotechnology,

54 chemistry, communications, consumer goods, defence, electronics, energy, environmental

55 remediation, heavy industries, material science, medicine, microbiology, optics, and various

56 engineering fields (Asfaram et al., 2017; Mokhtari et al., 2016).

57 Metals and their corresponding oxides are extensively converted into nanoparticles using

58 both physical and chemical processes (Ghaedi et al., 2013; Raul et al., 2012). The chemical

59 synthesis methods, like element lowering and sol serum approach, intensively use toxic and

60 hazardous substances such as sodium borohydride, hypophosphite, and hydrazine hydrate,

61 which harm the environment (Changmai et al., 2017; Goswami et al., 2014). So, the

62 development of a competent, cost-efficient and sustainable green process for the synthesis of

63 nanoparticles is an on-going effort. Stable and well-functionalized nanoparticles have been

64 produced from organisms like bacteria, actinomycetes, fungi, yeast, viruses, and other

65 microbes (Mandal et al., 2006; Jebali et al., 2011). These microorganisms serve as

66 environment-friendly and sustainable precursors. However, factors like local availability of

67 resources, social adaptability, and economic feasibility heavily influence the overall

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68 sustainability of the process (Hosseini et al., 2016; Dey and Purkait, 2015). Apart from metal

69 NPs, metal-based nanocomposites have also been extensively utilized for various

70 environmental hazard purposes (Ghaedi et al., 2016; Mazaheri et al., 2015; Asfaram et al.,

71 2015; Ghaedi et al., 2012).

72 The nanoparticle synthesis employing green chemistry techniques has several advantages

73 concerning the conventional methods, namely being safe to handle, does not contaminate the

74 environment, and relatively inexpensive. Gonzalez-Moragas et al. (2015) prepared super

75 papramagnetic iron-oxide nanoparticles (SPIONs) of size 5.9 ± 1.4 nm through microwave

76 assisted commercial chemical process using iron (III) acetylacetonate as a precursor with a

77 production cost of €130 per 10 g of SPION. Whereas for preparing green synthesized iron

78 NPs from plant extract it costed around USD 0.5-10 per gram depending upon species and

79 purity (Bolado et al., 2020). The advantage of such green synthesized NPs is that it doesn’t

80 require synthetic reducing agents which is environmentally hazardous. Moreover, such

81 process doesn’t require external capping and stabilizing agents. Commercially available Fe

82 NPs have a diverse price spectrum depending on factors like oxidation state, particle size,

83 functionalization, and a dispersion medium which can range from USD 50-500 per gram

84 (Sigma Aldrich, St. Loius, MO, USA). Various chemical conventional techniques have

85 shown such disadvantages of high cost (Goswami and Purkait, 2015; Dey et al., 2014). Other

86 advantages and salient features of green synthesis processes are: firstly, the dual utility of the

87 active natural component, like the extract, both as reducing and capping agent. This ability

88 enables the production of small size nanoparticles in large scale units (Ghaedi et al., 2015).

89 Secondly, the time taken for reducing the metal ions is short, and the product formed after

90 that is immensely stable due to the presence of stabilizing agents in the extract (Mondal and

91 Purkait, 2019). Last but not least, a plethora of both microscopic and macroscopic organisms

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 92 are available that could be utilized for the desired nanoparticle functionality (Mohanpuria et

93 al., 2008).

94 Iron nanoparticles (Fe NPs) exhibit superb dimensional stability, non-toxicity and have an

95 affinity to form oxides. Apart from having a high surface area, electrical and thermal

96 conductivity, Fe NPs also possess magnetic properties and are known as magnetic

97 nanoparticles (Arabi et al., 2016). Superparamagnetism is a unique consequence of magnetic

98 nanoparticles. It is observed in ferromagnetic or ferrimagnetic nanomaterials, only when the

99 size and number of domains, are both adequately small, broadly between 10-150 nm in

100 diameter depending on the material (Clemons et al., 2019). At these extreme sizes, they

101 become a single domain magnetic material that has no hysteresis loop; also, their

102 magnetization can randomly flip direction under the influence of temperature (Frenkel et al.,

103 1930). Iron nanoparticles that exhibit superparamagnetism are termed as superparamagnetic

104 iron oxide nanoparticles (SPIONs), and it finds wide application in biomedical field.

105 Iron is abundant in nature, less expensive and its magnetic behavior has engrossed synthesis

106 of NPs having enormous scope in environmental separation application. However, it is

107 envisaged that NPs of various metal and metal oxides such as silver, gold, copper, and zinc

108 have been studied thoroughly than that of iron NP. Few review papers concentrated on

109 specific green methods using sources from plant parts (Bolade et al., 2020; Saif et al., 2016;

110 Herlekar et al., 2014; Fahmy et al., 2018) In addition to this, the present review article

111 discusses the state of artwork on the green synthesis of iron NPs and iron nanocomposites

112 using various biocompatible green reagents such as biopolymers, cellulose, haemoglobin,

113 glucose, along with microorganisms and low-cost energy related processes. Again, iron-based

114 nanocomposites through green routes and their environmental application are also elaborated

115 which is scant in the recent literature. The tables provide a detailed insight of morphological

116 structure of iron nanomaterials/nanocomposites prepared from each specific source, along

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117 with their specific applications and efficiency. The readers of this paper will be highly

118 benefitted by getting up to date information and critical expert suggestion on the green

119 synthesis of iron nanoparticles/nanocomposites and their enormous potential in

120 environmental separation application.

121

122 2. Green Route Synthesis of iron NPs

123 An efficient and eco-friendly methodology to synthesize nanoparticles ideally should use

124 renewable energy, minimize waste discharge, and optimize energy consumption according to

125 the principles of green chemistry (Anastas et al., 1998). Thus it may be conceptualized that

126 the green synthesis process must utilize plants, microbes, bio-polymers, and waste materials

127 for the active bio-component along with low heating requirements and benign solvents

128 (Bolade et al., 2019). Water is considered as the universal solvent, has been reported in many

129 studies as a solvent with biomolecules, mostly polyphenols, extracted from plants as

130 reducing, capping, and stabilizing agents. These bioactive polyphenols have been extracted

131 from leaves, stems, roots, flowers, fruits, fruit peels, seeds, gums, and even wastes of various

132 vegetation (Yew et al., 2020). Agglomeration being the main problem in chemical synthesis

133 of NPs, green route techniques have quite significantly limited that aspect. Especially for

134 plant extract and microorganism mediated synthesis, the polyphenolic content and natural

135 proteins acts as stabilizer and coating agent over the prepared NPs, which restrict the

136 agglomeration. Most of the prepared NPs through green route techniques are generally stored

137 in aquoues form at definite pH to provide stability and uniform particle size (Bolade et al.,

138 2019). Better stabilization can also be obtained by utilizing biocompatible reagents and other

139 chemical surface coatings, which provide less reactivity when comes in contact with

140 environmental fluids. NPs stored in powder form should be kept in vacuum otherwise

141 agglomeration occurs in presence of moisture from the environment.

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142 Prabhakar et al. (2017) have synthesized Fe NPs using extracts from both aquatic and

143 terrestrial weeds and explored its application in eutrophic wastewater treatment for the

144 removal of nitrates and phosphates. Production of toxic by-products and their subsequent

145 disposal with other harmful reagents can be reduced substantially by using aqueous media

146 and ambient temperature and pressure. Time for synthesis and energy consumption can be

147 reduced by incorporating a microwave heating source instead of conventional methods.

148 Microwave assisted technique undergoes hydrothermal process and thus has been widely

149 used by various researchers for scaling up iron NPs synthesis purpose. Gonzales-Moragas et

150 al. (2015) adopted microwave based thermal technique for synthesizing SPIONs at a rate of

151 3g h-1 with batch mode utilizing multi-mode microwave unit. The study implemented a multi-

152 vessel rotor system, which may help to overcome the production bottleneck associated with

153 single-mode microwave systems. Moreover, Bowman et al. (2008) utilized both batch and

154 continous flow model to synthesize NPs which provided yield of several multigrams per

155 hour. Production of NPs in the range of kg or ton per day has not yet been reported. However,

156 scalled version of production of such NPs can be enhanced with continous flow type reactor

157 aided with multi-mode microwave system. Iron nanoparticle formation facilitated by

158 microorganisms like actinomycetes, algae, fungi, and yeast at neutral pH and close to room

159 temperature is extensively reported (Schrofel et al., 2014; Thakur et al., 2014). Catalytic,

160 biological, and environmental applications of iron nanoparticles synthesized via green route

161 are widely reported (Ahmed et al., 2014; Iqbal et al., 2017).

162 This review paper enlists all the possible greener routes for synthesizing iron NPs along with

163 iron-based nanomaterials, its composites, and bimetallic nanocomposites. Synthesis involving

164 biocompatible reagents, microorganisms, various plant parts, plant waste materials,

165 microwave assisted synthesis, and hydrothermal processes have been discussed elaborately to

166 provide a vivid idea and literature survey regarding the green synthesis of Iron and iron-based

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167 nanomaterials. Moreover, the focus has been made on various iron-related bimetallic

168 nanocomposites, which was found to have better catalytic and adsorptive properties in

169 comparison to only iron NPs. Various environmental applications of such iron NPs and iron-

170 based nanomaterials have been discussed related to dye degradation, heavy metal removal,

171 fluoride removal along with wastewater treatment, and other waterborne pollutant removals.

172 Moreover, the tables enlist all possible green synthesis plant sources and the morphology of

173 prepared iron NPs with specific application and efficiency. Such a compact state of artwork

174 on green synthesized iron NPs has not been reported elsewhere.

175 Figure 1 gives an overall schematic presentation of the review article. The figure explains all

176 the possible green synthesis routes utilized to date for preparing iron nanoparticles along with

177 the new inclusion of their derivatives with specific applications. Moreover, the hazards and

178 toxicity of such green synthesized nanomaterials on living organisms have been discussed

179 when it comes to direct contact with soil and water. Future challenges have been outlined

180 with a suitable scope of improvement in preparation and proper management of iron-based

181 NPs have also been discussed.

182

183 2.1. Biocompatible reagents utilized for green synthesis

184 2.1.1. Biopolymers

185 The use of innocuous synthetic biocompatible substances for the preparation and stabilization

186 of magnetic nanoparticle polymer composites is well documented in the literature. He et al.

187 (2005) investigated starch stabilized bimetallic Fe/Pd nanoparticles in an aqueous medium.

188 Starch is a hydrophilic polymer with around 20% amylose content, is reported to significantly

189 improve the stability and dispersion of the iron NPs. Moreover, Gao et al. (2008) prepared a

190 magnetic Fe3O4 nanoparticle using sodium alginate biopolymer via a redox-based

191 hydrothermal method from ferric chloride hexahydrate and urea as precursors. The resultant

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192 nanoparticles were of uniform spherical morphology with a mean diameter of 27.2 nm. Jegan

193 et al. (2011) pioneered the synthesis of a magnetite (Fe3O4) agar nanocomposite via co-

194 precipitation of ferric and ferrous ions. The nanomaterial was well dispersed in the solution

195 with size 50-200 nm. In Table 1 various iron NPs synthesis utilizing numerous biocompatible

196 green reagents acting as reducing and capping agents are mentioned.

197

198 2.1.2. Ascorbic Acid

199 Nadagouda et al. (2007) studied the synthesis of Fe and Cu NP using Vitamin C (ascorbic

200 acid). The salts of the transition metals were readily reduced to their respective nanostructure

201 in aqueous ascorbic acid solution. Similarly, Savasari et al. (2015) synthesized zero-valent

202 iron (ZVI) nanoparticle in ascorbic acid medium. The individual particles also exhibited

203 spherical morphology, having an average particle size of 20-75 nm assembled in a chain

204 formation. Furthermore, ascorbic acid has stabilizing property and has been reported as a

205 functionalizing agent. Ascorbic acid was utilized by Sreeja et al. (2015) to prepare, coat, and

206 functionalize superparamagnetic iron oxide nanoparticles (SPION) with 5 nm diameter in a

207 stable dispersion for medical application. The size and shape of the SPION were determined

208 using a transmission electron microscope (TEM).

209

210 2.1.3. Amino Acid

211 Krishna et al. (2012) employed the wet chemical co-precipitation method to synthesize

212 amine-functionalized γ-Fe2O3 nanoparticles using L-Lysine (lys). The magnetization of γ-

213 Fe2O3/lys magnetic NPs was 40.6 emu g-1, with an average particle size of 14.5 nm.

214 Likewise, a study by Siskova et al. (2013) reported the production of ZVI using various

215 amino acids, namely L-glutamic acid, L-glutamine, L arginine, and L-cysteine along with the

216 effect of pH on ZVI yield.

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217 2.1.4. Haemoglobin and Myoglobin

218 Haemoglobin and myoglobin are naturally occurring biomolecules that contain iron. An

219 investigation by Sayyad et al. (2012) reported the synthesis of Fe NPs stabilized at room

220 temperature in a single-phase reduction reaction. The nanoparticles, thus produced, were

221 crystalline with a narrow size band of 2-5 nm. This protocol is vital for the production of bio-

222 compatible NP required for medical applications.

223

224 2.1.5. Sugar and Glucose

225 Utilizing D-glucose as a reducing agent, polycrystalline Fe3O4 nanoparticles were prepared

226 by Lu et al. (2010) with gluconic acid as a stabilizer and dispersing agent. The prepared NPs

227 were spherical in nature with an average diameter of 12.5 nm. Furthermore, glucose and

228 gluconic acid were utilized as capping agents by Sun et al. (2009) for fabricating magnetite

229 nanoparticles by the hydrothermal reduction process. Moreover, Yan et al. (2015) utilized

230 wood derived sugars and synthesized carbon encapsulated iron nanoparticles through the

231 hydrothermal carbonization process. Nano-spheres having a diameter of 100-150 nm were

232 formed with an iron core of size 10-25 nm capable of catalytically converting syngas into

233 liquid hydrocarbons.

234 Demir et al. (2014) studied the effect of lactose, mannose, galactose, maltose, and fructose

235 (different saccharides) on the synthesis of magnetite nanoparticles. All saccharides, except

236 fructose, exhibited dual-purpose applicability both as a reducing agent as well as a capping

237 agent. Since due to it’s non-reducing nature fructose acts as only a capping agent. The

238 particle size distribution of synthesized Fe3O4 NPs was in the range of 3.8-13.1 nm, and the

239 morphology of the nanoparticles was a combination of a slightly agglomerated sphere, rod,

240 and dendritic nanostructure. Superparamagnetic characteristics were exhibited by Fe3O4 NPs

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241 prepared with galactose, mannose, and maltose. Consequently, the saccharides capped

242 magnetite (Fe3O4) NPs can be used in biomedical imaging applications.

243

244 2.1.6. Synthetic Tannic and Gallic Acid

245 Both Tannic and Gallic acids are polyphenols and are considered as weak acids. They can be

246 obtained from both natural and synthetic sources. Herrera-Becerra et al. (2010) obtained a

247 well-dispersed spherical iron oxide (Fe2O3) nanoparticles of less than 10 nm diameter with

248 high crystallinity, using the synthetic tannic acid solution at pH 10 combined with ultra-

249 sonication. Similarly, Dorniani et al. (2012) prepared magnetic Fe NPs via the sonochemical

250 process and applied a coat of Chitosan and Gallic acid on the nanoparticles to form a core-

251 shell arrangement. XRD analysis confirmed that pure Fe3O4 nanoparticles were synthesized

252 having a cubic inverse spinel structure. The average particle size obtained was 11 nm with a

253 spherical structure. The synthesized magnetic NPs were found to be smaller than iron oxide-

254 chitosan-gallic acid (FCG) nanostructure, having an average diameter of 13nm. The prepared

255 nanoparticles showed a magnetic saturation of 26.07 emu g-1. The FCG NPs were

256 demonstrated to be capable of targeted drug delivery.

257

258 2.1.7. Polysaccharides

259 Polysaccharides are polymeric carbohydrates with glycosidic linkages. Chang et al. (2011)

260 synthesized superparamagnetic Fe3O4 nanoparticles using different polysaccharides, like

261 soluble starch, carboxymethyl cellulose sodium (CMC), and agar. The polysaccharides

262 enhanced the biocompatibility and biodegradability of Fe3O4 NPs apart from acting as a

263 capping and stabilizing agent. Starch stabilized nanoparticles were found to be 10 nm smaller

264 than CMC and agar. The saturation magnetization of agar-based NPs was found to be

265 20.43 emu g-1, whereas that of starch and CMC based NPS were found to be 36.16 emu g-1,

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266 and 35.75 emu g-1 respectively. Extremely small hysteresis loop and coercivity characteristics

267 were exhibited by the polysaccharide–Fe3O4 NPs.

268

269 2.1.8. Cellulose

270 Cellulose is the most abundant naturally occurring polymer in the world as it is an essential

271 structural component of the primary cell wall of all plants, various types of algae, and the

272 oomycetes (Klemm et al., 2005). Materials with high cellulosic content can be used to

273 prepare and stabilize Fe NPs. López-Téllez et al. (2013) extracted cellulosic components

274 from ethanol cured powdered Orange peel to prepare iron oxide nano-rods. The study

275 demonstrated the interaction between reduced metal ions and functional groups of cellulosic

276 components through electrostatic and weak van der Waals forces. Such interactions helped to

277 stabilize the nanoparticles after formation. The resultant nano-rods acted like an adsorbent

278 with an adsorption capacity of 7.44 mg g-1 for the removal of hexavalent chromium.

279

280 2.1.9. Clay

281 Clay is fine particles of withered rocks, mainly consist of phyllosilicate minerals, organic

282 matter, and variable amounts of water trapped in the mineral structure. Clay is intensively

283 used in making pottery, bricks, and tiles. It was suggested that clay can be utilized as

284 supporting materials for nanoparticles synthesis. Kalantari et al. (2014) used montmorillonite

285 (MMT) as a rigid support for the synthesis of magnetite Fe3O4 nanoparticles. The Fe3O4 NP

286 formation occurred in the interlayer space or on the surface of MMT, as confirmed with the

287 help of TEM images. The saturation magnetization was found to increase from 12 to 32.4

288 emu g-1 for the MMT/Fe3O4 composite with Fe3O4 content increasing from 1 to 12 wt%. In

289 another study, Ding et al. (2016) used a type of nano-clay smectite known as LAPONITE®

290 to prepare LAPONITE®-Fe3O4 nanoparticle (LAP-Fe3O4-NPs) via co-precipitation method

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291 for in-vivo magnetic resonance imaging of tumors. The LAP-Fe3O4-NPs is reported to have

292 excellent colloidal stability.

293

294 2.2. Synthesis by Microorganisms

295 The synthesis of nanoparticles based on microorganisms has gained substantial popularity

296 due to its benefits over traditional chemical protocols. The advantages are enlisted as

297 synthesis at ambient conditions, highly energy-efficient, production of limited toxic by-

298 products, naturally abundant and renewable precursors, robust and scaling-up is easy (Park et

299 al., 2016). Through extracellular or intracellular processes, microorganisms like fungi,

300 bacteria, and yeast can synthesize nanoparticles. These mechanisms involve the reduction of

301 metal ions by enzymes along with producing well-dispersed nanoparticles with lower average

302 particle size distribution. The nanoparticle surface gets incorporated with natural proteins,

303 tannins, and peptides as capping agents. Such surface coating provides better stability and

304 dispersion of nanoparticles by reducing agglomeration (Singh et al., 2016). The intracellular

305 mechanism involves diffusion of metal ions into the cell, and the enzymes resent reduce the

306 ions to form nanoparticles. Whereas, the extracellular mechanism involves the electrostatic

307 attraction of metal ions to the cell wall and carrying out the enzymatic reduction of metal

308 ions. Table 2 represents various microorganisms utilized by various research groups for

309 synthesizing iron and iron-based nanomaterials as reducing and capping agents.

310

311 2.2.1. Bacteria

312 In a study by Bharde et al. (2008) reported the use of Actinobacteria sp. under aerobic

313 conditions to prepare spherical iron oxide nanoparticles. In another study, the same bacterium

314 species was used to synthesize maghemite (γ-Fe2O3) and greigite (Fe3S4) by changing the

315 metal ion precursor (Bharde et al., 2005). Furthermore, it was established that Actinobacter

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316 sp. employed extracellular mechanism, involving iron reductase enzyme, to synthesize the

317 magnetic nanoparticles. Moon et al. (2010) in a similar study synthesized mono-dispersed,

318 sphere-shaped 13.1 nm magnetite Fe3O4 NPs under anaerobic conditions from FeOOH using

319 Thermoanaerobacter sp., an extremophile. The results suggest that, around $500/kg is the

320 estimated cost for commercial production of nano-magnetite (25–50 nm). In comparison to

321 chemical synthesis, a fraction of cost is required to produce 5-90 nm pure or substituted

322 magnetites through the microbial process. Sundaram et al. (2012) used Bacillus subtilis

323 strains isolated from rhizosphere soil to prepare Fe3O4 nanoparticles with spherical

324 morphology and 60-80 nm diameter. Elcey et al. (2014) isolated Thiobacillus thioparus from

325 iron ore mining zones to produce iron oxide NPs termed as magnetosomes, having magnetic

326 properties. Likewise, Mukherjee (2017) isolated and incubated Microbacterium marinilacus

327 from sediments of Damodar River in India to synthesize magnetosomes having a size

328 distribution from 32 to 48nm. Further the synthesized nanoparticles were tested against gram-

329 positive Bacillus cereus, and gram-negative Escherichia coli for antimicrobial studies,

330 through agar-plate-well-diffusion. In another study, Das et al. (2018) reported the synthesis of

331 maghemite nanoparticles, with an average diameter of 18 nm, in an anaerobic process, using

332 native hypersaline sulfate-reducing bacterial strain LS4, isolated and cultured from sediment

333 of saltpan, Goa, India.

334

335 2.2.2. Fungi

336 Fungi like Fusarium oxysporum and Verticillium sp., are exploited to prepare magnetic

337 nanoparticles of different sizes at ambient temperature via extracellular hydrolysis of the

338 anionic iron complexes. Bharde et al. (2006) reported the synthesis of magnetite

339 nanoparticles using fungi that showed the ferrimagnetic transition signature with negligible

340 spontaneous magnetization at low temperatures. Kaul et al. (2012) explored five different

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341 species of fungi, namely P. chlamydosporium, A. fumigates, A. wentii, C. lunata, and C.

342 globosum, to prepare iron nanoparticles. Pavani et al. (2013) isolated Aspergillus sp. from the

343 soil sample collected near the metal plating industry in Hyderabad, India, to synthesize Fe

344 NPs and consequently remove iron from wastewater. A study by Mohamed et al. (2015)

345 reported the formation of cubic Fe NPs of size 9 ± 3 nm, having antibacterial activity against

346 B. subtilis, E. coli, S. aureus, and P. aeruginosa, employing Alternaria alternata fungus in

347 lightless conditions. Sarkar et al. (2017) used Alternaria alternate, a phytopathogenic fungus

348 for the synthesis of iron oxide nanoparticles via an extracellular mechanism to study its

349 mechanical properties. Abdeen et al. (2016) explored the green processes to synthesize

350 magnetic Fe NPs and magnetite nanoparticles using Asperigillus niger via the intracellular

351 mechanism. Mazumdar et al. (2011) employed a filamentous fungus Pleurotus sp. to prepare

352 iron NPs and ferrous sulfate as a precursor. Characterization study of the nanoparticles was

353 carried out using TEM, SEM, and FTIR spectroscopy. Another method for synthesizing

354 spherical Fe NPs with particle size 10–24.6 nm, using Aspergillus oryzae TFR9 (fungus), was

355 proposed by Tarafdar et al. (2013) which found large application in the field of engineering,

356 agriculture, and biomedical.

357

358 2.2.3. Algae

359 Algae refer to a diverse group of photosynthetic eukaryotic organisms that are polyphyletic.

360 They consist of both unicellular and multicellular organisms. Mahdavi et al. (2013) used the

361 extract from the macroalgae, brown seaweed (Sargassum muticum) to synthesize iron oxide

362 (Fe3O4) nanoparticles with superparamagnetic characteristics and having an average particle

363 size of 18 ± 4 nm. X-ray diffraction (XRD) revealed that the nanoparticles were crystalline

364 and had a cubic morphology. The authors also reported that the functional bioactivity, i.e.,

365 antimicrobial activity of Fe3O4 NPs, prepared using the green synthesis route is comparably

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366 higher than the nanoparticles synthesized by conventional chemical methods. In a different

367 study carried out by Subramaniyam et al. (2015) reported the formation of spherical-shaped

368 Fe NPs ranging in size from 20–50 nm using soil microalgae, Chlorococcum sp., with an iron

369 chloride precursor. The study suggested that the amine and carbonyl functional groups on

370 polysaccharides and glycoproteins present in the algal cell were involved in the nanoparticle

371 formation and verified by FTIR analysis.

372

373 2.3. Plant mediated synthesis

374 The nanoparticles prepared from microorganisms have low dispersion, and the rate of

375 formation is slow as well when compared to plant-mediated synthesis (Dhillon et al., 2012).

376 A study by Kalaiarasi et al. (2010) reported that plant-based synthesis of metallic

377 nanoparticles is facile, most cost-efficient with high repeatability and reproducibility. It has

378 been well established that plant extracts are most suitable for producing highly stable metal

379 NPs at rapid rates and large quantities (Iravani, 2011). Plant-based nanomaterial synthesis is

380 preferred as a plethora of different naturally occurring, and robust biomolecular reducing

381 agents can be extracted from various plants (Mukunthan et al., 2012). Various herbs and

382 plants have a high concentration of antioxidants as active phytochemical constituents in

383 fruits, leaves, seeds, and stems. The production of nanomaterials from processes utilizing

384 botanical phytochemicals significantly reduces environmental pollution, thereby setting

385 benchmarks in economically feasible and ultra-sustainable clean and green technologies

386 (Zambre et al., 2012). Table 3 represents various plant parts utilized as a source for reducing

387 agent and capping agents in synthesizing iron and iron-based nanomaterials by several

388 researchers.

389

390 2.3.1 Synthesis by Leaf Extract

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391 Extracts from the leaves of various plants have been extensively studied for estimating their

392 polyphenolic contents along with other phytochemicals that have medicinal value.

393 Optimization of several parameters, like precursor moiety, solvent, ration of biomass to the

394 volume of solvent, amount of extract, pH, and temperature of the solution, needs to be carried

395 out during nanoparticle synthesis. Huang et al. (2015) investigated the factors that determine

396 the efficiency of Fe NPs prepared using green tea leaf extracts for the removal of Malachite

397 Green dye. The study explored the variation in the volume of tea extract, temperatures, and

398 pH of the solution to understand the optimum conditions and reported that increasing the

399 volume of extract and pH of the solution negatively impacted dye removal. However,

400 increasing temperature improved nanoparticle reactivity. A maximum dye degradation of

401 90.56% was obtained by the prepared Fe NPs.

402 Wang et al. (2014) prepared spheroidal 20-80 nm, Fe NPs employing extract from dried

403 eucalyptus leaf for the treatment of eutrophic wastewater. Through investigation it was

404 observed about 71.7% of total N and 84.5% of COD was removed from the wastewater.

405 Machado et al. (2013a) conducted a study in which leaf extracts were prepared from twenty-

406 six species of trees, namely Apple, Apricot, Avocado, Cherry, Eucalyptus, Kiwi, Lemon,

407 Mandarin, Medlar, Mulberry, Oak, Olive, Orange, Passion fruit, Peach, Pear, Pine,

408 Pomegranate, Plum, Quince, Raspberry, Strawberry, Tea-Black, Tea-Green, Vine, and

409 Walnut to evaluate the viability of each extract capable of reducing trivalent iron in aqueous

410 solution to form ZVI NPs of diameter 10-20 nm. Extracts of dried leaf contained higher

411 antioxidant content than fresh leaves, moreover, the most favorable extraction conditions

412 varied for each leaf. The leaf extract obtained from oak, pomegranate, and green tea at 80˚C

413 performed the best amongst all.

414 In another study, Machado et al. (2013b) explored the application of the green-synthesized

415 ZVI NPs to remove one of the prevalent anti-inflammatory drug, ibuprofen, from sandy soils.

17
416 About 54-66% removal was obtained when nano zero-valent iron (nZVI) NPs were utilized

417 in aqueous solution, whereas about 95% degradation was obtained when nZVI was utilized as

418 a catalyst in the Fenton process to remove ibuprofen. Fazlzadeh et al. (2017) prepared zero-

419 valent iron nanoparticles (ZVI NPs) of irregular morphology with an average particle size of

420 100 nm from three plant extracts, inclusive of Rosa damascene (RD), Thymus vulgaris (TV),

421 and Urtica dioica (UD) for the removal of hexavalent chromium in the aqueous phase.

422 Prasad et al. (2017a,b,c,d) conducted several studies to produce functionalized magnetic iron

423 oxide nanoparticles from leaf extracts of four plant species, namely pomegranate,

424 Murrayakoenigii, Moringa oleifera, and Pisum sativum to remove lead and organic dyes, like

425 Congo red, Malachite green and Methyl orange from wastewater. The particle size of the NPs

426 varied according to the plant extract. The authors reported the formation of spherical 12 nm

427 reduced graphene oxide – magnetic iron oxide nanocomposites from Murrayakoenigii leaf

428 extract. In contrast, rod-shaped Fe3O4 NPs with a uniform size distribution of 45-60 nm and a

429 high specific surface area of 14.6 m2g-1 were synthesized using the extract from pomegranate

430 leaf.

431 Khalil et al. (2017) utilized leaves of Sageretia thea for synthesizing tetragonal crystalline-

432 shaped iron oxide nanoparticles. The average nanoparticle size was found to be ~29 nm. The

433 bioactive components were extracted from pulverized plant leaves with deionized water

434 which further acted as a reducing agent. The synthesized nanoparticles were utilized for

435 studying the antibacterial effect against five human pathogenic bacterial strains, and out of

436 which Pseudomonas aeruginosa was found to be most susceptible.

437 Dried green tea was reported by Borja et al. (2015) for synthesizing nano zerovalent iron.

438 Green tea leaves composed of abundant polyphenols, and bioactive compounds that were

439 extracted through microwave assistance. The obtained nanoparticles were spherical in nature

440 which ranged from 8-23 nm. Ethanol was utilized as the extractant solvent for extracting the

18
441 bioactive components. Maximum nanoparticle yield was investigated to depend on factors

442 like precursor: plant extract ratio, plant material: solvent ratio, and plant extract delivery rate

443 into precursor solution.

444 Prabhakar et al. (2017) similarly reported the utilization of Eichhornia crassipes, Lantana

445 camara, and Mimosa pudica leaves for the synthesis of iron nanoparticles. Extract of

446 Eichhornia crassipes leaves synthesized spherical iron nanoparticles with an average particle

447 size of 20−60 nm. Irregular and aggregated quasi-spherical morphology of nanoparticles

448 were obtained from L. Camara and M. pudica leaf extract. The synthesized nanoparticles

449 were utilized for nitrate removal study and compared with chemically synthesized iron NPs.

450 Eichhornia crassipes, Lantana camara and Mimosa pudica mediated iron nanoparticles

451 showed 74.52%, 71.12%, and 65.23% of nitrate removal respectively, whereas 85.27%

452 removal was obtained for chemically synthesized iron NPs.

453 Coriandrum sativum leaves were utilized by Sathya et al. (2017a) for synthesizing iron oxide

454 nanoparticles. The synthesized nanoparticles were spherical in nature with an average size

455 ranging from 20−90 nm. Continuous stirring and ultrasonication techniques were utilized for

456 synthesis. Shorter synthesis time was obtained for the ultrasonication method, which was

457 further utilized for antimicrobial activity test. Micrococcus luteus and Staphylococcus aureus

458 show higher antimicrobial activity with a mean zone diameter of 22 mm and 18 mm

459 respectively.

460 Singh et al. (2017) synthesized uniform shaped 10±3nm iron oxide nanoparticles from green

461 tea leaves extract. The synthesized iron oxide nanoparticles were superparamagnetic in nature

462 with a magnetic saturation of 61emu g-1. Further the synthesized nanoparticle was applied for

463 methylene blue dye removal. A maximum adsorption capacity of 7.25 mg g-1 was obtained

464 with reaction kinetic following pseudo-second-order along with the Langmuir isotherm

465 model.

19
466 Neem leaf extract was utilized by Madhubala and Kalaivani (2017) for preparing iron

467 oxide nanoparticles supported on zinc oxide. The synthesized iron oxide nanoparticles were

468 found to be brick-like structures with an average particle size of 38 nm. Subsequently, the

469 synthesized iron oxide nanoparticles were mixed with zinc oxide through ultrasonication and

470 further autoclaved for 18 h at 200 °C. The nanocomposite prepared was found to be ellipsoid-

471 shaped with an average size ranging from 45 to 61 nm. Vero cells were used for studying the

472 toxicity of the Fe3O4@ZnO core-shell nanoparticles using MTT assay. Results show that with

473 a higher concentration of nanoparticles the cell viability decreases.

474 Harshiny et al. (2015) synthesized both chemically synthesized iron oxide nanoparticles

475 along with Amaranthus dubius leaf extract mediated nanoparticles. Various phytochemicals

476 present in the leaf extract such as flavonoids, phenols, and lysine generated higher zeta

477 potential -44 to-66mV with better stability than chemical synthesized iron nanoparticles.

478 Particle size analysis showed green synthesized NPs had particle range between 43-220nm,

479 whereas chemically synthesized nanoparticles varied between 70-700 nm. Morphological

480 analysis showed green synthesized nanoparticles had spherical structures with less

481 aggregation and particle size ranging from 60-300 nm. Furthermore, both synthesized

482 nanoparticles were utilized for the degradation of methyl orange (MO). The degradation

483 efficiency was found to be higher for chemical synthesized nanoparticles (90%), whereas

484 green synthesized nanoparticles had an efficiency of 81%, under the experimental condition

485 of 20 ppm MO, and 20 mg of NPs.

486 Murraya koenigii (curry leaves) leaf extract was utilized by Mohanraj et al. (2014) for

487 synthesizing iron oxide NPs. The synthesized nanoparticles were spherical in nature with

488 irregular aggregates having an average size of ~59nm. Lower particle size distribution was

489 observed due to capping agents from the extract which consist of alkaloids, flavonoids,

490 carbazole, and polyphenols. Moreover, the synthesized Fe NPs were utilized for hydrogen

20
491 production from glucose by Clostridium acetobutylicum NCIM 2337. During controlled

492 experiment 1.74±0.08 mol H2/mol glucose of hydrogen yield was observed, whereas 175

493 mgL-1 FeNPs mediated process achieved hydrogen yield of 2.33±0.09 mol H2/mol glucose.

494 Results conveyed that increase in hydrogen content from 34±0.8 to 52±0.8 % and hydrogen

495 production rate from 23 to 25.3 mLh-1, were obtained.

496 Senthil and Ramesh (2012) reported the antibacterial effect of Tridox procumbens leaf extract

497 mediated iron nanoparticles. Due to the higher carbohydrate content of the leaf it acted as an

498 efficient reducing agent. Morphological analysis showed irregular spherical shaped iron

499 oxide NPs with a rough surface. The crystalline structure of Fe3O4 was confirmed by XRD

500 analysis which confirmed the crystalline size ranging from 80-100 nm. Pseudomonas

501 aeruginosa was utilized for studying the antibacterial activity of green synthesized iron oxide

502 NPs using agar well diffusion method, and results showed its efficient antibacterial activity.

503 Another synthesis method was employed by Kiruba-Daniel et al. (2013), where Dodonaea

504 viscosa leaf extract was utilized to synthesis Fe NPs. During the experiment 5 mL of leaf

505 extracted was added to 10 mL of 10mM FeCl3 solution. The immediate color change

506 indicated the formation of nZVI nanoparticles. The synthesized nanoparticles were found to

507 be spherical in nature with an average diameter within 50-60 nm. The rich content of

508 polyphenols such as tannins, santin, saponins, and Pendleton in Dodonaea viscosa leaf

509 extract was found useful in synthesizing nanoparticles with stabilized capping.

510 Naseem & Farrukh (2015) reported the synthesis of Fe NPs using Lawsonia inermis (henna)

511 and Gardenia jasminoides leaf extract by a simple conventional heating method. The average

512 diameter of Fe NPs obtained using Lawsonia inermis leaf extract was 21nm, whereas an

513 average diameter of 32nm was obtained for Gardenia leaf extract mediated Fe NPs. Through

514 the experiment it was found that lawsone (2-hydroxy-1,4-naphthoquinone) was the main

515 component within henna, which consists of units such as p-benzoquinone, benzene, and

21
516 phenols. Hence such bioactive components synthesized better stabilized coated Fe NPs.

517 Henna synthesized Fe NPs were found to be agglomerated and had distorted hexagonal-like

518 shape. Whereas shattered rod-like Fe NPs were observed in agglomerated form using

519 Gardenia, leaf extract. The synthesized Fe NPs due to better bioactive coatings were found to

520 show better antibacterial activity against the human pathogens such as Escherichia coli and

521 Staphylococcus aureus.

522 Moreover, nano zero-valent iron (nZVI) NPs were synthesized by Kumar et al. (2015)

523 utilizing Emblica officinalis leaf extract. The high content of polyphenol and ascorbic acid

524 reduced the metal ions and further formed stabilizing agents over nZVINPs. Morphological

525 analysis revealed the spherical morphology of the nZVI NPs with an average diameter of

526 22.6 nm. Zeta potential value of -26.7 mV indicated moderate stabilization of nZVI NPs.

527 Further the nanoparticles were utilized for Pb(II) removal study. A maximum removal of

528 99% was obtained for 10ppm Pb (II) solution, at the end of 24h with an adsorbent dosage of

529 2ml L-1.

530 In a similar study, Wang et al. (2014) utilized Eucalyptus leaves and through very simple,

531 and efficient technique synthesized iron oxide NPs. Experimental studies involved mixing of

532 the leaf extract and 0.10 M FeSO4 in a volume ratio of 2:1. The solutional color change from

533 yellow to black signified the formation of iron oxide NPs. The NPs were found to be

534 spherical in nature with an average diameter in the range of 20-80 nm. Further the

535 synthesized iron NPs were utilized towards remediation of swine wastewater, and was found

536 to remove 71.7% of total N and 84.5% of COD.

537

538 2.3.2 Fruit extract

539 The reduction potential of various plant extracts plays an important role in the selection to be

540 utilized for nanoparticle synthesis. Researchers need to keep this in mind while exploring

22
541 various plant materials and need to choose extracts with most bioactive components for

542 efficient nanoparticle synthesis having better capping and stabilization and further it will lead

543 to their appropriate application in various fields. Mohan Kumar et al. (2013) utilized

544 Terminalia chebula fruit extract, a plant rich in polyphenolic content, and studied its redox

545 potential through Cyclic voltammetry. Sufficient reduction potential of 0.63 V was obtained

546 concerning Camellia sinensis (green tea), with a redox potential of 0.33 V. Morphology

547 analysis showed that chain like iron NPs were formed in the agglomerate form with an

548 average particle diameter of 80nm.

549 Saikia et al. (2017) reported the utilization of fruit extract and rice paddy husk for the

550 synthesis of silica-supported iron oxide nanocomposite. In the first step, Zanthoxylum rhetsa

551 fruit extract was employed for synthesizing iron-oxide nanoparticles through an iron (III)

552 solution as a precursor. Second step comprised of utilizing rice straw for preparing silica by

553 boiling the raw material with sodium hydroxide solution and sulphuric acid. Finally iron

554 oxide-silica composite was prepared by mixing the prepared raw materials and refluxed with

555 methanol. An average spherical particle diameter of 5-21nm was obtained. Further the

556 prepared Fe2O3@silica nanocomposite was utilized for ipso-hydroxylation of phenylboronic

557 acid to phenols. A maximum yield of 98% was obtained at the end of 120 min in the presence

558 of H2O2 as a catalyst.

559 Blueberries were utilized by Manquián-Cerda et al. (2017) as a source for green synthesis of

560 nZVI NPs. An agglomerated form was obtained with an average particle diameter of 52.4

561 nm. Ferric reducing antioxidant power along with the total phenolic content of the prepared

562 fruit extract showed the capability of forming better-stabilized iron NPs. The surface area of

563 the synthesized nanoparticle was found to be 70.7m2g-1. The synthesized NPs were utilized

564 for removing As (V) and were found to have a sorption capacity of 52.23±6.06 mg g-1.

23
565 Similarly, watermelon rinds were utilized by Prasad et al. (2015) for preparing Fe3O4

566 magnetic nanoparticles. Watermelon rinds were non-toxic and biodegradable in nature and

567 were found to be rich in polyphenol, acid derivatives, and protein. The presence of such

568 functional groups was confirmed through FTIR spectra. Morphological analysis conveyed

569 that the particles were crystalline in nature and spherical in shape. The average particle

570 diameter was found to be 20 nm. The magnetic nanoparticle showed a saturation

571 magnetization of 14.2emu g-1. The prepared magnetic Fe3O4 NPs were utilized for the

572 synthesis of 2-oxo-1,2,3,4-tetrahydropyrimidine compounds due to its catalytic property.

573 Experimental results showed at a catalyst loading of 5mmol highest yield of 94% was

574 obtained. Moreover, the magnetic nanoparticles had the advantage of being easily separated

575 from the process product formed by using a strong magnet and can be recycled further.

576

577 2.3.3 Seed extract

578 Researchers found it suitable to utilize the seeds from the fruit as a source of green reducing

579 solvent for preparing nanomaterials. Hence, Venkateswarlu et al. (2014) utilized Syzygium

580 cumini seed extract to prepared magnetic Fe3O4-NPs. The huge content of carbohydrates and

581 polyphenols helped in synthesizing Fe3O4 nanoparticles by simple reduction reaction acting

582 both as reducing and capping agent. The synthesized nanomaterials showed excellent

583 ferromagnetic behavior with a saturation magnetization value of 13.6emu g-1. However,

584 Raman spectroscopy characterization confirmed the formation of pure Fe3O4 without any

585 impurity. Morphological characteristics conveyed crystalline inverse spinel cubical structure

586 with an average particle diameter ranging from 9-20 nm. An average surface area of

587 3.517m2g-1 was obtained. Such prepared magnetic nanoparticle was believed to have wide

588 application in the field of biomedicine and separation aspects.

24
589 Moreover, Sajadi et al., 2016 utilized Silybum marianum L. seed extract to synthesize

590 copper supported iron oxide nanoparticles. Cu/Fe3O4 nanoparticles were synthesized by

591 mixing plant extract with a mixture containing iron (III) chloride and copper (II) chloride

592 solutions as precursors. The morphological analysis confirmed the synthesis of crystalline

593 spherical nanoparticles with an average particle diameter ranging from 8.5-60 nm. Further the

594 prepared nanomaterial was utilized for catalytic reduction of nitroarenes in an ethyl alcohol

595 solution in the presence of sodium borohydride as a catalyst. An experimental study reveals

596 that a maximum of 95% yield was obtained in the first cycle, whereas the yield reduced to

597 92% at the end of the fifth recycle. This suggests the practical reusability of the synthesized

598 nanomaterial in catalytic application purposes.

599

600 2.3.4 Stolon and root

601 A recent study suggests that few research works are available where the part of plants such as

602 stolon (potato), root, and gum have not been utilized for synthesizing Fe3O4-NPs. Buazar et

603 al., (2016) utilized starch-rich potato extract for synthesizing Fe3O4-NPs. The starch content

604 extract plays an effective role in reducing along with stabilizing the Fe3O4-NPs with capping

605 agents mainly consisting of carbohydrate groups. The oxidation of starch extract was started

606 with the addition of NaOH, which further produced electrons for producing Fe0

607 nanoparticles. The crystalline structure of magnetite NPs were formed with a face-centered

608 cubic shape having an average particle diameter of 40±2.2 nm. The superparamagnetic nature

609 of the nanoparticle produced a saturation magnetization of 28.78 emu g-1. Furthermore, the

610 synthesized magnetite NPs were utilized for catalytic degradation of organic methylene blue

611 contaminants at room temperature.

612 Niraimathee et al. (2016) by using Mimosa pudica root extract reported the production of

613 Fe3O4-NPs. The synthesized iron oxide NPs showed a sharp absorbance peak of 294 nm

25
614 through UV analysis. The superparamagnetic behavior of the Fe3O4-NPs was indicated by the

615 saturation magnetization value which was found to be ~55.40 emu g-1, considerably higher

616 than reported values. Morphological analysis showed that the synthesized NPs were spherical

617 in shape with an average particle diameter of 67 nm. The single-crystal domain of the

618 magnetic NPs was observed which signifies a single orientation of magnetic moment. The

619 magnetization value was found to decrease to zero from the plateau value on the removal of

620 the magnetic field.

621

622 2.3.5 Marine plant

623 Marine plant, usually known as seaweed or algae, was also considered to be utilized as a

624 source for synthesizing Fe3O4-NPs. Seaweed is found in abundant in South-East Asia which

625 is considered vital for marine organisms since it provides food and habitat. Due to the

626 presence of abundant lipids, minerals, and some vitamins it is considered as a source of food.

627 Moreover, due to the presence of various phytochemicals such as proteins, polyphenols, and

628 polysaccharides it has medicinal applicability too. Two major groups of marine algae can be

629 divided into microalgae and macroalgae. Mostly, macroalgae are used for nanoparticle

630 synthesis which plants like organisms. The presence of phytochemicals plays an important

631 role as metal-reducing agents and capping agents and generates better-stabilized

632 nanoparticles.

633 Madhavi et al. (2013) synthesized Fe3O4-NPs by utilizing brown seaweed (Sargassum

634 muticum). The synthesis of Fe3O4-NPs was described as by simple mixing of FeCl3 solution

635 and the extract of brown seaweed. After mixing a few minutes was required to initiate the

636 reaction and after then, Fe3O4-NPs was immediately produced. The reduction of Fe3+ ions

637 and surface coating for stabilization was carried out by the presence of sulfate, hydroxyl, and

638 aldehyde group in seaweed. The participation of the –OH group in the reaction was

26
639 confirmed by the reduction of the solution pH. Due to the oxidation of aldehyde groups to

640 carboxylic acid molecules by the sulphate group, hence it was suggested that the reduction of

641 metal ions was performed by sulfate ions. The synthesized Fe3O4-NPs were found to be

642 cubical in shape with an average diameter of 18±4 nm, with a saturation magnetization value

643 of 22.1 emu g-1, and negligible coercivity signifying superparamagnetic nature of Fe3O4-NPs.

644

645 2.3.6 Fruit peel

646 Fruit peel/skin protects the fruit’s flesh from the environment and insects. Fruit and vegetable

647 peels have been used as a natural fertilizer which is otherwise considered as waste in the

648 society. However, such agro-waste was utilized as a natural source and utilized for

649 nanoparticle synthesis. Intensive research work has been performed utilizing fruit peel extract

650 as a source for NPs synthesis. Venkateswarlu et al. (2015a, b) utilized Ananas comosus

651 (pineapple) and Citrullus lanatus (watermelon) fruit peel extract for synthesizing Fe3O4-NPs.

652 Such fruit peel extracts both generated spherical shaped Fe3O4-NPs with an average size of

653 ~17 nm. The pineapple peel extract mediated magnetic Fe3O4-NPs possessed a saturation

654 magnetization of 21.7emu g-1. Batch adsorption studies revealed that for 60 mgL-1 Cd(II)

655 solution about 0.1mgL-1 adsorbent dosage resulted in 96.1% removal at pH=6. The maximum

656 adsorption capacity of 49.1 mg g-1 was obtained. Similarly, for watermelon peel extract

657 mediated Fe3O4-NPs was found to possess magnetic property with 28.4emu g-1 of saturation

658 magnetization. The prepared magnetic iron oxide nanoparticle was utilized for Mercury (II)

659 removal. The experimental batch study confirmed about 97.8% removal of Hg (II) for 60

660 mgL-1 stock solution, when treated with 0.1 mgL-1 dosage at pH=7. Maximum adsorption

661 capacity of 52.1 mg g-1 was obtained for watermelon peel extract mediated Fe3O4-NPs. The

662 surface-modified Fe3O4-NPs with various ligands were found to be more effective in heavy

663 metal removal when compared with chemically synthesized iron oxide NPs. Such prepared

27
664 nanoparticles had the advantage of easily being separated from large-volume samples with

665 the help of an external magnetic field. Besides, easy recyclability without significantly

666 degrading its removal efficiency is the brighter side of such nanoparticles.

667 Wei et al. (2016b) utilized Citrus maxima peels as a reducing agent for synthesizing

668 iron oxide nanoparticles, which were further utilized for removing Cr(VI) from aqueous

669 solution. Such usage of fruit peel served for resource utilization along with waste

670 minimization, which otherwise would have been discarded as waste for landfills. The extract

671 was prepared by putting the peels with ultrapure water at a high temperature for 80 min. The

672 obtained extract was then centrifuged and membrane filtered. The obtained iron oxide NPs

673 were spherical in shape with an average diameter of 93.8nm. Batch experiments were

674 conducted using 100 mgL-1 of Cr(VI) solution using 2mL of the nanoparticle. Results

675 conveyed that 99.29% Cr(VI) removal was obtained at the end of 90 min.

676 Similarly Ehrampoush et al., 2015 synthesized magnetic iron oxide nanoparticles

677 utilizing tangerine peel extract. The synthesized nanoparticles were employed for Cd(II)

678 removal from aqueous solution. Morphological investigated revealed spherical-shaped

679 nanoparticles with an average diameter of 50nm. The highest removal of 89.6% was observed

680 at pH 4 for 20 mgL-1 Cd(II) concentration with 0.4 gL-1 adsorbent dosage, at the end of 90

681 min.

682

683 2.3.7 Gum

684 On exploring various new raw materials as a source for green synthesis, Horst et al. (2017)

685 carried out successful research utilizing gum Arabic (GA) to produce Fe3O4-NPs and further

686 investigated the mechanism of iron oxide NPs formation. Eventually the experimental study

687 suggests that mainly the gum polysaccharides and iron oxide nucleus went through

688 electrostatic and/or hydrophobic interactions for iron complex formation. The biopolymer

28
689 template bridging over the iron oxide nucleus was thought to be another route for complex

690 formation. The synthesis process happens to begin with an acidic nature due to the presence

691 of an iron salt precursor along with the polymer moieties of GA. Iron oxide nanoparticles

692 start precipitation on increasing the pH with the addition of NH4OH. Opposite charges

693 between the interacting molecules of iron oxide and GA prevailed in this situation.

694 Electrostatic interaction was thought to prevail which was better confirmed by FTIR data,

695 showing the interaction between the carboxylic group and the hydroxyl group of GA and iron

696 oxide NPs respectively via. hydrogen bonding. Steric interactions might occur at higher pH

697 since both the iron oxide NPs and polymer had negative charge over their surface, further GA

698 binding over the iron oxide NPs were resulted due to steric interactions occurring in such

699 condition. The charged functional groups were considered to be arranged in such a way that it

700 remains exposed over the surface. Hence the interaction between GA-Fe3O4 resulted in

701 hydrophilic nature, since the surface negatively charged groups showed electrostatic

702 repulsion between nanoparticles.

703

704 2.3.8. Other Plant materials and wastes

705 Beccera et al. (2007) utilized Medicago sativa (alfalfa) biomass as raw material for obtaining

706 biosynthesized iron oxide nanoparticles. Such utilization of waste biomass acted as a source

707 of recycling waste products. The obtained iron oxide nanoparticles had an average diameter

708 of <5 nm. Alfalfa biomass was first milled down to powder form and was then introduced to

709 the ferrous ammonium sulfate salt solution. In this study, the effect of pH condition was

710 determined, since it played a vital role as a size-limiting parameter during the synthesis of the

711 iron nanoparticle. Through experimental results it was found that at optimum pH=10 average

712 nanoparticle diameter was 3.6 nm. Moreover, a detailed characterization of the synthesized

713 nanoparticles was carried out. To determine the presence of Fe and O, characterization

29
714 technique EELS (electron energy loss spectroscopy) was adopted; however, HRTEM images

715 were deeply investigated for atomistic distribution along with FFT spectra to analyze the

716 structure and the corresponding iron oxide species. The clusters produced were mainly

717 consisted of magnetite and wustite types (fcc crystalline). In quantum dot scale such

718 structures were considered to be most stable for most of the materials. Both magnetites

719 coexisted along with wustite like clusters with smaller particle size at optimum conditions.

720 In different study sorghum bran was utilized by Njagi et al. (2011) to explore the

721 effect of abundant phenolic compounds present for synthesizing iron oxide nanoparticles.

722 The process started off utilizing 0.1 M FeCl3 solution and sorghum bran extract in a volume

723 ratio of 2:1 for 1h. The amorphous nature of the synthesized iron oxide nanoparticles was

724 noticed with an average spherical particle diameter of 40–50 nm. The synthesized iron oxide

725 nanoparticles were utilized for catalytic degradation of bromomethyl blue in the presence of

726 H2O2. Maximum degradation of 90% was achieved for 500 mgL-1 bromomethyl blue solution

727 with 0.66 mM iron nanoparticles dosage in the presence of 2% H2O2 within 30 min.

728 Depending on the substrate used for synthesis, the applications of Fe3O4-NPs might

729 vary as well. Natural wastes in our daily life such as rice straw, fruit and vegetable peels,

730 coffee, and waste residues possess substantial ingredients to be utilized for green synthesis of

731 nanoparticles due to the abundance of polyphenolic content they store. Lunge et al. (2014)

732 utilized tea residues for synthesizing Fe3O4-NPs and further employed it for Arsenic removal

733 studies. Experimental studies revealed that maximum adsorption capacity of 188.69 mg g-1

734 and 153.8 mg g-1 were obtained for arsenic (III) and arsenic (V) removal. In another study

735 Khataee et al. (2017) prepared coffee waste hydrochar loaded Fe3O4 nanoparticles and

736 applied for Acid Red 17 (azo dye) removal study. An effective surface area 34.7 m2g-1 was

737 obtained, and it was found that with an increase in initial dye concentration removal

738 efficiency decreases from 100 to 74%. The coexistence of NaCl and Na2SO4 salts decreased

30
739 the efficiency from 100 to 91%, and 100 to 85% respectively. Hence such studies prove that

740 natural residuals provide excellent surface stabilizing properties and can be utilized towards

741 various environmental applications.

742

743 2.4. Microwave assisted synthesis

744 Electromagnetic irradiation was utilized through microwave assisted synthesis where via

745 ionic and molecular conduction the precursor solvents and reducing agents were involved in

746 the reaction. Łuczak et al. (2016b) utilized this method where heating at the high temperature

747 employed within the sample directly. Since the requirement of energy is less hence

748 microwave irradiation provides rapid heating facilitating greener preparation of

749 nanoparticles. Such a process regulates uniform dispersion of nanoparticles, whereas

750 nucleation accelerates. Preparation of nanoparticles within minutes through such heating

751 methods with efficiency in control over size regulation, crystallinity, and dispersion are

752 considered as crucial factors for greener synthesis techniques (Amores et al., 2016; Ortega et

753 al., 2015). A list of various microwave assisted iron and iron-based nanomaterials

754 synthesized by various researchers are mentioned in Table 4.

755 Kombaiah et al. (2017a) in his studies showed that the microwave technique was

756 considerably more efficient and economical concerning other thermal techniques where

757 energy consumption and fabrication cost of nanoparticle synthesis are relatively lower.

758 Schneider et al. (2017) described the fast synthesis of alendronic acid (a reactive

759 biphosphate) coated magnetic nanoparticle through a green microwave assisted technique.

760 Synthesis of uniform nanoparticles at a heating temperature of 200°C was obtained having a

761 small particle size average. The process includes iron acetylacetonate in triethylene glycol

762 (TEG) as a precursor solution and reaction was maintained at the inert condition. TEG is

31
763 considered a green component due to its low isoelectric point, high viscosity, non-toxicity,

764 and high boiling point.

765 Low yield of nanoparticle generation has been one of the main drawbacks for its large scale

766 application due to limited reaction vessel dimension in microwave assisted synthesis. To

767 overcome such limitation Gonzalez-Moragas et al. (2015) utilized a multi-mode microwave

768 unit to scale-up the synthesis of multigram iron oxide nanoparticles. Firstly, utilizing Iron

769 (III) acetylacetonate (Fe(acac)3 in anhydrous benzyl alcohol as a precursor the nanoparticle

770 synthesis at laboratory-scale was carried out. Increment of temperature was performed from

771 room temperature to 180°C within 20 min and then at 300 W the process was cooled over 3

772 min. The average particle size analyzed through DLS and TEM characterization was obtained

773 around 3.8±0.8 nm. During scale-up, the process was carried out at higher microwave power

774 of 500W under optimized conditions and the heating temperature was kept maximum at

775 200°C. The reaction time was extended for the process which resulted in tenfold times scale

776 up. Utilizing the scale-up technique an excellent yield >80 % was achieved.

777 A magnetically recoverable nanocatalyst was successfully fabricated by Li et al.

778 (2016) utilizing the grafting technique of grafting silver nanoparticles on a carboxymethyl

779 cellulose support. The process was carried out under microwave irradiation which resulted in

780 impregnating magnetic iron oxide nanoparticles into the support and further utilized for

781 degradation of carbonyls to carboxylic acids by catalyzed hydrogenation in water.

782 Similarly, the synthesis of multifunctional magnetite nanoparticles impregnated on

783 polymer support was reported by Williams et al. (2016) via the microwave heating method.

784 The process was carried out at 150°C for 20 min. In this process FeCl3.6H2O and FeCl2.4H2O

785 were used as precursors and single-step synthesized aggregated, high crystalline

786 nanoparticles were generated with better aqueous stability. Moreover, a study showed that a

787 two-step microwave heating process could be utilized for the synthesis of magnetite and

32
788 maghemite nanoparticles. In such process iron (III) acetylacetonate was utilized as the

789 precursor, dissolved in a mixture of oleic acid and oleylamine acting as the stabilizing agent.

790 The average particle size of 5nm was obtained when different ratios of both stabilizers were

791 utilized for nanoparticle synthesis. Such a process was operated by heating the different

792 stabilizers obtained mixture at 120°C for 1h and another at 185°C for 1.5h respectively with

793 continuous stirring. Among the stabilizers oleic acid was found to have a greater effect in

794 minimizing agglomeration of nanoparticles formed (Lastovina et al., 2017).

795 Grindi et al. (2018) reported the synthesis of nanoparticles utilizing the combination

796 of the microwave with other thermal techniques like hydrothermal and solvothermal

797 methods. Liang et al. (2017) in his study stated the advantage of such a process in preparing

798 high crystalline nanoparticles due to the extremely fast heating rate at high temperatures.

799 Moreover, such methods apply to both polar and non-polar solvents. Grindi et al. (2018)

800 synthesized one-pot strontium hexaferrite nanoparticles, utilizing Iron (III) nitrate

801 nonahydrate and strontium nitrate as precursors utilizing the microwave assisted

802 hydrothermal technique. The process was carried out at an optimum irradiation condition

803 which was achieved at 200°C with a heating rate of 25 °C min-1 maintained for one hour. Due

804 to the high heating rate of microwave assisted irradiation in a shorter time, the crystallization

805 of prepared haematite was avoided, thus microwave assisted synthesis proves to be beneficial

806 in comparison with the classical hydrothermal process.

807 Mahmoud et al., 2016a reported that through microwave assisted techniques it was

808 possible to synthesize surface impregnated nanoparticles over or within polymeric supports

809 which enhances the dispersion and stability of nanoparticles. Such enhanced property was

810 hard to achieve for unsupported nanoparticles. Moreover, the synthesis of MCM-41 silica-

811 supported surface loaded with iron oxide nanoparticles was reported by Carrillo et al. (2013).

812 Tetraethylorthosilicate as a precursor and ammonium hydroxide solution as a surfactant was

33
813 utilized for synthesizing silica with helical mesoporous and well-ordered sphere structures

814 having a core-shell design. FeCl2.4H2O precursor based iron oxide nanoparticles were coated

815 over silica support through microwave assisted technique by heating the mixture containing

816 precursor and support at 200W for 15min. The average pore diameter of 3nm was obtained

817 for the nanoparticles incorporated over silica support through XRD analysis. Kombaiah et al.

818 (2017a,b) biosynthesized ceramic iron-based nanoparticles assisted by microwave-based

819 technique, such reactions utilized okra plant extracts as reducing agents. The study compares

820 the advantage of such a process over other conventional heating methods. Both microwave

821 assisted, and conventional techniques procured agglomerated, spherical nanoparticles of

822 cobalt and zinc ferrite nanoparticles respectively. Better optical and magnetic property

823 oriented nanoparticles were synthesized through a microwave heating method as compared to

824 conventional methods with lower average nanoparticle diameter.

825

826 2.5. Hydrothermal synthesis

827 The hydrothermal synthesis method involves utilizing the desired plant extract mixed along

828 with the required metal salt molarity. Then by utilizing a Teflon-lined autoclave the mixture

829 was allowed to react at different temperatures under atmospheric pressure for a fixed interval

830 of time. Such a process is beneficial since it requires a lower temperature to produce

831 crystalline materials from precursor than calcination.

832 Ahmmad et al. (2013) using green tea (Camellia sinensis) leaf extract, through the

833 hydrothermal synthesis method successfully prepared highly pure hematite α-Fe2O3

834 nanoparticles. TEM characterization indicated spherical nanoparticles with an average

835 diameter of 60 nm and highly porous in nature. The synthesized hematite nanoparticles were

836 found to have a higher surface area (22.5 m2g-1) and enhanced photocatalytic activity as

837 compared to commercially available hematite nanoparticles. The surface area was nearly four

34
838 times higher, whereas the photocatalytic activity was found nearly two times higher than

839 commercially available ones.

840 Moreover, Fe3O4 nanoparticles were synthesized using the aloe vera plant extract by the

841 hydrothermal method (Phumying et al., 2012). In the process ferric acetylacetonate

842 (Fe(C5H8O2)3) acted as the precursor. Crystalline spherical nanoparticles with an average

843 diameter 6-30 nm were obtained as revealed through TEM characterization. Detailed study

844 through XRD and HR-TEM conveys that the Fe3O4 nanoparticles had inverse cubic spinel

845 morphology with the absence of phase impurities. Superparamagnetic nature was confirmed

846 based on the coercivity experiment. The study shows that magnetic nanoparticles with

847 enhanced crystallinity and saturation magnetization could be procured by increasing the

848 reaction temperature and time.

849

850 3. Green synthesis of iron-based bimetallic nanoparticles

851 Mondal and Purkait (2019) synthesized iron-aluminum nanocomposite utilizing clove extract

852 as the reducing agent. The synthesized nanocomposite was found to be coated with various

853 groups such as –OH, -COOH and -C=O obtained from the bioactive components of clove

854 extract, confirmed by FTIR analysis. Morphological analysis showed an irregular spindle-like

855 structure (Figure 2). The structure confirmed the presence of carbon coating which was due

856 to the presence of several polyphenolic and flavonoid components present in clove extract.

857 The average particle size of the nanocomposite was found to vary with pH. With an increase

858 in pH from 3 to 12, the average size decreased from 148.9 nm to 81.6 nm. Furthermore, the

859 prepared Fe-Al nanocomposite was utilized for fluoride removal applications. Maximum

860 adsorption capacity of 42.95 mg g-1 with 82.1% fluoride removal was obtained at 25ºC for

861 1.25 gL-1 nanocomposite dosage. The reaction followed pseudo-second-order kinetics with a

862 multistage diffusion control process. It showed a very good efficiency of 83% fluoride

35
863 removal for fluoride contaminated water collected from various districts of Assam, India.

864 Various coexisting ions such as Cl-, HCO3-, SO4-2 were found to decrease the fluoride

865 adsorption, with chloride affecting the most ~31.8%. The fluoride removal mechanism was

866 reported to be due to the ion exchange mechanism, where the surface phenolic –OH groups

867 of the nanocomposite were replaced by the fluoride ions in the aqueous solution (Figure 3).

868 The Figure 3a shows that the bending and stretching mode of vibrations for –OH diminishes

869 after fluoride adsorption. Figure 3b confirms that fluoride due to its higher electro negativity

870 replaces the polyphenolic –OH groups of the clove extract from the surface. The studies

871 revealed that on such green synthesized Fe-Al nanocomposite proved to be a better adsorbent

872 towards removing fluoride from water sample collected from various districts of India-

873 Assam (82.6 % removal), and Manipur (83% removal).

874 Similarly for synthesizing bimetallic Fe/Ni nanocomposite Weng et al. (2017) utilized

875 methanol extract of a eucalyptus leaf as the reducing agent. GCMS analysis of extracts was

876 carried out for identifying the various components present. Mostly alkanes, phenols,

877 aldehydes, and amines were found in the majority, and suggest that those bioactive

878 components acted as reducing and capping agent. The prepared bimetallic nanocomposite

879 was utilized for the degradation of methyl orange (MO). Experiments were carried out for 10

880 mgL-1 MO with an adsorbent dosage of 0.5 gL-1 and were observed a maximum degradation

881 of 29.2% using green synthesized Fe NPs, and about 99.6% degradation using Fe/Ni NPs

882 following pseudo-first-order kinetics.

883

884 4. Environmental application of green synthesized iron-based nanoparticles

885 4.1. Degradation of dyes

886 For synthesizing iron nanoparticles Hoag et al. (2009) employed green tea and utilized for

887 catalyzing hydrogen peroxide for bromomethyl blue degradation in aqueous solution. It was

36
888 concluded from the study that concerning Fe-EDTA and Fe-EDDS, enhanced catalytic

889 activity was produced by such nanoscale zero-valent iron obtained by green synthesis (nZVI).

890 With an increasing dosage of green synthesized nZVI, the degradation of bromomethyl blue

891 was found to increase due to enhanced catalyzation of hydrogen peroxide. Several studies

892 related to dye removal application utilizing various green synthesized iron-based

893 nanomaterials are reported in Table 5.

894 Similarly, Njagi et al. (2011) synthesized iron nanoparticles utilizing sorghum bran

895 extracts and studied its catalytic activity towards degradation of dye bromothymol blue.

896 Degradation of bromomethyl blue in the presence of iron nanoparticles and H2O2 dictates that

897 the synthesized nanoparticles produced free radicals from H2O2 which catalyzed the

898 degradation reaction for bromothymol blue. The rate of reaction depends on the catalysis of

899 H2O2 which ultimately enhanced the degradation rate of bromothymol blue.

900 In another report, Shahwan et al. (2011) synthesized nZVI nanoparticles utilizing green tea

901 extract. The as-synthesized nZVI was applied towards the degradation of methylene blue

902 (MB) and methylene orange (MO) dyes. With an adsorbent dosage of 10-200 mgL-1 nearly

903 100% removal of methylene blue (MB) and methyl orange (MO) was achieved. From an

904 experimental study it was observed that MB removal was achieved faster than MO dye. In

905 the first 5 min, about 80% of MB was removed whereas, after 1h MO dye attained 80%

906 removal. Complete removal of MB and MO dye was achieved after 200 min and 350 min

907 respectively. Studies convey that iron nanoparticles synthesized through green route are

908 comparatively more effective than chemically reduced nanoparticles for acting as Fenton-like

909 catalyst.

910 Oolong tea extract was utilized for the synthesis of iron nanoparticles by Huang et al.

911 (2013). The nanoparticles were employed for malachite green (MG) degradation. The

912 experimental results conveyed that the polyphenolic content in oolong tea extract served the

37
913 purpose of both reducing and capping agents during the synthesis. The high polyphenolic

914 content paved the way for lesser aggregation along with enhanced reactivity of the

915 synthesized nanoparticles. On application towards 50 mgL-1 MG solution the nanoparticles

916 resulted in 75.5% dye removal.

917 A similar study was carried out by Kuang et al. (2013) where three different tea

918 extracts were used such as oolong tea (OT), green tea (GT), and black tea (BT) separately for

919 iron nanoparticles synthesis. Furthermore, the synthesized nanoparticles were utilized as a

920 catalyst for the degradation of monochlorobenzene (MCB) for Fenton-like oxidation. The

921 highest polyphenol content of the chosen extracts resulted in better synthesized Fe NPs for

922 enhanced degradation purposes. GT based iron NPs resulted in 69% MCB degradation,

923 whereas OT and BT based nanoparticles resulted in 53% and 39% MCB degradation in 180

924 min.

925 Wang (2013) for combating dye degradation synthesized nanoparticles involving

926 iron-polyphenol complex. Eucalyptus leaves were utilized as reducing and capping agents,

927 and the synthesized nanoparticles were employed against Acid black 194 dye for the

928 adsorption-flocculation test. The adsorption capacity of the synthesized nanoparticles was

929 found to be 1.6g Acid black 194 per gram of nanoparticles at 25ºC. Moreover, Wang et al.

930 (2014) utilized three different plant sources i.e., E. tereticornis, M. nesophila, and R.

931 officinalis for synthesizing Fe NPs and were utilized towards decolorization of Acid black

932 dye. The extract of E. tereticornis generated Fe NPs showed 100% removal of Acid black

933 dyealong with 87% removal of total organic carbon (TOC). Such Fe NPs showed better

934 catalytic properties as compared to the others. The as-synthesized nanoparticles showed a

935 lower average diameter with better dispersion property in an aqueous medium.

936 In another work, Luo et al. (2014) studied the removal of acid orange II dye by

937 utilizing iron nanoparticles synthesized by grape leaf extract. The study revealed the

38
938 reactivity of plant-mediated Fe-NPs was better than the Fe-NPs synthesized from methanolic

939 and aqueous extract of grape leaves. Hence, under various experimental conditions plant-

940 mediated Fe nanoparticles proved to be more effective for catalytic degradation of dyes. Plant

941 mediated Fe-NPs proved to be more suitable for Fenton-like reaction compared to the

942 conventional Fenton reaction, where it acts as a Fenton catalyst with H2O2.

943 Moreover, further research investigated iron oxide nanoparticle synthesis utilizing

944 Pisum sativum peels (Prasad et al., 2017d). Results show that at the optimum condition of pH

945 6, removal of 96% of the dye was attained within one hour with an adsorbent dosage of 0.3

946 gL-1. Similarly Moringa oleifera leaves were utilized by Prasad et al. (2017c) for synthesizing

947 iron oxide nanoparticles supported on nickel composite for degradation study of Malachite

948 green dye. On analyzing the samples after 25 min of reaction through UV-Vis Spectrometer,

949 it was noticed that 90 % of the organic dye was removed.

950 Singh et al. (2017) investigated the removal of methylene blue dye utilizing green tea

951 mediated synthesized iron oxide nanoparticles. The results showed that the degradation

952 efficiency of 95% was achieved within 16 min. Moreover, iron oxide nanoparticles

953 successfully synthesized by utilizing Syzygium cumini leaf extract showed 99% removal of

954 Blue 235 dye within 4h of reaction (Natarajan and Ponnaiah, 2017). Ahmed et al. (2014a,b)

955 utilized microwave and microwave-hydrothermal techniques for synthesizing hematite

956 quantum dots, and nanorods respectively. The prepared nanomaterials were utilized for the

957 degradation of an organic dye and further the results were compared with commercially

958 available hematite. The average particle size of ionic-liquid synthesized quantum dots, and

959 nanorods were found to be ~10 nm, and 60 nm respectively. Microwave assisted quantum

960 dots due to its higher surface area were found to have better catalytic efficiency as compared

961 to synthesized nanorods, and commercially available hematite. It was observed from

962 literature that the chemically synthesized Au-Fe3O4-NPs supported on activated carbon (AC)

39
963 showed better removal efficiency at nearly 4 min for R123 and DSB dyes with maximum

964 adsorption capacity of 71.46 and 76.38 mg g−1 respectively under ultrasound assisted process

965 (Bagheri et al., 2018). Moreover, Dastkhoon et al. (2017) prepared Ni doped Ferric Oxy-

966 hydroxide FeO(OH) nanowires supported on AC for removing Indigo Carmine (IC) and

967 Safranin-O (SO) dyes. The maximum adsorption capacities for IC and SO were found to be

968 37.85 mg g-1 and 29.09 mg g-1for IC and SO, respectively at pH 5.0. Chemically prepared

969 iron based nanocomposites also proved to be efficient adsorbent for dye removal applications

970 under small reaction time.

971

972 4.2. Removal of heavy metals

973 Rao et al. (2013) reported the removal of Chromium (VI) utilizing bio Fe0/Fe3O4

974 nanocomposite and yeast cells. Such prepared nanocomposite proved to be good bio-sorbents

975 for Cr (VI) removal. The sorption capacity of the iron oxide modified yeast cells enhanced by

976 three times when compared to the unmodified yeast cells. The better adsorption capacity of

977 modified adsorbent ~186.32 mg g-1 was reported for 1000 mgL-1 of Cr (VI) solution under

978 optimum conditions when compared to unmodified adsorbent with adsorption capacity

979 137.31 mg g-1. Moreover, many research studies related to heavy metal removal applications

980 through various green synthesized iron-based nanomaterials are reported in Table 6.

981 Stable and efficient green synthesized nZVI were reported by Savasari et al. (2015)

982 obtained utilizing ascorbic acid. The prepared nZVI was employed for the reduction of Cd

983 (II) by adsorption studies. Mystrioti et al. (2014, 2015) reported in two different studies, the

984 preparation of nZVI in colloidal suspension utilizing green tea extract with polyphenol

985 coating. The efficiency of synthesized nZVI for chromium removal was studied in

986 groundwater. The average particle diameter of the green synthesized nZVI was found to be

987 5–10 nm and was effective in removing Cr(VI) from groundwater passing through permeable

40
 988 soil bed. Polyphenolic coating acted as both reducing and capping agent for the prepared

989 nZVI. To analyze the effect of contact time on the reduction of Cr (VI), different flow rates

990 were maintained in the column test study. The study shows, by increasing the contact time

991 the reducing efficiency of Cr (VI) enhances. Chromium is generally insoluble when found in

992 precipitated form as confirmed by the leaching test. Moreover, Cr (VI) in the precipitated

993 form found in test soil was in the range of 280-890 mg kg-1 of soil, whereas less than 1.4 mg

994 kg-1 of the soluble Cr was obtained in the soil. Since, stable nanoparticles are known to be

995 useful for groundwater remediation purpose hence nZVI serves this purpose quite well

996 (Mystrioti et al. 2014). Ponder et al. (2000) reported that by utilizing green synthesized iron

997 nanoparticles heavy metals get removed via redox reaction, and surface adsorption process.

998 The main factor which influences the reactivity of iron nanoparticles depends on the variable

999 oxidation states of iron. Tang and Lo (2013) reported that with a varying oxidation state of

1000 any metal the chemical characteristics along with the mechanism of the reaction between

1001 metal and contaminants will vary.

1002 Xiao et al. (2016) in a recent study synthesized iron nanoparticles from various plant

1003 leaf extracts and utilized for chromium removal. The selected plants showed good antioxidant

1004 properties due to the reduction of potential activity. The study uses S. jambos (L.) Alston

1005 (SJA) extract, Oolong tea (OT) extract, and A. moluccana (L.) Wild (AMW) extract. The

1006 antioxidant property of the leaf extracts mentioned is in decreasing order respectively.

1007 Results showed that 1mL of SJA-Fe NPs solution due to its highest antioxidant property

1008 removed Cr (VI) to 91.9% in the first 5 min, whereas complete removal was attained after 60

1009 min of reaction. The average particle diameter of the SJA-Fe NPs was ~5nm and was found

1010 to be amorphous in nature.

1011 The similar study involved Syzygium jambos (L.) Alston leaf extract was utilized by

1012 Xiao et al. (2017) for synthesizing nZVI to remove hexavalent chromium ions from aqueous

41
1013 solution. Factors such as nanoparticle dosage, solution pH, temperature, and Cr(VI) initial

1014 concentration influences the removal efficiency of chromium. The availability of active sites

1015 increases with increasing nanoparticle dosage for a fixed concentration of chromium, which

1016 in turn enhances the removal rate. Results convey that removal efficiency got enhanced by

1017 15% with temperature increasing from 20ºC to 60ºC. Due to electrostatic attraction between

1018 protonated nanoparticle surface and hexavalent chromium at acidic pH, hence Chromium

1019 (VI) removal was found favorable at low pH. The experimental results conveyed that at

1020 optimum pH of 5.5, with 0.5mL of synthesized nanoparticles, and initial chromium

1021 concentration of 50 mgL-1 complete removal of chromium was obtained. Similarly, Sebastian

1022 et al. (2018) developed magnetite nanoparticle using coconut husk extract and applied for the

1023 adsorption of calcium and cadmium present in low levels. Results confirmed that cadmium

1024 and calcium removal was more than 40% and 50% respectively at the end of 120 min.

1025 Experiments suggest that maximum removal was achieved by 30min and reached equilibrium

1026 after that. The initial concentration of metal ions was fixed at 50 mgL-1, and it was noticed

1027 that with increasing adsorbent dosage adsorption rate enhanced until attaining saturation.

1028 Tangerine peel extract was utilized by Ehrampoush et al. (2015) for preparing iron

1029 oxide nanoparticles and utilized for removing trace amount cadmium present in water bodies.

1030 Experimental studies revealed maximum removal of 90% was achieved at pH 4 within 90

1031 min. Similarly, to remove Pb(II) from water, graphene oxide-based iron oxide nanocomposite

1032 was synthesized by Prasad et al. (2017b). Experimental results report removing Pb (II) about

1033 96% at pH 5, where rapid adsorption occurred within 40min and equilibrium reached at

1034 80min. The adsorption study was found to be pH-dependent, and the adsorbents were

1035 reusable by treating with definite concentration acid to desorb Pb(II) ions.

1036 Studies have shown that by utilizing Lantana camara fruit extract superparamagnetic

1037 iron oxide nanoparticles were synthesized for the removal of Ni(II) ions from aqueous

42
1038 solution (Nithya et al., 2017). Experimental batch studies were performed to optimize the

1039 influencing parameters on adsorption processes such as stock solution concentration,

1040 adsorbent dosage, pH, temperature, and contact time. Due to the electrostatic attraction

1041 phenomenon between adsorbate and adsorbent at high pH, the adsorption process enhanced.

1042 An optimum pH 6 was chosen for the process since at high basicity nickel tends to form

1043 hydroxides. Higher pH involves the presence of negative ions such as hydroxides and

1044 carboxyl which indulges the better adsorption for nickel. Similarly, at lower pH desorption

1045 occurs distorting the electrostatic balance between adsorbate and adsorbent. Sorption capacity

1046 enhances with increasing nickel ion concentration in the solution, but on the other hand the

1047 adsorption efficiency decreases due to lack of active sites. Due to greater surface area

1048 possessed by smaller sized adsorbents, adsorption efficiency increases with a smaller particle

1049 size of nanoparticles.

1050 In a report synthesis of magnetic iron oxide coated with amino-silica support was

1051 performed by Mahmoud et al. (2016b) utilizing a modified co-precipitation method.

1052 Adsorption of heavy metals ions like Pb2+, Cu2+, Cd2+, and Hg2+ was done by utilizing the

1053 synthesized nanocomposite using microwave heating. Microwave heating was performed

1054 while keeping the dissolved metal ion, and nanocomposite in contact for a short time.

1055 Sorption process of the metal ion occurs on the nanocomposite. Within 15 sec among the

1056 other ions, Pb2+ showed better sorption capacity. Experimental results suggest that an

1057 increase in temperature desorption of metals didn’t occur.

1058

1059 4.3. Wastewater treatment

1060 Transportation of iron nanoparticles synthesized from green tea extract was investigated by

1061 Chrysochoou et al. (2012) by utilizing media such as refined silica sand, and aluminum

1062 hydroxide coated sand. A rapid decline in effluent pH was noticed from 8.5 to 2 on injecting

43
1063 green synthesized nZVI. Such a phenomenon was denoted due to the presence of Fe3+ as

1064 residuary discharge in the solution, along with hydrolysis reactions. Redox potential was

1065 observed to increase from 150 mV to 550 mV, instead of the presence of Fe0 in the

1066 synthesized nanoparticles. Such behavior was denoted as a result of polyphenol oxidation

1067 available in green tea, which denotes an indication of green synthesized nZVI transportation

1068 through the medium.

1069 On a similar note He et al. (2005) investigated the degradation of trichloroethylene

1070 (TCE) utilizing bimetallic Fe/Pd nanoparticles synthesized by starch. Less agglomerated

1071 starch coated nanoparticles were synthesized which proved to be effective in TCE

1072 degradation as compared to those synthesized without stabilizer. Maximum degradation of

1073 98% was obtained within 1h when the reaction was carried out with nanoparticle dosage of

1074 0.1 gL-1. There are numerous studies related to wastewater treatment and pollutant removal

1075 from wastewater by utilizing various green synthesized iron and iron-based nanomaterials

1076 shown in Table 7. The performance of green synthesized iron nanoparticle with that of

1077 nonferrous nanoparticles are also compared and shown in the table

1078 Wang et al. (2014) investigated the treatment of eutrophic wastewater by employing

1079 iron nanoparticles biosynthesized using eucalyptus leaf extract. Such an investigation first

1080 reported the treatment of such wastewater using green synthesized nanoparticle. Fe NPs

1081 synthesized from eucalyptus leaf extract was found to have smaller average particle size as

1082 compared to those synthesized by chemical synthesis. Removal percentage of total nitrogen,

1083 total phosphorus, and COD was studied after 21 days and was found to 71.7%, 30.4%, and

1084 84.5% respectively. The absence of precipitating agents such as calcium, or aluminum results

1085 in very low phosphorus removal.

1086 Wang et al. (2014) have reported the removal of nitrate from wastewater by iron oxide

1087 nanoparticles synthesized utilizing green tea and eucalyptus leaves separately. Both the

44
1088 synthesis formed spheroidal particles. The study reports a comparison of nitrate removal from

1089 iron nanoparticles synthesized by plant materials and chemical synthesis. Results showed

1090 about 59.7% and 41.4% nitrate removal were obtained utilizing green tea and eucalyptus

1091 mediated NPs respectively, whereas nZVI and Fe3O4 nanoparticles provided 87.6% and

1092 11.7% removal respectively. Green synthesized nanoparticles were more stable and preferred

1093 over nZVI despite its higher removal efficiency. Experiments were also conducted to

1094 compare the reactivity efficiency of the green synthesized Fe NPs and nZVI after 2 months of

1095 exposure. Reactivity efficiency of the green synthesized NPs were found to be retained at

1096 51.7% (green tea) and 40.7% (eucalyptus), whereas the efficacy by 2.1 fold to 45.4% for

1097 nZVI prepared by chemical synthesis.

1098 Groiss et al. (2017) reported the synthesis of iron oxide nanoparticles utilizing

1099 Cynometra ramiflora leaf extract and employed it for degradation of Rhodamine B (a

1100 carcinogen) by Fenton-like catalytic process in the presence of hydrogen peroxide. The

1101 degradation was found to be optimum within 15 min when 1.11 mM nanoparticles were

1102 utilized with 2% H2O2. Such a process was found to produce minimum sludge and thus

1103 advantageous to other Fenton-catalyzed processes.

1104 Withania coagulans was reported by Atarod et al. (2016) for synthesizing reduced

1105 graphene oxide/iron oxide-based palladium nanoparticles (Pd/RGO/Fe3O4). On reacting

1106 graphene oxide suspension with Withania coagulans leaves extracts along with ferric

1107 chloride solution, reduced graphene oxide-based iron-oxide nanocomposite was synthesized.

1108 To separate the RGO/Fe3O4 nanocomposite, the mixture was stirred, refluxed, and

1109 magnetically separated. Finally, to obtain Pd/RGO/Fe3O4 nanocomposite with an average

1110 particle size of 7−13 nm, palladium chloride was very carefully introduced into the as-

1111 prepared nanocomposite. The catalytic degradation effect of the prepared nanocomposite

1112 towards 4- nitrophenol in the presence of sodium borohydride was studied. Fading of yellow

45
1113 color was obtained during the reaction in the presence of nanocatalyst while forming 4-

1114 aminophenol. Whereas, no appreciable reduction was observed in the absence of the

1115 nanocatalyst. The study further conveys that Pd/RGO/Fe3O4 nanocomposite had better

1116 catalytic properties compared to RGO/Fe3O4 nanocomposite, which indicates the enhancing

1117 property of palladium nanoparticles.

1118 Wang et al., 2014 reported the removal study of total nitrogen, phosphorus, and COD from

1119 poultry breeding wastewater utilizing iron nanoparticles synthesized from eucalyptus leaves

1120 extract. The study shows that maximum removal of 71.7%, 30.4%, and 84.5% was obtained

1121 for total nitrogen, phosphorus, and COD respectively. Similarly, iron nanoparticles were

1122 synthesized by Wei et al. (2016b) utilizing Citrus maxima peel extracts for the removal of Cr

1123 (VI). Optimum citrus maxima peel extract: Iron (III) solution of 1:3 was maintained to

1124 synthesize better property iron nanoparticles which resulted in complete Cr(VI) removal

1125 within 90 min. Similarly, removal of Cr(VI) was also reported by Fazlzadeh et al. (2017)

1126 using iron nanoparticles synthesized from three different plant extracts Rosa damascene,

1127 (RD), Thymus vulgaris (TV), and Urtica dioica (UD). Experimental studies show greater

1128 than 90% efficiency was obtained within 10 min. Shanker et al., 2017 reported the

1129 degradation of eight selected priority polycyclic aromatic hydrocarbons (PAHs) in soil and

1130 water. Initial such high molecular weight PAHs vary from 50−250 mg L-1. The optimum

1131 experimental condition at pH of 7.0 resulted in 80–90% degradation of anthracene and

1132 phenanthrene within 48 h.

1133 Mehrotra et al. (2017) employed protein capped zero-valent iron NPs synthesized using

1134 yeast, for complete degradation of organophosphorus insecticide (Dichlorvos). At an

1135 optimum experimental condition with 2000 mgL-1 nanoparticles dosage, 1000μl H2O2 a

1136 maximum degradation of 99.9% was obtained within 60 min of reaction.

46
1137 Moreover, copper supported iron oxide nanocatalyst was synthesized by Sajadi et al. (2016)

1138 for studying the reduction of nitroarenes in wastewater. The degradation process was

1139 employed with sodium borohydride acting as a reducing agent. Experimental studies

1140 conveyed the fact that the prepared nanocatalyst along with NaBH4 obtained a maximum

1141 degradation of 90% within 90 min, whereas no degradation was observed in the presence of

1142 NaBH4 alone.

1143 Machado et al., 2017 reported the synthesis of nanoscale zerovalent iron utilizing oak leaves

1144 to extract for studying the degradation of a common antibiotic, amoxicillin in wastewater.

1145 With an optimum nanoparticle to analyte ratio of 15:1, about 100% degradation was observed

1146 in aqueous solution within 95min of reaction time. Whereas, about 1800h was required at the

1147 same condition for 53% degradation to occur in soil, due to nanoparticle soil matrix

1148 interaction.

1149 Al-Ruqeishi et al. (2016) reported the treatment of high viscous oil utilizing iron oxide

1150 nanorods synthesized using mango tree leaves extract. Experimental study involved the

1151 blending of iron oxide nanoparticles with heavy crude oil and microwaved for the 80s. An

1152 appreciable reduction in viscosity up to 50% was obtained with 0.6 gL-1 nanorods at 30-50ºC.

1153 He et al. (2014) synthesized surfactant (CTAB) coated silica-stabilized iron oxide

1154 nanoparticles for microextraction of luteolin, quercetin, and kaempferol flavonoids. The

1155 process was performed utilizing the synthesized nanoparticles and ionic liquid (C16mimBr) at

1156 room temperature. Results signified that CTAB-coated iron oxide nanoparticles showed an

1157 efficiency of 25–72% while ionic liquid coated iron oxide nanoparticles showed better

1158 performance with the efficiency of 85–93%.

1159

1160 4.4. Green synthesized Fe NPs immobilized on polymer and other supports for pollutant

1161 degradation

47
1162 Since, nanoparticles are prone to agglomeration which reduces its effectiveness towards the

1163 catalytic and adsorptive activity. Such limitation was overcome by immobilizing

1164 nanoparticles within polymeric, zeolitic, and silica-based supports. Smuleac et al. (2011)

1165 utilized polyvinylidene fluoride (PVDF) membrane as support to incorporate Fe and

1166 bimetallic Fe/Pd nanoparticles through the green synthesis technique. Through

1167 polymerization reaction PVDF membranes were modified with polyacrylic acid (PAA),

1168 whereas for synthesizing Fe and Fe/Pd nanoparticles, green tea extract served as a reducing

1169 agent. Nanoparticle embedded PVDF/PAA membrane was found to incorporate nanoparticles

1170 with average particle diameter 20–30 nm. The synthesized nanoparticle impregnated

1171 membrane was utilized for studying the degradation of toxic organic pollutant,

1172 trichloroethylene (TCE). Catalytic reactivity of the membrane dechlorinated TCE compound,

1173 and was found to increase with more nanoparticle incorporation within the membrane.

1174 Moreover, it was reported that bimetallic Fe/Pd incorporation enhanced the catalytic process,

1175 rather than only Fe nanoparticles.

1176 In another study, Tandon et al. (2013) synthesized zerovalent iron (nZVI) nanoparticles using

1177 tea liquor and stabilized on montmorillonite K10. The synthesized nZVI had an average

1178 particle size of 59.08 ± 7.81nm. The nZVI impregnated montmorillonite support was then

1179 employed for arsenic removal study. Experimental observations revealed 90% removal of

1180 As(III) within 30min of reaction at both high and low pH of 2.75 and 11.1 respectively. It

1181 was observed that nZVI impregnated montmorillonite K10 resulted in better As(III) removal

1182 than only montmorillonite K10.

1183 Prasad et al. (2014) reported the synthesis of iron nanoparticles by Mentha spicata L. Leaf

1184 extract supported on chitosan composite and studied its efficiency in the removal of

1185 arsenite(III) and arsenate(V) from aqueous solution. The average particle diameter obtained

1186 through the Transmission electron microscope (TEM) ranged from 20-45nm. The

48
1187 nanoparticle resembled a core-shell structure with functional groups like N–H, C=O, C=C,

1188 and C=N present on the surface. The results conveyed that 2 gL-1 nanoparticle-chitosan

1189 composite was efficient in removing 100 mgL-1 As(III) and As(V) about 98.79% and 99.65%,

1190 respectively at the end of 60min.

1191 Cabanas et al. (2016) studied with different extracts like the chestnut tree (Castanea sativa),

1192 eucalyptus (Eucalyptus globulus), gorse (Ulex europaeus), and Pine (Pinus pinaster), for

1193 synthesizing iron nanoparticles. The study reported the effect of plant extract ratio on the

1194 formation of iron nanoparticles, and high antioxidant property present in eucalyptus was

1195 found to be most suitable for nanoparticle synthesis. Prepared nanoparticles were mixed with

1196 chitosan, and further the chitosan beads were characterized. Iron nanoparticle encapsulated

1197 with chitosan was utilized for As(V) removal. Moreover, the maximum adsorption capacity

1198 of 147µg g-1 was achieved with 25 gL-1 adsorbent dosage at pH 6-7.

1199 Saikia et al. (2017) reported the synthesis of iron oxide nanoparticles supported on silica

1200 through a cheap green method, and utilized it further as a catalyst for preparing phenol from

1201 boronic acids through ipso-hydroxylation reaction, instead of using hydrogen peroxide

1202 (H2O2). Experimental studies show, about 98% yield in aqueous solution when about 4 mg of

1203 nanocatalyst was utilized within 2h at 50ºC.

1204 Zheng et al., 2014 to extract organophosphorus pesticides from a solution prepared nano

1205 sorbent of iron oxide and ionic liquid upon polymeric support. Methanol proved to be the

1206 better dispersion medium for the prepared nano-adsorbents, as well as effective elution

1207 solvent. At an optimum condition of 2.4 gL-1 adsorbent dosage maximum yield of 81.4–

1208 112.6% was obtained at the end of 80 min.

1209 Mondal and Purkait (2017) synthesized iron nanoparticles by employing cardamom extract

1210 with an average diameter of 32nm. Furthermore the nanoparticles were incorporated within

1211 pH-responsive poly(vinylidene fluoride-co-hexafluro propylene) (PVDF-co-HFP) by mixing

49
1212 method. The prepared nanoparticle embedded membrane was studied for nitrobenzene (NB)

1213 reduction purpose by varying iron NP content (wt%), pH, and time (min). At an optimum pH

1214 11.9, iron content 0.01 wt%, NB degradation of 57% was obtained at the end of 50 min.

1215 Aniline conversion of 9.65ppm was obtained from 100ppm nitrobenzene.

1216 In another work Mondal and Purkait (2018), utilized iron oxide incorporated pH-responsive

1217 polymeric membrane for degradation of nitrobenzene and fluoride rejection purpose

1218 simultaneously. In this work, clove extract was employed for synthesizing iron NPs with an

1219 average diameter of 13.5nm having a core-shell structure with Fe0 at the core (Figure 4). The

1220 iron NPs impregnated membrane as shown in Figure 5. The figure shows that the iron NPs

1221 were homogenously dispersed over the surface and the cross-section revealed the same

1222 dispersity. At the optimized condition of pH=3, iron content 0.01 wt%, and time 39min, NB

1223 reduction of 86.7% was obtained with an aniline formation of 12.7ppm. Fluoride rejection

1224 was highest for a 20ppm stock solution of 72% at optimized conditions.

1225

1226 5. Critical analysis of the green synthesis routes for iron based nanomaterial synthesis

1227 The stability, size distribution, zeta potential, cost of preparation, and scaling up ability plays

1228 an important role for evaluating the different green synthesis routes. Stability plays an important

1229 role where the NPs make meta-stable aqueous suspensions or aerosols when it enters into

1230 surface or water from environment. It was found through several studies that plant extract and

1231 microorganism mediated green synthesis produced better stabilized NPs at low cost. Effective

1232 surface coating was formed due to the presence of various poly-phenolic components in plant extract,

1233 and natural proteins, tannins etc. in microorganisms which provided better stabilization, and size

1234 distribution (Sun et al., 2014; Singh et al., 2016). Biocompatible reagents obtained from plant

1235 source such as cellulose, clay, polysaccharides, and ascorbic acids are usually less expensive apart

1236 than the sources like sugar, haemoglobin, synthetic tannins and gallic acid. But such process mediated

1237 nanoparticles serves for better stabilization and less reactivity in environment with narrow particle

50
1238 size distribution. Hydrothermal route is energy efficient, but requires low external power for heating

1239 and incurs high cost if chemical coating agents required for better stabilization, otherwise if natural

1240 plant extracts are utilized as reducing agents it can also be very economical (Ahmmad et al., 2013).

1241 With better coating arises better stabilization which provides higher zeta potential indicating better

1242 dispersion in aqueous medium. Moreover, microwave based green synthesis adopts hydrothermal

1243 process and proved to have better scalability property. If microorganism and plant extract is used as

1244 the reducing agent then such route is most economical way to produce NPs with better crystalline

1245 nature, stabilization and size distribution (Amores et al., 2016). Moreover, the green synthesized

1246 nanoparticles are found to be better dispersed and stabilized with higher zeta potential in aqueous

1247 medium at definite pH (Sadeghi et al. 2015). The scale up advantage persists for all the different

1248 green synthesis routes mentioned in this article especially for microwave assisted technique (Bowman

1249 et al. 2008). Usually plant based and microorganism based green synthesis occurs at normal

1250 conditions and thus regarded as less expensive (Sharma et al. 2014), whereas the other synthesis

1251 routes requires an external power source for heating and thermal decomposition for generating NPs.

1252

1253 6. Separation strategy of magnetic iron NPs

1254 Usually in lab process magnetic separation is performed by low-gradient magnetic separation

1255 technique. In such process a low magnetic field gradient is generated (<100 T/m) by placing

1256 a permanent magnet adjacent to the sample, and separation of magnetic NPs takes place in

1257 batch mode. On the other hand, for industrial purpose high gradient magnetic separation is

1258 generally adopted. The setup consists of a column packed with magnetic NPs matrix

1259 composed of stainless steel wool. The NP matrix is left exposed to an external magnetic field.

1260 The suspension to be treated then flows continuously throught he column. A large localized

1261 magnetic field gradient (~104 T/m) generated near the matrix surfaces serves to capture the

1262 magnetic materials from the flowing stream. On switching off the external magnetic field

1263 releases the captured magnetic materials since the magnetic matrix gets demagnetized. Such

51
1264 process is successfully implemented in various chemical engineering plants such as food

1265 processing, power plant as well as wastewater treatment plant.

1266

1267 7. Environmental hazards and toxicity study of iron NPs

1268 Iron-based nanomaterials despite its tremendous environmental applications posses high risk

1269 towards environmental concern. Improper management of wastewater and other trashes from

1270 industries could lead to specific environmental hazards in groundwater and soil. Whereas

1271 synthesized iron nanomaterial for specific remediation purposes can get transported from one

1272 medium to another. Zero-valent iron nanoparticles (nZVI) is considered to be the most

1273 reactive, among other iron nanoparticles. During the treatment of groundwater contaminants

1274 with zero-valent iron nanoparticles (nZVI), it was observed that it gets transport through the

1275 permeable soil and undergoes transformation on interacting with contaminants as well with

1276 the exposed environment. The environment gets directly or indirectly affected due to the

1277 toxic impacts generated by iron NPs to microorganisms and soil fauna. It was reported that

1278 the induced stress of nano-sized iron exerts a toxic effect on soil microorganisms and causes

1279 an alteration in microbial biomass (Sacca et al., 2014). The nano-sized iron particles interact

1280 strongly with enzymes of living bodies and metals in the environmental arena due to its

1281 unique morphological features, particle size, surface energy, self-assembly, and synthesis

1282 process. However, the biosynthesized nanoparticles being deployed of harmful chemicals like

1283 hydrazine as capping agents make it a mild toxic agent for the environment. Antisari et al.

1284 (2013) reported the change in microbial mass of the soil due to the toxic impacts of

1285 engineered iron nanoparticles. Moreover, Fajardo et al. (2013) studied the transcriptional and

1286 proteomic stress activity due to nano zero-valent iron on soil bacterium Bacillus cereus.

52
1287 Das et al. (2018), in a recent study utilized strain LS4- a Desulfovibrio bacterium for

1288 preparing maghemite nanoparticles (Fe2O3) from saltpan sediments, through in situ synthesis.

1289 An average particle diameter of 18nm was obtained by the in vitro synthesis. Furthermore,

1290 Zebrafish embryo was employed for testing the toxicity effect of prepared nanoparticle in

1291 varying dosage. The studies confirmed the developmental impairment and DNA damage of

1292 the Zebrafish embryo. Increased mortality rate along with slower beat and hatching rate was

1293 noticed with increasing nanoparticle concentration in Zebrafish eggs. The adverse effect of

1294 high concentration maghemite nanoparticles resulted in larvae malformation and suggested to

1295 harm aquaculture.

1296 Auffan et al. (2008) through experimental studies has drawn a direct relationship

1297 between the cytotoxicity and oxidation state of iron nanoparticles. The cytotoxic impacts of

1298 different iron oxides such as nZVI, magnetite, and maghemite were tested towards gram-

1299 negative bacteria E. Coli and were compared. From the tests it was found that nZVI had

1300 higher toxicity effect as compared to another iron oxide NPs. Hence, the study suggested the

1301 oxidation state of iron nanoparticles played a vital role in toxicity. Such a phenomenon arises

1302 due to the generation of oxidative stress from reactive oxygen species (ROS). ROS denotes

1303 highly unstable radicals such as superoxide radicals, and hydroxyl radicals which disrupt the

1304 functioning of cells on getting adsorbed over the cell membrane.

1305 In another study Lee et al. (2008) reported strong bactericidal activity at anaerobic

1306 conditions exhibited by nZVI. The study revealed a linear correlation between the nZVI dose

1307 and the log inactivation of E. coli. Under aerobic conditions due to the oxidation

1308 phenomenon, the toxicity of nZVI significantly gets reduced due to the formation of an oxide

1309 layer. Li et al. (2010) confirmed the reduced bactericidal effects of nZVI due to complete

1310 oxidation in aerobic conditions. Further studies concluded that Fe(II) released from nZVI

1311 under anaerobic conditions was found to be more toxic. Hence, the studies revealed that

53
1312 physical disruption of the cell membrane was triggered by nZVI and led to physical damage

1313 whereas cell inactivation was enhanced by the biocidal effects of Fe(II).

1314 Phenrat et al. (2009) reported the effect of age and surface modification on the toxicity

1315 behavior of nZVI. The study utilized tests on mammalian cells by fresh nZVI, aged nZVI

1316 (nearly a year old), magnetite, and polyaspartate surface-modified nZVI. Various properties

1317 of nanoparticles such as “redox” activity, agglomeration, and sedimentation rate were found

1318 to impose morphological changes on neuron cells and rodent microglia of mammalian cells

1319 were found getting cultured. However, capping of surface-modified nZVI by polyaspartate,

1320 imposed less toxicity behavior due to limited exposure of the iron particle to the cells. The

1321 remarkable impact was observed for fresh nZVI, whereas insignificant morphological

1322 changes were induced by aged nZVI in mitochondrial cells, and in neuron cells the ATP

1323 levels got reduced. The toxic effect of iron in three different forms was studied by Chen et al.

1324 (2013). The study employed solutions of nZVI coated with carboxymethyl cellulose (CMC-

1325 nZVI), magnetite (Fe3O4), and ferrous ion solution Fe(II). Such solutions were introduced to

1326 test toxicity effects on early life stages of medaka fish. Comparable to magnetite and Fe(II)

1327 solution, CMC-nZVI was found to have a more toxic effect on the embryo. Due to the

1328 presence of various oxidized forms of iron in the CMC-nZVI solution, effects such as

1329 hypoxia, developmental toxicity, and ROS oxidative stress occurred in the embryos. The

1330 results conveyed that physicochemical properties such as chemical reactivity, oxidation state,

1331 and particle aggregation of nZVI alter in the aqueous medium, which further affects the

1332 toxicity characteristics of nZVI in medaka fish.

1333 The toxicity of iron oxide nanoparticles was found not to reduce through stabilization or

1334 capping agents in many studies. Baumann et al. (2014) studied the toxicity behavior with four

1335 different iron NPs coated with ascorbate, citrate, dextran, and polyvinylpyrrolidone. The

1336 toxicity tests were performed on the neonates of Daphnia magna (water flea). Ascorbate and

54
1337 dextran-coated iron NPs showed the highest immobilization, whereas citrate coated NPs

1338 showed lower immobilization. Incomplete ecdysis was observed for acerbate, dextran, and

1339 citrate coated iron NPs when present in high dosage, whereas polyvinylpyrrolidone coated

1340 iron NPs showed a negligible negative effect. For other functionalized iron NPs, PVP coated

1341 NPs showed the highest colloidal stability. Moreover, it was found that stabilizing forces

1342 controlling hydrodynamic diameter didn’t have any effect on toxicity, but factors like

1343 colloidal stability and release of ions induce ROS in daphnids.

1344 Barhoumi and Dewez (2013) studied the toxicity effect of superparamagnetic iron oxide NPs

1345 towards green algae Chlorella vulgaris, since algae act as ecological indictor and provide the

1346 health of the aquatic ecosystem. The study includes exposure of three different chemical

1347 concentration iron oxide NPs suspension towards Chlorella vulgaris cells. Through

1348 investigation it was found that iron NPs imposed oxidative stress, and inhibits cell division

1349 which further disrupts the photochemical activity of algal cells.

1350 The toxicity of nanosized and bulk iron oxide NPS was evaluated by Blinova et al. (2017)

1351 and tested on Daphnia Magna (water flea) and Lemna minor (duckweed). Both the iron oxide

1352 NPs showed negligible biological effects with very low toxicity (EC50 < 100 ppm), but at

1353 magnetite concentrations of 10 and 100 ppm, a decrease in the number of neonates hatched

1354 for Daphnia Magna was noticed.

1355 To overcome such toxicological issues various researches were carried out to advance and

1356 modify the production of green nanomaterials, which are found to be less toxic and eco-

1357 friendly for engineered nanoparticles (Shakibaie et al., 2013; Usha Rani and

1358 Rajasekharreddy, 2011). Nadagouda et al. (2010) investigated the studied the toxic effects of

1359 biosynthesized nZVI on human keratinocyte cell. Green tea extract and borohydride were

1360 utilized for synthesizing nZVI. The biocompatibility was assessed for 24-48h using an assay

1361 of methyl tetrazolium (MTS) and lactate dehydrogenase (LDH), which were exposed to cell

55
1362 lines. Due to higher average particle diameter LDH leakage increased which induced stress

1363 on cellular membrane. Hence, green synthesized nZVI was utilized owing to much smaller

1364 particle size and non-toxic effect to human keratinocytes compared to chemically synthesized

1365 nZVI. Similarly, in another study Markova et al. (2014) utilized ecologically important

1366 organisms such as cyanobacterium (Synechococcus nidulans), green alga

1367 (Pseudokirchneriella subcapitata), and invertebrate organisms (Daphnia magna) to study the

1368 effect of green synthesized iron nanoparticles on them. Experimental results conveyed that

1369 green synthesized iron nanoparticles obtained by using green tea extract induced a negative

1370 effect on toxicological assays prepared. Though studies indicate that green synthesized NPs

1371 are biocompatible to living organisms, but still there is a lack of literature studying its

1372 toxicology effects on the environment.

1373

1374 8. Challenges and future prospective of green synthesized iron-based nanomaterials

1375 More research and advancements are required to explore the uniqueness of green synthesized

1376 nanomaterials, and various other available resources for such synthesis should be practiced.

1377 Understanding the underlying mechanism of such synthesis plays an important role in

1378 discovering out new modifications and advancements. Moreover, developments should lead

1379 toward an economically competitive process, can be scaled up, and eco-friendly in nature

1380 compared to conventional methods. Future studies should involve the use of more local

1381 resources to make things economically viable, and research should focus more on stability

1382 issues of synthesized nanomaterials for better biocompatible applications. Research should

1383 emphasis on synthesizing such green nanomaterials towards better efficiency in tackling

1384 contaminants with minimum eco-toxicological effects. Again, attention should focus more on

1385 discussing and controlling the risk management, fate, and toxicological effects of green

1386 synthesized iron nanoparticles concerning chemical synthesis.

56
1387 a) It has been noticed that some researchers have pointed out the fact of food security,

1388 regarding plant products being used as a source of reducing agent in green synthesis. Hence

1389 more attention should be given towards agro/biowaste as well as indigenous herbs to

1390 overcome this. Moreover, extensive studies are required regarding the fate and transport of

1391 nanoparticles in the environment.

1392 b) The mechanism of reaction for the biosynthesis of nanoparticle varies according to

1393 different microorganisms such as bacteria, fungi, or yeast. Nanoparticles with varying

1394 morphology and characteristics arise due to the diverse reactions between metal ion

1395 precursors and different biological agents. Intracellular synthesis involves bioreduction of

1396 metal ions on the cell wall, whereas extracellular synthesis occurs through electron transfer

1397 between enzymes and metal ions. Since such reactions are very complicated, hence intensive

1398 research needs to be carried out for a better understanding of such process mechanisms,

1399 which can cater to effective control over morphology and other properties of synthesized

1400 nanoparticles.

1401 c) Since iron oxide nanoparticles are reactive in nature, specifically zerovalent irons due to

1402 their higher oxidation state. Such nanomaterials during transport from one medium to another

1403 can cause serious toxic effects on soil and aqueous system, which can negatively affect the

1404 ecosystem. Thus researches should be more focussed on better stabilization of prepared

1405 nanomaterials through green route, and better management of nanomaterial waste.

1406 d) Research should be oriented towards utilizing agro-based waste for the green synthesis of

1407 nanomaterials. Moreover, metal-metal nanocomposite synthesis through green route should

1408 be more focussed which can enhance the effectivity in wastewater treatment, and heavy metal

1409 removal application purposes.

1410 e) Through this study it has been observed that different parts of the same plant species

1411 produce nanoparticles with different morphology and physic-chemical properties. Research

57
1412 should be motivated in dealing with a thorough study of the active biomolecules primarily

1413 responsible for capping and stabilizing the synthesized nanomaterials.

1414 f) Exploration of new microorganisms is required for synthesis of iron nanoparticles. From

1415 past literatures it was observed that microorganism related synthesis forms less stabilized and

1416 narrower morphological oriented nanomaterials, resulting in lower yield value. To obtain

1417 nanoparticles of uniform, crystalline, and monodisperse properties, new microorganisms

1418 research should be focussed for exploring different species.

1419 g) To control the risk management due to the toxic nature of the synthesized iron

1420 nanoparticles there should exist a standard method for the synthesis. Since different synthesis

1421 methods adopted by researchers lead to different property and characteristic oriented

1422 nanomaterials thus proper screening of the nano waste before discarding is overlooked. This

1423 creates inconsistency in research output and difficulty in human health prediction along with

1424 environmental risk assessment.

1425 h) Bimetallic nanoparticles are found to be a very interesting research area which tends to

1426 improve the properties of Fe NPs alone but is found less in literature. Such bimetallic

1427 nanoparticles can improve the catalytic property, surface area for adsorption, and other

1428 various chemical properties. Research should be more focussed on such bi-metallic

1429 nanocomposites for various environmental applications.

1430 i) The real challenge of utilizing such NPs as adsorbent in column operation is the huge

1431 pressure drops which builds upon due to exceptionally reduced bed void volume. Such

1432 challenges could be handled by incorporating NPs over support such as adsorbent beads,

1433 carbon composites, and activated carbon. For such operation chemisorption should be the

1434 ideal interaction between the adsorbate and adsorbent. Hence preparing and choosing

1435 particular NPs with better surface functional groups would be the main priority.

1436

58
1437 9. Conclusion

1438 This review emphasizes on the various methods of green synthesis of iron-based

1439 nanomaterials (nanoparticles and nanocomposites) and their potential application towards

1440 environmental remediation. The effort is made to categorize various raw materials under

1441 green synthesis and analyze their respective application towards various environmental-

1442 related applications. The analysis made here brings forward minute details of nanomaterial

1443 size, shape, properties, and application of iron NPs. Various plant sources and biocompatible

1444 reagents along with energy efficient methods have been summarized in detail for preparing

1445 iron-based nanomaterials and nanocomposites. Numerous role of iron nanoparticles as

1446 catalyst, adsorbent, and their toxicological effects were discussed in this review. Moreover,

1447 iron bimetallic nanocomposite synthesis through such a green route which is evolving

1448 nowadays has been pointed out. The plant-based synthesis has been compared with graphene-

1449 based composites due to their surface coatings with numerous plant metabolites, which act as

1450 excellent adsorbent. Moreover crirical analysis of the different green synthesis routes with

1451 respect to their stability, size distribution, and various other parameters has been evaluated.

1452 Finally, challenges and prospects of green synthesis of iron NPs are discussed. In summary,

1453 various green nanotechnology processes have been described in this paper, which would be

1454 helpful in the future study as a resource to analyze and utilize it for further advancements in

1455 building better iron-based nanomaterials to tackle real-life wastewater and contaminated

1456 solutions with least risk of a toxicological effect on the environment. This paper might be

1457 useful to the readers for acquiring in-depth knowledge on green synthesis of iron NP and its

1458 amazing success for the various environmental application.

1459

1460

1461

59
1462 Acknowledgement

1463 The study is supported by (DST/TM/WTI/WIC/2K17/84(C)) from the Department of Science

1464 and Technology (DST), New Delhi, India. All the opinions, findings, and conclusions shown

1465 in this work are those of the authors, and do not necessarily reflect the views of DST, New

1466 Delhi.

1467

1468 Credit Author Statement

1469 Piyal Mondal: Data curation, Writting original draft, Conceptualization A. Anweshan:

1470 Writting- review and editing, Software Mihir K Purkait: Supervision, Visualization

1471

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2147

2148

2149

83
Table 1: Iron based nanoparticle synthesis utilizing biocompatible green reagents

Green reagents Nanoparticle NPs Size Morphology Reference

α-D-glucose Fe3O4 NPs ~12.5 nm Spherical Lu et al. (2010)

Starch Fe/Pd bimetallic 14.1 nm Discrete (well dispersed) He et al. (2005)

nanoparticle
Maltose Fe3O4 NPs 12.1 ± 2.1 nm Spherical Demir et al. (2013)

Sucrose Fe3O4 NPs 4.0-16.0 nm Spherical Sun et al. (2009)

α-D-maltose Fe3O4 NPs 9.7 ± 1.0 nm Mostly spherical Demir et al. (2014)

α-D-mannose Fe3O4 NPs 13.1 ± 0.3 nm Rod like

α-D-galactose Fe3O4 NPs 12.4 ± 0.3 nm Spherical

α-D-lactose Fe3O4 NPs 3.8 ± 0.21 nm Dendritic nanostructure

D-glucose Fe3O4 NPs 10.0-20.0 nm Coral like Qin et al. (2011)

Agar Fe3O4-polymer composite 50.0-200.0 nm Spherical Jegan et al. (2011)

Sodium alginate Fe3O4 NPs 27.2 nm Spherical, and hexagonal Gao et al. (2008)
Ascorbic acid (Vitamin C) Fe metal nanoshell <100.0 nm Cubical Nadagouda et al. (2007)

Ascorbic acid nZVI 20.0-75.0 nm Spherical chain Savasari et al. (2015)

Ascorbic acid Fe3O4 NPs 15.0 ± 4.0 nm Irregular Nene et al. (2016)

Urease Fe3O4 NPs 19.0±5.0 nm Nanosphere at 60 ºC Shi et al. (2014)

Thickness <2-3nm Nanosheet at 40 ºC

L>100nm, C.S~10±4 nm Nanorods at 40 ºC

Yeast Fe3O4 NPs 16.0 nm Wormhole like Zhou et al. (2009)

Chitosan Fe3O4 NPs 22.0 ± 7.8 nm Roughly spherical Shrifan-Esfahni et al. (2015)

Agar Fe3O4 NPs 20.0-30.0 nm Non spherical Hsieh et al. (2010)

Ascorbic acid Superparamagnetic iron 5.0 nm Spherical Sreeja et al. (2014)

oxide

L-lysine amino acid Fe3O4 NPs 17.5 nm Spherical Krishna et al. (2012)

Haemoglobin and Fe NPs 2.0-5.0 nm Aggregates Sayyad et al. (2012)

myoglobin

D-glucose gluconic acid Fe3O4 NPs 12.5 nm Roughly spherical Lu et al. (2010)

Glucose and gluconic acid Fe3O4 NPs 4.0-16.0 nm Spherical crystalline Sun et al. (2009)
Wood derived sugar Iron NPs carbon coated Iron core:10-25 nm Nanosphere Yan et al. (2015)

Nano-sphere:100-150 nm

Tannic acid Iron Oxide <10.0 nm Spherical Herrera-Becerra et al. (2010)

Chitosan-Gallic acid Fe NPs core shell ~11.0 nm Cubical Dorniani et al. (2012)

Starch Fe3O4 NPs <10.0 nm Spherical Chang et al. (2011)

Carboxymethyl cellulose Fe3O4 NPs >10.0 nm Spherical Chang et al. (2011)

sodium

Agar Fe3O4 NPs >10.0 nm Spherical Chang et al. (2011)

Pectin Fe3O4 NPs 5-18 nm Cubical Namanga et al. (2013)

Arginine Fe3O4 NPs Fe/Ar (1:1)-5-18 nm Spherical Wang et al. (2009)

Fe/Ar (1:2)-9-15 nm
Table 2: Microorganism mediated synthesis of Iron based nanoparticles.

Microorganisms Species name Nanoparticle Average size Morphology Reference

Bacteria Actinobacter sp. Fe3O4 10-40 nm Cubical Bharde et al. (2005)

Actinobacter sp. γ-Fe2O3 <50.0 nm Spherical Bharde et al. (2008)

Thermoanaerobacter sp. Fe3O4 ~13.0 nm Spherical Moon et al. (2010)

Bacillus subtilis Fe3O4 60-80 nm Spherical Sundaram et al. (2012)

Thiobacillus thioparus Fe3O4 - - Elcey et al. (2014)

Microbac- terium Magnetic Iron oxide 2-10 nm Spherical Mehrotra et al. (2017)
marinilacus
nanoparticles

Desul- fovibrio, strain LS4 Maghemite (Fe2O3) 19.0 nm Round shaped Das et al. (2018)

nanoparticles

Fungi Fusarium oxysporum and Fe3O4 20-50 nm Spherical Bharde et al. (2006)
Verticillium sp.
P. chlamydosporium, Maghemite (Fe2O3) ~12-50 nm Spherical Kaul et al. (2012)
A. fumigates, A. wentii,
nanoparticles
C. lunata and C. globosum
Aspergillus sp. Fe3O4 50-200 nm Spherical Pavni et al. (2013)
 Alternaria alternate Fe Nanoparticles ~9.0nm Cubical Mohamed (2015)

Pleurotus sp. Fe Nanoparticles Mazumdar and Haloi

(2011)

Aspergillus niger YESM 1 Magnetic Fe and 18 and 50 nm for Fe Spherical Abdeen et al. (2016)
Fe3O4 (magnetite) and Fe3O4 NPs
nanoparticles respectively
Alternaria alternate γ-Fe2O3 (iron oxide) 75-650 nm Quasi-spherical as Sarkar et al. (2017)
nanoparticles well as
rectangular NPs
Algae Sargassum muticum Magnetic Fe3O4 18 ± 4 nm Cubical Adhavi et al. (2013)
nanoparticles
Chlorococcum sp. Iron nanoparticles 20-50 nm Spherical Subramaniyam et al.

(2015)
Table 3: Green synthesized iron based nanoparticles from plant sources

Part Name of source Average size Morphology Reference

Plant Soya bean sprouts ~8.0 nm Spherical Cai et al. (2010)

Aloe vera 93-227 nm Spherical Ngernpimai et al. (2012)

Aloe vera ~6-30 nm Agglomerated irregular Phumying et al. (2013)

Alfalfa biomass 3.1 nm Agglomerated Herrera-Becerra et al. (2007)

Pine wood shavings 1-10 nm Irregular, rod and spherical Ramasahayam et al. (2012)
shaped
Marine plant Sargassum muticum 18 ± 4 nm Cubic Mahdavi et al. (2013b)

Kappaphycus alvarezii 14.7 ± 1.8 nm Spherical Yew et al. (2016)

Padina pavonica 10.0-19.5 nm Spherical El-Kassas Hala et al. (2016)

Sargassum acinarium 21.6-27.4 nm Spherical El-Kassas Hala et al. (2016)

Seed Grape seed ~30.0 nm Irregular shape Narayanan et al. (2011)

proanthocyanidin
Syzygium cumini 9-20 nm Agglomerated spherical Venkateswarlu et al. (2014a)

Carom and clove 0.088-3.95 Spherical, irregular Afsheen et al. (2018)

Leaf Carob 4-8 nm Well monodisperse Awwad and Salem (2012)

Tridax procumbens < 100.0 nm Irregular shape Senthil and Ramesh (2012)

Artemisia annua 3-10 nm Spherical Basavegowda et al. (2014a)

Caricaya Papaya 33.0 nm Agglomerated plate and Latha and Gowri (2014)
capsule like structures
Perilla frutescens ~50.0 nm Spherical Basavegowda et al. (2014b)

Euphorbia wallichii 10-15 nm Spherical Atarod et al. (2015)

Green tea 5.7 ± 4.1 nm Spherical Xiao et al. (2015a)

Zea mays L. <100.0 nm Aggregated spherical Patra et al. (2017)

Sesbania grandiflora 25-60 nm Agglomerated non-spherical Rajendran and Sengodan

(2017)
Rubus glaucus Benth 40-70 nm Aggregated spherical Kumar et al. (2016)

Calliandra ~85.4-87.9 nm Bead-like spherical Sirdeshpande et al. (2018)

haematocephala
Lagenaria siceraria 30-100 nm Cubic Kanagasubbulakshmi and
Kadirvelu (2017)
Moringa oleifera ~4.14 nm Spherical and irregular Silveira et al. (2017)

Coriandrum sativum 20-90 nm Spherical Sathya et al. (2017a)

Eucalyptus 20-50 nm Spherical and irregular Weng et al. (2017)

Eucalyptus 80-90 nm Spherical Gan et al. (2018)

Eucalyptus 20-70 nm Spherical Sangami and Manu (2017)

Oak 20-100 nm Irregular shape Machado et al. (2017)

Lantana camara 10-20 nm Crystalline nanorods Rajiv et al. (2017b)

Cynometra ramiflora >100 nm Spherical aggregated Groiss et al. (2017)

Eichhornia crassipes >100 nm Rod shaped Jagathesan and Rajiv (2018)

Syzygium jambos (L.) 13.7 ± 5.0 nm Spherical Xiao et al. (2017)

Alston
Vaccinium corymbosum 52.4 nm Irregular shape non Manquian-Cerda et al.
agglomerated (2017)
Azadirachta indica (neem) 38.0 nm Brick-like structure Madhubala and
Kalaivani (2017)
Mangifera indica L. 3.0 ± 0.2 nm Polycrystalline nanorods Al-Ruqeishi et al.
(2016)
Mansoa alliacea (Garlic 18.22 nm Spherical nanoparticles Prasad (2016)
Vine)
Eichhornia crassipes 20-80 nm Amorphous NPs Wei et al. (2017)
Fruit peel Plantain peel 30-50 nm Spherical Venkateswarlu et al. (2013)

Punica Granatum D: 40 nm, L: >200 nm Rod shaped Venkateswarlu et al. (2014b)

Rambutan 100-200 nm Agglomerated spinel Yuvakkumar and Hong

(2014)
Ananas comosus 10-16 nm Aggregated spherical Venkateswarlu and Yoon
(2015a)
Citrullus lanatus < 17.0 nm Aggregated spherical Venkateswarlu and Yoon
(2015b)
Citrus aurantium 17-25 nm Slightly elongated Bano et al. (2016)

Punica granatum Slightly rod-shaped Bano et al. (2016)

Malus domestica Spherical Bano et al. (2016)

Citrus limon Spherical Bano et al. (2016)

Plantain peel <50.0 nm Spherical 27

Banana peel 10-25 nm Agglomerated 28

Fruit Passiflora tripartita 18.2-24.7 nm Spherical Kumar et al. (2014a)

Averrhoa carambola 1.9-3.1 nm Spherical Ahmed et al. (2015)

Lemon 14-17 nm Spherical Bahadur et al. (2017)

 Couroupita guianensis 17 ± 10 nm Spherical Jha (2017)

Pomegranate Agglomerate 100-200 nm 26

Pomegranate, mulberry, 80-100 nm Irregular 30

and cherrt
Pepper 50.0 nm Dendrite like Khaghani and Ghanbari
(2017)
Terminalia chebula <80.0 nm Amorphous Kumar et al. (2013)

Zanthoxylum rhetsa 12.2 ± 0.8 nm Cluster like Saikia et al. (2017)

Root & Shoot Mimosa pudica (root) 60-80 nm Agglomerated rough Niraimathee et al. (2016)
spherical
Vaccinium corymbosum 52.4 nm Irregular shape, non Manquian-Cerda et al.
(shoot) agglomerated (2017)
Stolon Potato 40 ± 2.2 nm Cubic Buazar et al. (2016)

Waste Tea waste 5-25 nm Cuboid/pyramid Lunge et al. (2014)

Rice straw 9.9 ± 2.4 nm Aggregated spherical Khandanlou et al. (2013)

Coffee waste hydrochar 10-40 nm Spherical Khataee et al. (2017)

Acacia mearnsii (biochar) 18-35 nm Uneven Khan et al. (2015)

Sorghum bran 40-50 nm Spherical 22

 Cynometra ramiflora 58.5 nm Spherical Bishnoi et al. (2017)
(Fruit extract waste)
Cocos nucifera L. 10-100 nm Clustered Sebastian et al. (2018)
Chandrakalpa (Husk
extract)
Gum Arabic gum 70-80 nm Spherical Horst et al. (2017)
 Table 4: Types of microwave-assisted biosynthesis of iron-based nanoparticles.

Nanoparticle Stabilizer NP Size Morphology Reference

Magnetic Iron oxide (Fe3O4) poly(sodium 4-styrenesulfonate

12 ± 2 nm Aggregated irregular NPs Williams et al. (2016)
Nanoparticles (PSSS) and sodium
polyphosphate (SPP)

Magnetic Iron oxide (Fe3O4 Mixture of oleic acid with ~5.0 nm Organic shell covered NPs Lastovina et al. (2017)
and γ-Fe2O3) nanoparticles oleylamine

MCM-41 supported iron Tetraethylorthosilicate (TEOS, ~3.0 nm Narrow distributed pore Carrillo et al. (2013)
oxide nanoparticles 98 %) with NH4OH solution as size
(FeO and Fe2O3) surfactant

Magnetic iron oxide 1.0 mol/L sodium silicate 33-66 nm Homogenous shaped Mahmoud et al. (2016a)
nanoparticles coated solution
with nano silica layer

Iron molybdate Ethanol (for synthesis of NPs) 5-20 nm Flower shaped Liang et al. (2016)
microspheres & act as dispersant microspheres
nanoparticles
Magnetite nanoparticles alendronic acid (a biphosphate) 5.9 ± 1.4 nm Uniform NPs Schneider et al. (2017)

Iron oxide nanoparticles Trisodium citrate dihydrate 5-50 nm Crystalline, irregular Gonzalez-Moragas et al.
(Na3Cit) shaped
(2015)

Cobalt ferrite (CoFe2O4) Okra (A. esculentus) plant 5-15 nm Spherical Kombaiah et al. (2017a)
Nanoparticles extract used as reductant

Zinc ferrite (ZnFe2O4) Okra (A. esculentus) plant 7.2 ± 1.3 nm Agglomerated spherical Kombaiah et al. (2017b)
Nanoparticles extract used as reductant

Superparamagnetic iron trimethylammonium hydroxide 19-44 nm Crystalline round lobular Carenza et al. (2014)
oxide nanoparticles (TMAOH) solution and sodium
(SPIONs) citrate used as anionic
stabilizers
Hematite (α-Fe2O3) (NH4)3PO4 Nanorod length Rod shaped Ahmed et al. (2014a)
Nanorods ~150-170 nm,
diameter ~60 nm
Table 5: Green synthesized iron based nanoparticles for dye degradation application

Source Nanoparticle Morphology Dye removed Efficiency Reference

Pomegranate leaves Fe3O4 NPs 45-60 nm, spherical Congo red 93% removal at 60 min Prasad et al.

(2017a)

Pisum sativum peels Iron oxide magnetic 20-30 nm, spherical Methyl orange 96.2% removal at 60 Prasad et al.
NPs min
(2017d)

Eucalyptus leaf extract Fe/Ni bimetallic NPs 20-50 nm, spherical Methyl orange 99.6% removal at 180 Weng et al. (2017)
min
abd irregular

Cupressus sempervirens nZVI 1.5 nm, nanoclusters Methyl orange 95.8% removal at 6h Ebrahinezhad et al.
leaf (2017)
Moringa oleifera leaves Ni/Fe3O4 NPs 16-20nm, spherical Malachite green ~91.6% removal at 25 Prasad et al.
min
(2017c)

Green tea leaves Superparamagnetic 10±3nm, spherical, Methylene blue 95% removal at 16 min Singh et al. (2017)
Fe3O4 nanoparticles narrow size
distribution
Pepper extract Iron oxide/palladium ~50.0 nm, spherical Acid black acid 97% removal at 120 Khaghani and
nanocomposite and dendrite brown min Ghanbari (2017)
nanostructures
Tie Guanyin tea extract nZVI 6.58±0.76nm, Bromothymol blue >90% removal at 30 Xin et al. (2016)
spherical
min

Cynometra ramiflora fruit Fe3O4 NPs 58.5-78.1 nm, Methylene blue 100% removal at 110 Bishnoi et al.
spherical min
extract (2017)

Cynometra ramiflora Fe3O4 NPs >100.0 nm, spherical Rhodamine B 100% removal at 15 Groiss et al. (2017)
aggregates min
Camellia sinensis nZVI 5-15 nm,spherical Bromothymol blue 83.3% removal at 20 Hoag et al. (2009)
crystalline min
Green tea Fe3O4 NPs 40-60 nm, Aqueous 100% removal at 6h Shahwan et al.
amorphous cationic and
(2011)
anionic dyes
Eucalyptus Tereticornis Fe-Polyphenol NPs 40-60 nm, cubical Azo dyes Maximum adsorption Wang (2013)
(adsorption) capacity 1.6g dye/g NPs
Eucalyptus tereticornis, Fe-Polyphenol NPs 50-80 nm, spherical Azo dyes 100% removal at 200 Wang et al. (2014)
Melaleuca nesophila, and
(degradation) min
Rosemarinus officinalis

Grape Fe3O4 NPs 15-100 nm, quasi- Acid orange (Azo 80% removal at 180 Luo et al. (2014)
spherical shaped dues) min
Sorghum bran Fe NPs 4-50 nm, spherical Bromomethyl blue 90% removal at 30 min Njagi et al. (2011)
amorphous
Oolong tea leaves Fe NPs 40-50 nm, spherical Malachite green 75.5% removal at 60 Huang et al. (2013)
min
Green tea Fe NPs 70-80 nm, spherical Malachite green 82.47% removal at 60 Huang et al. (2015)
amorphous min
nZVI refers to nano zero-valent iron
Table 6: Green synthesized iron based nanoparticles for heavy metal romoval application

Source Nanoparticle Morphology Metal removed Efficiency Reference

Syzygium jambos L. nZVI Spherical, Chromium (VI) 99.45% at 90 min Xiao et al. (2017)
Alston leaf extract crystalline
Coconut husk extract Fe3O4 NPs Amorphous Calcium and Ca ~55%, Cd ~40% Sebastian et al.
Cadmium at 120 min (2018)
Citrus maxima Fe NPs Irregular Chromium (VI) 99.29% at 90 min Wei et al. (2016b)

Plant extracts: Rosa Fe NPs Irregular and non- Chromium (VI) 100% efficiency for Fazlzadeh et al.
damascene, Thymus uniform shapes all extract mediated (2017)
vulgaris,and Urtica dioica NPs at 25 min
Eucalyptus leaf extracts nZVI and Fe-oxide NPs Spherical Chromium (VI) 98.9% at 35 min Jin et al. (2017)

Tangerine peel extract Fe-oxide NPs Spherical Cadmium 90.% at 90 min Ehrampoush et al.
(2015)
Plant leaves Graphene oxide/Fe- Spherical NPs Lead 96% at 80 min Prasad et al. (2017b)
oxide NPs assembled over
RGO sheets
Eichhornia crassipes nZVI Mostly spherical Chromium (VI) 89.9% at 90 min Wei et al. (2017)
leaves
Moringa oleifera leaves Fe-oxide NPs Nanosphere Fluoride 1.4 mg/g at 40 min Silveira et al. (2017)
agglomerate
Lantana camara fruit Fe-oxide NPs Spherical Nickel 99% at 100 min Nithya et al. (2017)
extract
Fatty acids in Olive oil Fe-oxide NPs Spherical Nickel 72% at 20 min Es’haghi et al. (2016)

Vaccinium corymbosum Fe (oxide, hydroxide), Spherical, Arsenate 76% at 120 min Manquian-Cerda
leaves and nZVI agglomerated et al. (2017)
and shoots extract
Eucalyptus leaves extract nZVI, Fe-oxide NPs Spherical, Chromium (VI) 58.9 % Cr (VI) and Weng et al. (2016)
and Copper ions 33.0 % Cu (II) at 60
min
Moringa oleifera seed and Fe-NPs Spherical, thick Nitrate For surface water: Katata-Seru et al.
leaf surface layer 70% (leaf extract) (2017)
extract 74% (seed extract) at
1440 min
Commercially available Fe/Clay supported Crystalline Arsenic (III) 99% at 30 min Tandon et al. (2013)
tea
Mentha spicata L. Fe/Chitosan supported Cubic, dispersed Arsenic (III), (V) 100% at 30 min Prasad et al. (2014)

Eucalyptus Fe/Chitosan supported Nono-sized clusters Arsenic (V) 147µg/g maximum Martínez-Cabanas et
globulus adsorption capacity al. (2016)
Emblica officinalis Fe3O4-NPs Uniform spherical Pb(II) removal ~46.18 mg/g max Venkateswarlu et al.
adsorption capacity (2014)
Punica granatum Fe-NPs Cubic inverse Pb(II) removal > 99.9% Hajdu et al. (2012)
spinel structure
Eucalyptus globulus nZVI Spherical Adsorption of 98.1% at 30 min Madhavi et al. (2013)
Chromium (VI)
S. jambos (L.) Oolong tea, Fe NPs Spherical Chromium(VI) 100% at 60 min Xiao et al. (2016)
A. moluccana
nZVI refers to nano zero-valent iron
Table 7: Green synthesized iron based nanoparticles for wastewater treatment application

Source Nanoparticle Morphology Pollutant removed Efficiency Reference

Silybum marianum L. Copper supports 8.5-60 nm, spherical Nitrobenzene 95% at 90 min Sajadi et al.
(plant seeds) on Magnetite (2016)
nanocatalyst
Euphorbia Iron oxide 100 nm, spherical 2,4-dichlorophenol 64% at 120 min Guo et al. (2017)
cochinchensis leaves nanoparticles
Extracts

Euphorbia bungei Cu/RGO/Fe3O4 RGO sheet dispersed Cyanation of 93% at 120 min Nasrollahzadeh et
boiss leaves with Fe3O4 and Cu NPs aldehydes al. (2017)

Withania coagulans Pd/RGO/Fe3O4 <15 nm, spherical Reduction of 4- 100% at 1 min Atarod et al.
leaf extract nitrophenol (2016)

Zanthoxylum rhetsa Fe2O3@SiO2 5-21 nm, cluster Ipso-hydroxylation 98% at 120 min Saikia et al.
fruit extract of boronic acid in (2017)
water
Cynometra ramiflora Iron oxide <100 nm, spherical Degradation of 100% at 15 min Groiss et al.
leaf extract nanoparticles aggregates Rhodamine B (2017)
Microwave-assisted Silica-supported <50nm, spherical Alkylation of 99% at 3 min Carillo et al.
synthesis (MCM-41) iron toluene with benzyl (2013)
oxide NPs chloride
Yeast Protein capped 3-10nm, irregular Pesticide 100% at 60 min Mehrotra et al.
nZVI (Dichlorvos) (2017)
Oak Leaves nZVI 20-100 nm, irregular Amoxicilin 100% at 95 min Machado et al.
(2017)
Grape marc, black tea nZVI 15-45 nm,spherical Ibuprofen 50%, 50%, 55% at 193 h Machado et al.
leaves, agglomerates (2013)
vine leaves
Eucalyptus leaves Fe-NPs 20-70 nm, spherical Ametryn 100% at 135 min Sangami and
Manu (2017)

Black tea extract and Iron oxide NPs 5-50 nm, irregular Propranolol >90% at 40 min Ali et al. (2017)
Ionic liquid (N-
methyl-
butylimidazolium-
bromide)
Eucalyptus leaves Fe NPs 20-80 nm, spheroidal COD, Total Nitrogen 71.7 % for total N, 30.4 % Wang et al. (2014)
and Phosphorus for total P, and 84.5 % for
COD at 21 days
Sapindus mukorossi Iron 10-60 nm, PAHs in water and Anthracene, phenanthrene Shanker et al.
hexacyanoferrate hexagonal nanorods, soil (benzo (a) >80%, benzo (a) pyrene, (2017)
spheres and rhombus pyrene, chrysene, chrysene, fluorine ~70-
fluorene, 80% at 48h
phenanthrene
anthracene)
Eucalyptus leaf Iron oxide 80-90nm, spherical Phosphate >95% at 100 min Gan et al. (2018)
extract nanoparticles

Mangifera indica L. Iron oxide Nanorods, Heavy oil 50% reduction in viscosity Al-Ruqeishi et al.
Leaves extract
L: 15 ± 2 nm (2016)
D: 3.0 ± 0.2 nm
Eichhornia crassipes, Iron nanoparticles 20-60nm spherical, Nitrate and Maximum 74.52 % of Prabhakar et al.
Lantana camara and
25-50 nm spherical, phosphate from nitrate and 55.39 % of (2017)
Mimosa pudica leaves
65nm chain like wastewater phosphate at 24h
Starch Bimetallic Fe/Pd 14.1-60nm, Dendritic Trichloroethylene 98% at 1h He et al. (2005)
NPs structure
nZVI refers to nano zero-valent iron
Figure 1: Schematic diagram of various green synthesis techniques and possible environmental applications of iron, and iron based
nanomaterials
Figure 2: a(i) TEM images of green synthesized Fe-Al composite scale 200 nm, a(ii) 100 nm scale
with HRTEM image for d-spacing analysis of the Fe-Al composite (inset) (Reproduced with
permission from Mondal et al. (2019) © Elsevier)

Figure 3: (a) FTIR analysis of Fe-Al nanocomposite before and after fluoride adsorption. (b)
Schematic diagram of ion exchange mechanism for fluoride removal. (Reproduced with
permission from Mondal et al. (2019) © Elsevier)
Figure 4: a(i) FESEM images of prepared Fe NPs, a(ii) average particle size analysis of Fe NPs
(Reproduced with permission from Mondal et al. (2018) © Elsevier)

Figure 5: a(i) Surface morphology of Fe NPs impregnated membrane (ii) Cross-section of Fe

NPs impregnated membrane (Reproduced with permission from Mondal et al. (2018) ©
Elsevier).
Highlights

• New techniques of green synthesis for preparing Iron-based NPs and nanocomposite.

• Advantages of green synthesis of iron nanoparticles over chemical synthesis.

• Iron NPs and nanocomposites for environmental remediation application.

• Advantages of bimetallic iron nanocomposites over iron nanoparticles.

• Future scope and development of better iron-based nanomaterials for efficient

environmental applications.
Declaration of interests

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.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: