Green synthesis of manganese nanoparticles: Applications and future perspective–A review

Accepted Manuscript Green synthesis of manganese nanoparticles: Applications and future perspective–A review

Vahid Hoseinpour, Nasser Ghaemi PII: DOI: Reference:

S1011-1344(18)30959-X https://doi.org/10.1016/j.jphotobiol.2018.10.022 JPB 11387

To appear in:

Journal of Photochemistry & Photobiology, B: Biology

Received date: Revised date: Accepted date:

21 August 2018 25 October 2018 29 October 2018

Please cite this article as: Vahid Hoseinpour, Nasser Ghaemi , Green synthesis of manganese nanoparticles: Applications and future perspective–A review. Jpb (2018), https://doi.org/10.1016/j.jphotobiol.2018.10.022

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Green synthesis of manganese nanoparticles: applications and future perspective - A review

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Vahid Hoseinpour 1*, Nasser Ghaemi 1

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1. School of Chemistry, College of Science, University of Tehran, Tehran, Iran

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* Corresponding author:

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* [email protected]

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ACCEPTED MANUSCRIPT Abstract Nanobiotechnology is a promising and appearing field of nanotechnology. In recent years, the necessity of making biocompatible materials for different applications in various area such as health, medicine, water treatment and purification, etc. caused more attention to this area. Today, green synthesis of different nanoparticles (NPs) has been extensively studied.

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However, less attention has been paid to manganese as a high-performance metal in various

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applications such as medicine, biomedicine, biosensors, water treatment and purification,

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electronics, electrochemistry, photoelectronics, catalysis, and etc. Manganese oxides (Mnoxides) has wealthy structures such as MnO, Mn5O8, Mn2O3, MnO2, and Mn3O4, and can be

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used in a variety of fields. Mn-oxide NPs potentially hold great promise for sustainable nanotechnology. This review focusses on the green synthesis, applications and future

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perspective of Mn NPs. Different methods of green synthesis of Mn NPs, including synthesis using plant extract, synthesis using microorganism, and low-temperature synthesis of Mn

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NPs have been investigated and presented. Structure, and size, of green synthesized Mn NPs

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via each method have been compared. Also, various applications of the green synthesized Mn

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NPs have been reviewed. Furthermore, the future perspective of green synthesis and applications of the green synthesized Mn NPs are expressed. Also, different applications

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explained for green synthesized Mn NPs are expressed as well as potential applications for green synthesized Mn NPs are suggested.

Keywords: Nanoparticles, Green Synthesis, Manganese, Nanobiotechnology,

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ACCEPTED MANUSCRIPT 1. Introduction In recent years, the study in nanotechnology has engrossed growing fondness because of its revolutionist and promising effects on many areas [1,2]. Nanotechnology is appearing as a new field of research dealing with preparation of nanomaterials and nanoparticles (NPs) for their applications in diverse fields due to their highly multifunctional, modular, and efficient such as food technology, healthcare, optical devices, space industry,

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properties

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pharmaceutics, cosmetics, electrochemistry, modify membrane, textile industry, water

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treatment and purification, water supply systems, biomedicines, mechanics, optics, energy science, catalysis, sensors, electronics, and, etc. [2–9]. and

nanobiotechnology

are

terms

that

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Nanobiology

appear

in conjunction with

nanotechnology and biology [10]. Nanobiotechnology is a promising and appearing field of

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nanotechnology and is involved with the diverse research area of expertise, such as chemistry, engineering, physics, material science, medicine, and biology [3,11,12].

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Nanotechnology has more benefits over another common process owing to the accessibility of more components by biological creatures for the preparation of NPs. The rich biodiversity

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[12].

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of suchlike biological creatures should be studied for the preparation of bionanomaterials

Usually, two strategies bottom-up and top-down are used to synthesize [13,14]. In the topdown approach, the bulk-materials are usually broken down to nanomaterials, whereas in the bottom-up approach, molecules or atoms are assembled to NPs [12]. The bottom-up approach is usually used for green synthesis and chemical synthesis of NPs. [12]. Green synthesis of NPs is an evolved method from the nanobiotechnology [15], and todays, green nanomaterials are the main purpose of nanotechnology research [3]. Green synthesis of nanoparticles has been emerging as a non-toxic, environmentally friendly, clean, less costly, and almost new approach, also, it can be done at room pressure and temperature [3,16,17]. Green synthesis of 3

ACCEPTED MANUSCRIPT nanoparticles can be considered as an alternative to synthesizing biocompatible NPs, which is the latest feasible method of connecting material-science and biotechnology [12]. Hence, green synthesis of NPs with controlled shape and size employing genetic engineering methods, molecular cloning, plants extracts, and other biological techniques will be a wonderful advancement in the nanobiotechnology [12].

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Nanomaterials (usually≤100 nm) can show excellent chemical and physical properties from

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their bulk due to their high specific surface area [5,18]. Biogenic-metallic NPs can be

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synthesized by various organisms, such as, plants, fungi, bacteria, yeasts, algae, and actinomycetes which causes considerable modifications of the properties of the metals

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[3,19]. Many research and review articles on the green synthesis of gold [20–25], silver [4,26–37], zinc [18,38–45], Iron [3], copper [46–49] and other metals have been presented

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[10,12–14,19,50–56].

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Meanwhile, manganese has not been taken into consideration despite its very interesting and

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practical properties. In this paper, a review of the green synthesis, applications and future perspective of manganese NPs is under consideration for the first time. Chart 1 presented a

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graphical abstract of green synthesis of Mn NPs.

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Chart 1 a graphical abstract of green synthesis of Mn NPs.

2. Manganese nanoparticles Manganese is the most abundant element of the earth, as Mn is the twelfth most common element on the planet and the third most abundant transition element after iron and titanium [57]. Manganese is a necessary micro-nutrient for reproduction, prevention, and growth of fish and terrestrial animals [58].

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ACCEPTED MANUSCRIPT Among different 3d transition metal-oxides, Mn-oxides have acquired specific interest due to their wealthy structural and compositional variants such as MnO, Mn5O8, Mn2O3, MnO2, and Mn3O4 [59]. Mn-oxide NPs potentially hold great promise for sustainable nanotechnology [57]. Mn-oxides can be used in molecular sieves, solar cells, batteries, catalysts, magnetic materials, optoelectronics, drug delivery ion-sieves, as well as other fields such as imaging magnetic storage devices, water treatment and purification, due to their

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contrast agents,

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privileged physical and chemical properties [60–66]. Moreover, Mn-oxides are usually less

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toxic materials than other compounds upon which NPs are generally based, such as diverse chalcogenides, also they have environmental compatibility, high specific capacitance, and

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cost-effectiveness [57,67]. In fact, the last studies display the potential for Mn-oxides, including Mn-Oxide NPs, to replace technologies based upon scarce-elements such as

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platinum catalytic converters for car publication [57]. Mn-Oxides NPs have structural flexibility composed of different physicochemical properties [68]. Diverse nanostructures of

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Mn-Oxides, such as nanorods, nanobelts, nanosheets, nanowires, nanotubes, nanofibers,

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mesoporous sieves, molecular sieves and branched structures, urchins, orchids, and other

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hierarchical structures have been prepared by different techniques [68]. MnO2 is one of the most significant materials and a number of researchers have paid special

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attention to the efficacy of manganese dioxide in addition to the electromagnetic attributes of the materials [63]. MnO2 is one of the most stable Mn-oxides with privileged physicochemical attributes under ambient conditions [67]. MnO2 NPs have also applications in ion-exchange, biosensor, medicine, molecular adsorption, supercapacitors, catalysis, and energy storage [65,67]. Mn3O4 is a mixed-valence oxide that has been a promising candidate for a wide range of applications containing being employed as microwave absorption materials, supercapacitors, catalysts, anode materials, sensors, and precursors for the manufacture of LiMn2O4, Which is 6

ACCEPTED MANUSCRIPT used for battery preparation [57,69,70]. Also, Mn3O4 is known to be an efficient catalyst for the oxidation of methane reduction of nitrobenzene and decomposition of waste gas NOx [69]. Diverse methods have been expanded to the synthesis of Mn-oxide NPs such as ambient

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temperature solid reactions, self-reacting microemulsion, sonochemical, precipitation, hydrothermal and green synthesis techniques [63,71]. Since, the attributes of NPs are shape

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and size related, the synthesis method having control on size, monodispersity, and shape is a

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significant area of study [60].

3. Green synthesis of Mn NPs

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From the perspective of the environment, green methods for synthesizing Mn NPs are considered, as a particular chemical it is not necessary to be stabilized and reduced, and also

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it’s preparation can be done under mild conditions such as ambient temperature and pressure

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[66,72]. In the biological synthesis of Mn NPs, raw materials, vegetables and fruits, plant

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extracts, microbes, and fungi are utilized to prepare Mn and Mn-oxide nanoparticles [2,19]. The control of the shape and size of green synthesized Mn NPs and their applications are still

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two major challenges in nanobiotechnology [10]. In general, three methods of green synthesis using plant extracts, green synthesis using microorganism, and low-temperature synthesis have been used for Mn green synthesis, which is presented below.

3.1.Green synthesis using plant extracts There are various reports of green synthesis of Mn NPs in different methods. Employing plant extract reduction and stabilization of manganese metal into Mn NPs are the simplest, inexpensive and environmentally friendly approaches in green chemistry [10,63]. Green 7

ACCEPTED MANUSCRIPT synthesis by plant extracts has advantages, including scalability, medical applicability, and biocompatibility [10,51]. In the synthesis of NPs employing plant extracts, the plant extract is simply mixed with the metal salt solution at ambient temperature and the reaction is complete in a few minutes. The metal reduction is attributed to the different compounds which are present in the plant extract such as polysaccharides, terpenoids, flavones, and phenolics

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[52,73]. So far, several plant extracts have been used in the synthesis of manganese NPs.

MnO2 NPs

Kalopanax pictus leaf extract clove, i.e., Syzygium aromaticum aqueous extract Phyllanthus amarus leaf extract Adalodakam leaf extract

MnO2 NPs

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lemon methanolic extract

Size

50 nm

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Mn NPs structure

1-60 nm 4 nm

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MnO NPs

MnO NPs

40-50 nm 44 and 66 nm 10–34 nm 38 nm

MnO2 NPs

80 nm

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MnO2 nanorods Mn3 O4 NPs

Ananas comosus (L.) peel extract Dittrichia graveolens (L.) extract Yucca gloriosa leaf extract

Mn3 O4 NPs

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Plant Extract

Organism

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Method

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Table 1 Green synthesis of Mn NPs using extracts of plants and their applications. Application/Property

References

Antibacterial and Antifungal Dye degradation

Jayandran et al. [63] Moon et al. [65]

Electrochemical

Kumar et al. [61]

Fluorescence studies

Prasad and Patra [66] Prasad [59]

Nutritional supplements Dye degradation Dye degradation

Asaikkutti, A. et al. [58] Souri et al. [64] Hoseinpour et al. [74]

Jayandran et al. (2015) reported the synthesis of manganese nanoparticles by reducing manganese acetate with the help of lemon methanolic extract as a reducing agent and turmeric curcumin as a stabilizing agent with an average crystallite size of particles in the range of 50 nm (Figure 1A). At their experience, pH was kept among 3-4 and the temperature was at 50-60 ˚C during the reaction [63].

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Figure 1 TEM and SEM images of green synthesized MN NPs using (A) lemon methanolic extract as

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reducing agent and turmeric curcumin as a stabilizing agent [63], (B) aqueous leaf extract of Kalopanax pictus [65], (C) clove, i.e., Syzygium aromaticum aqueous extract [61], (D) Phyllanthus

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amarus leaf extract [66], (E) Ananas comosus (L.) peel extract [58], (F) Bacillus sp. cells [60], and

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(G) Streptomyces sp. HBUM171191 [75]

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Moon et al. (2015) used an aqueous leaf extract of Kalopanax pictus as the reduction agent of potassium permanganate (KMnO4) to produce manganese dioxide (MnO2) nanoparticles that had an average particle size of 19.2 nm with a particle diameter ranging from 1 to 60 nm (Figure 1B). The synthesis was occurred without stirring at ambient temperature. [65].

Kumar et al. (2017) reported the synthesis of MnO NPs with different sizes via clove, i.e., Syzygium aromaticum aqueous extract as reducing and stabilizing agents. The TEM image (Figure 1C) and XRD analysis showed that MnO NPs were 2.5 and 1.8 nm in size, respectively [61]. To obtain MnO NPs of different sizes, they synthesized MnO NPs in 9

ACCEPTED MANUSCRIPT various conditions (metal concentration: 1 to 80 mM, plant extraction concentration: 0.25 to 1 ml, metal ion volume, 1 to 5 ml, plant extraction: 1 to 4 ml, temperature: 25 to 85 ˚C).

Synthesis of manganese nanorods using a leaf extract of Phyllanthus amarus was reported by Prasad and Patra (2017) with an average size of 40–50 nm and TEM images are shown in

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figure 1D. in this research, the mixture was stirred 1 h at ambient temperature and pH 6.8

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[66].

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In an experiment conducted by Prasad, Mn3O4 NPs were prepared using manganese sulphate monohydrate and the leaf extract of Malabar Nut (Adhatoda vasica Nees / Justicia adhatoda)

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was employed as the precursor salt and reductant respectively (pH 7, temperature 90). In his research, crystallographic structure, optical characteristics, the mechanism of the formation,

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the crystallite sizes, and thermal behavior of the NPs were studied. The XRD analysis confirmed the formation of Mn3O4 in tetragonal body-centered lattice system. Also, the

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average size of 44 nm and an effective crystallite size of 66 nm were measured using Debye-

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Scherer equation and Hall-Williamson technique, respectively. The optical analysis in the

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UV–Vis-NIR range displayed the energy band gap of Mn3O4 equal to 2.50 eV. Furthermore, the thermo-gravimetric analysis study showed the absolute phase transformation from Mn3O4

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to Mn5O8 at 498.3 °C and more decomposition to Mn2O3 which crystallized at 581.3 °C [59]. In another study, Mn3O4 NPs (10–34 nm) were synthesized using Ananas comosus (L.) peel extract at room temperature. HR-SEM images (Figure 1E) displayed Mn3O4, with an average size of 40–50 nm and spherical in shape. The Zeta potential showed the negative surface charge for Mn3O4 NPs [58]. Souri et al. (2018) reported the optimization of green synthesis of MnO NPs with Dittrichia graveolens (L.) extract via RSM. The central composite design was employed to measure the

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ACCEPTED MANUSCRIPT effect of the extract, metal ratio, time, and pH on the preparation of MnO NPs (Figure 2). The experience occurred at room temperature.

The result showed that the most effective

parameter was the extract to the metal ratio. The MnO NPs average size at optimal condition

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was measured about 38 nm [64].

Figure 2. 3D plot showing the effect of (a) pH and Dittrichia graveolens (L.) extract, (b) Dittrichia

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graveolens (L.) extract and time, (c) pH and time, On absorbance of green synthesized MnO NPs and (d) normal plot [64]

Also, Hoseinpour et al. (2018) described the green synthesis of MnO2 NPs by Yucca gloriosa leaf extract [74]. The reaction condition was pH 8 and room temperature. The XRD analysis confirmed the formation of MnO2. Also, the average size of 80 nm was measured using Debye-Scherer equation [74].

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ACCEPTED MANUSCRIPT Green synthesis of Mn NPs using different plant extracts and their structure and size are compared in Table 1.

3.2. Green synthesis using microorganism

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Microorganisms have a high potential for synthesizing NPs [19]. Ever, various

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microorganisms, containing yeast, bacteria, and funguses have been used for the preparation

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of metal NPs [19]. Microorganisms have the capability to remove and accumulate heavy metals owning to several reeducates enzymes, which are capable to reduce metal salts to

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metal NPs with a limited size distribution and, thus, better dispersity [19]. The literature on manganese green synthesis using microorganisms is presented below

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In one work MnO2 NPs were synthesized via Bacillus sp. cells [60]. A control experiment was similarly run without inoculating with the cells to check for any abiotic precipitation of

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the manganese during the operational experimental conditions. The cells efficiently synthesized MnO2 NPs of the average size of 4.62 nm (Figure 1F). In another study, Mn

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sulfate was synthesized using Streptomyces sp. HBUM171191 in 35˚C with the size ranging from 10 to 20 nm (Figure 1G). [75]. Also, in a work, Mn0.6Fe2.4O4 magnetic NPs were

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prepared via Thermoanaerobacter sp. TOR-39 on a large scale with the average size of 80 nm and a maximum yield of 4.5 (g/l). The incubation was kept at 65 ˚C for 3 weeks, and the mixture was supplemented with 10 mM glucose every 4 days. pH was kept between 7.2 and 7.5. Pending the incubation, continuous purging with an N2 gas maintained anaerobic conditions of the mixture and abducted CO2 gas in the headspace. The contents of the reactor were stirred continuously at 40 rpm, and vigorous mixing was performed for more than 30 min every day [76].

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ACCEPTED MANUSCRIPT Green synthesis of Mn NPs using microorganisms and their structure, and size, are compared

Mn NPs structure MnO2 NPs

Bacillus sp. cells Microorganism

Streptomyces sp. HBUM171191

Mn sulfate

Thermoanaerobacter sp. TOR-39

Mn0.6 Fe2.4 O4 magnetic NPs

Size

Application/Property

References

4.62 nm

-

Sinha, A. et al. [60]

-

Waghmare, S.S. et al. [75] Moon, J.-W. et al. [76]

10 to 20 nm 80 nm

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Organism

Magnetic property

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Method

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in Table 2.

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3.3.Low-temperature synthesis

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Table 2 Green synthesis of Mn NPs using microorganisms and their applications.

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Low-temperature synthesis in aqueous solutions ever showed a user and environmentally

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friendly approach, which may be considered to be a green chemical alternative of important applications [77]. The flowerlike NPs of Ag-doped MnO2 were synthesized by Jana et al.

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through an environment-friendly approach (Figure 3). In their research, flowerlike NPs of Ag-doped MnO2 were obtained by photochemical and facile wet chemical methods. UVvisible absorption spectroscopy study was disclosed that doping of Ag NPs in MnO2 NPs leads to a redshift of the absorption peak and reduces the optical band gap energy compared with MnO2. Flowerlike Ag-doped MnO2 NPs were achieved by a facile wet chemical as well as photochemical methods .They also argued that the proposed green method is capable of scale-up due to its simplicity and cost [77]. Also, Veeramani et al. reported one green ambient temperature preparation of polycrystalline Mn3O4 nanowires. In this method, Mn(II)

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ACCEPTED MANUSCRIPT aqueous solution was oxidized under neutral conditions by atmospheric oxygen in the presence of a low-cost catalyst (α-Fe2O3), and a biochemical buffer (pH 7.5). The time was varied from 1 to 36 h [57].

Green synthesis of Mn NPs using Low-temperature method and their structure and size are

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compared in Table 3.

Figure 3 SEM images of Ag-doped MnO2 nanoflower NPs prepared via Low-temperature technique

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[77]

Method

Organism -

Mn NPs structure flowerlike NPs of Ag-doped MnO2

Lowtemperature -

polycrystalline Mn3 O4 nanowires

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Size

Application/Property

References

1.25 µm × 500 nm 7 nm

Application in surfaceenhanced Raman scattering (SERS)

Jana et al. [77]

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Veeramani et al. [57]

ACCEPTED MANUSCRIPT Table 3 Green synthesis of Mn NPs using Low-temperature method and their applications.

4. Application of green synthesized Mn NPs So far, several applications have been presented for green synthesized Mn, which is reviewed

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below. Also, a summary of different applications of Mn NPs is given in Table 1, Table 2, and

4.1.Antibacterial and antifungal activities

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Table 3.

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The antifungal and antibacterial property of NPs has been interpreted by their capability to the making of highly reactive oxygen species (OH-, H2O2, and O22-) on the surface of the NPs

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connected with deadly damage to the fungal and bacteria [1]. Most studies focus on the application of the Mn NPs in electronic properties and catalytic activities, but the

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antibacterial properties of Mn NPs are seldom investigated [63]. In one study, the

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antibacterial activities of curcumin and curcumin stabilized Mn NPs against Staphylococcus

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aureus and Bacillus subtilis (gram-positive) and Escherichia coli and Staphylococcus bacillus (gram-negative) were appraised by disc diffusion method, and the zone of inhibition was

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compared to Chloramphenicol [63]. The results are displayed in Table 4 and it was found out that the antibacterial activities of curcumin stabilized Mn NPs were superior to the curcumin for all bacteria. The Mn NPs exhibited stronger antibacterial activities to Chloramphenicol against S. aureus and almost similar activities against E. coli [63]. Also in the same work, the antifungal activities of Curcumin and Mn NPs were studied with diffusion method against four fungal strains Trichophyton simii, Curvularia lunata, Aspergillus niger, and Candida albicans, and were compared with Fluconazole as a standard drug. The results are displayed

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ACCEPTED MANUSCRIPT in Table 4 and it was found out that the antifungal activities of curcumin stabilized Mn NPs were superior to the curcumin and standard drug [63].

Species

Fungal

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S. aureus B. subtilis E. coli S. bacillu C. albicans C. lunata A. niger T. simii

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Bacterial

Zone of inhibition diameter (mm) Standard Drag Curcumin MnO2 NPs 16 13 18 18 16 11 20 17 19 21 15 17 17 16 20 17 14 19 20 15 18 17 16 20

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Type

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Table 4 Effect of curcumin and green synthesized MnO2 NPs on antifungal and antibacterial activity

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[63]

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4.2. Nutritional supplements

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Manganese is a necessary micronutrient for reproduction, growth, and prevention of skeletal abnormalities in terrestrial animals and fish [58]. In one study, the green synthesized Mn3O4

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NPs were used as dietary supplements for freshwater prawn Macrobrachium rosenbergii

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[58]. According to the results, supplementations of green synthesized MnO NPs significantly improved the activity of metabolic activities and antioxidant defense systems such as glutamic pyruvate transaminase, antioxidants enzymatic activity, and glutamic oxaloacetate transaminase. Also, Mn3O4 NPs supplements cured the efficiency in final weight, growth, and survival of M. rosenbergii. In conclusion, green synthesized Mn2O4 NPs were effective and safe as diet supplements for freshwater prawn Macrobrachium rosenbergii [58]. According to this study, it could be used as a diet supplement for other aquatic animals [58].

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ACCEPTED MANUSCRIPT 4.3.Dye degradation activity The production of electron-hole (ĕ–h+) pairs between in conduction and valence bands of NPs with the high surface area is usually responsible for producing the active oxygen species (O2•, O2-, HOO•, and OH-). On the other hand, the active oxygen species are responsible for the

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degradation of dye into less harmful organics or minerals [78]. The massive volume of environmental pollutants, carcinogenic natural and nondegradable dyes, is drained by the

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paper and textile industries. Todays, photocatalytic technique got the extensive attention

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owing to its efficient degradation of dyes [47,79,80]. In on work, dye degradation activity of MnO2 NPs was studied to degrade safranin O and congo red [65]. In their work, the MnO2

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NPs were also prepared by a chemical method employing Na2S2O3 as a reducing agent at

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ambient temperature. Time analysis of the Congo red degradation displayed faster dye degradation for green synthesized MnO2 NPs as compared with chemically synthesized

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MnO2 NPs. The dye degradation potential of green synthesized MnO2 NPs and chemically

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synthesized MnO2 NPs to degrade Safranin O was similar. The difference in the efficiency of green synthesized and chemically synthesized Mn NPs may be due to their size and shape

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differences [65]. The green method displayed the presence of spherical NPs and chemical

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method showed whisker-shaped MnO2 NPs [65]. The comparative of chemical and green synthesized MnO2 NPs are summarized in Table 5.

Table 5. Comparative study of chemical and green synthesized MnO2 NPs for dye degradation according to Moon et al. (2015) report [65]. Samples

UV

Congo red degradation

Safranin O degradation

20 min (68.7%

10 to 15 min (complete

peaks Chemical synthesized

410 nm

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degradation)

degradation)

Green synthesized MnO2

360-404

8 min (complete

10 to 15 min (complete

NPs

nm

degradation)

degradation)

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In another work, MnO NPs were used for degradation of light green and Rhodamine B dyes

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[64]. Figure 4 illustrates the UV–Visible spectra of the degradation of the light green and

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Rhodamine B. Light green and Rhodamine B degraded completely in 17 and 22 min, respectively [64]. Also, in another study, green synthesized MnO2 NPs were employed for

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decolorization of Acid orange dye and showed promising results for the degradation of this

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organic contaminant [74].

Figure 4 a) Light green degradation and b) Rhodamine B degradation using MnONPs with time [64]

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4.4.Electrochemical sensing In one work, the application of the synthesized MnO NPs was examined in an electrochemical sensing area [61]. The Green synthesized MnO NPs were employed for the

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electrochemical detection of p-nitrophenol (PNP). The electrocatalytic activity of the MnO NPs/ butyl carbitol acetate (BCA)/gold electrode had a good low limit and sensitivity of

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detection for PNP. Furthermore, the green synthesized MnO NPs can be useful for other

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chemical sensors [61].

4.5.Fluorescence property

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In one work, the solid state fluorescence emission spectra of the green synthesized Mn NPs at ambient temperature was studied and the emission intensity was observed at 518 nm (λex =

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5. Future perspective

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320 nm). [66].

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5.1. Green synthesis

As it was noted above, there are many methods for the green synthesis of nanoparticles [81] and only a few methods for the synthesis of manganese have been used. Due to the existence of various structures for Mn-oxides (MnO, Mn5O8, Mn2O3, MnO2, and Mn3O4) [59], and also the diversity of organisms, such as, plants, fungi, bacteria, yeasts, algae, and actinomycetes have been used to green synthesis, further study on the green synthesis of manganese NPs can be

interesting.

In addition, investigating the

possibility of synthesizing metallic

nanocomposites (such as ZnO-MnO, CuO-MnO and etc.) [82–84] can help to further expand

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ACCEPTED MANUSCRIPT the applications of Mn NPs. As a suggestion, plants with high antioxidant properties can be studied for the green synthesis of metallic nanocomposites.

5.2. Applications

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So far, the green synthesized Mn NPs have been used for several different applications, as reviewed above. But with regard to features of the green synthesized Mn NPs, they can be

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studied in various medical, biological, environmental and other applications. For example,

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several applications that have been studied for manganese synthesized by chemical methods are reviewed below . These applications can potentially be studied for the green synthesized

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Mn NPs.

5.2.1. Purification of DNA

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Functionalized magnetic NPs are frequently noteworthy for different applications in

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biochemistry, molecular diagnostics, environment protection, etc. [85–87]. The merger of

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magnetic particles along with existing and new emerging methods can develop potential areas of their applications [88]. Super-paramagnetic materials have been noteworthy for analytical

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chemistry and molecular diagnostics applications due to their capability to interact with different biomolecules and their inimitable magnetic properties [88]. In a study, silica coated La 0.75Sr0.25MnO3 perovskite manganite nanoparticles were employed for purification and extraction of DNAs. The surface of such particles was exposed both to the deprotonated silanol groups (Si–O−) and silanol groups (Si–OH) under neutral pH producing a negative zeta potential [88].

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ACCEPTED MANUSCRIPT 5.2.2. Water treatment and purification Arsenic is an abundant element in the earth's crust and is one of the water pollutants. Arsenic is found in four oxidation states and arsenic(III) are more toxic than arsenic(V) [70]. Arsenic can cause circulatory disorders, liver and skin cancer, and hyperpigmentation [70].

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In a work, MnO–coated sand (MnCD) was provided for removing arsenic(V) and arsenic(III) from water [70]. The study of the kinetics of arsenic(III) removal alone and in the presence of

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arsenic(V) showed that MnCDs in both of these conditions were effective and had the highest

[89,90]:

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2+ HAsO4− 2 + Mn + H2O

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effect at the first hour [70]. The adsorption of arsenic is based on the following reaction

H3AsO3 + MnO2

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In another work, MnO2-modified Clinoptilolite-Ca zeolite was prepared and its ability of adsorption of arsenic(V) was studied [91]. The removal of arsenic(V) efficiency of MnO2-

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modified Clinoptilolite-Ca zeolite (MCZ) was compared to natural clinoptilolite-Ca zeolite

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CZ [91]. Also, the effect of feed concentration and pH was studied on arsenic (V) removal

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efficiency. According to the results, the arsenic removal efficiency of MCZ was twice as much as CZ. The MCZ was completely independent of pH. As a result, MCZ can remove

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arsenic, even at low concentrations [91]. GNS/GO-Mn NPs have a high potential in the field of water treatment and purification. In a study, Graphene-nanosheets/delta-MnO2 (GNS-MnO2) nanocomposite was provided for the removal of nickel ions from wastewater [92]. GNS-MnO2 nanocomposite can be used for five times with ~91 %. The capacity of the adsorption of Ni(II) for GNS/MnO2 is found to be about 5 and 1.5 times higher than GNS and delta-MnO2, respectively [92]. Some other GNS/GO-MnNPs employed for water treatment and purification were presented in Table 6 [5]. 21

ACCEPTED MANUSCRIPT In a study, silicon-doped semicrystalline MnO2 (Si-MnO2) was employed as a catalyst for the degradation of Rhodamine B (RhB) at room temperature [71]. Si-MnO2 removed RhB from water at room temperature in 15 min [71].

Efficiency 10.8 mg/g (30 ˚C) 46.5–66.0 mg/g (25–45 ˚C) 34.7 mg/g (25 ˚C) 22.5 mg/g (25 ˚C) Detection limit: 0.8 μM

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Application Adsorption of Hg(II) Adsorption of Ni(II) Degradation of MB Degradation of RB Detection of change in electrical current (H2 O2)

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materials MnO2 -GNs delta-MnO2 -GNs MnFe2O4–GNs MnFe2O4–GNs MnO2-GO

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Table 6 various applications of Mn-based NPs for water treatment and purification [5]

5.2.3. Epoxidation of olefin and water oxidation

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In a study, The MnO NPs showed effective catalytic activities toward the epoxidation of olefins and water oxidation in the attendance of hydrogen peroxide and cerium(IV)

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ammonium nitrate, respectively [93]. The MnO NP displayed suitable catalytic property for

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epoxidation of aromatic olefins and slight catalytic property for epoxidation of several

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nonaromatic olefins in the attendance of bicarbonate ions and H2O2 (Figure 5) [93].

22

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5.2.4. Optical and magnetic properties

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Figure 5 Epoxidation of olefine catalyzed by Mn-oxide [93]

Djerdj et al. (2007) studied the magnetic properties of MnO NPs [69]. In their work, the

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super-paramagnetic behavior of MnO NPs was proved by SQUID analysis. The SQUID

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results clearly unfolded MnO NPs super-paramagnetic behavior, which is unlike prior reports

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that anticipated weak ferromagnetic property of MnO NPs [69].

xS

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In another work, Mn incorporated ZnS Nano-rods (MnxZn1-xS NRs) were prepared. MnxZn1NRs showed strong orange luminescence at ∼585 nm [94]. Lower Mn concentrations

showed six-line hyperfine splitting, while higher Mn concentrations displayed broad Lorentzian-shaped EPR spectra. Three diverse emissions in the orange, blue, and green regions were ostensibly in the ambient temperature photoluminescence spectra .EPR analysis confirms the attendance of magnetic dipole interaction for the MnxZn1-xS NRs with a higher Mn concentration. MnxZn1-xS NRs with well emission attributes could be employed in emissive devices [94].

23

ACCEPTED MANUSCRIPT 5.2.5. Supercapacitors and lithium-ion batteries In a work, electrochemical behaviors of graphene-oxide supported by needlelike MnO2 nanoparticles (GO-MnO2 nanocomposites) were studied [67]. The prepared GO-MnO2 nanocomposites showed good electrochemical behaviors that are beneficial as a material for supercapacitors electrodes. Also, GO-MnO2 nanocomposites can be used in other

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applications such as catalysis reactions, absorbents, and electronica electrodes for different

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devices [67].

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In another work, hierarchical α-MnO2 Nanowires@Ni 1-xMnxOy Nanoflakes Core-Shell Nanostructures with high electrochemical efficiency were examined for supercapacitors [95].

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The prepared nanomaterial with an Mn concentration of 75% showed excellent performance in supercapacitors application [95]. Also, in another study, manganese was used in a

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6. Concluding remarks

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nanocomposite composition for lithium-ion battery application [96].

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Nanobiotechnology is expanding as an emerging area of nanotechnology. In recent years, the necessity of making biocompatible materials for different applications in various area such as

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health, medicine, water treatment and purification, biosensors, food industrially, etc. caused more attention to this area. On the other hand, the design of the green approach has become a necessity for the industry in the future. Therefore, further research on the green synthesis of nanoparticles can be very promising. So far, many studies were done in the green synthesis of metallic nanoparticles. Also, many applications have been proposed for metallic NPs such as gold, silver, zinc, iron, etc. However, despite the great capabilities, limited research has been done on Mn NPs.

24

ACCEPTED MANUSCRIPT In this study, different green synthesis methods including green synthesis using plant extracts, green synthesis using microorganisms, and low-temperature synthesis have been reviewed. Structure, and size, of green synthesized Mn NPs via each method have been compared. Also, various applications of the green synthesized Mn NPs have been reviewed. Furthermore, the future perspective of green synthesis and applications of the green synthesized Mn NPs are

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expressed. Due to the existence of various structures for Mn-oxides (MnO, Mn5O8, Mn2O3,

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MnO2, and Mn3O4), and also the diversity of plants and microorganisms that have the ability

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of green synthesizing, further study on the green synthesis of manganese NPs can be interesting. In addition, investigating the possibility of synthesizing metallic nanocomposites

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(such as ZnO-MnO, CuO-MnO and etc.) can help to further expand the applications of Mn NPs. Green synthesized Mn NPs can also be used in medical, biological, environmental,

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biomedical and other applications such as tissue engineering.

Here are some of the

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applications of chemical synthesized Mn NPs as a suggestion.

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Methods of green synthesis of Mn NPs was reviewed. Different applications of green synthesized Mn NPs were reviewed. Future perspective of green synthesis of Mn NPs was studied. Future perspective of applications of green synthesis of Mn NPs was studied.

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