Accepted Manuscript

Eco-friendly synthesis of magnetite (Fe3O4) nanoparticles with tunable size:

dielectric, magnetic, thermal and optical studies

Ali Bahadur, Aamer Saeed, Muhammad Shoaib, Shahid Iqbal, Muhammad Imran
Bashir, Muhammad Waqas, Muhammad Nasir Hussain, Nasir Abbas

PII: S0254-0584(17)30430-3

DOI: 10.1016/j.matchemphys.2017.05.061

Reference: MAC 19737

To appear in: Materials Chemistry and Physics

Received Date: 27 January 2017

Revised Date: 28 April 2017

Accepted Date: 30 May 2017

Please cite this article as: Ali Bahadur, Aamer Saeed, Muhammad Shoaib, Shahid Iqbal,
Muhammad Imran Bashir, Muhammad Waqas, Muhammad Nasir Hussain, Nasir Abbas, Eco-
friendly synthesis of magnetite (Fe3O4) nanoparticles with tunable size: dielectric, magnetic,
thermal and optical studies, Materials Chemistry and Physics (2017), doi: 10.1016/j.matchemphys.
2017.05.061

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 ACCEPTED MANUSCRIPT

Eco-friendly synthesis of magnetite (Fe3O4) nanoparticles with tunable size: dielectric,

magnetic, thermal and optical studies

Ali Bahadur a, , Aamer Saeed a, , Muhammad Shoaib a, Shahid Iqbal b, Muhammad Imran

Bashir c, Muhammad Waqas d, Muhammad Nasir Hussain a, and Nasir Abbas a

aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan.

b School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing100049, PR
China
cDepartment of Physics, Quaid-i-Azam University, Islamabad 45320, Pakistan
d Key Laboratory of Multi-Phase Complex System, Institute of Process Engineering, Chinese Academy of Sciences,

Beijing 100080, China

 To whom corresponding should be addressed:

alibahadur138@yahoo.com, aamersaeed@yahoo.com

Abstract

In this paper, a detailed study on dielectric, magnetic, thermal, and optical properties of citric acid

modified ultrafine superparamagnetic magnetite (Fe3O4) nanoparticles (Cit-USPMNs) was

conducted. Water dispersible Cit-USPMNs were synthesized by modified co-precipitation

technique. Hydrazine (N2H4) and sodium hydroxide were used as precipitating agents. The size of

Cit-USPMNs was tuned by changing the volume of added N2H4. Lemon juice; a source of citric

acid was used as a stabilizing agent for this ferrofluid. Phase purity was obtained by annealing at

150 and 250 ºC for 4 h. The X-ray diffraction (XRD) pattern was used to confirm the formation of

pure magnetite nanoparticles (NPs). The size of Cit-USPMNs lies in the range of 11-15 nm, as

calculated by Scherrer's formula which was confirmed by TEM images. The prepared Cit-

USPMNs were studied for magnetic and dielectric properties by vibrating sample magnetometer

(VSM) and four probe LCR meter respectively. The MH-loop shows that the magnetic NPs are

superparamagnetic in nature. The dielectric behavior and tangent losses as a function of required

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frequency range were also studied. Optical properties were studied with the help of UV-Vis

spectrophotometer. Direct and indirect energy band gaps for Cit-USPMNs were calculated from

the UV-Vis spectrum. Size, shape, and surface morphology were tested by TEM image. Surface

functionality of Cit-USPMNs and formation of the Fe-O bond was verified by FTIR spectroscopy.

Thermal properties were studied by thermogravimetric analysis (TGA).

Keywords: Co-precipitation; ultrafine superparamagnetic; Fe3O4; dielectric; magnetic; optical;

thermal; magnetite.

1. Introduction

From the last decade, considerable attention has been given to the synthesis and characterization

of nanoscale materials such as nanoparticles (NPs), nanowires, nanotube, nanosheets, nanoflower,

hollow sphere, hollow cage and multilayer materials [1-7]. Nanoscale materials have shown

interesting properties as compared to the bulk material [8]. The morphology, composition,

crystallinity, shape and size has the prevailing effect on dielectric, magnetic, thermal and optical

properties of magnetic NPs [9]. Current area of research is focused on the applications of magnetic

NPs, where their unique properties allow considerable uplifts in research [10]. In the field of

electronics, it was needed to inquire magnetically ordered superstructures thoroughly and

systematically for improving the sensitivity of sensors [11]. Magnetically ordered superstructures

can be only possible by controlling sheath thickness, inter-particle interactions, minimizing layer

defects and improving packing efficiency [12, 13]. Enhanced magnetization and susceptibilities of

magnetic NPs are the basic requirements for its potential applications as the photo-electronic

device, catalyst, rechargeable battery, data storage device, biosensor, drug delivery carrier, and

biomedical diagnosis agents [14-16]. NPs of iron oxide with biocompatible surface stabilizer have

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been used extensively in hyperthermia for cancer therapy, magnetic resonance imaging (MRI) and

nano-vehicles in drug delivery system [17]. Superparamagnetic NPs having low blocking

temperature and narrow size distribution is best drug delivery vehicles. Therefore, narrow and

controllable size magnetic NPs architecture is a great challenge for today science. Many ways to

prepare Fe3O4 NPs are in practice such as sol-gel, arc-discharge, hydrothermal/solvothermal,

micro-emulsion, spray pyrolysis, high-temperature decomposition of organic precursors,

microwave irradiation, and laser ablation synthesis [18-23]. All the above methods have not been

used on the industrial scale due to poor yield, aggregates formation and wide size distribution

which limited biomedical applications [24, 25]. However modified co-precipitation method is the

best method due to high control over size, favorable kinetics, cheap, narrow size distribution,

environmental friendly [26]. So, it can be used for commercial purpose. In co-precipitation

synthesis, divalent/trivalent iron salts in 1:2 ratio and a base such as aqueous NaOH as precipitation

agent were used for the synthesis NPs of magnetite [27]. In continuation of our previous work, in

this work, modified co-precipitation method was used to obtain homogeneously, impurity free

phase pure, narrow in size distribution and water dispersible Cit-USPMNs because well water

dispersible Cit-USPMNs are the basic requirement of biomedical applications [10, 15, 28].

Dielectric properties of Cit-USPMNs were not elaborated recently. So the main object of current

research was to look into the dielectric constant, electrical conductivity and relaxation time of Cit-

USPMNs along with the magnetic and optical study. The scope of this work was to study the

dielectric properties of Cit-USPMNs as a function of the frequency and the temperature. Dielectric

properties of NPs have potential applications in electronic memories, batteries, and optical filters

[29, 30]. Low loss factors over a broad range of frequency and high dielectric permittivity are

necessary for these applications. Dielectric properties change with the change in crystallinity,

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boundaries, shape and size of NPs. So, keeping in view all these factors, NPs were synthesized

and characterized for dielectric, magnetic and optical properties for exploring its potential

applications in the field of material science.

2. Materials and Method

2.1. Materials

All the chemicals of analytical grade were used. Ferric chloride hexahydrate (FeCl3.6H2O, 99%,

Fluka), ferrous chloride tetrahydrate (FeCl2.4H2O, 99%, Fluka), ethanol (C2H5OH, 95%, Sigma)

hydrochloric acid (HCl, 12 M, Sigma), hydrazine (N2H4, 98%, Fluka) and sodium hydroxide

(NaOH, 99%, Sigma) were used for the synthesis of Cit-USPMNs. Distilled water and ethanol

were used as solvents which were deoxygenated by bubbling N2 gas for 1 h prior to use while all

the other reagents were used as supplied. Lemon juice as the source of citric acid was used as the

surface capping agent.

2.2. Synthesis of Cit-USPMNs ferrofluid

Cit-USPMNs ferrofluid was prepared by modified co-precipitation technique, using FeCl3.6H2O

and FeCl2.4H2O salts solution in basic medium. For in situ synthesis of Cit-USPMNs, a mixture

containing 10 mL of 1 M FeCl2.4H2O, 20 mL of 1 M FeCl3.6H2O and 1 mL of lemon juice were

added at once in a boiling solution of 20 mL of N2H4 and 100 mL of 2 M NaOH under vigorous

mechanical stirring for 5 min. under N2 atmosphere. Dark black precipitates of Cit-USPMNs were

developed instantly. The overall reaction that takes place is shown in equation 1.

Fe 2+ + 2Fe3+ + 8OH ¯  Fe3O 4 + 4H 2 O (1)

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Cit-USPMNs were heated further at 60 °C for 1.5 h under ultrasonic agitation. pH of reaction

media was monitored continuously and maintained throughout at 11-12 by adding 0.5 M NaOH

solution. Stability of colloidal was verified by a magnet. Stable colloidal did not settle down by a

strong magnet that endorsed the formation of citric acid base surface capped magnetite Cit-

USPMNs. To separate the precipitate from impurities, ferrofluid was centrifuged for 10 min. at

3000 rpm. Impurities free Cit-USPMNs were obtained by washing with double distilled deionized

water and ethanol repeatedly until pH 7 of the solution was attained. Finally, thick dark black

precipitates of Cit-USPMNs were obtained and dried overnight at 80 ºC. The acquired material

was ground into fine powder. The phase of Fe3O4 was very sensitive to the annealing temperature.

Fe3O4 is changed to γ-Fe2O3 and α-Fe2O3 at 270 ºC and 335 ºC respectively. So, Cit-USPMNs were

annealed at two different temperatures at 150 ºC and 250 ºC for 4 h to perform an XRD. Annealing

removed the impurity phases of Cit-USPMNs, water contents, and crystallite phase defects as

shown in Fig. 1(A-C). These were the unique modified standard conditions for this experimental

work which were not reported elsewhere. The size of as-synthesized Cit-USPMNs was tuned by

controlling the amount of hydrazine. Cit-USPMNs having the size of 11 nm and 15 nm were

synthesized by using 20 mL and 15 mL amount of N2H4 respectively.

2.3. Characterizations

The morphology observation of the Cit-USPMNs was performed on TEM analysis Philips EM

400 (Philips EM 400) transmission electron microscope. Phase purity and the structure of the Cit-

USPMNs were confirmed by using X-ray diffractometer MSAL XD2 with Cu, Kα (λ = 0.15406

nm. Formation of Cit-USPMNs and surface functionality was verified by using Bruker Vertex 70

FTIR spectrometer with a wavelength range of 4000-400 cm-1. The magnetic measurements were

performed with a quantum design PPMS magnetometer and a vibrating sample magnetometer

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(VSM) (Lakeshore 7300). Dielectric properties were examined by using Wayne Kerr LCR meter

bridge (WK4275) over the frequency range of 20 Hz to 1 MHz. Capacitance and dissipation factor

were recorded from LCR meter bridge simultaneously. Thermal changes and thermal instability

of Cit-USPMNs were studied by TGA, obtained by using NETZSCH Simultaneous Thermal

Analyzer STA 429. The optical absorption spectra and the band gap of Cit-USPMNs were

determined by using UV-Vis spectrometer (Model UV-2502) in the wavelength range of 200 nm

to 800 nm.

3. Results and Discussion

3.1. X-ray powder diffraction analysis

The phase purity and crystallinity of the Cit-USPMNs were confirmed by using MSAL XD2

diffractometer with Cu (Kα, λ = 0.15406 nm) at room temperature. The XRD diffraction pattern

was collected at room temperature with a step size of 0.20o for the angular range of 20 2 80

and counting time 0.5s for each step. XRD diffraction pattern of the Cit-USPMNs is shown in Fig.

1(A-C). The intensity and position of diffraction peaks were according to standard XRD diffraction

pattern (JCPDS Card No. 19-0629) of magnetite with cubic single phase [31]. Interplanar spacing

"dhkl = 2. 4993 Ǻ” and the lattice constant “a = 8. 211 Ǻ" of Cit-USPMNs were determined by

using Braggs equation which agreed with magnetite in bulk (d=2.531 Ǻ and a=8.394 Ǻ). XRD

diffraction pattern represents spinel cubic lattice of Cit-USPMNs [32]. Hence it was confirmed

that the crystalline structure of prepared magnetite agreed with standard one. Crystallite size of

Cit-USPMNs was determined by using Scherrer's formula as shown in equation 2.

K
Dhkl  (2)
 cos

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The sample showed the wide peaks which indicted ultrafine nature of magnetite NPs. [33]. The

average crystallite dimensions were calculated from the most intense peak D311 and it was found

to be 11 nm and 15 nm respectively. Cit-USPMNs became more crystalline on annealing at a high

temperature which results in a decrease in noise and broadness of the peaks of the XRD diffraction

pattern. This indicated that size and crystallinity of Cit-USPMNs increase with annealing

temperature.

(311) Fe3O4
(440)
(220)
400 (511)
Intensity (a.u.)

(422) (533)
(620)
(C) At 2500C

(B) At 1500C

(422)

(A) Without Annealing JCPDS Card No. 19-0629

20 30 40 50 60 70
2 Degree

Figure 1: XRD diffraction pattern of Cit-USPMNs annealed at different temperatures.

3.3 Optical Properties

The optical absorption spectra and the band gap of magnetite Cit-USPMNs were determined by

using UV-Vis spectrometer (Model UV-2502), the wavelength ranges 200-800 nm. The Cit-

USPMNs were dispersed ultrasonically in deionized water for making a uniform dispersion of

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magnetite Cit-USPMNs before measurement. De-ionized water is used to overcome the addition

of impurity atoms in the specimen. UV-Vis spectrum of Cit-USPMNs is given in Fig. 2. Cit-

USPMNs of size 11 nm and 15 nm show λmax at 400 nm and 418 nm respectively which show a

red shift as size increase. Narrow peaks of UV-Vis spectrum also confirmed the monodispersity

of the Cit-USPMNs. Davis and Mott gave an expression for absorption coefficient α (v) as a

function of photon energy (hν) for direct and indirect transition through the following equation.

I
A=-log( )=α(υ)L (3)
Io

A
α(υ)= (4)
L

α o (hυ-E opt
g )
n

α(υ)= (5)
hυ

in this formula “A” was for absorption of light, “I” represent for the intensity of transmitted light,

Io represents an intensity of incident light, α(ν) for absorption coefficient, L for the thickness of

the cell. Egopt is optical band gap energy and n=1/2 for allowed direct transition and n=2 for an

indirect transition. Fig. 3(A-D) shows that there is a red shift in absorption spectrum for Cit-

USPMNs and band gap varies from 2.6 eV (15 nm) to 2.8 eV (11 nm) for direct transition and 1.7

eV (15 nm) to 1.82 eV (11 nm) for an indirect transition. The direct and indirect band gap values

of Cit-USPMNs were greater than its bulk value. These results show that the energy band gap of

Cit-USPMNs depended on its particle size which is inversely proportional to its grain size hence

the band gap is tunable simply by controlling the size of Cit-USPMNs. Direct and indirect band

gap values of the Cit-USPMNs lies in the range of 1.7 eV to 2.8 eV. These band gap values

classified the Cit-USPMNs as the semiconductor.

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Fe3O4 of size 11 nm
Fe3O4 of size 15 nm

11 nm

Absorbance (a.u.)
15 nm

350 400 450 500 550 600 650 700 750

Wavelength (nm)

Figure 2: UV/Vis spectra of Cit-USPMNs

(A) Direct band gap for 11 nm (B) Indirect band gap for 11 nm
2 [eV-cm-1]1/2
2 [eV-cm-1]2
h]

  h ]

Eg=2.8 eV Eg=1.82 eV
1.5 2.0 2.5 3.0 3.5 4.0
1.5 2.0 2.5 3.0 3.5 4.0
h eV
h eV
(C) Direct band gap for 15 nm (D) Indirect bang gap for 15 nm
2 [eV-cm-1]2

2 [eV-cm-1]1/2
h]

h]

Eg=2.6 eV Eg=1.7 eV

1.5 2.0 2.5 3.0 3.5 4.0

h eV 1.5 2.0 2.5 3.0 3.5 4.0
h [eV]

Figure 3: Optical energy band gap (A) direct transition of Cit-USPMNs for 11 nm (B) indirect

transition of Cit-USPMNs for 11 nm (C) direct transition of Cit-USPMNs for 15 nm (D) indirect

transition of Cit-USPMNs for 15 nm

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3.4 Magnetic properties

The magnetic behavior and magnetic properties like saturation magnetization Ms, Coercively Hc

of Cit-USPMNs were determined by vibrating sample magnetometer (VSM) with a magnetic field

of  7 KOe at room temperature. M-H loops of Cit-USPMNs clearly showed that the magnetic

NPs were superparamagnetic with a negligible value of coercivity and zero remanence as shown

in Fig. 4(A-B). Saturation magnetization is the maximum possible magnetization of the magnetic

material, characterized by parallel orientation of all magnetic moments inside the material. It is

determined from M-H loops that are the highest magnetization value Saturation magnetization

values of Cit-USPMNs are 31.387 emu/g to 61.834 emu/g corresponding 11 to 15 nm which were

smaller than that of its bulk value (92 emu/g). It was due to spin-glass-like phase (canting spin) on

the surface of Cit-USPMNs because of oxygen vacancies and lower coordination number at the

surface [34]. The saturation magnetization depended on the size of Cit-USPMNs by the following

equation

 1

r   Ms  2 
t= 1-   (6)
2   M so  
 

Where MS is saturation magnetization of Cit-USPMNs and MSO is saturation magnetization of the

conventional bulk sample. The saturation magnetization decreased with the decrease in the size of

Cit-USPMNs. This is due to the glass like phase (canting spin) on the surface of Cit-USPMNs

[30]. At the nanoscale, the ratio of surface atoms to core atoms and volume to size ratio is increased

tremendously which means that most of the atoms are present on the surface of Cit-USPMNs.

Some canted spins are present on the surface which hindered the movement of core spin with the

field direction. This factor decreased the saturation magnetization of Cit-USPMNs. Below some

critical size, the particles have a single domain which is called superparamagnetic. These Cit-

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USPMNs fluctuated due to thermal energy. This fluctuation tended to randomize the magnetic

moment unless magnetic field was applied and coercively was negligible as observed in Cit-

USPMNs. These Cit-USPMNs are suitable for medical application such as hyperthermia, drug

delivery and MRI (magnetic resonance imaging) due to its tunable magnetic properties by

controlling the size of Cit-USPMNs [33].

(A) (B) 60
Fe3O4 of 11 nm size 30 Fe3O4 of 15 nm size
40
20

10 20

M (emu/g)
M (emu/g)

0 0
-8 -6 -4 -2 0 2 4 6 8 -8 -6 -4 -2 0 2 4 6 8
-10

M (emu/g)
-20
M (emu/g)

0 0
-20
-40
-20
-30 -1 0 1 -0.9 0.0 0.9 1.8
H (kOe) -60
H (KOe)
-40
H (kOe) H (KOe)

Figure 4: (A) M-H loop for Cit-USPMNs of size 11nm at room temperature (B) M-H loop for

Cit-USPMNs of size 15nm at room temperature

3.5. Dielectric Properties

Dielectric properties of Cit-USPMNs were examined by using Wayne Kerr LCR meter bridge

(WK4275) over the frequency range of 20 Hz to 1 M Hz. Capacitance and dissipation factor were

recorded from LCR meter Bridge simultaneously. Cit-USPMNs sample in the form of a pallet of

1mm thickness that was painted with the silver paste for good electrical contact. Cit-USPMNs

were placed in a three-terminal crystal holder that was put inside a vacuum tube. The dielectric

properties varied with the synthetic method, composition, structure, size, vacancies, impurities,

sintering temperature and morphology of Cit-USPMNs. The dielectric behavior of Cit-USPMNs

was explained qualitatively on the basis of electronic exchange between divalent (Ferric) and

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trivalent (Ferrous) ion like conduction process [17]. When the frequency of applied field was low

then the dipoles in the materials follow the electric field and they have enough time to align

themselves in the direction of applied field. In this case, the value  ` is high. With the increase in

the frequency, the relaxation time (time required by dipole to align themselves in the direction of

applied field) was larger than the available time (1/f) and the dipoles due to their inertia were not

aligned themselves. The dielectric constant was calculated by using equation 3.

Cd
 ` (3)
0 A

In this equation, C is the capacitance of dielectric sample holder loaded with sample, d = thickness

of sample pallet,  0 = permittivity of free space and A = area of the active electrode surface of the

sample holder. Dispersion of dielectric constant and tangent losses at room temperature have

shown in Fig. 5(A-B). The behavior of dielectric constant (  ` ) and dissipation factor ( tan  )

showed an inverse relationship with frequency. The decrease in  ` with frequency up to 8.4 kHz

is due to dipole relaxation and the high value of dielectric constant at low frequency is due to

Maxwell-Wagner [10, 15] type interfacial polarization. The tanδ showed similar dispersion as that

of dielectric constant. The loss in dielectric was due to domain wall motion and rotation of electric

dipole in the presence of an alternating electric field. At a low-frequency loss in dielectric was due

to domain wall motion. It dissipated a large amount of heat and at the higher frequency the domain

wall motion is inhibited and polarization is forced to change by the rotation that does not respond

the electric field and small amount of heat are produced during this rotation and it seems to remain

constant at the higher frequency.

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(A) Dielctric constnt 103.0 (B)

120 1.0
Dielctric constnt
Tangent Loss
400 Tangent Loss
102.5
100 0.8

Dielectric Constant
102.0
Diectric Constant

300
80
0.6

tan 
101.5

tan 
60 200
0.4
101.0

40 100
100.5 0.2

20 100.0
0
0.0
0 200 400 600 800 0 200 400 600 800 1000
Frequency (KHz) Frequency (kHz)

Figure 5: (A) Dielectric constant and tangent loss versus frequency of Cit-USPMNs (11 nm) (B)

Dielectric constant and tangent loss versus frequency of Cit-USPMNs (15 nm)

3.6. FTIR Spectroscopy

Fe-O bond formation, spinel structure and successful fixing of citric acid on the surface of Cit-

USPMNs were confirmed by FTIR spectra. FTIR spectra of pure Cit-USPMNs and Cit-USPMNs are

shown in Fig. 6(A). Pure USPMNs show peaks at 585 cm-1, 1115 cm-1, and 1615 cm-1 which confirm

the formation of Fe-O bond and successful synthesis of USPMNs [32]. These were fundamental

peaks of inverse ferrite spinel structure of USPMNs. Surface hydroxyl groups (OH) show the peak

at 3410 cm-1 due to O-H stretching. Citric acid modified USPMNs show additional peaks at 1720

due to stretching vibrations of C=O bond of COOH group of citric acid, 1250 cm-1 assigned to

symmetric stretching of C-O and an intense peak at 1610 cm-1 due to chemical binding of citric

acid to the surface OH of USPMNs. Peaks appeared at 2950 cm-1and 2890 cm-1 due to CH2 groups

of citric acid, 3200 cm-1 due to OH of citric acid and 3440 cm-1 due to surface OH groups of Cit-

USPMNs

3.7. TGA Study

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TGA-DTG curve is shown in Fig. 6(B) which shows three step degradation profile. In the first

step, a 10% weight loss was observed at a temperature range of 30-150 ºC due to loss of residual

water and physical absorbed citric acid on the surface of USPMNs. In a second step, 11% weight

loss was observed from 150 to 460 ºC due to loss of surface hydroxyl groups and chemically

adsorbed citric acid. In a third step, 5% weight loss above 460 ºC was due to phase

transformation of Fe3O4 to Fe2O3. TGA-DTG curve has confirmed formation of citric acid

modified USPMNs

3.6. TEM

The size and morphology of Cit-USPMNs were observed directly from TEM image (Fig. 6(C-D)).

The size of the Cit-USPMNs measured from the TEM image was 14-17 nm, slightly greater than

the size calculated from Scherer's formula. This is due to dead layers on the crystalline layers of

Cit-USPMNs. During the TEM sample preparation, it was noted that Cit-USPMNs were fully

dispersible in ethanol. Fig. 6(C-D) clearly showed that Cit-USPMNs were spherical in shape and

uniform in size.

0.20
(A) Pure USPIONs (B) TGA
100 DTG
Cit-USPIONs

95
0.15 Derivative weight loss (%/°C)
Transmittance (a.u.)

Weight loss (%)

90
0.10

85

0.05
80

75 0.00

3500 3000 2500 2000 1500 1000 500 100 200 300 400 500 600 700
Wavelength (cm-1) Temperature (°C)

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(C) (D)

Figure 6: FTIR spectra of pure USPMNs and Cit-USPMNs (B) TGA-DTG curve of Cit-USPMNs (C)

TEM image of Cit-USPMNs (11nm) (D) TEM image of Cit-USPMNs (15 nm)

4. Conclusion

Water dispersible Cit-USPMNs were successfully synthesized by environmentally friendly and

modified co-precipitation method. Lemon juice was used as a source of citric acid and stabilizing

agent for these Cit-USPMNs. The size was successfully controlled between 11-15nm by an amount

of N2H4 as calculated and confirmed by Scherrer's formula and TEM respectively. The Peaks at

30.07o, 35.51o, 43.33o, 53.44, 57.18o, 62.88o and at 74.02o in X-ray diffractogram confirmed the

formation of pure Cit-USPMNs. Size-dependent red shift and band gap were observed which

classified these Cit-USPMNs as semiconductors. The band gap varied from 2.6 eV to 2.8 eV for

direct and 1.7 eV to 1.82 eV for indirect transition, which was greater when the material was

present in bulk. These NPs were superparamagnetic with zero remanence, negligible coercivity

and saturation magnetization of 31.387 emu/g to 61.834 emu/g. TGA curve confirms chemical

adsorbed citric acid and phase transformation of Fe3O4 to γ-Fe2O3.

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Graphical Abstract

(311) Fe3O4 0.30

(440)
(220) 11 nm
400 (511)
0.27
Intensity (a.u.)

(422) (533)

Abs. (%)
(620)
(C) At 2500C
0.24

15 nm
(B) At 1500C O 0.21
O
OH
(422) HO OH
0.18
(A) Without Annealing JCPDS Card No. 19-0629 O O
350 400 450 500 550 600 650 700 750
20 30 40 50 60 70  (nm)
2 Degree HO
OH
O O O O
HO Fe3O4 OH
O O O O
OH HO

(A) O O Pure USPIONs

Fe3O4 of 11 nm size 30 Cit-USPIONs
HO OH
20
OH
O O
Transmittance (a.u.)

10
M (emu/g)

0
-8 -6 -4 -2 0 2 4 6 8
-10
M (emu/g)

0
-20

-20
-30 -1 0 1
H (kOe)
-40
H (kOe) 3500 3000 2500 2000 1500 1000 500

Wavelength (cm-1)

Research highlights:

 Water dispersible Cit-USPMNs were synthesized by modified co-precipitation technique

 Size of Cit-USPMNs was tuned from 11 to 15 nm by changing the volume of added N2H4

 Cit-USPMNs are superparamagnetic with negligible value of coercively and zero

remanence

 Direct and indirect energy band gaps for Cit-USPMNs were calculated from the UV-Vis

spectrum which lies in the range of 1.7 eV to 2.8 eV

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Research highlights:

 Water dispersible USPMNs were synthesized by co-precipitation technique

 Size of was tuned by changing the volume of added N2H4

 USPMNs are superparamagnetic with negligible coercively and zero remanence

 Direct and indirect energy band gaps lies in the range of 1.7 eV to 2.8 eV