Catalysis Letters

https://doi.org/10.1007/s10562-019-02906-4

Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective

Biodiesel Production from Waste Cooking Oil
A. Ashok1 · L. John Kennedy1

Received: 26 September 2018 / Accepted: 21 July 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
ZnFe2O4 nanocatalysts synthesized by microwave combustion method is employed for biodiesel production from waste cook-
ing oil (WCO). The zinc ferrite samples are prepared by varying the microwave power from 500 to 1500 W. The nanocatalysts
are characterized by XRD, FTIR, DRS, HR-SEM and VSM techniques. Transesterification of WCO are investigated and
maximum biodiesel yield of 98.6% is achieved with 4 wt% of Z ­ nFe2O4 nanocatalyst (ZF-1500 sample), methanol/oil molar
ratio of 21:1, reaction temperature about 60 °C and reaction time 1 h. The nanocatalyst ­(ZnFe2O4) was reused at least for 10
times. The activation energy (Ea) and frequency factor (A) is calculated to be 59.4 kJ mol−1 and 1.66 × 108 min−1 respectively.
The thermodynamic parameters ∆H and ∆S were found to be 88.76 kJ mol−1 and − 0.096 kJ mol−1 K−1. The positive values
of ∆G for transesterification process is found to be non-spontaneous and endergonic.
Graphic Abstract

Keywords  Biodiesel production · Transesterification · Heterogeneous catalysis · Spinels

Extended author information available on the last page of the article

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Abbreviations
WCO Waste cooking oil
ZF-500 Zinc ferrite using 500 W
ZF-600 Zinc ferrite using 600 W
ZF-900 Zinc ferrite using 900 W
ZF-1200 Zinc ferrite using 1200 W
ZF-1500 Zinc ferrite using 1500 W
XRD X-ray diffraction
FTIR Fourier transformed infrared
HRSEM High resolution scanning electron microscopy
DRS Diffuse reflectance spectroscopy
VSM Vibrating sample magnetometer
GCMS Gas chromatography mass spectroscopy
FAME Fatty acid methyl ester
1 Introduction
Diesel is a widely used fuel in combustion engines besides
petrol. Despite these being classified to be clean fuel, still
we suffer from the problem of pollution and toxic exhaust.
The rise in vehicle population and increased industriali-
zation lead to emission problems and depletion of fossil
fuels. Therefore to overcome the fossil fuel depletion, one
of the alternate fuels to match the demands of mankind are
the fuels from bio-ethanol, biodiesel and biomass. Among
these, biodiesel is one of the preferred alternative fuel
because, it is non-toxic, biodegradable and environmental
friendly with low emission profiles [1]. In addition, bio-
diesel possess other technical advantages like, have high
flash point, higher cetane number and better lubrication
than petroleum fuel [2]. Although biodiesel is produced
from vegetable oils, the cost is much higher than the regu-
lar diesel. Hence research is concentrated in producing
biodiesel from cheaper raw materials and one among those
is from waste cooking oils (WCO). Moreover, producing
biodiesel from WCO solves the problem of (i) oil contami-
nation in soils and water bodies as they are just thrown
or poured after repeated use and (ii) cheap feed stock for
biodiesel production from oil wastes. WCO cannot be used
again as a substitute for fresh vegetable oils because the
physical and chemical properties are different from those
of fresh vegetable oils. Despite the change in properties,
WCO is still a preferred feed stock as the cost of WCO
is 2 to 3 times less than fresh vegetable oils and does not
affect the quality of the biodiesel produced [3]. The WCO
is obtained as a waste product from many food processing
plants, restaurants and local fast food shops. Mostly as a
matter of disposal, the price involves only in collection
and transportation. Therefore the WCO is comparatively
cheap than the fresh edible oils. In addition the price of
WCO is only Rs. 35/L compared to the price of groundnut,
gingerly, coconut and mustard oils which cost around Rs.
13
A. Ashok, L. J. Kennedy
250/L, Rs. 300/L, Rs. 140/L, Rs. 260/L respectively. Due
to the increasing human population, fast food culture, the
amount of WCO generated at homes and food restaurants
are increasing rapidly. Thus from economic and environ-
mental point of view, WCO can be a promising biodiesel
(Fatty Acid Methyl Esters) feedstock.
Biodiesel is generally produced by the transesterification
of vegetable oil (triglyceride) or animal fat with an alcohol
(mostly methanol) to form fatty acid methyl ester (FAME)
and glycerol in the presence of suitable catalyst. Three major
reaction steps involved in the transesterification are, triglyc-
eride to diglyceride with one ester in step one, diglyceride
to monoglyceride with another ester in step two and finally
monoglyceride to glycerol with one more ester in step three
[4]. Thus each step gives one ester and finally leading to
three esters (FAME). Therefore the reaction kinetics in every
step becomes dominant for efficient biodiesel production.
The reaction kinetics can be catalyzed either by using
homogeneous or heterogeneous catalyst and biocatalyst
otherwise [5–7]. Generally, heterogeneous catalyst are pre-
ferred for biodiesel production, as they have high catalytic
activity sites, longer life time, easy separation, recyclable,
selectivity and does not dissolve in methanol. Even though,
alkaline earth metal oxide like calcium oxide (CaO) are
reported [8] to be an effective catalyst for biodiesel pro-
duction, they suffer from the problem of water and carbon
di-oxide absorption which further leads to separation dif-
ficulty by the increase in viscosity and thereby retarding the
reaction kinetics [7]. ZnO based heterogeneous nanocatalyst
are also used for biodiesel production, and appeared to have
good catalytic activity for maximum biodiesel conversion
[9] but still suffered from catalyst separation in the biodiesel
process. Therefore recovery or separation of catalyst from
the biodiesel/glycerol mixture still remains a great challenge
in the biodiesel industry, especially when nanostructured
catalyst are employed.
The combustion based synthesis is one of the most acces-
sible, fast and low energy soft method for synthesis of ferrite
materials. Microwave assisted combustion method recently
gained importance over the conventional method because,
microwave interacts with the reactant at the molecular level.
In the microwave mechanism, the electromagnetic energy is
converted to heat energy using propellant chemistry princi-
ple. The choice of nitrate precursor as oxidizer and organic
compound as a fuel at suitable stoichiometric ratios, control
the combustion process. The microwave energy is trans-
formed into heat energy by strong intermolecular friction
and raises the temperature of the precursor materials sud-
denly. As a result the crystal size, morphology, other physi-
cal and chemical properties are altered. This results in the
formation of nanoparticles, early phase formation, different
morphologies and high efficiencies with in few minutes of
time [10, 11].
Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…
Hence in the present study, herein the attempt is to use
zinc ferrite spinel as heterogeneous catalyst to overcome the
problem of separation and efficient biodiesel production.
­ZnFe2O4 spinel type catalyst have more advantages such as,
better catalytic activity, allow a great cationic mobility, non-
toxic, inexpensive, thermal and chemical stability, catalytic
resistance and attraction by magnets by superior magnetiza-
tion. Therefore the focus of this study is to prepare ­ZnFe2O4
nanoparticles by microwave combustion method and employ
for the transesterification of WCO to biodiesel using metha-
nol. l-arginine is found to facilitate the homogeneous mixing
of cations in solution and it undergoes decomposition and
promotes combustion. The literature on the preparation of
zinc ferrite using l-arginine is found to be scarce. We have
investigated the effect of this fuel to evaluate the character-
istics like surface morphology, size distribution, and mag-
netic properties of pure zinc ferrite nanoparticles [12]. The
prepared ­ZnFe2O4 nanocatalyst are characterized by X-ray
diffraction (XRD), Fourier transform infrared spectroscopy
(FTIR), High resolution scanning electron microscopy (HR-
SEM), Diffuse reflectance spectroscopy (DRS), Vibrating
sample magnetometer (VSM) analysis to study the physico-
chemical properties. Maximum biodiesel yield is optimized
by varying the process parameters. Reusability, kinetic and
thermodynamic parameters are also evaluated. The purity of
synthesized biodiesel were characterized using Gas chroma-
tography–Mass spectroscopy.
2 Materials and Methods
2.1 Materials
All the chemicals used, such as zinc nitrate, ferric nitrate
and l-Arginine are analytical grade purchased from Merck,
India and is used as received without further purification.
Waste cooking oil (WCO) is collected from a local restau-
rant in Chennai, India. The collected oil is subjected to pre-
treatment to remove the suspended solid materials by filtra-
tion. The physicochemical properties of WCO are listed in
Table 1. The impurities in WCO was removed by continuous
filtration and repeated washing with water so that the soluble
metal ion and other impurities are eliminated. In our present
study, the acid value of WCO is 0.33 mg KOH/g (Table 1)
which is less than 1 mg KOH/g oil (permissible limit) and
hence favorable for alkali catalyzed transesterification.
Therefore the oil was directly used without any deacidifica-
tion treatment for transesterification reaction [4, 13].
2.2 Zinc Ferrite Nanocatalyst Preparation
Zinc ferrite nanoparticles are prepared by microwave
assisted combustion method. Stoichiometric amounts of
Table 1  Physicochemical properties of waste cooking oil used in the
present study
Parameters Values
Acid value (mg KOH/g) 0.33
Density (g/m3) 0.929
Kinematic viscosity at 40 °C (­ mm2/s) 10.89
Saponification value (mg KOH/g of oil) 193.5
Molecular weight (g/mol) 871.0
Calorific value (MJ/kg) 32.98
Cetane number 33
Iodine value (mg KOH/g) 8.65
Flash point (°C) 209
FFA (%) 0.165
Oxidation stability (h at 110 °C) 5.8
ferric nitrate (0.808 g), zinc nitrate (0.297 g) in mole ratio
(Fe:Zn) 2:1 and l-Arginine (0.204 g) were dissolved, each
in 10 ml of demineralized water separately and then mixed.
The mixture is sonicated using 3  mm titanium probe at
25 kHz and approximately 528 W (44% of total power) using
a probe sonicator (Esquire Biotech – EBT 1200, India) for
5 min at room temperature until a clear transparent solu-
tion is obtained. This clear solution is poured in silica cru-
cible and placed inside and industrial microwave oven at
2.45 GHz with the different power values (500 W, 600 W,
900 W, 1200 W and 1500 W) for 10 min. The solution is
initially boiled and underwent spontaneous combustion with
evolution of gases and finally resulting in the formation of a
brown colored puffy powder. The incident microwave power
varied from 500 to 1500 W to study the effect of nanostruc-
ture formation and is labelled as ZF-500, ZF-600, ZF-900,
ZF-1200 and ZF-1500 respectively. The final product is
washed well with alcohol and dried at 110 °C for further
use. During the combustion process, the chemical reaction
involved in the formation of zinc ferrite using l-Arginine as
fuel is as follows:
( ) ( )
Zn NO3 2 6H2 O(s) + 2Fe NO3 3 9H2 O(s)
+ 1.176 C6 H14 N4 O2(s) → ZnFe2 O4(s)
+ 8.235H2 O(g) ↑ + 7.058CO2(g) ↑ + 6.352N2(g) ↑
2.3 Characterization
The microwave (MW) system operating at 2.45 GHz fre-
quency is supplied by INFURR Super heat furnaces, Chen-
nai India. The microwave oven as inner chamber area
12″L × 12″B × 8″H, heating achieved by two number of
magnetrons of power rating about 1200 W each for alternate
option automatically on a preselected time cycle, so as to
operate the unit continuously for a minimum of 120 min
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 A. Ashok, L. J. Kennedy

at a stretch. Maximum temperature 1000 °C. The MW sys- ln(1 − X) = −kt (2)

tem has provisions like rotation table, exhaust through top, where, X is the conversion of triglyceride at time t.
power selection process, timer, insert Teflon bush etc. The The pseudo second order rate is given in Eq. 3 and from
structural characterization of ­ZnFe2O4 is performed using the plot of (X/1 − X) versus time (t) yielded the second order
a Rigaku (Smart Lab) X-ray diffractometer with Cu Kα rate constants.
radiation at λ = 1.5406 Å. The surface functional groups
are analyzed by Perkin Elmer FT-IR spectrometer. Sur- X
= CTG ⋅ k ⋅ t (3)
face morphologies are observed with a Joel JSM6360 high 1−X
resolution scanning electron microscope. The UV–visible where, CTG is the initial triglyceride molar concentration
diffuse reflectance (DRS) spectra of samples are recorded (mol L−1), X is the conversion of triglyceride at time t.
using Thermo scientific evolution 300 UV–visible spectro- The activation energy (Ea) required for the transesterifi-
photometer. Magnetic measurements are carried out at room cation process is calculated according to Arrhenius Eq. 4,
temperature using the PMC MicroMag3900 model vibrating ( )
sample magnetometer (VSM) equipped with 1 T magnet. k = A. exp − a
E
(4)
For TPD-NH3 and ­CO2 analysis, the zinc ferrite sample was RT
pre-treated under He flow of 10 ml/min at 400 °C. ­NH3/
where, k is the reaction rate constant (­ min−1), A is the Arrhe-
CO2 adsorption was carried out under standard condition
nius constant or frequency factor, Ea is the activation energy
by flowing of 10% ­NH3/He and 10% ­CO2/He over the fer-
(J/mol), T is the temperature and R is the universal gas con-
­ H3/
rite nanoparticle still saturation and then desorption of N
stant (8.3145 J mol−1 k−1). The slope of the graph between
CO2 by temperature-programmed analysis under constant
ln (k) versus 1/T (Eq. 5) gives the value of activation energy
He flow from room temperature to 800 °C with a heating
[15].
rate of 10 °C/min.
Ea
ln k = ln A − (5)
RT
2.4 Synthesis of Biodiesel

Transesterification reaction are carried in a 3-neck jacketed 3 Result and Discussion

type glass reactor of 500 mL capacity attached with a water
cooled reflux condenser. The reaction mixtures, methanol, 3.1 Catalyst Characterization
WCO and zinc ferrite are fed into the reactor and subjected
to constant mixing using magnetic stirrer. Transesterification 3.1.1 X‑Ray Diffraction (XRD)
reaction is carried out by varying the catalyst concentration
(1 to 8 wt%), methanol to oil molar ratio (3:1 to 30:1), tem- The X-ray diffraction patterns of zinc ferrite nanostruc-
perature (35 °C to 60 °C), and reaction time up to 80 min. tures are shown in Fig. 1. All diffraction peaks are matched
Consequently after transesterification reaction, the mixture
was left to settle and the catalyst was recovered by using
a magnet. Using a separating funnel, the biodiesel (lighter
phase) and glycerol (denser phase) was separated and the
biodiesel product is analyzed by gas chromatography–mass
spectroscopy. The percentage yield of biodiesel is calculated
using the formula [14],
total weight of biodiesel produced
%yield = × 100 (1)
total weight of oils used

2.5 Reaction Kinetics

The reaction kinetics are evaluated by considering the

pseudo first order and pseudo second order kinetic model.
The pseudo first order rate kinetics is evaluated using the
Eq. 2, where the rate constants are obtained from the slope
of plot of ln(1 − X) versus time (t). Fig. 1  XRD patterns of (a) ZF-500, (b) ZF-600, (c) ZF-900, (d)
ZF-1200, (e) ZF-1500

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Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…

with standard JCPDS card no: 82-1042. The characteristics almost similar to the values reported by Ferrari et al. and
peaks at 2θ values of 30.16°, 35.57°, 43.19°, 53.52°, 57.01°, Shoushtari et al. [19, 20].
62.69° and 74.32° are indexed to (220), (311), (400), (422), Williamson–Hall (W–H) method gives the effective par-
(511), (440) and (533) planes of the zinc ferrite spinel type ticles size (D) and strain component using the formula given
cubic structure with Fd3m space group [16]. The average in Eq. 8,
crystallite size of synthesized ­ZnFe2O4 nanostructures from
k𝜆
the most intense diffraction peak (311) plane were estimated 𝛽 cos 𝜃 = + 4𝜀 sin 𝜃 (8)
by the Scherer formula [17], D
where, β is the full width half maximum (FWHM) of the
0.89𝜆
L= (6) X-ray diffraction peak, θ is the diffraction angle, k is a con-
𝛽cos𝜃
stant equal to 0.89, λ is the wavelength of the X-ray source
where, L, is the crystallite size; λ, is the X-ray wavelength (λ = 0.15406 nm), and ε is the strain associated with the
(0.15406 nm); β, is the full width at half maximum (FWHM) nanoparticles. From Eq. 8, W–H plot between 4sinθ versus
of diffraction peak; and 2θ, is the diffraction angle. The βcosθ (Fig. 2) gives the strain (ε) and the effective particle
average crystallite size for Z­ nFe2O4 samples are shown in size (D) from slope and intercept (k/D) respectively. The
Table 2. The crystallite size were found in the range 8.55 nm effective particle size values (Table 2) calculated from W–H
to 13.04 nm [18]. From our previous studies [18], zinc fer- method is little lesser than the average crystallite size calcu-
rite nanoparticles prepared by conventional method showed lated by using Debye–scherrer’s formula, may be due to the
a larger crystallite size around 74 nm, while the present reason that former is associated with the strain components,
study shows an average crystallite size in the range from while the later is not. A negative slope in W–H plot indi-
8.55 to 13.04 nm. Lower the size, better would be the sur- cates the presence of compressive strain in the zinc ferrite
face area and available active sites. More over the magneti-
zation properties were also better than the conventionally
prepared zinc ferrites, as it would facilitate the separation
of the catalyst using external magnet. The results shows,
varying the microwave power (Watts) from 500 to 1500 W
doesn’t seem to have any remarkable impact in controlling
­ nFe2O4. However, ZF-500 possessed
the crystallite size of Z
lesser size (8.55 nm) in comparison to the other samples.
Therefore it is suggestive that minimum microwave energy
of about 500 W is sufficient enough to synthesis small sized
zinc ferrite nanoparticles. The lattice parameter ‘a’ of zinc
ferrite spinel’s is calculated from the X-ray diffraction data
using the formula [10],
√
a = dhkl h2 + k2 + l2 (7)

where, a is the lattice parameter, dhkl is the interplanar spac-

ing corresponding to the miller indices, h, k, and l are the
miller indices. The calculated lattice parameters are shown
in Table 2. When increased Watts from 500 to 1500 W of Fig. 2  Williamson-Hall plots of zinc ferrite (ZF-500 to ZF-1500)
­ZnFe2O4 samples, the lattice parameter of all samples are samples

Table 2  Crystallite size, strain, lattice constant and band gap values prepared zinc ferrite nanoparticles
Sample code Average crystallite size, L (nm) Effective particle size, D (nm) by Band gap, Eg Lattice constant Strain (× 10−3)
by Scherrer’s formula the Williamson–Hall plot (eV) a (nm)

ZF-500 8.55 7.61 1.90 0.8384 − 4.0

ZF-600 13.04 8.21 1.88 0.8361 − 2.7
ZF-900 10.46 7.79 1.87 0.8358 − 3.5
ZF-1200 10.15 7.83 1.94 0.8346 − 3.3
ZF-1500 10.15 8.06 1.91 0.8304 − 3.2

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 A. Ashok, L. J. Kennedy

Table 3  Bulk density, X-ray density and porosity percentage of zinc

ferrite spinels
Sample code Molecular Bulk den- X-ray den- Porosity, P
weight, M sity, 𝜌b (g/ sity, 𝜌x (g/ (%)
(g) cm3) cm3)

ZF-500 241.07 2.17 5.441 60.12

ZF-600 241.07 2.19 5.477 60.01
ZF-900 241.07 2.15 5.484 60.80
ZF-1200 241.07 2.10 5.508 61.87
ZF-1500 241.07 2.18 5.453 60.02

samples. The X-ray density [21] and percentage porosity

(P) [22] is calculated using the formula according to Eqs. 9
and 10,
8M
𝜌x = (9)
Na3
[ ]
Bulk density
P= 1− × 100 (10)
X − ray density

where, M is the molecular weight of zinc ferrite (241.07 g/

mol), N is the Avogadro constant (N = 6.02214 × 10 23
­mol−1), a is the lattice parameter. It is observed that the
values of X-ray density, bulk density and porosity param-
eter varies minimal, despite increasing the microwave Watts
(Table 3). The bulk densities along with molecular weight
calculated are listed in Table 3. The values of X-ray density
is found to be greater than that of bulk densities which are
attributed to the presence of pores that is formed during the
microwave combustion synthesis adopted.
3.1.2 Fourier Transform Infrared (FTIR)
The FT-IR spectra of zinc ferrite samples are shown in
Fig. 3. The broad band at 3414 cm−1 exhibit the O–H group
stretching vibrations of water molecule [23]. The band at
2357 cm−1 indicates the presence of H–O–H bending vibra-
tion of absorbed water [12]. The bending modes of absorbed
water is assigned to the band at around 1635 cm−1 [23]. The
sharp band at around 1377 cm−1 signifies adsorbed moisture
in the system of FeOOH and adsorbed nitrate ions [24]. The
characteristic bands at 419 cm−1 and 550 cm−1 confirms
the intrinsic stretching vibrations of tetrahedral (­ Zn2+–O2−)
bond and octahedral ­(Fe3+–O2−) bond and confirms the for-
mation of ­ZnFe2O4 spinel structure [18].
3.1.3 High Resolution Scanning Electron Microscope
(HR‑SEM)
The surface morphology of synthesized zinc ferrite nano-
structures observed by the HR-SEM are shown in Fig. 4. For
Fig. 3  FT-IR spectra of (a) ZF-500, (b) ZF-600, (c) ZF-900, (d)
ZF-1200, (e) ZF-1500
ZF-500, well defined crystallite grains with distinct grain
boundaries with inter and intra angular pores are observed.
In addition, all the grain wall surfaces are not smooth or
plain but are made of tiny spherical particles. Thus a unit
area of grain surfaces are made of numerous spherical parti-
cles, which would lead to inherit high surface area followed
by high catalytic activities. However for ZF-600, ZF-900,
ZF-1200 and ZF-1500, the grains are broken down and the
spherical particles on the grain surfaces get fused, as the
microwave power is increased. This effect is well observed
in ZF-1500 sample.
3.1.4 Energy Dispersive X‑Ray (EDX) Analysis
The prepared zinc ferrite nanoparticles were composed of
Zn, Fe and O confirmed by EDX analysis at room tempera-
ture as show in Fig. 5. The variation in the values shall be
due to the presence of defects and oxygen vacancies. Gen-
erally, HR-SEM and EDX analysis was performed using
thin layer of gold particle on the surface of the zinc ferrite
nanoparticles. The gold (Au) peak at 2.1 to 2.2 keV for all
the samples, is due to the coating of gold on the surface of
the zinc ferrite sample during HR-SEM and EDX analysis.

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Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…

Fig. 4  HR-SEM images of a ZF-500, b ZF-600, c ZF-900, d ZF-1200, e ZF-1500

13
 A. Ashok, L. J. Kennedy

Fig. 5  Energy dispersive X-ray analysis spectra of a ZnF-500, b ZnF-600, c ZnF-900, d ZnF-1200, e ZnF-1500

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Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…
3.1.5 Diffuse Reflectance Spectroscopy (DRS)
The band gap, Eg of the zinc ferrite nanoparticles was
evaluated from the diffuse reflectance spectra using the
Kubelka–Munk function (Eq. 11) [25] in the Tauc relation
as in Eq. 12,
(1 − R)2
𝛼 = F(R) =
2R
where, R is the diffuse reflectance and F(R) is the
Kubelka–Munk function.
F(R)h𝜈 = A(h𝜈 − Eg )n (12)
where, n = 1/2 and 2 represents direct and indirect transi-
tions, thereby giving direct and indirect band gaps. A graph
(Tauc plot) is plotted between (F(R)hʋ)2 versus hʋ (eV)
and the extrapolation of the linear region of plots, until the
intersection with x-axis gives the band gap energy values as
shown in Fig. 6. The calculated band gap ranges from 1.87
to 1.94 eV (Table 4) and are closer to the previous reported
value, 2.08 eV [18]. The Eg values obtained in our study
is less than the bulk zinc ferrite nanoparticles and can be
attributed to the quantum confinement phenomenon taking
place at the nano regime.
3.1.6 Vibrating Sample Magnetometer (VSM)
The magnetic properties of the zinc ferrite nanoparticles
were recorded at room temperature using vibrating sample
magnetometer (VSM) with the applied field ranging from
− 15 kOe to + 15 kOe (Fig. 7). The magnetic moment (μB)
[26] is calculated from the Eq. 13
M × MS
𝜇B =
5585
where, Ms is the saturation magnetization, M is the molecu-
lar weight of zinc ferrite and 5585 is the magnetic factor.
From the hysteresis curves, the magnetic properties like sat-
uration magnetization (Ms), coercivity (Hc), remanence mag-
netization (Mr) and magnetic moment (μB) are calculated
and are reported in Table 4. The magnetization of all the
samples are in the range 16.04 emu/g to 61.46 emu/g, cor-
responding to the results obtained by Wiriya et al. [17]. The
M–H plot of magnetic hysteresis confirms, all the samples
have ferromagnetic performance with soft magnetic nature.
Figure 7 shows that all the samples possessed a satisfactory
magnetic responsiveness with an external magnetic field
which can be effective during the magnetic separation of the
catalyst. In comparison to the other samples, ZF-1500 sam-
ple have high magnetization (61.46 emu/g) and high mag-
netic moment (2.6528) and hence can be easily separated in
quicker time from the reaction mixture when employed for
any applications.
3.2 Acid Base Properties of Zinc Ferrite
Nanoparticles by Temperature Programmed
Desorption Studies (TPD‑NH3/CO2)
The TPD analysis of pure zinc ferrite nanocatalsyt (ZF-
1500) using N ­ H3 and C­ O2 as probe gases are shown in
Fig. 8. Generally, the peak temperature and peak area can
(11) be used to estimate the acid strength and acidity, respectively
(Fig. 8a). For ferrite samples, the ammonia desorbed from
room temperature to 200 °C as treated as Bronsted (Weak
sites), medium acid sites for 201 °C to 500 °C, and strong
acid sites (Lewis sites) for 501 °C to 800 °C. Figure 8a
shows clearly the zinc ferrite sample possess both weak and
strong acid sites. The total amount of acidity was found to
be 0.010 mmol/g.
The surface basicity exhibited by zinc ferrite nanopar-
ticle was studied and characterized by TPD-CO2 as shown
in Fig. 8b. The desorption of zinc ferrite gives two intense
peaks were observed between 30 and 150  °C treated as
weak basic sites and > 500 °C treated as strong basic sites
respectively. The zinc ferrite total basicity was found to be
0.014 mmol/g. From the TPD–NH3/CO2 result shows the
zinc ferrite nanocatalyst possesses both strong acid and
strong basic sites which is main advantages for catalytic
reactions.
3.3 Reactions Variables Effect
3.3.1 Catalyst Comparison on the Transesterification
of WCO
All the zinc ferrite nanocatalysts synthesized at different
microwave power are used in the transesterification process
(13) for optimization. In this process the zinc ferrite catalysts are
compared under the following reaction conditions: 4 wt%
of catalyst amount, 21:1 methanol to oil molar ratio, 60 °C
reaction temperature and 1  h reaction time as shown in
Fig. 9. For a catalyst loading at 4 wt% for ZF-500, ZF-600,
ZF-900, ZF-1200 and ZF-1500 the biodiesel yield were
97%, 97.2%, 97.7%, 98.1% and 98.6% respectively. The bio-
diesel yield values are invariably close to the same value,
despite varying the incident microwave power for catalyst
preparation.
3.3.2 Ferrites Amount Effect
During the transesterifiction reaction, one the most impor-
tant factors that affect the biodiesel yield is catalyst loading
and therefore, it needs to be optimized. Figure 10a shows the
loading of zinc ferrite samples, ranging from 1 to 8 wt% pre-
pared between 500 and 1500 W at identified reaction condi-
tions like methanol to oil molar ratio 21:1, reaction tempera-
ture 60 °C and 1 h reaction time. The result showed that the
13
 A. Ashok, L. J. Kennedy

Fig. 6  (F(R)hʋ)2 versus hʋ plot of a ZF-500, b ZF-600, c ZF-900, d ZF-1200, e ZF-1500

13
Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…

Table 4  Magnetic properties (coercivity, remanent magnetization,

saturation magnetization and magnetic moment) of zinc ferrite nano-
particles

Sample code Coerciv- Rema- Magnetiza- Magnetic

ity (Hc) nence (Mr) tion (Ms) moment
(Oe) (emu/g) (emu/g) (μB)

ZF-500 410 5.69 16.04 0.692

ZF-600 400 18.77 47.26 2.039
ZF-900 383 20.73 57.56 2.484
ZF-1200 404 11.78 28.78 1.242
ZF-1500 408 21.96 61.46 2.652

Fig. 7  Magnetic hysteresis loops of (a) ZF-500, (b) ZF-600, (c)

ZF-900, (d) ZF-1200, (e) ZF-1500

transesterification strongly depends on the catalyst amount
with maximum biodiesel yield of 98.6% at 4 wt% using
ZF-1500 catalyst. While increasing the catalyst amount from
1 to 4 wt%, the initial reagents get adsorbed on the catalysts
active centre effectively, leading to the formation of reaction
products. Also increase in catalyst concentration, leads to
higher exposure of the catalyst surface area which in turn,
increases the product yield in the reaction mixture. Catalyst
loading beyond 4 wt% however decreased the biodiesel yield
for all the samples. This could be due to the difficulty in
high viscous mixing of liquid reactants at high solid catalyst
concentration [15]. Moreover, an excess amount of catalyst
would lead to the saponification of biodiesel and also occa-
sionally, biodiesel may get adsorbed on the catalyst surface
which would be the possible reason for decreased yield of
biodiesel during the reaction of transesterification process.
Additionally, some amount of the catalyst would remain
unused due to more mass transfer resistance and poor mix-
ing, resulting in low biodiesel yield [27]. Deshmane et al.
Fig. 8  TPD-NH3/CO2 profile for zinc ferrite (ZF-1500) nanoparticles
and Mazaheri et al. reported similar trends indicating that
the catalyst concentration above a threshold value can have
negative impact during mixing in the transesterification reac-
tion [28, 29]. Therefore, 4 wt% of the catalyst amount is
optimized for transesterification process.
3.3.3 Methanol‑to‑Oil Molar Ratio Effect
Generally, 3 mol of alcohol and 1 mol of triglyceride react
together producing 3 mol of alkyl ester and 1 mol of glyc-
erol. An excess of alcohol is required to shift the equi-
librium towards the formation of biodiesel (alkyl esters)
because the transesterification of triglyceride is a revers-
ible reaction [30]. Figure 10b shows the ratio of metha-
nol to oil on the yield of biodiesel for all the zinc ferrite
nanocatalyst. In the present study, in order to shift the

13

Fig. 9  Catalyst comparison for the yield of biodiesel (methanol/oil
molar ratio 21:1, reaction temperature 60 °C, reaction time 1 h)
equilibrium of the reaction to get maximum FAME, the
methanol to oil molar ratio is varied in different propor-
tions like 3:1, 6:1, 9:1, 12:1, 15:1, 18:1, 21:1, 24:1, 27:1
and 30:1. The maximum biodiesel yield, 98.6% is achieved
at methanol to oil molar ratio of 21:1 under the reaction
conditions catalyst concentration 4 wt%, reaction tempera-
ture 60 °C and 1 h reaction time. Beyond this ratio and up
to 30:1, the yield of the biodiesel declined. A least ratio
of triglyceride to catalyst mass and subsequent increase in
contact time for the triglyceride with the surface shall be
reason for it. Excess of methanol favors triglycerides to
monoglycerides conversion and in turn, would facilitate
the solubility of glycerol in FAME resulting in glycerolize
of FAME and finally leading to a low product yield [31].
3.3.4 Reaction Time Effect
The experiment are carried out to investigate the perfor-
mance of zinc ferrite catalyst with the reaction time vary-
ing from 10 to 80 min, at the optimal reaction conditions
like methanol to oil molar ratio 21:1 and reaction tem-
perature 60 °C with 4 wt% catalyst loading as shown in
Fig. 10c, increasing the reaction time has influence on the
biodiesel yield is produced. The conversion percentage is
increased as the reaction time is increased to 60 min but
no significant change in biodiesel yield is observed beyond
60 min until 80 min. The surface energy and the catalytic
sites available on the zinc ferrite catalysts are sufficient
enough to complete the transesterification process with a
stipulated time of 60 min favoring a maximum biodiesel
yield.
13
A. Ashok, L. J. Kennedy
3.3.5 Reaction Temperature Effect
The reaction temperature are varied from 35 to 60 °C for all
samples (1 h duration) using 21:1 methanol to oil molar ratio
and 4 wt% of catalyst as shown in Fig. 10d. It is observed
that maximum biodiesel yield of about 98.6% is reached at
60 °C. The highest biodiesel yield at 60 °C can be attributed
to accelerated chemical reaction by increasing the collision
among the reactant molecules and thus enhancing the mis-
cibility and mass transfer [32]. As the methanol ebullition
temperature is 64.7 °C, the experiments were not conducted
at T > 60 °C. Moreover as the reaction takes place into the
liquid phase, when the temperature exceeds the ebullition
temperature of the methanol, the concentration of the metha-
nol in the liquid phase decreases leading in a decrease of the
reaction yield. The condenser avoid the evaporation of the
methanol into the atmosphere and allows its condensation.
Nevertheless, the concentration in methanol into the liquid
phase is not constant. Above 60 °C, no methanol remains
into the liquid phase, all methanol is under gas form. Hence
the temperature studies were restricted between 35 and
60 °C.
3.3.6 Nanocatalyst Recovery and Reuse
The reusability of the optimized, zinc ferrite (ZF-1500)
nanocatalyst is tested for 10 cycles of transesterification
process of WCO under optimized reaction parameters like
reaction temperature of 60 °C, reaction time 60 min, metha-
nol to oil molar ratio of 21:1 and catalyst loading of 4 wt%.
The biodiesel yield after 10th cycle decreased to 93.6% from
initial 98.6% (Fig. 11). This marginal decrease show that the
activity and the stability of the catalyst is not much affected.
This reduction in the yield shall be due to mass loss of the
catalyst by repeated washing after magnetic separation. The
recovered catalyst is generally washed with methanol to
remove any organic compounds like unreacted oil, biodiesel
and glycerol, followed by drying at 110 °C for 1 h before
next use. The structural composition of the catalyst before
and after 10 runs were evaluated using X-ray diffraction
studies as shown in Fig. 12. For both the samples, the peak
corresponding to 2θ values remain to be same. However
distortion or noisy like pattern is observed in the recovered
catalyst shall be due to the deposition of oil, biodiesel and
other organic matters on the surface of the catalyst. The lat-
tice parameters d-spacing for the fresh and the recovered cat-
alyst is almost same with values 0.2504 nm and 0.2530 nm
respectively. The leaching test were also performed in the
biodiesel by XRF analysis. The results indicate that there
are Zn and Fe ions were leached. This may be due to ineffi-
cient filtering process of the catalyst after transesterification
reaction.
Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…
Fig. 10  Effect of process variables on transesterification of WCO for
a catalyst concentration. Methanol to oil molar ratio 21:1, reaction
temperature 60 °C, 1 h reaction time; b methanol to oil molar ratio.
Catalyst concentration 4  wt%, reaction temperature 60  °C, 1  h reac-
3.3.7 Reaction Kinetics
Kinetic study for the transesterification process is deter-
mined under optimal conditions for ZF-1500 at six different
temperatures (35 °C, 40 °C, 45 °C, 50 °C, 55 °C and 60 °C).
The overall rate constant calculated from this study gave an
insight to the transesterification of WCO. Using the plots
of the pseudo first order and second order equation, given
in Eqs. 2 and 3, the best fitting kinetic model is determined
from the regression value coefficient R2. It is found that the
R2 value of the first order reaction plot − ln(1 − X) versus
time (Fig. 13) is greater than 0.98 which is much higher
than the R2 value of the pseudo second order plot (figure not
tion time; c reaction time. Catalyst concentration 4 wt%, methanol to
oil molar ratio 21:1, reaction temperature 60 °C; d reaction tempera-
ture. Methanol to oil molar ratio 21:1, catalyst concentration 4 wt%,
1 h reaction time
shown). Thus it is concluded that the transesterification pro-
cess of WCO using ZF-1500 follows the first order kinetic
model. The obtained rate constants, ­k1 were 0.0132 min−1,
0.0205 min−1, 0.0256 min−1, 0.0431 min−1, 0.0587 min−1
and 0.0731 min−1 for reactions carried out at 35 °C, 40 °C,
45 °C, 50 °C, 55 °C and 60 °C respectively. The reaction
rate rises with rise in temperature with a comparatively high
value at 60 °C.
The activation energy is calculated from the plot of ln (k)
versus (1/T) as shown in Fig. 14. The microwave power add
an influence on the catalytic performance that was reflected in
the activation energy on the samples with increase in micro-
wave power during sample synthesis from 500 to 1500 W the
13
 A. Ashok, L. J. Kennedy

Fig. 11  Effect of reusability on ZF-1500 catalyst. Reaction

condition:methanol/oil molar ratio 21:1, reaction time 1  h, reaction
temperature 60 °C

activation energy (Ea) varied from 49 to 59.40 kJ/mol. The

highest activation energy was achieved for ZF-1500 (59.40 kJ/
mol) indicating the limitation mass transfer or diffusion pro-
cess while the reaction is chemically controlled. The activa-
tion energy for transesterification of WCO using ZF-1500 was
found to be 59.40 kJ/mol and the value of A (frequency factor)
was 1.66 × 108 ­min−1 [33]. The Ea value obtained in the pre-
sent study is in agreement with other reported value [34–36],
generally lying between 33.6 and 84 kJ/mol.

3.3.8 Thermodynamic Analysis ­ nFe2O4 catalyst a before and b

Fig. 12  X-ray diffraction pattern of Z
after transesterification reaction
The most important thermodynamic parameters to be
determined for the transesterification reactions are ∆H
(enthalpy), ∆S (entropy) and ∆G (Gibbs free energy). From
the Eyring–Polanyi equation expressed in Eq. 14, Gibbs free
energy value can be calculated,
K T (
ΔG
)
k = 𝜅 B exp − (14)
h RT
where, 𝜅 (equal to one) is the transmission coefficient, kB
is the Boltzmann constant (1.38 × 10−23 J K−1), and h is the
Planck’s constant (6.63 × 10−34 J s). The general Gibbs free
energy equation can be written in Eq. 15
ΔG = ΔH − TΔS (15)
Taking the logarithm of Eq. 14 and substituting the Gibbs
free energy Eq. 15 gives,
( ) [ ( )
kB
]
k −ΔH 1 ΔS
( )
ln = + ln 𝜅 + ln + (16)
T R T h R
Fig. 13  Determination of kinetic rate constants on the basis of the
pseudo first-order kinetic model

13
Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…

to be 56.80 kJ mol−1 and − 0.096 kJ mol−1 K−1, respectively.

The kinetic and thermodynamics values are listed in Table 5.
The positive values of ∆H in our present study indicates,
that the transesterification reaction is an endothermic pro-
cess. The value of ΔS (entropy) is an important thermo-
dynamic property suggesting the degree of disorder of the
system. The negative value of ΔS in the transesterification
process indicates that either the ordered geometry degree or
the transition state alignment is higher than reactants in the
ground state. The Gibbs free energy gives an idea on, either
spontaneity or non-spontaneity of the reaction depending on
the negative or positive values of ∆G. The positive values of
∆G obtained indicates the nonspontaneous and endergonic
nature of transesterification process.

3.3.9 Physicochemical Properties of Synthesized Biodiesel

Fig. 14  Arrhenius graph for estimation of activation energy
The physicochemical properties of synthesized biodiesel
from WCO are determined and compared with previous
reported literatures and ASTM D-6751 standards as shown
in Table 6. The obtained results matching with the standards
suggest that zinc ferrite catalyst had good catalytic activity
for the large scale biodiesel production from WCO.

3.3.10 Characterization of Prepared Biodiesel

The fatty acid methyl ester composition are analysed by

GC–MS technique with the help of NIST library. Figure 16
shows the peaks corresponding to the presence of methyl
esters. The maximum peaks at retention time at 18.5 indi-
cates the presence of 9-octa decanoic acid methyl ester. The
fatty acid methyl esters corresponding to different retention
times are listed in Table 7.

3.3.11 Mechanism of Zinc Ferrite Catalyzed Reaction

Fig. 15  Plot of ln k versus 1/T ­(K−1) for biodiesel production with

optimal zinc ferrite (ZF-1500) nanocatalyst for WCO
Equation 16 shows the interrelationship between enthalpy,
entropy and rate constant. The slope and intercept of the plot
of 1/T versus ln (k/T), yields the thermodynamic parameters.
From Fig. 15, the enthalpy and entropy values are calculated
The reaction mechanism of ­ZnFe2O4 catalyzed transesteri-
fication are proposed as in Fig. 17. The active site of the
prepared samples may have different functions co-existing
on the surface, and shall be composed of surface ensem-
­ n+/Mn+1 ion
bles of atoms to permit the reaction to occur. M
pairs (M = Zn, Fe) and acid–base sites in Z­ nFe2O4 behaves
as the active sites promoting a structure sensitive catalytic

Table 5  Kinetics and T (K) ∆G (kJ mol−1) ∆H (kJ mol−1) ∆S (kJ mol−1 k−1) Ea (kJ mol−1) A ­(min−1)

thermodynamic parameters
involved in biodiesel production 308 86.36 56.80 − 0.096 59.40 1.66 × 108
313 86.84
318 87.32
323 87.80
328 88.28
333 88.76

13
 A. Ashok, L. J. Kennedy

Table 6  Fuel properties of Property ASTM specification for standard Measured value of

biodiesel produced from WCO biodiesel (D-6751) biodiesel in present
work

Kinematic viscosity at 40 °C (­ mm2/s) 1.9 to 6.0 3.79

Density (g/cm3) 0.860 to 0.894 0.836
Flash point (°C) 120 minimum 176
Cetane number 47 minimum 46
Fire point (°C) – 210
Calorific value (MJ/kg) – 43.29
Iodine value (mg KOH/g) – 0.19
Acid number (mg KOH/g) 0.5 maximum 0.03
Oxidation stability (h at 110 °C) – 3

Fig. 16  GC-MS chromatogram for biodiesel produced using prepared zinc ferrite (ZF-1500) catalyst

reactions [37]. Initially, the reaction between the catalyst
and methanol produces methoxide ion, which is attached
to the surface of the catalyst and the carbonyl carbon of
triglyceride molecule to forms a tetrahedral intermediate
[34]. In the next step, rearrangement of the unstable tetra-
hedral intermediate occurs, which is later broken down to
form diglyceride anion and fatty acid methyl ester (FAME).
Then, the diglyceride anion is stabilized by a proton from
the surface of the catalyst to form diglyceride in the active
site, and the surface of the catalyst is regenerated at the same
time. Later, the methoxide anion attacks another carbonyl
carbon atom in diglyceride, forming another mole of FAME
and monoglyceride. These three steps are repeated until the
three triglyceride carbonyl centers are attacked by the meth-
oxide ions to give three moles of methyl esters and one mole
of glycerol [35]. It is clearly depicted in Fig. 17.

13
Magnetically Separable Zinc Ferrite Nanocatalyst for an Effective Biodiesel Production from…

Table 7  Fatty acid methyl esters composition of biodiesel synthesized energy is found to be non-spontaneous. The mechanism
form WCO for the formation of fatty acid methyl esters are discussed.
Peak no Retention Fatty acid methyl ester
time (min) Acknowledgements  All the authors sincerely thank VIT Chennai Cam-
pus, Chennai, Tamil Nadu, India, for providing financial assistance
1 15.03 MethylZ-11-tetradecenoate through research associateship to the first author.
2 16.87 Hexadecanoic acid, methyl ester
3 17.7 Pentadecanoic acid, methyl ester Compliance with Ethical Standards 
4 18.5 9-Octadecenoic acid, methyl ester
5 18.73 Heptadecanoic acid, methyl ester Conflict of interest  The authors declare no conflict of interest.
6 19.23 Oleic acid
7 21.82 Hexadecanoic acid, butyl ester
8 23.27 Methoxyacetic acid, octadecyl ester
9 23.85 9-Octadecenoic acid (Z); 2-butoxyethyl ester References
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1
Materials Division, School of Advanced Sciences,
Vellore Institute of Technology (VIT) Chennai Campus,
Chennai 600 127, India