Journal of Environmental Chemical Engineering 9 (2021) 106829

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Synergetic effects of lanthanum substituted Ni-Zn-Cu-Co ferrite

nanocomposite with enhanced NH3 sensing performance
S. Deepapriya a, John D. Rodney a, S. Jerome Das a, S. Lakshmi Devi b, P. Nagaraju c, J.
R. Anusha d, Suresh Perumal e, J. Ermine Jose f, C. Justin Raj g, *
a
Department of Physics, Loyola College, Chennai 600034, India
b
PG Department of Physics, Women’s Christian College, Chennai 600006, India
c
Nanosensor Research Laboratory, Department of Physics, CMR Technical Campus, Hyderabad 501401, India
d
Department of Advanced Zoology and Biotechnology, Loyola College, Chennai 600034, India
e
Laboratory for Energy and Advanced Devices (LEAD), Department of Physics and Nanotechnology, SRM Institute of Science and Technology, Kattankulathur 603203,
India
f
Loyola-ICAM College of Engineering and Technology, Loyola Campus, Chennai 600034, India
g
Department of Chemistry, Dongguk University-Seoul Campus, Jung-gu, Seoul 04620, South Korea

A R T I C L E I N F O A B S T R A C T

Editor: Despo Kassinos The increase in modern technologies upsurges the pollution of air by ten-fold in the past decade leading to the
cause of an increased number of deaths and infectious diseases. This has provoked the research community in
Keywords: developing variable gas sensing materials to detect harmful gases in the present condition. Herein, the lanthanum
Ferrite (La) substituted Ni-Zn-Cu-Co ferrite nanocomposite (La (Ni-Zn-Cu-Co-Fe2O4)) was synthesized via an eco-
Nanocomposite
friendly co-precipitation technique and is utilized as ammonia (NH3) gas sensor. The structural and morpho­
Ammonia gas sensor
logical studies showed the formation of a typical inverse spinel structure of the cubic phase, with spherically
Biocompatible
agglomerated and interconnected nanostructures. Further, the saturation magnetization (Ms) of the as-
synthesized nanocomposite was found to be 1.66 emu using the Vibrating Sample Magnetometer (VSM). The
fabricated La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite thin film exhibited an outstanding sensing capability towards
ammonia gas with a response and recovery time of 20 s and 15 s respectively, which was on par with the current
generation ammonia sensors and posted a sensor response of 86.2% with good repeatability and stability.
Moreover, the synthesized material was also found to be more biocompatible, which stands as a bonus.

1. Introduction techniques such as spectrometry gas chromatography (GC) [16],

high-performance liquid chromatography (HPLC) [31] are used to
The rapid development of sophisticated modern industries has pro­ accurately detect gases, yet these techniques impose requirements of
gressed humanity marching towards excellence, yet the existence of complicated procedures which is expensive and time-consuming. This
such industries and the development of modern equipment has brought has forced the research community to develop the gas sensors that are
in the expulsion of various toxic, harmful, and volatile gases which easy to manufacture and less expensive to be employed in industries as
stands as a never-ending threat to humans and environmental safety. well as in government agencies. The competence of gas sensors to detect
According to a recent report from the World Health Organisation various gases has been established with the change in electrical resis­
(WHO), about 91% of the world’s population resides at places where the tance. The most common successful gas sensors are based on metal oxide
air quality exceeds WHO’s guideline limits and almost every year 4.2 semiconductors, polymer composites, carbon nanotubes, optic methods,
million deaths occur because of exposure to ambient and household air gas chromatography, acoustic methods and calorimetric methods [6,22,
pollution respectively. Therefore, the need for analysis of gas outlets, 32]. Metal oxide semiconductor-based gas sensors were developed
detection, and alarm of specific harmful gases stood out to be a great intensively ever since Seiyama et al. [26] first proposed back in 1962,
concern for the governments and industries. Conventional gas analysis after which numerous works have been carried out using various

* Corresponding author.
E-mail addresses: [email protected], [email protected] (C.J. Raj).

https://doi.org/10.1016/j.jece.2021.106829
Received 28 August 2021; Received in revised form 21 October 2021; Accepted 15 November 2021
Available online 22 November 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

materials as a gas sensors. Semiconductor materials such as Fe2O3, WO3, (Co(NO3)2⋅9H2O) and sodium hydroxide pellets (NaOH) were purchased
SnO2 and ZnO have been extensively studied due to their capability in from Merck (AR graded) and were used without any further purification.
detecting most of the reducing gases and is less expensive to develop
[36]. However, there are persisting issues such as high working tem­ 2.2. Synthesis of La (Ni-Zn-Cu-Co-Fe2O4) nanoparticles
perature (400–450 ◦ C) for ZnO while poor selectivity and recovery for
SnO2. In order to overcome these hurdles, noble metal (Ag, Pt, Pd etc.) The stoichiometric ratio of nickel nitrate, zinc nitrate, cobalt nitrate,
catalyst, doped materials and mixed metal oxides were employed to copper nitrate, lanthanum nitrate and ferric nitrate was taken and dis­
address the pertaining issue by enhancing the sensing properties [38]. solved in 75 ml of double-distilled water by stirring for 45 min to obtain
Despite the convenience of different types of the nanomaterial-based gas a homogeneous solution. Subsequently, a few drops of NaOH solution
sensor as mentioned above, the scientific community continued to work were added to the homogeneous solution to adjust the pH 8 and stirred
for developing a better nanomaterial for gas sensors which has high continuously using a magnetic stirrer until the formation of its hy­
sensitivity, fast recovery time, rapid response with no cross-sensitivity droxides. The admixed solution was stirred constantly and retained at
and the selectivity to detect gases even at a very low concentration [27]. 80 ◦ C for 3 h. The final brown precipitate was magnetically centrifuged
In the past few decades, various complex metal oxide nanoparticles twice with distilled water and once with ethanol at 9000 rpm to remove
have attracted researchers as a potential gas sensing material due to nitrates and other impurities. The obtained precipitate was further dried
their enriched physicochemical properties [19]. Out of which, the in a hot air oven at 70 ◦ C for a duration of 24 h. Finally, the mixture was
transitional metal ferrites (TMF) (MFe2O4) were considered as a prom­ grounded to powder and was calcined at 500 ◦ C for 3 h in a muffle
ising gas sensing material due to their extensive properties like struc­ furnace to acquire the final ferrite nanocomposite of La (Ni-Zn-Cu-Co-
tural and chemical composition of the material, whereas two cationic Fe2O4).
sites are occupied by post-transition or transition cations [24]. The
cations varying in charge and chemical nature are arranged in two types
2.3. Sensor fabrication and gas sensing measurement
of polyhedral structure, which is present in-between the cations and the
encapsulated lattice oxygen. Thus, TMF brings in versatile variations in
The gas sensing measurement was carried out on a custom-made
the varied properties required for a gas sensor. Since this, a surface
vacuum chamber by depositing the nanocomposite on a glass sub­
reactivity related work is required for the synthesis of low density and
strate with the exposure of volatile gases. Typically, 0.1 g of La (Ni-Zn-
high surface area material for gas sensing applications. Recently Chen
Cu-Co-Fe2O4) nanocomposite was ground with 0.3 µL of double distilled
et al. [5] demonstrated MFe2O4 (M = Cu, Zn, Cd, Mg) as a gas sensing
water and 0.25 µL of acetylacetone for 10 min to form a viscous paste.
material for CO, H2, LPG, C2H5OH and C2H2 gases. It was found that
Then 20 µL of Triton X-100 (surfactant) was added drop-wise to the
MgFe2O4 and CdFe2O4 were the most sensitive and selective materials
viscous paste and was continuously ground well to form a slurry paste. A
towards LPG and C2H2 respectively. Similarly, Kamble et al. [14]
glass substrate of dimension 3 × 1.5 cm2 was cleaned by sonicating
showcased NiFe2O4 as a gas sensor and found that the NiFe2O4 thick film
twice with double distilled water and acetone for 10 min respectively.
was able to detect Cl2, ammonia, LPG and O2 with a maximum response
The obtained slurry paste was uniformly coated over the glass substrate
of 96% and 98% for Cl2 and LPG respectively. Since doping is considered
using the doctor blade technique and the film was dried at ambient
as an extensive approach to tune a base material according to the per­
temperature for 10 h. Eventually, the film was pre-heated at 200 ◦ C for
taining need of the application. The rare earth metal oxide (Lanthanum)
30 min and a silver paste was dropped into the edges of the thin film to
is employed as a dopant in the present work due to its interesting feature
assure ohmic contact between the probe and the sample as shown in
of enriching the oxygen vacancies and developing a much better elec­
Fig. 1. The obtained La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite film on a
tronic structure for fast charge transfer and also improving the surface
glass substrate was used for gas sensing measurement. All the mea­
area of the material [17]. Similarly, various works have been carried out
surements were carried out in a custom-made air-sealed gas chamber
on rare-earth doped ferrite, for example, Yadav et al. [37] fabricated
[35] with two microprobes at room temperature (32 ◦ C) with relative
LPG gas sensors utilizing lanthanum doped ferrite and their percentage
humidity (RH) of 25%. The sensing measurements were studied by
of sensor response was found to be 394% for 5000 ppm of LPG gas inlet.
allowing the different concentrations of Ammonia (NH3), Acetone
In this investigation, a novel magnetic nanocomposite ferrite La
((CH3)2CO), Ethanol (C2H6O) and Toluene (C7H8) through the vacuum
(Ni-Zn-Cu-Co-Fe2O4) was synthesized by an eco-friendly co-precipita­
chamber fitted with a k-type thermocouple and heating element to
tion technique and its structural, morphological, and magnetic proper­
vaporize after the chamber was sealed. The gas sensing recovery was
ties were studied. The synthesis of multi transitional mixed ferrites holds
analyzed by allowing the sample to atmospheric air. Keithley 6517B
good for various reasons such as availability of increased oxidation state,
Electrometer (USA) was used for a time interval of 0.5 s with the source
revamped conductivity with different activation sites towards the target
voltage and the applied − 3 V DC bias voltage for all gas sensing mea­
gas. Recent applications of multi-transitional nanocomposite ferrites
surements. The variation in resistance as a function of time with expo­
aim at providing a better understanding of multi-ferroic materials and
sure to analyte at constant voltage was monitored using a computer
are gaining suitable attention to provide improved efficiency. Further,
running LabVIEW developed GUI. The sensor response was calculated
the novel magnetic nanocomposite ferrite was fabricated as a gas sensor
using the following formula
and the sensing capability of the devised sensor was found by exposing it
in sensing the vapor gases like Ammonia (NH3), Acetone ((CH3)2CO), Ra − Rg
S(%) = × 100%
Ethanol [EtOH] (C2H6O), and Toluene (C7H8). This novel magnetic Ra
nanocomposite ferrite-based gas sensor stood out as an outstanding
vapor gas-sensing unit. where, Ra and Rg are resistance in air and the resistance in presence of
test gas respectively. The response and recovery time are defined as the
2. Experimental section time taken by the sensor to reach a maximum value of 90% of the total
resistance after switching off the gas in step function for adsorption and
2.1. Chemicals desorption at room temperature respectively.

The starting materials iron nitrate nonahydrate (Fe(NO3)3⋅9H2O), 2.4. Characterization

lanthanum nitrate trihydrate (La(NO3)3⋅3H2O), nickel nitrate hexahy­
drate (Ni(NO3)2⋅9H2O), copper nitrate trihydrate (Cu(NO3)2⋅9H2O), The crystalline structure of the ferrites and nanocomposite was
zinc nitrate hexahydrate (Zn(NO3)2⋅9H2O), cobalt nitrate hexahydrate recorded using Bruker D8 Advance Diffractometer with an X-ray source

2
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

Fig. 1. Schematic diagram of La (Ni-Zn-Cu-Co-Fe2O4) thin film working electrode and gas sensing set up.

Fig. 2. a) XRD patterns of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite and the single transitional metal-based ferrites, b) TEM image, c) HR-TEM image, and d) SAED
pattern of La (Ni-Zn-Cu-Co-Fe2O4) sample.

3
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

CuKα1 of wavelength 1.5406 Å. The morphological parameter was transitional metal ferrites as shown in Fig. 2a. The pertinent diffraction
studied using FEI, Quanta 200, Field Emission Scanning Electron Mi­ peaks corresponding to planes (220), (311), (400), (422), (511), (440)
croscope (FE-SEM) along with Energy Dispersive X-Ray Analysis (EDS) and (533) are well in match with the standard JCPDS card no. 10-0325,
for elemental analysis and Jeol/JEM 2100F High-Resolution Trans­ exhibiting the occurrence of spinel and inverse structure. The presence
mission Electron Microscope (HR-TEM) with Selected Area Electron of sharp and intense peaks reveals the formation of the sublime crys­
Diffraction (SAED). The magnetic behavior of the material was studied talline structure of the as-synthesized material. The mean crystallite size
using Lakeshore 7410 S Vibrating Sample Magnetometer. was calculated using the Scherrer equation [20,25] (Eq. (S1)) and was
found to be 16 nm (Table S1). The change in structural parameters was
3. Results and discussion cross verified with our previous work and is tabulated in Table S1. It is
clearly seen that the as-synthesized nanocomposite exhibited the largest
3.1. Structural, morphology and magnetic properties crystallite size than the previous works. Since the ionic radii are larger
for La3+ ions when compared with Fe3+ ions and the La3+ ions require
The X-ray diffraction pattern XRD of La (Ni-Zn-Cu-Co-Fe2O4) nano­ much larger activation energy to enter the octahedral sites as bond en­
composite was compared with the lanthanum substituted single ergy of La-O is also higher than that of Fe-O. Therefore, rather than

Fig. 3. a) EDAX pattern of La (Ni-Zn-Cu-Co-Fe2O4) and Hysteresis loop of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite.

4
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

occupying the Fe3+ sites in the crystal lattice, the La3+ ventures into the paramagnetic natured La3+ ions maintaining the inverse spinel structure
interstitial sites in-between the lattice, enforcing strain on the system and thus eradicating the possibility of conversion of the spin magnetic
[18]. Thus, suppressing the crystallization by confining the grain moment between A-B sublattices into anti-ferromagnetic coupling [7].
boundaries and reducing the crystallite size eventually. Whereas in the In addition, the presence of varied ions in the A-site also overcomes the
case of as-synthesized nanocomposite La (Ni-Zn-Cu-Co-Fe2O4), the surface effect caused by the La3+ ions on the crystal lattice as they tend
involvement of varied ions such as Cu2+, Zn2+, Co2+ and Ni2+ overcome to confine the grain boundaries due to their higher ionic radii [13]. This
the formation of crystalline anisotropy during the substitution of La3+ by overhaul leads to the achievement of larger particle sizes even at room
forming a state of equilibrium between the crystal anisotropy and vol­ temperature. Thus, achieving multi-domain walls in the system which in
ume strain formed in the system [34]. This enables the material to turn leads to a higher saturation magnetization.
overcome the size induced effect by the lanthanum ions, thus enabling
them to achieve a larger crystallite size at room temperature without any 3.2. Gas sensing studies and discussion
loss in grain boundaries. The morphology of as-synthesized nano­
composite was studied by using the scanning electron microscope (SEM) The gas sensing mechanism was examined after the successful
shown in Fig. S1, the resultant image depicts the formation of highly characterization of single transitional metal-based ferrites and nano­
agglomerated spherical shaped particles in the size range of 25 nm to composite towards ammonia. The variable composition and good
3 µm. Fig. 2b shows the transmission electron microscopic (TEM) image structural stability are key to making ferrites a good sensing material.
of the La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite. The image reveals the The ability to detect a discrete gas is an important property of a gas
presence of highly interconnected chain-like morphology with the dis­ sensor to study the selectivity range. To understand this property,
tribution of nearly spherical shaped nanoparticles in the size range of NiLaFe2O4, ZnLaFe2O4, CuLaFe2O4, CoLaFe2O4 and La (Ni-Zn-Cu-Co-
5–20 nm. Moreover, the HR-TEM image (Fig. 2c) shows the well-defined Fe2O4) nanocomposite were tested in gas phase ammonia, ethanol,
lattice fringes of the nanoparticles with d-spacing values of 0.294 nm toluene, and acetone at 50 ppm constant concentration as shown in
and 0.160 nm corresponding to the (220) and (511) planes respectively Fig. 4a. An extraordinary gas sensing response was found towards
(JCPDS 10-0325). Further, the selected area electron diffraction (SAED) ammonia indicating the presence of lone pair of electrons while a rela­
patterns of the as-synthesized nanocomposite (Fig. 2d) reveal tively low gas sensing response was obtained for ethanol, toluene and
well-defined ring patterns. This might be due to the composite and acetone due to the absence of unshared pair of electrons [11].
polycrystalline structure of as-synthesized nanocomposite and the ob­ Thereby, the sensing resistance decreases with exposure to ammonia
tained planes are in accordance with the XRD data and was far superior when compared to other volatile gases, signifying magnificent selec­
to the single transitional metal-based ferrites as shown in Fig. S2. tivity towards ammonia. Thus, ammonia is preferred over other volatile
Further, the EDS analysis shows the complete composition of the syn­ gases due to the reduced response of ethanol, toluene, and acetone gases.
thesized nanocomposite (Fig. 3a). Moreover, the rare earth elements have a bigger crystallite size
The variation in magnetization was studied using a vibrating sample compared to transitional elements [23]. Thus, rare earth elements can
magnetometer and the hysteresis loop of the synthesized La (Ni-Zn-Cu- be used to modify the structural properties of p-type semiconductors
Co-Fe2O4) nanocomposite is shown in Fig. 3b. From the plot, La (Ni-Zn- (copper ferrites, cobalt ferrites, and nickel ferrites) and n-type semi­
Cu-Co-Fe2O4) nanocomposite exhibited a quintessential super- conductors (Zn ferrites). The inclusion of rare earth metal oxides attri­
paramagnetic nature, and the saturation magnetization was found to butes to an excellent oxygen absorption property [4]. Despite other rare
be 1.66 emu. The hysteresis loop and remanence signify the magnetic earth metals, Lanthanum of considerable crystallite size (1.06 Å) and
behavior, indicating the convenient behavior to discrete the magnetic + 3 valency are found to be effective, to occupy the octahedral sites in
particles using an applied external magnetic field. This illustrates a spinel structure to change electrical resistance. The La3+ ions enhance
single domain structure for La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite [2]. gas sensing response and refine sensor selectivity with increased active
The saturation magnetization of the as-synthesized nanocomposite and sites which lead to the reduced operating temperature. The incorpora­
our previous reports were comparatively listed in Table 1. tion of bigger crystallite La3+ ions increases the distortion in the crystal
The synthesized nanocomposite demonstrates higher Ms than the lattice of ferrites accounting for its superior gas sensing performance
previous works based on single transitional metal ferrites (Fig. S3). The [33].
smaller saturation magnetization of the single transitional metal based The gas sensing properties of NiLaFe2O4, ZnLaFe2O4, CuLaFe2O4,
ferrites can be due to the presence of the non-magnetic La3+ ions in the CoLaFe2O4 and La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite was character­
crystal system. For as the iron in the B-site is a huge contributor to the ized under ammonia vapor gas concentration ranging from 10 ppm to
magnetization and the La3+ ion has no electron in the 4f orbit [28]. The 100 ppm at room temperature as shown in Fig. 4b–f. The ferrite semi­
paramagnetic nature is introduced at the expense of the Fe3+ ions in the conductor property can be studied with the inclusion of M2+ ions into
B-site which eventually suppresses the net overall magnetic moment, the crystal lattice of the parent Fe2O4 structure pertaining to the
leading to a reduced saturation magnetization. Whereas, the composition of the amalgamated ferrite nanocomposite. Copper ferrite,
as-synthesized nanocomposite posts a commendable saturation magne­ cobalt ferrite and nickel ferrite usually exhibit p-type semiconductor
tization value even with the presence of the La3+ ion in the system. This properties due to their dependence on chemical composition while iron
is hugely due to the presence of complex ions in the A-site (Ni2+, Zn2+, excess zinc ferrites exhibit n-type semiconductor properties due to the
Co2+, Cu2+), which in turn compensates for the lost Fe3+ ions. The electron exchange between Fe2+ and Fe3+ [12].
presence of a complex entity in the A-site overrules the activity of The gas sensing response and recovery time curves for a constant
50 ppm of ammonia vapour is shown in Fig. 5a–e. A swift response to­
wards high ammonia concentration can be observed due to the inter­
Table 1 action of increased ammonia molecules with adsorbed oxygen ions. The
Saturation magnetization (Ms) of as-synthesized La (Ni-Zn-Cu-Co-Fe2O4) nano­ gas sensing response of n-type semiconductor (ZnLaFe2O4), p-type
composite and single transitional metal ferrites. semiconductor (NiLaFe2O4, CoLaFe2O4, CuLaFe2O4) and La (Ni-Zn-Cu-
Samples Saturation magnetization (Ms) (emu) Ref. Co-Fe2O4) nanocomposite for 50 ppm of ammonia vapour concentration
La (Ni-Zn-Cu-Co-Fe2O4) 1.66 This work is tabulated in Table 2. The La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite
NiLaFe2O4 0.36 [9] show excellent gas sensing response due to the application of metallic
ZnLaFe2O4 1.06 [8] nanoparticles composed of different organic matrices granting engi­
CoLaFe2O4 0.55 [8] neered interactions with analytes to form a successful sensor [15]. The
CuLaFe2O4 0.72 [10]
addition of lanthanum into the nanocomposite enhances the gas sensing

5
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

Fig. 4. a) Sensing response and selectivity of La (Ni-Zn-Cu-Co-Fe2O4), CuLaFe2O4, ZnLaFe2O4, NiLaFe2O4 and CoLaFe2O4 towards different gases; Response and
recovery time towards ammonia vapor at different ppm b) La (Ni-Zn-Cu-Co-Fe2O4), c) NiLaFe2O4, d) ZnLaFe2O4, e) CoLaFe2O4, and f) CuLaFe2O4.

response towards a relative ammonia vapour gas. The tailored con­ magnificent sensitivity of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite can be
struction of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite accredits the gas observed in Fig. 5f, when exposed to a wide range of ammonia con­
sensing property of thin film that has out-performed the other single centration and thus recovers to its original baseline value with the
transitional metal-based ferrites examined in this work. Moreover, a exposure of air molecules signifying the vital property of a gas sensor

6
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

Fig. 5. Response and recovery time towards 50 ppm of ammonia a) La (Ni-Zn-Cu-Co-Fe2O4), b) NiLaFe2O4, (c) ZnLaFe2O4, d) CoLaFe2O4, e) CuLaFe2O4 and f)
Response of the sensor towards various concentration (10–100 ppm) of ammonia gas.

[21]. While a reduced gas sensitive response was obtained for other A remarkable gas sensing response towards ammonia indicate good
single transitional metal-based ferrite nanomaterials (Fig. S4). This selectivity of the nanocomposite material. To study the suitability, the
enhanced gas sensing property towards La (Ni-Zn-Cu-Co-Fe2O4) nano­ curve fitting of sensor response versus different ammonia gas concen­
composite material can be attributed to the increased adsorption and trations suitably 10–100 ppm was measured. The correlation coefficient
desorption of ammonia molecules. R2 from the curve fitting in the range 10–25 ppm was analyzed to be

7
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

Table 2
Comparison of La (Ni-Zn-Cu-Co-Fe2O4) thin film sensor towards ammonia sensing with single transitional metal ferrites.
Sample composition Sensor morphology Response time (s) Recovery time (s) % sensor response NH3 (ppm) Ref.

La (Ni-Zn-Cu-Co-Fe2O4) Thin film 20 15 86.2 50 This Work

CuLaFe2O4 42 64 23.5
NiLaFe2O4 32 46 74.3
ZnLaFe2O4 27 49 57.1
CoLaFe2O4 33 52 52.3

0.998 and for 30–100 ppm it was 0.997 signifying good linear behavior, studied utilizing bran of foxtail millets in a recurrent process to under­
to study the sensing application towards ammonia gas. The slope in the stand the environmental stability of the materials used in the gas sensor.
range 10–25 was determined to be 0.32, which rapidly decreased to Two drops of Tween-80 (detergent) in deionized water were added to
0.092 after 50 ppm of ammonia (Fig. S5). Therefore, from the above millet seed and was dried for 10 min. The obtained seeds were washed in
data, it can be concluded that the presence of varied transitional metal deionized water to remove strands of dust. Further, 70% of Ethyl alcohol
ions in a single system contributes to the advancement of conductivity, and 0.1% mercuric chloride mixture was used to completely rinse the
reactivity and perfect tuning of the material with more active sites than test seeds to derive contamination-free seeds. And subsequently, the
other single transitional metal-based ferrite nanomaterials [1]. seeds were washed with sterilized double distilled water to remove
The gas sensing properties of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite surface impurities. The obtained pure foxtail millets seeds were
can be further studied with different relative humidity. The gas sensing immersed in La (Ni-Zn-Cu-Co-Fe2O4), CH (Chitosan) and La (Ni-Zn-Cu-
property of a sensor depends on the change in operating temperature Co-Fe2O4)-CH solutions for 10 s and then directly shifted to agar me­
and the impact at room temperature can be studied by varying relative dium with plant nutrients [29,30]. This medium was incubated for a
humidity in the range of 25–95% towards 50 ppm of ammonia as shown period of 48 h at room temperature. Seed germination of La (Ni-Zn-­
in Fig. 6a. A gradual decrease in the response value was observed with Cu-Co-Fe2O4), CH, and La (Ni-Zn-Cu-Co-Fe2O4)-CH solutions was
the increase in relative humidity from 25% to 95% for NiLaFe2O4, observed as shown in Fig. 10(a-c). Seed germination of La (Ni-Zn-Cu-­
ZnLaFe2O4, CuLaFe2O4, CoLaFe2O4 and La (Ni-Zn-Cu-Co-Fe2O4) nano­ Co-Fe2O4) was found to be more effective compared to CH and La
composite (Fig. S6). This can be attributed to the stronger adsorption (Ni-Zn-Cu-Co-Fe2O4)-CH. The seeds were allowed to grow in the agar
ability of water molecules on La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite, plates for a week (Fig. S8) and the growth index of the seeds was found
signifying the obstruction of large active sites. Thus, relative humidity is to be as La (Ni-Zn-Cu-Co-Fe2O4) > La (Ni-Zn-Cu-Co-Fe2O4)-CH > CH
a vital property to study the gas sensing response of the developed (Fig. 7), without the formation of any fungal or other impurities. This
ammonia gas sensor at room temperature and its application must be illustrates the biocompatible nature of nanocomposite material with no
evaluated under the appropriate measurements [3]. The stability fea­ contamination of the seeds or the medium. This confirms that the
tures are a key parameter of the sensor and are pre-eminent for the gas as-synthesized material is eco-friendly and can be used as a potential
sensing characteristics of the single transitional metal-based ferrites gas-sensing material.
shown in (Fig. S7) and La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite sensor.
The stability of the nanocomposite gas sensor was evaluated for 15 days 4. Conclusion
and is shown in Fig. 6b. The average response towards 50 ppm con­
centration of ammonia was found to be 64.5 ± 0.3% to that of its prime La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite was successfully synthesized
value 64.8% revealing good stability of the developed La (Ni-Zn-Cu-­ via swift and eco-friendly co-precipitation technique. The precise con­
Co-Fe2O4) based ammonia gas sensor. trol of composition in the gas sensing spinel matrix for the reproducible
The biocompatibility of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite was fabrication of nanocomposite seems to be viable for achieving high

Fig. 6. a) Stability of La (Ni-Zn-Cu-Co-Fe2O4) nanocomposite towards 50 ppm of ammonia at room temperature for 15 days and b) effect of humidity.

8
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

Fig. 7. Snapshot of the agar plates containing foxtail millets after 2 days of incubation a) La (Ni-Zn-Cu-Co-Fe2O4), b) La (Ni-Zn-Cu-Co-Fe2O4) – CH, c) CH, and d) Fox
millets seeds growth index after 1 week.

sensitivity and enhanced selectivity. In this investigation, we have CRediT authorship contribution statement
attempted the spinel compounds with transitional metal ferrites and
doping non-noble metal (Lanthanum) which revamp the ammonia gas S. Deepapriya: Conceptualization, Methodology, Investigation,
sensing response at room temperature. The synthesis of La (Ni-Zn-Cu- Visualization, Writing – original draft. John D Rodney: Investigation,
Co-Fe2O4) nanocomposite with enhanced oxidation state, revamped Formal analysis. S. Jerome Das: Supervision, Writing – review & edit­
conductivity with different activation sites might be accounted for ing, Visualization. S. Lakshmi Devi: Formal analysis, Visualization. P.
excellent gas sensing property towards target ammonia gas. La (Ni-Zn- Nagaraju: Investigation, Formal analysis. J. R. Anusha: Formal anal­
Cu-Co-Fe2O4) nanocomposite showcased a paramagnetic behavior with ysis, Writing – review & editing. Suresh Perumal: Technical help,
saturation magnetization of 1.66 emu assisting to the improved sensing Formal analysis, Writing – review & editing. J. Ermine Jose: Investi­
properties when compared to single metal lanthanum doped ferrites. gation, Writing – review & editing. C. Justin Raj: Conceptualization,
The increased gas sensing response of the transitional metal ferrites was Writing – review & editing, Project administration, Supervision.
related to the Lanthanum dopant in cationic sites and adsorbed oxygen
ions. It has been observed that the combination of La (Ni-Zn-Cu-Co-
Declaration of Competing Interest
Fe2O4) show a definite preferential sensitivity to ammonia gas of
50 ppm among all the other test gases studied with a peak response of
The authors declare that they have no known competing financial
86.2% with a response time of 20 s and a recovery time of 15 s. The
interests or personal relationships that could have appeared to influence
different relative humidity was also measured using ammonia at room
the work reported in this paper.
temperature suggesting the vital condition for gas sensing measurement.
The biocompatible nature of nanocomposite material has been exten­
sively studied with the growth index of seeds without any fungal im­ Acknowledgements
purities. The versatile gas sensing response of La (Ni-Zn-Cu-Co-Fe2O4)
nanocomposite give room to development with long-term stability as an The author (S.J. Das) is grateful to the Management of Loyola Col­
environmental gas sensor in industrial applications. lege, Chennai-34 for providing required area to conduct research ac­
tivity and acknowledges the technical help rendered by sophisticated

9
S. Deepapriya et al. Journal of Environmental Chemical Engineering 9 (2021) 106829

Analytical Instrumentation Facility, Cochin for TEM analysis. [18] A. Majeed, M.A. Khan, F.U. Raheem, A. Hussain, F. Iqbal, G. Murtaza, M.N. Akhtar,
I. Shakir, M.F. Warsi, Structural elucidation and magnetic behavior evaluation of
rare earth (La, Nd, Gd, Tb, Dy) doped BaCoNi-X hexagonal nano-sized ferrites,
Appendix A. Supplementary material J. Magn. Magn. Mater. 408 (2016) 147–151, https://doi.org/10.1016/j.
jmmm.2016.02.061.
Supplementary data associated with this article can be found in the [19] B. Timmer, W. Olthuis, A. van den Berg, Ammonia sensors and their applications —
a review, Sens. Actuators B Chem. 107 (2005) 666–677, https://doi.org/10.1016/
online version at doi:10.1016/j.jece.2021.106829. j.snb.2004.11.054.
[20] A.L. Patterson, The scherrer formula for X-ray particle size determination, Phys.
References Rev. 56 (1939) 978–982, https://doi.org/10.1103/PhysRev.56.978.
[21] M. Poloju, N. Jayababu, M.V.R. Reddy, Improved gas sensing performance of Al
doped ZnO/CuO nanocomposite based ammonia gas sensor, Mater. Sci. Eng. B 227
[1] L.S.K. Achary, A. Kumar, B. Barik, P.S. Nayak, N. Tripathy, J.P. Kar, P. Dash, (2018) 61–67, https://doi.org/10.1016/j.mseb.2017.10.012.
Reduced graphene oxide-CuFe2O4 nanocomposite: A highly sensitive room [22] S.S. Rathnakumar, K. Noluthando, A.J. Kulandaiswamy, J.B.B. Rayappan,
temperature NH3 gas sensor, Sens. Actuators B Chem. 272 (2018) 100–109, K. Kasinathan, J. Kennedy, M. Maaza, Stalling behaviour of chloride ions: a non-
https://doi.org/10.1016/j.snb.2018.05.093. enzymatic electrochemical detection of α-Endosulfan using CuO interface, Sens.
[2] L. Avazpour, H. Shokrollahi, M.R. Toroghinejad, M.A. Zandi Khajeh, Effect of rare Actuators B Chem. 293 (2019) 100–106, https://doi.org/10.1016/j.
earth substitution on magnetic and structural properties of Co1− xRExFe2O4(RE: Nd, snb.2019.04.141.
Eu) nanoparticles prepared via EDTA/EG assisted sol-gel synthesis, J. Alloy. [23] N. Rezlescu, E. Rezlescu, C.L. Sava, F. Tudorache, P.D. Popa, On the effects of Ga3+
Compd. 662 (2016) 441–447, https://doi.org/10.1016/j.jallcom.2015.11.188. and La3+ ions in MgCu ferrite: humidity-sensitive electrical conduction, Cryst. Res.
[3] N. Bouhadouza, A. Rais, S. Kaoua, M. Moreau, K. Taibi, A. Addou, Structural and Technol. 39 (2004) 548–557, https://doi.org/10.1002/crat.200310223.
vibrational studies of NiAlxFe2− xO4ferrites (0 ≤ x ≤ 1), Ceram. Int. 41 (2015) [24] L. Satyanarayana, K.M. Reddy, S.V. Manorama, Synthesis of nanocrystalline Ni1-
0–17, https://doi.org/10.1016/j.ceramint.2015.05.132.
xCoxMnxFe2-xO4: a material for liquid petroleum gas sensing, Sens. Actuators B
[4] N. Chen, X. Yang, E. Liu, J. Huang, Reducing gas-sensing properties of ferrite Chem. 89 (2003) 62–67, https://doi.org/10.1016/S0925-4005(02)00429-X.
compounds MFe2O4 (M=Cu, Zn, Cd and Mg), Sens. Actuators B: Chem. 66 (2000) [25] P. Scherrer, Bestimmung der Größe und der inneren Struktur von Kolloidteilchen
178–180, https://doi.org/10.1016/S0925-4005(00)00368-3. mittels Röntgenstrahlen, Math. Kl. 29 (1918) 98–100.
[5] N.S. Chen, X.J. Yang, E.S. Liu, J.L. Huang, Reducing gas-sensing properties of [26] T. Seiyama, K. Fujiishi, M. Nagatani, A. Kato, A new detector for gaseous
ferrite compounds MFe2O4 (M = Cu, Zn, Cd and Mg), Sens. Actuators B Chem. 66 components using zinc oxide thin films, J. Soc. Chem. Ind. Jpn. 66 (1963)
(2000) 178–180, https://doi.org/10.1016/S0925-4005(00)00368-3. 652–655, https://doi.org/10.1246/nikkashi1898.66.5_652.
[6] S.L. Darshane, S.S. Suryavanshi, I.S. Mulla, Nanostructured nickel ferrite: a liquid [27] G.U.G. Sensors, Graphene Gas Sens. (2013) (Total cost: 2–3).
petroleum gas sensor, Cream. Int. 35 (2009) 1793–1797, https://doi.org/10.1016/ [28] R. Sharma, P. Thakur, M. Kumar, N. Thakur, N.S. Negi, P. Sharma, V. Sharma,
j.ceramint.2008.10.013. Improvement in magnetic behaviour of cobalt doped magnesium zinc nano-ferrites
[7] Y.K. Dasan, B.H. Guan, M.H. Zahari, L.K. Chuan, Influence of La3+ substitution on via co-precipitation route, J. Alloy. Compd. 684 (2016) 569–581, https://doi.org/
structure, morphology and magnetic properties of nanocrystalline Ni-Zn ferrite, 10.1016/j.jallcom.2016.05.200.
PLoS One 12 (2017) 1–14, https://doi.org/10.1371/journal.pone.0170075. [29] J. Singh, A. Roychoudhury, M. Srivastava, V. Chaudhary, R. Prasanna, D.W. Lee, S.
[8] S. Deepapriya, P. Annie Vinosha, J.D. Rodney, S. Jerome Das, Progression in H. Lee, B.D. Malhotra, Highly efficient bienzyme functionalized biocompatible
structural, magnetic and electrical properties of La-doped group IV elements, AIP nanostructured nickel ferrite–chitosan nanocomposite platform for biomedical
Conf. Proc. (2018), https://doi.org/10.1063/1.5028702. application, J. Phys. Chem. C 117 (2013) 8491–8502, https://doi.org/10.1021/
[9] S. Deepapriya, S.L. Devi, P.A. Vinosha, J.D. Rodney, C.J. Raj, J.E. Jose, S.J. Das, jp312698g.
Estimating the ionicity of an inverse spinel ferrite and the cation distribution of La- [30] P. Singh, D. Rathore, A biosensor system using nickel ferrite nanoparticles, AIP
doped NiFe2O4 nanocrystals for gas sensing properties, Appl. Phys. A Mater. Sci. Conf. Proc. 1728 (2016) 020259, https://doi.org/10.1063/1.4946310.
Process. (2019) 125, https://doi.org/10.1007/s00339-019-2978-x. [31] J. Tamaoka, Y. Katayama-Fujimura, H. Kuraishi, Analysis of bacterial
[10] S. Deepapriya, P.A. Vinosha, J.D. Rodney, M. Jose, S. Krishnan, J.E. Jose, S.J. Das, menaquinone mixtures by high performance liquid chromatography, J. Appl.
Investigation on lanthanum substitution in magnetic and structural properties of Bacteriol. 54 (1983) 31–36, https://doi.org/10.1111/j.1365-2672.1983.tb01297.
group IV elements, Vacuum 161 (2019) 5–13, https://doi.org/10.1016/j. x.
vacuum.2018.12.015. [32] G.J. Thangamani, S.K.K. Pasha, Titanium dioxide (TiO2) nanoparticles reinforced
[11] M. Dziubaniuk, R. Bujakiewicz-Korońska, J. Suchanicz, J. Wyrwa, M. Rȩkas, polyvinyl formal (PVF) nanocomposites as chemiresistive gas sensor for sulfur
Application of bismuth ferrite protonic conductor for ammonia gas detection, Sens. dioxide (SO2) monitoring, Chemosphere 275 (2021), 129960, https://doi.org/
Actuators B Chem. 188 (2013) 957–964, https://doi.org/10.1016/j. 10.1016/J.CHEMOSPHERE.2021.129960.
snb.2013.08.020. [33] U.B. Tumberphale, S.S. Jadhav, S.D. Raut, P.V. Shinde, S. Sangle, S.F. Shaikh, A.
[12] D. Gherca, A. Pui, V. Nica, O. Caltun, N. Cornei, Eco-environmental synthesis and M. Al-Enizi, M. Ubaidullah, R.S. Mane, S.K. Gore, Tailoring ammonia gas sensing
characterization of nanophase powders of Co, Mg, Mn and Ni ferrites, Ceram. Int. performance of La3+-doped copper cadmium ferrite nanostructures, Solid State Sci.
40 (2014) 9599–9607, https://doi.org/10.1016/j.ceramint.2014.02.036. 100 (2020), 106089, https://doi.org/10.1016/j.solidstatesciences.2019.106089.
[13] A.I. Iorgu, F. Maxim, C. Matei, L.P. Ferreira, P. Ferreira, M.M. Cruz, D. Berger, Fast [34] R.H. Vignesh, K.V. Sankar, S. Amaresh, Y.S. Lee, R.K. Selvan, Sens. Actuators B
synthesis of rare-earth (Pr3+, Sm3+, Eu3+ and Gd3+) doped bismuth ferrite powders Chem. (2015), https://doi.org/10.1016/j.snb.2015.04.115.
with enhanced magnetic properties, J. Alloy. Compd. 629 (2015) 62–68, https:// [35] Y. Vijayakumar, P. Nagaraju, V. Yaragani, S. Reddy, N.S. Awwad, M.V.R. Reddy,
doi.org/10.1016/j.jallcom.2014.12.108. Nanostructured Al and Fe co-doped ZnO thin films for enhanced ammonia
[14] R.B. Kamble, V.L. Mathe, Nanocrystalline nickel ferrite thick film as an efficient gas detection, Phys. B Phys. Condens. Matter 581 (2020), 411976, https://doi.org/
sensor at room temperature, Sens. Actuators B Chem. 131 (2008) 205–209, https:// 10.1016/j.physb.2019.411976.
doi.org/10.1016/j.snb.2007.11.003. [36] C.Y. Wang, X. Zhang, Q. Rong, N.N. Hou, H.Q. Yu, Ammonia sensing by closely
[15] S. Li, A. Liu, Z. Yang, J. He, J. Wang, F. Liu, H. Lu, X. Yan, P. Sun, X. Liang, Y. Gao, packed WO3 microspheres with oxygen vacancies, Chemosphere 204 (2018)
G. Lu, Room temperature gas sensor based on tindioxide@polyaniline 202–209, https://doi.org/10.1016/j.chemosphere.2018.04.050.
nanocomposite assembled on flexible substrate: ppb-level detection of NH3, Sens. [37] A.K. Yadav, R.K. Singh, P. Singh, Fabrication of lanthanum ferrite based liquefied
Actuators B Chem. 299 (2019), 126970, https://doi.org/10.1016/j. petroleum gas sensor, Sens. Actuators B Chem. 229 (2016) 25–30, https://doi.org/
snb.2019.126970. 10.1016/j.snb.2016.01.066.
[16] J. Lisec, N. Schauer, J. Kopka, L. Willmitzer, A.R. Fernie, Gas chromatography mass [38] X. Zhao, A. Sun, W. Zhang, L. Yu, Z. Zuo, N. Suo, X. Pan, Y. Han, Enhancement of
spectrometry-based metabolite profiling in plants, Nat. Protoc. 1 (2006) 387–396, the magnetic properties of Ni–Cu–Co ferrites by the magnetic Ce3+-ions
https://doi.org/10.1038/nprot.2006.59. substitution, J. Mater. Sci. Mater. Electron. 31 (2020) 762–778, https://doi.org/
[17] Y-L. Liu, Z-M. Liu, Y. Yang, H-F. Yang, G-L. Shen, R-Q. Yu, Simple synthesis of 10.1007/s10854-019-02583-4.
MgFe2O4 nanoparticles as gas sensing materials, Sens. Actuators B Chem. 107
(2005) 600–604, https://doi.org/10.1016/j.snb.2004.11.026.

10