sensors

Article
Nb2O5 Microcolumns for Ethanol Sensing
Gayan W. C. Kumarage 1,2 , Shasika A. Panamaldeniya 3,4 , Valentin A. Maraloiu 5 , Buddhika S. Dassanayake 4 ,
Nanda Gunawardhana 6 and Elisabetta Comini 1, *

1 SENSOR Laboratory, Department of Information Engineering, University of Brescia, Via Valotti 9,

25133 Brescia, Italy; g.wadumasthree@unibs.it
2 Department of Physics and Electronics, Faculty of Science, University of Kelaniya, Kelaniya 11600, Sri Lanka
3 Postgraduate Institute of Science, University of Peradeniya, Peradeniya 20400, Sri Lanka
4 Department of Physics, Faculty of Science, University of Peradeniya, Peradeniya 20400, Sri Lanka
5 Laboratory of Atomic Structures and Defects in Advanced Materials, National Institute of Materials Physics,
Atomistilor Str. 405 A, 077125 Magurele, Romania; maraloiu@infim.ro
6 Research and International Affairs, Sri Lanka Technological Campus, Padukka 10500, Sri Lanka
* Correspondence: elisabetta.comini@unibs.it

Abstract: Pseudohexagonal Nb2 O5 microcolumns spanning a size range of 50 to 610 nm were

synthesized utilizing a cost-effective hydrothermal process (maintained at 180 ◦ C for 30 min), followed
by a subsequent calcination step at 500 ◦ C for 3 h. Raman spectroscopy analysis unveiled three distinct
reflection peaks at 220.04 cm−1 , 602.01 cm−1 , and 735.3 cm−1 , indicative of the pseudohexagonal
crystal lattice of Nb2 O5 . The HRTEM characterization confirmed the inter-lattice distance of 1.8 Å for
the 110 plain and 3.17 Å for the 100 plain. The conductometry sensors were fabricated by drop-casting
a dispersion of Nb2 O5 microcolumns, in ethanol, on Pt electrodes. The fabricated sensors exhibited
excellent selectivity in detecting C2 H5 OH (∆G/G = 2.51 for 10 ppm C2 H5 OH) when compared to
a variety of tested gases, including CO, CO2 , NO2 , H2 , H2 S, and C3 H6 O. The optimal operating
temperature for this selective detection was determined to be 500 ◦ C in a dry air environment.
Moreover, the sensors demonstrated exceptional repeatability over the course of three testing cycles
and displayed strong humidity resistance, even when exposed to 90% relative humidity. This excellent
Citation: Kumarage, G.W.C.;
humidity resistance gas sensing property can be attributed to their nanoporous nature and elevated
Panamaldeniya, S.A.; Maraloiu, V.A.; operating temperature.
Dassanayake, B.S.; Gunawardhana,
N.; Comini, E. Nb2 O5 Microcolumns Keywords: Nb2 O5 ; microcolums: MOX; gas sensors; ethanol sensor
for Ethanol Sensing. Sensors 2024, 24,
1851. https://doi.org/10.3390/
s24061851
1. Introduction
Academic Editors: Erica Perry Murray,
Gaurab Dutta, Agnivo Gosai Nb2 O5 gas sensors exhibit promising potential for multifarious applications en-
and Maria Rachele Guascito compassing environmental monitoring, industrial processes, and automotive domains.
Notably, extensive investigations by researchers have explored the efficacy of Nb2 O5 gas
Received: 9 February 2024
sensors in detecting H2 S [1,2], H2 [3,4], NOx [5,6], CO [7], and VOCs [8,9] in environ-
Revised: 28 February 2024
mental monitoring applications.
Accepted: 12 March 2024
Ethanol has been found in broad applications across various fields, including food
Published: 14 March 2024
safety, biomedicine, and fuel processing [10,11], that could potentially pose safety hazards
if undetected. Its flammability and capacity for explosiveness in specific concentrations
warrant prompt and accurate detection of any ethanol leaks or spills to avert potential
Copyright: © 2024 by the authors. risks. The integration of ethanol gas sensors plays a crucial role in the implementation of
Licensee MDPI, Basel, Switzerland. appropriate safety measures. By detecting the presence of ethanol in the air, these sensors
This article is an open access article can alert workers to impending dangers, safeguarding them from potential adverse effects
distributed under the terms and such as irritations of the eyes, nose, and throat, as well as inducing headaches, dizziness,
conditions of the Creative Commons and even unconsciousness [12]. Consequently, ethanol gas sensing has emerged as a subject
Attribution (CC BY) license (https:// of utmost significance, garnering considerable attention in recent years, as evidenced by
creativecommons.org/licenses/by/ numerous scholarly works [13–18].
4.0/).

Sensors 2024, 24, 1851. https://doi.org/10.3390/s24061851 https://www.mdpi.com/journal/sensors

Sensors 2024, 24, 1851 2 of 11

Metal oxides serve as fundamental elements in the evolution of gas sensor tech-
nology, with a significant emphasis on ethanol detection, which is attributable to their
intrinsic characteristics and surface reactivity, as extensively documented in the litera-
ture [11,14,16,19,20]. Moreover, gas sensors based on metal oxides offer a plethora of
advantages, encompassing cost-effectiveness, inherent stability, and compatibility with
microfabrication methodologies, rendering them indispensable across a spectrum of
sectors encompassing industrial, environmental, and medical domains. Their utilization
spans from breath alcohol analysis to industrial process supervision and automotive
emission regulation systems. As research endeavors progress, the fine-tuning of metal
oxide attributes and sensor architectures presents a promising avenue towards elevat-
ing the sensitivity, selectivity, and dependability of gas detection mechanisms, thereby
catering to exigent requisites in safety, healthcare, and environmental surveillance. The
continued exploration in this domain holds the potential to revolutionize gas sensing
technologies, advancing societal well-being and environmental sustainability.
Nb2 O5 , characterized as a typical n-type metal oxide, has garnered significant research
interest in ethanol gas detection due to its distinct physical and chemical properties. In
a recent scientific study, Mozalev et al. presented a novel 3-D niobium-oxide nanofilm,
featuring a 200 nm thick NbO2 layer adorned with upright-standing Nb2 O5 nanocolumns,
each with a diameter of approximately 50 nm and a length of 900 nm. This sensor was
fabricated using a porous-anodic-alumina-assisted anodizing technique of a refractory
metal. It demonstrated remarkable capabilities in detecting 500 ppm of C2 H5 OH within a
mere one-minute timeframe [21]. Furthermore, Khatoon et al. applied facile hydrothermal
and solid-state methods to synthesize an alpha-Fe2 O3 (nanorods)/Nb2 O5 (nanoparticles)
heterostructure for the detection of 100 ppm C2 H5 OH at an elevated temperature of 160 ◦ C.
The sensor exhibited a rapid response time of 8 s and a recovery time of 2 s, marking
a significant advancement in ethanol sensing technology [22]. In another development,
Lombardo and colleagues introduced Nb2 O5 thin-film-based sensors designed to estimate
blood ethanol levels. These sensors operated effectively at a relatively high temperature
of 350 ◦ C, contributing to potential applications in the medical field [23]. Additionally,
Park et al. reported the creation of Pd and Au-functionalized Nb2 O5 nanorods through
thermal oxidation. These functionalized nanorods exhibited excellent performance in
detecting 200 ppm C2 H5 OH at an operational temperature of 200 ◦ C, with a noteworthy
response rate of 183.54 (Ra/Rg%) [24].
One of the critical factors that affect the performance of Nb2 O5 gas sensors is their
sensing mechanism. The sensing mechanism of Nb2 O5 gas sensors is based on the principle
of metal oxide gas sensing, which involves the interaction between gas molecules and
the surface of the sensing material. The adsorption of gas molecules on the surface of the
sensing material can cause a change in its electrical conductivity. Another critical factor
in the development of Nb2 O5 gas sensors is the synthesis method used to prepare the
sensing material. Researchers have investigated various synthesis methods, including
hydrothermal [2–4] and sol–gel [25–27]-assisted methods, to prepare Nb2 O5 gas sensors
with different morphologies and properties.
The present study elucidates the synthesis process of pseudohexagonal Nb2 O5 mi-
crocolumns through a low-cost hydrothermal method, emphasizing their remarkable
conductometric characteristics for ethanol detection down to sub-parts per billion (ppb) lev-
els. The investigation reveals that the synthesized Nb2 O5 microcolumns exhibit exceptional
sensitivity and selectivity towards ethanol, owing to their unique structural and composi-
tional properties. Notably, the sensors demonstrate negligible response fluctuations even
under high relative humidity conditions of up to 90%, underscoring their robustness and
reliability in real-world applications. The observed stability and high sensitivity of the
Nb2 O5 microcolumns suggest their potential for integration into advanced gas sensing
platforms for precise and reliable ethanol detection in diverse fields, including automo-
tive, industrial, and environmental monitoring. Moreover, the insights gained from this
Sensors 2024, 24, 1851 3 of 11

study contribute to the ongoing efforts to develop efficient and cost-effective gas sensing
technologies for addressing critical societal and environmental challenges.

2. Materials and Methods

Nb2 O5 microcolumns were synthesized using a specific procedure. Initially, commer-
cially available Nb2 O5 micro powder with a particle size of −325 mesh and a purity of
99.9% trace metals basis from Sigma Aldrich, Saint Louis, MO, USA was employed as
the starting material. To synthesize the Nb2 O5 microcolumns, 1.000 g of the commercial
Nb2 O5 powder was combined with 64 mL of a 10 mol dm−3 Sodium Hydroxide (NaOH)
solution, which was of analytical-reagent grade (AR) and had a purity of 98%, obtained
from Techno Pharmchem Haryana, Rohtak, India. The mixture was stirred for 30 min,
and subsequently subjected to ultrasonication for 15 min. This stirring and ultrasonication
process was repeated four times.
Next, the resulting mixture was transferred to an 80 mL autoclave and heated at
180 ◦ C for a duration of 30 min. After this step, the formed precipitate was collected and
subjected to a washing procedure. The washing process involved using a total of 1.2 L
of a 1 mol dm−3 acetic acid (CH3 COOH, Saint Louis, MO, USA) solution in increments
of 300 mL each time. This was followed by another washing step with a total volume of
3.2 L of deionized water (DI) with a measured conductivity of 0.055 µS cm−1 , performed in
increments of 400 mL.
The basic chemical reactions during the Nb2 O5 microwires growth can be written as
follows [28].
The reaction starts with the dissolving of Nb2 O5 , in the presence of NaOH.

Nb2 O5(s) + 2NaOH(aq) → 2NaNbO3(s) + H2 O(l) (1)

During the CH3 COOH washing, due to ion exchange;

NaNbO3(s) + CH3 COOH(aq) → HNbO3(s) + CH3 COO− Na+

(aq)
(2)

In the calcination process (700 ◦ C), HNbO3 will convert to Nb2 O5 .

2HNbO3(s) → Nb2 O5(s) + H2 O(g) (3)

Subsequently, the washed product was dried in a vacuum oven at 60 ◦ C for a duration
of 24 h and given a designation. Finally, the as-synthesized Nb2 O5 microcolumns were
subjected to a calcination process at 500 ◦ C for 3 h, which resulted in the formation of the
pseudohexagonal phase.
The Nb2 O5 microcolumns obtained in this study were characterized by using X-ray
diffraction (XRD) with a PANalytical diffractometer (Empyrean, PANalytical, Almelo,
The Netherlands) equipped with a monochromatic CuKα beam (λ = 1.54184 Å). The
measurements were conducted with a 2◦ incident angle, and the tube operated at 40 kV
with a current of 40 mA. The diffraction pattern was scanned in steps of 0.05◦ with a step
time of 25 s, covering the 2θ range of 20–80◦ . To examine the morphological properties
of the prepared materials, a field emission scanning electron microscope (FE-SEM, model
TESCAN MIRA 3, Brno, Czech Republic) was employed. Additionally, an analytical
transmission electron microscope (TEM, JEM ARM 200F, JEOL, Munich, Germany) operated
at 200 kV and equipped with a JED-2300T (JEOL, Munich, Germany) unit for Energy
Dispersive X-ray (EDX) spectra was used for further analysis. For the TEM and EDX
measurement, the Nb2 O5 microcolumn powder was gently crushed in a mortar and diluted
with ethanol. Next, the solution was sonicated for 5 min, and a drop of suspension was
deposited on a copper grid with lacey carbon support film.
The conductometric measurements were conducted within a custom-designed climatic
gas chamber. A constant flow of 200 standard cubic centimeters per minute (sccm) of
different gases, namely hydrogen (H2 ), ethanol (C2 H5 OH), acetone (C3 H6 O), nitrogen
Sensors 2024, 24, 1851 4 of 11

dioxide (NO2 ), hydrogen sulfide (H2 S), carbon dioxide (CO2 ), and carbon monoxide (CO),
was maintained during the experiments. The sensing elements were subjected to a fixed
voltage of 1 V throughout the measurements.
To evaluate the sensor’s response to n-type behavior, the conductance of the sensor was
compared under two conditions: firstly in the presence of the target gas, and secondly in syn-
thetic air. The sensor’s response was quantified using the equation S (∆G/G) = (Gg − Ga )/Ga
for reducing gases or (Ga − Gg )/Gg for oxidizing gases, where Ga represents the conductance
of the sensor in synthetic air and Gg corresponds to the conductance of the sensor when
exposed to the analyte gas [18,29]. This approach allowed for the characterization of the
sensor’s performance in detecting and distinguishing between different gases, providing
valuable insights into its sensitivity and selectivity.

3. Results
3.1. Material Characterization
The X-ray diffractogram of the synthesized Nb2 O5 is presented in Figure 1a. The
observed two theta reflection peaks align with the pseudohexagonal crystal structure
Sensors 2024, 24, x FOR PEER REVIEW 5 of 11
characteristic of Nb2 O5 (JCPDS No. 00-028-0317). Moreover, Figure S1 provides evidence
that the synthesized material comprises solely Nb and O elements. In Figure 1b, the Raman
spectra reveal three distinct reflection peaks located at 220.04 cm−1 , 602.01 cm−1 , and
735.3 cm−1 , which correspond to the pseudohexagonal crystal structure of Nb2 O5 [30].

Figure 1.1.(a)
Figure (a)XRD
XRDdiffractogram;
diffractogram;(b)
(b)Raman
Raman spectra;
spectra; (c)(c) FE−SEM
FE–SEM of before
of before the annealing;
the annealing; (d) FE−
(d) FE–SEM
SEM of the synthesis Nb2O5 microcolumns.
of the synthesis Nb2 O5 microcolumns.

The field emission scanning electron microscope (FE-SEM) image shown in Figure 1c
depicts the intriguing morphological evolution of Nb2 O5 micro powder (particle size
less than 45 µm, −325 mesh size) during the hydrothermal reaction at a temperature of
180 ◦ C. As the hydrothermal reaction proceeded for 30 min, the result was the formation
of high-purity niobate microcolumns. The final product exhibits Nb2 O5 microcolumns
Sensors 2024, 24, 1851 5 of 11

with dimensions on the order of tens of micrometers in length, hundreds of nanometers in

width, and hundreds of nanometers in height, as illustrated in Figure 1d.
These results offer valuable insights into the structural and morphological characteris-
tics of the synthesized Nb2 O5 microcolumns, contributing to the understanding of their
properties and potential applications in various fields.
Conventional Transmission Electron Microscope (TEM) images (Figure 2a,c,d) show
that microcolumns have thicknesses ranging from 50 to 610 nm and that there is no variation
in the thickness along the length of microcolumns. The selected Area Electron Diffraction
(SAED) pattern (Figure 2b) confirms the pseudohexagonal crystal structure characteristic of
Nb2 O5 determined by XRD. In Figure 2d and Figure S1, the contrast inside the microcolumn
with small bright areas (examples indicated with red arrows) surrounded by darker areas
demonstrates that there is some porosity in the structure. High-Resolution TEM (HRTEM)
images (Figure 2e,f) evidence the fact that the microcolumns contain grains. The boundary
between such grains, evidenced by a red dotted line, is illustrated in Figure 2e. HRTEM
also proves that the pores are amorphous areas between grains like the one delimited
with a red line in Figure 2f. The diameter of pores ranges from 3 to 8 nm. EDX spectrum
(Figure
Figure 1.S2)
(a) confirms the presence
XRD diffractogram; in the sample
(b) Raman spectra; of
(c)Nb and Oofbesides
FE−SEM theannealing;
before the signals of(d)
C and
FE−
SEMoriginating
Cu of the synthesis
fromNb 2O5 microcolumns.
TEM grid.

Figure 2. (a,c,d) CTEM images; (b) SAED pattern; (e,f) HRTEM images of Nb2O5 microcolumns.
Figure 2. (a,c,d) CTEM images; (b) SAED pattern; (e,f) HRTEM images of Nb2 O5 microcolumns.

3.2. Gas Sensing

Figure 3a displays the dynamic response of the chemiresistor ethanol sensors to 10,
25, and 50 ppm ethanol in the air. All the sensors show rising conductance upon exposure
to ethanol. However, the sensor response was insignificant when the temperature was
below 350 ◦ C (Figure S3). This is due to the adsorption or reduction reaction of ethanol
on the Nb2 O5 , releasing trapped electrons and increasing electron density. The increase
in conductance confirms the n-type nature of the prepared Nb2 O5 microcolumns, with
positive electrons as the dominant charge carrier. Additionally, the sensors showed clear
recovery after ethanol was cleared from the test chamber. The sensor response (∆G/G%)
Sensors 2024, 24, 1851 6 of 11

and response and recovery times (time to reach 90% change in response during full response
Sensors 2024, 24, x FOR PEER REVIEW
and
recovery) were used to evaluate sensor performance. Figure 3b shows that higher 7 of 11
sensor response and faster response and recovery times were achieved when the sensors
were operating at 500 ◦ C in dry air.

Figure 3.
Figure Gas sensing
3. Gas sensing functionality
functionality of
of the
the Nb O55 microcolumns;
Nb22O microcolumns; (a)
(a) dynamic
dynamic response
response to
to ethanol
ethanol at
at
300–500 ◦ C; (b) response value, response/recovery times; (c) repeatability of the sensors signal at
300−500 °C; (b) response value, response/recovery times; (c) repeatability of the sensors signal at
◦ C;
500 °C; (d) modified power fitting.

The impact
The working oftemperature plays on
relative humidity a crucial role inperformance
the sensor’s the responsetoofethanol
sensorswasto ethanol.
investi-
The temperature affects the sensing reaction by providing thermal energy that
gated at different humidity levels (0, 10, 20, 40, 60, 80 and 90 RH%). Figure 4b displays facilitates
the
the reaction,
response andwhich leads to an increased
response/recovery times of theresponse
sensorstotoethanol. For example,
10 ppm ethanol a study
at 500 °C by
in vary-
Zhou et al. showed that an increase in working temperature leads to an increase
ing humidity. No substantial change in response was observed with increasing humidity, in the
response
but of sensors
the baseline to ethanol
conductance [31]. Additionally,
decreased by 41% with the10%
temperature affects
RH (as seen the amount
in Figure S5). Evenof
adsorbed ethanol molecules and oxygen species on the surface of the sensors,
with 90% RH, the baseline conductance remained unchanged from the baseline value with in which
a higher
10% RH. working temperature
Usually, water leads
molecules aretoabsorbed
an increase in the
on the amount
MOXs by twoof means:
adsorbed ethanol
physisorp-
molecules, which results in a higher response to ethanol. The study also showed that a
tion (at higher RH%) and chemisorption (at lower RH%), which hinder the gas sensing
higher amount of adsorbed ethanol molecules and oxygen species with increasing working
functionality as well as the baseline conductance [32]. In this context, resistance change is
temperature could affect the sensing response, which is temperature dependent. The
caused by hydroxyl ions and mobile protons generated from the dissociation and adsorp-
highest response (∆G/G%) was 251.23 with a response/recovery time of 240 s and 950 s,
tion of water molecules on the MOXs surface (active sites). Hydroxyl ions bond with metal
respectively, for detecting 10 ppm ethanol. Besides, it may be noted that the system needs
cations while mobile protons (hydrogen ions) attach to oxygen at the MOX surface, creat-
5 min to change its 1L environment with a flow rate of 200 sccm. Additionally, the response
ing additional hydroxyl ions. This process can impact the electrical conductance baseline
and recovery time was found to decrease with the increase in the operating temperature. It
based on the amount of hydroxyl ions and oxygen molecules present [33]. High humidity
showed complete recovery and outstanding repeatability at optimal temperature (Figure 3c),
causes water molecules to absorb by transferring protons (H+) between incoming water
making it ideal for practical use, as it eliminates baseline drift issues. Table 1 summarizes the
and forming H3O+ at the MOX surface, leading to fluctuating electrical conductance. Our
comparison of ethanol sensors. However, operating a Nb2 O5 sensor at 500 ◦ C poses several
study found no significant decrease in baseline conductance compared to low humidity,
which may be due to the high operating temperature. Despite changes in humidity, the
response time remained constant, but the recovery time decreased by 59% compared to
dry conditions. The quick recovery time of sensors in the presence of humidity may be
due to the formation of C2H5OH2+·(H2O) with a low ionic diffusion coefficient [9,34].
Sensors 2024, 24, 1851 7 of 11

challenges, including ensuring material stability, the reliability of electrical contacts, and
the necessity of proper packaging and encapsulation to maintain the sensor’s performance
and longevity.
The sensor performance was further investigated, covering aspects such as selectiv-
ity, long-term stability (Figure S4), detection limit (LOD), and stability in humidity. The
sensor response shows a linear relationship with ethanol concentration (Figure 3d) with a
power-fitting (y = a·xb ) correlation coefficient (R2 ) of over 0.99, meaning the experimental
data fit well with a linear model. The LOD was determined using a 10% method, revealing
the sensor’s capability to detect ethanol at 1.4 ppb when operating at 500 ◦ C. Gas selectiv-
ity stands as a pivotal facet within gas sensor technology, especially in scenarios where
discerning specific gases within a mixture holds paramount importance. The attainment
of improved selectivity serves as a basis for ensuring the reliability and precision of gas
sensors across diverse domains encompassing environmental surveillance, industrial safety
protocols, and healthcare applications. In this study, we thoroughly assessed the perfor-
mance of fabricated Nb2 O5 sensors across a spectrum of gases, including CO, CO2 , NO2 ,
H2 , H2 S, and C3 H6 , alongside C2 H5 OH, at the optimal operational temperature of 500 ◦ C.
Remarkably, the sensors exhibited higher selectivity in ethanol detection, evidenced by
a selectivity of 251.53%, when contrasted with CO (9.04%), CO2 (49.65%), NO2 (34.01%),
Sensors 2024, 24, x FOR PEER REVIEW 8 of 11
H2 (113.55%), H2 S (159.79%), and C3 H6 O (89.8%) at the lowest tested concentration, as
depicted in Figure 4a.

Figure 4.
Figure (a) Selectivity
4. (a) Selectivity of
of the
the Nb
Nb2OO55 sensors
sensors towards
towards C
C22H
H55OH
OH(10
(10ppm)
ppm)compared
comparedto toCO
CO(100
(100 ppm),
ppm),
(100 ppm), NO22 (1 (1 ppm), H22 (100
(100 ppm), H22SS (10
(10 ppm),
ppm), and C22H H55OH
OH(10(10 ppm)
ppm) at
at 500 ◦ C in
500 °C
CO22 (100 in dry
air; (b) humidity-dependent response, response/recovery
response/recovery time
time towards
towards 10
10 ppm
ppm CC22H
H55OH.
OH.

TableThe impact
1. The of relative
comparison humidity onperformances
of ethanol-sensing the sensor’sof
performance
MOXs. to ethanol was investi-
gated at different humidity levels (0, 10, 20, 40, 60, 80 and 90 RH%). Figure 4b displays the
response and response/recovery times of the Temp.
sensors(°C) Ethanol
to 10 ppm 500 ◦ C in varying
ethanol atResp.
Materials Methods Ref.
(ppm)
humidity. No substantial change in response was observed with increasing humidity, but
Au/SnO
the baseline conductance
2 Hydrothermal
decreased by 41% with340 10% RH (as 100 18.0S5). Even
seen in Figure [35]
with
ZnO Nanowires Oxidation 240 100 5.0
90% RH, the baseline conductance remained unchanged from the baseline value with 10% [36]
NiO/ZnO
RH. Usually, VLSabsorbed on the
water molecules are 400MOXs by two 50 means: physisorption
6.7 [37] (at
higher
NiORH%) and chemisorption
nanowires VLS (at lower RH%),400 which hinder 50the gas sensing
2.9 functional-
[37]
ity asNb
well
2O5as the2 baseline conductance [32]. In this context, resistance change is caused by
-TiO
hydroxyl ions and mobileElectrospinning
nanofibers protons generated from 250 500 and adsorption
the dissociation 21.6 of[9]
water
molecules on
CuO-Fe2O3the MOXs surface (active sites). Hydroxyl ions bond with metal cations while
mobile protons (hydrogenTemplate
ions) method
attach to oxygen 380
at the MOX 500
surface, 17.5 additional
creating [38]
hollow spheres
hydroxyl ions. This process can impact the electrical conductance baseline based on the
This
Nb2O5 microcolumns
amount of hydroxyl ions Hydrothermal
and oxygen molecules 500 10 humidity
present [33]. High 2.51 causes water
Work
molecules to absorb by transferring protons (H+ ) between incoming water and forming
3.3. Ethanol Sensing Mechanism
Nb2O5 is widely recognized as a wide-band n-type semiconductor, with conductivity
affected by the surface depletion layer, a characteristic of surface-controlled sensing ma-
terials. Figure 4a indicates that the highest response among tested gases was seen with
ethanol, making it crucial to examine the gas-sensing properties of the Nb2O5 sensors spe-
Sensors 2024, 24, 1851 8 of 11

H3 O+ at the MOX surface, leading to fluctuating electrical conductance. Our study found
no significant decrease in baseline conductance compared to low humidity, which may be
due to the high operating temperature. Despite changes in humidity, the response time
remained constant, but the recovery time decreased by 59% compared to dry conditions.
The quick recovery time of sensors in the presence of humidity may be due to the formation
of C2 H5 OH2 + ·(H2 O) with a low ionic diffusion coefficient [9,34].

Table 1. The comparison of ethanol-sensing performances of MOXs.

Materials Methods Temp. (◦ C) Ethanol (ppm) Resp. Ref.

Au/SnO2 Hydrothermal 340 100 18.0 [35]
ZnO Nanowires Oxidation 240 100 5.0 [36]
NiO/ZnO VLS 400 50 6.7 [37]
NiO nanowires VLS 400 50 2.9 [37]
Nb2 O5 -TiO2
Electrospinning 250 500 21.6 [9]
nanofibers
CuO-Fe2 O3
Template method 380 500 17.5 [38]
hollow spheres
Nb2 O5 This
Hydrothermal 500 10 2.51
microcolumns Work

3.3. Ethanol Sensing Mechanism

Nb2 O5 is widely recognized as a wide-band n-type semiconductor, with conductivity
affected by the surface depletion layer, a characteristic of surface-controlled sensing materi-
als. Figure 4a indicates that the highest response among tested gases was seen with ethanol,
making it crucial to examine the gas-sensing properties of the Nb2 O5 sensors specifically
concerning this gas for practical purposes. The detection mechanism is typical for chemore-
sistive gas sensors, as it involves the presence of oxygen forms (O2− , O− or O2 − ) adsorbed
on the Nb2 O5 surface, which vary depending on the detection temperature [39,40]. The
presence of oxygen species on Nb2 O5 creates an electron depletion layer (EDL) on the
surface by trapping electrons in the Nb2 O5 conduction band during the reduction of O2 -O− .
However, it is crucial to understand the correct oxygen species that may be absorbed on
the Nb2 O5 surface to complete the discussion.
The relationship between gas concentration (Cg ) and response (Sg ) is widely
recognized [39].
Sg = 1 + a·Cag (4)
where the perfector and surface species charge parameters are represented by a and b,
respectively. The value of b equals 0.5 or 1, indicating the absorbed oxygen ions on the
surface to be either O2− or O− [40].
By taking the logarithm on either side of Equation (4), we can gain another equation
that can be written as
(Sg − 1) = log(a) + b·log(Cg ) (5)
Figure 5 displays a log(Sg − 1) vs. log(Cg ) plot. The fit is linear, with a correlation
coefficient exceeding 0.999. Thus, our study concludes that the dominant oxygen species is
O2− . This leads to a redox reaction on the Nb2 O5 surface between O2− and C2 H5 OH upon
exposure to C2 H5 OH, resulting in oxidation as follows [38].

C2 H5 OH (ads) + 6O2− (ads) → 3H2 O (g) + 2CO2 (g) + 12e− (6)

 O2−. This leads to a redox reaction on the Nb2O5 surface between O2− and C2H5OH upon
exposure to C2H5OH, resulting in oxidation as follows [38].
C2H5OH (ads) + 6O2− (ads) → 3H2O (g) + 2CO2 (g) + 12e− (6)
Sensors 2024, 24, 1851 As a result, when C2H5OH interacts with the oxygen species, the release of trapped
9 of 11
electrons back to the conduction band of Nb2O5 causes an increase in conductance.

The plot of log(Sgg−−1)1)vs.

Figure 5. The vs.log(C
log(C
g).g ).

As a result, when C2 H5 OH interacts with the oxygen species, the release of trapped
4. Conclusions
electrons back to the conduction band of Nb2 O5 causes an increase in conductance.
In conclusion, the synthesis of pseudohexagonal Nb2O5 microcolumns through a
cost-effective
4. Conclusions hydrothermal process, followed by calcination, has yielded promising re-
sults for the development of high-performance conductometry sensors. Raman spectros-
In conclusion, the synthesis of pseudohexagonal Nb2 O5 microcolumns through a
copy, HRTEM, SAED, and XRD confirmed the pseudohexagonal crystal lattice structure
cost-effective hydrothermal process, followed by calcination, has yielded promising results
of Nb2O5, with thickness ranging from 50 to 610 nm and with pores ranging from 3 to 8
for the development of high-performance conductometry sensors. Raman spectroscopy,
nm.
HRTEM, SAED, and XRD confirmed the pseudohexagonal crystal lattice structure of Nb2 O5 ,
with The sensors
thickness exhibited
ranging fromoutstanding
50 to 610 nm selectivity
and with for C2H5ranging
pores OH, even at low
from 3 toconcentrations
8 nm.
(2.51/10 ppm C 2H5OH), surpassing their responsiveness to various other tested gases. Fur-
The sensors exhibited outstanding selectivity for C2 H5 OH, even at low concentrations
thermore,
(2.51/10 ppm the optimal operational
C2 H5 OH), surpassing temperature for this selectivity
their responsiveness was found
to various to be 500
other tested °C
gases.
in a dry air environment.
Furthermore, the optimal Notably,
operationalthe temperature
fabricated sensors
for thisdemonstrated
selectivity was remarkable
found to re-
be
peatability
◦ over four cycles and proved to be highly stable to humidity,
500 C in a dry air environment. Notably, the fabricated sensors demonstrated remarkable even when ex-
posed to 90% over
repeatability relative
fourhumidity.
cycles andThese excellent
proved to begas sensing
highly properties
stable can beeven
to humidity, attributed
when
to the nonporous nature of the Nb 2O5 microcolumns and the elevated operating tempera-
exposed to 90% relative humidity. These excellent gas sensing properties can be attributed to
ture, making them
the nonporous naturepromising
of the Nbcandidates for innovative solutions in various industries,
2 O5 microcolumns and the elevated operating temperature,
including
making them environmental monitoring
promising candidates forand industrial
innovative safety sensors.
solutions in various industries, including
environmental monitoring and industrial safety sensors.
Supplementary Materials: The following supporting information can be downloaded at:
www.mdpi.com/xxx/s1,
Supplementary Materials: Figure
TheS1: Magnified
following TEM images
supporting of Figurecan
information 2d; be
Figure S2: EDX spectrum
downloaded at: https:
of Nb2O5 microcolumns confirming the presence of Nb
//www.mdpi.com/article/10.3390/s24061851/s1, andS1:
Figure O; Magnified
Figure S3: Nb
TEM2O5 microcolumns sen-
images of Figure 2d;
sor response to 10 ppm ethanol at different operating temperatures (300–500 °C); Figure S4: Long
Figure S2: EDX spectrum of Nb2 O5 microcolumns confirming the presence of Nb and O; Figure
term stability of the Nb2O5 microcolumns sensor response to 10 ppm ethanol at 500 °C; Figure S5:
S3: Nb2 O5 microcolumns sensor response to 10 ppm ethanol at different operating temperatures
Nb2O5 microcolumns sensor dynamic response to 10 ppm ethanol at different humidity levels when
(300–500 ◦ C); Figure S4: Long term stability of the Nb2 O5 microcolumns sensor response to 10 ppm
operating at optimum working temperatures (500 °C).
ethanol at 500 ◦ C; Figure S5: Nb2 O5 microcolumns sensor dynamic response to 10 ppm ethanol at
different humidity levels when operating at optimum working temperatures (500 ◦ C).
Author Contributions: Conceptualization, G.W.C.K., S.A.P., N.G. and B.S.D.; methodology, G.W.C.K.
and S.A.P.; validation, B.S.D., N.G. and E.C.; formal analysis, G.W.C.K., S.A.P. and V.A.M.; investiga-
tion, G.W.C.K., S.A.P. and V.A.M.; resources, B.S.D., E.C., N.G. and V.A.M.; data curation, G.W.C.K.,
S.A.P. and V.A.M.; writing—original draft preparation, G.W.C.K.; writing—review and editing,
G.W.C.K., S.A.P., V.A.M., N.G., E.C. and B.S.D.; visualization, G.W.C.K. and V.A.M.; supervision, E.C.,
N.G. and B.S.D.; project administration, B.S.D., N.G. and E.C.; funding acquisition, B.S.D., N.G. and
E.C. All authors have read and agreed to the published version of the manuscript.
Funding: This project was financially supported by the Solar Edu-Training project of the State
Ministry of Skills Development, Vocational Education, Research & Innovation, Sri Lanka.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Sensors 2024, 24, 1851 10 of 11

Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: A portion of the research was conducted at the Department of Physics and
Electronics, Faculty of Science, University of Kelaniya, Sri Lanka. This study was carried out within
the MOST—Sustainable Mobility National Research Center and received funding from the European
Union Next-GenerationEU (PIANO NAZIONALE DI RIPRESA E RESILIENZA (PNRR)—MISSIONE
4 COMPONENTE 2, INVESTIMENTO 1.4—D.D. 1033 17/06/2022, CN00000023), Spoke 5 “Light
Vehicle and Active Mobility”. This manuscript reflects only the authors’ views and opinions; neither
the European Union nor the European Commission can be considered responsible for them. VAM
acknowledges funding through contract POC 332/390008/29.12.2020-SMIS 109522. This paper is
dedicated to the memory of our collaborator and co-author, Buddhika S. Dassanayake, who tragically
passed away on 25 December 2023.
Conflicts of Interest: The authors declare no conflict of interest.

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