pubs.acs.

org/acssensors Article

Low-Temperature Hydrogen Sensor: Enhanced Performance

Enabled through Photoactive Pd-Decorated TiO2 Colloidal Crystals
Ebtsam K. Alenezy, Ylias M. Sabri,* Ahmad E. Kandjani,* Dilek Korcoban,
Syed Sulthan Alaudeen Abdul Haroon Rashid, Samuel J. Ippolito, and Suresh K. Bhargava*
Cite This: https://dx.doi.org/10.1021/acssensors.0c01387 Read Online

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ABSTRACT: The high demand for H2 gas sensors is not just limited to
industrial process control and leak detection applications but also
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extends to the food and medical industry to determine the presence of

various types of bacteria or underlying medical conditions. For instance,
sensing of H2 at low concentrations (<10 ppm) is essential for
developing breath analyzers for the noninvasive diagnosis of some
gastrointestinal diseases. However, there are major challenges to
overcome in order to achieve high sensitivity and hence low limit of
detection (LoD) toward H2. In this study, it is demonstrated that light-
assisted amperometric gas sensors employing sensitive layers based on
Pd-decorated TiO2 long-range ordered crystals can achieve excellent H2
sensing performance. This unique combination of materials and novel
layered structure enables the detection of H2 gas down to 50 ppm with
highly promising LoD capabilities. The sensor response profiles revealed
that the sensor’s signal-to-noise ratio was higher in the presence of light when operated with a 9 V bias (relative to other conditions
used), producing a LoD of only 3.5 ppm at an operating temperature of 33 °C. The high performance of the sensor makes it
attractive for applications that require low-level (ppm as opposed to conventional % levels) H2 gas detection. Most importantly, the
developed sensor exhibited high selectivity (>93%) toward H2 over other gas species such as CO2, C4H8O, C3H6O, CH3CHO, and
NO, which are commonly found to coexist in the environment.
KEYWORDS: light-assisted amperometric sensor, photocatalyst, long-range ordered crystals (LROCs), photocatalytic oxidation,
hydrogen gas sensing

H ydrogen has the potential to become the major source of

renewable energy because of its clean and potentially
exhaustible nature.1,2 The detection of low concentrations of
H2 is required because of its high flame propagation velocity,
low ignition energy, and wide explosive concentration range.3,4
Additionally, because of its inflammable and explosive nature,
safety issues must be addressed during its production,
transportation, and usage; thus, its detection at the 4%
explosive limit and below is imperative to enhance the end-user
confidence in uptaking future H2-based fuel technologies.5
From the medical sector perspective, the H2 gas expelled from
human breath is currently being sampled and quantified for the
noninvasive diagnosis of gastrointestinal diseases (GIDs). The
breath of a person suffering from a GID has been reported to
contain more than 20 ppm H2, which is more than twice the
level for a healthy person.2 The analytical techniques currently
employed in the laboratory to detect such low levels (ppm
range) of H2 are mostly based on gas chromatography/mass
spectrometry and proton-transfer reaction mass spectrometry.6
However, these techniques require the pretreatment of the
exhaled volatile organic compounds and the instruments are
usually operated by skilled experts. In order to overcome the
issues associated with the mentioned techniques, researchers
are now focusing on developing highly sensitive and accurate
sensors based on solid-state transducers. Solid-state sensors
based on chemiresistive or amperometric mechanisms possess
several advantages, such as excellent miniaturization potential,
simple operation, low power consumption, fast measurement
capacity, portability, and low cost.7,8 Chemiresistive sensors are
based on measuring the resistance change on the sensitive layer
when interacting with the analyte of interest. Similarly, in the
case of amperometric gas sensors (AGSs), a fixed operating
voltage (bias) is used, and the change in the current flow when
gas species interact with the sensitive layer is used to correlate
the target gas concentration.7 A specific advantage of
Received: July 8, 2020
Accepted: November 20, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acssensors.0c01387

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employing AGS-based sensors over the more traditional
chemiresistive sensors is that different input bias potentials
can be applied to the AGSs to alter the surface electrical
properties of the sensitive layer, thus resulting in the
modification of the gas adsorption properties of the surface.
The selectivity of AGSs toward a chosen analyte can also be
achieved by optimizing the electrode material to facilitate or
undergo the catalysis of selected reactions or by selecting an
applied bias that thermodynamically favors either the oxidation
reaction or the reduction reaction for a specific gas specie.7
The application of different biases can also provide the
opportunity to control an additional input parameter that may
enhance the sensor performance via changing the Schottky
properties of the semiconductor materials and junctions that
typically form between the metallic contacts and the metal
oxides forming the sensitive layer. Chemiresistive and AGS-
based H2 gas sensing techniques have been extensively studied
and make use of solid-state sensor platforms with sensitive
layers commonly comprising metal oxide based semiconduc-
tors such as titanium dioxide (TiO2), zinc oxide (ZnO), and
tungsten trioxide (WO3).1,9−12 Although AGSs possess unique
advantages, there are still issues that may affect their function
with regard to gas sensing applications. These relate to their
irreproducibility, nonselectivity, and high operating temper-
atures required for low analyte concentration analysis.13
Working at low temperatures (140 °C) usually reduces any
catalytic activity of the sensitive layer toward the gaseous
analyte,53 partly because of the difficulty (i.e., lack of energy) in
overcoming the activation energy or the excitation of electrons
to initiate the reaction; thus, another method to effectively
enhance the reaction rate while maintaining low operating
temperatures needs to be employed. Optical excitation of
metal oxide semiconductor-based catalysts may enhance the
oxygen (second reactant) sorption capacity on the surface
through the separation of electron and hole pairs, resulting in
the excitation of the electron to the conduction band, thus
providing a higher number of electrons on the surface to
participate in the reaction. Light illumination is one of the best
methods to lower the working temperature down to ambient
conditions.1,13 Once H2 gas reacts with the adsorbed oxygen
ions trapped via the excited electrons, it converts into products
that commonly consist of H2O.14 This leads to a significant
change in layer conductivity as a result of the change in the
number of charge carriers and enables the gas concentration
measurement by monitoring the conductance change over
time.13 However, because of the insufficient selectivity and
sensitivity, the real-time measurement of the biomarker
molecules in complex gas mixtures, such as the human breath
or industrial processes, is particularly challenging and improve-
ments need to be made in order to develop highly sensitive,
selective, and accurate sensors with metal oxide based
semiconductor material sensors. The sensitivity can be
improved by several approaches, including the modification
of size, surface area, and type of the material used as the
sensitive layer.4,15,16 Among numerous materials used for
amperometric H2 gas sensors, for example, tungsten trioxide
(WO3),17,18 tin dioxide (SnO2), and TiO2 (an n-type
semiconductor with a wide band gap of ∼3.2 eV for anatase
phase structure)19,20 have been widely studied because of their
good stability in harsh environments, low toxicity, and stable
crystal structure at wide temperature ranges.14,21,22 When
developing chemical-sensitive layers for applications, which
utilize optical excitation, it is important that the sensitive layer
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is formed with a uniform topology and minimal changes in
particle size, packing/ordering configuration over long ranges
so that the optical properties of the layer can be optimized and
identical throughout the surface.23 Therefore, many efforts
have been focused on developing sensors with uniform long-
range ordered crystals (LROCs) or photonic crystals (PCs) in
order to achieve consistent response from across the
surface.24,25 Several techniques exist for the synthesis of
surfaces formed of semiconductor-based LROCs, including
electron beam lithography and colloidal lithography pro-
cesses.26 Of particular interest is colloidal lithography process
for forming surfaces from ZnO27,28 and TiO2.29 The advantage
of this method relates to the high surface area, large-scale
structure uniformity, and low-cost synthesis processes that can
be achieved relative to the other available techniques.30 If
correctly designed, the long-range order of the fabricated
surfaces leads to the reproducible uniform excitation within
different areas of the sensitive layer regardless of the excitation
light beam location on the surface. Therefore, such uniformity
is of particular importance when developing photoactive
sensors.29,31 This patented technique that involves a unique
combination of materials and novel layered structure enables
the detection of H2 gas down to 50 ppm with highly promising
limit of detection (LoD) capabilities.32
In this work, TiO2 LROC surfaces were fabricated by
colloidal lithography in order to produce high surface area and
uniformity that will assist the better detection of H2. To
enhance the selectivity of AGSs toward the H2 analyte, the
choice of catalytic materials that are specific toward H2
oxidation becomes an important factor. Furthermore, the
process of introducing the specific material needs to be
compatible, so decoration of a base the materials with catalysts
such as noble metal (i.e., Pd, Pt, and Au) nanoparticles (NPs)
can be performed to synthesize the resulting sensitive layer.
Decorating sensitive layers with Pd has been reported to be
very effective in enhancing the sensitivity and selectivity of
AGSs toward H2 gas21,33 and also potentially lowering the
required operating temperature of the sensor and improving its
response/recovery times.22,34 Among the different methods
used to deposit Pd NPs, an electroless plating (ELP)
technique34−36 has several advantages related to its simplicity,
low cost, and formation of uniform NPs.37,38 The use of TiO2
thin films with various morphologies decorated with Pd NPs
and employed for H2 gas sensing under UV illumination is
expected to enhance the sensitivity and selectivity, which is
envisaged to enable the operation of the AGS at ambient
temperature.39,40 Achieving an operating temperature close to
room temperature (RT) is an important requirement (i.e.,
safety aspect, reduced energy consumption, compatibility, etc.)
for applications requiring H2 gas detection at low concen-
trations. Thus, the developed light-assisted AGSs can serve as
excellent candidates for a wide range of applications and
process control in H2 processing industries.
■
EXPERIMENTAL SECTION
Chemicals and Substrates. All chemicals utilized in the analysis
were purchased from Sigma-Aldrich and used as received. The
interdigitated transducers were acquired from MicruX Technologies.
These sensors were fabricated using BOROFLOAT glass substrates
and were rated for temperatures of up to 600 °C. The transducers
were formed with platinum interdigitated electrodes comprising 120
finger pairs with 10 μm width and 5 μm spacing. The active sensing
zone was 3.5 mm in diameter. All substrates used in this study were
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Figure 1. Steps to produce Pd-decorated TiO2 LROC sensors: (a) sensor substrate, (b) PS LROCs, (c) PS size modified via plasma etching, (d)
TiO2 deposition via CVD and annealing process at 550 °C to form TiO2 LROCs, and (e) uniformly deposited Pd NPs through seeding and ELP
processes to obtain Pd-decorated TiO2 LROCs.
washed with acetone, ethanol, and Milli-Q water and then dried under
dry nitrogen before use.
Synthesis Procedure. The Pd NP-decorated TiO2 LROC
surfaces were developed on the AGS-based sensors using the
following preparation methods.
TiO2 LROCs. PS LROCs were formed on the sensor substrates by
using the procedure described in our previous study.26 Briefly, a
standard Petri dish containing 3 mM of sodium hydroxide (NaOH)
solution was used to form a water/air interface. Polystyrene (20 μL)
with 1350 nm PS solution was prepared and injected into the surface,
followed by a 10 μL sodium dodecyl sulfate solution to make the
interface more compact. The process resulted in a closely packed
hexagonal monolayer that was then transferred onto the sensor
substrates from the interface. After the surface was dried, the closely
packed PS LROC surface was etched by using a plasma cleaner
[Gatan model 950, RF 50 W, 10 mTorr, and a 10 standard cubic
centimeters (sccm) gas flow for 20 min] under pure oxygen to reduce
the PS size and form a uniform nonclosely packed PS LROC surface.
The particle size distribution was estimated with an image processing
program based on MATLAB reported in our previous work using the
Hough transform.41
Chemical Vapor Deposition of TiO2. The chemical vapor
deposition (CVD) reaction explained in our previous work23 was
carried out for 10 min to obtain a thin layer of TiO2 coating on the PS
LROCs. Briefly, in a 100 mL round bottom flask, 1 mL of titanium
(IV) isopropoxide (TTIP) was added, and the assembly was kept at a
constant temperature of 68 °C under the inert atmosphere using N2
gas. The sensor substrates and other electrodes were placed in a
specific manner with side facing down toward the TTIP solution in
the flask. Water vapor, generated in a separate Dreschel bottle, was
transferred to the flask assembly using 10 sccm of dry N2 as the carrier
gas passing through 100 mL of Milli-Q water, thus initiating the CVD
coating of TiO2 on the sensor substrate at a constant temperature. To
obtain a 68 nm thick layer of TiO2, the deposition was performed for
a period of 10 min before the reaction was ceased by stopping the
water vapor flow rate, introducing dry N2, and instantly removing the
heat source to allow the flask (containing TTIP) to cool down to RT.
The coated substrate was then removed from the flask with a pair of
tweezers. Thereon, the polystyrene template was removed and
crystalline hollow TiO2 LROCs were formed by a one-step annealing
process at 550 °C for 1 h in air. The thickness of the deposited TiO2
layer was determined by first placing a control substrate (a polished
thin film of silicon wafer) with the sensor device during the CVD
process. Half of the control sample area was covered with photoresist,
which was removed with its deposited TiO2 layer through a lift-off
process (acetone etching) following the CVD process. The step
change on the substrate thus represented the equivalent thickness of
TiO2 deposited on the PS LROCs.
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Pd Decoration. An ELP method was used to decorate the TiO2
LROCs with Pd NPs using a two-step process. The first step was to
deposit a seed layer of Pd. This was achieved by dipping the PS TiO2
LROC-coated substrates into a solution of tin chloride [2 mM of
SnCl2 and 2.5 mL/L of HCl (32%) at RT] for 5 min, followed by 5
min of rinsing in Milli-Q water. The substrates were then dipped in
palladium salt solutions [2.5 mL of Pd (NO3)2 (10 wt %) and HNO3
(70%) at RT] to be preseeded with palladium nuclei for 10 min,
followed by another 5 min of rinsing in Milli-Q water. The procedure
was repeated 10 times to form a reliable Pd seed layer. After the
seeding procedure, the substrates were transferred immediately into
the ELP bath (2.2 mM of PdCl2, 20 mM of Na2EDTA, 40 mL/L of
NH3·H2O (30%), 1.1 mL/L of N2H4 (1 M), and pH = 10) for a
deposition period of 20 s at a constant temperature of 60 °C. Then,
the substrate was rinsed with Milli-Q water and dried overnight at 120
°C.
Gas Testing Setup. The current−voltage (I−V) curve was
conducted to investigate the electrical properties of the TiO2 thin film
as well as TiO2 LROCs and Pd-seeded and Pd-decorated TiO2
LROCs. Sensors were mounted in a custom-made Teflon test
chamber with an in-built optically polished quartz window lid for light
activation and an internal ceramic heating bed. UV LED source
(Edmund Optics) with a wavelength of 365 nm was used for
photoactivation at a maximum intensity of 2024 μW·cm−2. The
intensity of light was adjusted to be 108, 562, 945, 1496, and 2024
μW·cm−2 by varying the applied bias. The light intensity was
calibrated using a PM16-140 power meter from THORLABS. The
sensors were exposed to H2 concentrations ranging from 50 to 500
ppm while maintaining the total gas flow rate at 200 sccm with the
balance being dry air. A computer-controlled multichannel mass flow
controller (MFC) system was utilized to control the flow rate and
concentration of hydrogen to the sensor chamber. The sensors were
operated in the AGS mode by applying different biases (0.1, 3, 6, and
9 V) with and without light illuminated. The operating temperature of
the sensor was maintained at 33 °C for the duration of all tests;
however, care was taken to stabilize the baseline of the sensor when
adjusting the applied operating bias of the sensor to another value.
This was achieved by exposing the sensor to dry air at 200 sccm under
the specific lighting condition being studied for 2 h before conducting
any tests toward H2 gas. The response magnitude was defined as the
difference between the output current under the H2 gas exposure
period (Ig) and that in air (Ia): ΔI = Ig − Ia.16,42 The sensor responses
(R) were defined as R (%) = Rg − Ra/Ra × 100, where Ra is the
current of the sensor in the presence of dry air and Rg is the current
after the sensor exposed to H2.33 The selectivity of the sensor was
determined by exposing the sensors toward five industrial relevant gas
species/concentrations such as carbon dioxide (500 ppm), methyl
ethyl ketone (26.1 ppm), acetone (25 ppm), acetaldehyde (3034
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Figure 2. SEM images of (a) hexagonal close-packed and (b) non-close-packed polystyrene monolayers, (c) TiO2 deposited via CVD for 10 min
on non-close-packed polystyrene, and (d) TiO2 LROCs annealed at 550 °C for an hour.
ppm), and nitric oxide (2000 ppm). The sensors were also tested
against 20% relative humidity.
Material Characterization. X-ray photoemission spectroscopy
(XPS) analysis was used to study chemical states by using a thermo K-
Alpha XPS equipped with an Al Kα monochromated X-ray radiation
source. The samples were prepared on titanium-coated silicon
substrates. All spectra were background-corrected using the Shirley
algorithm, and all binding energies (BEs) were aligned considering
adventitious carbon (C 1s) having a BE of 285 eV. A FEISEM Quanta
and a FEI Nova NanoSEM was used to conduct scanning electron
microscopy (SEM) characterization. All images were collected using
an accelerating voltage of 5 kV and a beam current of 50 pA. The D8
Discover Micro X-ray diffraction (XRD) instrument equipped with a
Cu Kα radiation source (40 kV, 40 mA) and a general area detector
diffraction system was utilized for studying the crystal structure on
prepared samples. The thickness of the prepared TiO2 layer on the
standard sample was measured by using a surface profiler (TencorP-
16+). For thickness measurements, half of the silicon wafer substrates
were covered with photoresist before CVD and after CVD deposition,
and the deposited TiO2 on the photoresist was removed with a lift-off
process to form the step edge for the thicknesses to be measured
(control sample).23 For optical property measurements, quartz
substrates were coated on one side with a TiO2 thin film, PS closely
packed and nonclosely packed, TiO2 LROCs before and after
annealing, Pd-seeded and Pd-decorated TiO2 LROCs, which were
placed in a cuvette and characterized using a UV−vis spectropho-
tometer (Varian Cary 60) in transmittance mode from the 200 to 800
nm wavelength range.
■
RESULTS AND DISCUSSION
The schematic in Figure 1 shows the fabrication procedure of
Pd-decorated TiO2 LROCs on the sensor substrates. Briefly,
the sensor substrate (Figure 1a) was covered with PS LROCs
to form a uniform mask via colloidal lithography (Figure 1b).
The PS LROCs were then uniformly etched by a plasma
cleaner to modify the PS particle size (Figure 1c). The next
step involved using CVD to deposit the uniform film of TiO2
over the LROC-covered substrate. The substrate was then
annealed at 550 °C to remove the polystyrene template. The
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annealing process simultaneously crystallized the amorphous
TiO2 material deposited on the LROCs (Figure 1d).
Thereafter, theTiO2 LROCs were decorated with uniform Pd
NPs through the ELP process (Figure 1e).
Surface Characterization. The low- and high-magnifica-
tion SEM images of hexagonal close-packed and non-close-
packed PS monolayer are shown in Figure 2a,b, respectively.
The SEM images with the same magnifications were obtained
to analyze the particle size distribution of the PS templates
before and after etching. As shown in Figure S1 (Supporting
Information), the synthesized PS microspheres had an average
diameter of 1350 nm with small variance in diameter of 32 nm.
After 20 min of etching, the size of the PS microsphere
diameter was uniformly decreased to 842 nm in average with a
variance of 52 nm, thus forming a uniform nonclosely packed
LROCs of PS. The SEM images of the nonclosely packed
TiO2/PS LROCs after 10 min of CVD and after the annealing
process at 550 °C in air for 1 h are shown in Figure 2c,d,
respectively. It can be observed that the structure and distances
between the colloids did not significantly change during the
annealing process. As the polystyrene degrades in temperatures
higher than 418.6 °C,43 the LROCs after the annealing process
form a hollow TiO2 microshell structure. The hollow nature of
the TiO2 microshell structure was confirmed by the image
presented in the Supporting Information, Figure S2. Following
the CVD process, the thickness of the deposited TiO2 layer
was measured on the control sample by a thickness
profilometer in order to determine the TiO2 thickness that
was deposited on the LROC samples. The surface profile
presented in Figure S3 in the Supporting Information
confirmed the thickness of the TiO2 film to be 68 ± 11 nm
following the CVD and calcination processes. The standard
deviation was calculated using five random points on the step
edge of the deposition after removal of the photoresist mask on
the control sample as detailed in the Experimental Section.
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Figure 3. (a) SEM images and EDS spectra for initial Pd seeds that were deposited over TiO2 LROC structures and (b) SEM image and EDS
spectra for the 20 s electroless deposition of Pd grown on the Pd seeds.

Figure 4. XPS spectra: (a) survey spectra of the TiO2 LROCs, Pd-seeded TiO2 LROCs, and Pd-decorated TiO2 LROCs; high-resolution (b) Ti 2p;
(c) O 1s, and (d) Pd 3d core-level spectra.

The SEM images of the seeded and decorated Pd NPs on any visible Pd NPs because of the small particle size. The Pd-
the TiO2 LROCs via ELP process are shown in Figure 3. The decorated TiO2 LROCs in Figure 3b shows uniform Pd
Pd-seeded TiO2 LROCs in Figure 3 (a1 and a2) did not show particles deposited over the TiO2 LROC surface. Figure 3 (b1
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Figure 5. UV−vis transmittance spectra of (a) quartz substrate coated with the TiO2 thin film; (b) PS closely packed and nonclosely packed
LROCs; (c) TiO2 LROCs before and after annealing; and (d) TiO2 LROCs as well as Pd-seeded and Pd-decorated TiO2 LROCs.
and b2) shows the Pd grains from the ELP having relatively
more Pd NPs than the seeded sample and which can lead to
higher H2 permeability and superior thermal stability. To
further confirm the formation of Pd NPs and study the
impurity contents introduced during the synthesis procedure,
all samples were studied using energy-dispersive X-ray
spectroscopy (EDS). The EDS results indicate that titanium,
oxygen, and palladium are present in the sample, which
confirms the successful deposition of Pd on the TiO2 LROCs
with no impurities being present. The percentage of Pd in the
Pd-seeded TiO2 LROC sample was determined to be 5 at %
from EDS data. The Pd content was found to increase to 28 at
% in the sample that underwent both seeding and 20 s
electroless deposition of Pd. The TiO2- and Pd−TiO2-based
LROC samples were also formed on quartz substrates and
annealed at 550 °C for independent analysis. Quartz was used
so that the samples could also undergo UV−vis analysis. These
samples were characterized using XRD and the data is shown
in Figure S4 in the Supporting Information. The distinct peaks
were indexed for (101), (004), (200), and (105) of the TiO2
crystal anatase44 and (111) for Pd NPs.45 The Pd-seeded TiO2
LROCs did not show any visible Pd peaks in XRD and was
postulated to be due to the small particle size and Pd content
that was present on the structure. The Pt peak observed in the
EDS spectra is attributed to the Pt electrodes present on the
AGS device.
XPS characterization was performed to examine the
oxidization states of each element on the structure surface
and to establish any possible surface contamination that may
have occurred during the synthesis procedure. Figure 4a shows
the survey spectra of TiO2 LROCs, Pd-seeded TiO2 LROCs,
and Pd-decorated TiO2 LROCs. The XPS data confirmed that
no surface contamination was present at the surface of the
samples. The high-resolution XPS spectra for Ti 2p, O 1s, and
Pd 3d BE associated with the 20 s Pd-decorated TiO2 LROCs
are shown in Figure 4b−d, respectively. Sn 3d5/2 was presented
in the spectra because of the intermediate Pd seeding
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process.46 The BE of Ti 2p3/2 at 458.7 eV indicates the
presence of Ti4+ oxidation states.45 However, the O 1s has two
separate BEs of 529.8 and 531.7 eV, which are related to the
formation of Ti−O and surface hydroxyl group in titania
structure, respectively.45 The deconvolution of Pd 3d spectra
showed three oxidation states for Pd. Considering Pd 3d5/2
deconvolution, a small peak appearing at 335.1 eV
corresponded to the metallic Pd, while the other two peaks
appearing at 335.7 and 341.0 can be vindicated by a partial
oxidation of Pd to PdO structure and formation of Pd/PdO
core shells. Gracia-Espino et al. have shown that the presence
of the third peak can indicate that a Pd oxide shell (Pd5/2,
335.1 eV) is present at the surface and the Pd−PdO interfacial
layer at the core that is depleted in oxygen, thus explaining the
presence of the third smaller peak at 337.6 eV.47
The UV−vis transmittance spectra were carried out for all
samples using quartz substrates (as per XRD samples). Figure
5a shows the titania thin film which was directly deposited on a
quartz substrate without any PS colloids or LROCs involved.
The results indicate an absorption edge at 380 nm (3.26 eV),
which is associated with the formation of a wide band gap
TiO2 layer. In Figure 5b, the transmittance spectra of PS-based
LROCs are presented. As a result of formation of a PC, the
transmittance shows a wave feature in the spectra which is
attributed to light coupling into periodic structure of the
nanoarray.48 After PS plasma etching process, the size of PS is
reduced and the distance between the PS colloids is increased,
thus forming a nonclosely packed LROC template and
resulting in a different type of transmittance wave profile.
After the deposition of TiO2, the wave pattern of the PS is
eliminated because of the formation of the secondary material
on the PS LROCs. However, the profile of the TiO2-based
LROCs before calcination and after calcination is different.
The hump shape in the deposited TiO2, over the LROCs, prior
to annealing comes from the PS cores. The TiO2 LROCs after
annealing show a similar absorption edge as a TiO2 thin film.
However, compared to the thin film control sample, the TiO2
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Figure 6. (a) Normalized response profiles of Pd-decorated TiO2 LROCs toward different concentrations of H2 at an operating temperature of 33
°C under different bias conditions; (b) calibration curve obtained from response profiles; (c) sensor response magnitudes toward 500 ppm of H2
operating under different light intensities and dark condition at an operation bias of 9 V; and (d) Pd-decorated TiO2 LROC sensor response profile
toward 500 ppm of H2 gas under 2024 μW·cm−2 of light stimulus and dark conditions operating at a bias of 9 V.

LROCs have been reduced in transmittance intensity because
of light scattering. A red shift in the absorption spectrum in
both Pd-seeded and Pd-decorated TiO2 LROCs has been
obtained.49−51
Sensing Performance. In order to explore the possibility
of the developed materials as highly selective and sensitive
materials toward H2 gas sensing, they were employed as
sensitive layers on AGSs. Furthermore, light-assisted AGS-
based H2 sensing tests were performed in order to achieve low-
temperature gas sensing. The sensing performance of the
developed sensor was tested by exposing it to H2 gas
concentrations of 50, 75, 100, 200, 300, 400, and 500 ppm
at an operating temperature of 33 °C. The H2 sensing
performance of the TiO2 thin film (control sensor) and TiO2
LROCs with and without Pd decoration was tested using a
computer-controlled gas delivery setup. The normalized
response of Pd decorated is presented in Figure 6a (the
sensor response profile for the Pd-decorated TiO2 LROC-
based sensor is shown in Figure S5) (Supporting Information).
It is noteworthy that the control sensors (i.e., the plain TiO2
thin film, TiO2 LROCs, and Pd-seeded TiO2 LROCs) did not
produce any detectable response toward the H2 concentrations
tested, even after the application of different biases (0.1, 3, 6,
and 9 V) with and without light illuminated at 33 °C. This lack
of readable response was attributed to the control sensors’
relatively higher resistance and lack of affinity toward H2 at the
test conditions used (see the Supporting Information, Figure
S6). In addition, the control sensors did not respond toward
H2 at 33 °C.33,39 The calibration curves for the developed Pd-
decorated TiO2 LROC sensor under various bias potentials are
shown in Figure 6b. The data indicates that the sensor
response under light illumination was higher than in dark
conditions under a 9 V bias potential, which increased from
∼55 to ∼91% with an increase in H2 concentration from 50 to
G https://dx.doi.org/10.1021/acssensors.0c01387
500 ppm (see the Supporting Information, Figure S7). A
reduced bias (9 < bias ≤ 3 V) deems the sensor unusable
under dark conditions and the sensor response toward H2
increases with increasing applied bias. Furthermore, the sensor
did not produce any response toward H2 (under light nor dark
conditions) under a bias of 0.1 V (see the Supporting
Information, Figure S6). The data indicates that the highest
sensor response is obtained from light-assisted H2 sensing
under the highest applied potential of 9 V. The response
magnitude for the developed Pd-decorated TiO2 LROC sensor
with highest tested bias (9 V) under a light illumination of 365
nm with an intensity of 2024 μW·cm−2 was linear (R2 = 0.99)
in the concentration range tested with a calculated sensitivity
of S = 6.2 μA/ppm (see Figure 6b). The LoD of the developed
Pd-decorated TiO2 LROC-based sensor toward H2 was
determined using the 3 standard deviations of the sensor
response output toward a blank sample (dry air), as explained
in our previous study.37 The LoD of the developed Pd-
decorated TiO2 LROC sensor toward H2 decreased when
increasing the applied bias at 33 °C. That is, the LoD under
light with a 9 V bias was calculated at 3.5 ppm, which is much
lower when compared with 3 and 6 V bias conditions (see the
Supporting Information, Table S1). The results obtained at
near RT are impressive, given that previous studies have
successfully reached an LoD of <10 ppm with good selectivity
and sensitivity toward H2 gas, however at temperatures above
100 °C.28,52 In other studies where the LoD has been reported
below 10 ppm at RT, there have been challenges or no reports
in terms of selectivity of the sensor toward H2 gas.53−56
Findings suggest that the sensor response magnitude in the
presence of light with a 9 V bias was better and has less
baseline noise and better signal-to-noise ratio (SNR = 72),
which also results in better detection limit when compared to
the SNR at a similar sensing condition in the absence of light
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ACS Sensors pubs.acs.org/acssensors Article

Figure 7. Dynamic response profile of the developed Pd-decorated TiO2 LROC sensor during the memory test at 33 °C at a bias of 9 V (a) under
dark and (b) under UV light illumination (2024 μW·cm−2). Analysis graphs show the CoV of the developed sensor toward each H2 gas
concentration detected following different H2 concentrations (c) with and (d) without light.

[SNR = 0.006, see Table S1 (Supporting Information)]. The
increase in the baseline noise in the absence of light at 9 V bias
was attributed to the reduced number of charge carries as
portrayed in an earlier analysis.57,58 Both response (t90‑res) and
recovery (t90‑rec) times were calculated for the sensor under the
conditions of 500 ppm H2, from 3 to 9 V bias, under light
illumination, at 33 °C, whose results are presented in Table S2.
The t90‑res value refers to the time needed for the sensor signal
to reach 90% of the overall change while t90‑rec refers to the
time required to return to 90% of the baseline signal. The
outcomes suggested that the t90‑res and t90‑rec values for the
developed Pd-decorated TiO2 LROC sensor increased with
increasing applied bias. The t90‑res and t90‑rec values for 500 ppm
H2 at 9 V bias and 33 °C under light were found to be 45 and
24 s, respectively. At a lower bias of 3 V, t90‑res and t90‑rec
improved to 15 and 18 s, respectively, however with the
drawback to lower sensitivity. The developed sensor was tested
by exposing 500 ppm H2 over five sequential pulses under
different light intensities and dark with a 9 V bias and an
operating temperature of 33 °C (Figure 6c). The data imply
that increased light intensity resulted in the production of
relatively more electron−hole pairs that enables the formation
of photo-induced oxygen ions, thus increasing the response
magnitude toward H2 gas.
The developed sensor (Pd-decorated TiO2 LROCs) at an
operating temperature of 33 °C was investigated by exposing
500 ppm of H2 concentration with a 9 V bias to five repeated
cycles under dark and UV light (365 nm at 2024 μW·cm−2)
illumination. The coefficient of variance (CoV) of the
developed Pd/TiO2 LROC-based AGS was calculated for the
different H2 concentrations as reported in the literature.59,60
That is, the CoV was calculated by taking the ratio of the
H https://dx.doi.org/10.1021/acssensors.0c01387
standard deviation to the average response magnitudes of the
sensor toward each hydrogen concentration by utilizing the
formula [CoV (%) = σ/x̅ × 100% and repeatability (%) =
100% − CoV (%)]. The results presented in Figure 6d indicate
that the developed Pd-decorated TiO2 LROC sensor exhibit a
good repeatability of 99.9% in both the absence and presence
of UV light illumination at an operating bias of 9 V.
Memory Effect. In order to determine whether the
developed sensor would be affected by a previous sensing
event, a memory test sequence was developed with five
different hydrogen gas concentrations (dubbed as a, b, c, d, and
e), which are a = 100, b = 200, c = 300, d = 400, and e = 500
ppm. Each concentration was repeated for a minimum of four
times and followed at least once by each of the other four
tested concentrations. Figure 7a,b shows the sensor response
profiles during the memory test at 33 °C without and with
light illumination, respectively, while the analysis graphs
(response magnitudes) of the same test are, respectively,
presented in Figure 7c,d. Interestingly, the memory effects
were found to be significant under UV light when quantified
through the CoV calculations presented in Table1. However, it
can be observed from Figure 7c (bar graph representation)
that the memory effects in the absence of light were significant
compared with the memory effect under UV light illumination
in Figure 7d (bar graph representation). It is the evident that
even the small memory effects (<1%) observed under dark
conditions had improved under UV light illumination (<0.5%).
That is, the sensor exhibited similar response magnitudes for
every repeated H2 gas concentration examined regardless of
the exposure sequence to the sensor. This was the case even
when the lowest H2 gas concentration (100 ppm) was tested
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ACS Sensors pubs.acs.org/acssensors Article

Table 1. Memory Test Results Quantified through CoV
Calculations of the Response Magnitude of the Developed
Sensor (Pd-Decorated TiO2 LROCs) toward Different
Hydrogen Gas Concentrations at an Operating
Temperature of 33 °Ca
Repeatability (%)
H2 concentration (ppm) A B C d
dark 99.2 99.5 99.0 99.3
light 99.8 99.9 99.7 99.5
a now the limiting current is controlled by the diffusion of the
Four pulses were used for each CoV calculation (i.e., n = 4)
following the event of highest H2 gas concentration (500
ppm).
Mechanism. The sensor data confirms that decoration of
Pd on the TiO2 LROCs played a major role in the catalytic
conversion of H2 on the sensitive layer. The Pd-decorated
TiO2 LROCs showed impressive sensing performance
(compared to most reports in literature as presented in
Table 2) when employed as a sensitive layer for light-assisted
amperometric H2 gas sensing. In contrast, the pristine TiO2
thin film, TiO2 LROCs, and Pd-seeded TiO2 LROC (low Pd
content)-based control sensors produced no readable sensor
output when exposed toward H2 gas in any of the mentioned
conditions. Pd NPs can also offer a reaction pathway which can
reduce the activation energy and then enhance the reaction
rate, sensitivity, selectivity, and reliability.14 Pd NPs can also
serve as a H2 sorbent that can feed H2 to the TiO2/Pd interface
for the reaction to occur,1 which can be explained by spillover
effect explained elsewhere.22 When oxygen (in dry air)
interacts with the developed Pd-decorated TiO2 LROC surface
on the sensor, oxygen captures the electrons from the surface
of the sensitive layers’ conduction band to form ionic species,
such as O−, O2−, and O2−.39 This results in the resistance of
the sensor to increase as the depletion layer increases.22 The
well-dispersed Pd NPs encourage an increased gas response by
creating active sites (electronic sensitization) because the
Schottky barrier between Pd NPs and TiO2 LROCs is a better
dissociation catalyst than TiO2 alone.14 Similarly, the Schottky
junction will also occur between the n-type TiO2 LROCs and
platinum IDT sensor electrodes.61 The generated Schottky
barrier height prevents the flow of electrons from TiO2 LROCs
to the metals (Pd NPs and Pt electrodes) without assistance
from an external energy source to elevate their energy above
that of the Schottky barrier height.14,62 Hence, the required
bias voltage for operation needs to be reached. The materials
exhibit different adsorption balances on the surface when
impacted by different biases. When biases are applied, the
semiconductor band will flow electrons into the metal, which
enhances the sensor performance and increases the response
magnitude. In addition, the response magnitude increased
when the bias is increased from 0.1 to 9 V, which could be a
result of operating the AGS in the diffusion-controlled mode
rather than kinetically controlled mode of the electrode.7,61
e Under this condition (where the rate of reaction ≫ rate of
99.1 diffusion), the rate of diffusion of the reactant toward the
99.7 electrode surface is much slower than the rate of reaction and
analyte. Thus, the combination of overcoming the energy
barrier and achieving a high reaction rate is postulated to be
the reasons for the relatively higher sensor response outputs at
relatively higher bias applied. Furthermore, when H2 interacts
with the material Pd-decorated TiO2 LROCs under UV light,
electron−hole pairs will be excited and separated at the
depletion layer near the surface (eq 1).Then, the hole will react
with the adsorbed oxygen (eq 2) at the interface and reduce
the thickness of the depletion layer which consumes the holes
and decrease the resistance and increase the current of TiO2
LROCs (as compared with the result under dark condition),
which will result in an equilibrium shift that will favor the
reaction toward consuming more electrons, and thus, electrons
will react with the oxygen molecules and trap them on the
sensor surface (eq 3).1,13,42,61
hv = e− + h+ (1)
O2(ads)− + h(hv)+ → O2(gas) (2)
O2(gas) + e(hv)− → O2(ads)− (3)
Regarding a previously proposed mechanism for the Pd/
TiO2 interface, Pd is one of the best catalytic materials for
hydrogen, which is also well known to act as a hydrogen
collector. When hydrogen is injected, H2 molecules dissociate
into active hydrogen species by Pd NPs. The active hydrogen
species can move toward the interface between Pd NPs and
TiO2 LROCs to form Pd hydride (PdHx), which reacts with
the adsorbed ionic oxygen and injects electrons into TiO2
LROCs. This results in an increased conductivity and decrease
in the height of the Schottky barrier that can be modeled via
the following possible reactions14,63
x
Pd + H 2 → PdHx
2 (4)

Table 2. Summary of Hydrogen Sensors that Employ TiO2 as the Sensitive Layer as Reported in the Literature

temp response detection range response/recovery

TiO2 structure preparation method catalyst (°C) (%) (ppm) times ref
mesoporous film Anodization 140 20−1000 5−125 s 63
thin film sputtering 340 99 300−10,000 1 min 64
nanotube anodization 25−150 8−20 100−5000 30 min 11
nanotubes electrochemical anodization Pd 25 8.5 10,000−50,000 2−1.5 min 39
nanotube anodization Pt, Pd 290 50−90 10−100,000 10−20 s 65
nanotubular on SiO2/Si electrochemical anodization Pd 180 91 100−5050 30−10 s 14
thin film DC reactive magnetron Pd, PdO 150 90 150−30,000 21
sputtering
nanofiber electrospinning Pd 150 40.8 6000−10,000 25−1 s 22
nanorods hydrothermal Pd 200 250−2000 33
LROCs CVD Pd 33 91 50−500 45−24 s present work

I https://dx.doi.org/10.1021/acssensors.0c01387
ACS Sens. XXXX, XXX, XXX−XXX
ACS Sensors pubs.acs.org/acssensors
Figure 8. Developed sensor’s selectivity data at (a) dark condition and (b) under UV light (365 nm, 2024 μW·cm−2) illumination.
x x x gas was more dominant, rendering the sensor selective toward
PdHx + O(ads)2 − → Pd + H 2O + e−
4 2 4 (5)
Selectivity toward H2. The Pd-decorated TiO2 LROC
sensor’s selectivity performance toward H2 was tested by
exposing the sensor to H2 as well as different interfering gas
species at concentrations that are common in most industries.
The tests were conducted both with and without light at an
operating temperature of 33 °C in the presence of air. These
gas species included CO2 (500 ppm), C4H8O (26.1 ppm),
C3H6O (25 ppm), CH3CHO (3034 ppm), and NO (2000
ppm), most of which were examined at the maximum
concentrations expected in industrial processes. Figure 8a,b
shows the sensor’s response when exposed to each gas species
balanced in air. The results show that the response of the
developed sensor toward H2 is much higher when compared to
other gas species tested, both in the absence and presence of
light because of selective adsorption of H2 on Pd NPs (the
normalized response profiles of the TiO2 LROCs are presented
in the Supporting Information, Figure S8).39 The developed
sensor showed no significant sensitivity toward other gas
species on repeated occasions and is postulated to be due to
the specific selectivity property of Pd NPs toward H2 gas as
explained previously in the mechanism discussion section.22
Furthermore, it was observed that both selectivity and
sensitivity can be controlled by the presence/absence of UV
light-assisted sensing, indicating that the developed sensor can
be used to detect a wide range of hydrogen concentrations
(low ppm to high % levels) for various applications. The lowest
selectivity experienced by the sensor was through the exposure
of humidity, resulting in an acceptable 93% selectivity in the
presence of UV light illumination. However, under dark
conditions, the sensor was observed to produce a readable
response magnitude toward CO2, however still with an
impressive output of 98% selectivity toward H2 gas. When
the metal oxide (TiO2 LROCs) sensor is operated in the
humid atmosphere, the adsorption of water vapor and
molecular oxygen releases electrons into the depletion layer
and results in decreased resistance and increased current on
the oxide surface, which potentially changes the baseline
current of the sensor when dry air is changed to humid air.14,66
The physisorption of H2O molecules on the oxide surface
could also hinder hydrogen chemisorption and hence
dissociation.67,68 The response magnitude of the sensor toward
500 ppm H2 and toward 0.5 g/m3 H2O is shown in Figure S8d
(Supporting Information). Under UV irradiation, the sensor
response for humidity was much higher (7%) compared to the
dark condition (0.4%) (see Figure 8a,b) Furthermore, it is
observed that the sensor produced response toward other
interferent gas species tested; however, the response toward H2
J https://dx.doi.org/10.1021/acssensors.0c01387
Article
H2 gas. The response observed from interferent gas species
tested is not surprising as the combination of bias and UV
irradiation would have promoted all gas species to undergo
chemical reaction/sorption on the catalytic sensitive layer;
however, the conditions has favored H2 reaction to be the most
dominant event though it was exposed at a low 500 ppm level.
■
CONCLUSIONS
Pd NPs were used to decorate TiO2 LROC-sensitive layers
deposited directly on the AGS device. The sensor was studied
with/without UV light illumination and different bias
conditions in a bid to improve the sensitivity and the
selectivity of the sensor toward H2 gas near RT. The LoD of
the developed Pd-decorated TiO2 LROC sensor toward H2
decreased with increasing applied bias. An LoD of 3.5 ppm was
achieved with a 9 V bias under light illumination, which was
much lower when compared to 6 and 3 V bias conditions. This
was attributed to increased rate of reaction and electron flow
due to employing Pd NPs as the dissociation catalyst and
application of external stimuli (i.e., bias and light illumination),
which would have increased the H2 reaction rate on the
catalytic sensitive layer. The data indicated that the approach
allowed for low hydrogen concentrations (50 ppm) to be
detected with high selectivity at near RT (33 °C). The ability
of the developed sensor to detect low ppm levels makes it
applicable to many applications including breath analysis
(noninvasive diagnostics), industrial leak tests, and process
control.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssensors.0c01387.
NP size distribution: (a) close-packed PS LROCs and
(b) non-close-packed PS LROCs, SEM image after
annealing to form TiO2 LROCs, thickness profile for
TiO2 LROCs, XRD pattern of TiO2 LROCs before and
after annealing, Pd-seeded TiO2 LROCs and Pd-
decorated, high dynamic response of Pd-decorated
TiO2 LROC sensor toward different concentrations of
H2 at an operating temperature of 33 °C; (a) 3 V bias;
(b) 6 V bias; and (c) 9 V bias under 2024 μW·cm−2 of
light; dynamic response of the sensor’s TiO2 thin film,
TiO2 LROCs, Pd-seeded TiO2 LROCs, and Pd-
decorated TiO2 LROCs under a bias of 0.1 V at 33
°C with different H2 concentrations; normalized
response of a developed sensor (Pd-decorated TiO2
LROCs) with hydrogen and various gases with a 9 V
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ACS Sensors pubs.acs.org/acssensors
bias and an operating temperature of 33 °C; H2,
CH3CHO, C4H8O, NO, H2O, CO2, and C3H6O; and
SNR, LoD, and sensitivity for the developed sensor Pd-
decorated TiO2 LROCs (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Ylias M. Sabri − Centre for Advanced Materials and Industrial
Chemistry (CAMIC), School of Science, RMIT University,
Melbourne 3001, Victoria, Australia; Email: ylias.sabri@
rmit.edu.au
Ahmad E. Kandjani − Centre for Advanced Materials and
Industrial Chemistry (CAMIC), School of Science, RMIT
University, Melbourne 3001, Victoria, Australia;
Email: ahmad.kandjani@rmit.edu.au
Suresh K. Bhargava − Centre for Advanced Materials and
Industrial Chemistry (CAMIC), School of Science, RMIT
University, Melbourne 3001, Victoria, Australia;
orcid.org/0000-0002-3127-8166;
Email: suresh.bhargava@rmit.edu.au
Authors
Ebtsam K. Alenezy − Centre for Advanced Materials and
Industrial Chemistry (CAMIC), School of Science, RMIT
University, Melbourne 3001, Victoria, Australia; Chemistry
Department, College of Science and Arts, Al Jouf University,
Al-Qurayyat 75911, Kingdom of Saudi Arabia
Dilek Korcoban − Centre for Advanced Materials and
Industrial Chemistry (CAMIC), School of Science, RMIT
University, Melbourne 3001, Victoria, Australia
Syed Sulthan Alaudeen Abdul Haroon Rashid − Centre for
Advanced Materials and Industrial Chemistry (CAMIC),
School of Science, RMIT University, Melbourne 3001,
Victoria, Australia
Samuel J. Ippolito − Centre for Advanced Materials and
Industrial Chemistry (CAMIC), School of Science and School
of Engineering, RMIT University, Melbourne 3001, Victoria,
Australia; orcid.org/0000-0002-6844-7963
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssensors.0c01387
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the RMIT Microscopy and Micro-
analysis Facilities (RMMF) and RMIT MicroNano Research
Facilities (MNRF) for the assistance received from their staff
and for providing microscopy facilities. E.K.A. is thankful to Al
Jouf University for a full scholarship. A.E.K. acknowledges
RMIT University for the Vice-Chancellor Fellowship. The
authors also acknowledge RMIT’s Enabling Capability Plat-
forms (ECP) for the Translation and Impacts fund awarded in
2019.
■
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