Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Analyst
View Article Online

PAPER

Cite this: DOI: 10.1039/c6an00326e

View Journal

Hybrid 3D structures of ZnO nanoowers and PdO

nanoparticles as a highly selective methanol sensor
D. Acharyya,a K. Y. Huang,b P. P. Chattopadhyay,c M. S. Ho,d H.-J. Fechte and
P. Bhattacharyya*a
The present study concerns the enhancement of methanol selectivity of three dimensional (3D)
nanoowers (NFs) of ZnO by dispersing nickel oxide (NiO) and palladium oxide (PdO) nanoparticles on
the surface of the nanoowers to form localized hybrid nano-junctions. The nanoowers were fabricated
through a liquid phase deposition technique and the modication was achieved by addition of NiCl and
PdCl2 solutions. In addition to the detailed structural (like X-ray diraction (XRD), electron dispersive
spectroscopy (EDS), X-ray mapping, XPS) and morphological characterization (by eld emission scanning
electron microscopy (FESEM)), the existence of dierent defect states (viz. oxygen vacancy) was also
conrmed by photoluminescence (PL) spectroscopy. The sensing properties of the pristine and metal
oxide nanoparticle (NiO/PdO)ZnO NF hybrid sensor structures, towards dierent alcohol vapors (methanol, ethanol, 2-propanol) were investigated in the concentration range of 0.5700 ppm at 100350 C.
Methanol selectivity study against other interfering species, viz. ethanol, 2-propanol, acetone, benzene,
xylene and toluene was also investigated. It was found that the PdOZnO NF hybrid system oered
enhanced selectivity towards methanol at low temperature (150 C) compared to the NiOZnO NF and

Received 9th February 2016,

Accepted 18th March 2016

pristine ZnO NF counterparts. The underlying mechanism for such improvement has been discussed with

DOI: 10.1039/c6an00326e

respective energy band diagram and preferential dissociation of target species on such 3D hybrid structures. The corresponding improvement in transient characteristics has also been co-related with the

www.rsc.org/analyst

proposed model.

1.

Introduction

Methanol (methyl alcohol) is widely used as a chemical agent

for biomedicines, food fermentation, manufacturing of
colours, dyes, perfumes etc. The extensive use of methanol in
brewing, as well as in automotive industries is also worth mentioning.1 However, its highly toxic nature is often fatal to
human health and warrants online monitoring with ecient
sensing systems.2 Unfortunately, owing to its very low boiling
point (64.7 C) and high cross-sensitivity towards other interfering species (mainly ethanol and 2-propanol), methanol
sensing calls for ecient selectivity of the sensor devices.2
a

Nano Thin Films and Solid State Gas Sensor Devices Laboratory, Department of
Electronics and Telecommunication Engineering, Indian Institute of Engineering
Science and Technology, Shibpur, 711103 Howrah, India.
E-mail: pb_etc_besu@yahoo.com; Fax: +913326682916; Tel: +913326684561
b
Graduate Institute of Photonics and Optoelectronics, National Taiwan University,
Taipei 10617, Taiwan
c
Department of Physics, National Chung Hsing University, Taichung 40227, Taiwan
d
Department of Metallurgy and Materials Engineering, Indian Institute of
Engineering Science and Technology, Shibpur, Howrah-711103, India
e
Institute of Micro- and Nanomaterials, Ulm University, 89081 Ulm, Germany

This journal is The Royal Society of Chemistry 2016

Several reports have so far been published on methanol

sensing properties of dierent metal oxides, employing
various nanoforms.314 However, very few have focused on the
selective detection of methanol vapor against the interfering
species (i.e. ethanol, 2-propanol, acetone etc.).1214 A scrutiny
of contemporary literature reveals that methanol sensitivity as
well as selectivity of dierent semiconducting metal oxides has
been improved by adopting the following measures: (i) incorporation of partially filled d-shell metal as a dopant or a
surface modifier to semiconducting oxides,4 (ii) use of the
composite structure of dierent metal oxides,4 (iii) use of an
organic or inorganic membrane to selectively allow the special
target molecules towards the metal oxide surface,5 (iv) depositing noble metal as a gate material for the chemical field eect
transistor (Chem-FET) sensor (e.g. Pt gate SiC-FET sensor)6
and (v) developing a sensor array combined with appropriate
pattern reorganization tools tuned for favourable target species
(e.g. surface acoustic wave (SAW) sensor).3,7 In this context,
Sahay et al.8 reported on the methanol sensing ability of the Al
doped ZnO structure. Improvement of methanol sensing properties of several composite structures such as, Fe2O3 and
SnO2 hybrid nanocubes,9 and sulphated SnO2 carbon nano-

Analyst

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Paper

tube2,12 were investigated by dierent research groups.

However, the issue of selectivity improvement has not been
duly addressed in these reports.822 Zhao et al.11 reported on a
Li-doped ZnO nanoparticle based senor where they tested the
selectivity only in the presence of formaldehyde at 350 C
(optimum temperature) and achieved promising results, but
the interference with the nearest neighbour (ethanol) was not
considered in this report. On the other hand, Tang et al.13
studied methanol selectivity of SnO2ZnO composite nanofibers at 350 C (optimum temperature) in the presence of
ethanol where they obtained a higher selectivity at higher concentrations of vapor than that in the lower regime. A molecularly imprinted AgLaFeO3 based methanol sensor was
reported by Zhu et al.14 They observed a sensitivity dierence
of 12 between methanol and ethanol towards 1 ppm concentration at 150 C. A methanol selective gas sensor based on
nano-structured conducting polypyrrole was proposed by
Babaei et al.15 Their sensor oered a sensitivity dierence of
2.51 between 210 ppm methanol and ethanol flow. In another
work, Mabrook et al.16 observed a sensitivity dierence of 10 at
350 ppm (for methanol and ethanol) in their TiO2 dispersed
polyvinylidene fluoride based sensor. For improvement of
methanol sensitivity, one dimensional (1D) oxide nanoforms
like nanorods17 and nanotubes18 have been introduced and
found to be a potential sensing element. Very recently, three
dimensional (3D) nanoflower based sensors have also been
investigated.22 However, a methanol sensing study with such
3D nanoforms has not been attempted earlier. The present
study, aims to explore the enhancement of selectivity and sensitivity of the methanol vapor, in the case of a 3D hybrid structure consisting of ZnO NFs and NiO/PdO nanoparticles, since
NiO and PdO are known to be potential catalysts for enhancing
the selectivity. ZnO NFs were fabricated on a Si/SiO2 substrate
through a liquid phase deposition technique. After successful
growth, the surface of ZnO NFs was modified by dispersion of
Ni and Pd nanoparticles on the surface of the nanoflowers.
Subsequently, three sensor devices (viz. pristine ZnO, NiO
modified ZnO NF and PdO modified ZnO NF) were fabricated
to investigate the methanol sensing properties in the concentration range of 0.5700 ppm. The response of the sensors in
the presence of interfering vapors, such as dierent alcohols
(ethanol and 2-propanol), ketone (acetone) and aromatic
hydrocarbons (benzene, xylene and toluene) was also investigated. It was found that the ZnO NFPdO based hybrid structure oered very high sensitivity (response magnitude (%) are
61.19/99.57% towards 0.5/700 ppm methanol) with excellent
selectivity (i.e., 50% response magnitude dierence with the
nearest interfering neighbour (i.e. ethanol) at all concentrations) at a relatively low temperature (150 C). The response
time in the case of PdO modified ZnO NF was also found to be
faster than that of the NiO modified and the pristine one.
Improvement of methanol sensitivity of the developed metal
ZnO NF 3D hybrid structure is discussed here, based on the
respective energy band diagram and selective catalytic dissociation of vapor adsorbents on the NiO and PdO modified
ZnO NF surface.

Analyst

Analyst

2. Experimental
2.1

Synthesis of ZnO NF and NiO/PdO hybrid 3D structures

Pristine ZnO nanoflowers (3D) were synthesized on a SiO2/n-Si

substrate through a liquid phase deposition technique. The
synthesis was conducted by using analytical grade chemicals
without further purification. The solution was prepared by
mixing 0.5 (M) Zn(NO3)2 (anhydrous, 99% purity) and NH3
solutions (25%) in 50 ml de-ionized water (18 M cm). The
NH3 solutions were added into the Zn(NO3)2 solution until the
pH reached the value of 10. Subsequently, the solution was
stirred at 500 rpm for 3 hours to improve the homogeneity.
A properly cleaned SiO2/Si substrate was placed vertically in
the solution and kept for 1 hour at 120 C. Consequently, the
samples were annealed in a horizontal tube furnace at 500 C for
3 hours in air (with a heating and a cooling rate of 5 C min1).
The pristine ZnO nanoflower surfaces were then modified
by Ni and Pd nanoparticles by using 0.1(M) aqueous solution of nickel chloride (NiCl2) and palladium chloride (PdCl2)
solution, respectively. For surface modification, a dip coating
technique (using Apex Xdip-XV1 equipment) was used. The
samples were dipped into the chloride solutions for 10 s with
a dipping and pulling speed of 1 cm min1. The samples were
then dried under a N2 jet and heat treated at 200 C for 1 hour.
The nanoparticles of Pd/Ni were subsequently converted to
PdO/NiO.23 Fig. 1 shows the schematic of the ZnO NF-NiO/
PdO 3D hybrid structure. The underlying mechanism concerning the ZnO nanoflower growth has already been discussed in
our earlier work.17
2.2

Characterization methods

The surface morphology of the pristine ZnO NF and NiO/PdO

modified ZnO NF 3D hybrid structures were investigated by
field emission scanning electron microscopy (FESEM, model:
ZEISS SIGMA operating at 5 kV ETH voltage). Elemental composition analysis was performed using an energy dispersive
X-ray analysis unit (EDAX, model: EAG AN461). Crystallinity
and phase composition were authenticated by using a Bruker
X-ray diractometer (with Cu K radiation ( = 0.154 nm)
maintaining the 2 scan rate of 0.33 per minute). The Horiba
Jobin Yvon, Flurolog-3 spectrofluorometer (model FL3-22) was

Fig. 1 A schematic of metal oxide (NiO/PdO)ZnO NF 3D hybrid

sensor device structure with requisite dimensions (not to scale).

This journal is The Royal Society of Chemistry 2016

View Article Online

Analyst

Paper

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

used to study the photoluminescence (PL) properties of the

pristine ZnO NF and NiO/PdOZnO NF structures. Further, the
composition was authenticated by an XPS (PHI-5400, PerkinElmer Com) technique with a Mg K X-ray source.
2.3

Sensor fabrication and measurement

The pristine ZnO NF and NiO/PdOZnO NF hybrid structure

based resistive sensors were fabricated on a thermally oxidized
(thickness of Si and SiO2 are 490 m and 150 nm, respectively) 5 mm 5 mm n-Si (resistivity: 110 cm, <101>) substrate. On the top of the sensing layer, two Pd electrodes (each
having dimensions of 1.5 mm 1.5 mm 50 nm) were deposited by an e-beam evaporation technique (107 mbar)
using a suitably designed metal shadow mask. In the present
study, the gas sensing measurement was carried out in a
system similar to the one reported earlier.18,22 Air was used as
a carrier as well as a diluent for achieving the desired gas/
vapor concentrations, during the experiments. The sensing
performance of three dierent types of sensors was tested
towards dierent vapors (methanol, ethanol, 2-propanol,
benzene, xylene, toluene and acetone) in the concentration
range of 0.5700 ppm. The sensor resistance/current was
measured by a Keithley 6487 picoammeter/programmable
voltage source, interfaced with a personal computer. The
sensor response magnitude (RM) is expressed as RM% =
((Ra Rg)/Ra) 100, where, Rg is the sensor resistance in target
vapor(s) and Ra is the sensor resistance in air. The response
time and recovery time were calculated as the time to reach/fall
from 90% of the saturation response.18

3. Results and discussion

3.1

Structural and morphological characteristics

The strong diraction peaks along (100), (002), (101) (in descending order of intensity) [JCPDF no: 80-0074] indicate that
the ZnO nanoflowers are highly crystalline in nature (Fig. 2(a)).
No diraction peaks related to other impurities were detected
(in pristine ZnO NF sample) indicating the highly pure nature
of the grown nanoflowers. On the other hand, diraction
peaks related to NiO[111] and [200] [JCPDF no: 75-0584] and
PdO [101], [110] and [112][JCPDF no: 78-0643] were found in
the case of NiO and PdO modified ZnO NF structures, respectively. In the case of NiO and PdO modified ones, the ZnO
peaks at [002] and at [101] are slightly shifted to larger lattice
constants which is possibly due to the diusion of Ni and Pd
into ZnO NFs or by replacing the Zn in the ZnO crystal. The
average grain size of ZnO nanoflowers, NiO and PdO was calculated using full width at half maxima (FWHM) values of the
XRD peak employing Scherer formula2 and found to be
30.08, 12.52 nm and 10.24 nm, respectively.
The nanoflower like morphology of the film was confirmed
by FESEM (Fig. 2(b)). The magnified view of the pristine
ZnO NFs and the NiO/PdO modified ZnO NFs are shown in
Fig. 2b(iiii). The uniform distribution of metal oxide nanoparticles on the 3D nanoflower matrix is also evident from the

This journal is The Royal Society of Chemistry 2016

Fig. 2 (a) X-ray diraction patterns of the synthesized pristine ZnO NFs,
NiO modied ZnO NFs and PdO modied ZnO NFs. (b) FESEM image of
pristine ZnO NF; inset shows magnied view of (i) pristine, (ii) NiO
modied and (iii) PdO modied ZnO NF. (c) Cross-sectional view of
grown ZnO NF on Si/SiO2 substrate.

FESEM images (inset of Fig. 2(b)). The particle sizes of NiO and
PdO were found to be of 13.5 2 and 11.4 3 nm, respectively.
Fig. 3(ac) depicts the elemental composition and uniform distribution of metal oxide nanoparticles (NiO and PdO) on the
ZnO NF matrix. The presence of well-defined peaks of zinc
(Zn), oxygen (O), Ni (atomic weight (%) = 2.9%) and Pd
(atomic weight(%) = 2.52%) are evident from Fig. 3(ac). In
addition, the homogeneous distribution of such surface modification agents was also confirmed by X-ray imaging (Fig. 3(ac)).
Photoluminescence spectroscopy (with excitation wavelength: 325 nm) was carried out to examine the surface properties and impurity level of the pristine and hybrid
structures. Principally two types of emissions are evident in
Fig. 4(a), viz. (a) near band edge emission (UV region)

Analyst

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Paper

Fig. 3

Analyst

EDX analysis and elemental X-ray mapping of (a) pristine ZnO NFs, (b) NiOZnO NFs and (c) PdOZnO NFs.

Fig. 4 PL emission spectra of the (a) dierent ZnO NF surface; Gaussian de-convolution of PL peaks for (b) pristine ZnO NF, (c) NiOZnO NF hybrid
structures and (d) PdOZnO NF hybrid structure.

(395422 nm) attributed to direct carrier recombination of

ZnO and (b) broad emission at around 495750 nm. This
broad emission band can be attributed to the presence of
several defect states, like zinc vacancies (VZn),2426 oxygen
vacancies (VO),2729 zinc interstitials (Zni),30 oxygen interstitials

Analyst

(Oi),31 and transition between dierent defect states (e.g. Zni to

VZn).32,33 It is revealed from the PL spectra that the broad emission peak is composed of several overlapping bands like green
(495570 nm), yellow (570590 nm), orange (590620 nm) and
red (620750 nm).3335 Green band emission is accounted for

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Analyst

recombination of the excited donor electrons with the deep

level donor or acceptor like defects such as zinc interstitials
(VZn) and oxygen vacancies (VO).2429 On the other hand, the
yellow emission observed in ZnO is generally assigned to the
interstitial oxygen (Oi) and oxygen antisites (OZn).30,31 According to the earlier reports,33,35 orange and red emission peaks
originate from the transition between dierent defect states
like (i) Zni to VZn, (ii) Zni to Oi or (iii) Zni to Vo. A shift in the
green peak is also observed in the PL spectrum which is in
agreement with the earlier reports33 that the green emission is
significantly influenced by the surface modification than that
of yellow, orange and red emission. In addition, as reported by
Shan et al.27 due to annealing at high temperature in air,

Paper

VZn decreases and VO increases which in turn increases the

gas/vapour adsorption on the surface. Moreover, it can be envisaged from Fig. 4(ad) that the green shift and the intensity
ratio of defect peaks is the highest in the case of the PdOZnO
NF hybrid structure (than that of NiOZnO and pristine structure). The possible cause for this might be, the PdOZnO NF
surface oered the highest amount of oxygen vacancies on the
surface than that of others (NiOZnO and pristine). This is
further authenticated by the XPS study presented in Fig. 5.
This feature promotes the PdOZnO NF hybrid structure as a
better candidate for methanol sensor particularly at relatively
lower temperatures. Moreover, the higher amount of oxygen
vacancies eventually absorb more oxygen species which lead to

Fig. 5 XPS spectra of pristine, NiO and PdO modied ZnO NFs; (a) Zn (2p3/2 and 2p1/2) and (b) O (1s) peak of (Gaussian curve tting demonstrating
lattice oxygen and chemisorbed oxygen related peaks) (c) Pd (3d5/2) of PdO/ZnO NF structure (PdS represents metallic Pd surface sites that adsorb
oxygen molecules) and (d) Ni (2p3/2) of NiO/ZnO NF structure.

This journal is The Royal Society of Chemistry 2016

Analyst

View Article Online

Paper

Analyst

the enhancement of the adsorbed oxygen ion (i.e. O, O2 and

O2) concentrations on the surface (the reaction is shown in
eqn (1)).

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

O2 gas Vo =Vo =Vo $ O =O2  =O2 ads Vo =Vo =h

where h represents the hole.

Consequently, concentrations of such adsorbed oxygen ions
greatly influence the sensing performance of the developed
sensor, which is further confirmed by the sensor characterization experiments.
The decreasing intensity of the band to band transition
peaks to defect related peaks was found to be in the order;
pristine (1) < NiO modified ZnO (1.54) < PdO modified ZnO
(3.01) for metal oxide nanoparticles modified samples and
suggest that the substitution of the Zn atom occurred from its
interstitial site. This is possible if metal ions (Pd2+ or Ni2+)
substitute the Zn from the ZnO crystal lattice site induced by
the defect driven reaction represented as:12
ZnO

NiO=PdO ! NiZn =PdZn OxO Vo =Vo =Vo

The methanol, ethanol and 2-propanol sensing performances

of pristine and hybrid NiOZnO and PdOZnO structures were
investigated in the resistive mode in the concentration range
of 0.5700 ppm at dierent temperatures (100350 C). The
sensor response for three dierent sensors towards methanol,
ethanol and 2-propanol (100 ppm) was observed as a function
of temperature and is depicted in Fig. 6(ac). It is clear from
Fig. 6(ac) that the response magnitude towards methanol is
higher than that of other species for all the sensors. The
sensing characteristics of the developed sensors were further
investigated as a function of temperatures with dierent
methanol concentrations (Fig. 7(ac)). As apparent from Fig. 7
(ac), the optimum operating temperature for methanol
sensing was the lowest in the case of the PdOZnO NF hybrid
structure (150 C), compared to that of the NiOZnO NF

According to the KrgerVinks notation12 for the defects,

NiZn/PdZn is the Ni or Pd ion in the Zn lattice site, Oox is
an oxygen ion in its regular site and Vo =Vo =Vo are the
oxygen vacancies with zero, one and two positive charge(s),
respectively.
In order to quantitatively substantiate the composition,
oxygen vacancy related defect states and oxidation states of the
metals (i.e. Pd and Ni) for the developed pristine and hybrid
ZnO NF structures, X-ray Photoelectron Spectroscopy (XPS) was
employed and the results are depicted in Fig. 5(ad). High
resolution XPS spectra of Zn 2p (Fig. 5(a)) reveals a doublet
that consists of a dominant peak (at 1021.63 0.05 eV) for the
higher energy band (Zn 2p3/2) and a weaker peak (at 1044.75
0.05 eV) for the low energy band (Zn 2p1/2). These peaks are
associated with the lattice Zn2+ in the ZnO wurtzite structure.36
The Gaussian deconvolution of O 1s spectra (Fig. 5(b)) shows
two dierent peaks at 529.7 0.1 eV and 531.45 0.1 eV,
where the lower binding energy (B.E.) peak represents oxygen
atoms in the ZnO lattice and the lower B.E. peak is attributed
to the chemisorbed oxygen on the surface of ZnO NFs.36 It is
also revealed from Fig. 5(b) that the amount of adsorbed
oxygen is higher in the case of PdO/ZnO NFs than that of its
pristine and NiO/ZnO counterparts. In the case of PdO/ZnO
NFs, Pd (3d5/2) XPS spectra (Fig. 5(c)) reveal that Pd is present
both in the oxide state (PdO, peak centred at 336.91 eV) and in
the metallic state (PdS, peak centred at 335.31 eV).23 On the
contrary, Ni (3d3/2) XPS spectra (Fig. 5(d)) of NiO/ZnO NFs validate the presence of metallic Ni ( peak at 852.41 eV) as well as
Ni+2 as oxides ( peak at 854.02 eV) and hydroxides ( peak at
855.89 eV).37 It is worth noting that in both the hybrid structures the amount of oxide states is higher than that of metallic
states. Therefore it can be concluded that the structures are
predominantly PdOZnO and NiOZnO, and not PdZnO and
NiZnO.

Analyst

3.2 Gas sensing performance of pristine ZnO NF and

NiO/PdOZnO NF hybrid structures

Fig. 6 The response magnitude (%) variations as a function of temperatures for (a) pristine ZnO NF, (b) NiOZnO NF, (c) PdOZnO NF structures at 700 ppm methanol, ethanol and 2-propanol concentration.

Fig. 7 The response magnitude (%) as a function of temperatures for

pristine ZnO NFs and NiO/PdOZnO NFs in (a) 1 ppm, (b) 100 ppm and
(c) 700 ppm methanol concentrations.

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Analyst

hybrid structure (220 C) and the pristine ZnO NF structure

(300 C). In the case of hybrid sensors, initially the sensor
response increased slowly with increase in the operating temperatures, and then gradually decreased with further increase in
temperature (after optimum temperature). On the other hand,
in the case of the pristine one, the response magnitude gradually increased up to optimum temperature with a saturation
tendency thereafter. The decreasing trend of optimum temperature towards the metal oxide nanoparticle incorporated
hybrid structures can be elucidated as: catalytic metal nanoparticles enhance the concentration of adsorbed oxygen ions
on the ZnO surface which in turn reduce the required activation energy for the chemical reactions in vapor sensing.
As the response magnitude of the PdOZnO based sensor is
higher than that of the others, transient response was investigated for this sensor (towards 0.5700 ppm concentrations of
methanol, ethanol and 2-propanol at the optimum temperature) and is presented in Fig. 8. It is also evident from Fig. 8
that the PdOZnO NF hybrid structure oers the highest
response towards methanol for all the concentrations and the
response magnitude (%) increases significantly with increasing concentrations of methanol, ethanol and 2-propanol. In
addition, as evident from the sensor characteristics, the PdO
ZnO NF based sensor oered 61.19/99.57%, 12.15/49.83%, and
11.28/44.87% response magnitude at 0.5/700 ppm concentration towards methanol, ethanol and 2-propanol, respectively. It is worth noting that the dierence in response
magnitude between methanol and the nearest interfering
neighbour (i.e. ethanol) remains almost constant (50%) for
all the concentrations (0.5700 ppm) establishing a promising
improvement with respect to selectivity.
The response times and recovery times for the PdOZnO NF
hybrid structure are shown in Fig. 9(a) (towards methanol,
ethanol and 2-propanol with a concentration range of
0.5700 ppm). The response time shows a decreasing nature

Fig. 8 Transient response characteristics (response magnitude (%) as a

function of time) of the PdOZnO NF hybrid structure towards methanol, ethanol and 2-propanol in the concentration range of 0.5700 ppm
at 150 C.

This journal is The Royal Society of Chemistry 2016

Paper

with increase in concentrations for three target vapors (methanol, ethanol and 2-propanol). This phenomenon is in good
agreement with the Freundlich law of gas diusion-reaction
on the semiconducting surface (i.e. diusion and reaction
process increase with the increase in gas/vapor concentration
on the sensing surface).
In contrast, in the case of methanol, the recovery time
almost saturated at lower concentrations (0.5200 ppm), while
after 400 ppm the recovery time decreases and oers the
lowest value at 700 ppm (18 s). On the other hand, in the presence of ethanol and 2-propanol, the recovery time increases
with increase in vapor concentrations. Such nature of recovery
time (rec) may be attributed to the dierent diusion coecient (D) values (as D (rec)1) of dierent VOCs (viz.
methanol: 14 106 m2 s1 ethanol: 11 106 m2 s1 and
2-propanol: 12 106 m2 s1).38
The response time and recovery time for pristine ZnO NFs
and (NiO/PdO)ZnO NFs are compared and depicted in
Fig. 9(b). It is revealed from Fig. 9(b) that the hybrid sensors
oer a faster response than that of the pristine one which is
attributed to the enhanced electron transfer eciency between
the target molecules and the sensing surface due to a larger
number of basic sites (metal cations i.e. Pd2+ or Ni2+) and
oxygen ion species (O and O2) on the ZnO NF surface. On
the contrary, a sluggish recovery characteristic of the hybrid
sensors is possibly due to the eect of in-diusion of oxygen
in air onto the surface, which eventually causes the slow oxidation of metal/metal ions (e.g. metal ions Ni2+ can be oxidized into Ni3+ and Ni can be oxidized into NiO).37 In
addition, it can be envisaged from Fig. 9(c) and (d) that the
PdOZnO NF hybrid structure oered a faster response and
recovery towards methanol than that of ethanol and 2-propanol. To investigate the sensitivity and selectivity improvement
towards methanol, response magnitudes (%) as a function of
dierent VOC (methanol, ethanol, 2-propanol, acetone, xylene,
benzene and toluene) concentrations (0.5700 ppm) are
plotted in Fig. 10(ac). It is evident from the radial beam plot
(Fig. 10(d)) that in the case of the PdOZnO NF hybrid structure, methanol oered 50% higher response magnitude (%)
compared to its immediate neighbour (ethanol) for all the concentrations. On the other hand, the NiOZnO NF based sensor
exhibits a lower selectivity window (1530%) for methanol
(Fig. 10(d)), than that of the PdOZnO system. However, for
pristine ZnO, this window is extremely small (only 10%
response magnitude dierence) and the sensor severely suers
from a cross sensitivity problem. Such selectivity enhancement
can be correlated with the presence of a hetero-junction
(between NiOZnO and PdOZnO) as well as a relatively lower
CH bond breaking energy of ethanol (than ethanol, 2-propanol and acetone) on PdO than NiO, which has been elaborately
discussed in the next section.
Table 1 represents a comparative performance study of the
PdO/ZnO NF based hybrid sensor ( present work) with the
results obtained from the earlier literature, based on dierent
nanostructured metal oxide based sensors for methanol detection. It is clearly evident from Table 1 that the methanol

Analyst

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Paper

Analyst

Fig. 9 (a) Response time and recovery time as a function of dierent methanol concentrations (0.5700 ppm) for the PdOZnO NF based sensor at
its optimum operating temperature. (b) Bar diagram of response time and recovery time for pristine, NiOZnO NF and PdOZnO NF hybrid structures towards dierent methanol concentrations (c and d) magnied dynamic response characteristics of the PdOZnO NF hybrid structure for
700 ppm methanol at 150 C.

Fig. 10 Bar diagram plot for selectivity study of (a) pristine ZnO, (b) NiOZnO and (c) PdOZnO NFs at their respective optimum temperatures.
(d) Radial beam plot for response magnitude of three dierent sensors towards various methanol concentrations (Sw represents the selectivity
window).

Analyst

This journal is The Royal Society of Chemistry 2016

View Article Online

This journal is The Royal Society of Chemistry 2016

Sensitivity dierence between methanol and its nearest interfering tested species. b All the response times/recovery times have been calculated as the time taken to reach/fall 90% of the
saturation value.
a

125 s
50 s
40 s
50 s
200 s
360 s
3955 s
21.4 s
60 s
110 s

52.2 s
200 s
80 s
20 s
40 s
1 s
120 s
819 s
17.7 s
35 s
40 s

18 s

2@5 ppm with ethanol

12@1 ppm with ethanol
2.51@210 ppm with ethanol
10@350 ppm with ethanol

38@200 ppm with formaldehyde

8@500 ppm with NH3

50@all concentrations (0.5700 ppm)
with ethanol
275 C
250300 C
350 C
130 C
120 C
25 C
150 C
100 C
230 C
200 C
350 C
150 C
Al-doped ZnO nanoparticle
CNTSnO2 nanocomposite
SnO2ZnO composite nanofibers
Molecularly imprinted AgLaFeO3
Nano-structured conducting polypyrrole
TiO2 disperse in poly(vinylidene fluoride)
Pd loaded ZnO nanorods
p-TiO2 nanoparticle
Nanocrystalline La0.8Pb0.2FeO3 perovskite
CdS-doped SnO2 thick film
Needle-shaped SnO2 nanorods
PdO/ZnO hybrid structure

100500 ppm
1001000 ppm
1500 ppm
0.25 ppm
0.6117.62%, mass/mass
150350 ppm
1901530 ppm
5100 ppm
201000 ppm
5000 ppm
10100 ppm
0.5700 ppm

R/Ra 100 = 44@500 ppm

Ra/Rg = 2@100 ppm
Ra/Rg = 4.5@5 ppm
Ra/Rg = 41@1 ppm
R/Ra 100 = 3@10 mL min1
R/Ra 100 = 23.5@350 ppm
R/Ra 100 = 90@950 ppm
R/Ra 100 = 102@100 ppm
Ra/Rg = 42@200 ppm
R/Ra 100 70%
I/Ia = 9 @ 30 ppm
R/Ra 100 = 99.57 @ 700 ppm

Recovery
timeb
Response
timeb
Selectivitya
Sensitivity
Optimum
temperature Detection range
Nanostructure

Comparison of methanol sensitivity and selectivity of the developed sensor ( present work) with the earlier reports
Table 1

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

8
12
13
14
15
16
17
18
19
20
21
Present
work

Paper

Ref.

Analyst

selectivity of the hybrid sensor reported in this paper is better

than the earlier reports. Moreover, in the present endeavour, a
constant selectivity window (sensitivity dierence between
methanol and nearest interfering species (i.e. ethanol)) of 50%
throughout the methanol detection range (0.5700 ppm), was
achieved which in turn improves the reliability of the sensor.

4.

Sensing mechanism

According to the gas/vapor adsorptiondesorption kinetics, the

sensitivity and selectivity of the sensor depend on the surface
properties of the sensor material as well as on the nature of
the target species. Moreover, overall influence of the gas on
the barrier height (at junction) and the dehydrogenation (or
dehydration) capability of the catalytic metal additive pivotally
determine the resultant sensitivity. On the other hand, the
relative CX (XvO, H, and C) bond breaking energy as well as
molecular size of the adsorbed species are the key determining
factors for selectivity.39,40
The hybrid structure comprising ZnO NFs and metal oxide
nanoparticles oers several advantages viz. (i) the metal oxide
nanoparticle and nanoflower based hybrid structures significantly increase active sites for the gas/vapor adsorption on the
surface, (ii) enhance the number of basic sites (metal cations
i.e. Pd2+ or Ni2+) for methanol adsorption and promote the
methanol oxidation/dissociation activity, (iii) an ecient
charge separation (or generation of built in potential) due to
the formation of a heterojunction (between pNiO/pPdOnZnO)
increases the transfer eciency of the interfacial charge to the
adsorbed oxygen and (iv) a higher concentration of charge carriers in the depletion region increases the lifetime of the
charge carriers.13,40,41
In the presence of air, atmospheric oxygen, gets adsorbed
as oxygen ions (O, O2 and O2) after capturing electron(s)
from the ZnO surface.17 These ionized oxygen species penetrate into the ZnO lattice (after occupying the oxygen vacancy
site) and consequently reduce the conductivity of the device.
In this context, the formation of the metal oxideZnO NF
hybrid facilitates the dissociation of oxygen on the dispersed
metal or metal oxide particles (on ZnO NF surface) and transfers the active oxygen species onto the ZnO NF surface through
spill overprocess.42 On the contrary, when methanol comes
into contact with the sensing surface, it reacts with these
enhanced number of adsorbed oxygen ions and consequently
increases the electron concentrations in the CB of ZnO.43 This
process mainly forms CO2 and H2O by the CH and CO scissions of methanol, respectively and consequently decrease the
device resistance. The reaction between methanol and the
adsorbed oxygen ion on the metal modified surface is represented schematically in Fig. 11. As revealed from the XPS
study, incorporation of metal oxide nanoparticles into the ZnO
NF matrix forms (i) a pn heterojunction [between p-type NiO/
PdO and n-type ZnO] and (ii) a metalsemiconductor junction
(between Ni/Pd and ZnO). Such a pn heterojunction and
metalsemiconductor junction synergistically determine the

Analyst

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Paper

Analyst

Fig. 11 A schematic, depicting methanol sensing reaction on the NiO/

PdOZnO NF hybrid structure.

resultant sensitivity of the devices.38 In the present study,

underlying mechanism of the sensitivity improvement has
been established on the basis of two dierent junction models
(i.e. (i) and (ii), mentioned above). It is imperative to mention
here that p-type conductivity of NiO (Eg = 3.7 eV) and PdO (Eg =
1.1 eV) is well established.19 Thus, a heterojunction is formed
when the surface of n-type ZnO (Eg = 3.4 eV) was modified by
either NiO or PdO. This heterojunction oers (i) higher carrier
concentrations at the depletion region, (ii) increases the
carrier life time and (iii) introduces a built in potential at the
junction.42
In this context, it is logical to conjecture that the improved
sensitivity and relatively low temperature sensing of the PdO
ZnO NF hybrid structure (than that of the NiOZnO NF structure) is due to the higher eective change in built in potential
(qVbi) at the PdOZnO junction. The energy band diagrams for
corresponding heterojunctions are also shown in Fig. 12.
Now, the sensor resistance in terms of qVbi and temperature
can be represented as:18
Rair=methanol R0 exp



qVbiair=methanol
kT

where R0 is the flat band resistance, qVbi(air/methanol) is the built

in potential at the junction in the presence of air/methanol, k
is the Boltzmann constant and T is the temperature in Kelvin.
Therefore, the response magnitude (RM) of methanol exposure
can be expressed as:

RM

Ra  Rg

Ra

exp



qVbiairmethanol
kT


qVbiair
exp
kT

where qVbi(airmethanol) is the resultant change in built in

potential due to methanol exposure. As revealed from Fig. 12
the qVbi(PdOZnO) is greater than that of qVbi(NiOZnO) (i.e.
qVbi(PdOZnO) > qVbi(NiOZnO)). Therefore, the relative change in
built in potential (qVbi(airmethanol)) in the presence of methanol vapour is higher in the case of the PdOZnO heterojunction. Thus, the response magnitude (according to eqn (4)) is

Analyst

also higher for the PdOZnO NF hybrid structure than that of

the NiOZnO NF system.
To investigate the role of a metalsemiconductor junction
on the sensitivity, the band bending near the semiconductor
surface is considered and correlated with the free carrier concentration on the surface. The gas/vapor sensitivity of the
semiconducting oxide is predominantly governed by the free
carrier concentration on its surface and it is also directly proportional to that of the trapped charge density on the semiconducting surface. The origins of these trap charges are;
(i) the presence of surface defects (i.e. oxygen vacancy) and
(ii) adsorbed oxygen ions (due to electron transfer from the semiconducting surface to atmospheric oxygen). These trap charges
increase the density of the surface charge which in turn forms
a depletion layer just below the surface region.41,43 In the presence of reducing gas, the eective change in surface potential
energy barrier (qVs) can be represented as,
qVs

q2 Nd 2
w
0 r

where q is the electronic charge, Nd is the donor concentration

and W is the depth of the depletion region.
Therefore, according to eqn (5), the surface band bending
qV(x) is directly proportional to the Nd, keeping other parameters constant. It is well established that in the presence of a
reducing gas a downward band bending occurs. Thus, eective
change in band bending is proportional to the sensitivity of
the corresponding sensor. The device resistance at air and its
change due to the presence of reducing environment could
explain this phenomenon more clearly (corresponding energy
band diagram is shown in Fig. 13). Hence, the response magnitude (RM) of the device can be represented as,18
RM



Rair  Rmethanol
qVs
1  exp
Rair
kT

According to eqn (5) and (6), as Nd qVs, therefore,

RM Nd. It is worth mentioning that the oxygen vacancy is
considered to be an intrinsic donor inside the ZnO NFs.36 It is
revealed from the PL study that the oxygen vacancy concentrations on the PdOZnO surface is relatively higher than that
of the pristine and NiOZnO hybrid structures. Thus, the
higher amount of oxygen vacancies on the PdOZnO surface,
inevitably increase the donor concentrations on its surface.
Therefore, in the presence of reducing vapors like methanol,
downward band bending of the PdOZnO hybrid structure is
also higher than that of the NiOZnO NF structure which is in
good agreement with the higher response magnitude of the
PdOZnO hybrid structure (compared to the NiOZnO system)
obtained in the experiments.
Usually, alcohol molecules react with the adsorbed oxygen
ions(O, O2 and O2)attached on the ZnO surface and subsequently form CO2 and H2O through the dehydrogenation
(CO bond scission) and dehydration (CH bond scission)
reactions.18 In this context, the metal ion additives on the
semiconductor surface act as a catalytic centre by enhancing

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Analyst

Paper

Fig. 12

Energy band diagram for NiOZnO and PdOZnO heterojunctions.

Fig. 13

Energy band diagram for (a) NiZnO and (b) PdZnO junctions.

the probability of dehydrogenation and dehydration of alcohol

molecules.44 Therefore, such dehydrogenation and dehydration capability of such metal ions eventually determine the
sensitivity and more importantly, selectivity of the sensor.
Moreover, such reaction capability of metal additives depends
on the metaloxygen bonding energy and electro-negativity of
that metal cations (Pd2+/Ni2+).10 More precisely, lower energy
for the isolation of the oxygen from an oxide (i.e. NiO or PdO)
and higher electro-negativity of metal (i.e. Ni or Pd) result in
higher possibility for complete oxidation of alcohols on the
oxide surface. It is revealed from the earlier reports44 that the
PdO has a lower metaloxygen binding energy (22 2 kJ mol1)
than that of the NiO (86.5 5 kcal mol1). Electro-negativity
of Pd (2.2 eV) is also higher than that of Ni (1.91 eV).10 As
a result, the PdO modified ZnO surface eventually oers a

This journal is The Royal Society of Chemistry 2016

greater dehydrogenation and dehydration ability towards alcohols (as it contains the hydroxyl group) than that of the NiO
modified and pristine ZnO NF surface.
The decomposition process of alcohol contains various
types of chemical bond breaking (viz. CH, CO, OH and
CC). Although, during the decomposition process of alcohol,
dierent intermediates of CH and CO bond scissions have
lower activation energy than that of the other bond scission
(i.e. CC).44 In the presence of metal nano-particles, the bond
strength of CH or CO is greatly influenced (or reduced) compared to its pristine counterpart.45 CH bond breaking of
alcohol is favourable on the Pd (111) and Ni (111) surface
because of the lower adsorption energy of ethoxy intermediates
than that of the intermediates corresponding to the other
bond breaking.46 The corresponding equation for the CH

Analyst

View Article Online

Paper

Analyst

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

bond breaking of methanol, ethanol and 2-propanol are

shown in eqn (7)(10). Dehydrogenation or CH bond breaking
of methanol, ethanol and 2-propanol are as follows:

CH3 OH ! CH2 OH ! CH2 O ! HCO ! CO

CH3 CH2 OH ! CH3 CH2 O ! CH2 CH2 O ! CH2 CHO

! CH2 CO ! CHCO ! CH CO ! CO C

CH3 CH3 OH ! CH3 CH3 O ! CH3 CH2 O ! CH2 CH2 O

! CH2 C ! CH2 CO ! CHCO ! CH CO ! CO C

10

In addition, the delocalized density of states (DOS) around

the Fermi level, which can accept/donate electrons and act as
an electron reservoir in the dehydration reaction, can be considered as an indicator of the reaction capability of Pd and
Ni.47 According to this study, Pd (111) has better dehydration
probability than that of Ni (111) for its high DOS distribution
near the Fermi level.47 This is also in good agreement with the
better sensing capability of the PdO modified ZnO NFs than
that of the NiO modified ones. The CH bond breaking energy
of alcohol was found to be in the order: 2-propanol > ethanol >
methanol.48 These characteristics reflect that methanol has a
higher probability of adsorption on the PdOZnO NF surface
than that of others.
According to the rate constant of the dehydrogenation and
dehydration process of alcohols on the semiconducting
surface, the adsorption and desorption rates follow the order:
methanol > ethanol > 2-propanol. This is owing to the larger
molecular size of ethanol and 2-propanol compared to that of
the methanol.49 Consequently, the activation energy for
adsorption of ethanol (60 10 kJ mol1) is much higher than
that of methanol (33 10 kJ mol1).49 Therefore, it can be concluded that due to the lower molecular size and lower adsorption energy of methanol, more number of such molecules can
interact ( per unit area of sensor surface) which eventually
increase its selectivity.

5. Conclusions
Methanol sensitivity and selectivity improvement by tuning
the surface properties of ZnO NFs using metal oxide nanoparticles has been investigated. Three devices with pristine
ZnO NF, NiOZnO NF and PdOZnO NF hybrid structures were
investigated for methanol, ethanol and 2-propanol sensing.
The PdOZnO hybrid structure was found to oer better
selectivity towards methanol than that of its NiOZnO and
pristine counterparts even at lower temperature (150 C). Moreover, the selectivity window (50% with the nearest neighbour
i.e. ethanol) was found to be persistent for all the concentrations (0.5700 ppm) under test conditions. This improve-

Analyst

ment in selectivity in the case of the PdOZnO hybrid sensor

may be attributed to: (i) a better pn heterojunction (higher
built-in voltage) and a metalsemiconductor junction (higher
band bending near the surface) formation between PdO and
ZnO, (ii) selective bond scission (CH bond) with lower
decomposition energy on the PdO surface and (iii) lesser
molecular size and lower activation energies for adsorption
of methanol.

Acknowledgements
This work was supported by Indian National Science Academy
(INSA) (no. SP/YSP/81/2013/735 and Intl/DFG/2014/1560 Dt:
16/12/2014), Deutsche Forschungsgemeinschaft (DFG) (no. GZ:
FE 313/16-1: AOBJ: 614734 Dt: 11/09/2014) and DST-NM, India
(no. SR/NM/NS-1385/2014(G)). Debanjan Acharyya thankfully
acknowledges CSIR, Gov. of India, for his fellowship for pursuing a PhD program.

References
1 H. Singh, V. B. Raj, J. Kumar, U. Mittal, M. Mishra,
A. T. Nimala, M. U. Sharma and V. Gupta, Sens. Actuators,
B, 2014, 200, 147156.
2 D. J. Guo and J. M. You, J. Power Sources, 2012, 198, 127
131.
3 M. Kang, J. F. D. Wild and A. Bhan, Sens, Actuators, B, 2003,
89, 269284.
4 G. Neri, A. Bonavita, G. Rizzo, S. Galvagno, S. Capone and
P. Siciliano, Sen. Actuators, B, 2006, 114, 687695.
5 H. Amandusson, L. G. Ekedah and H. Dannetun, Surf. Sci.,
1999, 442, 199205.
6 Z. Darmastuti, P. Bhattacharyya, M. Andersson, J. Kanungo,
S. Basu, P. O. Kll, L. Ojame and A. L. Spetz, Sens.
Actuators, B, 2013, 187, 553562.
7 M. Penza and G. Cassano, Sens. Actuators, B, 2003, 89, 269
284.
8 P. P. Sahay and R. K. Nath, Sen. Actuators, B, 2008, 134,
654659.
9 M. M. Rahman, S. B. Khan, A. Jamal, M. Faisal and
A. M. Asiri, Talanta, 2012, 95, 1824.
10 K. Lee, J. W. Lee, S.-I. Kim and B. K. Ju, Carbon, 2011, 49,
787792.
11 J. Zhao, C. Xie, L. Yang, S. Zhang, G. Zhang and Z. Cai,
Appl. Surf. Sci., 2015, 330, 126133.
12 C. Wongchoosuk, A. Wisitsoraat, A. Tuantranont and
T. Kerdcharoen, Sens. Actuators, B, 2010, 147, 392399.
13 W. Tang, J. Wanga, P. Yao and X. Li, Sens. Actuators, B,
2014, 192, 543549.
14 Q. Zhu, Y. M. Zhang, J. Zhang, Z. Q. Zhu and Q. J. Liu,
Sens. Actuators, B, 2015, 207, 398403.
15 M. Babaei and N. Alizadeh, Sens. Actuators, B, 2013, 183,
617626.

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 18 March 2016. Downloaded by Bengal Engineering and Science University on 08/04/2016 04:40:22.

Analyst

16 M. Mabrook and P. Hawkins, Sens. Actuators, B, 2001, 75,

197202.
17 N. Banerjee, S. Roy, C. K. Sarkar and P. Bhattacharyya, IEEE
Sens., 2013, 13, 16691676.
18 A. Hazra, B. Bhowmik, K. Dutta, V. Manjuladevi,
R. K. Gupta and P. Bhattacharyya, IEEE Trans. Nanotechnol.,
2015, 14, 187195.
19 C. Doroftei, P. D. Popa and F. Iacomi, Sens. Actuators, B,
2012, 161, 977981.
20 L. Yadava, R. Verma and R. Dwivedi, Sens. Actuators, B,
2010, 144, 3742.
21 A. Forleo, L. Francioso, S. Capone, F. Casino, P. Siciliano,
O. K. Tan and H. Hui, Sens, Actuators, B, 2011, 154, 283
287.
22 D. Acharyya and P. Bhattacharyya, Solid-State Electron.,
2015, 106, 1826.
23 Y. J. Chiang and F. M. Pan, J. Phys. Chem. C, 2013, 117,
1559315601.
24 A. F. Kohan, G. Ceder, D. Morgan and C. G. Walle, Physical
Review B: Condens. Matter, 2000, 61, 60.
25 B. Guo, Z. R. Qiu and K. S. Wong, Appl. Phys. Lett., 2003,
14, 2290.
26 D. C. Reynolds, D. C. Look, B. Jogai and H. Morkoc, Solid
State Commun., 1997, 9, 643646.
27 F. K. Shan, G. X. Liu, W. J. Lee, G. H. Lee, I. S. Kim and
B. C. Shin, Appl. Phys. Lett., 2005, 86, 221910.
28 D. M. Hofmann, D. Pfisterer, J. Sann, B. K. Meyer,
R. Tena-Zaera, V. Munoz-Sanjose, T. Frank and
G. Pensl, Appl. Phys. A: Mater. Sci. Process, 2005, 88, 147
151.
29 F. H. Leiter, H. R. Alves, N. G. Romanov, D. M. Hofmann
and B. K. Meyer, Physica B, 2003, 340, 201204.
30 N. O. Korsunska, L. V. Borkovska, B. M. Bulakh,
L. Yu. Khomenkova, V. I. Kushnirenko and I. V. Markevich,
J. Lumin., 2003, 733, 102103.
31 B. Lin and Z. Fu, Appl. Phys. Lett., 2001, 79, 943.

This journal is The Royal Society of Chemistry 2016

Paper

32 . zgr, Ya. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov,

S. Doan, V. Avrutin, S.-J. Cho and H. Morko, J. Appl.
Phys., 2005, 98, 041301.
33 A. B. Djurii, Y. H. Leung, K. H. Tam, L. Ding, W. K. Ge,
H. Y. Chen and S. Gwo, Appl. Phys. Lett., 2006, 88, 103107.
34 R. Dingle, Phys. Rev. Lett., 1969, 23, 579.
35 C. X. Xu, X. W. Sun, X. H. Zhang, L. Ke and S. J. Chua,
Nanotechnology, 2004, 15, 856861.
36 O. Game, U. Singh, A. A. Gupta, A. Suryawanshi,
A. Banpurkar and S. Ogale, J. Mater. Chem., 2012, 22,
17302.
37 A. Dutta and J. Datta, J. Mater. Chem. A, 2014, 2, 3237.
38 N. Matsunaga, G. Sakai, K. Shimanoe and N. Yamazoe,
Sens. Actuators, B, 2002, 83, 216221.
39 A. N. Mallya and P. C. Ramamurthy, Analyst, 2014, 139,
64566466.
40 S. C. Hernandez, C. M. Hangarter, A. Mulchandani and
N. V. Myung, Analyst, 2012, 137, 25492552.
41 T. Hyodo, T. Yamashita and Y. Shimizu, Sens. Actuators, B,
2015, 207, 105116.
42 G. J. Cadena, J. Riu and F. X. Rius, Analyst, 2007, 132,
10831099.
43 P. Rai, R. Khan, S. Raj, S. M. Majhi, K. K. Park, Y. T. Yu,
I. H. Lee and P. K. Sekhar, Nanoscale, 2014, 6, 581588.
44 S. P. Walch and W. A. Goddard III, J. Am. Chem. Soc., 1978,
100(5), 13381348.
45 J. Greeley and M. Mavrikakis, J. Am. Chem. Soc., 2004, 126,
39103919.
46 M. Kang, J. F. D. Wild and A. Bhan, Sens. Actuators, B, 2003,
89, 269284.
47 J. H. Wang, C. S. Lee and M. C. Lin, J. Phys. Chem. C, 2009,
113, 66816688.
48 M. Orzol, I. Martin, J. Kocisek, I. Dabkowsk, J. Langer and
E. Illenberger, Phys. Chem. Chem. Phys., 2007, 9, 34243431.
49 A. J. Fletcher, E. J. Cussen, D. Bradshaw, M. J. Rosseinsky
and K. M. Thomas, J. Am. Chem. Soc., 2004, 126, 97509759.

Analyst