Sensors and Actuators B 214 (2015) 8291

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Sensors and Actuators B: Chemical

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

Development of selective and sensitive bicarbonate chemical sensor

based on wet-chemically prepared CuO-ZnO nanorods
Mohammed M. Rahman , Abdullah M. Asiri
Chemistry Department and Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, P.O. Box 80203,
Jeddah 21589, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 2 August 2014
Received in revised form 23 February 2015
Accepted 26 February 2015
Available online 9 March 2015
Keywords:
CuO doped ZnO nanorods
Bicarbonate sensors
Wet-chemical method
Sensitivity
IV technique
Real water samples

a b s t r a c t
We have prepared calcined copper oxide doped zinc oxide nanorods (CuO-ZnO NRs) by a facile wetchemical method using reducing agents in alkaline medium. The doped NRs were totally characterized
by UV/vis, FT-IR, X-ray photoelectron, energy-dispersive X-ray spectroscopy, X-ray powder diffraction,
and eld-emission scanning electron microscopy. The NRs were deposited on at silver electrode (AgE)
to result in a sensor that has a fast response to selective bicarbonate in buffer system. Features including
high sensitivity, lower-detection limit, reliability, reproducibility, ease of integration, long-term stability,
selective, and enhanced electrochemical performances were investigated in detail. The calibration plot is
linear (r2 = 0.99) over the large concentration range (1.0 nM to 1.0 mM). The sensitivity and detection limit
are calculated as 1.667 A cm2 M2 and 0.89 0.02 nM (at a signal-to-noise-ratio, SNR of 3) respectively. Finally, the efciency of the proposed chemi-sensors can be applied and effectively utilized for the
detection of bicarbonate in various environmental real water samples with acceptable and reasonable
results.
2015 Elsevier B.V. All rights reserved.

1. Introduction
A chemical sensor is a sensor that produces an electric signal proportional to the concentration of chemical or biochemical
analytes. These chemi-sensors use chemical as well as physical
principles in their operation. The sensor signal is signicantly
enhanced in the presence of nanomaterials or functional materials whether doped or undoped fabricated onto the sensor surfaces
in chemical or biological systems. Doped nanomaterials have
attracted a wide interest due to their unique properties and
potential application in chemi-sensor fabrication [1,2]. Semiconductor material has been also recognized as a promising host
nano-material for transition metal oxides at room conditions. It is
revealed a stable morphological structure and composed of a number of irregular phases with geometrically coordinated metals and
oxide atoms, piled alternately along the three dimensional axes [3].
Transition metals codoped in semiconductor nano-materials have

Corresponding author at: Center of Excellence for Advanced Materials Research

and Chemistry Department, Faculty of Science, King Abdulaziz University,
P.O. Box 80203, Jeddah 21589, Saudi Arabia. Tel.: +966 59 6421830;
fax: +966 026952292.
E-mail addresses: mmrahman@kau.edu.sa, mmrahmanh@gmail.com
(M.M. Rahman).
http://dx.doi.org/10.1016/j.snb.2015.02.113
0925-4005/ 2015 Elsevier B.V. All rights reserved.

concerned insightful research effort for its exceptional and outstanding optical, structural, electrical, photocatalytic properties,
and versatile applications [4]. Last decade, an extensive development has been executed on the research leading of transition
metal oxides incorporated ZnO materials actuated by both fundamental sciences and prospective advanced technologies [57].
The doped semiconductor nanostructures exhibit promising uses
as eld consequence transistors [8], UV photo-detectors [9,10],
gas sensors [11], eld emission electron sources [12], nanomaterials [13,14], nanoscale power generators [15], and many other
functional devices [16]. Transition metal doped nanostructure is
also an effective method to regulate the energy level in surface
states of ZnO, which can further progress by the changes in doping
concentrations of host-guest materials. Chemical sensing expedition has been utilized with the metal oxide nanostructures for the
detection of various chemicals such as ethanol, phenyl hydrazine,
methanol, hydrazine, chloroform, dichloromethane, acetone, and
ethanol which are not environmental friendly. The sensing mechanism with doped metal oxides thin lms utilized mainly the
properties of porous lm formed by the physi-sorption and chemisorptions methods. The chemical detection is based on the current
changes of the fabrication thin lms caused by the chemical components of the reacting system in aqueous medium [1720]. The
main effort is focused on detecting the minimum quantity aqueous

M.M. Rahman, A.M. Asiri / Sensors and Actuators B 214 (2015) 8291

chemical necessary for the fabrication doped sensors for electrochemical investigation. Nanomaterials offer many opportunities of
tuning the chemical sensing properties.
In physiological systems, carbon dioxide is obviously linked with
bicarbonate (HCO3 ) via carbonic anhydrases, and numerous biological processes are dependent upon a mechanism for sensing
the level of HCO3 or carbon dioxide, and/or pH. In human body,
the discovery that soluble adenylyl cyclase is directly regulated
by bicarbonate (HCO3 ) provided a link between HCO3 /CO2 /pH
chemi-sensing and signalling through the widely used second messenger cyclic adenosine monophosphate. This review summarizes
the evidence that bicarbonate-regulated adenylyl cyclase, and additional, subsequently identied bicarbonate-regulate nucleotidyl
cyclases, function as evolutionarily conserved HCO3 /pH/CO2
chemi-sensors in a wide variety of physiological systems [21]. In
physiological system, carbon dioxide and water are the major end
products of energy producing pathways in living organisms according to Eq. (1). As such, in non-photosynthetic organisms, CO2 and
water represent the most fundamental catabolites.
Glucose (or other energy sources) + O2 CO2 + H2 O

CO2 + H2 O H2 CO3 HCO3 + H

(1)
(2)

In unicellular organisms, carbon dioxide gas can simply diffuse

away, but once multi-cellular organisms evolved, they had to devise
methods for safely dealing with carbon dioxide. In solution, CO2
combines with water to form carbonic acid (H2 CO3 ), which dissociates to liberate a proton and a bicarbonate ion (HCO3 ) (Eq. (2)).
Bicarbonate, carbon dioxide and pH equilibrate on their own within
minutes, but in biological systems, equilibrium is reached nearly
instantaneously due to the ubiquitous presence of carbonic anhydrases [22,23]. This equilibrium is used to buffer pH inside cells and
in intercellular uids; for example, intracellular pH is regulated via
interplay between carbon dioxide diffusion, and bicarbonate and
proton transporters and/or exchangers. In mammals, and terrestrial vertebrates in general, this equilibrium is tightly controlled
in two ways; the kidneys regulate the bicarbonate concentration
and the breathing frequency determines the concentration of carbon dioxide. Each of these processes requires a sensor i.e., an
exquisitely sensitive and rapid way to measure the precise concentration of bicarbonate and/or carbon-dioxide and/or pH and elicit
an appropriate response. Many other physiological processes, in
addition to diuresis and breathing rate regulation, are modulated
by bicarbonate and/or carbon dioxide and/or pH (i.e., sperm activation, blood ow, aqueous humour in the eye and cerebrospinal uid
formation), and they also require a HCO3 /carbon-dioxide/pH sensor. For many years, the effects of carbon dioxide and pH had been
ascribed to undened chemo-receptors, and the effects of bicarbonate were traditionally thought to be mediated by changes in
cellular pH. In 2000, researcher demonstrated that HCO3 directly
modulates the activity of soluble adenylyl cyclase, a novel form of
the enzyme generating the ubiquitous second messenger, cyclic
adenosine monophosphate [2426], revealing that physiological
HCO3 /carbon dioxide/pH could be sensed via second messenger signalling. In physiological systems, HCO3 , carbon dioxide,
and pH are intimately linked via carbonic anhydrases and a
variety of biological processes, in mammals and throughout evolution, depend upon a HCO3 /carbon-dioxide/pH chemosensor.
Bicarbonate-regulated adenylyl cyclase, which links intracellular
HCO3 , carbon-dioxide, and/or pH levels with cyclic adenosine
monophosphate signal transduction, serves as the HCO3 /carbondioxide/pH chemi-sensor in at least a subset of these processes.
The future will reveal whether other HCO3 /carbon-dioxide/pH
chemi-sensing functions are also mediated by adenylyl cyclase.
Bicarbonate regulation is observed in other mammalian nucleotidyl
cyclases and in adenylyl cyclases across evolution implying that

83

cyclic nucleotide signalling is an evolutionarily conserved mechanism for HCO3 /carbon-dioxide/pH chemi-sensing.
In the present study, it is employed the wet-chemical technique to prepare CuO doped ZnO semiconductor nanomaterials
with nearly controlled rod-shape structure, which revealed a continuous morphological advancement in nanostructure materials
and potential applications. With most of the existing works focused
on undoped ZnO, there have been more and more attention
dedicated to explore the doped counterparts. For semiconductor nanomaterials, doping is an inuential application to conform
the optical and electrical properties, expediting the development
of many electronic and opto-electronic devices. Semiconductor
nanostructures CuO-ZnO NRs allow very sensitive transduction of
the liquid/surface interactions into a change in the electrochemical properties. The possibility is to form a variety of structural
morphologies suggests various prospects of tuning the chemical
sensing properties. CuO-ZnO NR is fabricated by a simple and efcient chemical sensors consisting on a side-polished at silver
electrode surface; and measured the chemical sensing performance
of bicarbonate in phosphate buffer system at room conditions. To
best of our knowledge, this is the rst report for detection of bicarbonate with prepared CuO-ZnO NRs using simple and reliable IV
technique in short response time.
2. Experimental
2.1. Materials and methods
Zinc chloride, copper chloride, sodium bicarbonate, butyl
carbitol acetate, ethyl acetate, ammonia solution (25.0%), and
all other chemicals were in analytical grade and purchased
from Sigma-Aldrich Company (http://www.sigmaaldrich.com).
The max (366.0 nm) of calcined CuO-ZnO NRs was executed using UV/visible spectroscopy Lamda-950, Perkin Elmer,
Germany (http://www.perkinelmer.com). FT-IR spectra of CuOZnO NRs were performed on a spectrum-100 FT-IR spectrophotometer in the mid-IR range purchased from Bruker
(http://www.bruker.com). The XPS measurement of CuO-ZnO NRs
was measured on a Thermo Scientic K-Alpha KA1066 spectrometer (http://www.thermoscientic.com). A monochromatic Al K1
X-ray radiation source was used as excitation sources, where beamspot size was kept in 300.0 m. The spectra were recorded in the
xed analyzer transmission mode, where pass energy was kept at
200.0 eV. The scanning of the spectra was performed at pressures
less 108 Torr. Morphology, size, and structure of calcined CuO-ZnO
NRs were recorded on FESEM instrument from JEOL (JSM-7600F,
Japan; http://www.jeol.com/). The powder X-ray diffraction (XRD)
patterns of CuO-ZnO NRs were recorded by X-ray diffractometer from PANalytical diffractometer (http://www.panalytical.com)
equipped with Cu K1 radiation ( = 1.5406 nm) using a generator voltage of 45.0 kV and a generator current of 40.0 mA
were applied for the determination. Raman spectrometer was
used to measure the Raman shift of calcined CuO-ZnO NRs using
radiation source (Ar+ laser line, ; 513.4 nm), which was purchased from Perkin Elmer (Raman station 400, Perkin Elmer,
http://www.perkinelmer.com). IV technique is measured with
CuO-ZnO NRs fabricated at AgE by using Kethley-Electrometer
(http://www.keithley.com) from USA.
2.2. Synthesis and growth mechanism of CuO-ZnO NRs
CuO-ZnO NRs have been synthesized by adding uni-molar concentration of copper chloride and zinc chloride precursor into
chemical reactors for 6 h. Copper chloride and zinc chloride were
slowly dissolved separately into the de-ionized water to make

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M.M. Rahman, A.M. Asiri / Sensors and Actuators B 214 (2015) 8291

Scheme 1. Growth mechanism of wet-chemically prepared calcined CuO-ZnO nanorods. Calcinations temperature set in mufe-furnace was 450 C.

0.1 M concentration at room temperature. Then these equi-molar

solutions were mixed gently and stirred until mix properly. The
solution pH was slowly adjusted drop wise by diluted alkaline solution (25.0% ammonium hydroxide). Then the mixture was put into
conical ux (reactor cell) to put in the oven for linger time and
maintained the temperature. The starting materials of ZnCl2 , CuCl2 ,
and NH4 OH (reducing agent) were used without further purication for co-precipitation method to CuO into ZnO nanocrystals. The
NH4 OH was added drop wise into the vigorously stirred ZnCl2 and
CuCl2 solutions mixture to produce a white precipitate. The growth
mechanism of the nanomaterials could be explained on the basis of
chemical reactions and nucleation, as well as the development of
ZnO crystals. The apparent reaction mechanisms are proposed for
obtaining the doped metal oxides, which are presented below:
NH4 OH(aq) NH4 + (aq) + OH (aq)
ZnCl2(s) + 2OH

(aq)

(3)

Zn(OH)2(aq) + 2Cl

Zn(OH)2(aq) + 2NH4 OH(aq) ZnO2

(aq)

(4)

(aq)

+ 2NH4

(aq)

+ 2H2 O

(5)

CuCl2(aq) + 4NH4 OH(aq) + ZnO2 1 (aq) CuO-ZnO(s) + 4NH4 + (aq)

+ 2Cl (aq) + 2H2 O

Zn(OH)2(aq) + CuO(aq) CuO-ZnO(s) + H2 O

(6)

(7)

The reactant precursors of CuCl2 and ZnCl2 are soluble in alkaline medium (NH4 OH reagent) according to Eqs. (3)(5). After
addition of NH4 OH into the mixture of metal oxides solution, it
was stirred gently for few minutes at room temperature. Then the
solution pH is adjusted (10.0) using NH4 OH and put into reactors
to set into oven at 95.0 C for 6 h, where the active temperature of
the solution mixture is approximately in the range of 90.0 C. The
reaction is progressed slowly according to Eqs. (6) and (7). Then
the solution was washed thoroughly with ethanol, acetone, and
water and then kept for drying at room temperature. During the
total synthesis process, NH4 OH acts a pH buffer to regulate the pH
value of the solution and slow supply of OH-ions [27,28]. When
the concentration of the Zn2+ and OH ions is reached over the
critical value, the precipitation of ZnO nuclei becomes started. As
there is high concentration of Cu2+ ion in the solution, the nucleation of ZnO crystals become formed co-precipitation, owing to
the lower activation energy barrier of heterogeneous nucleation.
However, as the concentration of Cu2+ presences in the mixture
of solution, some larger ZnO crystals with a rod-like morphology developed among the nanostructures, which composed of CuO
doped ZnO nanomaterials. The shape of CuO doped ZnO rods is
approximately consistent with the growth habit of ZnO crystals
[29,30]. In doped nanorods growth mechanism, initially CuO and
ZnO nucleus growth takes place by self-aggregation, which then
re-aggregates and produced CuO-ZnO nanocrystal according to the

well-known Ostwald ripening method. Nano-material crystallizes

and re-aggregates with each other through Vander-Waals forces
and forms doped CuO-ZnO nanorods morphology, which is presented in Scheme 1. Finally, the as-grown CuO doped ZnO nanorods
were calcined at 450.0 C for 3 h in the furnace (Barnstead Thermolyne, 6000 Furnace, USA). The calcined products were totally
characterized in detail in terms of their morphological, elemental,
structural, optical properties, and applied for bicarbonate sensing
using reliable IV methods.
2.3. Fabrication and detection technique of bicarbonate
0.1 M phosphate buffer solution (PBS) at pH 7.0 is prepared by
mixing 0.2 M Na2 HPO4 and 0.2 M NaH2 PO4 solution in 100.0 mL
de-ionize water. Flat silver electrode is fabricated with calcined
CuO-ZnO NRs, where butyl carbitol acetate (BCA) and ethyl acetate
(EA) as a conducting coating agent. Then it is transferred into the
oven at 70.0 C for 4 h until the lm is completely uniform and dried.
An electrochemical cell is mounted with NRs coated at AgE as a
working electrode and Pd wire is used a counter electrode. As prepared sodium bicarbonate (NaHCO3 , stock solution 1.0 M) is diluted
at different concentrations in buffer solution and used as a target.
Amount of 0.1 M PBS was kept constant in the beaker as 10.0 mL
throughout the chemical investigation. Analyte solution is prepared
with various concentrations of aqueous sodium bicarbonate from
1.0 M to 1.0 nM. The sensitivity is calculated from the slope of current vs. concentration (I vs. C) from the calibration plot divided by
the value of active surface area of sensors/AgE electrodes. Electrometer is used as a voltage sources for IV technique in two electrode
system.
3. Results and discussion
3.1. Analysis of optical and structural properties
The calcined CuO-ZnO NRs is also characterized from the atomic
and molecular vibrations. To anticipate the actuated recognitions clearly, FT-IR spectra only in the region of 4004000 cm1
are employed. Fig. 1A represents the FT-IR spectrum of the calcined CuO-ZnO nanomaterials. It exhibits a band at 745 cm1 . This
observed vibration band may be assigned as metaloxygenmetal
(MOM) stretching vibration. The observed vibration bands at low
frequencies regions suggest the formation of metal-oxide bond in
doped nano-materials [31,32].
The optical absorption spectra of CuO-ZnO NRs are executed by
using UV-vis spectrophotometer in the visible range. The absorption spectrum of calcined doped NRs solution is presented in
Fig. 1B. It represents the absorption maxima at 366.0 nm in visible
range between 200.0 and 800.0 nm wavelengths, which indicated
the formation of CuO-ZnO NRs formation by wet-chemical route
[33,34]. Band gap energy is calculated on the basis of the maximum

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85

Fig. 1. (A) FT-IR spectroscopy, (B) UV/visible spectroscopy, and (C) powder X-ray diffraction pattern of calcined CuO-ZnO nanorods.

absorption band of CuO-ZnO NRs and obtained to be 3.3879 eV,

according to following equation:
Ebg =

1240
(eV)


(8)

where Ebg is the band-gap energy and max is the wavelength

(366.0 nm) of the NRs.
The CuO-ZnO NRs samples were analyzed and exhibited as
wurtzite structure with hexagonal shapes. The sample was calcined
at 450.0 C in mufe furnace to improve the crystallinity or formation of nanocrystalline phases. Fig. 1C shows typical crystallinity of
the calcined CuO-ZnO nanorods and their aggregation. The reection peaks were observed to match with CuO phase (Tenorite)
having base-centred monoclinic [JCPDS # 073-6234]. The phases
represented the major characteristic peaks (symbol, *) with indices
for calcined crystalline CuO at 2 values of (1 1 0), (1 1 1), (1 1 1),
(1 1 2), (2 0 2), (0 2 0), (2 0 2), (1 1 3), (1 1 3), (2 2 1), (2 2 2),
(1 1 4), and (3 1 2) degrees. The monoclinic lattice parameters
are a = 4.662, b = 3.417, c = 5.118, = 99.48, point group: C2/c, and
radiation: Cu K1 ( = 1.5406). These indicate that there is signicant amount of crystalline CuO present in nano-materials. All
the reection peaks in this pattern were found to match with ZnO
phase (zincite) having hexagonal geometry [JCPDF # 071-6424].
The phases showed the major characteristic peaks (symbol, #)
with indices for calcined crystalline ZnO at 2 values of (1 0 0),
(0 0 2), (1 0 1), (1 0 2), (1 0 3), (2 0 0), (2 0 1), and (2 0 3) indices. The
hexagonal (unit cell) lattice parameters are a = 3.2494, b = 5.2038,
point group: P63mc, and radiation: Cu K1 ( = 1.5406). These indicate that there is signicant amount of crystalline ZnO present in
nano-materials. The diffraction patterns of calcined samples can
be indexed to the hexagonal structure of ZnO. The other peaks corresponding to CuO related secondary phase was found in copper

oxide doped sample, which may be attributed to the incorporation

of CuO into the ZnO lattice site [35,36].
The crystalline size was also calculated and conrmed by using
the well-known Scherrer formula (9):
D=

0.9
cos q

(9)

where  is the wavelength of X-ray radiation, is the full width at

half maximum (FWHM) of the peaks at the diffracting angle . The
average diameter of CuO-ZnO NRs is close to 42.5 nm.
3.2. XPS analysis
Quantitative spectroscopic method (X-ray photoelectron spectroscopy, XPS) is studied in details to determine the elemental
analysis of doped CuO-ZnO NRs. XPS is a quantitative spectroscopic
method that determines the chemical-states of the elements that
present within doped materials. XPS spectra are acquired by irradiating on CuO-ZnO NRs with a beam of X-rays, while simultaneously
determining the kinetic energy and number of electrons that getaway from the top one to ten nm of the material being analyzed.
XPS was also used to resolve the chemical state of the CuO-ZnO
NRs and their depth of binding energy of each element with others.
Here, XPS measurements were measured for doped CuO-ZnO NRs
semiconductor nanomaterials to investigate the chemical states of
CuO and ZnO. The XPS spectra of Cu2p, Zn2p, and O1s are presented in Fig. 2A. The O1s spectrum shows a main peak at 528.5 eV
in Fig. 2B. The peak at 528.5 eV is assigned to lattice oxygen may be
indicated to oxygen (i.e., O2 ) presence in the doped CuO-ZnO NRs
[37]. In Fig. 2C, the spin orbit peaks of the Cu2p(3/2) and Cu2p(1/2)
binding energy for all the samples appeared at around 934.3 eV

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M.M. Rahman, A.M. Asiri / Sensors and Actuators B 214 (2015) 8291

Fig. 2. XPS of (A) doped CuO-ZnO NRs, (B) O1s level, (C) Cu2p level, and (D) Zn2p level acquired with Mg K1 radiation.

and 956.72 eV respectively, which is in good agreement with the

reference data for CuO [38]. In Fig. 2D, the spin orbit peaks of the
Zn2p(1/2) and Zn2p(3/2) binding energy for all the samples appeared
at around 1023.8 eV and 1049.2 eV respectively, which is in good
agreement with the reference data for ZnO [39,40]. XPS compositional analyses evidenced the co-existence of the two single-phase
of CuO and ZnO materials. Therefore, it is concluded that the wetchemical prepared CuO-ZnO materials have NRs phase contained
two materials. Also, this conclusion is reliable with the XRD data
noticeably.

3.3. Morphological analysis

FESEM images of CuO-ZnO NRs structures are presented in
Fig. 3AD. It exhibits the images of the rod-shapes with nanodimensional sizes of CuO-ZnO NRs. The dimension of NR is
calculated in the range of 35.060.0 nm, which composed of
nanorods (43.0 10.0 nm). It is clearly exposed from the FESEM
images that the facile wet-chemically synthesized CuO-ZnO is
nanostructures in rod-shape, which is grown in very high-density
and possessing almost uniform nanorods. When the size of doped

Fig. 3. (AD) Low to high magnied FESEM images of calcined CuO-ZnO NRs. Probe current: 7.0; beam: 15.0 KeV; mode: SEM; magnication: 14,000 to 170,000.

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87

Scheme 2. Schematic view of (A) and (B) uncoated and coated of AgE with NRs and
coating binders, (C) detection IV method (theoretical), and (D) proposed adsorption
mechanisms of bicarbonate detection in the presence of semiconductor CuO-ZnO
nanomaterials. Surface area of AgE: 0.0216 cm2 ; method: IV.

Fig. 4. Elemental analysis by XEDS of calcined doped CuO-ZnO nanorods.

material decreases into naonometer-sized scale, the surface area

increases signicantly, this improves the energy of the system,
making re-distribution of Zn and Cu ions possible. The nanometersized CuO-ZnO NRs could have tightly packed into the lattice, which
is an agreement with the publish reports [4143].
3.4. Elemental analysis
The X-ray electron dispersive spectroscopy (XEDS) analysis of
these CuO-ZnO NRs is indicated the presence of copper (Cu), zinc
(Zn), and oxygen (O) composition in the pure calcined doped
nanostructure material, which is presented in Fig. 4A. It is clearly
displayed that the calcined prepared nanomaterials contained only
Cu, Zn, and O elements with the 2.18, 73.52, 24.3 wt% respectively,
which is presented in Fig. 4B (inset). No other peak related with any
impurity has been detected in the XEDS, which conrms that the
nanoparticles are composed only with Cu, Zn, and O.
4. Chemical sensor application
4.1. Fabrication of bicarbonate sensor using CuO-ZnO NRs
The prospective application of CuO-ZnO NRs assembled onto at
AgE as chemical sensors (especially bicarbonate analyte) has been
executed for measuring and detecting target chemical. Enhancement of doping of this prepared CuO-ZnO NRs on AgE as chemical
sensors is in the initial stage and no other reports are available. The CuO-ZnO NRs sensors have advantages such as stability
in air, non-toxicity, chemical inert-ness, electro-chemical activity, simplicity to assemble, ease in fabrication, and chemo-safe
characteristics. As in the case of bicarbonate sensors, the incident

of rationale is that the current response in IV method of CuO-ZnO

NRs considerably changes when aqueous bicarbonate analytes are
adsorbed. The calcined CuO-ZnO NRs were applied for fabrication
of chemi-sensor, where bicarbonate was measured as target analyte. The fabricated-surface of CuO-ZnO NRs sensor was prepared
with conducting binders (EC and BCA) on the at AgE surface, which
is presented in Scheme 2(A) and (B). The fabricated AgE electrode
was put into the oven at low temperature (60.0 C) for 2.0 h to make
it dry, stable, and uniform the surface totally. IV signals of bicarbonate chemical sensor are anticipated having CuO-ZnO NRs on
thin-lm as a function of current vs. potential. The resultant electrical responses of target bicarbonate are investigated by simple and
reliable IV technique using CuO-ZnO NRs fabricated AgE, which
is presented in Scheme 2C. The holding time of electrometer was
set for 1.0 s. A signicant amplication in the current response with
applied potential is perceptibly conrmed. The simple and possible
reaction mechanism is generalized in Scheme 2D in the presence of
bicarbonate on CuO-ZnO NRs sensor surfaces by IV method. The
bicarbonate is converted to water and carbon dioxide in the presence of doped nanomaterials, which improved and enhanced the
current responses against potential during the IV measurement at
room conditions.
4.2. Detection of bicarbonate by CuO-ZnO NRs
Fig. 5A shows the current responses of uncoated (grey-dotted)
and coated (dark-dotted) AgE electrode surfaces with CuO-ZnO
NRs. With NRs fabricated surface, the current signal is reduced compared to uncoated surface, which indicates the modied surface
is slightly inhibited with CuO-ZnO NRs. The current changes for
the NRs modied lm before (dark-dotted) and after (blue-dotted)
injecting of 50.0 L bicarbonate (1.0 nM) onto CuO-ZnO NRs modied electrode, which is presented in Fig. 5B. This signicant change
of surface current is investigated in every injection of the target bicarbonate onto the NRs/AgE by electrometer. IV responses
with CuO-ZnO NRs modied sensor surface are investigated from
the various concentrations (1.0 nM to 0.1 M) of bicarbonate, which
is showed in Fig. 5C. It shows the current changes of fabricated
CuO-ZnO NRs/AgE lms as a function of analyte concentration
in room condition. It was also found that at low to high concentration of target bicarbonate analyte, the current responses
were increased gradually. The potential current changes at lower
to higher potential range (potential, +0.10 V to +1.5 V) based on

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M.M. Rahman, A.M. Asiri / Sensors and Actuators B 214 (2015) 8291

Fig. 5. IV responses of (A) bare AgE and NRs/AgE; (B) NRs/AgE (in the absence of bicarbonate) and NRs/AgE (in the presence of bicarbonate); (C) concentration variations of
bicarbonate (1.0 nM to 0.1 M); and (D) calibration plot (at +0.5 V) of CuO-ZnO NRs/AgE. Magnied view of LDR of calibration plot (inset).

various analyte concentration are observed, which is clearly presented in Fig. 5C. A large range of analyte concentration is executed
with the probable analytical limit, which is calculated in 1.0 nM
to 0.1 M. The calibration curve was plotted from the variation
of bicarbonate concentrations (at +0.5 V), which is presented in
Fig. 5D. The sensitivity is calculated from the calibration curve,
which is close to 1.667 A cm2 M2 . The linear dynamic range
of this bicarbonate sensor displays from 1.0 nM to 1.0 mM [linearity,
R = 0.99; Fig. 5D (inset)] and the detection limit was considered as
0.89 0.02 nM [3 noise (N)/slope(S)]. Signal-to-noise ratio (often
abbreviated SNR or S/N) is a measure used in science and engineering that compares the level of a desired signal to the level of
back-ground noise. It is dened as the ratio of signal magnitude to
the noise magnitude, often expressed in decibels [4447].
IV characteristic of the CuO-ZnO NRs/AgE is activated as a
function of bicarbonate concentration at room conditions, where
current response is observed to be maximum. As measured, the
current response of the nanostructure-lms increases with the
increasing concentration of target analytes. Similar phenomenas
have also been reported in the literature [4851]. For a low concentration of bicarbonate in liquid medium, there is a smaller
surface coverage of bicarbonate molecules on the NRs/AgE and
hence the surface reaction proceeds slowly. On an increase in bicarbonate concentration, the surface reaction of NRs/AgE increases
due to a large surface area contacted with bicarbonate molecules,
resulting in a gradually increase the response. On a further
increase in bicarbonate concentration of the CuO-ZnO NRs/AgE
lm, which has low-dimensional crystallite size and low-lattice

disorder, presents a more rapid increase in response because of

the much larger surface coverage of bicarbonate chemical on the
CuO-ZnO NRs/AgE lm surface. Generally, the surface coverage
of bicarbonate molecules on the NRs/AgE lms starts to achieve
saturation, which follows to a gradual increase in response. The
bicarbonate-sensing mechanism of the NRs/AgE lm is explained
as follows. Initially, oxygen (dissolved) is chemisorbed on the CuOZnO NRs/AgE surfaces, when the NRs lm is immersed in phosphate
buffer solution system. Actually the response time was around
10.0 s for the fabricated CuO-ZnO NRs/AgE to reach in saturated
steady state system. The high sensitivity of the fabricated NRs/AgE
can be attributed to the excellent absorption (porous surfaces
in NRs/AgE) and adsorption ability, high catalytic-decomposition
activity, and good biocompatibility of the NRs. The estimated sensitivity of the fabricated sensor is relatively higher and detection
limit is comparatively lower of new fabricated bicarbonate chemisensors, based on doped nano-materials modied electrodes. Due
to high specic surface area, the nanostructure materials (here,
NRs/AgE) offer a favourable nano-environment for the target analyte detection with large quantity [5261]. The high sensitivity of
NRs/AgE provides high-electron communication features, which
enhanced the direct electron transfer between the active sites
of NRs and at AgE. The fabricated NRs/AgE had a good reproducibility and stability. The NRs/AgE system exemplied a simple
and effective approach to the detection of bicarbonate chemicals,
which can demonstrated the signicant access to a large group of
chemicals for wide range bio-medical applications in health-care
elds.

M.M. Rahman, A.M. Asiri / Sensors and Actuators B 214 (2015) 8291

89

Fig. 6. Selectivity studied with various analytes using semiconductor CuO-ZnO nanomaterials. (A) IV responses of various analytes and (B) current responses of analytes at
+0.5 V (presented in percentage); analyte concentration was taken at 0.1 M. Potential range: 0 to +1.5 V; delay time: 1.0 s.

Oxygen (dissolved) is chemisorbed onto the NRs/AgE surfaces,

while NR coated-lm electrode is immersed into PBS system. During the chemi-sorption, the dissolved oxygen is converted to ionic
species (such as O2 and O ) which is gained electrons from the
conduction band of doped NRs. The reaction mechanism between
bicarbonate and ionic oxygen species adsorbed on NRs/AgE is presented in below in Eqs. (10)(12).
O2(diss) O2(ads)

O2(ads) + e O2
O2

(ads)

(10)

(ads)

(11)

(12)

+ e 2O

(ads)

NaHCO3(liq) + nO (adsonNRs) HCO3 + Na+ + nO (ads)

H2 O + CO2 + NaOH + ne

(13)

Here, the reaction (Eq. (13)) is directly depended in the presence of carbonic acid into reaction system. On NRs/AgE surfaces,
carbonic acid is oxidized to convert as bicarbonate and H+ , which is
reacted with O (ads) to release electrons into the conduction band.
Therefore it is decreased the resistance (increasing the conduction
current) of the NRs lm embedded on AgE. Actually the response
time was around 10.0 s for the fabricated NRs/AgE to reach the saturated steady-state level. The higher sensitivity of the fabricated
NRs/AgE could be attributed to the excellent absorption (porous
surfaces in NRs/binders/AgE) and adsorption ability, high catalyticdecomposition activity, and good biocompatibility of the NRs.
In liquid phase, the dependent on reactant constituents,
mechanism of dissociation, and further chemi-sorption of a bicarbonate analytes on the particular CuO-ZnO NRs/AgE surfaces were
executed and explained in details later. The NRs/AgE is exhibited semiconductor behaviours, where the electrical resistance
decreases under the presence of bicarbonate agents. The lm resistance is decreased gradually (increasing the resultant current) upon
increasing the bicarbonate concentration in solution phase. Interference (for selectivity) was studied for bicarbonate sensor in the
presence other chemicals like ethanol, acetone, uoride, chloride,
bicarbonate, nitrate, sulfate, and iodide using the doped CuO-ZnO
NRs embedded on at AgE (Fig. 6A). Current responses (at 0.5 V)
of all inferring analytes converted into percentile (% responses) by
deducting the blank current are calculated and presented in Fig. 6B.
By deducting the current value of blank solution, it is found the
current value is less than 5% for all chemicals (sulphide 3.9%; acetone 4.6%; nitrate 4.4%; uoride (4.1%; ethanol 2.1%; methanol 3.7%;
iodide 2.5%; blank 0%) compared to target bicarbonate (98.7%).

Therefore, it is clearly demonstrated the sensor is most selective

towards biocarbonate compared with other chemicals. To check
the reproducibly and storage stabilities, IV response for CuO-ZnO
NRs/coated AgE sensor was examined (up to 2 weeks). After each
experiment, the fabricated NRs/AgE substrate was washed thoroughly with the phosphate buffer solution and observed that the
current response was not signicantly decreased. The sensitivity
was retained almost same of initial sensitivity up to week (1st
to 2nd week), after that the response of the fabricated electrode
gradually decreased.
To conrm the validity of the IV method, the CuO-ZnO NRs/AgE
was applied to the determination of bicarbonate in various real
water samples. In real sample study, a standard addition method
was used to estimate the accuracy of bicarbonate in water samples collected from Jeddah in Saudi Arabia. The xed amount
(100.0 L) of real water sample mixed and analyzed in 50.0 mL
bulk solution by fabricated CuO-ZnO NRs/AgE electrodes. Results
displayed (Table 1) that the detection of bicarbonate in ground
water samples was reasonable for trace analysis and apparently
conrmed that the IV method is satisfactory, reliable and suitable
for analyzing real samples with CuO-ZnO NRs/AgE systems. Bicarbonate exhibited the maximum current response by IV system
using nanomaterials fabricated AgE electrode compared to others
chemicals [6265].
A series of six successive measurements of 1.0 nM bicarbonate in 0.1 M PBS yielded a good reproducible signal at CuO-ZnO
NRs/AgE sensor with a relative standard deviation (RSD) of 3.8%.
The sensor-to-sensor and run-to-run repeatability for 1.0 nM bicarbonate detection were found to be 1.7% using CuO-ZnO NRs/AgE.
To investigate the long-term storage stabilities, the response for
the NRs sensor was determined with the respect to the storing
time. The long-term storing stability of the CuO-ZnO NRs/AgE sensor was investigated signicantly. The sensitivity retained 93.0% of

Table 1
Determination of bicarbonate concentration at different real water samples by CuOZnO NRs/AgE (amount of injection: 100.0 L; bulk solution: 50.0 mL; calibrated
concentration range: 1.0 nM to 0.1 M).
Real samples

Measured current
at +1.0 V (A)

Respective
concentration (nM)

DI water
Mineral water
Distilled water
Tape water
Sea water (Jeddah, Saudi Arabia)

1.306
1.315
1.345
1.437
1.767

0.99
0.99
3.5
4.3
7.6

0.2
0.2
0.2
0.2
0.2

90

M.M. Rahman, A.M. Asiri / Sensors and Actuators B 214 (2015) 8291

initial sensitivity for several days. The above results clearly suggested that the sensor can be used for several weeks without any
signicant loss in sensitivity [6570].
5. Conclusion
Finally, we have successfully fabricated bicarbonate chemical
sensor based on low-dimensional CuO-ZnO NRs immobilized at
AgE with conducting binders for the rst time. CuO-ZnO NRs are
prepared by wet-chemical method with reducing agents in aqueous alkaline system, which represents a simple, convenient, and
economical approach. CuO-ZnO NRs/AgE sensor for bicarbonate is
studied by simple IV method at room conditions and investigated
the analytical performances thoroughly in terms of sensitivity,
detection limit, response time, selectivity, and storage stability as
well as reproducibility. The present work is provided extensive
research activities that convened on the synthesis, characterization
and bicarbonate sensing application of CuO-ZnO NRs using AgE. The
nally, the proposed IV method provided reasonable and reliable
results for a selective determination of bicarbonate in ground water
samples. Thus, the method may play an important role for using it
as an effective approach for a selective detection of bicarbonate
using CuO-ZnO NRs/AgE. This novel approach is introduced a wellorganized route of efcient chemical sensor development for the
detection of bicarbonate chemicals in environmental elds in broad
scale.
Acknowledgements
This work was funded by the Deanship of Scientic Research
(DSR), King Abdulaziz University, Jeddah, under grant no. 130144-D1435. The authors, therefore, acknowledge with thanks DSR
technical and nancial support.
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Biographies
Mohammed M. Rahman received his Ph.D. degree last 2007 on Electrochemistry under the School of Natural Science, Chonbuk National University, Korea. He
has successfully completed two years post-doctoral research fellowship in Pusan
National University (2007/2008, South Korea) and Toyohashi University of Technology (2008/2009, Japan) respectively. Recently he completed two-year contract as
an assistant professor in the chemistry department and CAMNE, Najran University,
KSA (2009/2011). Presently, he is working as an assistant professor in the chemistry
department and CEAMR, King Abdulaziz University, KSA since 2011. His current
research interest is the development and potential applications of chemi-sensors
using semiconductor doped and un-doped nanostructure materials.
Abdullah M. Asiri received Ph.D. from University of Wales, College of Cardiff, UK
in 1995. He is the Head of the Chemistry Department at King Abdulaziz University since October 2009 and he is the founder and the Director of the Center of
Excellence for Advanced Materials Research (CEAMR). He is a professor of Organic
Photochemistry. His research interest covers colour chemistry, synthesis of novel
photochromic, thermochromic systems, synthesis of novel colouring matters and
dyeing of textiles, materials chemistry, nanochemistry, nanotechnology, polymers,
and plastics. He is the Editor-in-Chief of King Abdulaziz University Journal of Science. He is also a member of the Editorial Board of Pigments and Resin Technology
(UK), Organic Chemistry in Sight (New Zealand), Recent Patents on Materials Science (USA). He is the Vice-President of Saudi Chemical Society (Western Province
Branch).