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Glucose and hydrogen peroxide dual-mode electrochemical sensing using hydrothermally grown CuO nanorods
Accepted Manuscript Glucose and hydrogen peroxide dual-mode electrochemical sensing using hydrothermally grown CuO nanorods
Pinak Chakraborty, Saurab Dhar, Kamalesh Debnath, Suvra Prakash Mondal PII: DOI: Reference:
S1572-6657(18)30810-5 https://doi.org/10.1016/j.jelechem.2018.11.060 JEAC 12769
To appear in:
Journal of Electroanalytical Chemistry
Received date: Revised date: Accepted date:
4 October 2018 17 November 2018 30 November 2018
Please cite this article as: Pinak Chakraborty, Saurab Dhar, Kamalesh Debnath, Suvra Prakash Mondal , Glucose and hydrogen peroxide dual-mode electrochemical sensing using hydrothermally grown CuO nanorods. Jeac (2018), https://doi.org/10.1016/ j.jelechem.2018.11.060
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ACCEPTED MANUSCRIPT Glucose and Hydrogen Peroxide dual-mode electrochemical sensing using hydrothermally grown CuO nanorods
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Abstract
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Pinak Chakraborty1, Saurab Dhar1,Kamalesh Debnath2and Suvra Prakash Mondal1* 1 Department of Physics, National Institute of Technology, Agartala, India -799046. 2 Department of Electronics and Communication Engineering, National Institute of Technology, Agartala, India -799046. *Corresponding Author’s email: [email protected]@nita.ac.in.
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Development of highly sensitive and selective sensors for glucose and hydrogen peroxide detection has immense importance in the fields of clinical diagnostics and food industry. Here,
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we have reported the growth and characteristics of non-enzymatic electrochemical sensor using CuO nanorods for simultaneous detection of glucose and hydrogen peroxide. The CuO based
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sensor demonstrated sensitivity towards glucose detection ~ 1319 µAmM-1cm-2 in the linear
cm-2 in the linear detection range of 0.25 to 18.75 mM. The nanorod based sensor also
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range 5 to 825 µM. The similar electrode showed sensitivity for H2O2 sensing ~ 84.89 µAmM-
demonstrated high selectivity towards interfering agents such as uric acid (UA), ascorbic acid
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(AA), urea (UR) and sucrose (SU).
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Keywords: CuO nanorod, Electrochemical Sensor, Non-enzymatic sensor, glucose sensor, H2O2 sensor
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ACCEPTED MANUSCRIPT 1. Introduction Development of highly sensitive, selective, low-cost and durable sensors for the detection of glucose and hydrogen peroxide (H2O2) are attractive for biomedical devices and food industries. A healthy human body maintains blood glucose levels at a concentration of 4.9–6.9 mMand
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increase of glucose level for a significant period of time causes diabetes [1]. At present, diabetes
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is a worldwide chronic disease causing millions of death each year [2]. Apart from this, the monitoring of glucose concentration has several applications in food industry. On the other hand,
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hydrogen peroxide (H2O2), is one of the most important markers for oxidative stress and also acts as a precursor during the formation of highly reactive and potentially harmful hydroxyl radicals
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[3, 4]. Any deviation from the normal concentration may cause some severe diseases, such as
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cancer and cardiovascular disease [5]. Moreover, H2O2 has been extensively used as an oxidizing agent in the food and chemical industries. Therefore, the accurate determination of glucose and
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H2O2 has equal importance in our daily life. For the detection of glucose and H2O2 both
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enzymatic and non-enzymatic electrochemical sensors have been developed by several researchers [6-10]. Enzymatic sensors have been demonstrated reliable results and utilized in
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various commercial application. However, the major bottlenecks of the enzyme based sensors
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arise due to complicated enzyme immobilization techniques, critical operating conditions viz. optimum temperature and pH, chemical instability, poor reproducibility and higher costs [6, 7]. On the other hand, non-enzymatic electrochemical sensors are highly sensitive with fast response time, long-term stability and lower cost of the electrode materials [11, 12]. Nowadays, transition metal oxide semiconductors have been attracted much attention in non-enzymatic glucose and H2O2 detection, due to their excellent catalytic properties, bio-compatibility, non toxic nature and low fabrication cost [3, 7]. CuO is a p-type semiconductor and has shown its potential
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ACCEPTED MANUSCRIPT applications in various fields, such as sensors, superconductors, magnetic storage media, solar cells, batteries and catalysis [13-18]. Due to the high electro-catalytic activity, nontoxic nature and fast electron transfer rates, CuO nonomaterials have been extensively used in non-enzymatic electrochemical sensors [11]. GuO et al. reported a non-enzymatic glucose sensing electrode
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based on CuO nanoparticle loaded TiO2 hollow nanofiber film [19]. The electrode showed a
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glucose detection sensitivity of 1027.6 µAmM-1cm-2 in linear detection range 19.26 mM.
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Cu/CuO/ZnO hierarchical nanostructured electrode reported by SoYoon et al. exhibited a sensitivity of 408 µAmM-1cm-2 with linear detection range from 0.1 to 1 mM [20]. Cu/Ag
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nanocomposite based electrode for enzymeless H2O2 sensing was reported by Antink et al [21].
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The reported sensor demonstrated sensing ability of H2O2 in the linear detection range of 50 µM to 500 µM. Daniela et al. reported non-enzymatic H2O2 sensing using CuO@Cu2O nanowires
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embedded into polyvinyl alcohol (PVA) matrix as electrode material [22]. The sensor showed a
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sensitivity of 39.5 µAmM-1cm-2, between 1 μM to 3 mM and 17.3 µAmM-1cm-2, between 3.0 to 10.0 mM. Among various nanostructure electrodes 1D nonomaterials are favorable for bio-
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sensing applications due to their excellent charge transport property, high electro-active surface
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area and easy synthesis process [23-27]. In this paper, we have grown CuO nanorods (NRs) on fluorine doped tin oxide (FTO) coated
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glass substrate using a facile, low cost and highly repeatable hydrothermal method. Nonenzymatic detection of glucose and H2O2 has been demonstrated using CuO NRs electrodes. 2. Experimental Section 2.1 Growth and characterization of CuO nanorods CuO nanorod sensing electrodes were fabricated on fluorine doped tin oxide (FTO) coated glass substrate using a two-step hydrothermal process. At first CuO nanoparticles were prepared from
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ACCEPTED MANUSCRIPT a solution of 5 mM copper acetate (Merck, 99%) in 20 ml methanol (Merck, 99%) and 10mM ethanolamine (Merck, 99%). To make CuO nanoparticle films, the above solution was spin coated on FTO substrates and dried at 100˚C followed by annealing at 300˚C to improve the crystallinity. CuO nanoparticle seeded substrates were dipped in equimolar (20 mM) solutions of
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copper nitrate (Merck, 99%) and hexamethylenetetramine (Merck, 99%) for hydrothermal
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growth of nanorods. The temperature of the solution was maintained at 85˚C for 3 hours. The
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nanorod samples were annealed at 350˚C to improve crystallinity. The microstructure of the
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samples was investigated by a scanning electron microscope (JEOL, JSM-6700F). 2.2 Electrochemical sensing measurements
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All sensing measurements were performed by using a CHI 660D electrochemical analyzer (CH
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Instruments, Inc., USA). In electrochemical measurement CuO NRs, Ag/AgCl (saturated KCl) electrodes and Pt wires were used as working, reference and counter electrode, respectively.
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3. Results and Discussion
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0.1M solution of NaOH was used as electrolyte during all sensing measurements.
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3.1 Growth and characterization of CuO nanorods Fig.1 (a) represents the top view SEM micrograph of CuO nanorods(NRs) grown on FTO
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substrates. The micrograph clearly shows the formation of vertically grown nanorods of average diameter ~21 nm. The energy dispersive X-ray analysis during SEM imaging shows the characteristics peaks of Cu and O atoms (inset of Fig. 1a) and confirmed the formation of CuO. For further investigation about the chemical composition of CuO NRs, X-ray photoelectron spectroscopy (XPS) study was carried out. Fig. 1(b) shows the full range XPS spectrum of CuO nanorods. The spectrum clearly revealed the presence of Cu and O elements in CuO NRs. The high-resolution XPS spectrum of Cu 2p electrons is shown at the inset of Fig. 1(b). The peaks at
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ACCEPTED MANUSCRIPT 933.91 and 953.95 eV are assigned to Cu2p3/2 and Cu2p1/2 electronic states, respectively. The values are in good agreement with the reported results for Cu(2p) electrons in CuO [28]. 3.2 Glucose and H2O2sensing with CuO NRs To study the electro-catalytic activities of CuO NRs, cyclic voltammograms (CV) were recorded
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using 0.1 M NaOH as electrolyte. Fig. 2 represents the CV profiles of CuO NRs without glucose
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and after addition of5 mM glucose. In positive scan of CV (0 to 0.8 V vs. Ag/AgCl) a large
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change in oxidation current has been observed at 0.4 V (vs. Ag/AgCl) applied bias, after
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injection of glucose. However, no significant change in current has been observed in negative potential range from 0 to -0.8 V (vs. Ag/AgCl).The CV plots of bare FTO electrode is also
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presented in Fig. 2 for comparison. The CV profiles of CuO NRs electrode without H2O2 and after addition of 5 mMH2O2is plotted in Fig. 3. Interestingly, a significant change in the peak
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current has been observed at an applied of -0.5 V (vs. Ag/AgCl) in negative scan of CV, which is
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attributed to the reduction of H2O2at CuO NRs electrode. More importantly, no current change in
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CV has been observed in the positive potential range (0 to 0.8 V, vs. Ag/AgCl). The bare FTO electrode did not show any electro-catalytic activity after addition of H2O2 into electrolyte
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solution as shown in Fig. 3. More importantly, the glucose oxidation current remained unaltered in the potential range 0 to 0.8 V vs. Ag/AgCl after addition of H2O2. Similarly, the H2O2
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reduction current in the potential range 0 to -0.8 V vs. Ag/AgCl was not affected after addition of glucose. The mechanisms of glucose oxidation and H2O2 reduction at CuO NR surface are represented in Fig. 4(a) and 4(b), respectively. Non-enzymatic electro-oxidation of glucose on CuO NR surface is mediated by the formation of a high valence Cu(III) intermediatestate [2931]. During glucose oxidation Cu(II) is electrochemically oxidized to Cu(III) which acts as an electron delivery system and the glucose is oxidized to gluconolactone followed by gluconic
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attractive for non-enzymatic dual sensing application for glucose and H2O2 in alkaline medium
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(0.1 M NaOH).
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3.3Amperometric detection of glucose and H2O2
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For continuous detection of glucose and H2O2, amperometric i-t measurements were carried out by successive addition of analytes at 30s time interval. Amperometric i-t measurement for
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glucose detection was carried out at an applied potential of 0.55 V vs. Ag/AgCl. The oxidation current density (J) vs. time curve is represented at Fig.5 (a). The inset of Fig. 5(a) shows the
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similar plot after addition of low concentration of glucose (5, 10 µM). Fig. 5(b) shows the
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calibration plot for glucose sensing (current density vs. glucose concentration) using CuO NRs.
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The glucose sensitivity of CuO NRs was found to be 1319 µAmM-1cm-2with linear detection range of 5 to 825 µM. The amperometric i-t measurement for the detection of H2O2 was carried
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out at an applied potential of -0.5 V (vs. Ag/AgCl). The resultant J-t plot is shown in Fig. 6(a). The calibration plot for H2O2 sensing (current density vs. H2O2 concentration) is presented in
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Fig. 6(b). The sensitivity for H2O2 detection was found to be 84.89 µAmM-1cm-2 with linear detection range of 0.25 to 18.75 mM. The interference study of the CuO NR electrode was demonstrated using common interfering agents during the detection of glucose and H2O2. To establish the dual sensing ability of CuO electrodes, the interference caused by H2O2 during glucose detection and interference caused glucose by during H2O2 detection were also demonstrated. Fig. 7(a) shows the interference study during glucose sensing measurements. For
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ACCEPTED MANUSCRIPT this study, 0.1 mM of dopamine (DA), uric acid (UA), ascorbic acid (AA), urea (UR), sucrose (SU) and 0.5 mM of H2O2 were added along with successive addition of 0.5 mM glucose. Interestingly, change in current density after addition of interfering agents is negligible compared to the change in current density for glucose addition. The similar interference study towards
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H2O2 detection is represented in Fig. 7(b). In this case, 0.1 mM of DA, UA, AA, UR, SU and 0.5
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mM of glucose were added along with addition of 0.5 mM H2O2. After addition of the interfering
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agents the current change in the sensing electrode is minimal compared to the reduction current due to H2O2. The above studies clearly demonstrated the capability of CuO NR electrodes in
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non-enzymatic dual sensing of glucose and H2O2. We have also studied the stability of CuO NR
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electrodes for glucose and hydrogen peroxide sensing, up to period of 30 days. In case of glucose detection, the sensing current (after 0.5 mM glucose addition) decreases only 20%. On the other
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hand, for H2O2 detection (after 0.1 mM H2O2 addition), the sensing current decreases up to 30%
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after 30 days measurements. During stability measurement, the applied bias and others experimental conditions were identical to the previous measurements. We have compared the
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sensing performance (linear detection range and sensitivity) using different CuO nanostructured
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based electrodes with our present report for glucose as well as H2O2 detection in Table 1 and Table 2, respectively. Our CuO Nanorod based electrode demonstrated superior sensing
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performance of both analytes compared to others reported results. 4. Conclusion
In conclusion, we have synthesized CuO nanorods on FTO coated glass substrate by using a facile, low cost hydrothermal technique. The CuO nanorod electrodes demonstrated nonenzymatic dual sensing properties of two important biomarkers (glucose and H2O2) in our human body. CuO NR electrode showed a sensitivity of 1319 µAmM-1cm-2 for glucose oxidation in the
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ACCEPTED MANUSCRIPT linear detection range 5 to 825 µM. The sensitivity of similar electrode for H2O2 reduction is 84.89 µAmM-1cm-2 with linear range 0.25 to 18.75 mM. The present study demonstrated the potential use of CuO nanorod electrodes for non-enzymatic detection of glucose and H2O2 for heath monitoring applications.
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Acknowledgement
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We acknowledged the central research facility (CRF) of NIT Agartala for various
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Fig. 7: (a) Interference study during glucose detection after addition of 0.1 mM of dopamine (DA), uric acid (UA), ascorbic acid (AA), urea (UR), sucrose (SU) and 0.5 mM of H2O2 along with 0.5mM glucose and (b) Interference during H2O2 detection due to addition of 0.1 mM of dopamine (DA), uric acid (UA), ascorbic acid (AA), urea (UR), sucrose (SU) and 0.5 mM of glucose along with 0.5 mM H2O2.
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Fig. 8: Stability study for CuO NR electrode (a) for glucose detection and (b) for H2O2 detection. The stability study was performed after addition of 0.5 mM glucose and 0.1 mM H2O2 over 30 days period of time. For glucose detection 0.55 V (vs. Ag/AgCl) and for H2O2 detection -0.5 V (vs. Ag/AgCl) of bias was applied.
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Table 1: Comparison of glucose detection using CuO nanostructures based electrodes Sensitivity (µAmM-1cm-2)
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0.02 to 19.26
1027.6
19
0.1 to 1
408
CuO nanoseed
0.1 to 13.3
CuO nanowire
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Rose-like CuO nanostructure
0.781 to 100
CuO nanorods
0.005 to 0.825
Electrode Material
Linear detection range (mM)
CuO/TiO2 hollow nanofiber
1101
35
648.2
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4.640
37
1319
This work
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hierarchical nanostructure
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film
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Table 2: Comparison of H2O2 detection using CuO nanostructures based electrodes Sensitivity (µAmM-1cm-2)
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0.05 to 0.5
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1 to 3
39.5
22
3 to 10
17.3
Grass like CuO
0.01 to 0.9
80.4
38
CuO decorated Si nanowire
0.01 to 13.18
22.27
39
CuO nanowires
Up to 28.87
30.11
40
CuO nanorods
0.25 to 18.75
84.89
This work
Electrode Material
Linear detection
CuO/Ag nanocomposite
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CuO@Cu2O nanowires
embedded into polyvinyl
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alcohol
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Graphical abstract
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CuO nanorods were grown hydrothermally on FTO coated glass substrates
Nanorod based sensor showed excellent dual sensing ability for glucose and H2O2
CuO nanorods are highly selective to both glucose and H2O2
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Pinak Chakraborty, Saurab Dhar, Kamalesh Debnath, Suvra Prakash Mondal PII: DOI: Reference:
S1572-6657(18)30810-5 https://doi.org/10.1016/j.jelechem.2018.11.060 JEAC 12769
To appear in:
Journal of Electroanalytical Chemistry
Received date: Revised date: Accepted date:
4 October 2018 17 November 2018 30 November 2018
Please cite this article as: Pinak Chakraborty, Saurab Dhar, Kamalesh Debnath, Suvra Prakash Mondal , Glucose and hydrogen peroxide dual-mode electrochemical sensing using hydrothermally grown CuO nanorods. Jeac (2018), https://doi.org/10.1016/ j.jelechem.2018.11.060
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT Glucose and Hydrogen Peroxide dual-mode electrochemical sensing using hydrothermally grown CuO nanorods
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Abstract
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Pinak Chakraborty1, Saurab Dhar1,Kamalesh Debnath2and Suvra Prakash Mondal1* 1 Department of Physics, National Institute of Technology, Agartala, India -799046. 2 Department of Electronics and Communication Engineering, National Institute of Technology, Agartala, India -799046. *Corresponding Author’s email: [email protected]@nita.ac.in.
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Development of highly sensitive and selective sensors for glucose and hydrogen peroxide detection has immense importance in the fields of clinical diagnostics and food industry. Here,
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we have reported the growth and characteristics of non-enzymatic electrochemical sensor using CuO nanorods for simultaneous detection of glucose and hydrogen peroxide. The CuO based
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sensor demonstrated sensitivity towards glucose detection ~ 1319 µAmM-1cm-2 in the linear
cm-2 in the linear detection range of 0.25 to 18.75 mM. The nanorod based sensor also
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range 5 to 825 µM. The similar electrode showed sensitivity for H2O2 sensing ~ 84.89 µAmM-
demonstrated high selectivity towards interfering agents such as uric acid (UA), ascorbic acid
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(AA), urea (UR) and sucrose (SU).
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Keywords: CuO nanorod, Electrochemical Sensor, Non-enzymatic sensor, glucose sensor, H2O2 sensor
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ACCEPTED MANUSCRIPT 1. Introduction Development of highly sensitive, selective, low-cost and durable sensors for the detection of glucose and hydrogen peroxide (H2O2) are attractive for biomedical devices and food industries. A healthy human body maintains blood glucose levels at a concentration of 4.9–6.9 mMand
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increase of glucose level for a significant period of time causes diabetes [1]. At present, diabetes
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is a worldwide chronic disease causing millions of death each year [2]. Apart from this, the monitoring of glucose concentration has several applications in food industry. On the other hand,
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hydrogen peroxide (H2O2), is one of the most important markers for oxidative stress and also acts as a precursor during the formation of highly reactive and potentially harmful hydroxyl radicals
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[3, 4]. Any deviation from the normal concentration may cause some severe diseases, such as
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cancer and cardiovascular disease [5]. Moreover, H2O2 has been extensively used as an oxidizing agent in the food and chemical industries. Therefore, the accurate determination of glucose and
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H2O2 has equal importance in our daily life. For the detection of glucose and H2O2 both
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enzymatic and non-enzymatic electrochemical sensors have been developed by several researchers [6-10]. Enzymatic sensors have been demonstrated reliable results and utilized in
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various commercial application. However, the major bottlenecks of the enzyme based sensors
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arise due to complicated enzyme immobilization techniques, critical operating conditions viz. optimum temperature and pH, chemical instability, poor reproducibility and higher costs [6, 7]. On the other hand, non-enzymatic electrochemical sensors are highly sensitive with fast response time, long-term stability and lower cost of the electrode materials [11, 12]. Nowadays, transition metal oxide semiconductors have been attracted much attention in non-enzymatic glucose and H2O2 detection, due to their excellent catalytic properties, bio-compatibility, non toxic nature and low fabrication cost [3, 7]. CuO is a p-type semiconductor and has shown its potential
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ACCEPTED MANUSCRIPT applications in various fields, such as sensors, superconductors, magnetic storage media, solar cells, batteries and catalysis [13-18]. Due to the high electro-catalytic activity, nontoxic nature and fast electron transfer rates, CuO nonomaterials have been extensively used in non-enzymatic electrochemical sensors [11]. GuO et al. reported a non-enzymatic glucose sensing electrode
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based on CuO nanoparticle loaded TiO2 hollow nanofiber film [19]. The electrode showed a
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glucose detection sensitivity of 1027.6 µAmM-1cm-2 in linear detection range 19.26 mM.
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Cu/CuO/ZnO hierarchical nanostructured electrode reported by SoYoon et al. exhibited a sensitivity of 408 µAmM-1cm-2 with linear detection range from 0.1 to 1 mM [20]. Cu/Ag
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nanocomposite based electrode for enzymeless H2O2 sensing was reported by Antink et al [21].
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The reported sensor demonstrated sensing ability of H2O2 in the linear detection range of 50 µM to 500 µM. Daniela et al. reported non-enzymatic H2O2 sensing using CuO@Cu2O nanowires
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embedded into polyvinyl alcohol (PVA) matrix as electrode material [22]. The sensor showed a
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sensitivity of 39.5 µAmM-1cm-2, between 1 μM to 3 mM and 17.3 µAmM-1cm-2, between 3.0 to 10.0 mM. Among various nanostructure electrodes 1D nonomaterials are favorable for bio-
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sensing applications due to their excellent charge transport property, high electro-active surface
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area and easy synthesis process [23-27]. In this paper, we have grown CuO nanorods (NRs) on fluorine doped tin oxide (FTO) coated
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glass substrate using a facile, low cost and highly repeatable hydrothermal method. Nonenzymatic detection of glucose and H2O2 has been demonstrated using CuO NRs electrodes. 2. Experimental Section 2.1 Growth and characterization of CuO nanorods CuO nanorod sensing electrodes were fabricated on fluorine doped tin oxide (FTO) coated glass substrate using a two-step hydrothermal process. At first CuO nanoparticles were prepared from
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ACCEPTED MANUSCRIPT a solution of 5 mM copper acetate (Merck, 99%) in 20 ml methanol (Merck, 99%) and 10mM ethanolamine (Merck, 99%). To make CuO nanoparticle films, the above solution was spin coated on FTO substrates and dried at 100˚C followed by annealing at 300˚C to improve the crystallinity. CuO nanoparticle seeded substrates were dipped in equimolar (20 mM) solutions of
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copper nitrate (Merck, 99%) and hexamethylenetetramine (Merck, 99%) for hydrothermal
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growth of nanorods. The temperature of the solution was maintained at 85˚C for 3 hours. The
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nanorod samples were annealed at 350˚C to improve crystallinity. The microstructure of the
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samples was investigated by a scanning electron microscope (JEOL, JSM-6700F). 2.2 Electrochemical sensing measurements
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All sensing measurements were performed by using a CHI 660D electrochemical analyzer (CH
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Instruments, Inc., USA). In electrochemical measurement CuO NRs, Ag/AgCl (saturated KCl) electrodes and Pt wires were used as working, reference and counter electrode, respectively.
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3. Results and Discussion
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0.1M solution of NaOH was used as electrolyte during all sensing measurements.
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3.1 Growth and characterization of CuO nanorods Fig.1 (a) represents the top view SEM micrograph of CuO nanorods(NRs) grown on FTO
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substrates. The micrograph clearly shows the formation of vertically grown nanorods of average diameter ~21 nm. The energy dispersive X-ray analysis during SEM imaging shows the characteristics peaks of Cu and O atoms (inset of Fig. 1a) and confirmed the formation of CuO. For further investigation about the chemical composition of CuO NRs, X-ray photoelectron spectroscopy (XPS) study was carried out. Fig. 1(b) shows the full range XPS spectrum of CuO nanorods. The spectrum clearly revealed the presence of Cu and O elements in CuO NRs. The high-resolution XPS spectrum of Cu 2p electrons is shown at the inset of Fig. 1(b). The peaks at
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ACCEPTED MANUSCRIPT 933.91 and 953.95 eV are assigned to Cu2p3/2 and Cu2p1/2 electronic states, respectively. The values are in good agreement with the reported results for Cu(2p) electrons in CuO [28]. 3.2 Glucose and H2O2sensing with CuO NRs To study the electro-catalytic activities of CuO NRs, cyclic voltammograms (CV) were recorded
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using 0.1 M NaOH as electrolyte. Fig. 2 represents the CV profiles of CuO NRs without glucose
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and after addition of5 mM glucose. In positive scan of CV (0 to 0.8 V vs. Ag/AgCl) a large
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change in oxidation current has been observed at 0.4 V (vs. Ag/AgCl) applied bias, after
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injection of glucose. However, no significant change in current has been observed in negative potential range from 0 to -0.8 V (vs. Ag/AgCl).The CV plots of bare FTO electrode is also
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presented in Fig. 2 for comparison. The CV profiles of CuO NRs electrode without H2O2 and after addition of 5 mMH2O2is plotted in Fig. 3. Interestingly, a significant change in the peak
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current has been observed at an applied of -0.5 V (vs. Ag/AgCl) in negative scan of CV, which is
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attributed to the reduction of H2O2at CuO NRs electrode. More importantly, no current change in
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CV has been observed in the positive potential range (0 to 0.8 V, vs. Ag/AgCl). The bare FTO electrode did not show any electro-catalytic activity after addition of H2O2 into electrolyte
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solution as shown in Fig. 3. More importantly, the glucose oxidation current remained unaltered in the potential range 0 to 0.8 V vs. Ag/AgCl after addition of H2O2. Similarly, the H2O2
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reduction current in the potential range 0 to -0.8 V vs. Ag/AgCl was not affected after addition of glucose. The mechanisms of glucose oxidation and H2O2 reduction at CuO NR surface are represented in Fig. 4(a) and 4(b), respectively. Non-enzymatic electro-oxidation of glucose on CuO NR surface is mediated by the formation of a high valence Cu(III) intermediatestate [2931]. During glucose oxidation Cu(II) is electrochemically oxidized to Cu(III) which acts as an electron delivery system and the glucose is oxidized to gluconolactone followed by gluconic
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attractive for non-enzymatic dual sensing application for glucose and H2O2 in alkaline medium
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3.3Amperometric detection of glucose and H2O2
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For continuous detection of glucose and H2O2, amperometric i-t measurements were carried out by successive addition of analytes at 30s time interval. Amperometric i-t measurement for
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glucose detection was carried out at an applied potential of 0.55 V vs. Ag/AgCl. The oxidation current density (J) vs. time curve is represented at Fig.5 (a). The inset of Fig. 5(a) shows the
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similar plot after addition of low concentration of glucose (5, 10 µM). Fig. 5(b) shows the
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calibration plot for glucose sensing (current density vs. glucose concentration) using CuO NRs.
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The glucose sensitivity of CuO NRs was found to be 1319 µAmM-1cm-2with linear detection range of 5 to 825 µM. The amperometric i-t measurement for the detection of H2O2 was carried
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out at an applied potential of -0.5 V (vs. Ag/AgCl). The resultant J-t plot is shown in Fig. 6(a). The calibration plot for H2O2 sensing (current density vs. H2O2 concentration) is presented in
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Fig. 6(b). The sensitivity for H2O2 detection was found to be 84.89 µAmM-1cm-2 with linear detection range of 0.25 to 18.75 mM. The interference study of the CuO NR electrode was demonstrated using common interfering agents during the detection of glucose and H2O2. To establish the dual sensing ability of CuO electrodes, the interference caused by H2O2 during glucose detection and interference caused glucose by during H2O2 detection were also demonstrated. Fig. 7(a) shows the interference study during glucose sensing measurements. For
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H2O2 detection is represented in Fig. 7(b). In this case, 0.1 mM of DA, UA, AA, UR, SU and 0.5
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mM of glucose were added along with addition of 0.5 mM H2O2. After addition of the interfering
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agents the current change in the sensing electrode is minimal compared to the reduction current due to H2O2. The above studies clearly demonstrated the capability of CuO NR electrodes in
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non-enzymatic dual sensing of glucose and H2O2. We have also studied the stability of CuO NR
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electrodes for glucose and hydrogen peroxide sensing, up to period of 30 days. In case of glucose detection, the sensing current (after 0.5 mM glucose addition) decreases only 20%. On the other
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hand, for H2O2 detection (after 0.1 mM H2O2 addition), the sensing current decreases up to 30%
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after 30 days measurements. During stability measurement, the applied bias and others experimental conditions were identical to the previous measurements. We have compared the
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sensing performance (linear detection range and sensitivity) using different CuO nanostructured
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based electrodes with our present report for glucose as well as H2O2 detection in Table 1 and Table 2, respectively. Our CuO Nanorod based electrode demonstrated superior sensing
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performance of both analytes compared to others reported results. 4. Conclusion
In conclusion, we have synthesized CuO nanorods on FTO coated glass substrate by using a facile, low cost hydrothermal technique. The CuO nanorod electrodes demonstrated nonenzymatic dual sensing properties of two important biomarkers (glucose and H2O2) in our human body. CuO NR electrode showed a sensitivity of 1319 µAmM-1cm-2 for glucose oxidation in the
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Acknowledgement
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We acknowledged the central research facility (CRF) of NIT Agartala for various
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Table 1: Comparison of glucose detection using CuO nanostructures based electrodes Sensitivity (µAmM-1cm-2)
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CuO nanorods were grown hydrothermally on FTO coated glass substrates
Nanorod based sensor showed excellent dual sensing ability for glucose and H2O2
CuO nanorods are highly selective to both glucose and H2O2
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