Simultaneous Detection of Dihydroxybenzene Isomers with ZnO

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Simultaneous Detection of Dihydroxybenzene Isomers with ZnO Nanorod/Carbon Cloth Electrodes Shangjun Meng, Ying Hong, Ziyang Dai, Wei Huang, and Xiao-Chen Dong ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b00546 • Publication Date (Web): 24 Mar 2017 Downloaded from http://pubs.acs.org on March 27, 2017

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ACS Applied Materials & Interfaces

Simultaneous Detection of Dihydroxybenzene Isomers with ZnO Nanorod/Carbon Cloth Electrodes Shangjun Meng, Ying Hong, Ziyang Dai, Wei Huang*, Xiaochen Dong* Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, China

E-mail: [email protected], [email protected]

ABSTRACT Herein, ZnO nanorods with average diameters of 50 nm were uniformly anchored on the surface of carbon cloth directly by a simply hydrothermal method. The nanorods growing in situ along the specific direction of (002) have single crystalline features and a columnar structure. Based on the ZnO nanorod/carbon cloth composite, free-standing electrodes were fabricated for the simultaneous determination of dihydroxybenzene isomers. The ZnO nanorod/carbon cloth electrodes exhibited excellent electrochemical stability, high sensitivity and selectivity. The linear ranges for hydroquinone (HQ), catechol (CC), and resorcinol (RC) were 2 μM - 30 μM, 2 μM - 45 μM, and 2 μM - 385 μM. And the detect limitation (S/N = 3) were 0.57 μM, 0.81 μM, and 7.2 μM, respectively. The outstanding sensing properties of ZnO/carbon cloth electrodes have a great promising for the development of free-standing biosensors and other electrochemical devices. Keywords: ZnO nanorod; carbon cloth; electrochemical sensor; simultaneous detection;

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dihydroxybenzene isomers

INTRODUCTION The simultaneous detection of dihydroxybenzene isomers has aroused worldwide attention in the past few years. They not only have extensive applications such as pesticides, cosmetics, medicines, dyes, tanning, flavoring agents and photography chemicals etc.1, but the three isomers is detrimental to the environment and human healthy on account of their low rate of degradation and high toxicity, even at very low concentrations2,3. More importantly, dihydroxybenzene isomers (HQ, CC and RC) possess similar structure, properties as well often coexist 4, which makes the detection and separation become more difficulty. Hence, it is urgent to launch a simple and rapid detection approach for simultaneous determination of HQ, CC and RC. To detect the dihydroxybenzene isomers, various techniques based on chromatograph5, fluorescence6, spectrophotometry7, chemiluminescence8 and electrochemical9, 10 have been emerged by now. Among these approaches, electrochemical method is a most promising and effective strategy thanks to their low price, high sensitivity, simple operation and specific selectivity11, 12. For reasons of the different electrochemical activity between dihydroxybenzene isomers, they can be simultaneously determined through the electrochemical methods13,

14

. However, the

dihydroxybenzene isomers with similar structure affect significantly each other during the simultaneous determination2, 14, 15. And the simultaneous detection of three isomers (HQ, CC and RC) with electrochemical approach rarely reported. At present, zinc oxide (ZnO) nanostructures, such as nanoflakes, nanoparticles and

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nanorods, have been intensively surveyed because of the advantages of chemical stability, non-toxicity and low cost

16, 17, 18

. Among them, one-dimensional ZnO nanorods with high

specific surface area and volume ratio, remarkable mechanical stability and excellent electrical conductivity, have received special interest in the application of various sensors19, 20

. For instance, Zhao et al.19 prepared CdS/RGO/ZnO nanowire heterostructure as

photoelectrochemical biosensor with good practicality and stability along with great precision and consistency. Liu et al. 20 prepared the carbon fibers/ZnO composite electrode to simultaneously detect ascorbic acid and uric acid with excellent sensitivity and selectivity. However, there are a few reports on the simultaneously detection of three isomers using ZnO nano-composite. Carbon cloth, one kind of carbonous materials, has good corrosion resistance, high conductivity, excellent flexibility, unique mechanical strength, which has widely applied in electrochemical files, relative to other carbon nanomaterials such as graphite, activated carbon and porous carbon, etc. In recent years, plenty of transition metal oxide/hydroxide with carbon cloth has been used to improve the sensing performance in electrochemical sensors and energy storage21-24. In this paper, ZnO nanorod modified carbon cloth composite are synthesized by hydrothermal method following a thermal treatment (Scheme 1). Based on the excellent electrical

performance

electrochemical

of

electrode

the is

composites, fabricated

for

the the

free-standing

three-dimensional

simultaneously

detection

of

dihydroxybenzene isomers. The measurements demonstrate that the ZnO nanorod/carbon cloth electrodes possess high electrocatalytic activity and excellent simultaneously

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detection performance to HQ, CC and RC. CHARACTERIZATION AND MEASUREMENT The phases of the as synthesized samples are analyzed by X-ray diffraction (XRD, Bruker D8 Advance). Surface structure and morphology of the samples are directly observed by high-resolution transmission electron microscopy (HRTEM, JEOL JEM-2010) with selected-area electron diffraction (SAED, JEOL JEM-2010) and scanning electron microscope (SEM, Hitachi S-4800). All cyclic voltammetrys (CVs) and amperometric measurements are carried out using a CHI 660 C electrochemical analyzer (CH Instruments Co., Ltd, Shanghai, China). ZnO/carbon cloth electrode serves directly as the working electrode, Pt foil and Ag/AgCl electrode as the counter electrode and the reference electrode, respectively. The aqueous electrolyte is 0.1 M PBS solution (pH = 7.0). Raman spectra were determined by WITeck CRM200 confocal microscopy Raman system with 488 nm wavelength laser. RESULTS AND DISCUSSION The XRD patterns of carbon cloth and ZnO nanorod/carbon cloth composite is shown in Figure 1, which has two strong peaks at 2θ = 26.2o and 44.4o attributed to (002) and (101) planes of carbon cloth, respectively25. After the formation of ZnO nanorod/carbon cloth composite, several characteristic diffraction peaks at 2θ = 31.850˚, 34.551˚, 36.357˚, 47.697˚, 56.749˚, 63.091˚, 68.166˚, and 69.289˚ (except peaks deriving from carbon cloth) are well indexed to (100), (002), (101), (102), (110), (103), (112), and (201) phases of ZnO nanorod, respectively (JCPDS No.79-0205). The XRD pattern demonstrates the successful integration of ZnO nanorod and carbon cloth.

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To explore the structure difference, Raman spectra of carbon cloth and ZnO/carbon cloth composite are characterized (Figure 1b). The peaks at 1350, 1580 and 2680 cm-1 represents the D, G, and 2D band of carbon cloth, respectively. Among them, the D band is a typical feature of disordered graphitic lattice, whereas the G band is the result of the sp2 hybridization of the C-C band. The Raman spectrum of ZnO/carbon cloth presents five distinct peaks at 92, 310, 423, 542 and 1110 cm-1, which can be characteristic of Wurtzite hexagonal phase ZnO17, 26. The morphologies and structures of carbon cloth and ZnO/carbon cloth composite are examined using SEM and TEM. As illustrated in Figure 2a, the fibers of the carbon cloth possess a smooth surface with an average diameter of 10 μm. After the formation of ZnO/carbon cloth composite, it can be observed that the ZnO nanorods are uniformly and tightly grown on carbon cloth (Figure 2b). The magnified SEM image indicates that the ZnO nanorods have flat section and uniform size distribution (diameter around 40-60 nm) and vertically arrange on carbon cloth’s surface (Figure 2c). To further survey the structure of ZnO nanorods, TEM and affiliated electron diffraction are measured. The low-magnification TEM image of ZnO nanorods, as shown in Figure 2d, indicates the morphology is in good accordance with the result of SEM. The HRTEM image (Figure 2e) demonstrates that ZnO nanorod presents well-resolved lattice with the interspacing about 0.26 nm, which is well corresponding to the (002) plane of ZnO Wurtzite structure. It also indicates the ZnO nanorod is grown along the c-axis direction

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. Figure 2f exhibits the

homologous selected-area electron diffraction (SAED) pattern, indicating the high single-crystalline property of ZnO nanorod.

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The electrochemical performance of three isomers are studied by cyclic voltammetry (CV) with carbon cloth and ZnO/Carbon cloth electrodes, respectively, in PBS solution (pH = 7.0, scan rate 100 mV s-1). As shown in Figure 3a, when the concentrations of HQ, CC and RC are 0.1 mM, respectively, three legible oxidation peaks can be obtained for ZnO/Carbon cloth electrode. Compared with carbon cloth electrode, the peak currents of HQ, CC and RC in ZnO/Carbon cloth electrode are obviously increased. What’s more, the anodic potential differences of ZnO/carbon cloth electrode between HQ and CC (0.1 V), RC and CC (0.394 V) are increased that of carbon cloth electrode (HQ and CC 0.096 V, RC and CC0.414 V). It suggests that HQ, CC and RC can be efficiently detected by ZnO/carbon cloth electrode. The phenomenon maybe comes from the fact that the electrochemical activity is enhanced by the synergistic effect of carbon cloth (good conductivity and high electronic mobility) and ZnO nanostructures (excellent electrocatalytic performance). Figure 3b shows the CVs of ZnO/carbon cloth electrode toward 0.1 mM RC, 0.1 Mm HQ, 0.1 mM CC and the commixture of 0.1 mM dihydroxybenzene isomers in PBS (pH = 7.0). The legible redox peaks of RC, CC and HQ (0.67V, 0.24V and 0.14V, respectively) further indicate that ZnO/carbon cloth electrode exhibits better electrocatalytic performance for the simultaneous and selective detection. Figure 4a CVs shows the CVs of ZnO/carbon cloth electrode at different scan rates with the existence of RC, CC and HQ (0.1 mM) in PBS (pH = 7.0). It is obvious that accompanying the raise of scan rate, both of the oxidation and redox peaks enhanced. Furthermore, with the increase of scan rates, the anodic peaks shift to more positive, indicating electron transfer is quasi-reversible and rapid in ZnO/carbon cloth electrode 30. Figure 4b shows that oxidation peak currents and the square root of the

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scan rates presents a linear relation, demonstrating the electro-oxidation reaction of three isomers is a diffusion-controlled process 27. From the Figure 4b, it can be calculated the equations of regression of three isomers, respectively. IHQ(mA) = -0.034 +0.014 ν1/2 (mV s-1)1/2 (R2 = 0.995) ICC(mA) = -0.031 +0.0136 ν1/2 (mV s-1)1/2 (R2 = 0.995) IRC(mA) = -0.0016 +0.006 ν1/2 (mV s-1)1/2 (R2 = 0.996) where I is oxidation peak current, R is correlation coefficient, and ν is square root of scan rate. The CVs of ZnO/carbon cloth electrode in the solution comprising HQ, CC and RC (0.1 mM) at difference pH values are shown in Figure 5. It indicates that with the raise of pH value the peak potentials of oxidation of three isomers shift negatively. This phenomenon is consistent with the potential shift derived from the Nernst equation28, which also suggests that the electrochemical oxidation of three isomers at ZnO/carbon cloth electrode involves two electrons and two protons transfer 29-31. Figure 5b show that the pH value and potentials is linear relation. The possible reaction mechanisms of three isomers on ZnO/carbon cloth are depicted as follows 29:

Figure 6a-6c show the CVs of ZnO/carbon cloth electrode with different concentration of

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three isomers in PBS (pH = 7.0, scan rate 100 mV s-1). With the increase of three isomers concentration, the anodic peak currents increase linearly (insert of Figure 6a-6c), indicating the excellent electrochemical performance of ZnO/carbon cloth electrode for selective and sensitive detection of three isomers. As a function of concentration, the regression equations can be obtained. IHQ (μA) = 13.93 (μM) + 0.638 (R2 = 0.999) ICC (mA) = 0.094 (μM) + 0.001 (R2 = 0.999) IRC (μA) = 7.206 (μM) + 0.281 (R2 = 0.995) Figure 6d-6f show the selectivity of ZnO/carbon cloth electrode for the determination of HQ or CC or RC in PBS solutions (pH = 7, scan rate 100 mV s-1). It can be found that the peak currents of oxidation increase with the detected specie concentration increase and two other species concentration constant. The insert of Figure 6d-6f indicate that the peak currents linearly increase with the detected specie concentration, revealing excellent structure resolution of isomer and strong anti-interference ability of ZnO/carbon cloth electrode for simultaneous detection of three isomers. Based on the results, it also can obtain the regression equations: IHQ (mA) = 0.0721 (M) + 0.3957 (R2 = 0.995) ICC (mA) = 0.2015 (mM) + 0.0635 (R2 = 0.996) IRC (mA) = 0.1127 (mM) + 0.206 (R2 = 0.995) To examine the detection sensitivity, CVs are employed to investigate the peak currents of oxidation of three isomers at ZnO/carbon cloth electrode. Figure 7a shows the CV curves of ZnO/carbon cloth electrode for different concentration of three isomers. The

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corresponding oxidation peak currents increase step by step during the successive addition of three isomers. The separated oxidation current peaks of three isomers can be observed clearly in the magnified CVs (Figure 7b). Figure 7c-7e present the relationship between the peak currents of oxidation and the concentration of HQ, CC, RC, respectively, suggesting that the peak currents of three isomers increases linearly with the concentrations in the range of 2 μM - 30 μM, 2 μM - 45 μM and 2 μM - 385 μM, respectively. The corresponding regression equations of the red line are as follow: Ipa (mA) = 0.00109 C (μM) + 0.03616 (R2 = 0.995) for HQ Ipa (mA) = 0.00102 C (μM) + 0.03023 (R2 = 0.995) for CC Ipa (mA) = 0.00045 C (μM) + 0.02768 (R2 = 0.997) for RC Additionally, the minimum detection limit (LOD) was calculated based on the equation: LOD = 3σ/S, where σ is the standard deviation of the intercept of regression line, S is the slope of the calibration curve. The calculated limitation of detect (LOD) for HQ, CC and RC are 0.57 μM, 0.81 μM and 7.2 μM (S/N = 3), respectively, indicating ZnO/carbon cloth electrode can simultaneously determine three isomers with high sensitive and excellent selective. Table 1 presents the comparison of ZnO/carbon cloth electrode with other reported electrochemical electrodes. It can be concluded that ZnO nanorods decorated carbon cloth electrode possesses rational linear range and acceptable LOD toward dihydroxybenzene isomers detection2, 32-34. The interference of various substances is further examined with ZnO/carbon cloth electrode. Figure S1a shows the CVs of HQ, CC and RC (0.1 mM) with the existence of some possible interferences including CuSO4, NaCl, Ni(NO3)2, Zn(NO3)2 and glucose in PBS

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solution. It can be found that 10 fold of Cu2+, Na+, Ni+, Zn2+ and 2 fold of glucose have no obvious impact on the signals of three isomers 31, further suggesting the excellent detection selectivity of ZnO/carbon cloth electrode towards dihydroxybenzene isomers. The detection stability of ZnO/carbon cloth electrode is investigated by 50 times repeated potential scans. From Figure S1b, the peak currents of three isomers at ZnO/carbon cloth electrodes haven’t remarkable change after 50 cycles, indicating the excellent stability of the as-prepared electrodes. After the long electrochemical test, the SEM image (the insert of Figure S1b) shows that ZnO nanorods still maintain the one dimensional morphology of ZnO. Figure S1c shows the CV curves of three isomers in PBS solution after ZnO/carbon cloth electrode is stored at 4 ˚C for 30 days. The ZnO/carbon cloth electrode preserves 98% of its initial peak current, demonstrating excellent stability after long-time storage. Conclusion In this study, we present the simultaneous detection of dihydroxybenzene isomers in PBS solutions by an electrochemical sensor based on the free-standing electrode comprising ZnO nanorods uniformly decorated carbon cloth. The ZnO/carbon cloth electrode exhibits greater electrocatalytic activities for the oxidation of dihydroxybenzene isomers and the strikingly oxidation peak current response, relative to some previous reports, as a result of the excellent electrocatalytic activity of ZnO nanorods and the sufficient conductivity of carbon cloth. In addition, the as-fabricated electrode demonstrates good analytical properties, such as high selectivity and sensitivity as well as excellent stability. The ZnO/carbon cloth electrode without any auxiliary materials opened new avenues for the development of electrochemical sensing.

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ASSOCIATED CONTENT Supporting Information Experimental section for preparation ZnO/carbon cloth electrode, the figure of anti-interference experiment and stability testing. AUTHOR INFORMATION Corresponding Author E-mail: [email protected], [email protected] Notes The authors declare no conflict of interest. ACKNOWLEDGMENTS The work was supported by NNSF of China (61525402), Key University Science Research Project of Jiangsu Province (15KJA430006), Program for New Century Excellent Talents in University (NCET-13-0853), QingLan Project. REFERENCES 1

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29 Zou, J.; Zhang, Y. X.; Huang, L.; Wan, Q. J. A Hydroquinone Sensor based on a New Nanocrystals Modified Electrode. J. Chem. Technol Biotechnol. 2014, 89, 259-264. 30 Ge, C.; Li, H. J.; Li, M. J.; Li, C. P.; Wu, X. G.; Yang, B. H. Synthesis of a ZnO Nanorod/CVD Graphene Composite for Simultaneous Sensing of Dihydroxybenzene Isomers. Carbon. 2015, 95, 1-9. 31 Yu, Q.; Liu, Y.; Liu, X. Y.; Zeng, X. D.; Luo, S. L.; Wei, W. Z. Simultaneous Determination of Dihydroxybenzene Isomers at MWCNTs/β-Cyclodextrin Modified Carbon Ionic Liquid Electrode in the Presence of Cetylpyridinium Bromide. Electroanalysis 2010, 22, 1012 – 1018. 32 Zhao, D. M.; Zhang, X. H.; Feng, L. J.; Jia, L.; Wang, S. F. Simultaneous Determination of Hydroquinone and Catechol at PASA/MWNTs Composite Film Modified Glassy Carbon Electrode. Colloids Surf., B 2009, 74, 317-321. 33 Ghanem, M. A. Electrocatalytic Activity and Simultaneous Determination of Catechol and Hydroquinone at Mesoporous Platinum Electrode. Electrochem. Commun. 2007, 9, 2501-2506. 34 Wang, L.; Huang, P. F.; Bai, J. Y.; Wang, H. J.; Zhang, L. Y.; Zhao, Y. Q. Direct Simultaneous Electrochemical Determination of Hydroquinone and Catechol at a Poly(glutamic acid) Modified Glassy Carbon Electrode. Int. J. Electrochem. Sci. 2007, 2, 123 - 132.

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Scheme S1. Schematic illustration for the preparation of ZnO/carbon cloth composite.

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Figure 1．(a) XRD spectra of carbon cloth and ZnO/carbon cloth composite. (b) Raman spectra of carbon cloth and ZnO/carbon cloth composite.

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Figure 2. (a) SEM image of carbon cloth. (b) SEM images of ZnO/Carbon cloth in low and (c) high magnifications (insert shows the magnified image of Figure 2c). (d-f) low- and high- magnification TEM images and corresponding SAED pattern of ZnO nanorod.

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Figure 3. (a) CVs of carbon cloth ZnO/carbon cloth electrode in PBS (pH = 7.0) with 0.1 mM HQ, CC and RC. Scan rate 100 mV s-1. (b) CVs of ZnO/carbon cloth in the presence of 0.1 mM CC, 0.1 mM HQ, 0.1 mM RC and the mixture of 0.1 mM HQ, CC, and RC in PBS (pH =7.0, scan rate 100 mV s-1).

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Figure 4. (a) CVs of ZnO/carbon cloth electrode at differences scan rates in pH = 7.0 PBS with the existence of HQ, CC and RC (0.1 mM). (b) The plots of oxidation peak currents versus square root of scan rate.

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Figure 5. (a) CVs of ZnO/carbon cloth electrode in the presence of HQ, CC and RC (0.1 mM) at difference pH values. (b) The plots of oxidation peak potential versus pH for HQ, CC and RC.

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Figure 6. (a-c) CVs of ZnO/carbon cloth electrode in PBS solution by changing the concentrations of HQ, CC, and RC, respectively. The insets show the plot of oxidation peak currents versus HQ, CC and RC concentration. (d-f) CVs of ZnO/carbon cloth electrode in PBS solution containing 0.1 M two other species and different concentrations of HQ, CC, and RC, respectively. The insets shows the plot of oxidation peak currents versus HQ, CC, and RC concentration, respectively.

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Figure 7. (a) CVs of ZnO/carbon cloth electrode containing various concentration of HQ (2 μM to 685 μM), CC (2 μM to 685 μM), and RC (2 μM to 685 μM) in PBS at the scan rate of 50 mV s-1. (b) The enlargement of the Figure a. (c-e) Calibration curve for the peak current vs the concentration of HQ, CC, and RC.

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Table 1 Comparison of HQ, CC and RC simultaneous detection performance with literatures. Linear range (μM)

LOD (μM)

Electrode

Reference HQ

CC

RC

HQ

CC

RC

PASA/MWNTs/GCE

6 - 100

6 - 180

-

1

1

-

32

ZnO/graphene

0-70

0-80

0-700

0.1

0.2

1

30

MPE

50 - 2000

20 - 50

-

-

-

-

33

p-Glu/GCE

5 - 80

1 - 80

-

1

0.8

-

34

Gr-Chitosan/GCE

1 - 300

1 - 400

1 - 550

0.75

0.75

0.75

2

ZnO/carbon cloth

2 - 30

2 - 45

2 - 385

0.57

0.81

7.2

This work

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TOC


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Simultaneous Detection of Dihydroxybenzene Isomers with ZnO

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