Next Article in Journal
Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas
Previous Article in Journal
A Novel Porous Ceramic Membrane Supported Monolithic Cu-Doped Mn–Ce Catalysts for Benzene Combustion
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Communication

Fabrication of Au Nanoparticle-Decorated MoS2 Nanoslices as Efficient Electrocatalysts for Electrochemical Detection of Dopamine

1
College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China
2
State Grid Jining Power Supply Company, Jining 272000, China
*
Author to whom correspondence should be addressed.
Catalysts 2019, 9(8), 653; https://doi.org/10.3390/catal9080653
Submission received: 10 July 2019 / Revised: 24 July 2019 / Accepted: 30 July 2019 / Published: 30 July 2019
(This article belongs to the Section Electrocatalysis)

Abstract

:
Herein, MoS2 nanoslices were simply prepared by using ultrasonic treatment, and were further decorated with Au nanoparticles (AuNPs) through an electrodeposition process to obtain the MoS2/Au nanocomposites. The obtained nanocomposites display synergetic electrocatalytic effect for the oxidation of dopamine due to the large surface area and two-dimensional structure of the MoS2 nanoslices, combining with the high catalytic activity and good conductivity of AuNPs. An electrochemical sensor was constructed based on MoS2/Au-modified carbon paste electrode, for sensitive and quantitative determination of dopamine. The prepared electrochemical sensor proves excellent analytical performances: very high sensitivity, wide linear ranges (0.5–300 μM), and low detection limit (76 nM). Moreover, the dopamine sensor also displays high selectivity, good reproducibility and stability, and can be used in real sample analysis. The method of fabricating high-efficiency electrocatalysts and electrochemical sensors proposed in this study provides a good reference for developing more functionalized nanocomposites and for extending practical applications.

Graphical Abstract

1. Introduction

Dopamine (DA) is a kind of key neurotransmitter, which plays an important role in the normal operation of multiple systems of human body [1,2,3]. Abnormal levels of DA in the body could cause several diseases, such as senile dementia, schizophrenia, and Alzheimer’s disease [1,4]. Development of new materials, methods, or techniques to improve the accuracy and sensitivity in DA detection has great significance. Of the various methods of DA determination [2,5,6], the electrochemical sensor is preferred due to its fast response, high sensitivity, good selectivity, and low cost [7,8]. In order to get better response signals, various nanomaterials or nanocomposites have been used as electrocatalysts towards the oxidation of DA, such as carbon-based nanomaterials, noble metal nanoparticles [9], and conducting polymers [3,10,11,12]. Among these materials, two-dimensional (2D) nanomaterials or their corresponding composites play major roles. That is because 2D nanomaterials generally possess large conjugated layer structure and specific surface area, which can easily adsorb more aromatic and conjugated compounds on the basal plane via the van der Waals force [13,14]. Besides, there are many active sites on the edges and surface defects of 2D nanomaterials [15] that possess excellent catalytic activity towards many kinds of reactions including the electrochemical oxidation of DA. For example, Yang et al. [16] reported an electrochemical sensor for DA detection based on electrochemically reduced graphene oxide, which showed a low detection limit of 0.5 μM. Taylor et al. [17] demonstrated that poly(3,4-ethylene dioxythiophene)/graphene oxide as electrode modifying material could increase the sensitivity and meanwhile decrease the detection limit for the electrochemical detection of DA.
Besides graphene family, MoS2 is another important 2D material that has been widely used in the fields of electronics, catalysis and sensing in recent years [18]. The 2D graphene-like structure, large surface area and available active sites also make MoS2 suitable for the electrochemical catalysis and detection of DA. Pramoda et al. [19], among others, reported that MoS2-reduced graphene oxide composite showed larger response signal than the sole reduced graphene oxide. In previous work [14], the poly(m-aminobenzenesulfonic acid)-reduced MoS2 nanocomposites were used to construct electrochemical sensor for DA detection, which showed satisfactory analytical performance due to the synergetic catalytic effect of the nanocomposites. It is worth noting that Hun et al developed a photoelectrochemical sensor based on nanoMoS2, which showed nearly the widest linear detection range of 10 pM to 10 μM with a lowest detection limit of 2.3 pM [20], demonstrating the promising application prospects in the field of analytical chemistry.
Although numerous publications have been reported for the electrochemical detection of DA, the higher sensitivity and lower detection limit remain pending research topic. As a representative of noble metal nanoparticles, AuNPs were widely used in electrocatalysis and electrochemical sensing [21,22,23,24], including the sensing of DA [25,26,27,28]. However, the AuNPs are prone to aggregation, which will reduce their catalytic activity to a large extent. In situ fabrication of AuNPs on the supporting materials with large surface area or special structure has been nowadays available and favored.
In this study, AuNPs decorated MoS2 nanoslices were prepared by sonicating bulk MoS2 and further electrodeposition of AuNPs. The resultant MoS2 nanoslices/AuNPs nanocomposites (MoS2/Au) retained the 2D structure and large surface area of the MoS2 nanoslices, which could support the deposition of AuNPs and prevent aggregation. As a result, the high catalytic activity of AuNPs was motivated, and the MoS2/Au nanocomposites attained synergetic catalytic effect towards the electrochemical oxidation of DA, as shown in Scheme 1. An electrochemical sensor was constructed based on MoS2/Au modified carbon paste electrode (CPE), for quantitative detection of DA. Under optimized condition, the sensor shows excellent analytical performance, superior than most of previously reported. The proposed method for fabricating efficient catalyst with synergetic catalysis and sensitive sensor provided a way for developing more functionalized nanocomposites and extending their applications.

2. Results and Discussion

2.1. Characterization of Materials

2.1.1. Morphological Characterization

The morphologies of MoS2 nanoslices and MoS2/Au nanocomposites were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results are shown in Figure 1. From Figure 1A, it can be seen clearly that the obtained MoS2 sample after ultrasonic treatment is thin slice-like shape. The nanoslices structure can also be confirmed from their TEM image (Figure 1C). This finding is consistent with our previous report, demonstrating that it is feasible to prepare MoS2 nanoslices using ultrasonic treatment of bulk MoS2 [7,14]. Compared with bulk MoS2, the delaminated MoS2 nanoslices should possess larger surface areas. Therefore, deposition of AuNPs on the surface of MoS2 nanoslices could be more and uniform, as can be seen in the SEM image of MoS2/Au (Figure 1B). The size of AuNPs on the surface of MoS2 is ~10–20 nm, and no obvious aggregation of AuNPs is observed. Likewise, the dark and separate dots appearing on the TEM image of the nanocomposites (Figure 1D) confirm the successful fabrication of MoS2/Au nanocomposites.

2.1.2. Electrochemical characterization

In order to investigate the electrochemical properties of the prepared materials, cyclic voltammetry (CV) and electrochemical impedance electrochemical impedance spectra (EIS) measurements of bare CPE and various modified CPEs (MoS2 nanoslice-modified CPE, AuNP-modified CPE, and MoS2/Au-modified CPE were notated as MoS2/CPE, Au/CPE, and MoS2/Au/CPE, respectively) were carried out in 1.0 mM [Fe(CN)6]3−/4− indicator solution (pH 7.0). As displayed in Figure 2A, no apparent redox peaks are observed on the CV curve of bare CPE, indicating the poor conductivity and very small electroactive surface area, similarly to those reported by Yang et al. [29]. A couple of redox peaks appear on the CV curves of MoS2/CPE, Au/CPE, and MoS2/Au/CPE, and the peak current values increase in turn, indicating the positive effects of the prepared nanomaterials on the improvement of the conductivity and electroactive surface area of CPE. However, compared with MoS2/CPE and Au/CPE, MoS2/Au/CPE shows the largest peak current values, implying the higher conductivity and electroactive surface area of MoS2/Au nanocomposites than the single nanomaterials. This is because the combination of MoS2 nanoslices and AuNPs can not only retain the large surface area of MoS2, but also effectively avoid the aggregation of AuNPs in deposition process. The EIS test results are illustrated in Figure 2B, from the Nyquist plot it is found that the semicircular capacitive loop of CPE, MoS2/CPE, Au/CPE, and MoS2/Au/CPE decreases in sequence, indicating the gradually decreasing charge-transfer resistance (Rct), that is, MoS2/Au/CPE facilitate the charge transfer in a greater degree [2,30]. It is in line with and further confirms the result drawn from CV tests.

2.2. The Elextrochemical Behaviors of DA

The catalytic effects of the prepared nanomaterials towards the electrochemical oxidations of DA were investigated by CV measurements. Figure 3A shows the different electrocatalytic effects of the various nanomaterials. It can be seen that a couple of small and irreversible redox peaks present at the CV curve of CPE, and the difference between anodic peak potential (Epa) and cathodic peak potential (Epc) exceeds 0.5 V, and Epa value is greater than 0.4 V, which indicates the inferior catalytic effect of bare CPE towards the oxidation of DA. Compared with bare CPE, MoS2/CPE and Au/CPE show more apparent redox peaks and smaller peak potential differences, demonstrating both MoS2 nanoslices and AuNPs have electrocatalytic effect on the oxidation of DA. The large surface area and 2D conjugated structure of MoS2 nanoslices could physically adsorb more aromatic and conjugated compounds on the basal plane via the van der Waals force [13,14]. The AuNPs has an intrinsic catalytic property and excellent conductivity. However, the MoS2/Au/CPE displays larger redox peaks and smaller peak potential difference than the sole nanomaterials modified CPE, indicating the MoS2/Au nanocomposites get the synergistic catalytic activity towards the oxidation of DA. It is attributed to the large electroactive surface area, special structure that can adsorb DA molecules and the high conductivity, as well as the retain of the catalytic activity of AuNPs.
In order to investigate the electrochemical catalytic effects of analytical performance of different electrodes more clearly and readily, differential pulse voltammetry (DPV) technique was adopted to measure the oxidation process of DA. As observed from Figure 3B, the DPV curves show the same variation trend with that in the oxidation process of CV curves, that is, the Epa values of bare CPE, MoS2/CPE, Au/CPE, and MoS2/Au/CPE decrease in turn while the anodic peak current (Ipa) values increase. The result that MoS2/Au/CPE possesses the best electrocatalytic effect towards the oxidation of DA coincides with that obtained from CV measurements. Therefore, the electrochemical sensor based on MoS2/Au nanocomposites for the detection of DA was constructed and considered feasible.
To further study the electrochemical behavior of DA at MoS2/Au/CPE, CV measurements of 0.2 mM DA at different scan rate (υ) were performed, and the results are shown in Figure S1. It is observed from Figure S1A that both the Ipa values and the cathodic peak current (Ipc) values increase with the scan rate gradually increasing from 20 to 300 mV/s. Figure S1B shows the linear relationships between redox peak currents and scan rates, which can be denoted by Equations (1) and (2), respectively.
Ipa (μA) = −0.1523υ − 6.0034 (R² = 0.9941)
Ipc (μA) = 0.1683υ + 4.7878 (R² = 0.9977)
The results confirm that DA molecules can be adsorbed onto the surface of the MoS2/Au/CPE, and indicate the electrode reaction of DA is an adsorption-controlled process [14,31,32].

2.3. Condition Optimization for Electrochemical Detection of DA

For the purpose of obtaining the optimal response signals for DA detection, the condition optimization was conducted. For the electrochemical deposition of AuNPs on MoS2/CPE, the deposition time has an important effect on the amount of AuNPs, and then results in different response signals for DA detection. As exhibited in Figure S2, with the deposition time increasing from 100 to 500 s, the Ipa value increases at first and reaches the maximum at 300 s, and then decreases with further increase of the deposition time. With the increase of deposition time from 100 to 300 s, more AuNPs were produced. The conductivity, surface area, and catalytic activity of the MoS2/Au/CPE were improved correspondingly. However, too long deposition time caused the stack and aggregation of abundant AuNPs, reducing the active surface area and hence resulting in the decreased Ipa values. Therefore, 300 s was the optimal deposition time of AuNPs in this experiment.
The electrochemical oxidation of DA is a kind of proton-involved reaction. The pH of detection solution has an effect on the electrocatalytic behavior of DA. This effect was studied by DPV measurements and the results are displayed in Figure S3A. It is observed that the pH has important effects on both Epa and Ipa, and the effects are more clearly depicted in Figure S3B. With the increase of pH from 5.0 to 9.0, the Epa value of DA decreases gradually, and it has a linear relationship with the pH, expressed by
Epa (V) = −0.0536pH + 0.522 (R2 = 0.9981).
The slope of the linear equation (Epa/pH) was -53.6 mV/pH that is close to the theoretical value for an equal number of proton and electron involved reaction (−59 mV/pH at 25 °C), implying the oxidation of DA at MoS2/Au/CPE is a 2-electron and 2-proton involved process [10,25,33]. Furthermore, it shows that the Ipa value of DA increases with increasing pH value from 5.0 to 7.0, and then decreases with the further increase of pH value from 7.0 to 9.0. Therefore, pH 7.0 is the optimal for DA detection.

2.4. Electrochemical Detection of DA

For analytical detection, the sensitivity and accuracy are the key. DPV measurement was performed for the quantitative detection of DA under the optimal conditions. Figure 4A shows the DPV curves of DA with a variety of different concentrations (from 0.5 to 300 μM) recorded at MoS2/Au/CPE. It is clearly observed that the current responses enlarge with the increase of the concentration, and even in very low concentration the anodic peaks are still apparently found from the inserted plot. Figure 4B displays a linear relationship of the Ipa values versus the concentrations of DA ranging from 0.5 to 300 μM. The linear regression equation is expressed by
|Ipa| (μA) = 0.110C (μM) + 1.786 (R2 = 0.9977),
where |Ipa| denotes the Ipa value in this paper. The detection sensitivity (the slope of linear equation) is up to 0.11 A/M, which is much higher than that in previous reports [10,34,35]. The detection limit was estimated to be 76 nM, based on the result analysis above and the formula
D = 3Sb/m,
where Sb denotes the standard deviation of blank signals of 10 parallel measurements and m is the detection sensitivity [14,25]. The comparison of the analytical performances of MoS2/Au/CPE with that of other reported electrochemical sensors is shown in Table 1. It can be found this study provides a relatively low detection limit and a wide linear range for DA detection.

2.5. Selectivity of the Eectrochemical Sensor

Interference tests from common foreign substances were carried out to evaluate the anti-interference performance of the proposed electrochemical DA sensor. As listed in Table S1, 10 mM KNO3, NaCl, CaCl2, and MgSO4 or 2 mM glucose and citric acid has little influence on the current response of 50 μM DA (the relative error is within ±5%).
Ascorbic acid (AA) and uric acid (UA) are the main interferents that always interfere the electrochemical detection of DA. The anti-interference towards AA and UA is a key performance of an electrochemical DA sensor. Figure S4 shows the DPV responses of the proposed electrochemical sensor for 50 μM DA with AA and UA in different concentrations, it can be seen that the anodic peaks are separate, and the presence of 500 μM AA and 100 μM UA have no obvious influence on the Ipa value of 50 μM DA, demonstrating the high selectivity of the electrochemical DA sensor.

2.6. Reproducibility and Stability of the Electrochemical Sensor

The reproducibility of the proposed electrochemical sensor was evaluated through the parallel measurements of DPV responses of 10 μM DA at five independent MoS2/Au/CPEs. The results are shown in Figure S5A. The relative standard deviation (RSD) of these Ipa values was calculated as 4.09%, indicating a good reproducibility. Besides, the stability of the prepared sensor was also investigated by the measurement of the DPV response of 10 μM DA after storage at 4 °C for a period of time. Figure S5B exhibits that the Ipa value retains about 96.4% of its original value after 5 days and ~90.3% after 20 days, demonstrating an acceptable long-time stability.

2.7. Real Sample Analysis

Urine samples were tested using standard addition method to evaluate the analytical performance of the DA sensor in real sample detections. Table 2 shows the detection results, from which it is found that the recoveries range from 96.3% to 104%, implying that the proposed electrochemical sensor has a satisfactory performance for DA detection in the real samples.

3. Materials and Methods

3.1. Reagents and Apparatus

3.1.1. Reagents

Bulk MoS2 (powder, <2 μm, 98%) and dopamine hydrochloride were obtained from Sigma-Aldrich (St. Louis, MO, USA). Ascorbic acid (99.99%) and uric acid (99%) were bought from Aladdin (Shanghai, China). HAuCl4·4H2O (99.9%), K3Fe(CN)6 (≥99.0%) and K4Fe(CN)6·3H2O (≥99.5%) were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). N,N-dimethylformamide (DMF, 99%), NaH2PO4·2H2O (≥99%) and Na2HPO4·2H2O (≥99%) were obtained from Adamas-beta (Shanghai, China). Other regents used in this study were provided by domestic regular reagent companies, and directly used without any treatment. Deionized water from a Milli-Q ultrapure water purification system was used for the preparation of aqueous solution. Phosphate buffer solution ((PBS) 0.1 M) consisting of NaH2PO4/Na2HPO4 was used as supporting electrolyte, and its pH was adjusted by 0.1 M HCl or NaOH aqueous solution. 1.0 mM [Fe(CN)6]3−/4 aqueous solution (pH 7.0) containing 0.1 M KCl that prepared with K3Fe(CN)6, K4Fe(CN)6·3H2O and KCl was used as electroactive indicator solution.

3.1.2. Apparatus

The electrochemical tests were conducted on a CHI 760D electrochemical workstation (Shanghai CH Instrument Company, Shanghai, China) with a three-electrode system, in which a bare CPE or modified CPE acted as working electrode and a saturated calomel electrode and a platinum wire acted as reference electrode and counter electrode, respectively. The ultrasonic treatment was carried out using a KQ-500B ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd., Kunshan, China). The measurements of pH values were performed with a PHS-25 digital pH meter (Shanghai Leici Factory, Shanghai, China). A JSM-6700F SEM (JEOL, Tokyo, Japan) and JEM-2100 TEM (JEOL, Tokyo, Japan) were used for the morphological characterizations.

3.2. Fbrication of Modified Electrodes

CPE was fabricated by the method reported previously [39]. Briefly, graphite powder and paraffin with the mass ratio of 3:1 were homogeneously mixed by stirring at 60 °C, and then the homogeneous carbon paste was filled in a glass tube (Φ = 4 mm) and compacted after vibration. A copper wire was inserted in the carbon paste as a conductive wire. It is required to be polished on a paper before use.
MoS2 nanoslice dispersion was prepared by ultrasonic treatment of bulk MoS2 in DMF for 4 h with the MoS2 concentration of 1 mg/mL [14]. 20 µL of the dispersion was dripped on the tip of CPE, then MoS2/CPE was obtained after the dispersion naturally dried in the air.
MoS2/Au/CPE was prepared through potentiostatic electrodeposition of AuNPs at MoS2/CPE in 0.1 M PBS containing 2.0 mM HAuCl4 under −0.2 V for a certain time. It should be noted that the MoS2/Au/CPE used in this study was prepared under the deposition time of 300 s except in the experiment of condition optimization.
As a contrast, Au/CPE was also fabricated under the same condition at CPE instead of MoS2/CPE.

3.3. Electrochemical Measurements

For CV measurements in 1.0 mM [Fe(CN)6]3-/4- indicator solution (pH 7.0), the potential was scanned between 0.6 and −0.3 V with a scan rate of 0.1 V/s, while in 0.1 M PBS (pH 7.0) containing 1.0 mM DA, the potential range was scanned between 0.6 and −0.2 V with the same scan rate. The potential and the frequency range for EIS measurements in 1.0 mM [Fe(CN)6]3−/4− indicator solution (pH 7.0) were set as 0.17 V and 10 kHz–0.1 Hz. For DPV measurements, the potential range, scan rate, pulse width, pulse amplitude, and pulse period were set as from −0.2 to 0.6 V, 0.05 V s−1, 0.2 s, 0.05 V, and 0.5 s, respectively.
Unless otherwise stated, all the experiment results in this study were the average of three parallel measurements.

4. Conclusions

MoS2 nanoslices and AuNPs nanocomposites were prepared by using ultrasonic treatment and electrodeposition technique. The obtained MoS2/Au nanocomposites retained the large surface area and 2D slice-like structure of MoS2 nanoslices and, simultaneously, the high catalytic activity and good conductivity of AuNPs, resulting in synergetic electrocatalytic effect for the oxidation of DA. The electrochemical sensor constructed based on MoS2/Au nanocomposites shows excellent analytical performances for the DA detection, including very high sensitivity (0.11 A/M), wide linear range (0.5–300 μM), low detection limit (76 nM), high selectivity, and good reproducibility, stability, and availability in real sample analysis.

Supplementary Materials

The following are available online at https://www.mdpi.com/2073-4344/9/8/653/s1. Figure S1: (A) The CV curves of MoS2/Au/CPE in 0.1M PBS (pH 7.0) containing 0.2 mM DA at a series of scan rate (from a to g: 20, 30, 50, 80, 100, 150, 200, 300 mV/s), (B) the linear relationships of Ipa and Ipc versus the scan rate; Figure S2: (A) the DPV curves of MoS2/Au/CPE prepared under different electrodeposition time of AuNPs in 0.1M PBS (pH 7.0) containing 1.0 mM DA, (B) the corresponding variation of Ipa value with the increase of the electrodeposition time; Figure S3: (A) the DPV curves of MoS2/Au/CPE in 0.1M PBS (pH 7.0) containing 1.0 mM DA at different pH, (B) the corresponding variation of Ipa and Epa values with the change of pH; Table S1: Detection of 50 μM DA in the presence of the common substance; Figure S4: The DPV curves of MoS2/Au/CPE in 0.1M PBS (pH 7.0) containing 50 μM DA and (a) 0μM AA + 0μM UA, (b) 100 μM AA + 20 μM UA, (c) 300 μM AA + 60 μM UA, and (d) 500 μM AA + 100 μM UA; Figure S5: (A) the Ipa values of DPV measurements recorded in 0.1M PBS (pH 7.0) containing 10 μM DA at five independent MoS2/Au/CPEs, (B) the Ipa values of DPV measurements in 0.1M PBS (pH 7.0) containing 10 μM DA at MoS2/Au/CPE after storage for different periods of time.

Author Contributions

Conceptualization, H.C. (Huaiyin Chen) and R.H.; methodology, H.C. (Huaiyin Chen); software, H.C. (Huaiyin Chen) and H.C. (Huaijin Chen); validation, H.C. (Huaiyin Chen), H.C. (Huaijin Chen), and R.H.; formal analysis, H.C. (Huaiyin Chen); investigation, H.C. (Huaiyin Chen) and H.C. (Huaijin Chen); resources, R.H.; data curation, H.C. (Huaiyin Chen); writing—original draft preparation, H.C. (Huaiyin Chen); writing—review and editing, H.C. (Huaiyin Chen), H.C. (Huaijin Chen), and R.H.; visualization, H.C. (Huaiyin Chen); supervision, R.H.; project administration, R.H.; funding acquisition, R.H.

Funding

This research was funded by the National Natural Science Foundation of China (No. 21675092), Minjiang Scholarship of Fujian Province (No. Min-Gaojiao[2010]-117), Central Government-Guided Fund for Local Economic Development (No. 830170778), R&D Fund for Strategic Emerging Industry of Fujian Province (No. 82918001), and Teaching and Researching Fund for Young Staff of Fujian Educational Department (No. JT180040).

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

References

  1. Oh, J.W.; Yoon, Y.W.; Heo, J.; Yu, J.; Kim, H.; Kim, T.H. Electrochemical detection of nanomolar dopamine in the presence of neurophysiological concentration of ascorbic acid and uric acid using charge-coated carbon nanotubes via facile and green preparation. Talanta 2016, 147, 453–459. [Google Scholar] [CrossRef] [PubMed]
  2. Rezaei, B.; Boroujeni, M.K.; Ensafi, A.A. Fabrication of DNA, o-phenylenediamine, and gold nanoparticle bioimprinted polymer electrochemical sensor for the determination of dopamine. Biosens. Bioelectron. 2015, 66, 490–496. [Google Scholar] [CrossRef] [PubMed]
  3. Zhao, Y.; Zhou, J.; Jia, Z.; Huo, D.; Liu, Q.; Zhong, D.; Hu, Y.; Yang, M.; Bian, M.; Hou, C. In-situ growth of gold nanoparticles on a 3D-network consisting of a MoS2/rGO nanocomposite for simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid. Mikrochim. Acta 2019, 186, 92. [Google Scholar] [CrossRef] [PubMed]
  4. Gu, X.; Jiang, G.; Jiang, G.; Chen, T.; Zhan, W.; Li, X.; Wu, S.; Tian, S. Detection of dopamine on a mercapto-terminated hexanuclear Fe(III) cluster modified gold electrode. Talanta 2015, 137, 189–196. [Google Scholar] [CrossRef] [PubMed]
  5. Pruneanu, S.; Biris, A.R.; Pogacean, F.; Socaci, C.; Coros, M.; Rosu, M.C.; Watanabe, F.; Biris, A.S. The influence of uric and ascorbic acid on the electrochemical detection of dopamine using graphene-modified electrodes. Electrochim. Acta 2015, 154, 197–204. [Google Scholar] [CrossRef]
  6. Canevari, T.C.; Nakamura, M.; Cincotto, F.H.; de Melo, F.M.; Toma, H.E. High performance electrochemical sensors for dopamine and epinephrine using nanocrystalline carbon quantum dots obtained under controlled chronoamperometric conditions. Electrochim. Acta 2016, 209, 464–470. [Google Scholar] [CrossRef]
  7. Yang, T.; Chen, H.; Ge, T.; Wang, J.; Li, W.; Jiao, K. Highly sensitive determination of chloramphenicol based on thin-layered MoS2/polyaniline nanocomposite. Talanta 2015, 144, 1324–1328. [Google Scholar] [CrossRef]
  8. Bergman, J.; Mellander, L.; Wang, Y.; Cans, A.-S. Co-detection of dopamine and glucose with high temporal resolution. Catalysts 2018, 8, 34. [Google Scholar] [CrossRef]
  9. Mazloum-Ardakani, M.; Abolhasani, M.; Mirjalili, B.F.; Sheikh-Mohseni, M.A.; Dehghani-Firouzabadi, A.; Khoshroo, A. Electrocatalysis of dopamine in the presence of uric acid and folic acid on modified carbon nanotube paste electrode. Chin. J. Catal. 2014, 35, 201–209. [Google Scholar] [CrossRef]
  10. Huang, K.-J.; Zhang, J.-Z.; Liu, Y.-J.; Wang, L.-L. Novel electrochemical sensing platform based on molybdenum disulfide nanosheets-polyaniline composites and Au nanoparticles. Sens. Actuators B 2014, 194, 303–310. [Google Scholar] [CrossRef]
  11. Qi, S.; Zhao, B.; Tang, H.; Jiang, X. Determination of ascorbic acid, dopamine, and uric acid by a novel electrochemical sensor based on pristine graphene. Electrochim. Acta 2015, 161, 395–402. [Google Scholar] [CrossRef]
  12. Li, Y.; Lin, H.; Peng, H.; Qi, R.; Luo, C. A glassy carbon electrode modified with MoS2 nanosheets and poly(3,4-ethylenedioxythiophene) for simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid. Microchim. Acta 2016, 183, 2517–2523. [Google Scholar] [CrossRef]
  13. Zhu, C.; Zeng, Z.; Li, H.; Li, F.; Fan, C.; Zhang, H. Single-layer MoS2-based nanoprobes for homogeneous detection of biomolecules. J. Am. Chem. Soc. 2013, 135, 5998–6001. [Google Scholar] [CrossRef] [PubMed]
  14. Yang, T.; Chen, H.; Jing, C.; Luo, S.; Li, W.; Jiao, K. Using poly(m-aminobenzenesulfonic acid)-reduced MoS2 nanocomposite synergistic electrocatalysis for determination of dopamine. Sens. Actuators B 2017, 249, 451–457. [Google Scholar] [CrossRef]
  15. Chia, X.; Pumera, M. Characteristics and performance of two-dimensional materials for electrocatalysis. Nat. Catal. 2018, 1, 909–921. [Google Scholar] [CrossRef]
  16. Yang, L.; Liu, D.; Huang, J.; You, T. Simultaneous determination of dopamine, ascorbic acid and uric acid at electrochemically reduced graphene oxide modified electrode. Sens. Actuators B 2014, 193, 166–172. [Google Scholar] [CrossRef]
  17. Taylor, I.M.; Robbins, E.M.; Catt, K.A.; Cody, P.A.; Happe, C.L.; Cui, X.T. Enhanced dopamine detection sensitivity by PEDOT/graphene oxide coating on in vivo carbon fiber electrodes. Biosens. Bioelectron. 2017, 89, 400–410. [Google Scholar] [CrossRef] [PubMed]
  18. Chen, H.-Y.; Wang, J.; Meng, L.; Yang, T.; Jiao, K. Thin-layered MoS2/polyaniline nanocomposite for highly sensitive electrochemical detection of chloramphenicol. Chin. Chem. Lett. 2016, 27, 231–234. [Google Scholar] [CrossRef]
  19. Pramoda, K.; Moses, K.; Maitra, U.; Rao, C.N.R. Superior performance of a MoS2-RGO composite and a borocarbonitride in the electrochemical detection of dopamine, uric acid and adenine. Electroanalysis 2015, 27, 1892–1898. [Google Scholar] [CrossRef]
  20. Hun, X.; Wang, S.; Wang, S.; Zhao, J.; Luo, X. A photoelectrochemical sensor for ultrasensitive dopamine detection based on single-layer NanoMoS2 modified gold electrode. Sens. Actuators B 2017, 249, 83–89. [Google Scholar] [CrossRef]
  21. Yadav, D.K.; Ganesan, V.; Sonkar, P.K.; Gupta, R.; Rastogi, P.K. Electrochemical investigation of gold nanoparticles incorporated zinc based metal-organic framework for selective recognition of nitrite and nitrobenzene. Electrochim. Acta 2016, 200, 276–282. [Google Scholar] [CrossRef]
  22. Lin, P.; Chai, F.; Zhang, R.; Xu, G.; Fan, X.; Luo, X. Electrochemical synthesis of poly(3,4-ethylenedioxythiophene) doped with gold nanoparticles, and its application to nitrite sensing. Microchim. Acta 2016, 183, 1235–1241. [Google Scholar] [CrossRef]
  23. Chen, H.; Yang, T.; Liu, F.; Li, W. Electrodeposition of gold nanoparticles on Cu-based metal-organic framework for the electrochemical detection of nitrite. Sens. Actuators B 2019, 286, 401–407. [Google Scholar] [CrossRef]
  24. Wang, Y.; Wang, L.; Chen, H.; Hu, X.; Ma, S. Fabrication of highly sensitive and stable hydroxylamine electrochemical sensor based on gold nanoparticles and metal-metalloporphyrin framework modified electrode. ACS Appl. Mater. Interfaces 2016, 8, 18173–18181. [Google Scholar] [CrossRef] [PubMed]
  25. Rezaei, B.; Havakeshian, E.; Ensafi, A.A. Decoration of nanoporous stainless steel with nanostructured gold via galvanic replacement reaction and its application for electrochemical determination of dopamine. Sens. Actuators B 2015, 213, 484–492. [Google Scholar] [CrossRef]
  26. Khan, M.Z.H.; Liu, X.Q.; Tang, Y.F.; Zhu, J.H.; Hu, W.P.; Liu, X.H. A glassy carbon electrode modified with a composite consisting of gold nanoparticle, reduced graphene oxide and poly(L-arginine) for simultaneous voltammetric determination of dopamine, serotonin and L-tryptophan. Microchim. Acta 2018, 185, 439. [Google Scholar] [CrossRef] [PubMed]
  27. Li, C.; Chen, X.J.; Zhang, Z.; Tang, J.L.; Zhang, B.L. Gold nanoparticle-DNA conjugates enhanced determination of dopamine by aptamer-based microcantilever array sensor. Sens. Actuators B 2018, 275, 25–30. [Google Scholar] [CrossRef]
  28. Mei, X.R.; Wei, Q.P.; Long, H.Y.; Yu, Z.M.; Deng, Z.J.; Meng, L.C.; Wang, J.; Luo, J.T.; Lin, C.T.; Ma, L.; et al. Long-term stability of Au nanoparticle-anchored porous boron-doped diamond hybrid electrode for enhanced dopamine detection. Electrochim. Acta 2018, 271, 84–91. [Google Scholar] [CrossRef]
  29. Yang, T.; Chen, H.; Qiu, Z.; Yu, R.; Luo, S.; Li, W.; Jiao, K. Direct vibrio DNA sensing adopting highly stable graphene-flavin mononucleotide aqueous dispersion modified interface. ACS Appl. Mater. Interfaces 2018, 10, 4540–4547. [Google Scholar] [CrossRef]
  30. Hu, L.; Ren, Y.; Yang, H.; Xu, Q. Fabrication of 3D hierarchical MoS2/polyaniline and MoS2/C architectures for lithium-ion battery applications. ACS Appl. Mater. Interfaces 2014, 6, 14644–14652. [Google Scholar] [CrossRef]
  31. Yao, Y.; Wen, Y.; Xu, J.; Zhang, L.; Duan, X. Application of commercial poly(3,4-ethylenedioxy-thiophene):poly(styrene sulfonate) for electrochemical sensing of dopamine. J. Serb. Chem. Soc. 2013, 78, 1397–1411. [Google Scholar] [CrossRef]
  32. Wang, P.; Li, Y.; Huang, X.; Wang, L. Fabrication of layer-by-layer modified multilayer films containing choline and gold nanoparticles and its sensing application for electrochemical determination of dopamine and uric acid. Talanta 2007, 73, 431–437. [Google Scholar] [CrossRef] [PubMed]
  33. Zhang, M.; Gong, K.; Zhang, H.; Mao, L. Layer-by-layer assembled carbon nanotubes for selective determination of dopamine in the presence of ascorbic acid. Biosens. Bioelectron. 2005, 20, 1270–1276. [Google Scholar] [CrossRef] [PubMed]
  34. Hammami, A.; Sahli, R.; Raouafi, N. Indirect amperometric sensing of dopamine using a redox-switchable naphthoquinone-terminated self-assembled monolayer on gold electrode. Microchim. Acta 2016, 183, 1137–1144. [Google Scholar] [CrossRef]
  35. Ma, L.; Zhang, Q.; Wu, C.; Zhang, Y.; Zeng, L. PtNi bimetallic nanoparticles loaded MoS2 nanosheets: Preparation and electrochemical sensing application for the detection of dopamine and uric acid. Anal. Chim. Acta 2019, 1055, 17–25. [Google Scholar] [CrossRef] [PubMed]
  36. Fritzen-Garcia, M.B.; Monteiro, F.F.; Cristofolini, T.; Acuña, J.J.S.; Zanetti-Ramos, B.G.; Oliveira, I.R.W.; Soldi, V.; Pasa, A.A.; Creczynski-Pasa, T.B. Characterization of horseradish peroxidase immobilized on PEGylated polyurethane nanoparticles and its application for dopamine detection. Sens. Actuators B 2013, 182, 264–272. [Google Scholar] [CrossRef]
  37. Zhang, Q.L.; Feng, J.X.; Wang, A.J.; Wei, J.; Lv, Z.Y.; Feng, J.J. A glassy carbon electrode modified with porous gold nanosheets for simultaneous determination of dopamine and acetaminophen. Microchim. Acta 2015, 182, 589–595. [Google Scholar] [CrossRef]
  38. Wang, J.; Yang, B.B.; Zhong, J.T.; Yan, B.; Zhang, K.; Zhai, C.Y.; Shiraishi, Y.; Du, Y.K.; Yang, P. Dopamine and uric acid electrochemical sensor based on a glassy carbon electrode modified with cubic Pd and reduced graphene oxide nanocomposite. J. Colloid Interface Sci. 2017, 497, 172–180. [Google Scholar] [CrossRef] [PubMed]
  39. Yang, R.; Zhao, J.; Chen, M.; Yang, T.; Luo, S.; Jiao, K. Electrocatalytic determination of chloramphenicol based on molybdenum disulfide nanosheets and self-doped polyaniline. Talanta 2015, 131, 619–623. [Google Scholar] [CrossRef] [PubMed]
Scheme 1. Preparation of electrochemical sensor based on MoS2/Au for Dopamine (DA) detection.
Scheme 1. Preparation of electrochemical sensor based on MoS2/Au for Dopamine (DA) detection.
Catalysts 09 00653 sch001
Figure 1. SEM images (A,B) and TEM images (C,D) of MoS2 nanoslices (A,C) and MoS2/Au nanocomposites (B,D).
Figure 1. SEM images (A,B) and TEM images (C,D) of MoS2 nanoslices (A,C) and MoS2/Au nanocomposites (B,D).
Catalysts 09 00653 g001
Figure 2. The (A) CV and (B) EIS curves recorded at bare CPE, MoS2/CPE, Au/CPE and MoS2/Au/CPE in 1.0 mM [Fe(CN)6]3−/4− solution (pH 7.0).
Figure 2. The (A) CV and (B) EIS curves recorded at bare CPE, MoS2/CPE, Au/CPE and MoS2/Au/CPE in 1.0 mM [Fe(CN)6]3−/4− solution (pH 7.0).
Catalysts 09 00653 g002
Figure 3. The cyclic voltammetry (CV) (A) and differential pulse voltammetry (DPV) (B) curves recorded at bare CPE, MoS2/CPE, Au/CPE, and MoS2/Au/CPE in 0.1M PBS solution (pH 7.0) containing 1.0 mM DA.
Figure 3. The cyclic voltammetry (CV) (A) and differential pulse voltammetry (DPV) (B) curves recorded at bare CPE, MoS2/CPE, Au/CPE, and MoS2/Au/CPE in 0.1M PBS solution (pH 7.0) containing 1.0 mM DA.
Catalysts 09 00653 g003
Figure 4. (A) The DPV curves of MoS2/Au/CPE in 0.1M PBS solution (pH 7.0) containing DA with a series of concentrations (0.5, 1, 2, 5, 10, 20, 50, 100, 150, 200, 250, and 300 μM) and (B) the relationship of Ipa value versus the concentration of DA.
Figure 4. (A) The DPV curves of MoS2/Au/CPE in 0.1M PBS solution (pH 7.0) containing DA with a series of concentrations (0.5, 1, 2, 5, 10, 20, 50, 100, 150, 200, 250, and 300 μM) and (B) the relationship of Ipa value versus the concentration of DA.
Catalysts 09 00653 g004
Table 1. Comparison of electroanalytical performances of different modified electrodes for DA detection.
Table 1. Comparison of electroanalytical performances of different modified electrodes for DA detection.
ElectrodeDetection MethodLinear Range (μM)Detection Limit (μM)Reference
3D-MoS2/rGO 1/Au@GCEDPV0.3–198.30.11[3]
MoS2/PEDOT 2/GCEDPV1–800.52[12]
PABSA-rMoS2 3/CPEDPV1–500.22[14]
GO 4/GCEDPV1–150.27[36]
porous AuNSs 5/GCEDPV2–2980.28[37]
Pd/rGO 1/GCEDPV0.45–4210.18[38]
MoS2/Au/CPEDPV0.5–3000.076This work
1 rGO: reduced graphene oxide; 2 PEDOT: poly(3,4-ethylenedioxythiophene); 3 PABSA-rMoS2: poly(m-aminobenzenesulfonic acid)-reduced MoS2; 4 GO: graphene oxide; 5 AuNSs: Au nanosheets.
Table 2. Detection of DA in urine samples (n = 3).
Table 2. Detection of DA in urine samples (n = 3).
Sample No.DA Added (μM)DA Found (μM)Recovery (%)RSD (%)
10Not found
2109.63 ± 0.4296.3 ± 4.24.2
32020.8 ± 0.62104 ± 3.13.5
44038.9 ± 1.4597.3 ± 3.63.8

Share and Cite

MDPI and ACS Style

Chen, H.; Chen, H.; Hong, R. Fabrication of Au Nanoparticle-Decorated MoS2 Nanoslices as Efficient Electrocatalysts for Electrochemical Detection of Dopamine. Catalysts 2019, 9, 653. https://doi.org/10.3390/catal9080653

AMA Style

Chen H, Chen H, Hong R. Fabrication of Au Nanoparticle-Decorated MoS2 Nanoslices as Efficient Electrocatalysts for Electrochemical Detection of Dopamine. Catalysts. 2019; 9(8):653. https://doi.org/10.3390/catal9080653

Chicago/Turabian Style

Chen, Huaiyin, Huaijin Chen, and Ruoyu Hong. 2019. "Fabrication of Au Nanoparticle-Decorated MoS2 Nanoslices as Efficient Electrocatalysts for Electrochemical Detection of Dopamine" Catalysts 9, no. 8: 653. https://doi.org/10.3390/catal9080653

APA Style

Chen, H., Chen, H., & Hong, R. (2019). Fabrication of Au Nanoparticle-Decorated MoS2 Nanoslices as Efficient Electrocatalysts for Electrochemical Detection of Dopamine. Catalysts, 9(8), 653. https://doi.org/10.3390/catal9080653

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop