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Article

Synthesis of Quaternary (Ni, Co, Cu)Se2 Nanosheet Arrays on Carbon Cloth for Non-Enzymatic Glucose Determination

by
Yuanyuan Chen
1,
Huan Wang
2,
Huinan Chen
2,
Jingyao Song
2,
Dongmei Deng
2,* and
Liqiang Luo
1,*
1
Department of Chemistry, Shanghai University, Shanghai 200444, China
2
Department of Physics, Shanghai University, Shanghai 200444, China
*
Authors to whom correspondence should be addressed.
Chemosensors 2023, 11(10), 530; https://doi.org/10.3390/chemosensors11100530
Submission received: 26 July 2023 / Revised: 18 September 2023 / Accepted: 7 October 2023 / Published: 9 October 2023
(This article belongs to the Special Issue Current Development on Electrochemical Glucose Biosensors)
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Versions Notes

Abstract

:
Unlike transition metal oxides and sulfides, transition metal-based selenides display higher electrical conductivity, more electroactive unsaturated edge sites, and better chemical stability, which have found extensive usage in electrocatalysis. In this work, simple hydrothermal and solvothermal procedures were employed to synthesize quaternary (Ni, Co, Cu)Se2 nanosheet arrays on carbon cloth (CC) to measure glucose. The conductivity of the material can be effectively elevated by adding Se element to form selenides, and the synergistic effect between the three selenides can improve the electrocatalytic performance. Consequently, in the ranges of 0.01–600 μM and 600–9000 μM, respectively, the current response of the synthesized material to glucose concentration exhibited linear relationships. The sensor demonstrated excellent sensitivity and a low detection limit of 5.82 nM. Furthermore, the practical applicability of the constructed biosensor was proved by using it to quantify the amount of glucose in human serum.

Graphical Abstract

1. Introduction

Glucose is a monosaccharide necessary for metabolism and can directly participate in the metabolic process within the human body [1,2]. It is crucial to the study of biology and serves as the primary source of energy for organisms. The capacity to detect glucose is critical in healthcare and the food sector. Usually, the standard of glucose content in human blood is 3.9–6.1 mM for fasting blood glucose and 5.1–7.0 mM for postprandial blood glucose, while the amount of glucose in human sweat is 10–200 μM. Low glucose levels, however, may result in hypoglycemia or seizures [3]. A chronic metabolic condition characterized by elevated blood glucose is diabetes mellitus. In the meantime, it is also used as a diabetes diagnosis indicator [4,5]. When the levels of glucose in the blood are high for an extended period, it can lead to significant health problems such as nephropathy, retinopathy, and cardiovascular disease [6]. Among these instances, abnormal blood glucose levels in diabetic people may result in issues with apoptosis in addition to certain types of inflammation. To prevent problems with this metabolic disease, blood glucose levels need to be regularly monitored. The requirement for a speedy and precise blood glucose measurement method is of paramount significance given the current rise in the number of diabetic patients worldwide.
Nowadays, with the increasing number of individuals suffering from diabetes, it is critical to come up with swift and effective glucose detection techniques. The electrochemical technique is regarded as the most efficient technique for glucose determination since it is affordable, convenient to operate, and extremely sensitive [7,8,9,10]. Currently, both enzyme-based and enzyme-free glucose sensors are applied as electrochemical glucose sensors. Since 1962, due to their excellent specificity, enzyme electrodes have been used to detect blood glucose [11]. In glucose enzymatic sensors, glucose dehydrogenase and oxidase are frequently utilized. The following features of the glucose–enzyme catalyst are apparent: (a) one enzyme molecule is capable of taking part in one type of reaction as a result of its high specificity; (b) every molecule of the enzyme has a high catalytic efficiency; and (c) enzymes possess extremely specific catalytic requirements. To participate in the procedure, they frequently require to be at normal temperature and pressure [12]. Unfortunately, the vast majority of conventional glucose sensors use natural enzymes as receptors, which severely restricts their practical use due to the drawbacks of natural enzymes, such as easy activity loss, a problematic fixation process, and instability. No matter what enzyme is employed or how the enzyme remains immobilized, enzyme-based electrochemical sensors are unable to offer perfect reproducibility, making their large-scale production and utilization relatively challenging. The detection performance of the enzyme-free glucose electrochemical sensor is marginally worse than that of the conventional glucose enzyme sensor, but it overcomes the dependence on the enzyme, has a wide detection range, good reproducibility, and other advantages. This greatly broadens the public understanding of the sensor. Enzyme-free glucose sensors are more stable, repeatable, and easy to use than enzyme-based glucose sensors [13,14].
As a result of their quick response time, high accuracy, affordable cost, and superior sensitivity, enzyme-free glucose electrochemical sensors have attracted an abundance of attention [15]. One of the most significant variables influencing sensor performance is speculated to be electrode materials. The fabrication of electrode materials with a large surface area, good catalytic capacity, and efficient and precise glucose detection becomes essential. More specifically, by modifying their shape, size, composition, adsorption capacity, electron transport capabilities, and specific surface area, numerous highly efficient materials have been created to enhance sensor performance [16,17]. Numerous metals and metal oxide materials have been employed for glucose-sensing applications throughout the last few decades. Noble metal (Ag, Au, Pd, and Pt) nanomaterials are among them and have been recognized as the best option for creating enzyme-free glucose sensors because of their excellent glucose catalytic effects. The prohibitively costly price of these metals for the creation of enzyme-free glucose sensors, nevertheless, restricts their application [18,19]. Consequently, for the purpose of creating enzyme-free glucose sensors, researchers have employed transition metal composites, particularly the oxides of transition metals, including Ni, Co, Zn, Cu, Mn, Sn, and Zn. Dong et al. employed the hydrothermal approach, for instance, to create reduced graphene oxide (rGO). On the substrate, NiMn2O4 nanosheets have been produced and utilized to detect glucose electrochemically. The developed NiMn2O4@rGO sensor might detect glucose with a broad linear range and high sensitivity [20]. It additionally offers good anti-interference and stability. A Co3O4 nanowire array and ZnO nanosheet were combined to create a composite electrode by Ye et al. utilizing a straightforward hydrothermal and pulsed electrodeposition technique. With a low detection threshold and a quick response time of only three seconds to glucose amperage, the constructed three-dimensional porous ZnO@Co3O4 sensor could selectively detect glucose [7]. In the past few years, transition metals and their compounds have increasingly been applied as suitable electrode materials for sensors [21,22]. Among them, Cu, Co, and Ni are inexpensive. Due to the electron-mediated effect in the redox pairs of Cu2+/Cu3+, Co2+/Co3+, and Ni2+/Ni3+, Cu-Co-Ni-based micro-nanomaterials can serve as efficient electrocatalysts for glucose oxidation in alkaline media [20,23]. In addition, the unique synergistic effects among multiple metals can provide multiple opportunities to improve their electrocatalytic performance. The majority of multi-metal catalysts, per the literature, perform catalytically far superior to mono-metal catalysts [24]. Consequently, Cu, Co, and Ni trimetal-based electrode materials are highly desirable for applications in glucose electroanalysis.
Currently, nanomaterials such as transition metal oxides [25], sulfides [26], and hydroxides [27] are widely used in glucose electrochemical sensors. In the periodic table of elements, oxygen, sulfur, and selenium have similar properties. Compared with oxygen and sulfur, selenium has an increased ionic radius and a decreased electronegativity [28]. Consequently, selenides exhibit enhanced polarizability, more electroactive unsaturated edge sites, and improved electrical conductivity and redox activity [29,30]. The advantages, as mentioned earlier, are additionally valid for the enzyme-based electrochemical sensing of glucose. Harish et al. used a one-step hydrothermal method to synthesize Cu2Se. The constructed Cu2Se sensor possesses excellent sensitivity and a low detection limit, permitting it to detect glucose in physiological bodily fluids in smaller amounts [31]. Ma et al. described the in situ fabrication of nickel selenide (Ni3Se2) nanosheet arrays on nickel foam (NF) and how they were utilized as an enzyme-free glucose sensor. With a detection range from 0.25 μM to 6.33 mM, the Ni3Se2/NF electrode demonstrated a high efficiency for electrocatalytic glucose oxidation [32]. Xu et al. synthesized rock-like NiSe2 nanoparticles on carbon nanorods using a simple thermal treatment method [33]. The unique core–shell structure of NiSe2/carbon nanorods increased the catalytic area and active sites, and the introduction of Se improved the charge transfer rate. The resulting glucose biosensor, comprising NiSe2 and carbon nanorods, displayed a broad linear range, excellent sensitivity, and a modest detection limit. Wang et al. prepared CoSe on carbon nanosheets with NaCl-assisted pyrolysis [34]. The sensor exhibited good selectivity and a wide linear range in detecting glucose.
In this work, we used straightforward hydrothermal and solvothermal techniques to successfully synthesize homogeneous (Ni, Co, Cu)Se2 nanosheet arrays on carbon cloth (CC). The nanosheet morphology of (Ni, Co, Cu)Se2 could offer more active areas and increase the kinetics of the reaction. Moreover, the synergistic effect of the three metals Cu, Co, and Ni improved the electrocatalytic performance of (Ni, Co, Cu)Se2. Thus, the fabricated (Ni, Co, Cu)Se2/CC electrode exhibited outstanding capability for the electrochemical oxidation of glucose. In addition, human serum samples were used to evaluate the potential application of the constructed sensor.

2. Materials and Methods

2.1. Chemicals

We purchased CC (hydrophilic, WOS1009) from Cetech Co., Ltd. in Taiwan, China. Co(NO3)2·6H2O, Cu(NO3)2·3H2O, NaCl, Ni(NO3)2·6H2O, NaOH, NaBH4, and selenium were bought from Sinopharm Chemical Reagent Co., Ltd. in Shanghai, China. Shanghai Macklin Biochemical Co., Ltd. in Shanghai, China, provided fructose (Fru), ammonium fluoride (NH4F), urea (CH4N2O), sucrose (Suc), and D-(+)-glucose (Glu). Sigma-Aldrich (St Louis, MO, USA) supplied dopamine (DA), uric acid (UA), maltose (Mal), ascorbic acid (AA), and glycine (Gly). Shanghai University Hospital provided serum. The entire experiment was conducted using deionized water (18.25 M cm).

2.2. Apparatus

Through the use of scanning electron microscopy (SEM, SU5000, Japan) and energy dispersive X-ray spectroscopy (EDS), the surface morphology and chemical elemental content of the samples were examined. With high-resolution transmission electron microscopy (HRTEM, JEM-2100F, JEOL, Japan), more details on the tiny crystal structure were revealed. Using X-ray diffraction (XRD, DLMAX-2200, Cu target, K rays, Japan), the crystal structure of samples was identified. X-ray photoelectron spectroscopy (XPS, ESCALAB 250 XI, USA) examined the chemical makeup of the samples and the valence state. The electrochemical performance of synthetic materials was tested on an electrochemical workstation (CHI 660 D, Shanghai, China) utilizing (Ni, Co, Cu)Se2/CC as the working electrode and Ag/AgCl (saturated KCl) and platinum wire as the reference and counter electrodes, respectively.

2.3. Synthesis of (Ni, Co, Cu)-LDH on CC

The precursor layered double hydroxide ((Ni, Co, Cu)-LDH) was fabricated on CC as follows: To prepare CC (2 cm × 3 cm) for usage, it was first ultrasonically cleaned for 15 min in a solution of ethanol, 0.5 M HCl, and deionized water. In 40 mL of water, stirring was used to dissolve 0.291 g Co(NO3)2·6H2O, 0.581 g Ni(NO3)2·6H2O, and 0.241 g Cu(NO3)2·3H2O. The solution was then used to dissolve 0.148 g NH4F and 0.480 g urea. Afterwards, a 50 mL autoclave was used to hydrothermally react the resulting solution and the pretreated CC for 6 h at 150 °C. After the reaction was finished, it was removed and washed in turns using ethanol and water. (Ni, Co, Cu)-LDH/CC was obtained after drying in a vacuum oven at 60 °C. Additionally, LDH arrays with ratios of 1:1:1, 1:1:3, 1:1:4, and 1:1:5 were prepared by adjusting the molar ratio of Cu:Co:Ni.

2.4. Synthesis of (Ni, Co, Cu)Se2 on CC

The selenization of fabricated precursors was processed using the solvothermal method to obtain (Ni, Co, Cu)Se2/CC. In 3 mL of water, 0.059 g selenium powder and 0.065 g NaBH4 were dissolved. Fresh NaHSe solution was made after 10 min of stirring, and 60 mL of absolute ethanol was added after 10 min of N2 flow to stop NaHSe oxidation. After that, the mixture and the precursor were put into a 100 mL autoclave and then heated to 140 °C for 12 h. Later, the samples were exposed to Ar gas while being calcined for 2 h at 350 °C.

3. Results and Discussion

3.1. Structure and Morphology Characterization of (Ni, Co, Cu)Se2/CC

Figure 1 depicts a schematic diagram of the (Ni, Co, Cu)Se2/CC synthesis process. First, the hydrothermal technique was used to create precursor (Ni, Co, Cu)-LDH nanosheets on CC with a Cu: Co: Ni ratio of 1:1:2 (Figure 2a). Then, the precursors were selenized using the solvothermal method. By comparing Figure 2a,b, the morphology of (Ni, Co, Cu)Se2 nanosheets can be clearly seen after the selenization of the precursor using the solvothermal method. Figure S1 shows the SEM images of LDHs fabricated from other Cu: Co: Ni salts with different ratios. The (Ni, Co, Cu)-LDH precursor was then reacted using fresh NaHSe as the Se source to create the appropriate metal selenides. As indicated in Figure S2, the precursors prepared from Cu: Co: Ni salt ratios of 1:1:1, 1:1:3, 1:1:4, and 1:1:5 exhibited large-area agglomeration after selenization. However, the (Ni, Co, Cu)Se2 obtained after selenization from the precursor with a Cu: Co: Ni ratio of 1:1:2 was still nanosheet-like, with some particles attached to the surface. This could result from specific precursors remaining partially separated during the selenization procedure and subsequently aggregating to produce particles on the surface of the nanosheets. Furthermore, the elements of (Ni, Co, Cu)Se2 were explored using EDS with SEM. The proportion of Co, Ni, Cu, and Se elements is 16%, 29%, 29%, and 25%, respectively. From Figure 2d, it is apparent that Ni, Co, Cu, and Se elements were dispersed with equal regard. The microstructure of the (Ni, Co, Cu)Se2 nanosheets was investigated with TEM. The TEM image (Figure 2e) reconfirms the nanosheet structure of (Ni, Co, Cu)Se2. Following the (311) crystal plane of the (Ni, Co, Cu)Se2 substance, the high-resolution TEM (Figure 2f) reveals that the lattice fringe spacing was 0.181 nm.
The crystal structure of (Ni, Co, Cu)Se2/CC was determined with XRD. The obtained diffraction peaks were consistent with the cubic (Ni, Co, Cu)(Se, S)2 phase (JCPDS No. 29–1417). As depicted in Figure 3a, the (200), (210), (211), (220), (311), (230), (321), (400), (421), and (332) planes of (Ni, Co, Cu)(Se, S)2 can be identified by the diffraction peaks, which have the following coordinates: 30.3°, 34.0°, 37.4°, 43.4°, 51.4°, 56.3°, 58.6°, 63.1°, and 75.6° [15]. Therefore, it can be proved that the synthesized sample is Ni/Co/Cu selenide. In addition, the diffraction peak observed at 26.3° corresponds to CC. XPS was used to study the constitutions and element chemical valence states of the (Ni, Co, Cu)Se2/CC. The survey scan spectrum shown in Figure 3b contained the characteristic peaks for the Ni, Cu, Co, Se, and C elements. Figure 3c presents the XPS spectra of Cu 2p with a satellite peak at 943.27 eV. The peaks at 933.12 and 952.98 eV, which correspond to the Cu0/Cu+ state, exhibit the distribution of Cu 2p3/2 and Cu 2p1/2. Cu2+ species are believed to be responsible for the peaks at 935.16 and 954.87 eV [35,36]. The Ni 2p XPS spectra are displayed in Figure 3d. The satellite peaks at 861.56 and 881.15 eV are attributed to Ni 2p3/2 and Ni 2p1/2 of Ni2+, respectively [37,38]. Co 2p3/2 and Co 2p1/2 of Co2+ are identified by the peaks at 781.55 and 796.15 eV in the XPS spectra of Co 2p (Figure 3e), and the associated satellite peaks are located at 786.97 and 803.69 eV [39,40]. The Se 3d spectra in Figure 3f exhibit peaks at 54.82 and 55.93 eV that are associated with Se 3d5/2 and Se 3d3/2, respectively. In contrast, the sizable sharp peak at 59.02 eV is correlated with SeOx and may be carried forth by the surface oxidation of selenides [41,42,43].

3.2. Electrochemical Performance of (Ni, Co, Cu)Se2/CC

Using cyclic voltammetry (CV) in an alkaline solution, the electrocatalytic property of (Ni, Co, Cu)Se2/CC was examined. As depicted in Figure 4a, the CV curves of bare CC, (Ni, Co, Cu)-LDH/CC, and (Ni, Co, Cu)Se2/CC electrodes were tested at a scan rate of 50 mV s−1 either with or without the addition of 2 mM glucose to 0.1 M NaOH solution. Due to the inferior catalytic efficiency, even in glucose, there was no response for the bare CC. The superior electrocatalytic activity of (Ni, Co, Cu)Se2/CC was discovered based on the excellent current response compared to (Ni, Co, Cu)-LDH/CC. As depicted in Figure S3, the electrochemical behaviors of CoSe, NiSe, CuSe, and (Ni, Co, Cu)Se2 in response to glucose in 0.1 M NaOH were examined. When 2 mM glucose was introduced, the oxidation current density produced by (Ni, Co, Cu)Se2 was significantly higher than that produced by CoSe, NiSe, and CuSe due to the synergistic effect between the various metals accelerating the electron transport speed and enhancing the electrochemical performance of the sensor.
To improve the sensing capacity of (Ni, Co, Cu)Se2/CC, the concentration of NaOH and the applied voltage were optimized using the current–time method. Figure 5a shows the response current curves of (Ni, Co, Cu)Se2/CC catalyzing 0.1 mM glucose with different concentrations of NaOH as the supporting electrolyte. The response current peaked in the 0.1 M NaOH concentration and then rapidly declined when the NaOH concentration increased further. As a result, 0.1 M NaOH was determined to be the optimal electrolyte solution. The response current curves of (Ni, Co, Cu)Se2/CC catalyzing 0.1 mM glucose at various applied voltages are shown in Figure 5b. With the increase in applied voltage in the range from 0.45 to 0.60 V, the response current also increased. Therefore, the subsequent experiments were conducted with a 0.1 M NaOH solution and 0.6 V applied voltage.
The CVs of (Ni, Co, Cu)Se2/CC were measured in a 0.1 M NaOH solution that had varying glucose concentrations. As can be seen in Figure 4b, as glucose concentration rose, the oxidation current also rose. In addition, the oxidation current was proportional to the glucose concentration, implying that (Ni, Co, Cu)Se2/CC with superior electrocatalytic activity was suitable as the electrode material for the electrochemical sensing of glucose. The impact of scan rate and kinetic analysis were additionally examined in a solution of 0.1 M NaOH with 1.0 mM glucose at scanning rates ranging from 10 to 320 mV s−1. (Figure 4c). Figure 4d shows that the oxidation peak current rose as the scanning rate rose, and the relationship appeared linear, demonstrating an electrode reaction controlled by adsorption [28,44]. In an alkaline solution, Cu (II) was combined with OH− to form the strong oxidizing agent CuOOH (III). Then, glucose was oxidized to glucoselactone by CuOOH (III) [23,45,46]. The mechanism of electrocatalytic oxidation of glucose in (Ni, Co, Cu)Se2/CC may be explained by the following chemical equations:
Ni (II) + 3OH−↔ NiOOH (III) + H2O + e−
Co (II) + 3OH−↔ CoOOH (III) + H2O + e−
Cu (II) + 3OH−↔ CuOOH (III)+ H2O + e−
NiOOH (III) + glucose→Ni(OH)2 (II) + gluconolactone
CoOOH (III) + glucose→Co(OH)2 (II) + gluconolactone
CuOOH (III) + glucose→Cu(OH)2 (II) + gluconolactone
The electrochemical active surface area (ECSA) of the electrode was evaluated from the CVs. The ECSA is proportional to the double layer capacitance (Cdl), and the ECSA calculation is more complicated, so the ECSA of the electrode is compared by calculating the Cdl. The electrochemical double layer capacitance is calculated according to the formula ic = νCdl, where ν is the sweep speed, ic is one half of the difference between the oxidation current and the reduction current, and ic = (ipa − ipc)/2. In order to calculate the ic relatively accurately, an intermediate value is selected to calculate the difference between the oxidation current and the reduction current. The CVs of the material at potentials of 0–0.1 V were examined utilizing multiple scan rates (20–160 mV s−1) to determine the electrochemical Cdl, being employed to gain access to the electrochemically active specific surface area of the material. The Cdl of CC is 1.06 mF cm−2, whereas that of (Ni, Co, Cu)Se2/CC is 10.05 mF cm−2, as depicted in Figure 6, demonstrating that the (Ni, Co, Cu)Se2/CC electrode encounters a rougher surface and is more exposed to active sites. Therefore, the (Ni, Co, Cu)Se2/CC electrode displays outstanding electrocatalytic capacity. The following two factors may be responsible for the outstanding electrocatalytic activity of (Ni, Co, Cu)Se2/CC: (1) the high inherent electrical conductivity and abundant redox reactions caused by the valence electron contact exists among the d orbitals of the Ni, Cu, and Co atoms; (2) the catalytic performance was substantially enhanced with the design of quaternary (Ni, Co, Cu)Se2 nanosheet arrays.
The current–time approach was used to assess the sensitivity and detectable range of the electrochemical catalysis of glucose by (Ni, Co, Cu)Se2/CC. Figure 7a displays the current–time curves of (Ni, Co, Cu)Se2/CC while 0.1 M NaOH solution continues to be injected with varying glucose concentrations. In the ranges of 0.01–600 μM and 600–9000 μM, the response currents were linearly connected with glucose concentration. The equations for linearity can be fitted as follows: I (mA cm−2) = 0.21 + 11.45C (mM) (R2 = 0.992) and I (mA cm−2) = 5.88 + 6.27 C (mM) (R2 = 0.990), respectively. The corresponding sensitivities are 11.45 mA mM−1 cm−2 and 6.72 mA mM−1 cm−2. Additionally, based on calculations, the glucose detection limit was 5.82 nM. The (Ni, Co, Cu)Se2/CC electrode showed greater sensitivity at low glucose concentrations and decreased sensitivity at high glucose concentrations. This might be because the glucose oxidation active sites on the electrode surface are partially covered by reaction intermediates that have adhered to the electrode surface, decreasing the sensitivity of the electrode [47]. Moreover, the performance comparison of the proposed (Ni, Co, Cu)Se2/CC and other reported electrochemical sensors is listed in Table 1. The proposed (Ni, Co, Cu)Se2/CC electrode presents remarkable performances in the linear range, sensitivity, and detection limit among several samples.

3.3. Selectivity, Stability, Repeatability, and Reproducibility Investigation of (Ni, Co, Cu)Se2/CC

Due to the complexity of biological systems, the selectivity of the electrode constitutes a crucial consideration for the utilization of glucose electrochemical sensors for practical purposes. By testing 0.01 mM of multiple interference-causing chemicals, the selectivity and anti-interference capacity of the (Ni, Co, Cu)Se2/CC electrode was investigated. As depicted in Figure 7c, the response current of the (Ni, Co, Cu)Se2/CC electrode to interferents was negligible compared to glucose. Hence, the exceptional selectivity of the (Ni, Co, Cu)Se2/CC electrode could be proven. Furthermore, the stability of the prepared electrodes was evaluated. As depicted in Figure 7d, the response current of the (Ni, Co, Cu)Se2/CC electrode to 0.1 mM glucose decreased slightly within 1200 s, indicating that the proposed sensor has excellent stability. Repeatability and reproducibility were also essential factors to evaluate the potential applicability of the sensor. The CVs of the same (Ni, Co, Cu)Se2/CC electrode were tested against 1 mM glucose six times under identical conditions. As displayed in Figure S4a, the peak current had a relative standard deviation (RSD) as low as 2.1%, indicating excellent repeatability of the electrode. To check the reproducibility of (Ni, Co, Cu)Se2/CC, six electrodes were tested in 0.1 M NaOH containing 1 mM glucose. As presented in Figure S4b, the peak current has an RSD as low as 1.9%, indicating satisfactory reproducibility of the electrode.

3.4. Real Sample Analysis

Serum analysis is a practical way to identify some disease indices. The level of glucose in human serum was measured utilizing the standard addition method to ascertain the practical usability of the constructed sensor. All serum samples were obtained from the hospital at Shanghai University. Three different human blood samples were centrifuged at 4000 rpm/min at 4 °C for 10 min to separate the supernatant to obtain serum. The current response to adding 20 μM glucose was detected. Each serum sample was retaken three times to confirm the accuracy of the experiment. The outcomes are displayed in Table 2. The recoveries were 101.2, 99.4, and 102.1%, respectively, demonstrating that the suggested sensor may be utilized for detecting glucose in actual serum samples.

4. Conclusions

Uniform (Ni, Co, Cu)Se2 nanosheet arrays were successfully synthesized on CC utilizing hydrothermal and solvothermal processes. The synergistic effect among the three metals Cu, Co, and Ni can effectively improve the catalytic ability of the (Ni, Co, Cu)Se2/CC electrode for glucose oxidation. In addition, selenides have higher electrical conductivity compared to other chalcogenides. The proposed (Ni, Co, Cu)Se2/CC sensor exhibits a wide linear range, significantly inferior detection limit, and superior stability. Additionally, the studied sensor has outstanding anti-interference capabilities and has been utilized to determine the amount of glucose in serum samples, implying that the proposed sensor is promising in clinical glucose tests.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/chemosensors11100530/s1, Figure S1: (a–d) SEM images of (Ni, Co, Cu)-LDH arrays with Cu:Co:Ni ratios of 1:1:1, 1:1:3, 1:1:4, and 1:1:5; Figure S2: (a–d) SEM images of (Ni, Co, Cu)Se2 arrays with Cu:Co:Ni ratios of 1:1:1, 1:1:3, 1:1:4, and 1:1:5; Figure S3: Response curves of (Cu, Co, Ni)Se2/CC, CoSe/CC, CuSe/CC, and NiSe/CC to the addition of 0 mM and 2 mM glucose in 0.1 M NaOH solution; Figure S4: The repeatability (a) and reproductivity (b) of (Ni, Co, Cu)Se2/CC electrode to glucose sensing.

Author Contributions

Conceptualization, Y.C.; methodology, Y.C.; discussed the results and corrected the paper draft, Y.C.; writing—review and editing, H.W.; investigation, H.C.; formal analysis, J.S.; supervision, D.D. and L.L.; project administration, L.L.; funding acquisition, D.D. and L.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China (grant numbers 62171268 and 61971274).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Schematic illustration of the synthetic procedure of (Ni, Co, Cu)Se2/CC.
Figure 1. Schematic illustration of the synthetic procedure of (Ni, Co, Cu)Se2/CC.
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Figure 2. (a) SEM image of (Ni, Co, Cu)-LDH. (b,c) SEM and (d) elemental mapping images of (Ni, Co, Cu)Se2 microspheres. (e) TEM and (f) high-resolution TEM images of (Ni, Co, Cu)Se2.
Figure 2. (a) SEM image of (Ni, Co, Cu)-LDH. (b,c) SEM and (d) elemental mapping images of (Ni, Co, Cu)Se2 microspheres. (e) TEM and (f) high-resolution TEM images of (Ni, Co, Cu)Se2.
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Figure 3. (a) XRD diffraction patterns of (Ni, Co, Cu)Se2/CC. (b–f) XPS spectra of Cu 2p, Ni 2p, Co 2p, and Se 3d for (Ni, Co, Cu)Se2/CC, respectively.
Figure 3. (a) XRD diffraction patterns of (Ni, Co, Cu)Se2/CC. (b–f) XPS spectra of Cu 2p, Ni 2p, Co 2p, and Se 3d for (Ni, Co, Cu)Se2/CC, respectively.
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Figure 4. (a) The CVs of CC, (Ni, Co, Cu)-LDH/CC, and (Ni, Co, Cu)Se2/CC in the presence and absence of 2 mM glucose (solid line and dashed line, respectively). (b) CVs of (Ni, Co, Cu)Se2/CC at 0–5 mM glucose in 0.1 M NaOH at a scan rate of 50 mV s−1. (c) CVs of (Ni, Co, Cu)Se2/CC in 0.1 M NaOH containing 1 mM glucose at various scan rates (10–320 mV s−1). (d) The scan rate response and peak current response linear relationship calibration curve.
Figure 4. (a) The CVs of CC, (Ni, Co, Cu)-LDH/CC, and (Ni, Co, Cu)Se2/CC in the presence and absence of 2 mM glucose (solid line and dashed line, respectively). (b) CVs of (Ni, Co, Cu)Se2/CC at 0–5 mM glucose in 0.1 M NaOH at a scan rate of 50 mV s−1. (c) CVs of (Ni, Co, Cu)Se2/CC in 0.1 M NaOH containing 1 mM glucose at various scan rates (10–320 mV s−1). (d) The scan rate response and peak current response linear relationship calibration curve.
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Figure 5. 0.1 mM glucose current response: effects of experimental parameters. (a) NaOH concentration. (b) Applied potential.
Figure 5. 0.1 mM glucose current response: effects of experimental parameters. (a) NaOH concentration. (b) Applied potential.
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Figure 6. (a,b) CVs of CC and (Ni, Co, Cu)Se2/CC electrodes measured in the applied potential range from 0.0 to 0.1 V at various scan rates from 20 to 160 mV s−1. (c) The capacitive current at 0.05 V as the function of scan rate for CC and (Ni, Co, Cu)Se2/CC.
Figure 6. (a,b) CVs of CC and (Ni, Co, Cu)Se2/CC electrodes measured in the applied potential range from 0.0 to 0.1 V at various scan rates from 20 to 160 mV s−1. (c) The capacitive current at 0.05 V as the function of scan rate for CC and (Ni, Co, Cu)Se2/CC.
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Figure 7. (a) Typical amperometric response (I-t) of (Ni, Co, Cu)Se2/CC with continuous addition of various glucose concentrations. (b) The associated calibration curve. (c) Selectivity of (Ni, Co, Cu)Se2/CC toward glucose. (d) Current variation in (Ni, Co, Cu)Se2/CC in 0.1 mM glucose during the 1200 s test time in 0.1 M NaOH at 0.60 V.
Figure 7. (a) Typical amperometric response (I-t) of (Ni, Co, Cu)Se2/CC with continuous addition of various glucose concentrations. (b) The associated calibration curve. (c) Selectivity of (Ni, Co, Cu)Se2/CC toward glucose. (d) Current variation in (Ni, Co, Cu)Se2/CC in 0.1 mM glucose during the 1200 s test time in 0.1 M NaOH at 0.60 V.
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Table 1. Comparison of the (Ni, Co, Cu)Se2/CC with some previously reported sensors for the detection of glucose.
Table 1. Comparison of the (Ni, Co, Cu)Se2/CC with some previously reported sensors for the detection of glucose.
Modified MaterialLinear Range
(μM)		Detection Limit (μM)Sensitivity
(μA mM−1 cm−2)		Reference
CeO2@CuO1–890.0193319.83[45]
CuCo2O4/CC1–9300.53930[48]
CuS/Cu2O/CuO/Cu20–40960.894262[49]
Ni@Cu-MOF5–25001.671703.33[23]
Co3O4-NiCo2O41–21000.1121463.13[50]
Ni/Cu0.5–25000.053924[51]
NiSe2/cellulose paper100–100024.8250[52]
Cu2-xSeup to 337550536[53]
CuCo2O40.01–8000.003654.23[54]
CoSe–rGO aup to 10,0002.5480[55]
(Ni, Co, Cu)Se2/CC0.01–600
600–9000		0.0058211,450
6720		This work
a Reduced graphene oxide.
Table 2. Determination of glucose in human serum.
Table 2. Determination of glucose in human serum.
Serum
Sample		Detected
(μM)		Added
(μM)		Found
(μM)		Recovery
(%)		RSD
(%)
19.402029.64101.20.68
214.212034.0999.41.83
316.012036.43102.10.97
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Chen, Y.; Wang, H.; Chen, H.; Song, J.; Deng, D.; Luo, L. Synthesis of Quaternary (Ni, Co, Cu)Se2 Nanosheet Arrays on Carbon Cloth for Non-Enzymatic Glucose Determination. Chemosensors 2023, 11, 530. https://doi.org/10.3390/chemosensors11100530

AMA Style

Chen Y, Wang H, Chen H, Song J, Deng D, Luo L. Synthesis of Quaternary (Ni, Co, Cu)Se2 Nanosheet Arrays on Carbon Cloth for Non-Enzymatic Glucose Determination. Chemosensors. 2023; 11(10):530. https://doi.org/10.3390/chemosensors11100530

Chicago/Turabian Style

Chen, Yuanyuan, Huan Wang, Huinan Chen, Jingyao Song, Dongmei Deng, and Liqiang Luo. 2023. "Synthesis of Quaternary (Ni, Co, Cu)Se2 Nanosheet Arrays on Carbon Cloth for Non-Enzymatic Glucose Determination" Chemosensors 11, no. 10: 530. https://doi.org/10.3390/chemosensors11100530

APA Style

Chen, Y., Wang, H., Chen, H., Song, J., Deng, D., & Luo, L. (2023). Synthesis of Quaternary (Ni, Co, Cu)Se2 Nanosheet Arrays on Carbon Cloth for Non-Enzymatic Glucose Determination. Chemosensors, 11(10), 530. https://doi.org/10.3390/chemosensors11100530

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