CN114965643B - Cu/Cu 2 O/Ni(OH) 2 Electrode, glucose sensor and application thereof - Google Patents
Cu/Cu 2 O/Ni(OH) 2 Electrode, glucose sensor and application thereof Download PDFInfo
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Abstract
The invention discloses a Cu/Cu alloy 2 O/Ni(OH) 2 An electrode, the method of making comprising: placing the activated glassy carbon electrode in electrolyte to deposit Cu/Cu 2 O/Ni(OH) 2 Nano material for preparing the Cu/Cu 2 O/Ni(OH) 2 An electrode; the electrolyte is Cu 2+ Precursor solution of (2) and Ni 2+ Is a mixed solution of precursor solutions of (a) and (b). The invention also discloses a Cu/Cu-containing alloy 2 O/Ni(OH) 2 Glucose sensors and applications of the electrodes. The invention directly grows the huperzia-shaped Cu/Cu on the glassy carbon electrode by a one-step method 2 O/Ni(OH) 2 A nanomaterial. Its sensitivity is 1900.3 μA mM ‑1 cm ‑2 The detection limit was 0.201. Mu.M (S/N=3), and the linear range was 0.4. Mu.M to 2000. Mu.M. In the process of catalytically oxidizing glucose, the catalyst has the advantages of large specific surface area, fast promotion of glucose diffusion, fast electron transfer rate and the like; meanwhile, due to the fact that the fir-shaped structure is unique, the bimetallic oxides have synergistic effect, and the catalytic oxidation activity of glucose can be effectively enhanced.
Description
Technical Field
The invention belongs to the technical field of sensors, and in particular relates to a Cu/Cu sensor 2 O/Ni(OH) 2 An electrode, a glucose sensor and applications thereof.
Background
Diabetes is a metabolic disease and is still one of public health problems, and the occurrence of diabetes is characterized by the inability of glucose in the body's blood to maintain a normal steady state. Therefore, the rapid and sensitive method for detecting the glucose has very important significance in the fields of clinical diagnosis biology, food industry, environmental protection and the like. In recent years, many methods have been successfully used for detecting glucose, and electrochemical sensors have been receiving attention because of their advantages of high sensitivity, short time consumption, low cost, and the like. Electrochemical sensors are classified into enzymatic type sensing and non-enzymatic type sensing, and researches show that the use condition of glucose oxidase is harsh, is easily affected by temperature, pH and other conditions, and the cost of the enzyme is high, which limits the practical application of the enzymatic type sensor, and the non-enzymatic type sensor can overcome the inherent limitations, so many researchers begin to research and develop the non-enzymatic catalyst.
In recent years, transition metal and oxide nanomaterials thereof are often used as synthetic raw materials for non-enzymatic catalysts due to their excellent catalytic properties and electrical conductivity. Noble metals such as Au, pt, pd and the like are one of the materials for synthesizing non-enzymatic catalysts, however, the noble metals have higher cost, can generate intermediates in the process of catalytically oxidizing glucose, and are easy to be poisoned by chloride ions. Thus, researchers have been focusing on non-noble metals such as Ni, cu, co, mn and their oxidized materials. Cu (Cu) 2 O crystals, which are a p-type semiconductor having a band gap of 2.17eV, have been attracting attention as having good stability and catalytic activity. Lakmini Jayasingha et al grown Cu on Cu foam and Cu plate, respectively, by electrochemical anodic oxidation 2 O nanorods/nanotubes and compares the sensing properties of the two materials, where Cu 2 The performance of the O/CF is better, and the sensitivity is as high as 5792.7 mu AmM -1 cm -2 . The synthesis of Au@Cu with core-shell structure by chemical reduction method is reported by Y.Su et al 2 The O nanocomposite material needs to be dripped on the glassy carbon electrode by nafion in the process of constructing the electrode, which leads to poor uniformity of material loading on the glassy carbon electrode and increases the complexity of testing. In addition, ni-based materials are also commonly used to construct non-enzymatic glucose sensors at low cost and high electrocatalytic activity. Since the mechanism of catalytic oxidation of glucose by Ni-based materials involves Ni 2+ /Ni 3+ Redox couple, ni (OH) 2 The sensor has stimulated the interest of a large number of researchers. Kaidong Xia et al use hydrothermal method in the absence of Nickel salts and additivesDirectly carrying out in-situ electrochemical corrosion on foam nickel in pure distilled water to obtain Ni (OH) 2 sheet-Ni foam, the sensor exhibits high sensitivity and stability to the electro-oxidation of glucose.
However, as research discovers that electrochemical performance of glucose sensors based on single metals, metal oxides and metal hydroxides still has certain defects, thereby limiting practical application of glucose sensors in detecting glucose; electrochemical performance may be enhanced by a synergistic effect between metals if two or three are combined to form a hybrid electrode. Perumal Viswanathan et al synthesized Cu/CuO/Cu (OH) under the action of dopamine as a catalyst 2 The presence of the electrocatalyst, cu phase, may enhance the metal oxide (CuO/Cu (OH) 2 ) However, the electrochemical performance may not be significantly improved due to the use of the same metal source, due to the conductivity of the resulting material and the biocompatibility of the material. There is therefore a need for further materials with significantly improved catalytic oxidation properties for glucose.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, the main object of the present invention is to provide a copper-nickel composite for the preparation of glucose sensors by depositing Cu/Cu with a huperzia shape on a glassy carbon electrode 2 O/Ni(OH) 2 The electrode is constructed to contain self-supporting binderless Cu/Cu 2 O/Ni(OH) 2 Glucose sensor of electrode.
The invention provides a Cu/Cu alloy 2 O/Ni(OH) 2 An electrode, the method of making comprising:
placing the activated glassy carbon electrode in electrolyte to deposit Cu/Cu 2 O/Ni(OH) 2 Nano material for preparing the Cu/Cu 2 O/Ni(OH) 2 An electrode; the electrolyte is Cu 2+ Precursor solution of (2) and Ni 2+ Is a mixed solution of precursor solutions of (a) and (b).
In some embodiments, the CU 2+ The precursor solution of (2) is CuSO 4 ·5H 2 O, the Ni 2+ Is Ni (Cl) 2 ·6H 2 O, said Cu 2+ Precursor solution of (2) and Ni 2+ The molar concentration ratio of the precursor solution of (2) is (1): (1-3).
Further, a potentiostatic timing amperometric method is adopted, the activated glassy carbon electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a Pt sheet is used as a counter electrode, and the temperature of the activated glassy carbon electrode is 0.1mol/L CuSO 4 ·5H 2 O and 0.2mol/LNi (Cl) 2 ·6H 2 Deposition of Cu/Cu from O-mixed solution 2 O/Ni(OH) 2 Nano material, after deposition, deionized water is used for Cu/Cu 2 O/Ni(OH) 2 Cleaning the nano material, and naturally airing at room temperature to obtain Cu/Cu 2 O/Ni(OH) 2 An electrode.
Further, the deposition time is 5s to 20s.
In certain embodiments, the activation treatment is specifically: placing the cleaned glassy carbon electrode in H by adopting a three-electrode system 2 SO 4 The activation is carried out in aqueous solution by cyclic voltammetry.
Further, the cleaning specifically comprises: the exposed glassy carbon electrode is polished by chamois leather, and then sequentially subjected to ultrasonic cleaning treatment by acetone, absolute ethyl alcohol and deionized water.
Further, the H 2 SO 4 The molar concentration of the aqueous solution was 0.1mol/L.
Depositing Cu/Cu in the electrolyte of glassy carbon electrode 2 O/Ni(OH) 2 The function principle of the nano material is as follows:
first, cuSO 4 ·5H 2 O and Ni (Cl) 2 ·6H 2 The O mixed solution is in a weak acid state, and Cu is electrolyzed under the condition 2+ Cu and Cu are generated 2 O, which reacts as follows:
Cu 2+ +2e - →Cu +
2CuOH→Cu 2 O+H 2 O
Cu + +e - →Cu 0
while Ni (OH) 2 Then is formed by hydrolysis, cl - The presence of (2) can promote the growth of nano-materials, change the morphology of the growth process, react and compete in the process, and at high concentration Ni (Cl) 2 ·6H 2 In O solution, the reaction is mainly carried out, thereby promoting H 2 Dissociation of O to produce OH - Will be with Ni 2+ Bonding to form Ni (OH) 2 The reaction is as follows:
Ni 2+ +2e - →Ni
2H + +2e - →H 2
Ni 2+ +2OH - →Ni(OH) 2
the invention also aims to provide a Cu/Cu alloy comprising any one of the foregoing 2 O/Ni(OH) 2 Glucose sensor of electrode.
Specifically, glucose is found in Cu/Cu 2 O/Ni(OH) 2 The electrochemical oxidation mechanism on the electrode is Cu and Cu as shown in figure 1 2 O and Ni (OH) 2 Under the condition of alkaline solution, cu (OH) is generated in the first step respectively 2 And Ni (OH) 2 And further generating CuOOH and NiOOH, wherein the two substances catalyze and oxidize glucose to generate gluconolactone.
The invention further provides a glucose monitoring device, a blood glucose monitoring device or a waste water glucose effect monitoring device or a food glucose detecting device comprising the glucose sensor. In particular, a blood glucose monitoring device comprising a glucose sensor may be used to monitor the blood glucose level of a blood glucose patient by detecting the sweat/urine/tears/blood of the patient; the waste water glucose effect monitoring device comprising a glucose sensor can be used for monitoring water pollution; a food glucose detection device comprising a glucose sensor may be used to detect the glucose content in a food product.
The invention further provides a method for detecting the glucose content in sweat, urine, tears and serum, which comprises the steps of using any one of the glucose sensors or any one of the blood glucose detection devices to perform i-t detection on the sweat, urine, tears and serum, and determining the glucose content in sweat, urine, tears and serum according to the detected current value.
Further, the detection potential of the detection method is 0.45V to 0.60V, and preferably, the detection potential is set to 0.55V for maximum current response, and relatively sensitive and stable signals and relatively small noise values.
In certain embodiments, the Cu/Cu is 2 O/Ni(OH) 2 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, and the Ag/AgCl is used as a reference electrode to form a glucose sensor for detection.
Compared with the prior art, the invention has at least the following advantages:
the invention provides a simple, rapid, low-cost and binder-free method for directly growing the huperzia serrata Cu/Cu on the glassy carbon electrode 2 O/Ni(OH) 2 A nanomaterial. According to the test result, it is shown that Cu/Cu 2 O/Ni(OH) 2 The sensitivity of the electrode for detecting glucose is 1900.3 mu A mM -1 cm -2 The detection limit was 0.201. Mu.M (S/N=3), and the linear range was 0.4. Mu.M to 2000. Mu.M. In the process of catalytically oxidizing glucose, cu/Cu is used for 2 O/Ni(OH) 2 The electrode has rich water fir-shaped active sites and large specific surface area, can promote glucose diffusion and improve electron transfer rate; meanwhile, due to the fact that the fir-shaped structure is unique, the bimetallic oxides have synergistic effect, and the catalytic oxidation activity of glucose can be effectively enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows a Cu/Cu-containing alloy according to the present invention 2 O/Ni(OH) 2 Schematic diagram of the action of the glucose sensor of the electrode;
FIG. 2 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 XRD characterization analysis pattern of the electrode;
FIG. 3 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 XPS characterization analysis graph of the electrode;
FIG. 4 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 SEM image of the electrode;
FIG. 5 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 CV diagram (a) of electrode under different scanning speeds, and Cu/Cu 2 O/Ni(OH) 2 A graph (b) of anodic and cathodic peak current densities of the electrode versus scan rate, and a graph (c) of CV at different glucose concentrations, and a graph (d) of glucose oxidation current density versus glucose concentration;
FIG. 6 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 The electrode continuously detects the relation graph (a), (b) Cu/Cu of the current density of glucose and the glucose concentration under different potentials 2 O/Ni(OH) 2 Response time when the electrode detects glucose (b) is continuously added with the ampere response curve (c) of glucose at the potential of 0.55v.
FIG. 7 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 Current density profile of the electrode with successive additions of glucose and interfering substances.
FIG. 8 shows 5 parallel Cu/Cu pairs according to the present invention 2 O/Ni(OH) 2 Current density profile of electrode in 0.1M NaOH solution containing 1mM glucose (a); the same Cu/Cu 2 O/Ni(OH) 2 Current density profile (b) of the electrode in 0.1M NaOH solution containing 1mM glucose; continuous monitoring of 24 days Cu/Cu 2 O/Ni(OH) 2 Current density plot (c) of the electrode in 0.1M NaOH solution containing 1mM glucose.
FIG. 9 is Cu/Cu 2 O、Ni(OH) 2 、Cu/Cu 2 O/Ni(OH) 2 A CV plot of the electrodes (a), and a current density difference plot of glucose detected at the different electrodes (b);
FIG. 10 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 Preparation of Cu/Cu by electrodes at different deposition times 2 O/Ni(OH) 2 A CV diagram (a) of an electrode, and a current density difference diagram (b) of the existence of glucose detected at different deposition times;
FIG. 11 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 The electrodes are arranged in different proportions (Cu 2+ ：Ni 2+ ) Preparation of Cu/Cu 2 O/Ni(OH) 2 A CV diagram (a) of an electrode, and a current density difference diagram (b) of the presence or absence of glucose is detected by different proportion;
FIG. 12 shows Cu/Cu provided by the present invention 2 O/Ni(OH) 2 CV diagram (a) of the electrode under different pH conditions, and current density difference diagram (b) of the electrode obtained by detecting glucose at different pH values.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings and examples which are given by way of illustration only and not by way of limitation, and are not intended to limit the scope of the invention.
In the following examples of the present invention, anhydrous glucose, nickel chloride hexahydrate (Ni (Cl) 2 ·6H 2 O), L-cysteine (L-Cys), uric Acid (UA) purchased from mikrin (Shanghai, china); pentahydrate copper sulfate (CuSO) 4 ·5H 2 O), glycine (Gly), ascorbic Acid (AA), potassium chloride (KCl), sodium chloride (NaCl) were purchased from Chengdu Kelong chemical reagent plant (Chengdu, sichuan) in Chengdu City, and deionized water was used throughout the experiment.
In the following examples of the present invention, a Scanning Electron Microscope (SEM) (Thermo Scientific Apero C) was used, and X-ray photoelectron Spectrometry (XPS) (Thermo Fisher ESCALAB Xi) + ) The method comprises the steps of carrying out a first treatment on the surface of the The adopted three-electrode system takes Ag/AgCl as a reference electrode, a Pt sheet as a counter electrode and Cu/Cu 2 O/Ni(OH) 2 The electrode is a three-electrode system of working electrodes, and the electrochemical performance of the prepared composite material is tested by Cyclic Voltammetry (CV) and amperometry (CA). CV is in the range of 0 to 0.8V at 20mV s -1 Is performed at a scanning rate of (a).
[ example 1 ] Cu/Cu 2 O/Ni(OH) 2 Method for producing electrode
1) Polishing bare glassy carbon electrode (GCE, 3 mm) with chamois, sequentially ultrasonic cleaning with acetone, anhydrous ethanol and deionized water, and ultrasonic cleaning with three-electrode system to obtain glassy carbon electrode with a concentration of 0.1mol/L H 2 SO 4 Activating the solution by cyclic voltammetry;
2) Adopting a potentiostatic Chronoamperometry (CA), taking the Glassy Carbon Electrode (GCE) obtained in the step 1) as a working electrode, ag/AgCl as a reference electrode, pt sheets as a counter electrode, and performing a reaction under the condition that the molar concentration is 0.1mol/LCuSO 4 ·5H 2 O and 0.2mol/L Ni (Cl) 2 ·6H 2 O mixed solution (CuSO) 4 ·5H 2 O and Ni (Cl) 2 ·6H 2 O molar ratio of 1:2) to yield Cu/Cu 2 O/Ni(OH) 2 After the nano material is deposited, cleaning the material by deionized water, and naturally airing the material at room temperature to obtain Cu/Cu 2 O/Ni(OH) 2 An electrode.
[ example 2 ] Performance detection
EXAMPLE 2 Cu/Cu was prepared as in example 1, embodiment 2 2 O/Ni(OH) 2 The electrode is used as an example for performance testing, and the following is specific:
1. characterization of materials
(1) Cu/Cu provided by the invention 2 O/Ni(OH) 2 An electrode for testing the composition of the material by using an X-ray diffractometer (XRD); the results are shown in FIG. 2, by electrodepositing Cu/Cu 2 O/Ni(OH) 2 The electrode material has a plurality of characteristic peaks, wherein 43.23 ° (111), 50.33 ° (200), and 74.05 ° (220) are diffraction peaks of Cu phase (PDF # 99-0034), 29.53 ° (110), 36.42 ° (111), 42.31 ° (200), 52.46 ° (211), 61.37 ° (220), 73.52 ° (311) belong to Cu 2 Diffraction peaks for the O phase (PDF # 99-0041).
(2) Using Thermo Fisher ESCALAB Xi + The composition and valence state of the material were measured by an X-ray electron spectrometer. The results are shown in FIGS. 3a-d, where the Cu/Cu is illustrated in the full spectrum of FIG. 3a 2 O/Ni(OH) 2 The electrode contains Cu, ni and O elements. FIG. 3b shows Cu/Cu 2 O/Ni(OH) 2 Cu 2p spectroscopy of electrodeThe peaks at 932.5eV and 952.2eV are assigned Cu 2p 3/2 And Cu 2p 1/2 The difference in binding energy between the two is 19.7eV, indicating Cu/Cu 2 O/Ni(OH) 2 Electrode presence of Cu 0 And Cu + The method comprises the steps of carrying out a first treatment on the surface of the Furthermore, there is a satellite peak at 942.8eV, indicating Cu/Cu 2 O/Ni(OH) 2 The electrode contains Cu 2 And O phase. FIG. 3c shows Cu/Cu 2 O/Ni(OH) 2 Ni 2p spectra of the electrode, peaks at 855.6eV and 873.4eV are allocated to Ni 2p 3/2 And Ni 2p 1/2 Accompanying the 17.8eV self-selective energy separation, cu/Cu is explained 2 O/Ni(OH) 2 The electrode contains Ni (OH) 2 A phase; secondly, two obvious oscillation satellite peaks are close to two spin orbit double peaks at 861.7eV and 878.9eV, and can be respectively summarized as Ni 2p of the belonging Ni (I) signal 3/2 And Ni 2p 1/2 . The spectra of O1 s are shown in FIG. 3d, with peaks at 531.2eV and 529.1eV identified as O-H and M-O, respectively.
(3) Observing the prepared Cu/Cu by adopting a Scanning Electron Microscope (SEM) 2 O/Ni(OH) 2 Electrode morphology. As a result, as shown in FIGS. 4a-h, it can be seen from FIGS. 4a-d that Cu/Cu 2 O/Ni(OH) 2 The growth mechanism of the water fir-like structure deposited on the glassy carbon electrode is probably due to the fact that the supersaturation growth degree of crystals is improved, so that the growth rate of the crystals is increased, the spreading growth trend is shown at the edge part of the surface of the material, the edge part of the surface is seen to grow faster than the inner part, the layer-by-layer growth of the crystals is promoted, and the water fir-like structure is finally shown. Next, we confirmed the elements contained in the material and analyzed it by EDS spectroscopy, and as can be seen from FIG. 4e, the material contains three elements of O, cu and Ni, wherein the atomic percent (at%) of O is 15.19%, the at% of Cu is 59.28%, the at% of Ni is 25.53%, and the data obtained by combining XRD and XPS shows that the solution contains oxygen in the presence of Cu in the solution when electrodepositing the material 2+ Can be reduced to Cu, cu 2 O, due to Cu 2+ The potential of the Cu standard electrode is 0.324V, cu 2+ /Cu + Standard electrode potential of 0.16V, ni 2+ The potential of the Ni standard electrode is-0.23V, and the higher the potential is, the easier the reduction isTherefore, we can infer Cu/Cu 2 O/Ni(OH) 2 The electrode is mainly composed of Cu-Ni composite materials enriched with Cu. To further determine the elemental composition of the material structure, analysis by EDS elemental Mapping, fig. 4f-h show that the O, cu, ni elements are relatively uniformly grown on the surface of the glassy carbon electrode.
2. Containing Cu/Cu 2 O/Ni(OH) 2 Electrochemical performance testing of glucose sensor of electrode
(1) Electrocatalytic activity on glucose
Study of Cu/Cu by CV method in the voltage range of 0-0.8V 2 O/Ni(OH) 2 Electrocatalytic activity of the electrode on nitrite. The results are shown in FIG. 5, FIG. 5a shows Cu/Cu 2 O/Ni(OH) 2 The electrodes are scanned at different speeds (10-100 mV s) -1 ) The CV plots were measured from 1.0mM glucose in 0.1M NaOH electrolyte. As the scanning rate increases, the peak current density of the anode and the cathode also increases obviously, and the current density of the anode and the cathode is equal to v 1/2 FIG. 5b shows a good linear relationship with linear correlation coefficients R respectively pa 2 ＝0.9962，R pc 2 = 0.9953. Description of Cu/Cu 2 O/Ni(OH) 2 Electrode glucose detection is a typical diffusion process.
FIG. 5c shows Cu/Cu 2 O/Ni(OH) 2 Cyclic voltammograms of the electrodes at different glucose concentrations (0-8 mM). As is clear from the graph, the current density of the oxidation peak gradually increased with increasing glucose concentration, while the current density of the reduction peak did not change significantly, indicating Cu/Cu 2 O/Ni(OH) 2 The catalytic oxidation of glucose by the electrode is an irreversible process, and the increase of the oxidation peak current density is mainly caused by the catalytic oxidation of glucose by two intermediate substances, namely CuOOH and NiOOH. In addition, the peak potential is shifted forward with increasing glucose concentration, but the overall potential is shifted<0.1V, negligible, indicates that efficient electron transfer occurs in the electrode. As can be seen from FIG. 5d, as the glucose concentration increases, the current density of the oxidation peak increases and has a good linear relationship, and the linear correlation coefficient is R 2 ＝0.9961, showing Cu/Cu in a broad glucose concentration range 2 O/Ni(OH) 2 The electrodes had a pronounced current response to glucose.
(2) Linear range, detection limit and sensitivity
And (3) optimizing detection voltage:
to obtain a structure containing Cu/Cu 2 O/Ni(OH) 2 Performance values such as a linear range, sensitivity, detection Limit (LOD) and the like of the glucose sensor of the electrode on glucose; FIG. 6a shows Cu/Cu using amperometric response test 2 O/Ni(OH) 2 The electrode is continuously injected with glucose solution with a certain concentration (0.01 mM) and the corresponding current density relationship under different voltages (0.45-0.60V). The current generated at 0.45V is stable but the current step is minimum, the gradient of the current density and concentration relation is minimum, and the gradient is only 4.38 multiplied by 10 -4 . The slopes of 0.50V and 0.60V differ slightly, 8.11×10 respectively -4 And 8.98X10 -4 The background noise is larger and the interference is large when the voltage is 0.60V; the slope was maximum at a voltage of 0.55V, 1.22×10 -3 . The larger the slope, the higher the sensitivity of the sensor, so that the voltage of 0.55V is selected for subsequent experimental study.
Fig. 6b shows that the steady state is reached with only 2s current when the electrode detects glucose, indicating that the electrode increases the electron transfer rate. Furthermore, as glucose concentration increases, baseline fluctuations occur, possibly due to faster glucose consumption than glucose diffusion, local pH changes, or adsorption of intermediates to the active site, resulting in baseline instability. From FIGS. 6c-d, it can be seen that the current density increases linearly with increasing glucose concentration from 0.4. Mu.M to 2mM, with a corresponding linear equation of y=1.7570x+0.0812 and a linear correlation coefficient of R 2 = 0.9934; calculated out, cu/Cu 2 O/Ni(OH) 2 The enzyme-free glucose sensor has a wide linear range (0.4. Mu.M-2000. Mu.M), a low detection limit (0.201. Mu.M), and high sensitivity (1900.3. Mu.A mM) -1 cm -2 ). The prepared Cu/Cu-containing alloy contains 2 O/Ni(OH) 2 The electrochemical performance of the electrode glucose sensor is compared with that of other non-enzymatic glucose sensors, such asAs shown in table 1,
TABLE 1 Cu/Cu 2 O/Ni(OH) 2 Comparison of enzyme-free glucose sensor with other enzyme-free glucose sensors
As can be seen from Table 1, the Cu/Cu-containing alloy prepared in the present application 2 O/Ni(OH) 2 The glucose sensor of the electrode has higher sensitivity, low detection limit and wider linear range.
(3) Anti-interference performance
In the actual detection process, the species such as Ascorbic Acid (AA), uric Acid (UA), L-cysteine (L-Cys), glycine (Cly), potassium chloride (KCl), sodium chloride (NaCl) and the like exist in human serum together with glucose in biological fluid, so that a certain interference may exist in the glucose detection of the species. Thus, the present inventors conducted an anti-interference experiment by sequentially adding 0.01mM glucose and 0.001mM interferents to a 0.1M NaOH solution, and as a result, as shown in FIG. 7, compared with the current response of 0.01mM glucose, the current response of these interferents was negligible because the concentration of these interferents in human blood was at least an order of magnitude lower than the glucose concentration, and thus contained Cu/Cu 2 O/Ni(OH) 2 The glucose sensor of the electrode has excellent selectivity.
(4) Reproducibility and stability
The application provides a Cu/Cu-containing alloy 2 O/Ni(OH) 2 The glucose sensor of the electrode, for reproducibility, can be modified by studying the current response of 5 identical electrodes to 1mM glucose at 0.55V with a Relative Standard Deviation (RSD) of 1.76% (FIG. 8 a). Similarly, for reproducibility, 5 replicates of 1mM glucose can be performed with one electrode with a relative standard deviation of 2.15% (FIG. 8 b). For long-term stability, can be continuously checkedThe current response of the same electrode to glucose at the same concentration was measured, and it was found from the results of FIG. 8c that the current density tended to fluctuate horizontally. From the above experimental results, it can be confirmed that Cu/Cu2O/Ni (OH) 2 The glucose sensor constructed by the nano material has excellent repeatability, repeatability and stability.
(5) Synergistic performance
To ensure the effectiveness of glucose sensing, we compared Ni, cu-Cu 2 O、Cu/Cu 2 O/Ni(OH) 2 The response of the electrode to the presence or absence of glucose in 0.1M NaOH solution (as shown in FIG. 9 a), and then determined based on the change in oxidation current density, FIG. 9b depicts Cu/Cu 2 O/Ni(OH) 2 (2.40mM cm -2 ) Oxidation current density and Cu/Cu of electrode 2 O(0.22mM cm -2 )、Ni(OH) 2 (0.85mM cm -2 ) The electrode phase is significantly increased, and secondly, cu/Cu 2 O/Ni(OH) 2 The electrode has a smaller oxidation potential (0.55V), ni (OH) 2 The oxidation potential of the electrode was 0.65V, cu/Cu 2 The oxidation potential of the O electrode was 0.6V, which revealed that Cu/Cu was 2 O/Ni(OH) 2 The metal of the nano material and the metal have synergistic effect, the active site is increased, the electron transfer rate is further improved, and the catalytic effect on the catalytic oxidation of glucose is better.
[ example 3 ] Cu/Cu-containing alloy 2 O/Ni(OH) 2 Use of glucose sensor for electrode
To evaluate Cu/Cu 2 O/Ni(OH) 2 Whether the electrode can be used in practical studies, we have simulated the detection of glucose in human serum. The current responses of different concentrations of glucose were recorded at 0.55v potential using chronoamperometry and the results are shown in table 2:
TABLE 2 amperometric detection of labeled glucose in human serum
As is clear from Table 2, the Cu/Cu ratio is 2 O/Ni(OH) 2 The electrode hasHigher recovery and smaller Relative Standard Deviation (RSD) of recovery, indicating good reliability of the electrode, therefore, the electrode is prepared by Cu/Cu 2 O/Ni(OH) 2 The sensor constructed by the nano material has great potential in practical application of detecting glucose.
Example 4 deposition time was optimized, electrolyte ratio was optimized, pH value was tested
(1) Deposition time optimization
We examined deposition time vs Cu/Cu by Cyclic Voltammetry (CV) 2 O/Ni(OH) 2 Electrocatalytic effect of the electrode. FIG. 10a shows CV plots of different deposition times after addition and non-addition of 1mM glucose in 0.1M NaOH, and current density differences (FIG. 10 b) when the nanomaterial obtained after the corresponding deposition time was examined for the presence or absence of glucose, and the results show that the deposition time was 15s for Cu/Cu 2 O/Ni(OH) 2 The oxidation current density of the electrode was equal to 5s (0.60 mM cm) -2 )、10s(0.73mM cm -2 )、20s(1.36mM cm -2 ) The electrodes showed a more pronounced current density difference compared to the electrodes, about 2.40mM cm -2 . The reason for this may be that the deposition time is insufficient to make Cu/Cu 2 O/Ni(OH) 2 The nano material has uneven thickness, reduces the catalytic activity, and the overlong deposition time can change the morphology of the composite material, cover the active site and further is unfavorable for the catalytic oxidation of glucose, namely Cu/Cu in the application 2 O/Ni(OH) 2 The optimal deposition time for the electrode was 15s.
(2) Electrolyte ratio optimization
The electrolyte dosage ratio is also one of the key factors affecting the catalytic oxidation of glucose, and therefore, cu was evaluated by cyclic voltammetry 2+ And Ni 2+ Different molar concentration ratios of Cu/Cu 2 O/Ni(OH) 2 Electrocatalytic effect of the electrode. FIG. 11a shows the current response for different ratios of ingredients with and without 1mM glucose in 0.1M NaOH, showing a molar ratio of 1: cu/Cu at 3 2 O/Ni(OH) 2 The nanomaterial catalyzes the current response of glucose oxidation best. However, by calculating the current density difference between the same molar concentration ratio in the presence or absence of glucoseFig. 11 b), it can be found that the molar concentration ratio is 1: cu/Cu at 2 2 O/Ni(OH) 2 The greatest current density difference measured by the nano material shows that the nano material has small interference in the process of catalyzing and oxidizing glucose and has better catalysis effect on glucose. The reason for this may be that the morphology of the nanocomposite is mainly composed of Ni 2+ Determination of Ni 2+ When the concentration is excessive, the composite material is tightly and excessively thick, so that Ni is agglomerated, and mass transfer at an interface is hindered; and Cu is 2+ The increase in concentration may inhibit the growth of Ni because of Cu 2+ The standard electrode potential of Cu is 0.337v, ni 2+ The standard electrode potential of Ni is-0.257 v, and the material with high potential is preferentially precipitated, namely Cu/Cu in the application 2 O/Ni(OH) 2 In the preparation method of the electrode, cu 2+ And Ni 2+ The optimal molar concentration ratio of (2) is 1:2.
(3) Experiment of pH value
Considering that the electrolyte is a NaOH solution, OH - Takes part in the generation of NiOOH and CuOOH, which are combined with Cu/Cu 2 O/Ni(OH) 2 The electrode plays an important role in the catalytic oxidation of glucose. Therefore, it is necessary to examine the effect of pH on the catalytic oxidation of glucose. FIG. 12a illustrates the current response with or without glucose at different pH values, with a weak current response at pH 12, with the oxidation peak moving negatively and the reduction peak moving positively as the pH value increases. Comparing the current density differences (FIG. 12 b) to find that the current density difference is increased sharply when the pH is more than or equal to 13, the glucose has better catalytic effect under the condition, and oxygen participates in the reaction in the electrocatalytic process, so that the pH is preferably selected to be 13 as the experimental pH value in order to reduce the interference of other reactions.
The invention adopts a simple one-step electrodeposition method to successfully grow the huperzia serrata Cu/Cu directly on the glassy carbon electrode 2 O/Ni(OH) 2 A nanomaterial. By combining SEM image and detection experiment result, it can be deduced that the huperzia-shaped Cu/Cu 2 O/Ni(OH) 2 The nano material has a larger specific surface area, provides rich active sites for catalytic oxidation of glucose, and further promotes diffusion of glucose; second, metal-to-metal synergyActing to facilitate the improvement of electron transfer rate to make Cu/Cu 2 O/Ni(OH) 2 The electrode has higher catalytic activity to glucose, namely Cu/Cu provided by the application 2 O/Ni(OH) 2 The glucose sensor of the electrode has high sensitivity, low detection limit, good long-term stability, good repeatability and reproducibility. Based on the experimental results, it can be seen that Cu/Cu was constructed 2 O/Ni(OH) 2 The electrode offers great potential for non-enzymatic glucose sensors.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (8)
1. Cu/Cu 2 O/Ni(OH) 2 The electrode is characterized in that the preparation method comprises the following steps:
placing the activated glassy carbon electrode in electrolyte to deposit Cu/Cu 2 O/Ni(OH) 2 Nano material for preparing the Cu/Cu 2 O/Ni(OH) 2 An electrode; the electrolyte is Cu 2+ Precursor solution of (2) and Ni 2+ A mixed solution of precursor solutions of (a); the Cu is 2+ The precursor solution of (2) is CuSO 4 ·5H 2 O, the Ni 2+ Is Ni (Cl) 2 ·6H 2 O, said Cu 2+ Precursor solution of (2) and Ni 2+ The molar concentration ratio of the precursor solution of (2) is (1): (1-3).
2. The Cu/Cu alloy according to claim 1 2 O/Ni(OH) 2 An electrode, characterized in that the deposition is in particular: using potentiostatic chronoamperometry to activate the treated materialThe glassy carbon electrode is a working electrode, the Ag/AgCl electrode is a reference electrode, the Pt sheet is a counter electrode, and the concentration of CuSO is 0.1mol/L 4 ·5H 2 O and 0.2mol/L Ni (Cl) 2 ·6H 2 Deposition of Cu/Cu from O-mixed solution 2 O/Ni(OH) 2 Nano material, after deposition, deionized water is used for Cu/Cu 2 O/Ni(OH) 2 Cleaning the nano material, and naturally airing at room temperature to obtain Cu/Cu 2 O/Ni(OH) 2 An electrode.
3. The Cu/Cu of claim 2 2 O/Ni(OH) 2 An electrode characterized by a deposition time of 5s to 20s.
4. The Cu/Cu alloy according to claim 1 2 O/Ni(OH) 2 The electrode is characterized in that the activation treatment specifically comprises the following steps: placing the cleaned glassy carbon electrode in H by adopting a three-electrode system 2 SO 4 The activation is carried out in aqueous solution by cyclic voltammetry.
5. The Cu/Cu composition according to claim 4 2 O/Ni(OH) 2 The electrode is characterized in that the cleaning specifically comprises the following steps: the exposed glassy carbon electrode is polished by chamois leather, and then sequentially subjected to ultrasonic cleaning treatment by acetone, absolute ethyl alcohol and deionized water.
6. The Cu/Cu composition according to claim 5 2 O/Ni(OH) 2 An electrode, characterized in that the H 2 SO 4 The molar concentration of the aqueous solution was 0.1mol/L.
7. Comprising the Cu/Cu of any one of claims 1-6 2 O/Ni(OH) 2 Glucose sensor of electrode.
8. A glucose monitoring device, a blood glucose monitoring device or a waste water glucose effect monitoring device or a food glucose detection device comprising the glucose sensor of claim 7.
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