Nickel-based monatomic catalyst suitable for glucose electrochemical sensor as well as preparation and application of nickel-based monatomic catalyst
By preparing nickel-based single-atom catalysts, the problems of low sensitivity and poor selectivity of existing glucose electrochemical sensors are solved, and the glucose detection effect with high electrocatalytic activity and high sensitivity are achieved.
Patent Information
- Application Number
- CN202411575240.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-06
- Publication Date
- 2025-02-14
AI Technical Summary
Existing glucose electrochemical sensors have problems with low sensitivity and poor selectivity to glucose.
Using a nickel-based single-atom catalyst, the powder was prepared by mixing and grinding bis(cyclopentadiene) nickel (II), melamine and carbon-based nanomaterials, dissolved in organic solvents, rotary evaporation, calcining, acidification and etching and vacuum drying. A nickel-based single-atom catalyst with high electrocatalytic activity is produced.
The sensitivity of glucose electrochemical sensor is improved, with a sensitivity of up to 546.86μA/(mM·cm2), and the detection limit is reduced to 0.24μM, enhancing the selectivity for glucose.
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Figure CN119425757A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method for preparing a single-atom catalyst, in particular to a method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor. Background Art
[0002] Diabetes is a common chronic metabolic disease characterized by high levels of glucose in the human blood, accompanied by complications such as renal failure, retinopathy, cardiovascular disease, and stroke. According to data from the International Diabetes Federation (IDF), the prevalence of diabetes is rising sharply in almost all regions of the world. By 2021, the number of adults with diabetes worldwide has reached 537 million, and is expected to reach 643 million in 2023. Therefore, whether it is a healthy person or a diabetic patient, accurately and timely understanding the changes in their own blood sugar levels is the cornerstone of preventing and treating diabetes.
[0003] In the development history of glucose electrochemical sensors, four generations of technology exploration and research have been carried out. Among them, the first three generations of enzyme-based glucose electrochemical sensors have dominated the market due to the high specificity of glucose oxidase to glucose. However, these sensors are faced with challenges such as environmental instability of biological enzymes and high manufacturing costs, and their applications are significantly limited. Therefore, researchers have turned their attention to enzyme-free glucose electrochemical sensors, hoping to break through the limitations of traditional enzyme-based sensors.
[0004] At present, a variety of electrode materials have been developed and applied to glucose electrochemical sensors, including carbon nanomaterials, various metal elements and their compounds, but they have disadvantages such as poor sensor selectivity, low sensitivity and poor stability. Single atom catalysts (SACs) generally refer to catalysts in which isolated metal atoms or mononuclear metals are embedded in appropriate solid matrix carriers. Compared with traditional nanomaterials, SACs have atomically dispersed and fully exposed metal active sites, which can theoretically achieve 100% metal atom utilization and low metal loss, thereby improving the catalytic activity of the material. At the same time, SACs have unique advantages in improving the signal amplification rate of electrochemical sensing. Electrochemical sensors based on SACs always have significant sensitivity, which is conducive to ultrasensitive analytical research. In addition, thanks to the adjustability of the strong interaction between metal atoms and carriers, SACs can be used as a preferred material for constructing electrochemical sensors with excellent selectivity and stability. Summary of the invention
[0005] In order to overcome the above-mentioned defects of the prior art, the present invention provides a method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor, which solves the problems of low sensitivity and poor selectivity for glucose in current glucose sensors, and can prepare SACs with high electrocatalytic activity for use in the working electrode of a glucose electrochemical sensor.
[0006] The invention provides a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor. The nickel-based single-atom catalyst comprises the following steps: uniformly mixing di(cyclopentadiene)nickel(II), melamine and a carbon-based nanomaterial, dissolving them in an organic solvent, stirring them, and subjecting the suspension to rotary evaporation to obtain a powder; calcining the obtained powder in a non-reactive gas, acid-etching the obtained product with an acid solution, and then centrifuging, washing and vacuum drying to obtain the nickel-based single-atom catalyst.
[0007] The carbon-based nanomaterial is one of graphene, carbon nanotube or carbon fiber.
[0008] The mass ratio of the bis(cyclopentadiene)nickel(II), melamine and carbon-based nanomaterial is 1:1:3-6.
[0009] The method for preparing the nickel-based single-atom catalyst suitable for glucose electrochemical sensor comprises the following steps:
[0010] 1) mixing and grinding bis(cyclopentadienyl)nickel(II), melamine and carbon-based nanomaterials, dissolving them in an organic solvent, stirring, and rotary evaporating the suspension to obtain powder;
[0011] 2) calcining the powder obtained in step 1) in a non-reactive gas, and etching the obtained product with an acid solution, followed by centrifugation, washing, and vacuum drying to obtain a nickel-based single-atom catalyst.
[0012] The organic solvent in step 1) is one of dichloromethane, methanol, ethyl acetate, petroleum ether, toluene, chloroform, toluene or tetrahydrofuran.
[0013] The solid-liquid ratio of the suspension in step 1) is 2:1 to 1:2.
[0014] The stirring in step 1) is magnetic stirring, the stirring temperature is 10-40° C., and the time is 10-60 min.
[0015] The calcination in step 2) is carried out in a tubular furnace at a temperature of 300 to 500° C., a heating rate of 2 to 100° C. / min, and a calcination time of 0.5 to 5 h.
[0016] In step 2), the non-reactive gas is one of nitrogen or argon; the vacuum drying temperature is 30-50° C., and the time is 1-2 hours.
[0017] In step 2), the acid is one of sulfuric acid or hydrochloric acid; the concentration of the acid solution is 0.5-2 mol / L.
[0018] The application of the nickel-based single-atom catalyst suitable for glucose electrochemical sensor in the glucose electrochemical sensor.
[0019] Beneficial effects:
[0020] 1) The nickel-based single-atom catalyst provided by the present invention is based on a carbon-based nanomaterial with a large specific surface area, uniformly loaded with Ni metal particles, and has excellent electrical conductivity.
[0021] 2) The synergistic effect of nickel and nitrogen-doped carbon in the nickel-based single-atom catalyst provided by the present invention can achieve uniform dispersion of nickel at the single-atom level on the carbon-based nanomaterial, with abundant redox active sites, enhancing reaction kinetics and electrocatalytic activity.
[0022] 3) The nickel-based single-atom catalyst provided by the present invention has excellent electrochemical catalytic performance when applied to glucose detection, with a sensitivity of up to 546.86 μA / (mM·cm 2 ), with a detection limit of 0.24 μM.
[0023] 4) The process provided by the present invention is simple, low-cost and suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 This is the spherical aberration corrected HAADF-STEM image of the nickel-based single-atom catalyst prepared in Example 1 of the present invention.
[0025] Figure 2 This is the CV response diagram of the nickel-based single-atom catalyst prepared in Example 1 of the present invention to different concentrations of glucose.
[0026] Figure 3 This is a linear curve diagram of the CV response of the nickel-based single-atom catalyst prepared in Example 1 of the present invention to different concentrations of glucose. DETAILED DESCRIPTION
[0027] The present invention is further described below through detailed implementation examples to make the technical solutions and advantages of the present invention clearer, but the technical parameters in the following implementation examples are not intended to limit the present invention.
[0028] A method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor, the technical scheme is as follows:
[0029] Step 1) mixing and grinding bis(cyclopentadienyl)nickel(II), melamine and carbon-based nanomaterials uniformly, dissolving them in an organic solvent and magnetically stirring them, and subjecting the suspension to a rotary evaporator to obtain a powder;
[0030] Step 2) placing the powder obtained in step 1) in a tubular furnace and calcining it in a non-reactive gas; the obtained product is acidified and etched using an acid solution, and then centrifuged, washed, and dried to obtain a nickel-based single-atom catalyst.
[0031] In the preparation scheme, preferably, the carbon-based nanomaterial in step 1) is one of graphene, carbon nanotubes or carbon fibers.
[0032] In the preparation scheme, preferably, the mass ratio of di(cyclopentadiene)nickel(II), melamine and carbon-based nanomaterial in step 1) is 1:1:3-6.
[0033] In the preparation scheme, preferably, the solid-liquid ratio of the suspension in step 1) is 2:1 to 1:2.
[0034] In the preparation scheme, preferably, the magnetic stirring temperature in step 1) is 10 to 40° C. and the time is 10 to 60 min.
[0035] In the preparation scheme, preferably, the calcination temperature in the tubular furnace in step 2) is 300-500° C., the heating rate is 2-100° C. / min, and the calcination time is 0.5-5 h.
[0036] In the preparation scheme, preferably, the non-reactive gas in step 2) is one of nitrogen or argon.
[0037] In the preparation scheme, preferably, the acid in step 2) is one of sulfuric acid or hydrochloric acid; the concentration of the acid solution is 0.5 to 2 mol / L.
[0038] In the preparation scheme, preferably, the vacuum drying temperature in step 2) is 30-50° C. and the time is 1-2 h.
[0039] Example 1
[0040] The present invention provides a method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor, comprising the following steps:
[0041] 1) 40 mg of bis(cyclopentadienyl)nickel(II), 40 mg of melamine and 120 mg of graphene were mixed and ground evenly, 200 mL of dichloromethane solution was mixed with the powder, and magnetic stirring was performed at 20° C. for 30 min. After stirring was completed, the dichloromethane solution was removed using a rotary evaporator to obtain a powder.
[0042] 2) The powder obtained in 1) was evenly spread in a porcelain boat, which was placed in the center of a tube furnace, and nitrogen was introduced. The temperature was raised from room temperature to 70°C for 30 minutes, and then raised to 300°C at a rate of 5°C / min and maintained for 2 hours. After naturally cooling to room temperature, the product was collected, acidified and etched with a 0.5 mol / L H2SO4 solution, and then the sample was washed with deionized water, centrifuged, and dried at a vacuum temperature of 30°C for 1 hour to obtain a nickel-based single-atom catalyst sample powder.
[0043] Example 2
[0044] The present invention provides a method for preparing a nickel-based single atom suitable for a glucose electrochemical sensor, comprising the following steps:
[0045] 1) 40 mg of bis(cyclopentadienyl)nickel(II), 40 mg of melamine and 200 mg of carbon nanotubes were mixed and ground evenly, 280 mL of dichloromethane solution was mixed with the powder, and magnetic stirring was performed at 20° C. for 30 min. After stirring was completed, the dichloromethane solution was removed using a rotary evaporator to obtain a powder.
[0046] 2) The powder obtained in 1) was evenly spread in a porcelain boat, which was placed in the center of a tube furnace, and nitrogen was introduced. The temperature was raised from room temperature to 70°C for 30 minutes, and then raised to 400°C at a rate of 10°C / min and maintained for 2 hours. After naturally cooling to room temperature, the product was collected, acidified and etched with a 0.5 mol / L H2SO4 solution, and then the sample was washed with deionized water, centrifuged, and dried at a vacuum temperature of 30°C for 1 hour to obtain a nickel-based single-atom catalyst sample powder.
[0047] Example 3
[0048] The present invention provides a method for preparing a nickel-based single atom suitable for a glucose electrochemical sensor, comprising the following steps:
[0049] 1) 40 mg of bis(cyclopentadienyl)nickel(II), 40 mg of melamine and 240 mg of carbon fiber were mixed and ground evenly, 320 mL of dichloromethane solution was mixed with the powder, and magnetic stirring was performed at 30° C. for 30 min. After stirring was completed, the dichloromethane solution was removed using a rotary evaporator to obtain a powder.
[0050] 2) The powder obtained in 1) was evenly spread in a porcelain boat, which was placed in the center of a tube furnace, and nitrogen was introduced. The temperature was raised from room temperature to 70°C for 30 minutes, and then raised to 500°C at a rate of 5°C / min and maintained for 2 hours. After naturally cooling to room temperature, the product was collected, acidified and etched with a 0.5 mol / L H2SO4 solution, and then the sample was washed with deionized water, centrifuged, and dried at a vacuum temperature of 30°C for 1 hour to obtain a nickel-based single-atom catalyst sample powder.
[0051] Application Examples
[0052] The nickel-based single-atom catalyst prepared in the embodiment was subjected to performance testing, as follows:
[0053] 5 mg of the nickel-based single-atom catalyst powder prepared in Example 1 of the present invention, 900 μL of isopropanol, 80 μL of deionized water and 20 μL of a perfluorinated resin solution (concentration of 5%) were used to prepare ink, and 6.6 μL of the ink solution was dripped onto a glassy carbon electrode to prepare a working electrode for glucose sensing detection. In a glucose / sodium hydroxide solution, electrochemical CV testing technology (electrochemical workstation, 760E, Shanghai Chenhua) was used to electrochemically detect glucose, and the results are as follows Figure 2 As shown, it can be seen that the nickel-based single-atom catalyst has an obvious oxidation peak at around 0.6V and the peak value becomes higher and higher with the increase of glucose concentration. Figure 3 The results showed that the minimum detection limit for glucose was 0.24 μM; the detection range was 0.1-10 mM; the sensitivity was 546.86 μA / (mM·cm 2 ); and exhibits good anti-interference and stability.
[0054] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A nickel-based single-atom catalyst suitable for a glucose electrochemical sensor, characterized in that: The method comprises the steps of mixing and grinding bis(cyclopentadienyl)nickel(II), melamine and carbon-based nanomaterials, dissolving them in an organic solvent, stirring them, and obtaining a powder by rotary evaporation of the suspension; calcining the obtained powder in a non-reactive gas, acid-etching the obtained product with an acid solution, and then centrifuging, washing, and vacuum drying to obtain a nickel-based single-atom catalyst.
2. The nickel-based single-atom catalyst suitable for glucose electrochemical sensor according to claim 1, characterized in that: The carbon-based nanomaterial is one of graphene, carbon nanotube or carbon fiber.
3. The nickel-based single-atom catalyst suitable for glucose electrochemical sensor according to claim 1, characterized in that: The mass ratio of the bis(cyclopentadiene)nickel(II), melamine and carbon-based nanomaterial is 1:1:3-6.
4. A method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor according to any one of claims 1 to 3, characterized in that: The following steps are involved: 1) mixing and grinding bis(cyclopentadienyl)nickel(II), melamine and carbon-based nanomaterials, dissolving them in an organic solvent, stirring, and rotary evaporating the suspension to obtain powder; 2) calcining the powder obtained in step 1) in a non-reactive gas, and etching the obtained product with an acid solution, followed by centrifugation, washing, and vacuum drying to obtain a nickel-based single-atom catalyst.
5. The method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor according to claim 4, characterized in that: The organic solvent in step 1) is one of dichloromethane, methanol, ethyl acetate, petroleum ether, toluene, chloroform, toluene or tetrahydrofuran; the acid in step 2) is one of sulfuric acid or hydrochloric acid; the concentration of the acid solution is 0.5-2 mol / L.
6. The method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor according to claim 4, characterized in that: The solid-liquid ratio of the suspension in step 1) is 2:1 to 1:
2.
7. The method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor according to claim 4, characterized in that: The stirring in step 1) is magnetic stirring, the stirring temperature is 10-40° C., and the time is 10-60 min.
8. The method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor according to claim 4, characterized in that: The calcination in step 2) is carried out in a tubular furnace at a temperature of 300 to 500° C., a heating rate of 2 to 100° C. / min, and a calcination time of 0.5 to 5 h.
9. The method for preparing a nickel-based single-atom catalyst suitable for a glucose electrochemical sensor according to claim 4, characterized in that: The non-reactive gas in step 2) is one of nitrogen or argon; The vacuum drying temperature is 30-50° C. and the time is 1-2 hours.
10. Use of the nickel-based single-atom catalyst suitable for glucose electrochemical sensor according to any one of claims 1 to 3 in a glucose electrochemical sensor.