CN-122010424-A - Preparation method and application of inverse opal structure nickel selenium compound

CN122010424ACN 122010424 ACN122010424 ACN 122010424ACN-122010424-A

Abstract

The invention discloses a preparation method and application of an inverse opal structure nickel selenium compound, and belongs to the technical field of material preparation. According to the method, a polystyrene nanosphere template is assembled on a conductive substrate through a vertical pulling method, then a nickel selenium compound precursor is filled into a template pore through constant potential electrodeposition, and after the template is removed, the nickel selenium compound with the inverse opal structure of a three-dimensional ordered macroporous network is obtained through inert atmosphere heat treatment. The invention also provides application of the material as a working electrode in non-enzymatic glucose electrochemical detection. The inverse opal structure nickel selenium compound has a highly ordered and communicated pore channel network, can expose a large number of active sites and accelerate diffusion mass transfer, thereby improving conductivity and electrocatalytic activity. Through the synergistic effect of structural design and element composition, the sensitivity, linear range and selectivity of glucose detection are further improved, and the application potential of the glucose detection in a non-enzymatic glucose sensor is highlighted.

Inventors

JIN MINGSHI
ZHOU BOKAI
Pu Guanghai
DING MENGYU
Shi Zuotong

Assignees

延边大学

Dates

Publication Date: 20260512
Application Date: 20260414

Claims (4)

1. The preparation method of the nickel selenium compound with the inverse opal structure is characterized by comprising the following steps: Step S1, preparing polystyrene nanospheres by an emulsion polymerization method, wherein 0.1 g sodium carbonate is taken as a buffering agent and 0.2 g sodium dodecyl sulfate is taken as an emulsifying agent to be dissolved in 300 mL distilled water to form a mixture, the mixture is purged with nitrogen for 30 minutes, then under the water bath condition, the temperature is 60 ℃,30 min of the mixture is vigorously stirred, 30 mL of styrene is taken as a monomer, then 15 mL of 0.23M potassium persulfate solution is taken as an initiating agent, the initiating temperature is 75 ℃ and 20 h is maintained, and the polystyrene nanospheres with the particle size of 200 nm are obtained; Step S2, sequentially ultrasonically cleaning an ITO glass substrate with the size of 1 multiplied by 0.5 cm < 2 > by using acetone, ethanol and deionized water, drying, vertically immersing the cleaned ITO substrate into polystyrene nanosphere dispersion liquid, self-assembling polystyrene nanospheres by a vertical pulling method to form a uniformly arranged polystyrene nanosphere template film, wherein the polystyrene nanosphere dispersion liquid comprises 0.3 g polystyrene nanospheres, 0.02 g sodium dodecyl sulfate and 10 g deionized water according to mass ratio, and slowly taking out the ITO glass substrate at a control rate of 0.005 mm/min by a dip-coating instrument in a vertical pulling process, and naturally airing the ITO glass substrate at room temperature to obtain the template film; step S3, adopting a three-electrode system to perform constant potential electrodeposition, wherein the template film prepared in the step S2 is used as a working electrode, a platinum plate is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode, wherein the electrolyte comprises 5mM nickel chloride hexahydrate as a nickel source, 10 mM selenium oxide as a selenium source and a supporting electrolyte, the potential is set to be-0.8V, a nickel selenium compound precursor is filled in the template pores, and the electrodeposition time is 2 min, 5min and 8 min; The supporting electrolyte is lithium chloride; s4, dissolving and removing the polystyrene nanosphere film by using toluene to obtain an inverse opal structure skeleton with a three-dimensional ordered macroporous network, wherein the treatment time is 2-4 h; s5, performing heat treatment on the inverse opal skeleton with the three-dimensional ordered macroporous network structure obtained in the step S4; the heat treatment is carried out in a tube furnace, the heat treatment atmosphere is high-purity nitrogen, the gas flow rate is 50-100 mL/min, the temperature is raised stepwise at the temperature raising rate of 5 ℃ per min, the temperature is raised to 100 ℃, 200 ℃ and 300 ℃ from room temperature in sequence, the temperature is kept at 300 ℃ for 2h, and then the temperature is naturally cooled to the room temperature; the final product is nickel selenium compound with inverse opal structure, which is IO-Ni 3 Se 4 .
2. A nickel selenium compound having an inverse opal structure, prepared by the method of claim 1.
3. An electrochemical sensor working electrode comprising the nickel selenium compound having an inverse opal structure of claim 2.
4. An electrochemical detection method of glucose, comprising the steps of: step S I, using the working electrode of the electrochemical sensor as a working electrode, and evaluating the electrocatalytic oxidation activity of the working electrode of the electrochemical sensor on glucose in 0.1M NaOH electrolyte by a cyclic voltammetry method; step S two, determining that the optimal working potential of glucose detection is 0.60V; Step S three, measuring the linear relation between the current response and the glucose concentration by an ampere method, and calculating the sensitivity and the linear range; and step S four, evaluating the selectivity of the sensor by adding common interferents.

Description

Preparation method and application of inverse opal structure nickel selenium compound Technical Field The invention belongs to the technical field of material preparation, and particularly relates to a preparation method and application of an inverse opal structure nickel selenium compound. Background The accurate detection of glucose is of vital importance in the fields of clinical medicine (e.g. diabetes management), food industry, biological process monitoring and the like. Current mainstream detection methods include optical, chromatographic, electrochemical methods, etc., with electrochemical methods being favored for their ease of operation, rapid response, low cost, and ease of miniaturization. The performance core of an electrochemical glucose sensor is the working electrode material. Although the traditional enzymatic sensor (such as glucose oxidase) has high selectivity, the biological activity of the enzyme is easily influenced by environmental factors (temperature and pH value), and the traditional enzymatic sensor has the inherent defects of poor stability, high cost, inconvenient preservation and the like. Therefore, development of non-enzymatic electrochemical sensors based on the catalytic activity of the material itself, independent of biological enzymes, has become an important trend. The performance of such sensors is directly dependent on the conductivity, catalytic activity and structural stability of the electrode material. Transition metal compounds, particularly nickel-based materials (e.g., nickel hydroxide, nickel oxide), have become star materials for non-enzymatic glucose sensors due to their high catalytic activity for glucose oxidation in alkaline media, good stability and low cost. However, conventional materials represented by nickel oxide still face challenges such as relatively insufficient intrinsic conductivity, limited active site exposure, low mass transfer efficiency, and the like, which limit further improvement of detection sensitivity and response speed. In recent years, transition metal selenides (e.g., niSe 2, Ni3Se2) have begun to exhibit great potential for use due to their superior metal conductivity and electrochemical activity over oxides/hydroxides. The structural design of the material is another key to breaking through performance bottlenecks. Three-dimensional ordered porous structures, particularly inverse opal structures, are considered ideal electrode structures because of their highly interconnected macroporous networks, large specific surface areas, and efficient mass transfer channels. This structure not only exposes more catalytically active sites, but also promotes rapid diffusion of reactants/products, thereby significantly improving sensor performance. However, in the prior art, the research of combining a highly conductive nickel selenium compound with a finely controllable inverse opal structure and applying the system to a high-performance glucose electrochemical sensor has been reported to be insufficient. The nickel selenium compound prepared by the conventional method is mostly compact particles or stacked nano sheets, and the structural advantage of the nickel selenium compound is not fully exerted. How to construct a nickel selenium compound with complete structure, uniform components and inverse opal structure by a simple and controllable synthesis strategy, and deeply dig the application potential of the nickel selenium compound in glucose detection, is a technical problem to be solved at present. Disclosure of Invention The invention aims to overcome the defect that a non-enzymatic electrochemical sensor has limited sensitivity and detection range to glucose under an alkaline condition, and prepare an inverse opal structure nickel selenium compound and application thereof. In order to achieve the above object, the present invention provides the following technical solutions: In a first aspect, the present invention provides a method for preparing a nickel selenium compound having an inverse opal structure, comprising the steps of: Step S1, preparing polystyrene nanospheres by an emulsion polymerization method, wherein 0.1 g sodium carbonate is taken as a buffering agent and 0.2 g sodium dodecyl sulfate is taken as an emulsifying agent to be dissolved in 300 mL distilled water to form a mixture, the mixture is purged with nitrogen for 30 minutes, then under the water bath condition, the temperature is 60 ℃,30 min of the mixture is vigorously stirred, 30 mL of styrene is taken as a monomer, then 15 mL of 0.23M potassium persulfate solution is taken as an initiating agent, the initiating temperature is 75 ℃ and 20 h is maintained, and the polystyrene nanospheres with the particle size of 200 nm are obtained; Step S2, sequentially ultrasonically cleaning an ITO glass substrate with the size of 1 multiplied by 0.5 cm < 2 > by using acetone, ethanol and deionized water, drying, vertically immersing the cleaned ITO substrate into polystyrene