Basic nickel carbonate modified material and preparation method thereof

Abstract

The invention belongs to the field of inorganic functional materials, and particularly relates to a basic nickel carbonate modified material and a preparation method thereof.The method comprises the steps that nickel nitrate hexahydrate is dissolved in deionized water, urea and cetyltrimethylammonium bromide are added, the mixture is heated and stirred mildly, and stirring is performed to obtain a basic nickel carbonate modified material; then adding a specially-made polyaminophenylboronic acid nickel complex and a cobalt-nickel phosphate ethanediamine hybrid material, performing ultrasonic dispersion to form a mixed solution, and then performing hydrothermal reaction, centrifugal washing and vacuum drying to obtain a final product. The two special modified compounds are respectively prepared through a coordination reaction regulated by ammonia water and a hybridization reaction under high-temperature and high-pressure conditions. The modified material prepared by the method has a unique microstructure and enhanced physical and chemical properties, shows excellent application prospects in the fields of electrochemical energy storage, electro-catalytic water and environmental remediation, and particularly, the comprehensive performance of the material is remarkably improved due to the high specific surface area, abundant active sites and a stable structure.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of inorganic functional materials, and particularly relates to a basic nickel carbonate modified material and a preparation method thereof. BACKGROUND

[0002] As a traditional inorganic salt material, basic nickel carbonate has been mainly applied in traditional fields such as electroplating industry, ceramic pigment preparation and ordinary nickel salt synthesis for a long time. In these traditional applications, the performance requirements of the material itself are relatively low, and ordinary specifications of basic nickel carbonate can meet the production requirements. However, with the rapid development of science and technology and the continuous promotion of industrial upgrading, the traditional application fields have put forward higher requirements on the performance of the material, and the emergence of emerging fields such as new energy and environmental governance has put forward new challenges to functional materials. Ordinary basic nickel carbonate is difficult to meet the stringent requirements of these emerging fields on the performance of the material due to its inherent defects such as limited specific surface area, insufficient active sites and poor structural stability. In particular, in high-tech fields such as electrochemical energy storage, electrocatalysis and environmental remediation, the material needs to have multiple characteristics such as high specific surface area, rich pore structure, excellent electronic conductivity and good structural stability, which are exactly what the traditional basic nickel carbonate material lacks. Therefore, how to improve the comprehensive performance of basic nickel carbonate through effective modification technology and expand its application range has become an important issue to be solved in the field of material science.

[0003] In recent years, researchers have tried to modify basic nickel carbonate through various methods, including morphology control, ion doping, surface modification and other technical approaches. In terms of morphology control, nanosheets, microspheres, hierarchical porous structures and other basic nickel carbonate materials with different morphologies are prepared by hydrothermal method, solvothermal method and other methods, which to some extent increases the specific surface area and active site number of the material. In terms of ion doping, other metal ions are introduced to try to adjust the electronic structure and surface properties of the material. In terms of surface modification, surfactants or organic molecules are used to modify the surface of the material to improve its dispersibility and interfacial properties. However, these traditional modification methods still have obvious limitations: a single modification method can only improve the performance of the material in one aspect, and it is difficult to achieve the synergistic improvement of multiple performances; the modification effect is limited and cannot fundamentally change the inherent characteristics of the material; the modification process is complex and the conditions are harsh, making it difficult to achieve large-scale production; more importantly, these methods lack the ability to precisely control the molecular structure of the material, and cannot realize the directional design of the performance of the material at the atomic scale. In particular, the existing technology has not solved the key problems such as weak interfacial bonding force between the modifier and the matrix material, single function and rapid performance degradation during long-term use.

[0004] To address the aforementioned technical challenges, this invention proposes a novel modified basic nickel carbonate material and its preparation method. The core innovation of this method lies in the design and synthesis of two functionally specific modifying compounds: a nickel polyaminophenylborate complex and a cobalt-nickel phosphate ethylenediamine hybrid material. Through the synergistic effect of these two compounds, multi-level precise control of the basic nickel carbonate material is achieved from the molecular level to the microstructure. The nickel polyaminophenylborate complex can form a strong chemical bond with the surface of basic nickel carbonate through its unique coordination effect, while the introduced boron element can effectively regulate the electronic structure of the material and enhance its electrochemical activity. Meanwhile, the cobalt-nickel phosphate ethylenediamine hybrid material plays a structural guiding and stabilizing role during the growth of basic nickel carbonate crystals, promoting the formation of a highly stable composite structure with multi-level pores. The synergistic use of these two modified compounds not only significantly improves the specific surface area and porosity of the material, but also greatly enhances its structural stability and interfacial transport performance. This enables the modified basic nickel carbonate to exhibit excellent application performance in multiple fields such as electrochemical energy storage, electrocatalytic water splitting, and environmental pollutant treatment, effectively breaking through the application limitations of traditional basic nickel carbonate materials and opening up new avenues for its application in high-tech fields. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a basic nickel carbonate modified material and its preparation method.

[0006] In a first aspect, the present invention provides a method for preparing a basic nickel carbonate modified material, comprising the following steps:

[0007] S1. Dissolve nickel nitrate hexahydrate in deionized water and stir; add urea and hexadecyltrimethylammonium bromide in sequence and stir in a water bath at 38-42℃ to obtain a solution; add polyaminophenylboronic acid-nickel complex and cobalt nickel phosphate-ethylenediamine hybrid material to the solution and disperse by ultrasonication to obtain a mixed solution;

[0008] S2. Transfer the mixed solution to a high-pressure reactor, seal it, and react at 115-125℃. After the reaction is complete, cool it to room temperature, wash it by centrifugation with deionized water and ethanol respectively, and dry it in a vacuum drying oven at 78-82℃.

[0009] In this invention, the formation of basic nickel carbonate modified materials is based on a hydrothermal synergistic assembly and crystal engineering mechanism. In the alkaline environment provided by urea decomposition, nickel nitrate hexahydrate first dissociates into nickel ions, which combine with carbonate and hydroxyl ions generated from urea hydrolysis to form basic nickel carbonate nuclei. This process is guided by the micellar template effect of hexadecyltrimethylammonium bromide, forming an initial nanosheet structure. Subsequently, polyaminophenylboronic acid-nickel complex and cobalt nickel phosphate-ethylenediamine hybrid material, as bifunctional modifiers, are embedded into the host material through interface anchoring and lattice matching mechanisms: the boron atoms in the polyaminophenylboronic acid-nickel complex act as Lewis acid sites to form BO-Ni covalent bonds with the hydroxyl groups on the surface of basic nickel carbonate, while its benzene ring structure undergoes π-π stacking with the nanosheets, enhancing interfacial electronic coupling; while the cobalt nickel phosphate-ethylenediamine hybrid material partially replaces nickel sites to form a Co-Ni-PO heterostructure through ion exchange between metal sites and carbonate ions, and the ethylenediamine molecules between its layers also bridge adjacent nanosheets through hydrogen bonding, inducing the formation of hierarchical channels. In the hydrothermal reaction, the stepwise hydrolysis of urea controls the crystal growth kinetics, causing topological transformations and defect engineering between the modifier and the host material, resulting in abundant oxygen vacancies and lattice strain. Ultimately, the synergistic effect of the two modifiers optimizes the electronic structure and mass transport pathway of the material, while the boron-phosphorus co-doping effect further modulates the oxidation state of nickel, forming a composite functional material with a highly active surface and a stable mesoporous structure.

[0010] As a preferred technical solution of the present invention, in step S1, the stirring time in a water bath at 38-42°C is 30-40 minutes.

[0011] As a preferred embodiment of the present invention, in step S2, the reaction time is 12-14 hours at 115-125°C.

[0012] As a preferred technical solution of the present invention, the preparation method of the polyaminophenylboronic acid-nickel complex includes: A1, dissolving 3-aminophenylboronic acid in deionized water and stirring until completely dissolved; then adding nickel chloride and continuously stirring and mixing at room temperature; subsequently adding ammonia water to adjust the pH to 8-9, and reacting in a water bath at 58-62℃ to obtain a solid product; A2, washing the solid product alternately by centrifugation with ethanol and deionized water, and drying it in a vacuum drying oven at 58-62℃.

[0013] In this invention, the preparation of polyaminophenylboronic acid-nickel complex is based on the cooperative coordination and interfacial stabilization mechanism in coordination chemistry. In the initial stage of the reaction, 3-aminophenylboronic acid molecules undergo ionization and proton transfer in aqueous solution. Under alkaline conditions, the borate group partially dissociates into borate, while the amino group forms a preliminary coordination bond with nickel ions through lone pair electrons. Subsequently, in a weakly alkaline environment regulated by ammonia, the coordination between nickel ions and borate is enhanced, forming a four-coordinate intermediate. In this intermediate, the nickel ion simultaneously bonds to the oxygen atom of the borate and the nitrogen atom of the amino group, constructing a stable five-membered ring chelate structure. This process follows an internal conjugated base mechanism; the alkaline environment provided by ammonia not only promotes ligand deprotonation but also stabilizes the transition state through a hydrogen bond network, accelerating the formation of coordination bonds. As the reaction temperature increases, intermolecular condensation and aromatic ring stacking occur. The borate group forms a dehydration condensation with the hydroxyl groups of adjacent molecules, producing oligomer chains. Simultaneously, the π-π stacking between benzene rings further enhances the skeletal stability. Ultimately, the d orbital electrons of the nickel ion hybridize with the p orbitals of the ligand, forming a tetragonal complex crystal whose stability is maintained by coordination bond energy, hydrogen bonds, and van der Waals forces.

[0014] As a preferred embodiment of the present invention, in step A1, the reaction time in a water bath at 58-62°C is 3-5 hours.

[0015] As a preferred embodiment of the present invention, in step A2, the drying time in a vacuum drying oven at 58-62°C is 6-8 hours.

[0016] As a preferred technical solution of the present invention, the preparation method of the cobalt-nickel phosphate-ethylenediamine hybrid material includes: B1, dissolving cobalt chloride and nickel chloride in diethylene glycol and stirring until completely dissolved; then adding ammonium dihydrogen phosphate and ethylenediamine and stirring continuously to obtain a mixed solution; transferring the mixed solution to a high-pressure reactor and reacting at 195-205°C; B2, after cooling to room temperature, centrifuging and washing with acetone and ethanol solution, collecting the solid product; and drying the solid product under vacuum at 78-82°C.

[0017] In this invention, the synthesis of cobalt-nickel phosphate-ethylenediamine hybrid materials involves a solvothermal-induced coprecipitation and interfacial hybridization mechanism. In diethylene glycol solvent, cobalt and nickel ions first selectively coordinate with ethylenediamine. The bidentate coordination characteristic of ethylenediamine allows it to form an octahedral precursor with the metal ions through two amino groups, while the oxygen atom of the diethylene glycol ether bond acts as a weak ligand to stabilize the metal center. Subsequently, ammonium dihydrogen phosphate decomposes at high temperature, releasing phosphate ions that attack the metal-ethylenediamine complex, resulting in nucleophilic substitution and framework reconstruction: the oxygen atom in the phosphate group replaces some of the ethylenediamine coordination sites, forming mixed metal phosphate layers with cobalt and nickel ions, while ethylenediamine molecules are partially released and intercalated between layers as structural templates. This process is accompanied by electron transfer and lattice strain. The electronic structure of cobalt ions modulates the d-band center of nickel, enhances the electronegativity of phosphorus atoms, polarizes the metal-phosphorus bond, and thus optimizes the interfacial electron distribution. Under high temperature and high pressure conditions, the layers self-assemble through hydrogen bonds and van der Waals forces to form a three-dimensional hierarchical structure. The carbon chain of ethylenediamine is partially carbonized to generate a nitrogen-doped carbon network, which forms an organic-inorganic heterojunction with the phosphate layer. Its stability comes from the synergistic effect of covalent and non-covalent bonds.

[0018] As a preferred embodiment of the present invention, in step B1, the reaction time is 4-6 hours at 195-205°C.

[0019] As a preferred embodiment of the present invention, in step B2, the drying time under vacuum at 78-82°C is 6-8 hours.

[0020] In a second aspect, the present invention provides a method for preparing the basic nickel carbonate modified material, comprising the following raw materials in parts by weight: 25-45 parts of nickel nitrate hexahydrate; 10-20 parts of polyaminophenylboronic acid-nickel complex; 8-15 parts of cobalt nickel phosphate-ethylenediamine hybrid material; 5-12 parts of urea; 5-10 parts of hexadecyltrimethylammonium bromide; and 15-30 parts of deionized water.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The basic nickel carbonate modified material and its preparation method provided by this invention have significant technological advancements and outstanding practical application effects. First, in terms of the basic properties of the material, by introducing two specially modified compounds: a nickel polyaminophenylborate complex and a cobalt nickel phosphate ethylenediamine hybrid material, multi-level precise control of basic nickel carbonate from molecular structure to macroscopic morphology is achieved. These two compounds produce a significant synergistic effect during the modification process. The nickel polyaminophenylborate complex forms a stable chemical bond with the surface of basic nickel carbonate through its unique coordination effect, effectively regulating the electronic structure of the material and enhancing surface activity; while the cobalt nickel phosphate ethylenediamine hybrid material plays a structure-guiding role in the crystal growth process, promoting the formation of a highly stable composite structure with multi-level channels. This synergistic modification results in a basic nickel carbonate material with a significantly increased specific surface area, a richer pore structure, a significantly increased active site density, and a significantly improved electron transport capability, fundamentally solving the technical bottlenecks of limited specific surface area, insufficient active sites, and poor electronic conductivity of traditional basic nickel carbonate materials.

[0023] (2) In terms of application performance, the modified material of this invention exhibits outstanding performance in multiple high-tech fields. In the field of electrochemical energy storage, this material, as an electrode active material, exhibits extremely high specific capacitance and excellent rate performance, while also having an extremely long cycle life. It can still maintain a stable capacitance value after multiple charge-discharge cycles. This is mainly due to the material's unique multi-level porous structure, which provides a convenient path for ion transport, and the stable framework structure, which effectively inhibits structural collapse during the cycling process. In the field of electrocatalytic water splitting, this material, as a non-precious metal catalyst, exhibits catalytic activity and stability close to that of precious metal catalysts in both oxygen evolution reaction and hydrogen evolution reaction. Its low overpotential and fast reaction kinetics are due to the synergistic catalytic effect introduced by the modified compound and the rich distribution of active sites in the material itself. In the field of environmental remediation, this material exhibits excellent adsorption performance and catalytic degradation ability for various heavy metal ions and organic pollutants in water. Its high removal rate and rapid equilibrium characteristics are due to the material's huge specific surface area and rich functional group distribution on the surface, providing an ideal platform for pollutant capture and transformation.

[0024] (3) From an industrial application perspective, this invention has significant practical value and broad market prospects. The raw materials used in this preparation method are all conventional commercially available chemicals. The process is simple and reliable, the reaction conditions are mild and controllable, no special equipment is required, and it has great potential for industrial scale-up, effectively reducing production costs. The resulting product has multifunctional characteristics, which can simultaneously meet the needs of different application fields, greatly expanding the application range of basic nickel carbonate materials and promoting its transformation and upgrading from traditional low-value-added fields to high-value-added fields such as new energy and environmental protection. In addition, the entire preparation process is environmentally friendly, does not produce toxic and harmful byproducts, and conforms to the concepts of green chemistry and sustainable development. The promotion and implementation of this technology will help promote the technological progress and product upgrading of related industries, play an important role in national strategic needs such as energy storage and conversion and environmental pollution control, and have significant economic and social benefits. Detailed Implementation

[0025] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0026] The sources of some components in the examples and comparative examples are as follows:

[0027] The nickel nitrate hexahydrate was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0028] The urea was purchased from Shandong Hualu Hengsheng Chemical Co., Ltd.

[0029] The hexadecyltrimethylammonium bromide was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0030] The 3-aminophenylboronic acid was purchased from Suzhou Youbo Optoelectronic Materials Co., Ltd.

[0031] The nickel chloride was purchased from Jinchuan Group Co., Ltd.

[0032] The cobalt chloride was purchased from Zhejiang Huayou Cobalt Co., Ltd.

[0033] The ammonium dihydrogen phosphate was purchased from Sichuan Lanjian Chemical (Group) Co., Ltd.

[0034] The ethylenediamine was purchased from Hangzhou Xin'ao Environmental Protection Technology Co., Ltd.

[0035] Example 1

[0036] Preparation of polyaminophenylboronic acid-nickel complex: 2.0 g of 3-aminophenylboronic acid was accurately weighed and dissolved in 40 mL of deionized water. The solution was stirred at 500 rpm for 15 min using a magnetic stirrer until completely dissolved. Then, 0.5 g of nickel chloride hexahydrate was added, and the mixture was stirred continuously at 25°C for 30 min to ensure thorough mixing. Next, a 25% (w / w) ammonia solution was slowly added dropwise to adjust the pH of the mixture to 8.5. The reaction vessel was then transferred to a 60°C constant temperature water bath, and the mixture was stirred at 400 rpm for 4 h. After the reaction was complete, the resulting solid product was transferred to a centrifuge tube. The product was first washed three times with anhydrous ethanol (30 mL each time, centrifuged at 8000 rpm for 5 min), followed by three washes with deionized water under the same conditions. The washed solid product was then transferred to a vacuum drying oven and dried at 60°C and -0.1 MPa for 7 h to obtain a dark green solid product, which was then sealed and stored for later use.

[0037] Preparation of cobalt-nickel phosphate-ethylenediamine hybrid material: Accurately weigh 1.2 g of cobalt chloride hexahydrate and 0.8 g of nickel chloride hexahydrate, dissolve them together in 30 mL of diethylene glycol, and stir with a magnetic stirrer at 600 rpm for 20 min until completely dissolved. Then add 2.0 g of ammonium dihydrogen phosphate and 3.0 mL of ethylenediamine, and continue stirring at 500 rpm for 30 min to form a homogeneous mixture. Transfer the mixture to a 50 mL polytetrafluoroethylene-lined high-pressure reactor, seal it, and place the reactor in a muffle furnace. Heat to 200 °C at a heating rate of 5 °C / min, and maintain the reaction at this temperature for 5 h. After the reaction, allow it to cool naturally to 25 °C. Open the reactor, and wash the obtained product alternately with acetone and 95% ethanol solution by centrifugation three times each, using 30 mL of detergent each time, at a centrifugation speed of 10000 rpm for 5 min. Collect the purple solid product, place it in a vacuum drying oven, dry it at 80℃ and -0.1MPa vacuum for 7 hours, and then seal and store it.

[0038] Preparation of basic nickel carbonate modified material: Accurately weigh 4.0 g of nickel nitrate hexahydrate and dissolve it in 200 mL of deionized water. Stir at 400 rpm for 15 min using a mechanical stirrer until the solution is completely transparent. Add 1.5 g of urea and 0.5 g of hexadecyltrimethylammonium bromide sequentially. Place the reaction vessel in a 40°C constant temperature water bath and stir continuously at 350 rpm for 35 min until completely dissolved. Then add 1.5 g of the previously prepared polyaminophenylboronic acid-nickel complex and 1.2 g of cobalt nickel phosphate-ethylenediamine hybrid material. Place the mixed solution in an ultrasonic cell disruptor and ultrasonically disperse at 300 W power and 40 kHz frequency for 30 min to ensure uniform dispersion of the modifier. Transfer the uniformly dispersed mixed solution to a 250 mL polytetrafluoroethylene-lined high-pressure reactor. After sealing, place the reactor in an oven and heat to 120°C at a heating rate of 3°C / min, and maintain the reaction at this temperature for 13 h. After the reaction was completed, the mixture was allowed to cool naturally to 25°C. The reaction vessel was then opened, and the product was washed three times each with deionized water and anhydrous ethanol by centrifugation, using 100 mL of detergent each time. The centrifugation speed was 8000 rpm, and the centrifugation time was 5 min. The washed solid product was transferred to a vacuum drying oven and dried at 80°C and -0.1 MPa vacuum for 10 h to obtain the final product of light green basic nickel carbonate modified material.

[0039] Example 2

[0040] Preparation of polyaminophenylboronic acid-nickel complex: 1.8 g of 3-aminophenylboronic acid was accurately weighed and dissolved in 35 mL of deionized water. The solution was stirred at 500 rpm for 15 min using a magnetic stirrer until completely dissolved. Then, 0.45 g of nickel chloride hexahydrate was added, and the mixture was stirred continuously at 25 °C for 30 min to ensure thorough mixing. Next, a 25% (w / w) ammonia solution was slowly added dropwise to adjust the pH of the mixture to 8.2. The reaction vessel was then transferred to a 59 °C constant temperature water bath, and the reaction was stirred at 400 rpm for 3.5 h. After the reaction was complete, the resulting solid product was transferred to a centrifuge tube. The product was first washed three times with anhydrous ethanol (25 mL ethanol each time, centrifuged at 8000 rpm for 5 min), followed by three washes with deionized water under the same conditions. The washed solid product was then transferred to a vacuum drying oven and dried at 59 °C and -0.1 MPa vacuum for 6.5 h to obtain a dark green solid product, which was then sealed and stored for later use.

[0041] Preparation of cobalt-nickel phosphate-ethylenediamine hybrid material: Accurately weigh 1.0 g of cobalt chloride hexahydrate and 0.7 g of nickel chloride hexahydrate, dissolve them together in 25 mL of diethylene glycol, and stir with a magnetic stirrer at 600 rpm for 20 min until completely dissolved. Then add 1.8 g of ammonium dihydrogen phosphate and 2.5 mL of ethylenediamine, and continue stirring at 500 rpm for 30 min to form a homogeneous mixture. Transfer the mixture to a 50 mL polytetrafluoroethylene-lined high-pressure reactor, seal it, and place the reactor in a muffle furnace. Heat to 198 °C at a heating rate of 5 °C / min, and maintain the reaction at this temperature for 4.5 h. After the reaction, allow it to cool naturally to 25 °C. Open the reactor, and wash the obtained product three times each with alternating centrifugation using 25 mL of acetone and 95% ethanol solution at 10000 rpm for 5 min. Collect the purple solid product, place it in a vacuum drying oven, dry it at 79℃ and -0.1MPa vacuum for 6.5h, and then seal and store it.

[0042] Preparation of basic nickel carbonate modified material: Accurately weigh 3.5 g of nickel nitrate hexahydrate and dissolve it in 180 mL of deionized water. Stir at 400 rpm for 15 min using a mechanical stirrer until the solution is completely transparent. Add 1.2 g of urea and 0.45 g of hexadecyltrimethylammonium bromide sequentially. Place the reaction vessel in a 39°C constant temperature water bath and stir continuously at 350 rpm for 32 min until completely dissolved. Then add 1.2 g of the previously prepared polyaminophenylboronic acid-nickel complex and 1.0 g of cobalt nickel phosphate-ethylenediamine hybrid material. Place the mixed solution in an ultrasonic cell disruptor and ultrasonically disperse at 300 W power and 40 kHz frequency for 25 min to ensure uniform dispersion of the modifier. Transfer the uniformly dispersed mixed solution to a 250 mL polytetrafluoroethylene-lined high-pressure reactor. After sealing, place the reactor in an oven and heat to 118°C at a heating rate of 3°C / min, and maintain the reaction at this temperature for 12.5 h. After the reaction was completed, the mixture was allowed to cool naturally to 25°C. The reaction vessel was then opened, and the product was washed three times each with deionized water and anhydrous ethanol by centrifugation, using 90 mL of detergent each time. The centrifugation speed was 8000 rpm, and the centrifugation time was 5 min. The washed solid product was transferred to a vacuum drying oven and dried at 79°C and -0.1 MPa vacuum for 9 h to obtain the final product of light green basic nickel carbonate modified material.

[0043] Example 3

[0044] Preparation of polyaminophenylboronic acid-nickel complex: 2.2 g of 3-aminophenylboronic acid was accurately weighed and dissolved in 45 mL of deionized water. The solution was stirred at 500 rpm for 15 min using a magnetic stirrer until completely dissolved. Then, 0.55 g of nickel chloride hexahydrate was added, and the mixture was stirred continuously at 25 °C for 30 min to ensure thorough mixing. Next, a 25% (w / w) ammonia solution was slowly added dropwise to adjust the pH of the mixture to 8.8. The reaction vessel was then transferred to a 61 °C constant temperature water bath, and the reaction was stirred at 400 rpm for 4.5 h. After the reaction was complete, the resulting solid product was transferred to a centrifuge tube. The product was first washed three times with anhydrous ethanol (35 mL each time, centrifuged at 8000 rpm for 5 min), followed by three washes with deionized water under the same conditions. The washed solid product was then transferred to a vacuum drying oven and dried at 61 °C and -0.1 MPa for 7.5 h to obtain a dark green solid product, which was then sealed and stored for later use.

[0045] Preparation of cobalt-nickel phosphate-ethylenediamine hybrid material: Accurately weigh 1.4 g of cobalt chloride hexahydrate and 0.9 g of nickel chloride hexahydrate, and dissolve them together in 35 mL of diethylene glycol. Stir at 600 rpm for 20 min using a magnetic stirrer until completely dissolved. Then add 2.2 g of ammonium dihydrogen phosphate and 3.5 mL of ethylenediamine, and continue stirring at 500 rpm for 30 min to form a homogeneous mixture. Transfer the mixture to a 50 mL polytetrafluoroethylene-lined high-pressure reactor, seal it, and place the reactor in a muffle furnace. Heat to 202 °C at a heating rate of 5 °C / min, and maintain the reaction at this temperature for 5.5 h. After the reaction, allow it to cool naturally to 25 °C. Open the reactor, and wash the obtained product three times each with alternating centrifugation using acetone and 95% ethanol solution (35 mL of detergent each time), centrifuging at 10000 rpm for 5 min. The purple solid product was collected, placed in a vacuum drying oven, and dried at 81℃ and -0.1MPa vacuum for 7.5h. It was then sealed and stored.

[0046] Preparation of basic nickel carbonate modified material: Accurately weigh 4.5 g of nickel nitrate hexahydrate and dissolve it in 220 mL of deionized water. Stir at 400 rpm for 15 min using a mechanical stirrer until the solution is completely transparent. Add 1.8 g of urea and 0.55 g of cetyltrimethylammonium bromide sequentially. Place the reaction vessel in a 41°C constant temperature water bath and stir continuously at 350 rpm for 38 min until completely dissolved. Then add 1.8 g of the previously prepared polyaminophenylboronic acid-nickel complex and 1.4 g of cobalt nickel phosphate-ethylenediamine hybrid material. Place the mixed solution in an ultrasonic cell disruptor and ultrasonically disperse at 300 W power and 40 kHz frequency for 35 min to ensure uniform dispersion of the modifier. Transfer the uniformly dispersed mixed solution to a 250 mL polytetrafluoroethylene-lined high-pressure reactor. After sealing, place the reactor in an oven and heat to 122°C at a heating rate of 3°C / min, and maintain the reaction at this temperature for 13.5 h. After the reaction was completed, the mixture was allowed to cool naturally to 25°C. The reaction vessel was then opened, and the product was washed three times each with deionized water and anhydrous ethanol by centrifugation, using 110 mL of detergent each time. The centrifugation speed was 8000 rpm, and the centrifugation time was 5 min. The washed solid product was transferred to a vacuum drying oven and dried at 81°C and -0.1 MPa vacuum for 11 h to obtain the final product of light green basic nickel carbonate modified material.

[0047] Comparative Example 1

[0048] The difference between this comparative example and Example 1 is that 4.0 g of nickel nitrate hexahydrate was accurately weighed and dissolved in 200 mL of deionized water. The solution was stirred at 400 rpm for 15 min using a mechanical stirrer until completely transparent. 1.5 g of urea and 0.5 g of hexadecyltrimethylammonium bromide were added sequentially, and the reaction vessel was placed in a 40°C constant temperature water bath and stirred continuously at 350 rpm for 35 min until completely dissolved. The mixed solution was directly transferred to a 250 mL polytetrafluoroethylene-lined high-pressure reactor. After sealing, the reactor was placed in an oven and heated to 120°C at a heating rate of 3°C / min, and maintained at this temperature for 13 h. After the reaction, the mixture was allowed to cool naturally to 25°C. The reactor was then opened, and the product was washed three times each with deionized water and anhydrous ethanol by centrifugation, using 100 mL of detergent each time, at a centrifugation speed of 8000 rpm for 5 min. The washed solid product was transferred to a vacuum drying oven and dried at 80°C and -0.1 MPa vacuum for 10 hours to obtain unmodified basic nickel carbonate material.

[0049] Comparative Example 2

[0050] The difference between this comparative example and Example 1 lies in the preparation of the polyaminophenylboronic acid-nickel complex: The preparation method is the same as in Example 1. 4.0 g of nickel nitrate hexahydrate was accurately weighed and dissolved in 200 mL of deionized water. The solution was stirred at 400 rpm for 15 min until completely transparent. 1.5 g of urea and 0.5 g of hexadecyltrimethylammonium bromide were added sequentially. The reaction vessel was placed in a 40°C constant temperature water bath and stirred continuously at 350 rpm for 35 min until completely dissolved. Only 1.5 g of the aforementioned prepared polyaminophenylboronic acid-nickel complex was added. The mixed solution was placed in an ultrasonic cell disruptor and ultrasonically dispersed at 300 W power and 40 kHz frequency for 30 min. The uniformly dispersed mixed solution was transferred to a 250 mL polytetrafluoroethylene-lined high-pressure reactor. After sealing, the reactor was placed in an oven and heated to 120°C at a heating rate of 3°C / min, and maintained at this temperature for 13 h. After the reaction was completed, the mixture was allowed to cool naturally to 25°C. The reaction vessel was then opened, and the product was washed three times each with deionized water and anhydrous ethanol by centrifugation, using 100 mL of detergent each time. The centrifugation speed was 8000 rpm, and the centrifugation time was 5 min. The washed solid product was then transferred to a vacuum drying oven and dried at 80°C and -0.1 MPa vacuum for 10 h.

[0051] Comparative Example 3

[0052] The difference between this comparative example and Example 1 lies in the preparation of the cobalt-nickel phosphate-ethylenediamine hybrid material: The preparation is the same as in Example 1. 4.0 g of nickel nitrate hexahydrate was accurately weighed and dissolved in 200 mL of deionized water. The solution was stirred at 400 rpm for 15 min until completely transparent. 1.5 g of urea and 0.5 g of hexadecyltrimethylammonium bromide were added sequentially. The reaction vessel was placed in a 40°C constant temperature water bath and stirred continuously at 350 rpm for 35 min until completely dissolved. Only 1.2 g of the aforementioned cobalt-nickel phosphate-ethylenediamine hybrid material was added. The mixed solution was placed in an ultrasonic cell disruptor and ultrasonically dispersed at 300 W power and 40 kHz frequency for 30 min. The uniformly dispersed mixed solution was transferred to a 250 mL polytetrafluoroethylene-lined high-pressure reactor. After sealing, the reactor was placed in an oven and heated to 120°C at a heating rate of 3°C / min, and maintained at this temperature for 13 h. After the reaction was completed, the mixture was allowed to cool naturally to 25°C. The reaction vessel was then opened, and the product was washed three times each with deionized water and anhydrous ethanol by centrifugation, using 100 mL of detergent each time. The centrifugation speed was 8000 rpm, and the centrifugation time was 5 min. The washed solid product was then transferred to a vacuum drying oven and dried at 80°C and -0.1 MPa vacuum for 10 h.

[0053] The performance of the basic nickel carbonate modified materials obtained in Examples 1-3 and Comparative Examples 1-3 was tested according to national and industry standards. All performance tests were conducted at a constant ambient temperature of 25℃. Before testing, all material samples were pretreated in a vacuum drying oven at 105℃ for 6 hours to completely remove surface adsorbed moisture. Specific surface area and pore size distribution were tested using a low-temperature nitrogen adsorption-desorption method with a fully automated physical adsorption analyzer. Before testing, the samples were degassed in a vacuum environment at 150℃ for 5 hours. The specific surface area was calculated using the BET method, and the pore size distribution was calculated using the BJH method. The relative pressure range was 0.05-0.35, and the nitrogen purity of the adsorbate reached 99.999%. Electrochemical performance testing employed a standard three-electrode system, using a platinum sheet electrode as the counter electrode and a saturated calomel electrode as the reference electrode. The working electrode was prepared by uniformly mixing the active material, conductive acetylene black, and polyvinylidene fluoride binder in a mass ratio of 80:15:5, adding an appropriate amount of N-methylpyrrolidone solvent to form a slurry, coating it onto a 1 cm² nickel foam current collector, vacuum drying at 120℃ for 12 h, and finally pressing it into a sheet under a pressure of 10 MPa. The electrolyte was a 6 mol / L KOH solution. Cyclic voltammetry and constant current charge-discharge tests were performed using an electrochemical workstation. The cyclic voltammetry scan rate was 5 mV / s, the constant current charge-discharge test current density was 1 A / g, and the voltage window was 0-0.4 V. Electrocatalytic performance was tested using a rotating disk electrode system with a catalyst slurry loading of 0.5 mg / cm² and an electrolyte of 1 mol / L KOH solution. Linear sweep voltammetry was used with a scan rate of 5 mV / s and a rotation speed of 1600 rpm. All potential data were corrected relative to a reversible hydrogen electrode, and the solution resistance compensation was 85%. Adsorption performance was tested by preparing a 100 mg / L Pb²⁺ standard solution, adding 20 mg of adsorbent to 50 mL of the solution, and shaking at 150 rpm for 24 hours in a constant-temperature shaker to ensure adsorption equilibrium. The residual lead ion concentration was determined using atomic absorption spectrometry, and the adsorption capacity was calculated based on the concentration difference before and after adsorption. The instrument detection limit was 5 μg / L. Cyclic stability was tested in a standard three-electrode system with 10,000 consecutive charge-discharge cycles at a current density of 1 A / g. The capacity retention rate was calculated by comparing the discharge capacity of the 100th cycle with that of the 10,000th cycle. All tests were performed in triplicate, and the final results were the arithmetic mean, with data errors controlled within 5%.

[0054] The performance test data above are shown in Table 1.

[0055] Table 1 Performance Test Results

[0056] Test item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Specific surface area (m2 / g) 285.6 271.3 279.8 95.2 198.4 176.9 Average pore diameter (nm) 8.9 9.2 8.7 5.3 7.6 7.2 Specific capacitance at 0.5 A / g (F / g) 1325.8 1258.3 1296.2 518.9 958.7 892.4 Specific capacitance at 1 A / g (F / g) 1252.4 1187.6 1224.9 482.7 893.5 827.3 Specific capacitance at 2 A / g (F / g) 1189.6 1124.7 1163.8 437.6 825.3 763.8 Specific capacitance at 5 A / g (F / g) 1057.3 984.5 1028.4 352.1 698.4 642.9 Specific capacitance at 10 A / g (F / g) 892.6 823.9 867.5 265.8 547.2 498.6 Capacitance retention rate (%) 85.1 82.7 83.9 62.4 73.2 70.5 Cycle stability (%) 92.5 90.8 91.7 65.3 82.7 78.9 OER overpotential (mV) 275.3 283.7 278.9 410.5 325.8 355.2 Tafel slope (mV / dec) 42.1 45.3 43.6 78.9 58.4 63.7 Pb2+adsorption capacity (mg / g) 215.8 203.5 209.7 85.3 145.2 165.8

[0057] The test results in Table 1 clearly show that Examples 1-3 effectively solved several key technical problems existing in current basic nickel carbonate materials compared to Comparative Examples 1-3. First, in terms of basic material properties, the specific surface area of ​​Examples 1-3 reached 271.3-285.6 m² / g, which is much higher than 95.2 m² / g of Comparative Example 1. This indicates that through the synergistic effect of the two modified compounds, a rich hierarchical porous structure was successfully constructed, fundamentally overcoming the defects of limited specific surface area and insufficient active sites in traditional basic nickel carbonate materials. Secondly, regarding electrochemical performance, Examples 1-3 achieved a specific capacitance of 1187.6-1252.4 F / g at a current density of 1 A / g, which is approximately 2.5 times higher than the 482.7 F / g of Comparative Example 1. Furthermore, they maintained a capacitance retention rate of over 85% even at a high current density of 10 A / g, significantly better than the 62.4% of Comparative Example 1. This demonstrates that the modified material possesses excellent rate performance and rapid charge transport capability, solving the problems of poor conductivity and rapid performance degradation at high rates inherent in traditional materials. Thirdly, regarding structural stability, Examples 1-3 maintained a capacitance retention rate of 90.8-92.5% after 10,000 cycles, far exceeding the 65.3% of Comparative Example 1. This indicates that the two modified compounds significantly enhanced the structural stability of the material through interface anchoring and lattice matching mechanisms, effectively suppressing structural collapse during cycling. Fourth, regarding electrocatalytic performance, the oxygen evolution reaction overpotential of Examples 1-3 was reduced to 275.3-283.7 mV, and the Tafel slope was 42.1-45.3 mV / dec, approaching the level of noble metal catalysts. This successfully achieved the development of high-performance non-noble metal catalysts and solved the problem of insufficient catalytic activity of traditional nickel-based materials. Fifth, in terms of environmental remediation applications, the adsorption capacity of lead ions in Examples 1-3 reached 203.5-215.8 mg / g, which is about 2.5 times higher than that of Comparative Example 1, proving that the number of active sites and binding capacity on the material surface were significantly enhanced. It is particularly noteworthy that although Comparative Examples 2 and 3 used a single modifier, their performance was better than that of Comparative Example 1 but significantly lower than that of Examples 1-3. This fully demonstrates that there is an irreplaceable synergistic effect between the electronic structure regulation function of polyaminophenylboronic acid-nickel complex and the structural stabilization function of cobalt nickel phosphate-ethylenediamine hybrid material. Only by using both in combination can the multiple technical bottlenecks faced by traditional basic nickel carbonate materials be fully solved, and a systematic improvement from microstructure to macroscopic performance be achieved.

Claims

1. A method for preparing a basic nickel carbonate modified material, characterized by the steps of include: S1. Dissolve nickel nitrate hexahydrate in deionized water and stir; Urea and hexadecyltrimethylammonium bromide were added sequentially, and the mixture was stirred in a water bath at 38-42°C to obtain a solution. Polyaminophenylboronic acid-nickel complex and cobalt nickel phosphate-ethylenediamine hybrid material were added to the solution and ultrasonically dispersed to obtain a mixed solution; S2. Transfer the mixed solution to a high-pressure reactor, seal it, and react at 115-125℃. After the reaction is complete, cool it to room temperature, wash it by centrifugation with deionized water and ethanol respectively, and dry it in a vacuum drying oven at 78-82℃.

2. The method for producing a nickel carbonate hydroxide modified material according to claim 1, characterized by, In step S1, the stirring time in a water bath at 38-42℃ is 30-40 minutes.

3. The method for producing a nickel carbonate hydroxide modified material according to claim 1, characterized by, In step S2, the reaction time is 12-14 hours at 115-125℃.

4. The method for producing a nickel carbonate hydroxide modified material according to claim 1, characterized by, The preparation method of the polyaminophenylboronic acid-nickel complex includes: A1, dissolving 3-aminophenylboronic acid in deionized water and stirring until completely dissolved; then adding nickel chloride and continuously stirring and mixing at room temperature; subsequently adding ammonia to adjust the pH to 8-9, and reacting in a water bath at 58-62℃ to obtain a solid product; A2, washing the solid product alternately by centrifugation with ethanol and deionized water, and drying it in a vacuum drying oven at 58-62℃.

5. The method for producing a nickel carbonate hydroxide modified material according to claim 4, characterized by, In step A1, the reaction time in a water bath at 58-62℃ is 3-5 hours.

6. The method for producing a nickel carbonate hydroxide modified material according to claim 4, characterized by, In step A2, the drying time in a vacuum drying oven at 58-62℃ is 6-8 hours.

7. The method for producing a nickel carbonate hydroxide modified material according to claim 1, characterized by, The preparation method of the cobalt-nickel phosphate-ethylenediamine hybrid material includes: B1, dissolving cobalt chloride and nickel chloride in diethylene glycol and stirring until completely dissolved; then adding ammonium dihydrogen phosphate and ethylenediamine and stirring continuously to obtain a mixed solution; transferring the mixed solution to a high-pressure reactor and reacting at 195-205℃; B2, after cooling to room temperature, centrifuging and washing with acetone and ethanol solution, collecting the solid product; and drying the solid product under vacuum at 78-82℃.

8. The method for producing a nickel carbonate hydroxide modified material according to claim 7, characterized by, In step B1, the reaction time is 4-6 hours at 195-205℃.

9. The method for producing a nickel carbonate basic modified material according to claim 7, characterized by, In step B2, the drying time under vacuum at 78-82℃ is 6-8 hours.

10. A basic nickel carbonate modified material produced according to the method of any one of claims 1 to 9, characterized in that, The raw materials include the following parts by weight: 25-45 parts of nickel nitrate hexahydrate; 10-20 parts of polyaminophenylboronic acid-nickel complex; 8-15 parts of cobalt nickel phosphate-ethylenediamine hybrid material; 5-12 parts of urea; 5-10 parts of hexadecyltrimethylammonium bromide; and 15-30 parts of deionized water.