阅读说明：本技术 一种双功能钴配合物材料的制备方法及其电化学性能应用 (Preparation method of bifunctional cobalt complex material and electrochemical performance application thereof ) 是由 不公告发明人 于 2019-02-28 设计创作，主要内容包括：发明的金属有机配合物是在水热条件下,通过调节反应温度、时间、溶剂比及pH值以获得其适宜的合成条件,以双功能配体4-((1氢-1,2,4-三氮唑-3-氨基)甲基)苯甲酸、七水合硫酸钴为原料合成的。所得目标化合物以单晶X射线衍射分析及红外光谱(IR)表征后,可确定其分子式为C<Sub>20</Sub>H<Sub>22</Sub>CoN<Sub>8</Sub>O<Sub>6</Sub>,同时,发明过程中还对其进行了电化学性质分析,明确了该配合物用作超级电容器电极材料在电化学储能方面的应用,在电化学储能方面表现出电容量高,可多次循环使用,电阻较低的特点,另一方面在该配合物用作电催化裂解水析氧反应电极催化剂时,可将反应过电位降低至1.595V,效能和商用二氧化钌相当,但在起始电位和催化速率上均优于商用二氧化钌,成本方面更是远低于商用二氧化钌。(The metal organic complex is synthesized by taking bifunctional ligand 4- ((1-H-1, 2, 4-triazole-3-amino) methyl) benzoic acid and cobalt sulfate heptahydrate as raw materials under hydrothermal conditions and adjusting reaction temperature, time, solvent ratio and pH value to obtain suitable synthesis conditions. After the obtained target compound is characterized by single crystal X-ray diffraction analysis and infrared spectrum (IR), the molecular formula of the target compound can be determined to be C 20 H 22 CoN 8 O 6 Meanwhile, the electrochemical property analysis is carried out in the invention process, and the complex is definitely used as super complexThe application of the capacitor electrode material in the aspect of electrochemical energy storage shows the characteristics of high capacitance, repeated recycling and low resistance in the aspect of electrochemical energy storage, and on the other hand, when the complex is used as an electrode catalyst for an electrocatalytic cracking water oxygen evolution reaction, the overpotential of the reaction can be reduced to 1.595V, the efficiency is equivalent to that of commercial ruthenium dioxide, but the initial potential and the catalytic rate are both superior to that of commercial ruthenium dioxide, and the cost is far lower than that of commercial ruthenium dioxide.)

1. The 3-amino triazole benzoate cobalt complex based on the bifunctional ligand is characterized in that the chemical name of the complex is 4- ((1-hydrogen-1, 2, 4-triazole-3-amino) methyl) benzoic acid-cobalt complex.

2. The cobalt 3-aminotriazole benzoate complex as claimed in claim 1, wherein: the complex has a one-dimensional linear structure, the crystal of the complex belongs to a monoclinic system, and the space group isP-1The unit cell parameters are a = 6.613(5) Å, b = 7.619(5) Å, c = 11.266(5) Å, α =81.152 ° β = 80.301 ° γ = 75.865 °, V = 538.8(6) ų。

3. The preparation method of the cobalt 3-aminotriazole benzoate complex according to claim 1, characterized in that; the method comprises the following steps: in a mixed solvent of water and N, N-dimethylformamide, mixing 4- ((1-hydro-1, 2, 4-triazole-3-amino) methyl) benzoic acid and cobalt sulfate, uniformly stirring to obtain a reaction liquid, putting the reaction liquid into a reaction kettle for hydrothermal reaction at 100 ℃ for 72 hours, and then cooling and crystallizing to obtain crystals, and sequentially filtering, washing and drying the crystals to obtain more pink crystals of the 3-aminotriazole benzoate cobalt complex.

4. The production method according to claim 3, characterized in that: the molar ratio of 4- ((1-hydrogen-1, 2, 4-triazole-3-amino) methyl) benzoic acid to cobalt sulfate is 1: 2.

5. The production method according to claim 3, characterized in that: the ratio of water to N, N-dimethylformamide was 4: 1.

6. the production method according to claim 3, characterized in that: the reaction solution is put into a reaction kettle and crystallized at 100 ℃ for 3 days, and then the reaction is closed and slowly cooled to room temperature.

7. The cobalt 3-aminotriazole benzoate complex as claimed in claim 1, wherein: the preparation method of the 4- ((1-H-1, 2, 4-triazole-3-amino) methyl) benzoic acid comprises the steps of firstly stirring and reacting p-carboxyl benzaldehyde and 3-amino-1, 2, 4-triazole in a methanol solvent at room temperature for two hours, then slowly adding sodium borohydride for reacting for two hours, evaporating the reaction solution to dryness, filtering, dissolving in distilled water, heating to separate out and purify the product, and drying to obtain a light yellow powdery solid, namely the 4- ((1-H-1, 2, 4-triazole-3-amino) methyl) benzoic acid.

8. The method of claim 7, wherein: the molar ratio of the p-carboxyl benzaldehyde, the 3-amino-1, 2, 4-triazole and the sodium borohydride is 1: 4.5.

9. The method of claim 7, wherein: the reaction solvent is methanol; the volume ratio of the reaction solution to distilled water is 1: 1.

10. Use of the complex of claim 1, preferably as an electrode material for producing supercapacitors.

11. The use of the complex of claim 1, preferably as a catalyst material for the preparation of electrocatalytic cleavage water evolution oxygen reaction electrodes.

Technical Field

The invention relates to the field of electrochemical energy storage and catalytic materials, in particular to a bifunctional cobalt complex material based on a 3-amino triazole benzoic acid ligand, and a preparation method and application thereof.

Background

In the modern society, energy problems become increasingly important due to exhaustion of fossil fuels and environmental pollution, on one hand, clean energy such as hydrogen is adopted, but various problems still exist in the process of electrolyzing water at present, a catalyst material is always a bottleneck, on the other hand, redundant energy needs to be stored for releasing when the energy is insufficient, such as energy storage of a super capacitor, and revolutionary changes are often brought to the development history of the super capacitor through appearance of novel electrode materials, so that research on the novel energy materials is a key for relieving the energy crisis of the state. With the recent intensive research on metal organic compound Materials (MOFs), hybrid materials constructed by using transition metals and electron-rich group derivatives containing nitrogen, oxygen and the like and having potential application prospects in the fields of light, electricity, magnetism, catalysis and the like have become a new research hotspot. The MOFs can provide a single-atom active metal center, not only can the metal mass consumption be reduced, but also the electrode/electrolyte interface can be increased, and therefore, the MOFs has the potential of becoming a new energy material.

At present, in order to improve the application of MOFs materials in energy, noble metals such as ruthenium, platinum, etc. are introduced into the materials to enhance the energy storage or electrocatalytic properties of MOFs, which is a solution to solve the bottleneck of the application of such materials in energy, but this undoubtedly increases the synthesis and research cost of the materials. Therefore, the research on the MOFs materials of inexpensive metals and their excellent electrochemical properties, thereby increasing their possibility in practical application transformation, has become a goal pursued by many scientists. Therefore, the 3-amino triazole benzoate cobalt complex based on the bifunctional ligand is invented, the structure is simple, the cost is low, and the complex material is found to have excellent performance in the oxygen evolution reaction of the supercapacitor and the electrolytic water serving as a catalyst, and has potential application value.

Disclosure of Invention

The invention aims to solve the technical problem of providing a novel 3-amino triazole benzoate cobalt complex which has a one-dimensional linear structure and can be used as an electrochemical energy storage and catalysis material so as to have potential application value.

The invention also aims to solve the technical problem of providing a preparation method of the complex.

The invention finally aims to solve the technical problem of providing the application of the complex.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the 3-amino triazole benzoate cobalt complex based on the bifunctional ligand is characterized in that the chemical name of the complex is 4- ((1-hydrogen-1, 2, 4-triazole-3-amino) methyl) benzoic acid-cobalt complex.

The complex has a one-dimensional linear structure, the crystal of the complex belongs to a monoclinic system, and the space group isP-1The unit cell parameters are a = 6.613(5) Å, b = 7.619(5) Å, c = 11.266(5) Å, α =81.152 ° β = 80.301 ° γ = 75.865 °, V = 538.8(6) ų。

The technical scheme of the invention also provides a preparation method of the 3-amino triazole benzoate cobalt complex, which comprises the following steps:

in a mixed solvent of water and N, N-dimethylformamide, mixing 4- ((1-hydro-1, 2, 4-triazole-3-amino) methyl) benzoic acid and cobalt sulfate, uniformly stirring to obtain a reaction liquid, putting the reaction liquid into a reaction kettle for hydrothermal reaction at 100 ℃ for 72 hours, and then cooling and crystallizing to obtain crystals, and sequentially filtering, washing and drying the crystals to obtain more pink crystals of the 3-aminotriazole benzoate cobalt complex.

The preparation method of the complex comprises the following steps: the molar ratio of 4- ((1-hydrogen-1, 2, 4-triazole-3-amino) methyl) benzoic acid to cobalt sulfate is 1: 2.

The preparation method of the complex comprises the following steps: the ratio of water to N, N-dimethylformamide was 4: 1.

the preparation method of the complex comprises the following steps: the reaction solution is put into a reaction kettle and crystallized at 100 ℃ for 3 days, and then the reaction is closed and slowly cooled to room temperature.

The preparation method of the complex comprises the following steps: the method is characterized in that: the preparation method of the 4- ((1-H-1, 2, 4-triazole-3-amino) methyl) benzoic acid comprises the steps of firstly stirring and reacting p-carboxyl benzaldehyde and 3-amino-1, 2, 4-triazole in a methanol solvent at room temperature for two hours, then slowly adding sodium borohydride for reacting for two hours, evaporating the reaction solution to dryness, filtering, dissolving in distilled water, heating to separate out and purify the product, and drying to obtain a light yellow powdery solid, namely the 4- ((1-H-1, 2, 4-triazole-3-amino) methyl) benzoic acid.

The technical scheme of the invention is that the preparation method of the 4- ((1H-1, 2, 4-triazole-3-amino) methyl) benzoic acid comprises the following steps: the molar ratio of the p-carboxyl benzaldehyde, the 3-amino-1, 2, 4-triazole and the sodium borohydride is 1: 4.5.

The technical scheme of the invention is that the preparation method of the 4- ((1H-1, 2, 4-triazole-3-amino) methyl) benzoic acid comprises the following steps: the reaction solvent is methanol; the volume ratio of the reaction solution to distilled water is 1: 1.

The complex is characterized by crystal X-ray diffraction data, infrared spectrum and electrochemical test. The complex is used as an active material to prepare a foamed nickel electrode, and the foamed nickel electrode is tested to see whether the foamed nickel electrode has the potential of being prepared into a super capacitor. The results are as follows: the material presents the characteristics of pseudo capacitance in cyclic voltammetry test and constant current charge and discharge test, and shows that the essence of the electrochemical characteristics of the material is derived from the oxidation reduction of Co ions.

The material can keep the structural temperature at 230 ℃ in a thermogravimetric test and has good thermal stability.

The current density of the material is 1.0, 2.0, 4.0, 6.0, 8.0, 10.0 and 15.0 A.g^-1The specific capacitances are 1001, 884.4, 765.6, 689.3, 635.2, 598 and 537F g, respectively^-1The specific capacitance is higher, and the energy transmission efficiency is higher than 80%.

The capacitance remained substantially or increased slightly in the 1000-cycle test, the cycle performance was good, and it was clear whether the capacitor could be used repeatedly.

In an impedance test, the hydraulic resistance of the electrode of the super capacitor made of the material is 0.5 omega, and the resistance is low.

In an electrocatalytic cracking water test, the material is directly used as an oxygen evolution reaction electrode catalyst, the test shows that the material can reduce the reaction over-point to 1.595V which is equivalent to that of commercial ruthenium dioxide, the initial potential of the reaction is improved, the catalytic rate calculated by the Tafel slope is superior to that of the commercial ruthenium dioxide, the cost is far lower than that of the ruthenium dioxide, and the material is definitely excellent in catalytic performance.

Has the advantages that: the metal organic complex prepared based on the bifunctional ligand still has good oxidation-reduction property and potential capability of being used for preparing a supercapacitor material, and on the other hand, the metal organic complex has potential capability of being used as a new-generation catalyst material with excellent performance and low cost when being used as a catalyst for electrocatalytic cracking water. The research on the MOFs materials of cheap metals and their excellent electrochemical properties, thus increasing their possibility in practical application transformation, has become the goal pursued by many scientists. The method obtains the crystal with the purity of more than 80 percent through a simple synthetic route. The complex can be directly used as an electrode material of a super capacitor or an electrode catalyst of an oxygen evolution reaction in an electrocatalytic water splitting reaction, has excellent performance in the aspect of electrochemical energy storage catalysis, and has potential capability of being used as a bifunctional material.