CN111621026A - Preparation method of bifunctional cobalt complex material and electrochemical performance application thereof - Google Patents
Preparation method of bifunctional cobalt complex material and electrochemical performance application thereof Download PDFInfo
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- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000011365 complex material Substances 0.000 title description 4
- 150000004700 cobalt complex Chemical class 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 11
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- -1 3-amino triazole benzoate cobalt Chemical compound 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- INYMVIMYGPZTDR-UHFFFAOYSA-N benzoic acid;cobalt Chemical compound [Co].OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 INYMVIMYGPZTDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003990 capacitor Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000002329 infrared spectrum Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
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 C20H22CoN8O6Meanwhile, 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.
Description
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) Å3。
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.
Drawings
FIG. 1 is a diagram of the unit cell structure of the complex of the present invention. FIG. 2 is a diagram of a cyclic structure of the complex of the present invention. FIG. 3 is an infrared spectrum of a complex of the present invention. FIG. 4 thermogravimetric analysis of the complex of the present invention. FIG. 5 Cyclic voltammograms of the inventive complexes at different sweep rates. FIG. 6 is a charge-discharge curve of the complex of the present invention at different current densities. FIG. 7 shows the specific capacitance variation of the complex of the present invention at different current densities. FIG. 8 is a graph of energy transfer efficiency for different current densities for the complex capacitor of the present invention. FIG. 9 is a graph of the circulating CV of the complex capacitor of the present invention. FIG. 10 is a Nyquist plot of the reflected resistance of the complex capacitor of the present invention. FIG. 11 is a graph comparing the catalytic performance of the complex of the present invention and a commercial ruthenium dioxide material for oxygen evolution in electrocatalytic cracking water. FIG. 12 is a Tafel slope plot of the reaction catalysis rate in the oxygen evolution reaction in electrocatalytic water using the inventive complexes and commercial ruthenium dioxide materials.
Claims (11)
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) Å3。
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.
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