CN115058737A - Synthesis method of indium-cobalt-based bimetal heterogeneous composite organic framework material - Google Patents
Synthesis method of indium-cobalt-based bimetal heterogeneous composite organic framework material Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an indium-cobalt-based bimetal heterogeneous composite organic framework material, which is characterized in that InCo is used as a material 2 -MOF with Ni (OH) 2 Carrying out in-situ compounding by a hydrothermal method. The method comprises the steps of utilizing a porous metal organic framework material obtained by self-assembling organic ligands 3,3 ', 5, 5' -azobenzene tetracarboxylic acid, indium chloride and cobalt acetate tetrahydrate in a mixed solution of deionized water, DMA and HCl, and assembling the synthetic material into a three-electrode system to perform electrocatalytic oxygen evolution and urea oxidation tests. The metal organic framework material has the advantages of simple synthesis process, high crystallization purity and high yield; and structureNovel, the porosity is large; 3,3 ', 5, 5' -Azophenyltetracarboxylic acid (H) 4 ABTC) has the advantages of low temperature, safety, and no harmful solvent. InCo 2 @Ni(OH) 2 the/NF bimetal composite heterogeneous material has excellent electrocatalytic oxygen evolution and urea oxidation activity.
Description
Technical Field
The invention relates to a compound of 3,3 ', 5, 5' -azozenetetracarboxylic acid (H) 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid is taken as a ligand, a transition metal cobalt and a metal indium center, and nickel hydroxide is introduced to construct a bimetallic heterogeneous composite organic framework material formed by a heterogeneous composite material, wherein the bimetallic heterogeneous composite organic framework material shows excellent oxygen evolution activity and urea oxidation activity through preparation of a catalyst electrode material.
Background
Hydrogen energy is a green, clean and efficient renewable energy source, and is a hot spot of people. Electrocatalysis is a simple and efficient hydrogen production mode, and Pt metal is a high-efficiency hydrogen production catalyst, but the expensive price and the rare storage amount of the Pt metal also prevent the Pt metal from being widely applied. There is therefore a compelling trend to find an efficient, inexpensive and non-noble metal hydrogen evolution catalyst to replace the expensive Pt material.
MOFs are metal-organic framework compounds, and are crystalline porous materials with periodic network structures formed by connecting inorganic metal centers (metal ions or metal clusters) and bridged organic ligands through self-assembly. At present, a metal organic framework material constructed by coordination of metal ions or metal clusters and organic ligands has extremely high specific surface area, adjustable pore size and diversity of framework components, and is considered as an important electrocatalyst. The starting point concerned in the patent is that the indium-cobalt-based bimetal heterogeneous composite organic framework material is synthesized to carry out electrocatalytic oxygen evolution and urea oxidation performance exploration.
The MOF derived nano material has unique multidimensional structure and adjustable functional performance, and can show excellent activity in the aspect of OER. Meanwhile, the MOF derived nano material has lower cost and better stability. However, there are still a number of key problems and challenges to be solved for the preparation of MOF derived metal/carbon materials and their use in catalysts. At present, except for the preparation of MOFs, MOFs derivatives are mainly pyrolyzed, which is time-consuming and labor-consuming and has the phenomenon of unstable synthesis process, so that the development of one-step synthesis or in-situ conversion method is of great significance for future research. In addition, the stability of the MOFs derivatives is poor, and the structures of most MOFs derivative catalysts are extremely easy to damage and difficult to recycle. Therefore, the method has great significance for the application of future MOF-derived nano materials in the aspect of electrocatalysis by improving the synthesis method of the catalyst, selecting a proper organic ligand and a proper heat treatment temperature and reducing adverse effects caused by molecular agglomeration. In terms of an electro-catalysis reaction mechanism, the stable structure and the large specific surface area can also provide enough active sites to provide a place for reaction.
In addition to having extensive application studies in the fields of adsorption, storage, separation and catalysis, MOFs have recently been recognized as CO 2 RR, OER, HER, etc. The electrocatalysis method for improving the material by a trace doping conductive substance is a composite synthesis method popular in recent years, a method for improving the electrocatalysis performance by doping nickel hydroxide to construct a composite material is a method which is milder, has a series of advantages of low temperature, safety, no harmful solvent and the like, and the specific operation method is a method for enabling the synthesized precursor and the nickel hydroxide to construct the composite material under a hydrothermal treatment method to have good response to Oxygen Evolution Reaction (OER).
Disclosure of Invention
The invention provides a compound of 3,3 ', 5, 5' -azozenetetracarboxylic acid (H) 4 ABTC) 3,3 ', 5, 5' -azobenzene tetracarboxylic acid as ligand, transition metal cobalt metal indium as metal center, and nickel hydroxide grown on the foam nickel.
3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed 4 ABTC) 3,3 ', 5, 5' -azophenyl tetracarboxylic acid, cobalt acetate, indium chloride and a hydrochloric acid solution are added into a glass bottle after being uniformly dispersed by ultrasonic waves, the glass bottle is sealed, the hydrothermal reaction condition is 100-120 ℃, the reaction time is 18-36 hours, and the temperature is reduced to the room temperature at a constant speed of 2-3 ℃/h to obtain the indium-cobalt-based metal organic framework mother liquor which is an orange square crystal. Drying to obtain the material for preparing the electrode material to test the oxygen evolution reaction.
Adding foamed nickel into water, transferring the foamed nickel into a hydrothermal reaction kettle for hydrothermal reaction to obtain Ni (OH) 2 A precursor; the hydrothermal condition is 150 ℃ and 160 ℃, and the reaction time is 10-15 hours;
ni (OH) to be prepared 2 Immersing the precursor into indium-cobalt-based metal organic framework mother liquor to carry out heating reaction for 12-24h under the heating reaction condition of 110-130 ℃, washing and drying after the reaction is finished to obtain a required sample, and carrying out ultrasonic cleaning in an ultrasonic instrumentAnd (4) drying in vacuum after washing, and collecting a sample to obtain the bimetal heterogeneous composite organic framework material.
The molar ratio of the organic ligand 3,3 ', 5, 5' -azophenyl tetracarboxylic acid to the metal salts of cobalt acetate and indium chloride is 1: 3-1: 4, and the molar ratio of the metal salts of cobalt acetate and indium chloride is 4: 1-2: 1; the molar concentration of the hydrochloric acid solution is 3.0-3.5M, and the pH value of the hydrothermal reaction system is 2.5-3.5.
Preferably, the molar ratio of the 3,3 ', 5, 5' -azophenyltetracarboxylic acid to the cobalt acetate and the indium chloride is 1:4, and the molar ratio of the cobalt acetate to the indium chloride metal salt is 3: 1; the hydrochloric acid solution had a molar concentration of 3.2M. Compared with neutral and alkaline conditions, the acidic condition is more favorable for crystallization and the crystal has higher purity and regular shape. The hydrothermal reaction condition is 100-120 ℃, and the reaction time is 18-36 hours. More preferably, the organic ligand 3,3 ', 5, 5' -azobenzylacetylcarboxylic acid (H) 4 ABTC) the molar ratio of the 3,3 ', 5, 5' -azophenyltetracarboxylic acid to the cobalt acetate to the indium chloride is 1:4, and the molar ratio of the cobalt acetate to the indium chloride metal salt is 3: 1; (ii) a The molar concentration of the hydrochloric acid solution is 3.2M, the hydrothermal reaction condition is 120 ℃, and the reaction time is 24 hours.
The room temperature referred to in the invention refers to the ambient temperature under normal pressure.
The crystal synthesized by the invention is characterized in that a micromolecule type single crystal X-ray diffractometer of Rigaku corporation in Japan is used for carrying out structure measurement on the crystal, Mo Kalpha rays monochromated by a graphite monochromator are used for measuring data such as diffraction intensity, unit cell parameters and the like under 293K, the scanning technology is used for carrying out empirical absorption correction on the collected data, the obtained result is directly analyzed by a Shelxtl-97 program, and the crystal is corrected by a full matrix least square method to obtain crystallographic data which are shown in a crystal parameter table 1.
TABLE 1 InCo 2 -MOF crystallographic parameter Table
The indium-cobalt-based bimetal heterogeneous composite organic framework material obtained by synthesis is used as an electrocatalyst to be applied to catalytic oxygen evolution or urea oxidation.
The metal organic framework material obtained by adopting the technical scheme of the invention has simple synthesis process, orange-yellow cubic crystals are obtained after the metal organic framework material is cooled to room temperature, and a pure sample picture (figure 1) is obtained by filtering and washing a raw material product by using DMA. According to In calculation, the yield is about 88%, and the structure is novel; 3,3 ', 5, 5' -Azophenyltetracarboxylic acid (H) 4 ABTC) has the advantages of low temperature, safety, and no harmful solvent. During the synthesis process, the temperature and the time are controlled, the reaction is most suitable for the growth of the seeds at the temperature of 120 ℃, the time is controlled to be about 2 days, the time is too short, the crystallization rate is too low, the structure in the crystal is collapsed for too long, and the appearance is cracked. After collecting the samples, the performance test was performed, and through experimental test data analysis, InCo 2 @Ni(OH) 2 the/NF bimetal composite heterogeneous material has excellent electrocatalytic oxygen evolution and urea oxidation activity.
Drawings
FIG. 1 is a sample diagram of the synthesis of MOF from example 7.
FIG. 2 is a sample plot of Ni (OH)2/NF synthesized in example 8.
FIG. 3 is the synthesis of InCo in example 9 2 @Ni(OH) 2 Sample plot of/NF.
FIG. 4 shows InCo obtained in examples 7 and 9 2 Crystal, InCo 2 @Ni(OH) 2 XRD spectrum of/NF heterogeneous composite material.
FIG. 5 shows InCo obtained in examples 7 and 9 2 Crystal and InCo 2 @Ni(OH) 2 LSV comparison curve of oxygen evolution performance of/NF heterogeneous composite material.
FIG. 6 shows the InCo obtained in example 11 2 @Ni(OH) 2 OER oxygen evolution Performance of/NF vs. LSV Performance of Urea Oxidation UOR.
Detailed Description
Example 1
0.01mmol of 3,3 ', 5, 5' -azozenetetracarboxylic acid (H) was weighed 4 ABTC) 3,3 ', 5, 5' -Azophenyltetracarboxylic acid, 0.02mmol of cobalt acetate and 0.02mmol of indium nitrate, and extracting 2 and 3 respectively by syringeAnd 4ml of deionized water are added into 10ml of glass vials, each reaction is subjected to ultrasonic treatment for 30mins respectively and is placed into a 120 ℃ oven for constant-temperature reaction for 48 hours, the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h, and the 3 glass vials have no change along with the increase of water quantity compared with the bottles before the reaction.
Example 2
0.01mmol of 3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed out 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid, 0.02mmol of cobalt acetate and 0.02mmol of indium nitrate, extracting 0.8ml of deionized water by using a syringe, adding the deionized water into 10ml of glass vials, dropwise adding NaOH (0.5M) into each vial by using a rubber head dropper, adjusting the pH of each vial to 8.5, 9, 9.5 and 10 respectively (measured by using a pH meter after dropwise adding), carrying out ultrasonic treatment for 30mins for each reaction, placing the reaction product into a 120 ℃ oven for constant-temperature reaction for 48 hours, reducing the reaction product to room temperature at a constant speed of 2-3 ℃/h, and comparing 4 glass vials with the comparison before the reaction at constant speed with the increase of alkali amount (8.5-10) without any change.
Example 3
0.01mmol of 3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed out 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid, 0.02mmol of cobalt acetate and 0.02mmol of indium nitrate, 4ml of N, N-Dimethylformamide (DMF), 0.8ml of deionized water were extracted with a syringe, and added to 10ml of glass vials, and NaOH (0.5M) was added dropwise to each vial with a rubber pipette, and the pH thereof was adjusted to 8.5, 9, 9.5, 10, respectively (measured with a pH meter after completion of addition). Then, the reaction is respectively treated by ultrasonic for 30mins and put into a 120 ℃ oven for constant temperature reaction for 48h, and the temperature is reduced to room temperature at a constant speed of 3 ℃/h, and when the pH value is 8.5-10, no change is caused compared with the pH value before the reaction.
Example 4
0.01mmol of 3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed out 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid, 0.02mmol of cobalt acetate and 0.02mmol of indium nitrate, 4ml of N, N-Dimethylacetamide (DMAC), 0.8ml of deionized water were extracted with a syringe, added to 10ml of glass vials, NaOH (0.5M) was added dropwise to each vial with a rubber pipette, and the pH was adjusted to 8.5, 9, 9.5, 10, respectively (measured with a pH meter after the addition). Then respectively carrying out ultrasonic treatment for 30mins on the reactions, putting the reactions into a 120 ℃ oven for constant-temperature reaction for 48h, and uniformly cooling to room temperature and pH at a constant speed of 3 ℃/hThe samples at 8.5 to 10 showed no change from the samples before the reaction, and were still clear.
Example 5
0.01mmol of 3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed out 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid, 0.02mmol of cobalt acetate and 0.02mmol of indium nitrate, 0.8ml of deionized water was drawn by a syringe, and added into 10ml glass vials, and HCl (3.2M) was added dropwise to each vial with a rubber dropper, and the pH thereof was adjusted to 3.5, 3, 2.5, 2 in this order (measured with a pH meter after completion of addition). Then, each reaction is subjected to ultrasonic treatment for 30mins respectively and is placed into a 120 ℃ oven for constant-temperature reaction for 48 hours, the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h, and the number of 4 glass vials has no change along with comparison of the acid amount and the number of vials before the reaction.
Example 6
0.01mmol of 3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed out 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid, 0.02mmol of cobalt acetate and 0.02mmol of indium nitrate, 4ml of N, N-Dimethylacetamide (DMAC) was withdrawn by a syringe, 0.8ml of deionized water was withdrawn by a syringe, added to 10ml of glass vials, HCl (3.2M) was added dropwise to each vial by a rubber dropper, and the pH was adjusted to 3.5, 3, 2.5, 2 in this order (measured by a pH meter after completion of dropping). Then, each reaction is subjected to ultrasonic treatment for 30mins respectively and is placed into a 120 ℃ oven for constant-temperature reaction for 48h, the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h, and the number of 4 glass vials is not changed along with the increase of the acid amount (when the pH is 3.5-2) compared with the number before the reaction.
Example 7
0.01mmol of 3,3 ', 5, 5' -azobenzylacetylenic acid (H) was weighed out 4 ABTC) 3,3 ', 5, 5' -azophenyltetracarboxylic acid, 0.03mmol of cobalt acetate and 0.01mmol of indium chloride, 4ml of N, N-Dimethylacetamide (DMAC) and 0.8ml of deionized water were extracted with a syringe, and added to 10ml of glass vials, HCl (3.2M) was added dropwise to each vial with a rubber pipette, and the pH was adjusted to 3.5, 3, 2.5 and 2 in this order (measured with a pH meter after the addition). Then, carrying out ultrasonic treatment for 30mins respectively for each reaction, putting the reaction product into a 120 ℃ oven for constant-temperature reaction for 48h, uniformly cooling to room temperature at a constant speed of 2-3 ℃/h, comparing 4 glass vials with the solution before the reaction along with the increase of the acid amount, and gradually changing the solution from a light blue purple solutionA dark blue-violet solution with a large number of bright sparkling orange yellow blocky crystals at the bottom of the vial at pH = 3.
Example 8
Nickel foam (size 1X 1.5 cm) was treated with ethanol, 1M dilute hydrochloric acid and deionized water separately 2 ) Ultrasonic cleaning is carried out for 15 min. The nickel foam was then transferred to a telfon lined autoclave containing ultra pure water. The temperature was maintained at 180 ℃ for 12h and after the experiment was completed, the prepared sample was dried at 60 ℃ for 4h, as shown in sample fig. 2.
Example 9
Mixing Ni (OH) prepared in example 8 2 The precursor was dried in a vacuum oven at 80 ℃ for 6h and then immersed in the InCo which had been synthesized in example 8 2 In the mother liquor of the crystal reaction solvent system, carrying out ultrasonic treatment in an ultrasonic instrument for 30mins to completely and uniformly mix the crystal reaction solvent system, then putting the crystal reaction solvent system into a 120 ℃ oven for constant temperature reaction for 24 hours, taking out the crystal reaction solvent system, respectively cleaning the crystal reaction solvent system for 2 times by using ethanol and deionized water, putting the crystal reaction solvent system into a 80 ℃ vacuum drying oven for drying for 6 hours, taking out the crystal reaction solvent system and collecting a sample to obtain the in-situ grown bimetal heterogeneous composite organic framework crystalline material InCo 2 @Ni(OH) 2 /NF, as in sample FIG. 3, the first layer is NF, the second layer is Ni (OH) 2 Attached to the NF surface and pore size, the last layer being InCo 2 The crystal is uniformly and compactly loaded in Ni (OH) 2 on/NF.
Example 10
The InCo collected in example 7 2 Directly using the sample for oxygen evolution reaction test after cleaning and drying the crystal, respectively testing in 0.1M KOH and 1M KOH after the CV curve scanning is stable, and InCo 2 The crystal materials of 0.1M KOH and 1M KOH have no ideal oxygen evolution performance, and even the data of the over potential of 10 can not be obtained.
Example 11
The bimetallic heterogeneous composite organic framework crystalline material InCo collected in example 9 2 @Ni(OH) 2 the/NF is directly used as an anode to test the oxygen evolution performance, after the CV curve is scanned to be stable in 1M KOH, the oxygen evolution reaction and the urea oxidation curve are respectively tested in the test environment of 1M KOH and 1M KOH +0.33M urea, and the test result is shown as a gray curve in figure 5 and 10mA/cm 2 The overpotential was 110 mV. And the compounded material InCo 2 @Ni(OH) 2 Overpotential of/NF oxygen evolution performance is more than that of InCo 2 The over potential of the crystal material is increased by 240 mV, InCo 2 The crystalline material is a black line as in fig. 5. The urea oxidation test of the material was only performed to demonstrate good oxygen evolution performance laterally, as shown in fig. 6. From the comprehensive views of FIG. 5 and FIG. 6, the crystalline material InCo of the bimetal heterogeneous composite organic framework 2 @Ni(OH) 2 the/NF is very suitable for researching the oxygen evolution performance.
Claims (9)
1. A synthesis method of an indium-cobalt-based bimetal heterogeneous composite organic framework material is characterized by comprising the following steps:
(1) adding organic ligands of 3,3 ', 5, 5' -azobenzene tetracarboxylic acid, cobalt acetate and indium chloride into a hydrochloric acid solution, and obtaining an indium-cobalt-based metal organic framework mother solution through hydrothermal reaction;
(2) adding foamed nickel into water, transferring the foamed nickel into a hydrothermal reaction kettle for hydrothermal reaction to obtain Ni (OH) 2 A precursor;
(3) ni (OH) to be prepared 2 Immersing the precursor into indium-cobalt-based metal organic framework mother liquor for heating reaction, and washing and drying after the reaction is finished to obtain the InCo 2 @Ni(OH) 2 the/NF heterogeneous composite organic framework material.
2. The synthesis method of the indium-cobalt-based bimetal heterogeneous composite organic framework material as claimed in claim 1, wherein the molar ratio of the organic ligand 3,3 ', 5, 5' -azophenyltetracarboxylic acid to the metal salts of cobalt acetate and indium chloride in step (1) is 1: 3-1: 4, and the molar ratio of the metal salts of cobalt acetate and indium chloride is 4: 1-2: 1; the molar concentration of the hydrochloric acid solution is 3.0-3.5M, and the pH value of the hydrothermal reaction system is 2.5-3.5.
3. The method for synthesizing the indium-cobalt-based bimetal heterogeneous composite organic framework material as claimed in claim 2, wherein the molar ratio of 3,3 ', 5, 5' -azophenyltetracarboxylic acid to cobalt acetate and indium chloride is 1:4, and the molar ratio of cobalt acetate to indium chloride metal salt is 3: 1; the hydrochloric acid solution had a molar concentration of 3.2M.
4. The method for synthesizing the indium-cobalt-based bimetal heterogeneous composite organic framework material according to claim 1, wherein the hydrothermal reaction condition is 100-120 ℃ and the reaction time is 18-36 hours.
5. The method for synthesizing the indium-cobalt-based bimetal heterogeneous composite organic framework material according to claim 1, wherein the hydrothermal reaction condition is 120 ℃ and the reaction time is 24 hours.
6. The method for synthesizing an indium-cobalt-based bimetal heterogeneous composite organic framework material as claimed in claim 1, wherein the hydrothermal reaction condition in the step (2) is 150-160 ℃ and the reaction time is 10-15 hours.
7. The method for synthesizing an indium-cobalt-based bimetal heterogeneous composite organic framework material as claimed in claim 1, wherein the temperature-raising reaction condition in the step (3) is that the reaction is carried out for 12-24h at 110-130 ℃.
8. The indium-cobalt-based bimetal heterogeneous composite organic framework material synthesized by the method of any one of claims 1 to 7, wherein the chemical formula of the indium-cobalt-based bimetal heterogeneous composite organic framework material is Co 2 InC 24 H 16 N 3 O 16 The crystal of the crystalline material belongs to a monoclinic system, the space group is I2/a, and the unit cell parameters are as follows: α =90 °, β =90 °, γ =90 °, a =22.2973(4) a, b =22.2973(4) a, c =22.2973(4) a.
9. The application of the indium-cobalt-based bimetal heterogeneous composite organic framework material synthesized by the method of any one of claims 1 to 7 as an electrocatalyst in catalyzing oxygen evolution or urea oxidation.
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