CN113058650A - Composite metal organic framework, preparation and application - Google Patents
Composite metal organic framework, preparation and application Download PDFInfo
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- CN113058650A CN113058650A CN201911275003.5A CN201911275003A CN113058650A CN 113058650 A CN113058650 A CN 113058650A CN 201911275003 A CN201911275003 A CN 201911275003A CN 113058650 A CN113058650 A CN 113058650A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 6
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000013299 conductive metal organic framework Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- 239000013179 MIL-101(Fe) Substances 0.000 description 8
- 229940032296 ferric chloride Drugs 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 4
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000013177 MIL-101 Substances 0.000 description 3
- 239000013206 MIL-53 Substances 0.000 description 3
- 239000013215 MIL-88B Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical group C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
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- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
The invention relates to a preparation method of a composite metal organic framework, which is characterized in that a conductive metal organic framework (TM-CAT, CAT is a metal organic framework formed by hexahydroxy triphenyl and transition metal TM, different types of the metal organic framework are distinguished by the transition metal TM) is modified on the surface of an iron-based metal organic framework (MIL-xx, MIL is short for a metal organic framework material, different types of the metal organic framework are distinguished by a number xx) to obtain the composite metal organic framework (MIL-xx @ TM-CAT). MIL-xx @ TM-CAT can be directly used as an electrolytic water or a secondary zinc-air battery oxygen electrode oxygen precipitation electrocatalyst, compared with independent TM-CAT or MIL-xx (Fe), MIL-xx @ TM-CAT makes up the defect that the cost of TM-CAT is too high, solves the problem of poor conductivity of MIL-xx, and can regulate and control the electrocatalytic activity according to the interaction of metals in the TM-CAT and the MIL-xx; meanwhile, the preparation process is simple, and raw materials are easy to obtain, so that the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation thereof, and discloses an oxygen electrode oxygen evolution electrocatalyst for an electrolytic water or a secondary zinc-air battery.
Background
The metal organic framework material has the advantages of high specific surface, rich metal content, convenient regulation and control of structural components, good stability and the like, and is widely applied to the research of electrocatalysts and electrode materials.
However, the conventional metal organic framework generally has no conductive property, and a conductive agent (carbon nanotube, graphene, etc.) needs to be additionally added in the process of preparing the electrode, so that the density of active substances in the electrode is reduced, and the complexity of the process is increased. A novel metal organic framework (TM-CAT) using 2,3,6,7,10, 11-hexahydroxy triphenyl as a ligand has excellent conductivity, but the ligand is expensive, and the cost is high when the TM-CAT is directly used as an electrocatalyst. In addition, the metal organic framework composed of a single metal cannot meet the requirements in terms of performance. In a bimetallic or polymetallic metal-organic framework, the activity of the catalyst can be greatly improved due to the interaction between different metals.
Disclosure of Invention
The common metal organic framework is directly used as a catalyst, and has the problems of poor conductivity, low catalytic activity and the like. Aiming at the defects, the invention provides a preparation method of a composite metal organic framework, which is characterized in that a conductive metal organic framework (TM-CAT, CAT is a metal organic framework formed by hexahydroxy triphenyl and transition metal TM, the different types of the metal organic framework are distinguished by the transition metal TM) is modified on the surface of an iron-based metal organic framework (MIL-xx, MIL is short for a metal organic framework material, and the different types of the metal organic framework are distinguished by the number xx) to obtain the composite metal organic framework (MIL-xx @ TM-CAT). MIL-xx @ TM-CAT can be directly used as an electrolytic water or a secondary zinc-air battery oxygen electrode oxygen precipitation electrocatalyst, compared with independent TM-CAT or MIL-xx (Fe), MIL-xx @ TM-CAT makes up the defect that the cost of TM-CAT is too high, solves the problem of poor conductivity of MIL-xx, and can regulate and control the electrocatalytic activity according to the interaction of metals in the TM-CAT and the MIL-xx; meanwhile, the preparation process is simple, and raw materials are easy to obtain, so that the application prospect is wide.
A composite metal organic framework takes MIL-xx as a core and TM-CAT is grown on the surface. The metal in MIL-xx is Fe, and the mol percent of Fe in the composite metal organic framework accounts for 30-90%, preferably 70-90% of the total metal content. The ligand in the TM-CAT is 2,3,6,7,10, 11-hexahydroxy triphenyl (HHTP), and the conductivity is excellent; the Metal (TM) is one or more of Mn, Co and Ni.
The preparation method comprises the following steps:
(1) synthesis of MIL-xx: preparing a mixed solution of Fe metal salt and a polycarboxyl organic ligand, carrying out solvothermal reaction on the mixed solution at high temperature, and separating a product to obtain a Fe-based metal organic framework;
(2) preparing a composite metal organic framework: ultrasonically dispersing the mixed solvent of the metal organic framework water and DMF obtained in the step (1), adding and Transition Metal (TM) salt and 2,3,6,7,10, 11-hexahydroxy triphenyl (HHTP), carrying out solvothermal reaction at high temperature, and separating a product to obtain a composite metal organic framework;
in the step (1), the Fe metal salt is one or two of ferric nitrate and ferric chloride; the organic ligand is one or more than two of terephthalic acid, trimesic acid and trans-butenedioic acid; the solvent is one or a mixture of more than two of DMF, methanol or water; the amount ratio of Fe ions to the substance with ligand in the mixed solution in the step (1) is 2:1-1: 2.
In the step (1), the solvothermal reaction temperature is 60-120 ℃, and the time duration is 8-48 hours.
The volume ratio of the water to the DMF in the step (2) is 2:1-1: 2; the Transition Metal (TM) salt is one or more of nitrate, chloride and acetate of Mn, Co and Ni; the molar ratio of Transition Metal (TM) salt to 2,3,6,7,10, 11-hexahydroxy triphenyl is 1: 1.
In the step (2), the solvothermal reaction temperature is 60-90 ℃, and the time duration is more than 1 hour.
Compared with the prior art, the invention has the following advantages: the conductivity of the material can be improved by modifying a small amount of TM-CAT on the surface of the MIL-xx, and meanwhile, the interaction between the MIL-xx and the TM-CAT can regulate and control the catalytic activity, so that the electrocatalytic performance of the material is greatly improved. Meanwhile, the preparation process is simple, and the raw materials are easy to obtain. In addition, the high oxygen precipitation performance and the good stability make the oxygen electrode have wide application prospect in the oxygen electrode of the electrolytic water and secondary metal air battery.
Drawings
FIG. 1X-ray fluorescence (XRF) spectrum of example 1.
FIG. 2 electrochemical performance test chart for oxygen evolution in example 1. The curve is tested in oxygen saturated 1M KOH electrolyte by using a three-electrode system, the catalyst is coated on a rotating disk electrode as a working electrode, and the loading capacity is 100mg cm-2The graphite rod is used as a counter electrode, a saturated calomel electrode externally connected with a salt bridge is used as a reference electrode, and the potential in the figure is corrected to be the potential relative to the reversible hydrogen electrode.
Detailed Description
Comparative example 1
Weighing 2.03g of ferric chloride hexahydrate in a beaker, adding 25ml of DMF, stirring to form a solution, weighing 0.618g of terephthalic acid in the beaker, adding 25ml of DMF, stirring to form a solution, slowly pouring the ferric chloride solution into the terephthalic acid solution, continuously stirring for 30min, then transferring to a reaction kettle, heating to 110 ℃, keeping the temperature for 8h, cooling the reaction kettle to room temperature after the reaction is finished, obtaining a product through centrifugal separation, washing with ethanol for three times to remove the solvent remained in the air, and using XRD to represent that the product is MIL-101 (Fe).
MIL-101(Fe) has poor conductivity and low performance of single metal catalysts.
Comparative example 2
20mg of nickel acetate tetrahydrate and 13mg of 2,3,6,7,10, 11-hexahydroxytriphenylene were weighed out and ultrasonically dispersed in 2ml of a mixed solvent of water and N, N-dimethylformamide (volume ratio: 1), placed in an oven at 80 ℃ for 8 hours, centrifugally separated, washed three times with water and methanol respectively, and characterized as Ni-CAT by XRD.
The price of 2,3,6,7,10, 11-hexahydroxy triphenyl is about 1200 yuan/gram, and the price of pure Ni-CAT is higher.
Example 1
Weighing 2.03g of ferric chloride hexahydrate in a beaker, adding 25ml of DMF, stirring to form a solution, weighing 0.618g of terephthalic acid in the beaker, adding 25ml of DMF, stirring to form a solution, slowly pouring the ferric chloride solution into the terephthalic acid solution, continuously stirring for 30min, then transferring to a reaction kettle, heating to 110 ℃, keeping the temperature for 8h, cooling the reaction kettle to room temperature after the reaction is finished, obtaining a product through centrifugal separation, and washing with ethanol for three times to remove the solvent remained in the air, thereby obtaining MIL-101 (Fe).
100mg of MIL-101(Fe) is dispersed in 8mL of mixed solvent of water and N, N-dimethylformamide (volume ratio is 1:1) for ultrasonic dispersion, 10mg of nickel acetate tetrahydrate and 6.5mg of 2,3,6,7,10, 11-hexahydroxy triphenyl are added and placed in an oven at 80 ℃ for 8 hours for centrifugal separation, and the mixture is washed with water and methanol for three times respectively to obtain MIL-101/Ni-CAT. XPS tests show that the mole percentage of Fe in the composite metal organic framework to the total metal is 87.4%, and the mole percentage of Ni in the composite metal organic framework to the total metal is 12.6%.
Example 2
Weighing 2.03g of ferric chloride hexahydrate in a beaker, adding 25ml of DMF, stirring to form a solution, weighing 0.618g of terephthalic acid in the beaker, adding 25ml of DMF, stirring to form a solution, slowly pouring the ferric chloride solution into the terephthalic acid solution, continuously stirring for 30min, then transferring to a reaction kettle, heating to 110 ℃, keeping the temperature for 8h, cooling the reaction kettle to room temperature after the reaction is finished, obtaining a product through centrifugal separation, and washing with ethanol for three times to remove the solvent remained in the air, thereby obtaining MIL-101 (Fe).
100mg of MIL-101(Fe) is dispersed in 8mL of mixed solvent of water and N, N-dimethylformamide (volume ratio is 1:1) for ultrasonic dispersion, 10mg of cobalt acetate tetrahydrate and 6.5mg of 2,3,6,7,10, 11-hexahydroxy triphenyl are added and placed in an oven at 80 ℃ for 8 hours for centrifugal separation, and the mixture is washed with water and methanol for three times respectively to obtain MIL-101/Co-CAT.
XPS tests show that the mole percentage of Fe in the composite metal organic framework is 90%.
XPS tests show that the mole percentage of Fe in the composite metal organic framework to the total metal is 88.3%, and the mole percentage of Co in the composite metal organic framework to the total metal is 11.7%.
Example 3
Weighing 2.03g of ferric chloride hexahydrate in a beaker, adding 25ml of DMF, stirring to form a solution, weighing 0.618g of terephthalic acid in the beaker, adding 25ml of DMF, stirring to form a solution, slowly pouring the ferric chloride solution into the terephthalic acid solution, continuously stirring for 30min, then transferring to a reaction kettle, heating to 110 ℃, keeping the temperature for 8h, cooling the reaction kettle to room temperature after the reaction is finished, obtaining a product through centrifugal separation, and washing with ethanol for three times to remove the solvent remained in the air, thereby obtaining MIL-101 (Fe).
100mg of MIL-101(Fe) is dispersed in 8mL of mixed solvent of water and N, N-dimethylformamide (volume ratio is 1:1) for ultrasonic dispersion, 10mg of manganese acetate and 6.5mg of 2,3,6,7,10, 11-hexahydroxy triphenyl are added and placed in an oven at 80 ℃ for 8 hours for centrifugal separation, and the mixture is washed with water and methanol for three times respectively to obtain MIL-101/Mn-CAT.
XPS tests show that the mole percentage of Fe in the composite metal organic framework to the total metal is 85.6%, and the mole percentage of Co in the composite metal organic framework to the total metal is 14.4%.
Example 4
Weighing 0.674g ferric chloride hexahydrate in a beaker, adding 25ml DMF, stirring to form a solution, weighing 0.415g terephthalic acid in the beaker, adding 25ml DMF, stirring to form a solution, slowly pouring the ferric chloride solution into the terephthalic acid solution, continuously stirring for 30min, then transferring into a reaction kettle, heating to 150 ℃, preserving heat for 15h, cooling the reaction kettle to room temperature after the reaction is finished, obtaining a product through centrifugal separation, and washing with ethanol for three times to remove the residual solvent in the air, thereby obtaining MIL-53 (Fe). 100mg of MIL-53(Fe) is weighed and dispersed in 8mL of mixed solvent of water and N, N-dimethylformamide (volume ratio is 1:1) through ultrasonic dispersion, 20mg of nickel acetate tetrahydrate and 13mg of 2,3,6,7,10, 11-hexahydroxytriphenyl are added and placed in an oven at 80 ℃ for 8 hours, centrifugal separation is carried out, and the mixture is washed with water and methanol for three times respectively, so that MIL-53/Ni-CAT is obtained.
XPS tests show that the mole percentage of Fe in the composite metal organic framework to the total metal is 73.7%, and the mole percentage of Ni to the total metal is 26.3%.
Example 5
Weighing 2.70g of ferric chloride hexahydrate in a beaker, adding 25ml of DMF, stirring to form a solution, weighing 1.66g of terephthalic acid in the beaker, adding 25ml of DMF, stirring to form a solution, slowly pouring the ferric chloride solution into the terephthalic acid solution, adding 4ml of 2M NaOH, continuously stirring for 30min, transferring the solution into a reaction kettle, heating to 100 ℃, keeping the temperature for 12h, cooling the reaction kettle to room temperature after the reaction is finished, obtaining a product through centrifugal separation, washing with ethanol for three times, and removing the solvent remained in the air to obtain MIL-88B (Fe). 100mg of MIL-88B (Fe) is weighed and dispersed in 8mL of mixed solvent of water and N, N-dimethylformamide (volume ratio is 1:1) through ultrasonic dispersion, 40mg of nickel acetate tetrahydrate and 26mg of 2,3,6,7,10, 11-hexahydroxy triphenyl are added and placed in an oven at 80 ℃ for 8 hours, centrifugal separation is carried out, and the mixture is washed with water and methanol for three times respectively, so that MIL-88B/Ni-CAT is obtained.
XPS tests show that the mole percentage of Fe in the composite metal organic framework to the total metal is 63.4%, and the mole percentage of Ni in the composite metal organic framework to the total metal is 36.6%.
Claims (9)
1. A composite metal organic framework, characterized by: taking an iron-based metal organic framework MIL-xx as a core, and growing TM-CAT on the surface of the core.
2. The composite metal organic framework of claim 1, wherein: the metal in MIL-xx is Fe, and the mol percent of Fe in the composite metal organic framework accounts for 30-90 percent of the total metal (Fe and TM), and the mol percent is preferably 70-90 percent.
3. The composite metal organic framework of claim 1 or 2, wherein: the ligand in the TM-CAT is 2,3,6,7,10, 11-hexahydroxy triphenyl (HHTP), and the conductivity is excellent; the Metal (TM) is one or more of Mn, Co and Ni.
4. A method for preparing a composite metal organic framework according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) synthesis of MIL-xx: preparing a mixed solution of Fe metal salt and a polycarboxyl organic ligand, carrying out solvothermal reaction on the mixed solution, and separating a product to obtain a Fe-based metal organic framework;
(2) preparing a composite metal organic framework: ultrasonically dispersing the metal organic framework obtained in the step (1) in a mixed solvent of water and DMF, adding and Transition Metal (TM) salt and 2,3,6,7,10, 11-hexahydroxy triphenyl (HHTP), carrying out solvothermal reaction, and separating a product to obtain a composite metal organic framework;
5. the method of preparing a composite metal organic framework according to claim 4, wherein: in the step (1), the Fe metal salt is one or two of ferric nitrate and ferric chloride; the organic ligand is one or more than two of terephthalic acid, trimesic acid and trans-butenedioic acid; the solvent is one or a mixture of more than two of DMF, methanol or water; the amount ratio of Fe ions to the substance with ligand in the mixed solution in the step (1) is 2:1-1: 2.
6. The method of preparing a composite metal organic framework according to claim 4, wherein: in the step (1), the solvothermal reaction temperature is 60-120 ℃, and the time duration is 8-48 hours.
7. The method of preparing a composite metal organic framework according to claim 4, wherein: the volume ratio of the water to the DMF in the step (2) is 2:1-1: 2; the Transition Metal (TM) salt is one or more of nitrate, chloride and acetate of one or more of Mn, Co and Ni; the molar ratio of Transition Metal (TM) salt to 2,3,6,7,10, 11-hexahydroxy triphenyl is 1: 1.
8. The method of preparing a composite metal organic framework according to claim 4, wherein: in the step (2), the solvothermal reaction temperature is 60-90 ℃, and the time duration is more than 1 hour.
9. A use as claimed in any one of claims 1 to 3, wherein: the composite metal organic framework is used as an oxygen evolution electrocatalyst of an oxygen electrode of an electrolytic water or a secondary zinc-air battery.
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| CN114029090A (en) * | 2021-12-17 | 2022-02-11 | 中国矿业大学 | Preparation method of photocatalyst for removing heavy metals in sewage |
| CN115739193A (en) * | 2022-11-25 | 2023-03-07 | 华北电力大学 | Synthesis and application of carbon nitride/MOFs composite material |
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