CN114433235A - Metal organic framework loaded substrate composite material and preparation method and application thereof - Google Patents

Metal organic framework loaded substrate composite material and preparation method and application thereof Download PDF

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CN114433235A
CN114433235A CN202111583045.2A CN202111583045A CN114433235A CN 114433235 A CN114433235 A CN 114433235A CN 202111583045 A CN202111583045 A CN 202111583045A CN 114433235 A CN114433235 A CN 114433235A
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substrate
metal
organic framework
composite material
metal organic
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梁作中
郑浩铨
曹睿
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Shaanxi Normal University
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • C08G83/008—Supramolecular polymers
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
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Abstract

The invention relates to a metal organic framework load substrate composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1: pretreating a substrate of the composite material; step 2: preparing a metal salt solution and an organic ligand solution corresponding to the metal-organic framework material; and step 3: and sequentially dipping the pretreated substrate into a metal salt solution and an organic ligand solution to complete one-time self-assembly, and then taking out and drying to obtain the metal-organic framework loaded substrate composite material. According to the method, the three-dimensional space structure, the larger specific surface area and the inherent high conductivity of the substrate material are utilized, the metal organic framework material is quickly loaded on the substrate through a continuous ion layer adsorption method, and the metal organic framework loaded substrate composite material is obtained.

Description

Metal organic framework loaded substrate composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of energy storage and conversion, and particularly relates to a metal organic framework load substrate composite material, and a preparation method and application thereof.
Background
In recent years, with the gradual consumption of fossil energy and the increasing prominence of environmental pollution problems, the demand of human beings for green, clean and renewable energy is sharply increased. The development of efficient, low cost energy storage and conversion technologies for water splitting, fuel cells, metal-air cells, and the like, has become a leading area of research. The zinc-air battery uses the water-based electrolyte, has the advantages of low cost, safety and environmental friendliness, has theoretical energy as high as 1084Wh/kg, and is expected to become a new generation of energy storage equipment.
According to the use requirement, the zinc-air battery can be made into a primary battery, a chargeable and dischargeable battery and a flexible battery. The discharge process of a zinc-air battery involves an Oxygen Reduction Reaction (ORR), while the charge process involves an Oxygen Evolution Reaction (OER). At present, the Pt-based catalyst is an excellent ORR catalyst, and Ir and Ru-based catalysts have excellent catalytic performance in OER reaction, but platinum group elements have the defects of rare reserves in the earth crust, high price, poor stability and single function.
Therefore, in recent years, the development of abundant non-noble metal catalysts has received great attention, and some non-noble metal catalysts can react with Pt and IrO2On a par with others, however, they have a great disadvantage in that most of the catalysts are powdery materials obtained by complicated processes, and they are used by fixing them to a specific conductive substrate such as carbon cloth as an electrode. The commonly used immobilization method is to adhere the catalyst to the conductive substrate with conductive adhesive such as Nafion, but these adhesive will cover part of the active sites, and the adhered catalyst will fall off with the violent release of gas, which is not good for charge transport and has adverse effect on the electrochemical performance of the zinc-air battery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a metal organic framework load base composite material, and a preparation method and application thereof. The technical problem to be solved by the invention is realized by the following technical scheme:
the invention provides a preparation method of a metal organic framework load substrate composite material, which comprises the following steps:
step 1: pretreating a substrate of the composite material;
step 2: preparing a metal salt solution and an organic ligand solution corresponding to the metal-organic framework material;
and step 3: and sequentially dipping the pretreated substrate into the metal salt solution and the organic ligand solution to complete one-time self-assembly, and then taking out and drying to obtain the metal-organic framework loaded substrate composite material.
In one embodiment of the present invention, the step 1 comprises: and sequentially putting the substrate into a water and ethanol solution for ultrasonic cleaning, and then drying to obtain the pretreated substrate.
In one embodiment of the present invention, the material of the substrate is one of carbon cloth, filter membrane, filter paper, foamed nickel, foamed copper and titanium mesh.
In one embodiment of the invention, the metal organic framework material is one of ZIF-8, ZIF-67, ZIF-90, MOF-5, MOF-74, MOF-801, UiO-66 and HKUST-1.
In one embodiment of the present invention, the step 3 comprises:
step 3.1: dipping the pretreated substrate into the metal salt solution for at least 10min under the normal temperature condition to obtain a substrate adsorbing metal ions;
step 3.2: dipping the substrate adsorbing the metal ions into the organic ligand solution for at least 10min to complete one-time self-assembly;
step 3.3: and taking the substrate out of the organic ligand solution and drying to obtain the metal organic framework loaded substrate composite material.
In one embodiment of the present invention, in step 3, the number of self-assembly times is greater than or equal to 1.
The invention provides a metal organic framework load substrate composite material which is prepared by adopting the preparation method in any one of the embodiments.
The invention provides an application of the metal organic framework load base composite material in a metal-air battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the metal organic framework loaded substrate composite material of the invention utilizes the three-dimensional space structure, larger specific surface area and inherent high conductivity of the substrate material, rapidly loads the metal organic framework material on the substrate by a continuous ion layer adsorption method to obtain the metal organic framework loaded substrate composite material, and then carries out high-temperature calcination on the material to obtain the integral electrode material, which has huge specific surface area and is used as a catalyst and a current collector, so that the problems of larger internal resistance and easy falling of active substances caused by a smearing method or an extrusion method of an electrode in the traditional zinc-air battery can be solved, the mass transfer and the load transfer efficiency are effectively improved, and the electrochemical performance of the battery is improved;
2. metal organic framework loaded substrate composites of the invention, with commercial Pt/C and RuO2Compared with a catalyst, the catalyst is used as an integral electrode and has excellent electrocatalytic activity and stability in a zinc-air battery under alkaline conditions;
3. the preparation method of the metal organic framework loaded substrate composite material has the advantages of cheap and easily-obtained raw materials, simple and economical preparation method and suitability for industrial large-scale production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a flow chart of a method for preparing a metal organic framework supported substrate composite according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a process for preparing a metal organic framework loaded substrate composite according to an embodiment of the present invention;
FIG. 3 is a high power SEM image of a Co-ZIF/carbon cloth composite of example 1 of the present invention;
FIG. 4 is a high power SEM image of the Co-ZIF/filter membrane composite of example 2 of the present invention;
FIG. 5 is a high power SEM image of the Co-ZIF/filter paper composite of example 3 of the present invention;
FIG. 6 is a high power SEM image of a Co-ZIF/nickel foam composite of example 4 of the present invention;
FIG. 7 is a high power SEM image of a Zn-ZIF/filter paper composite of example 5 of the present invention;
FIG. 8 is a high power SEM image of a Zn-Co-ZIF/filter paper composite of example 6 of the present invention;
FIG. 9 is a discharge curve for zinc-air battery performance testing after high temperature calcination of the Co-ZIF/carbon cloth composite of example 1.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, a metal organic framework loaded substrate composite material, a preparation method thereof and applications thereof according to the present invention are described in detail below with reference to the accompanying drawings and the detailed description.
The foregoing and other technical matters, features and effects of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings. The technical means and effects of the present invention adopted to achieve the predetermined purpose can be more deeply and specifically understood through the description of the specific embodiments, however, the attached drawings are provided for reference and description only and are not used for limiting the technical scheme of the present invention.
Referring to fig. 1 and fig. 2 in combination, fig. 1 is a flowchart of a method for preparing a metal organic framework supported substrate composite material according to an embodiment of the present invention, and fig. 2 is a schematic flowchart of a process for preparing a metal organic framework supported substrate composite material according to an embodiment of the present invention. As shown in the figure, the preparation method of the metal organic framework supported substrate composite material of the embodiment includes:
step 1: pretreating a substrate of the composite material;
specifically, step 1 comprises:
and sequentially putting the substrate into a water and ethanol solution for ultrasonic cleaning, and then drying to obtain the pretreated substrate.
In this example, the substrate was sequentially ultrasonically cleaned in water and ethanol for 30min each, and then placed in an oven for drying for 30min to obtain a pretreated substrate.
Optionally, the substrate is made of one of carbon cloth, filter membrane, filter paper, foamed nickel, foamed copper and titanium mesh.
Step 2: preparing a metal salt solution and an organic ligand solution corresponding to the metal-organic framework material;
in this embodiment, the metal organic framework material is one of ZIF-8, ZIF-67, ZIF-90, MOF-5, MOF-74, MOF-801, UiO-66, and HKUST-1.
Correspondingly, the metal salt solution corresponding to the metal organic framework material ZIF-8 is obtained by dissolving nitrate, sulfate or hydrochloride of zinc in methanol, and the organic ligand solution is obtained by dissolving 2-methylimidazole in methanol.
The metal salt solution corresponding to the metal organic framework material ZIF-67 is obtained by dissolving nitrate, sulfate or hydrochloride of cobalt in methanol, and the organic ligand solution is obtained by dissolving 2-methylimidazole in methanol.
The organic ligand solution is related to the metal-organic framework material, and generally, the metal-organic framework material is different from the metal-organic framework material, and the corresponding organic ligand solution is different from the metal-organic framework material.
And step 3: and sequentially dipping the pretreated substrate into a metal salt solution and an organic ligand solution to complete one-time self-assembly, and then taking out and drying to obtain the metal-organic framework loaded substrate composite material.
Specifically, step 3 includes:
step 3.1: dipping the pretreated substrate into a metal salt solution for at least 10min at normal temperature to obtain a substrate adsorbing metal ions;
step 3.2: dipping the substrate adsorbing the metal ions into an organic ligand solution for at least 10min to complete one-time self-assembly;
in this embodiment, the metal ions adsorbed on the substrate and the particles in the organic ligand solution self-assemble to obtain the metal-organic framework.
Step 3.3: and taking the substrate out of the organic ligand solution and drying to obtain the metal organic framework loaded substrate composite material.
Wherein, in the step, the self-assembly times are more than or equal to 1.
It should be noted that, in this embodiment, after the substrate is taken out from the metal salt solution, the substrate may be washed with a solvent corresponding to the metal salt solution, the washing is performed to remove the metal ions with weak adsorption, and then a drying process is performed, the drying is performed to make the adsorption of the adsorbed metal ions stronger, and finally, the substrate is immersed in the organic ligand solution.
After the substrate organic ligand solution is taken out, the substrate can also be washed by a solvent corresponding to the organic ligand solution, and then the substrate is dried to obtain the metal organic framework loaded substrate composite material.
In this embodiment, the pretreated substrate is sequentially immersed in a metal salt solution and an organic ligand solution, and the metal-organic framework supported substrate composite material is obtained by continuously performing ion layer absorption and reaction for multiple times.
After the metal organic framework load base composite material prepared by the embodiment is calcined at high temperature, the metal organic framework load base composite material can be used as an integral electrode to be applied to a metal-air battery.
Optionally, the calcination temperature is 800-1100 ℃, and the calcination atmosphere is N2Ar or NH3The calcination time is 2-6 h.
According to the preparation method of the metal organic framework loaded substrate composite material, the metal organic framework material is quickly loaded on the substrate by utilizing the three-dimensional space structure, the larger specific surface area and the inherent high conductivity of the substrate material through a continuous ion layer adsorption method to obtain the metal organic framework loaded substrate composite material, and the material is calcined at high temperature to obtain the integral electrode material which has huge specific surface area and is used as a catalyst and a current collector, so that the problems of larger internal resistance and easy falling of active substances caused by a smearing method or an extrusion method of an electrode in a traditional zinc-air battery can be solved, the mass transfer and load transfer efficiency is effectively improved, and the electrochemical performance of the battery is improved;
the following is a specific example of the preparation method of the metal organic framework-supported substrate composite material of the present invention.
Example 1
Preparation of Co-ZIF/carbon cloth composite material
Step 1: sequentially putting 2cm × 2cm of carbon cloth into water and ethanol, respectively ultrasonically cleaning for 30min, and then putting into an oven for drying for 30min for later use;
step 2: 0.29g of Co (NO)3)2Dissolving in 25ml of methanol to prepare a Co salt solution, and dissolving 0.33g of 2-methylimidazole in 25ml of methanol to prepare a 2-methylimidazole solution;
and 3, step 3: at normal temperature, firstly, the carbon cloth is put into Co salt solution to be soaked for 10min, and then the obtained Co is put into2+Soaking the adsorbed carbon cloth in a 2-methylimidazole solution for 10min, continuously performing ion layer absorption and reaction (namely, self-assembly) for 1 time, 2 times and 3 times, cleaning the carbon cloth by using a methanol solution, and drying in the air to obtain the Co-ZIF/carbon cloth composite material.
As shown in fig. 3, fig. 3 is a high power SEM image of the Co-ZIF/carbon cloth composite material of example 1 of the present invention, wherein a is a high power SEM image of a blank carbon cloth, b is a high power SEM image of a Co-ZIF/carbon cloth composite material obtained by performing self-assembly for 1 time, c is a high power SEM image of a Co-ZIF/carbon cloth composite material obtained by performing self-assembly for 2 times, and d is a high power SEM image of a Co-ZIF/carbon cloth composite material obtained by performing self-assembly for 3 times.
Example 2
Preparation of Co-ZIF/Filter Membrane composite Material
In this example, a filter membrane is selected as the substrate material, and other preparation steps are the same as those in example 1, as shown in fig. 4, fig. 4 is a high power SEM image of the Co-ZIF/filter membrane composite material in example 2 of the present invention, wherein a is a high power SEM image of a blank filter membrane, and b is a high power SEM image of a Co-ZIF/filter membrane composite material obtained by performing 3 times of self-assembly.
Example 3
Preparation of Co-ZIF/filter paper composite material
In this example, filter paper was selected as the substrate material, and other preparation steps were the same as those in example 1, as shown in fig. 5, fig. 5 is a high power SEM image of the Co-ZIF/filter paper composite material of example 3 of the present invention, wherein a is a high power SEM image of blank filter paper, and b is a high power SEM image of Co-ZIF/filter paper composite material obtained by performing 3 times of self-assembly.
Example 4
Preparation of Co-ZIF/foamed nickel composite material
In this example, the substrate material is selected to be nickel foam, and other preparation steps are the same as those in example 1, as shown in fig. 6, fig. 6 is a high power SEM image of the Co-ZIF/nickel foam composite material in example 4 of the present invention, wherein a is a high power SEM image of blank nickel foam, and b is a high power SEM image of Co-ZIF/nickel foam composite material obtained by performing 3 times of self-assembly.
Example 5
Preparation of Zn-ZIF/filter paper composite material
Step 1: sequentially putting 2cm × 2cm filter paper into water and ethanol, respectively ultrasonically cleaning for 30min, and then putting into an oven for drying for 30min for later use;
step 2: 0.29g of Zn (NO)3)2Dissolving in 25ml of methanol to prepare a Zn salt solution, and dissolving 0.33g of 2-methylimidazole in 25ml of methanol to prepare a 2-methylimidazole solution;
and step 3: soaking filter paper in Zn salt solution for 10min at normal temperature, and obtaining Zn2+And soaking the adsorbed filter paper in a 2-methylimidazole solution for 10min, washing the filter paper by using a methanol solution, and drying in the air to obtain the Zn-ZIF/filter paper composite material. As shown in fig. 7, fig. 7 is a high power SEM picture of Zn-ZIF/filter paper composite of example 5 of the present invention.
Example 6
Preparation of Zn-Co-ZIF/filter paper composite material
Step 1: sequentially putting 2cm × 2cm filter paper into water and ethanol, respectively ultrasonically cleaning for 30min, and then putting into an oven for drying for 30min for later use;
step 2: 0.145g of Zn (NO)3)2And 0.145g Co (NO)3)2Dissolving in 25ml methanol to prepare a mixed metal salt solution, and dissolving 0.33g of 2-methylimidazole in 25ml methanol to prepare a 2-methylimidazole solution;
and step 3: soaking filter paper in mixed metal salt solution for 10min at normal temperature, and obtaining Zn2+And Co2+And soaking the adsorbed filter paper in a 2-methylimidazole solution for 10min, cleaning the filter paper by using a methanol solution, and drying in the air to obtain the Zn-Co-ZIF/filter paper composite material. As shown in fig. 8, fig. 8 is a high power SEM picture of Zn-Co-ZIF/filter paper composite of example 6 of the present invention.
Application example 1
In this embodiment, the Co-ZIF/carbon cloth composite material of example 1 is calcined at a high temperature to obtain an integral electrode material, a zinc-air battery is prepared from the electrode material, and a discharge performance test is performed on the zinc-air battery, wherein the test is performed at room temperature, as shown in fig. 9, fig. 9 is a discharge curve of the Co-ZIF/carbon cloth composite material of example 1, which is calcined at a high temperature and then used for a performance test of the zinc-air battery, and it can be seen that the zinc-air battery exhibits higher performance of the zinc-air battery.
Metal organic framework loaded substrate composites of the invention, with commercial Pt/C and RuO2Compared with the prior art, the catalyst is used as an integral electrode, the zinc-air battery shows excellent electrocatalytic activity under alkaline conditions, and in addition, the adopted raw materials are cheap and easy to obtain during preparation, and the preparation method is simple and economic, and is suitable for industrial large-scale production.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (8)

1. A preparation method of a metal organic framework loaded substrate composite material is characterized by comprising the following steps:
step 1: pretreating a substrate of the composite material;
step 2: preparing a metal salt solution and an organic ligand solution corresponding to the metal-organic framework material;
and step 3: and sequentially dipping the pretreated substrate into the metal salt solution and the organic ligand solution to complete one-time self-assembly, and then taking out and drying to obtain the metal-organic framework loaded substrate composite material.
2. The method of preparing a metal organic framework supported substrate composite as claimed in claim 1, wherein the step 1 comprises: and sequentially putting the substrate into a water and ethanol solution for ultrasonic cleaning, and then drying to obtain the pretreated substrate.
3. The method of claim 1, wherein the substrate is made of one of carbon cloth, filter membrane, filter paper, nickel foam, copper foam, and titanium mesh.
4. The method of making a metal organic framework supported substrate composite material of claim 1, wherein the metal organic framework material is one of ZIF-8, ZIF-67, ZIF-90, MOF-5, MOF-74, MOF-801, UiO-66 and HKUST-1.
5. The method of making a metal organic framework supported substrate composite material according to claim 1, wherein the step 3 comprises:
step 3.1: dipping the pretreated substrate into the metal salt solution for at least 10min under the normal temperature condition to obtain a substrate adsorbing metal ions;
step 3.2: dipping the substrate adsorbing the metal ions into the organic ligand solution for at least 10min to complete one-time self-assembly;
step 3.3: and taking the substrate out of the organic ligand solution and drying to obtain the metal organic framework loaded substrate composite material.
6. The method of preparing a metal organic framework supported substrate composite according to claim 1, wherein in step 3, the number of self-assembly times is greater than or equal to 1.
7. A metal organic framework supported substrate composite material, characterized in that it is prepared by the process according to any one of claims 1 to 6.
8. Use of the metal organic framework supported substrate composite of claim 7 in a metal air battery.
CN202111583045.2A 2021-12-22 2021-12-22 Metal organic framework loaded substrate composite material and preparation method and application thereof Pending CN114433235A (en)

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