CN112778535B - Preparation method and application of multi-element heterogeneous metal organic framework material - Google Patents
Preparation method and application of multi-element heterogeneous metal organic framework material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
- 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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- B01J35/33—
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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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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a multi-element heterogeneous metal organic framework material, which comprises the following steps: s101, uniformly mixing an iridium trichloride/ruthenium trichloride mixture and cobalt nitrate hexahydrate as metal sources and anhydrous sodium acetate as a ligand in water at room temperature to obtain brown mixed liquor, namely a precursor; s102, transferring the precursor into a high-pressure reaction kettle, adding a Ti skeleton, and reacting at 80-150 ℃ for 12-72 hours to finally obtain a mixed product; s103, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the obtained mixed product to obtain a black precipitate, and purifying the black precipitate to obtain the multi-element heterogeneous metal organic framework material. The invention provides a multi-element heterogeneous metal organic framework material prepared by the method and application thereof. The preparation method of the multi-element heterogeneous metal organic framework material is simple and easy to operate, and the obtained material has small particle size, uniform size and very large specific surface area.
Description
The technical field is as follows:
the invention relates to the technical field of nano materials, in particular to a preparation method and application of a multi-element heterogeneous metal framework material.
Background art:
energy and environment are two key issues associated with the sustainable development of human society. At present, fossil fuels (petroleum, coal and natural gas) still account for a major portion of the world's energy consumption. The fossil fuels are in fact diversifiedThe valuable natural resources of the learning industry. In addition to the rapid exhaustion of these non-renewable resources as fuels for combustion in the near future, the combustion of fossil fuels can emit greenhouse gases such as CO2，NOxAnd SOxThis can lead to serious environmental problems. There is an urgent need to replace fossil energy with renewable energy.
Electrochemical water splitting is a promising method for storing clean energy in the form of hydrogen, an energy carrier with high energy density and no carbon emissions. However, in practical water electrolysis processes, additional energy, called overpotential, is required to overcome the high activation energy, kinetic lag, low energy efficiency, and other disadvantages. Therefore, it is necessary to make wide implementation of the decomposition of the water content economically feasible. A key requirement is the development of highly active, stable electrocatalysts composed of earth-rich materials.
The research, development and preparation of high-performance catalyst materials are crucial to promoting the development of environment-friendly and sustainable new energy technology. Due to the unique structure and excellent electrocatalytic performance of the multi-element heterogeneous metal organic framework, the multi-element heterogeneous metal organic framework is widely used as an OER catalyst material and applied to a plurality of aspects such as electrode materials, air batteries, lithium ion batteries, water electrolysis devices and the like, so that the research on the application of the catalyst material in various fields has very important practical value. The nano material has higher specific surface area due to the unique quantum size effect, thereby enhancing the effective contact of a reaction interface and being beneficial to energy conversion.
MOFs are considered by the catalytic community as an ideal platform for homogeneous catalyst heterogenizations. Indeed, MOFs can be understood to a large extent as molecules arranged in a crystal lattice, and thus, through crystal engineering, a given homogeneous catalyst can extend through such a lattice, thereby producing a solid with inherent catalytic activity. With this spirit, many synthetic MOFs can be considered single-site catalysts. To date, most three different approaches have been proposed to achieve intrinsic catalytic activity: (i) by introducing open metal sites (coordinatively unsaturated sites), (ii) by creating defects, and (iii) by using organic linkers as catalysts, it is possible to proceed through these sites, either directly or indirectly (post-synthesis modification). It should be noted that during this time MOF design has been focusing on the use of robust MOFs based on trivalent and tetravalent metals and extending the active catalytic reaction range of MOFs. Although in most cases the catalytic activity of MOFs in these reactions has not reached the latest state of the art, we believe this is an important advance in the field as it addresses the question of stability under the reaction conditions.
Cobalt-based MOFs have recently been demonstrated as electrode materials with high activity in OERs. The multi-element heterogeneous metal has remarkable advantages. First, we can increase the active site: increasing the loading, exposing the number of active sites. Secondly, we can increase intrinsic activity: the multi-metal is catalyzed synergistically. Thirdly, the first two are mutually crossed and act together, so that the catalytic activity of the electrode material can be greatly improved.
Through the analysis, although a plurality of preparation methods and applications of the multi-element heterogeneous metal organic framework materials exist in the prior art, researches on the attachment of noble metals iridium trichloride and cobalt nitrate hexahydrate as metal sources and anhydrous sodium acetate as a ligand synthesis precursor on a Ti framework are not available, and relevant disclosures on the superiority and inferiority of the three-element metal MOF are also unavailable.
The invention content is as follows:
aiming at the problems in the prior art, the invention provides controllable preparation and application of a multi-element heterogeneous metal organic framework material.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a multi-element heterogeneous metal organic framework material comprises the following steps:
s101, uniformly mixing an iridium trichloride/ruthenium trichloride mixture and cobalt nitrate hexahydrate as metal sources and anhydrous sodium acetate as a ligand in water at room temperature to obtain brown mixed liquor, namely a precursor;
s102, transferring the precursor into a high-pressure reaction kettle, adding a Ti skeleton, and reacting at 80-150 ℃ for 12-72 hours to finally obtain a mixed product;
s103, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the obtained mixed product to obtain a black precipitate, and purifying the black precipitate to obtain the multi-element heterogeneous metal organic framework material.
In one embodiment according to the present invention, the step S101 further includes: dissolving a proper amount of anhydrous sodium acetate in water to obtain a sodium acetate aqueous solution, then dissolving an iridium trichloride/ruthenium trichloride mixture in a proper amount of water to obtain a metal source aqueous solution, and finally uniformly mixing the sodium acetate aqueous solution and the metal source aqueous solution.
In one embodiment according to the present invention, in the S101 step, the ratio of iridium trichloride/ruthenium trichloride mixture, cobalt nitrate hexahydrate, anhydrous sodium acetate and deionized water is 1: 2-5: 12-30: 100.
in one embodiment according to the invention, the mass ratio of iridium trichloride to ruthenium trichloride in the iridium trichloride/ruthenium trichloride mixture is 1: 0.3-3.
In one embodiment according to the present invention,
in S102, the unitary Ti skeleton is BET up to 3000m2More than g of Ti-MOF.
In S103 according to an embodiment of the present invention, the purification process includes: and centrifuging the obtained black precipitate, washing with water and ethanol sequentially for several times, and drying.
In S103 in one embodiment according to the present invention, the drying treatment includes drying in an oven at 60 to 100 ℃; preferably, the centrifugal rotation speed is 8000-10000 r/min, and the centrifugal time is 5-10 min.
The invention also provides the multi-element heterogeneous metal organic framework material prepared by the preparation method.
The invention further provides application of the multi-element heterogeneous metal organic framework material in preparation of catalysts, electrodes or batteries.
In one embodiment according to the invention, the catalyst is a catalyst for catalytically electrolyzing water to produce hydrogen.
The Ti-MOF provided by the invention has the following beneficial effects:
the Ti skeleton used in the invention has BET of 3000m2More than g of Ti-MOF. The synthesis method of the unitary metal organic framework material is quite mature. The multi-element heterogeneous metal organic framework nano-particle material with ultra-small particle size, controllable morphology, uniform size and large specific surface area is obtained by regulating the feeding ratio of the metal source and the ligand added before the reaction, and is expected to play an important role in wide emerging fields, such as electrocatalysis, fuel cells and the like.
The invention relates to a simple method for hydro-thermally synthesizing a multi-element heterogeneous metal organic framework material, which comprises the steps of dissolving noble metals of iridium trichloride/ruthenium trichloride and cobalt nitrate hexahydrate as metal sources and anhydrous sodium acetate as a ligand in an aqueous solution, uniformly stirring, adding a unitary Ti-MOF framework, and centrifuging and washing an obtained product through a hydro-thermal reaction to obtain a black product, namely the multi-element heterogeneous metal organic framework material. The preparation method of the multi-element heterogeneous metal organic framework material is simple and easy to operate. The multielement heterogeneous metal organic framework material can be obtained through simple hydrothermal reaction. It is expected to play an important role in a wide range of emerging fields, such as electrocatalysis, fuel cells and the like.
Description of the drawings:
FIG. 1 is a flow chart of a method for preparing a multi-element heterogeneous metal organic framework material according to an embodiment of the present invention.
FIG. 2 is an SEM image of the noble metal iridium-doped multi-element heterogeneous metal organic framework material prepared in example 1, and the sample morphology is ultra-small nanoparticles.
FIG. 3 is an SEM image of the precious metal ruthenium-doped multi-element heterogeneous metal organic framework material prepared in example 2, wherein the sample morphology is ultra-small nanoparticles.
FIG. 4 is a graph comparing the performance of the multi-element heterogeneous metal organic framework materials prepared in example 1 and example 2 provided by the present invention.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention more readily understood by those skilled in the art, and thus will more clearly and distinctly define the scope of the invention.
The invention provides a preparation method and application of a multi-element heterogeneous metal organic framework material, and the invention is described in detail with reference to the accompanying drawings.
As shown in fig. 1, the preparation method of the multi-element heterogeneous metal organic framework material provided by the invention comprises the following steps:
s101: noble metal iridium trichloride/ruthenium trichloride and cobalt nitrate hexahydrate are used as metal sources, anhydrous sodium acetate is used as a ligand, and the noble metal iridium trichloride/ruthenium trichloride and the cobalt nitrate hexahydrate are uniformly mixed in an aqueous solution at room temperature to obtain brown mixed liquor, namely a precursor;
s102: pouring the obtained brown mixed solution into a high-pressure reaction kettle, adding a Ti skeleton, and reacting at the temperature of 80-150 ℃ for 12-72 hours to finally obtain a mixture;
s103: and cooling the reacted high-pressure reaction kettle to room temperature, centrifuging the obtained mixture to obtain black precipitate, and washing and drying the precipitate to obtain the multi-element heterogeneous metal organic framework material.
The preparation method of the multi-element heterogeneous metal organic framework material provided by the embodiment of the invention specifically comprises the following steps:
in the first step, 0.05-0.10g of anhydrous sodium acetate is dissolved in 10mL of an aqueous solution. 0.03 to 0.06g of cobalt nitrate hexahydrate and 0.01 to 0.03g of iridium trichloride/0.01 to 0.03g of ruthenium trichloride were dissolved in 10mL of an aqueous solution. The completely dissolved anhydrous sodium acetate is poured into a metal source and stirred uniformly.
Secondly, transferring the prepared precursor into a lining of a reaction kettle, adding a unitary Ti-MOF framework into the lining, rapidly and magnetically stirring for 5-10min at room temperature, transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into a drying oven at the temperature of 80-150 ℃, and keeping for 12-72 h;
and thirdly, cooling the high-pressure reaction kettle to room temperature, centrifuging the product to obtain black precipitate, alternately washing the black precipitate for 2-5 times by using deionized water and ethanol, finally centrifuging and collecting, and drying in an oven at 60-100 ℃ for 6-12 hours to obtain the black product.
In a preferred embodiment of the present invention, in the "one-pot boiling" process in the first step, in the step S101, the ratio of iridium trichloride/ruthenium trichloride, cobalt nitrate hexahydrate, anhydrous sodium acetate and deionized water is 1: 2-5: 12-30: 100.
in the preferred embodiment of the present invention, the solvent is deionized water.
In a preferred embodiment of the present invention, wherein in the centrifugal collection process of the third step, the centrifugal rotation speed is 8000-10000 r/min, and the centrifugal time is 5-10 min.
In a preferred embodiment of the present invention, wherein the magnetic stirring speed in the first step is 8000-10000 rpm.
The preparation method of the multi-element heterogeneous metal organic framework material provided by the invention can also be implemented by adopting other steps by persons skilled in the art, and the preparation method of the multi-element heterogeneous metal organic framework material provided by the invention in fig. 1 is only one specific example.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1: preparing the noble metal iridium-doped multi-element heterogeneous metal organic framework material
First 0.05-0.10g of anhydrous sodium acetate was dissolved in 10mL of an aqueous solution. 0.03 to 0.06g of cobalt nitrate hexahydrate and 0.01 to 0.03g of iridium trichloride were dissolved in 10mL of an aqueous solution. The completely dissolved anhydrous sodium acetate is poured into a metal source and stirred uniformly. Then transferring the prepared precursor into a lining of a reaction kettle, adding a unitary Ti-MOF framework into the lining, rapidly magnetically stirring for 5-10min at room temperature, transferring the mixture into a stainless steel high-pressure reaction kettle, and putting the high-pressure reaction kettle into a drying oven at the temperature of 80-150 ℃ for 12-72 h; and cooling the high-pressure reaction kettle to room temperature, centrifuging the product to obtain a black precipitate, alternately washing the black precipitate for 2-5 times by using deionized water and ethanol, finally centrifuging and collecting, and drying in an oven at 60-100 ℃ for 6-12 hours to obtain a black product.
FIG. 2 is an SEM image of a noble metal iridium-doped multi-element heterogeneous metal organic framework material prepared in example 1 of the invention, and the sample morphology is ultra-small nano-particles.
Example 2: preparing the noble metal ruthenium doped multi-element heterogeneous metal organic framework material according to the invention:
first 0.05-0.10g of anhydrous sodium acetate was dissolved in 10mL of an aqueous solution. 0.03 to 0.06g of cobalt nitrate hexahydrate and 0.01 to 0.03g of ruthenium trichloride were dissolved in 10mL of an aqueous solution. The completely dissolved anhydrous sodium acetate is poured into a metal source and stirred uniformly. Then transferring the prepared precursor into a lining of a reaction kettle, adding a unitary Ti-MOF framework into the lining, rapidly magnetically stirring for 5-10min at room temperature, transferring the mixture into a stainless steel high-pressure reaction kettle, and putting the high-pressure reaction kettle into a drying oven at the temperature of 80-150 ℃ for 12-72 h; and cooling the high-pressure reaction kettle to room temperature, centrifuging the product to obtain a black precipitate, alternately washing the black precipitate for 2-5 times by using deionized water and ethanol, finally centrifuging and collecting, and drying in an oven at 60-100 ℃ for 6-12 hours to obtain a black product.
The properties of the final product obtained were observed, as shown in particular in fig. 3.
FIG. 3 is an SEM image of the precious metal ruthenium-doped multi-element heterogeneous metal organic framework material prepared in example 2, wherein the sample morphology is ultra-small nanoparticles.
Example 3: performance testing
Electrochemical testing of all samples was performed in 1.0M KOH using an electrochemical workstation of a rotating disk electrode system at room temperature. The working electrode on the rotating disk electrode (GC) is made of a multicomponent heterogeneous metal organic framework material. To 5mg of the sample catalyst and 5mg of carbon powder were added 750 μ L of deionized water and 250 μ L of isopropyl alcohol and 40 μ L of Nafion117 solution, and after adding an appropriate amount of zirconium beads, it was transferred to a ball mill to be ball-milled for 24 hours, and then sonicated for 30 minutes to obtain a uniform suspension. Then, 10 μ L of the multinary heterogeneous metal organic frame material was dropped onto the polished GC electrode. Calibration was performed with reference to a reference and converted to a Reversible Hydrogen Electrode (RHE) by a formula.
ERHE＝E(Hg/HgO)+0.89
The rotating disk electrode system was cycled through with a constant temperature water bath system prior to each OER test. To explore the OER activity, linear sweep voltammetry tests were performed at a rate of 5mV/s at a sweep rate of 0V to 0.8V. Electrochemical Impedance Spectroscopy (EIS) measurements were obtained at a voltage of 0.61V and fitted by Zview software. An Hg/HgO electrode in 1M KOH aqueous solution was used as a reference electrode.
The multi-element heterogeneous metal organic framework materials prepared in examples 1 and 2 were respectively subjected to performance tests according to the methods described above, as shown in fig. 4.
FIG. 4 is a graph comparing the performance of the multi-element heterogeneous metal organic framework materials prepared in example 1 and example 2 provided by the present invention. As is obvious from the figure, the electrochemical performance of the ternary iridium-doped noble metal MOF is 10mA/cm2The overpotential at current density of (a) is only 0.195V. The electrochemical performance is very excellent and is obviously superior to that of the ternary ruthenium-doped noble metal MOF.
Compared with the prior art, the method takes iridium trichloride/ruthenium trichloride and cobalt nitrate hexahydrate as metal sources, takes anhydrous sodium acetate as a ligand, adds a Ti framework into an aqueous solution, and prepares the final product, namely the multi-element heterogeneous metal organic framework material by a hydrothermal synthesis method. The results presented in the present invention may provide new opportunities for finding effective electrocatalytic materials for producing hydrogen by electrolyzing water, which have excellent performance and good stability.
The above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements may be made by those skilled in the art within the spirit and principles of the invention. The scope of the invention is to be determined by the appended claims.
Claims (10)
1. A preparation method of a multi-element heterogeneous metal organic framework material is characterized by comprising the following steps:
s101, taking one compound of iridium trichloride and ruthenium trichloride and cobalt nitrate hexahydrate as a metal source, taking anhydrous sodium acetate as a ligand, and uniformly mixing in water at room temperature to obtain brown mixed liquor, namely a precursor;
s102, transferring the precursor into a high-pressure reaction kettle, adding a Ti skeleton, and reacting at 80-150 ℃ for 12-72 hours to finally obtain a mixed product;
s103, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the obtained mixed product to obtain a black precipitate, and purifying the black precipitate to obtain the multi-element heterogeneous metal organic framework material.
2. The method of claim 1, wherein S101 further comprises: dissolving a proper amount of anhydrous sodium acetate in water to obtain a sodium acetate aqueous solution, then dissolving iridium trichloride or ruthenium trichloride in a proper amount of water to obtain a metal source aqueous solution, and finally uniformly mixing the sodium acetate aqueous solution and the metal source aqueous solution.
3. The method according to claim 1, wherein in the step S101, the ratio of iridium trichloride or ruthenium trichloride, cobalt nitrate hexahydrate, anhydrous sodium acetate and water is 1: 2-5: 12-30: 100.
4. the method according to claim 1, wherein in S102, the Ti skeleton is Ti-MOF having BET of 3000m2/g or more.
5. The method according to claim 1, wherein in S103, the purification treatment comprises: and centrifuging the obtained black precipitate, washing with water and ethanol sequentially for several times, and drying.
6. The method according to claim 5, wherein the drying treatment comprises drying in an oven at 60-100 ℃ in S103.
7. The method as set forth in claim 5, wherein the centrifugation is carried out at a centrifugation speed of 8000-10000 rpm for 5-10 min.
8. The preparation method according to any one of claims 1 to 7, wherein the multi-element heterogeneous metal organic framework material is prepared.
9. Use of the heterogeneous metallo-organic framework according to claim 8 for the preparation of catalysts, electrodes or batteries.
10. The use of claim 9, wherein the catalyst is a catalyst for the catalytic electrolysis of water to produce hydrogen.
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