CN112553654B - Preparation method and application of transition metal-based metal-organic framework composite material - Google Patents

Preparation method and application of transition metal-based metal-organic framework composite material Download PDF

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CN112553654B
CN112553654B CN202011415899.5A CN202011415899A CN112553654B CN 112553654 B CN112553654 B CN 112553654B CN 202011415899 A CN202011415899 A CN 202011415899A CN 112553654 B CN112553654 B CN 112553654B
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transition metal
composite material
organic framework
framework composite
based metal
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CN112553654A (en
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叶宝华
薛真洪
张海波
范鹏元
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Dongguan Pulom Electronic Co ltd
Huazhong University of Science and Technology
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Dongguan Pulom Electronic Co ltd
Huazhong University of Science and Technology
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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
    • 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 and application of a transition metal-based metal organic framework composite material, belonging to the field of electrochemical catalysis, wherein the preparation method of the catalytic material comprises the following steps: firstly, silver nitrate is reduced into a silver simple substance by an in-situ reduction method, then an organic ligand and a transition metal source are added, and the transition metal-based organic metal framework composite material is synthesized by a solvothermal method, so that the method improves the poor inherent conductivity of the organic metal framework and shows excellent catalytic performance under an alkaline condition: the internal resistance is reduced by 56.9-97.4%, the hydrogen evolution overpotential can reach 47mV, and the catalyst has ideal stability, can replace commercial platinum carbon under certain conditions, and greatly reduces the required cost.

Description

Preparation method and application of transition metal-based metal-organic framework composite material
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method and application of a transition metal-based metal organic framework composite material.
Background
Hydrogen energy has high energy density and non-pollution properties and can effectively cope with rising energy consumption, increasingly serious environmental problems and the like. And due to the sustainability and no carbon emission, the hydrogen energy is expected to replace fossil energy such as petroleum, coal, natural gas and the like. Electrocatalytic water splitting consisting of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) is considered to be an effective technique for producing high purity hydrogen gas. In order to elucidate the cost-effective HER performance of electrolytic generation in acidic electrolytes, great efforts have been made to prepare high performance electrocatalysts to reduce dynamic overpotentials. Even less material is used for HER in alkaline solutions, which need to be able to overcome higher energy barriers compared to acidic electrolytes.
In recent years, Metal Organic Frameworks (MOFs), especially two-dimensional (2D) MOF nanosheets, have gained widespread attention in various fields such as gas adsorption/separation, catalysis, and sensors due to their high specific surface area and easy-to-use function. As electrocatalysts, MOFs are commonly used as precursor materials for the immobilization of other active guest substances due to their poor electrical conductivity. In view of the above problems, the design and construction of a bottom-up approach from a MOF architecture with open and strong three-dimensional (3D) would be one of the best solutions to the above problems by enhancing its electrical conductivity through simple guest metal introduction.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a transition metal-based metal-organic framework composite material and the application thereof; the second purpose is to provide a transition metal-based metal-organic framework composite material; the third purpose is to provide the application of the catalytic material in electrocatalytic hydrogen evolution reaction in alkaline solution.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a transition metal-based metal organic framework composite material comprises the following steps:
1) dissolving a proper amount of silver nitrate in a beaker filled with deionized water, adding excessive sodium borohydride after uniformly stirring, standing for 12 hours, centrifugally cleaning to obtain a precipitate, and drying the precipitate in vacuum for later use.
2) Dissolving a certain amount of organic ligand in a beaker A filled with N, N-dimethylformamide and absolute ethyl alcohol, uniformly stirring, dissolving a proper amount of transition metal source in a beaker B filled with deionized water and absolute ethyl alcohol, uniformly stirring and ultrasonically dispersing, then dropwise adding the solution in the beaker A while stirring the solution in the beaker B, then adding a proper amount of silver simple substance, uniformly stirring, then transferring to a stainless steel reaction kettle, reacting at the temperature of 160 ℃ and 200 ℃ for 12-24h, centrifuging to obtain precipitate, washing the precipitate, and drying in vacuum to obtain the transition metal-based metal organic framework composite material; the mass ratio of the transition metal source to the organic ligand to the silver simple substance is 1-10: 1-5: 0.1-1.
Preferably, in the step 2), the solution in the beakers A and B is mixed in the order that the solution in the beaker A is added dropwise into the beaker B.
Preferably, in the step 2), the stirring dispersion is specifically stirring for 20-30min under the conditions that the magnetic stirring speed is 200-500r/min and the temperature is 25-35 ℃; the ultrasonic dispersion is specifically ultrasonic for 10-60min under the conditions that the ultrasonic power is 80-100W and the ultrasonic frequency is 20-40 Hz.
Preferably, the centrifugation is specifically performed at the speed of 8000-12000r/min for 3-5 min; the vacuum drying is specifically drying for 6-24h under the conditions that the pressure is 0.08-0.10MPa and the temperature is 50-80 ℃.
Preferably, in the step 2), the transition metal source is one of iron salt, cobalt salt, nickel salt and zinc salt; the organic ligand is one of nitrogen heterocyclic ligands and organic carboxylic acid ligands.
In a second aspect, the invention provides a transition metal-based metal-organic framework composite material prepared by the method.
In a third aspect, the invention provides an electrochemical catalytic system, which comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, and is characterized in that the surface of the working electrode is coated with the transition metal-based metal-organic framework composite material.
Preferably, the working electrode is prepared as follows:
dispersing the transition metal-based metal organic framework composite material in water according to the proportioning concentration of 5mg/mL, adding a proper amount of Nafion solution to obtain an electrode modification solution, coating the electrode modification solution on a working electrode, and naturally airing.
Preferably, the amount of the catalytic material loaded with the working electrode is 0.20-0.25 mg-cm-2.
Preferably, the mass fraction of Nafion in the Nafion solution is 0.05%.
The invention provides the application of the electrochemical catalytic system in the electrocatalytic hydrogen evolution under the condition of alkaline solution.
The invention has the beneficial effects that: the invention provides a preparation method and application of a transition metal-based metal organic framework composite material, and belongs to the field of electrochemical catalysis. The invention combines a firm three-dimensional (3D) metal organic framework system structure and introduces guest metal silver with excellent conductivity to make up the defect of poor inherent conductivity of the metal organic framework, and the synthesized transition metal-based metal organic framework composite material has ideal catalytic stability and excellent hydrogen evolution performance under alkaline conditions.
Specifically, when the transition metal-based metal organic framework composite material is prepared, by introducing guest metal silver with excellent conductivity and reasonably selecting the types and the dosage of a metal source and an organic ligand and synthesis conditions, the finally prepared transition metal-based metal organic framework composite material has the advantages that in the electrocatalytic hydrogen evolution reaction, the internal resistance of the catalyst is reduced by 56.9-97.4% compared with a single transition metal-based metal organic framework, the hydrogen evolution over-potential can reach 47mV, the ideal stability is realized, commercial platinum and carbon can be replaced under certain conditions, and the required cost is greatly reduced.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
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In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings, in which:
FIG. 1 is an X-ray powder diffraction pattern (XRD) of example 2, example 4, example 6 and example 8;
FIG. 2 is a Scanning Electron Microscope (SEM) image of examples 1 and 2; (wherein a in FIG. 2 is an SEM picture of Ni-MOF, and b in FIG. 2 is an SEM picture of Ag/Ni-MOF)
FIG. 3 is an X-ray spectral analysis (EDS) of example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) image of examples 3 and 4; (wherein a in FIG. 4 is an SEM picture of Fe-MOF, and b in FIG. 4 is an SEM picture of Ag/Fe-MOF)
FIG. 5 is an X-ray spectral analysis (EDS) of example 4;
FIG. 6 is a Scanning Electron Microscope (SEM) image of examples 5 and 6; (wherein a in FIG. 6 is an SEM picture of Co-MOF, and b in FIG. 6 is an SEM picture of Ag/Co-MOF)
FIG. 7 is an X-ray spectral analysis (EDS) of example 6;
FIG. 8 is a Scanning Electron Microscope (SEM) image of examples 7 and 8; (wherein a in FIG. 8 is an SEM picture of Zn-MOF, and b in FIG. 8 is an SEM picture of Ag/Zn-MOF)
FIG. 9 is an X-ray spectral analysis (EDS) chart of example 8;
FIG. 10 is a graph comparing the hydrogen evolution linear scan profile (LSV) of LSVs of examples 1 and 2 and commercial platinum carbon;
FIG. 11 is a graph comparing the hydrogen evolution linear scan profiles (LSVs) of the LSVs of examples 3 and 4;
FIG. 12 is a graph comparing the hydrogen evolution linear scan profiles (LSVs) of the LSVs of examples 5 and 6;
FIG. 13 is a graph comparing the hydrogen evolution linear scan profiles (LSVs) of the LSVs of examples 7 and 8;
FIG. 14 is a graph of Electrochemical Impedance Spectroscopy (EIS) and comparison of example 1, example 2, example 3, example 4, example 5, example 6, example 7 and example 8; (wherein a in FIG. 14 is a graph showing a comparison between EIS of examples 1 and 2, b in FIG. 14 is a graph showing a comparison between EIS of examples 3 and 4, c in FIG. 14 is a graph showing a comparison between EIS of examples 5 and 6, and d in FIG. 14 is a graph showing a comparison between EIS of examples 7 and 8)
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of transition Metal-based Metal organic frameworks (Ni-MOF)
Dissolving organic ligand trimesic acid in a beaker A filled with N, N-dimethylformamide and absolute ethyl alcohol, and dissolving transition metal source nickel chloride hexahydrate in a beaker B filled with deionized water and absolute ethyl alcohol;
stirring A and B by magnetic force at the rotation speed of 500r/min at the temperature of 30 ℃ for 20min, and then performing ultrasonic dispersion at the ultrasonic power of 80W and the ultrasonic frequency of 40Hz for 20 min;
then dropwise adding the solution in the beaker A while stirring the solution in the beaker B, uniformly stirring and dispersing the mixed solution, transferring the mixed solution into a stainless steel reaction kettle, reacting for 12 hours at 180 ℃, centrifuging to obtain a precipitate, washing the precipitate, and drying in vacuum for 12 hours at 60 ℃ to obtain a transition metal-based metal organic framework;
the mass ratio of the nickel chloride hexahydrate to the trimesic acid is 5.6: 1.2.
Example 2
Preparation of transition Metal-based Metal-organic framework composite (Ag/Ni-MOF)
1) Dissolving a proper amount of silver nitrate in a beaker filled with deionized water, adding excessive sodium borohydride after uniformly stirring, standing for 12 hours, centrifugally cleaning to obtain a precipitate, and drying the precipitate at 60 ℃ in vacuum for later use.
2) Dissolving organic ligand trimesic acid in a beaker A filled with N, N-dimethylformamide and absolute ethyl alcohol, and dissolving transition metal source nickel chloride hexahydrate in a beaker B filled with deionized water and absolute ethyl alcohol;
stirring A and B by magnetic force at the rotation speed of 500r/min at the temperature of 30 ℃ for 20min, and then performing ultrasonic dispersion at the ultrasonic power of 80W and the ultrasonic frequency of 40Hz for 20 min;
then dropwise adding the solution in the beaker A while stirring the solution in the beaker B, adding the silver simple substance prepared in the step 1) into the mixed solution, uniformly stirring and dispersing, transferring the mixed solution into a stainless steel reaction kettle, reacting at 180 ℃ for 12 hours, centrifuging to obtain a precipitate, washing the precipitate, and vacuum-drying at 60 ℃ for 12 hours to obtain the transition metal-based metal organic framework composite material;
the mass ratio of the nickel chloride hexahydrate to the trimesic acid to the silver simple substance is 5.6:1.2: 0.1.
Example 3
Preparation of transition Metal-based Metal organic frameworks (Fe-MOF)
The procedure was similar to example 1, except that the transition metal source was anhydrous ferric chloride.
Example 4
Preparation of transition Metal-based Metal organic frameworks (Ag/Fe-MOF)
The procedure was similar to that of example 2, except that the transition metal source was anhydrous ferric chloride.
Example 5
Preparation of transition Metal-based Metal organic frameworks (Co-MOF)
The procedure was similar to example 1 except that the transition metal source was cobalt chloride hexahydrate.
Example 6
Preparation of transition Metal-based Metal organic frameworks (Ag/Co-MOF)
The procedure was similar to example 2, except that the transition metal source was cobalt chloride hexahydrate.
Example 7
Preparation of transition Metal-based Metal organic frameworks (Zn-MOF)
The procedure was similar to example 1, except that the transition metal source was zinc chloride.
Example 8
Preparation of transition Metal-based Metal organic frameworks (Ag/Zn-MOF)
The procedure was similar to example 2, except that the transition metal source was zinc chloride.
Example 9
When the XRD phase analysis was performed on example 2, example 4, example 6 and example 8, it can be seen from fig. 1 that the silver element was successfully doped into the four transition metal-based metal-organic frameworks.
Example 10
SEM topography analysis and EDS elemental analysis are carried out on the embodiment 1, the embodiment 2, the embodiment 3, the embodiment 4, the embodiment 5, the embodiment 6, the embodiment 7 and the embodiment 8, and the prepared materials are different in topography and show two-dimensional or three-dimensional structures according to the graphs in FIGS. 2, 4, 6 and 8, and the obvious change of the topography after the silver simple substance is doped indicates that the transition metal-based metal organic framework composite material is successfully prepared; from fig. 3, 5, 7 and 9, the EDS elemental analysis showed results consistent with XRD, with successful incorporation of elemental silver into the transition metal-based organometallic framework.
Example 11
Preparing an electrochemical catalytic material and a working electrode coated with the material, and constructing an electrochemical catalytic hydrogen evolution system.
1) The catalytic materials prepared in example 1, example 2, example 3, example 4, example 5, example 6, example 7 and example 8 were dispersed in water at a stoichiometric concentration of 5mg to obtain an electrode modification solution, which was applied to a working electrode at a loading of 0.21 mg-cm-2And coating 3 mu L of Nafion solution after drying, and drying again.
2) Assembling the working electrode coated with the nickel-metal organic framework catalytic material on the surface, which is prepared in the step 1), with an electrochemical workstation, a counter electrode (carbon rod), a reference electrode (Ag/AgCl electrode), an electrolytic cell and electrolyte (1MKOH) to form an electrochemical catalytic hydrogen evolution system.
Example 12
The working electrode prepared in example 11 was subjected to a hydrogen evolution test to obtain a hydrogen evolution linear scanning curve diagram in fig. 10, and it can be seen from fig. 10 that the catalytic hydrogen evolution performance of the transition metal-based metal organic framework is greatly improved after the silver element is doped: initial potential (i.e., current density of-1 mA cm)-2Potential) of 175-387 mV and at-10 mA/cm current density-2When the voltage is over-potential, the over-potential is shifted by 197-512 mV. The performance of Ag/Ni-MOF is comparable to that of commercial platinum carbon, and the Ag/Ni-MOF can replace the commercial platinum carbon to a certain extent, so that the required cost is greatly reduced.
Example 13
The working electrode prepared in example 11 was subjected to an electrochemical impedance test, whereby it was further demonstrated whether the introduction of elemental silver served to improve the poor conductivity inherent to the transition metal-based metal-organic framework. From fig. 11, the conductivity of the transition metal-based metal-organic framework is greatly improved after the silver simple substance is introduced, the internal resistance is reduced by 173-755 Ω, and the reduction rate is 56.9-97.4%. It is further proved that the conductivity of the metal is enhanced by simple and convenient introduction of guest metals, and the design and construction of a three-dimensional (3D) MOF system structure with opening and firmness from bottom to top is one of the best schemes for solving the problems of insufficient conductivity and poor electrocatalytic performance of a metal organic framework.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The invention is not the best known technology.

Claims (9)

1. The preparation method of the transition metal-based metal organic framework composite material is characterized by comprising the following steps:
1) dissolving a certain amount of silver nitrate in a beaker filled with deionized water, adding excessive sodium borohydride after uniformly stirring, standing for 6-12h, centrifugally cleaning to obtain a precipitate, and drying the precipitate in vacuum for later use to obtain simple substance silver;
2) dissolving a certain amount of organic ligand in a beaker A filled with N, N-dimethylformamide and absolute ethyl alcohol, uniformly stirring, dissolving a proper amount of transition metal source in a beaker B filled with deionized water and absolute ethyl alcohol, uniformly stirring and ultrasonically dispersing, then dropwise adding the solution in the beaker A while stirring the solution in the beaker B, uniformly stirring, then adding a proper amount of precipitate in 1), transferring to a stainless steel reaction kettle, reacting at 160-;
wherein the mass ratio of the transition metal source, the organic ligand and the silver simple substance in the step 2) is 1-10: 1-5: 0.1-1.
2. The method for preparing a transition metal-based metal-organic framework composite material according to claim 1, wherein in the step 2), the solution in the beakers A and B is mixed in a sequence that the solution in the beaker A is dripped into the beaker B.
3. The method for preparing a transition metal-based metal-organic framework composite material as claimed in claim 1, wherein in the step 2), the stirring dispersion is specifically performed by stirring at a magnetic stirring rotation speed of 200-; the ultrasonic dispersion is specifically ultrasonic for 10-60min under the conditions that the ultrasonic power is 80-100W and the ultrasonic frequency is 20-40 Hz.
4. The method for preparing a transition metal-based metal-organic framework composite material as claimed in claim 1, wherein the centrifugation is specifically performed at a speed of 8000- > 12000r/min for 3-5 min; the vacuum drying is specifically drying for 6-24h under the conditions that the pressure is 0.08-0.10MPa and the temperature is 50-80 ℃.
5. The method for preparing a transition metal-based metal-organic framework composite material according to any one of claims 1 to 4, wherein the transition metal source is one of iron salt, cobalt salt, nickel salt, zinc salt; the organic ligand is one of nitrogen heterocyclic ligands and organic carboxylic acid ligands.
6. A transition metal-based metal-organic framework composite prepared according to the method of any one of claims 1-5.
7. An electrochemical catalytic system comprising an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, wherein the surface of the working electrode is coated with the transition metal-based metal-organic framework composite of claim 6.
8. An electrochemical catalytic system according to claim 7, wherein the working electrode is prepared by:
dispersing the transition metal-based metal-organic framework composite material of claim 6 in water at a concentration of 5mg/mL, and adding a proper amount of Nafion solution to obtainAn electrode modification solution applied to a working electrode, wherein the loading amount is 0.20-0.25 mg-cm-2And naturally drying the mixture.
9. An electrochemical catalytic system according to claim 7, for electrocatalytic hydrogen evolution in alkaline solution conditions.
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CN113930782B (en) * 2021-09-24 2023-06-20 南京信息工程大学 Preparation method and application of self-supporting electrode
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