CN108080034B - Preparation method and application of nickel-based three-dimensional metal organic framework catalyst - Google Patents
Preparation method and application of nickel-based three-dimensional metal organic framework catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a nickel-based three-dimensional metal organic framework catalyst and application of the catalyst in electrolysis of water and oxygen evolution, and belongs to the technical field of nano materials, nano catalysis and metal organic framework materials. The method mainly comprises the steps of electrodepositing polyaniline on foamed nickel to prepare the Ni @ PANI composite material; ligand H3Coating a gel prepared from TATAB and cobalt nitrate on the Ni @ PANI composite material, and heating in air atmosphere to prepare Ni @ Co2O3The catalyst is a nickel-based three-dimensional metal-organic framework catalyst. The catalyst has the advantages of low cost of raw materials for preparation, simple preparation process, low reaction energy consumption and industrial application prospect. The catalyst is used for efficiently catalyzing electrolysis water to generate oxygen, and has good oxygen generation electrocatalytic activity and electrochemical stability.
Description
Technical Field
The invention relates to a preparation method of a nickel-based three-dimensional metal organic framework catalyst and application of the catalyst in electrolysis of water and oxygen evolution, and belongs to the technical field of nano materials, nano catalysis and metal organic framework materials.
Background
With the rapid development of social economy and the increasing world population, air pollution and global climate change caused by the combustion of fossil fuels become increasingly concerned, and effective electrochemical energy conversion and storage technologies such as fuel cells, metal-air storage batteries, and electrolyzed water have become more and more significant. In order to meet the requirements of new energy consumption and improvement of the existing population life quality, sustainable clean energy carriers are urgently sought in all countries in the world. Electrocatalytic direct decomposition of water to produce hydrogen is considered an effective way to achieve this process. The electrocatalytic water splitting reaction includes two half reactions of Hydrogen Evolution (HER) and Oxygen Evolution (OER), and in these energy-based applications, the electrochemical Oxygen Evolution (OER) is an important process. Oxygen Evolution Reactions (OERs) are key links in many energy storage and conversion fields, such as water pyrolysis oxygen evolution, regenerative fuel cells, rechargeable metal gas cells. Because of the inherent high energy barrier, the oxygen evolution reaction needs an acid-resistant or alkali-resistant high-efficiency electrocatalyst, and is also the core process of a metal-air battery and a hydrolysis device, and the reaction kinetics is slow, so the development of the high-efficiency OER electrocatalyst becomes a research hotspot in the field. However, the intrinsic energy loss of the system from three aspects of resistance, reaction and transmission, and the factors of price, activity and stability of the existing catalyst greatly limit the popularization and wide application of the catalyst. Therefore, the novel oxygen evolution electrocatalyst which is cheap and easy to obtain and has stable performance is searched, and the method has wide and important practical significance for long-term development of hydrogen energy, reduction of environmental pollution and even alleviation of energy problems in the world.
Among many of the systems explored, iridium dioxide (IrO)2) And ruthenium dioxide (RuO)2) Is considered most effective. However, their scarce and expensive prices limit their wide practical application, and for this reason, it is an opportunity and challenge to develop efficient, inexpensive, and earth-rich non-noble metal oxygen evolution catalysts to reduce the consumption of oxygen evolution electricity.
Inexpensive iron, cobalt, nickel catalysts are promising catalysts for achieving high activity oxygen evolution. In addition, the composite material with heteroatom doping carried by base materials such as foamed nickel or carbon cloth is also an innovative choice of the oxygen evolution catalyst. In addition to the material composition, the activity of the catalyst and its morphology are closely related. Therefore, research and development of new compositions and new catalysts with rich resources have important significance for realizing high-activity oxygen evolution.
As a new class of porous crystalline materials, Metal Organic Frameworks (MOFs) have recently gained wide application in the fields of gas storage, separation, catalysis, identification, drug delivery, and the like. 8.6.2017, Sinkiang professor of Nanjing aerospace university, Zhang school just professor, XuGuiyin doctor, etc. [ E ] inxploring metal organic frameworks forenergy storage in batteries and supercapacitors.Mater.Today,2017,20,191-209.]The application of MOFs in lithium ion batteries, sodium ion batteries, lithium sulfur batteries, lithium selenium batteries, lithium oxygen batteries and super capacitors is introduced. The periodic porous structure, high specific surface area and structural diversity of MOFs offer unique advantages for the construction of carbon or (and) metal-based nanomaterials with them as precursors. Currently, there is an increasing research on functional materials derived from MOFs precursors or templates, for example, porous carbon, metal oxide, metal/carbon and metal oxide/carbon nanomaterials have been reported, and the constructed 3D metal oxides, used for high-efficiency supercapacitors, lithium ion batteries and oxygen reduction, have exhibited excellent properties. One innovative strategy that is currently being adopted is to load MOFs with nanocarbon materials such as graphene and multi-walled Carbon Nanotubes (CNTs), and then prepare carbon-based composite electrocatalysts through high-temperature pyrolysis to prevent product agglomeration and increase the specific surface area thereof. Although many kinds of MOFs exist, the number of the electrocatalysts MOFs precursor which is easy to prepare and can be converted into controllable forms is limited, and the addition of polyaniline can improve the performance of the MOF material in heterogeneous nucleation on base materials such as foamed nickel or carbon cloth and the like, and is beneficial to the generation of MOF on the surface of the base materials and the matching of metal atoms. In 2016, professor Ligaoren of Zhongshan university and team thereof initially report that NF @ NC-CoFe is synthesized by pyrolyzing bimetallic MOFs through polyaniline-assisted one-step method2O4Method of/C nanorod array [ Bimetallic-Organic Framework removed CoFe2O4/C Porous Hybrid NanorodArrays as High-Performance Electrocatalysts for Oxygen EvolutionReaction.Advanced Materials.,2017,29:4437-4444.](ii) a The paper firstly deposits a layer of polyaniline on the surface of foamed nickel by an electrochemical deposition method, then grows MOF-74-Co/Fe nano-rod arrays on the surface of the foamed nickel by a hydrothermal method, and finally obtains CoFe by a one-step method of pyrolysis in nitrogen atmosphere2O4The porous composite/C nanorod array avoids the consumption of carbon materials and the structural damage during secondary air treatment. The paper also indicates that polyaniline deposited on the surface of the foamed nickel plays a role in capturing transition metal ions and inducing crystal growth orientationFor the purpose of this pyrogenically obtained CoFe2O4the/C nanorod array has good electrochemical oxygen evolution activity and good stability.
The development of a one-step room temperature process, the preparation of the nickel-based MOF composite material containing polyaniline by using foamed nickel as a base material and the pyrolysis of the composite material in air by using the foamed nickel as a precursor have important significance in preparing the nickel-based transition metal oxide high-efficiency catalyst with high cost performance.
Disclosure of Invention
One of the technical tasks of the invention is to make up the defects of the prior art, and provide a preparation method of a nickel-based three-dimensional metal organic framework catalyst, namely a nickel-based cobalt oxide composite catalyst.
The second technical task of the invention is to provide the application of the nickel-based three-dimensional metal organic framework catalyst, namely, the nickel-based cobalt oxide composite material is used for efficiently catalyzing electrolysis water to generate oxygen, and the catalyst has good oxygen generation electrocatalytic activity and electrochemical stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. a preparation method of a nickel-based three-dimensional metal organic framework catalyst comprises the following steps:
placing activated foam nickel with the area of 0.5cm multiplied by 1cm into a mixed solution consisting of 10mL of water, 0.270-0.290g of sodium sulfate and 40-52 mu L of aniline, and carrying out electrodeposition for 25-35min to prepare a composite material of polyaniline loaded on the foam nickel, namely a Ni @ PANI composite material;
mixing 0.045-0.055g H3Dissolving the L ligand in a mixed solution of 1mL of DMF, 0.2mL of absolute ethyl alcohol and 0.1mL of water, adding 0.025-0.035g of cobalt nitrate, and performing ultrasonic treatment to obtain Co (II) -MOF gel;
uniformly coating 12-15 mu L of Co (II) -MOF gel on the Ni @ PANI composite material, placing the composite material in a tubular furnace, heating the composite material to 230-270 ℃ at a temperature rise rate of 2 ℃/min under an air atmosphere, preserving heat for 2h, and then cooling the composite material to room temperature at a temperature fall rate of 2 ℃/min; to obtain Ni @ Co2O3Composite catalysis of/CNAgents, i.e. catalysts based on nickel-based three-dimensional metal-organic frameworks.
The activated foam nickel is prepared by sequentially performing ultrasonic treatment on the foam nickel in acetone, absolute ethyl alcohol and distilled water for 2-4min, washing to remove surface impurities, and then soaking the foam nickel in 37-43% nitric acid by mass fraction for ultrasonic treatment for 1 min.
The electrodeposition adopts constant potential deposition, takes foam nickel as a counter electrode, a platinum sheet as a working electrode and a silver/silver chloride reference electrode, the constant potential is 0.6V, and the deposition time is 20-35 min; in the electrodeposition process, aniline is subjected to electrodeposition, oxidation and polymerization at an anode to obtain polyaniline, and the structural formula of the polyaniline is as follows:
said H3An L ligand, herein termed 4,4',4 ″ - (triazine-1, 3, 5-triamino) -tribenzoic acid, having the structural formula:
said H3The preparation method of the L ligand comprises the following steps: adding 20mL of aqueous solution containing 16mmol of sodium hydroxide and 5mL of dioxane solution containing 3mmol of cyanuric chloride into 14mmol of 4-aminobenzoic acid under stirring, heating and refluxing for 10H, adjusting pH to 2-3 with hydrochloric acid, vacuum filtering, washing the filtered solid with water for three times to obtain H3L, yield 88%.
The Co (II) -MOF has a chemical formula of [ [ Co ]2L(OH)(H2O)2]·H2O·0.6O]nOne structural unit of the material consists of 2 Co (II) positive ions, 1L (III) negative ions, 1 OH (I) negative ions and 2 host water molecules, 1 object water molecule and 0.6 oxygen atom.
The Ni @ Co2O3the/CN composite catalyst is foam nickel loaded nanometer Co2O3And SP2The hybrid nitrogen codoped with the composite on the graphitic carbon matrix.
2. The application of the nickel-based three-dimensional metal organic framework catalyst prepared by the preparation method as the electrolytic water oxygen evolution catalyst comprises the following steps:
clamping foamed nickel loaded with the Co (II) -MOF catalyst by using a copper clamp to prepare a Co (II) -MOF-based catalyst working electrode;
using a three-electrode electrochemical workstation, with a co (ii) -MOF based catalyst as the working electrode, a Pt sheet (5mm x 0.1mm) as the counter electrode, an Ag/AgCl electrode as the reference electrode, the electrocatalytic decomposition performance was tested in an aqueous solution with 0.5M KOH as the electrolyte;
when the current density J is 5mA/cm, the nickel-based three-dimensional metal organic framework catalyst is used for electrolyzing water to generate oxygen2When the potential is 1.39V (vs RHE); when the current density J is 10mA/cm2When the potential is 1.55V (vs RHE), the high-efficiency oxygen evolution catalytic activity of the material is shown; before and after 500 times of circulation, no obvious change is found in the polarization curve of the material, which indicates that the catalyst has good stability.
The invention has the beneficial technical effects that:
1. the nickel-based three-dimensional metal organic framework catalyst prepared by the invention is generated by heating and pyrolyzing a metal organic framework Co (II) -MOF in an air atmosphere, and the preparation process is simple, simple and easy to control, high in product preparation efficiency and easy to industrialize.
2. The nickel-based three-dimensional metal organic framework catalyst prepared by the invention is Ni @ Co2O3the/CN composite catalyst is foam nickel loaded nanometer Co2O3And SP2The hybrid nitrogen codoped with the composite on the graphitic carbon matrix. Graphite carbon matrix confines Co2O3So that Co grows2O3The particle size of the semiconductor nano particles is not more than 30nm, more and different active sites are exposed, the nitrogen codoping on the graphite carbon substrate synergistically enhances the electric conduction and oxygen evolution catalytic performance, and the catalytic efficiency is high and the stability is good.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples, and modifications made by those skilled in the art to the technical solutions of the present invention should fall within the scope of the present invention.
Example 1 preparation method of nickel-based three-dimensional metal organic framework
Placing activated foam nickel with the area of 0.5cm multiplied by 1cm into a mixed solution consisting of 10mL of water, 0.270g of sodium sulfate and 40 mu L of aniline, and electrodepositing for 25min to prepare a composite material of polyaniline loaded on the foam nickel, namely a Ni @ PANI composite material;
0.045g H3Dissolving the L ligand in a mixed solution of 1mL of DMF, 0.2mL of absolute ethyl alcohol and 0.1mL of water, adding 0.025g of cobalt nitrate, and performing ultrasonic treatment to obtain Co (II) -MOF gel;
uniformly coating 12 mu L of Co (II) -MOF gel on the Ni @ PANI composite material, placing the composite material in a tube furnace, heating the composite material to 230 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving the heat for 2h, and then cooling the composite material to room temperature at the cooling rate of 2 ℃/min; to obtain Ni @ Co2O3The catalyst is a nickel-based three-dimensional metal-organic framework catalyst;
the activated foam nickel is prepared by sequentially performing ultrasonic treatment on the foam nickel in acetone, absolute ethyl alcohol and distilled water for 2min, washing to remove surface impurities, and then soaking the foam nickel in 37 mass percent nitric acid for ultrasonic treatment for 1 min;
the electrodeposition adopts constant potential deposition, takes foam nickel as a counter electrode, a platinum sheet as a working electrode and a silver/silver chloride reference electrode, the constant potential is 0.6V, and the deposition time is 20 min; in the electrodeposition process, aniline is subjected to electrodeposition, oxidation and polymerization at an anode to obtain polyaniline, and the structural formula of the polyaniline is as follows:
the Co (II) -MOF has a chemical formula of [ [ Co ]2L(OH)(H2O)2]·H2O·0.6O]nOne structural unit of the material consists of 2 Co (II) positive ions, 1L (III) negative ions, 1 OH (I) negative ions and 2 host water molecules, 1 object water molecule and 0.6 oxygen atom.
The Ni @ Co2O3the/CN composite catalyst is foam nickel loaded nanometer Co2O3And SP2The hybrid nitrogen codoped with the composite on the graphitic carbon matrix.
Example 2 preparation method of nickel-based three-dimensional metal organic framework
Placing activated foam nickel with area of 0.5cm × 1cm in mixed solution composed of 10mL water, 0.290g sodium sulfate and 52 μ L aniline, electrodepositing for 35min to obtain polyaniline-loaded composite material, i.e. Ni @ PANI composite material, and mixing the above materials, 0.055g H3Dissolving the L ligand in a mixed solution of 1mL of DMF, 0.2mL of absolute ethyl alcohol and 0.1mL of water, adding 0.035g of cobalt nitrate, and performing ultrasonic treatment to obtain Co (II) -MOF gel;
uniformly coating 15 mu L of Co (II) -MOF gel on the Ni @ PANI composite material, placing the composite material in a tube furnace, heating to 270 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving the heat for 2h, and then cooling to the room temperature at the cooling rate of 2 ℃/min; to obtain Ni @ Co2O3The catalyst is a nickel-based three-dimensional metal-organic framework catalyst;
the activated foam nickel is prepared by sequentially performing ultrasonic treatment on the foam nickel in acetone, absolute ethyl alcohol and distilled water for 2-4min, washing to remove surface impurities, and then soaking the foam nickel in 43% nitric acid in percentage by mass for ultrasonic treatment for 1 min;
the electrodeposition adopts constant potential deposition, takes foam nickel as a counter electrode, a platinum sheet as a working electrode and a silver/silver chloride reference electrode, the constant potential is 0.6V, and the deposition time is 35 min; in the electrodeposition process, aniline is subjected to electrodeposition, oxidation and polymerization at an anode to obtain polyaniline, and the structural formula of the polyaniline is as follows:
the Co (II) -MOF has a chemical formula of [ [ Co ]2L(OH)(H2O)2]·H2O·0.6O]nOne structural unit of the water purification device consists of 2 Co (II) positive ions, 1L (III) negative ions, 1 OH (I) negative ions and 2 host water molecules, and 1 guest waterMolecule and 0.6 oxygen atom.
The Ni @ Co2O3the/CN composite catalyst is foam nickel loaded nanometer Co2O3And SP2The hybrid nitrogen codoped with the composite on the graphitic carbon matrix.
Example 3 preparation method of nickel-based three-dimensional metal-organic framework catalyst
Placing activated foam nickel with area of 0.5cm × 1cm in mixed solution composed of 10mL water, 0.280g sodium sulfate and 46 μ L aniline, electrodepositing for 30min to obtain polyaniline-loaded composite material, i.e. Ni @ PANI composite material, and mixing the mixture with 0.050g H3Dissolving the L ligand in a mixed solution of 1mL of DMF, 0.2mL of absolute ethyl alcohol and 0.1mL of water, adding 0.030g of cobalt nitrate, and performing ultrasonic treatment to obtain Co (II) -MOF gel;
uniformly coating 14 mu L of Co (II) -MOF gel on the Ni @ PANI composite material, placing the composite material in a tube furnace, heating to 250 ℃ at the heating rate of 2 ℃/min under the air atmosphere, preserving the heat for 2h, and then cooling to the room temperature at the cooling rate of 2 ℃/min; to obtain Ni @ Co2O3The catalyst is a nickel-based three-dimensional metal-organic framework catalyst;
the activated foam nickel is prepared by sequentially performing ultrasonic treatment on the foam nickel in acetone, absolute ethyl alcohol and distilled water for 3min, washing to remove surface impurities, and then soaking the foam nickel in nitric acid with the mass fraction of 40% for ultrasonic treatment for 1 min;
the electrodeposition adopts constant potential deposition, takes foam nickel as a counter electrode, a platinum sheet as a working electrode and a silver/silver chloride reference electrode, the constant potential is 0.6V, and the deposition time is 25 min; in the electrodeposition process, aniline is subjected to electrodeposition, oxidation and polymerization at an anode to obtain polyaniline, and the structural formula of the polyaniline is as follows:
the Co (II) -MOF has a chemical formula of [ [ Co ]2L(OH)(H2O)2]·H2O·0.6O]nOne structural unit is composed of 2 Co (II) positive ions, 1L (III) negative ions and 1OH (I) negative ions, 2 host water molecules, 1 object water molecule and 0.6 oxygen atom.
The Ni @ Co2O3the/CN composite catalyst is foam nickel loaded nanometer Co2O3And SP2The hybrid nitrogen codoped with the composite on the graphitic carbon matrix.
Example 4 examples 1-3 described for H3Process for preparing L ligands
Adding 20mL of aqueous solution containing 16mmol of sodium hydroxide and 5mL of dioxane solution containing 3mmol of cyanuric chloride into 14mmol of 4-aminobenzoic acid under stirring, heating and refluxing for 10H, adjusting pH to 2-3 with hydrochloric acid, vacuum filtering, washing the filtered solid with water for three times to obtain H3L, yield 88%; said H3An L ligand, herein termed 4,4',4 ″ - (triazine-1, 3, 5-triamino) -tribenzoic acid, having the structural formula:
example 5 use of Co- (II) -MOF-based catalyst as oxygen evolution catalyst for the electrolysis of water
Clamping foamed nickel loaded with the Co (II) -MOF catalyst by using a copper clamp to prepare a Co (II) -MOF-based catalyst working electrode;
the electrocatalytic decomposition performance of water was tested in an aqueous solution of 0.5M KOH as electrolyte using a three-electrode electrochemical workstation, the co (ii) -MOF based catalyst prepared in example 1, example 2 or example 3 as working electrode, Pt sheet (5mm x 0.1mm) as counter electrode, Ag/AgCl electrode as reference electrode;
when the current density J is 5mA/cm, the nickel-based three-dimensional metal organic framework catalyst is used for electrolyzing water to generate oxygen2When the potential is 1.39V (vs RHE); when the current density J is 10mA/cm2When the potential is 1.55V (vs RHE), the high-efficiency oxygen evolution catalytic activity of the material is shown; before and after 500 times of circulation, no obvious change is found in the polarization curve of the material, which indicates that the catalyst has good stability.
Claims (4)
1. A preparation method of a nickel-based three-dimensional metal organic framework based catalyst is characterized by comprising the following steps:
placing activated foam nickel with the area of 0.5cm multiplied by 1cm into a mixed solution consisting of 10mL of water, 0.270-0.290g of sodium sulfate and 40-52 mu L of aniline, and carrying out electrodeposition for 25-35min to prepare a composite material of polyaniline loaded on the foam nickel, namely a Ni @ PANI composite material;
mixing 0.045-0.055g H3Dissolving the L ligand in a mixed solution of 1mL of DMF, 0.2mL of absolute ethyl alcohol and 0.1mL of water, adding 0.025-0.035g of cobalt nitrate, and performing ultrasonic treatment to obtain Co (II) -MOF gel;
uniformly coating 12-15 mu L of Co (II) -MOF gel on the Ni @ PANI composite material, placing the composite material in a tubular furnace, heating the composite material to 230-270 ℃ at a temperature rise rate of 2 ℃/min under an air atmosphere, preserving heat for 2h, and then cooling the composite material to room temperature at a temperature fall rate of 2 ℃/min; to obtain Ni @ Co2O3The catalyst is a nickel-based three-dimensional metal-organic framework catalyst;
said H3An L ligand, designated 4,4',4' ' - (triazine-1, 3, 5-triamino) -tribenzoic acid, having the structural formula:
the Co (II) -MOF has a chemical formula of [ [ Co ]2L(OH)(H2O)2]·H2O·0.6O]nOne structural unit of the material consists of 2 Co (II) positive ions, 1L (III) negative ions, 1 OH (I) negative ions, 2 host water molecules, 1 object water molecule and 0.6 oxygen atom;
the Ni @ Co2O3the/CN composite catalyst is foam nickel loaded nanometer Co2O3And SP2The hybrid nitrogen codoped with the composite on the graphitic carbon matrix.
2. The preparation method of the nickel-based three-dimensional metal organic framework catalyst according to claim 1, wherein the activated foam nickel is prepared by sequentially performing ultrasonic treatment on the foam nickel in acetone, absolute ethyl alcohol and distilled water for 2-4min, washing to remove surface impurities, and then immersing the foam nickel in 37-43% by mass of nitric acid for 1 min.
3. The preparation method of the nickel-based three-dimensional metal-organic framework catalyst according to claim 1, wherein the electrodeposition is constant potential deposition, foam nickel is used as a counter electrode, a platinum sheet is used as a working electrode, a silver/silver chloride reference electrode is used, the constant potential is 0.6V, and the deposition time is 25-35 min; in the electrodeposition process, aniline is subjected to electrodeposition, oxidation and polymerization at an anode to obtain polyaniline, and the structural formula of the polyaniline is as follows:
4. use of the nickel-based three-dimensional metal organic framework catalyst prepared by the preparation method of claim 1 as an electrolytic water oxygen evolution catalyst.
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| CN106449179A (en) * | 2016-11-26 | 2017-02-22 | 桂林理工大学 | Method of assembling MOF/nitrogen-doped active carbon asymmetric supercapacitor device |
| CN107486233A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst |
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| CN106449179A (en) * | 2016-11-26 | 2017-02-22 | 桂林理工大学 | Method of assembling MOF/nitrogen-doped active carbon asymmetric supercapacitor device |
| CN107486233A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst |
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| Bimetal-Organic Framework Derived CoFe2O4/C Porous Hybrid Nanorod Arrays as High-Performance Electrocatalysts for Oxygen Evolution Reaction;Lu, Xue-Feng;《ADVANCED MATERIALS》;20161116;第29卷(第3期);第6页左栏第2段、Supporting Information实验部分 * |
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