CN107570166B - Preparation method and application of composite carbon and transition element oxide nano-catalyst - Google Patents
Preparation method and application of composite carbon and transition element oxide nano-catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of composite carbon and transition element oxide nano-catalyst and application based on the catalyst for water electrolysis and oxygen evolution, belonging to the technical field of nano-catalysis, nano-materials and metal organic framework materials.
Description
Technical Field
The invention relates to a preparation method of composite carbon and transition element oxide nano-catalysts and application of the catalysts in electrolysis of water for oxygen evolution, belonging to the technical field of nano-catalysis, nano-materials and metal-organic framework materials.
Background
According to statistics of 2003, the worldwide natural gas recoverable storage capacity is 2.4 Gt, the crude oil 138.3 Gt, the total amount is 140.7 Gt, the storable and recoverable age limit is 44 years, the petroleum is used by aviation, spaceflight, chemical engineering, ships and automobiles, the global high dependence on the petroleum causes petroleum shortage, the whole world is faced with the stop of operation, and the fossil fuel contains carbon, dust, sulfur and the like, and the environment pollution cannot be avoided after the fossil fuel is combustedThe acquisition of clean and efficient energy (hydrogen and oxygen) is the hot spot of contemporary scientific research.Water is , which is the most abundant source of hydrogen and oxygen on earth, water decomposes to form hydrogen and oxygen, hydrogen exothermically burns to water, the process regenerates, cleans and greens2) And ruthenium dioxide (RuO)2) However, their scarce and expensive prices have limited their widespread practical application, for which the development of efficient, inexpensive, and earth-rich non-noble metal oxygen evolution catalysts has become opportunities and challenges to reduce the consumption of oxygen evolution electricity.
At present, the research on functional materials derived from MOFs precursors or templates is increasing, for example, porous carbon, metal oxide, metal/carbon and metal oxide/carbon nano materials are reported, the constructed 3D metal oxide is used for high-efficiency super capacitors, lithium ion batteries and oxygen reduction and has shown excellent properties, in 2014, Chaiktitisilp and other groups report that an electrocatalyst is prepared by taking MOFs as a precursor for decomposing water for the first time, and the metal organic complex adopts zeolite-like Co-MOF (zeolitic Imidazolate framework-9, ZIF-9) for preparing nano porous CoxOy-C composite electrocatalytic OER. The process of direct pyrolysis of MOFs precursors often results in frame collapse and agglomeration intoThus, innovative strategies currently in use are MOFs supported on nanocarbon materials such as graphene, multi-walled Carbon Nanotubes (CNTs), and carbon-based composite electrocatalysts prepared by high temperature pyrolysis to prevent product agglomeration and increase specific surface area2High-temperature reduction and oxidation calcination in atmosphere to obtain kinds of Co @ Co3O4Although the MOFs are various in types, the MOFs are easy to prepare and can be converted into electro-catalyst MOFs precursors with controllable forms, and the quantity is limited, at present, researches on preparation of oxygen evolution catalysts by taking three-dimensional (3D) MOFs microcrystals or nanocrystals as precursors are reported, and as far as we know, researches on preparation of oxygen evolution catalysts based on -dimensional MOFs nanofibers are not reported.
Disclosure of Invention
, which is a technical task of the invention, aims to make up the defects of the prior art, and provides a preparation method of composite carbon and transition element oxide nano-catalysts.
The second technical task of the invention is to provide the application of the composite carbon and transition element oxide nano catalyst, namely, the composite carbon and transition element oxide nano catalyst is used for 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. the preparation process of kinds of composite carbon and transition element oxide nanometer catalyst includes the following steps:
dissolving copper nitrate, manganese nitrate and cobalt nitrate into 15-18mL of water to obtain blue clear copper nitrate-manganese nitrate-cobalt nitrate mixed solution; dissolving 0.40mmol of L-aspartic acid and 0.50-0.58mmol of sodium hydroxide in 2.0-4.0mL of water to obtain a clarified aspartic acid alkali solution; adding the aspartic acid alkali solution into the mixed solution of copper nitrate, manganese nitrate and cobalt nitrate, and generating a precipitate at room temperature for 5 min; after 1h, performing suction filtration, and drying at 60 ℃ to prepare Cu-MOF nanofiber loaded Mn (II) and Co (II) ion nanofibers, namely CuMnCo-MOF nanofibers; placing CuMnCo-MOF nano-fibers in a tube furnace for heating to obtain a composite carbon and transition element oxide nano-catalyst;
1) the weight ratio of the copper nitrate to the manganese nitrate to the cobalt nitrate is 1: 3: 1, the dosage of the copper nitrate is 1.5-2.6 mmol;
2) the Cu-MOF nanofiber has a chemical formula of [ CuL (H)2O)]n, L is aspartic acid H2L (II) ion of L, unit structures of Cu-MOF nanofiber, which are composed of Cu (II) ion centers, L (II) ions and H2O molecule composition;
3) the CuMnCo-MOF nanofiber consists of Cu-MOF nanofibers with the diameter width of 90-160nm and the length of 400-900um loaded with Co (II) and Mn (II) ions;
4) the composite carbon and transition element oxide nano catalyst is prepared from semiconductors CuO and MnO2And Co2O3The nano particles are loaded on the carbon microcrystal to form the fibrous composite material, the fiber diameter is 80-130nm wide, and the length is 300-;
5) the CuMnCo-MOF nano-fiber is placed in a tubular furnace to be heated under the air atmosphere, the heating rate is 3-5 ℃/min, the temperature is heated to 250-300 ℃, the temperature is kept for 1.5-2.5h, and then the temperature is cooled to the room temperature at the cooling rate of 2 ℃/min.
2. The application of the composite carbon and transition element oxide nano catalyst as an electrolytic water oxygen evolution catalyst comprises the following steps:
dispersing 6mg of composite carbon and transition element oxide nano catalyst in 250 mu L of isopropanol, 720 mu L of water and 30 mu L of 5 wt% perfluorinated resin solution, and carrying out 120W ultrasonic treatment at room temperature for 10-15min to obtain a uniform mixed solution; dripping 6 mu L of the mixed solution on a glassy carbon electrode, and drying at room temperature to prepare a composite carbon and transition element oxide nano catalyst working electrode;
a three-electrode electrochemical workstation, a composite carbon and transition element oxide nano-catalyst working electrode, a Pt sheet (5 mm multiplied by 0.1 mm) as a counter electrode and an Ag/AgCl electrode as a reference electrode are used, and the electrocatalytic water decomposition performance is tested in a 0.5M KOH aqueous solution of electrolyte.
Electrolyzing the carbon-based copper-cobalt oxide nanosheet to generate oxygen by water when the current density J =10mA/cm2When the voltage is higher than the reference voltage, the potential is 1.48V vs RHE; tafel slope of 65mV dec-1The 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 beneficial technical effects of the invention are as follows:
1. the composite carbon and transition element oxide nano-catalyst obtained by the invention is prepared by heating and pyrolyzing -dimensional metal organic framework CuMnCo-MOF nano-fibers at 300 ℃ under the air atmosphere condition of 250-.
2. The present invention provides the application of composite carbon and transition element oxide nano-catalyst as oxygen evolution catalyst for electrolyzing water2And Co2O3The nano-fiber formed by loading the semiconductor nano-particles on the carbon microcrystal has regular appearance, single dispersion and high specific surface area, exposes more and different active sites, and exerts CuO and MnO2And Co2O3The synergistic effect of the semiconductor nano particles and the carbon microcrystals ensures that the composite material based on the catalytic oxygen evolution has high catalytic efficiency and good stability.
Detailed Description
The present invention is further described in with reference to the following examples, but the scope of the present invention is not limited to the examples, and those skilled in the art should be able to make modifications to the technical solution of the present invention within the scope of the present invention.
Example 1
Preparation method of composite carbon and transition element oxide nano-catalyst
1.5 mmol of copper nitrate in a weight ratio of 1: 3: 1, dissolving copper nitrate, manganese nitrate and cobalt nitrate in 15-18mL of water to obtain blue clear copper nitrate-manganese nitrate-cobalt nitrate mixed solution; dissolving 0.40mmol of L-aspartic acid and 0.50 mmol of sodium hydroxide in 2.0 mL of water to obtain a clarified aspartic acid alkali solution; adding the aspartic acid alkali solution into the mixed solution of copper nitrate, manganese nitrate and cobalt nitrate, and generating a precipitate at room temperature for 5 min; after 1h, performing suction filtration, and drying at 60 ℃ to prepare Cu-MOF nanofiber loaded Mn (II) and Co (II) ion nanofibers, namely CuMnCo-MOF nanofibers; and (2) placing the CuMnCo-MOF nano-fiber in a tubular furnace to heat under the air atmosphere, wherein the heating rate is 3 ℃/min, heating to 250 ℃, preserving heat for 1.5 h, and then cooling to room temperature at the cooling rate of 2 ℃/min to prepare the composite carbon and transition element oxide nano-catalyst.
Example 2
Preparation method of composite carbon and transition element oxide nano-catalyst
2.6mmol of copper nitrate in a weight ratio of 1: 3: 1, dissolving copper nitrate, manganese nitrate and cobalt nitrate in 18mL of water to obtain blue clear copper nitrate-manganese nitrate-cobalt nitrate mixed solution; dissolving 0.40mmol of L-aspartic acid and 0.58mmol of sodium hydroxide in 4.0mL of water to obtain a clarified aspartic acid alkali solution; adding the aspartic acid alkali solution into the mixed solution of copper nitrate, manganese nitrate and cobalt nitrate, and generating a precipitate at room temperature for 5 min; after 1h, performing suction filtration, and drying at 60 ℃ to prepare Cu-MOF nanofiber loaded Mn (II) and Co (II) ion nanofibers, namely CuMnCo-MOF nanofibers; and (2) placing the CuMnCo-MOF nano-fiber in a tubular furnace to heat under the air atmosphere, wherein the heating rate is 5 ℃/min, heating to 300 ℃, preserving heat for 2.5h, and then cooling to room temperature at the cooling rate of 2 ℃/min to prepare the composite carbon and transition element oxide nano-catalyst.
Example 3
Preparation method of composite carbon and transition element oxide nano-catalyst
2.0 mmol of copper nitrate in a ratio of 1: 3: 1, dissolving the copper nitrate, the manganese nitrate and the cobalt nitrate in 16.5 mL of water to obtain blue and clear copper nitrate-manganese nitrate-cobalt nitrate mixed solution; dissolving 0.40mmol of L-aspartic acid and 0.54 mmol of sodium hydroxide in 3.0 mL of water to obtain a clarified aspartic acid alkali solution; adding the aspartic acid alkali solution into the mixed solution of copper nitrate, manganese nitrate and cobalt nitrate, and generating a precipitate at room temperature for 5 min; after 1h, performing suction filtration, and drying at 60 ℃ to prepare Cu-MOF nanofiber loaded Mn (II) and Co (II) ion nanofibers, namely CuMnCo-MOF nanofibers; and (2) placing the CuMnCo-MOF nano-fiber in a tubular furnace to heat under the air atmosphere, wherein the heating rate is 4 ℃/min, heating to 275 ℃, preserving heat for 2.0 h, and then cooling to room temperature at the cooling rate of 2 ℃/min to prepare the composite carbon and transition element oxide nano-catalyst.
Example 4
Cu-MOF nanofibers of examples 1-3 having the formula [ CuL (H)2O)]n, L is aspartic acid H2L (II) ion of L, unit structures of Cu-MOF nanofiber, which are composed of Cu (II) ion centers, L (II) ions and H2O molecule composition; the CuMnCo-MOF nanofiber consists of Cu-MOF nanofibers with the diameter width of 90-160nm and the length of 400-900um loaded with Co (II) and Mn (II) ions; the composite carbon and transition element oxide nano catalyst is prepared from semiconductors CuO and MnO2And Co2O3The nano-particles are loaded on the carbon micro-crystals to form the fibrous composite material, the fiber diameter is 80-130nm wide and 300-850 mu m long.
Example 5 application of composite carbon and transition element oxide nanocatalyst as catalyst for oxygen evolution from electrolyzed water
Dispersing 6mg of the composite carbon and transition element oxide nano-catalyst prepared in the example 1 in 250 muL of isopropanol, 720 muL of water and 30 muL of 5 wt% perfluorinated resin solution, and carrying out 120W ultrasonic treatment at room temperature for 10-15min to prepare a uniform mixed solution; dripping 6 mu L of the mixed solution on a glassy carbon electrode, and drying at room temperature to prepare a composite carbon and transition element oxide nano catalyst working electrode;
a three-electrode electrochemical workstation, a composite carbon and transition element oxide nano-catalyst working electrode, a Pt sheet (5 mm multiplied by 0.1 mm) as a counter electrode and an Ag/AgCl electrode as a reference electrode are used, and the electrocatalytic water decomposition performance is tested in a 0.5M KOH aqueous solution of electrolyte.
Example 6 the procedure and method were the same as in example 5 except that the composite carbon and transition element oxide nanocatalyst prepared in example 1 was replaced with the catalyst prepared in example 2.
Example 7 the procedure and method were the same as in example 5 except that the composite carbon and transition element oxide nanocatalyst prepared in example 1 was replaced with the catalyst prepared in example 3.
Example 8 composite carbon and transition element oxide nanocatalysts made in examples 1-7 electrolyze water to evolve oxygen when the current density J =10mA/cm2When the voltage is higher than the reference voltage, the potential is 1.48V vs RHE; tafel slope of 65mV dec-1The 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 (6)
1, preparation method of compound carbon and transition element oxide nanometer catalyst, characterized by, the step is as follows:
dissolving copper nitrate, manganese nitrate and cobalt nitrate into 15-18mL of water to obtain blue clear copper nitrate-manganese nitrate-cobalt nitrate mixed solution; dissolving 0.40mmol of L-aspartic acid and 0.50-0.58mmol of sodium hydroxide in 2.0-4.0mL of water to obtain a clarified aspartic acid alkali solution; adding the aspartic acid alkali solution into the mixed solution of copper nitrate, manganese nitrate and cobalt nitrate, and generating a precipitate at room temperature for 5 min; after 1h, performing suction filtration, and drying at 60 ℃ to prepare Cu-MOF nanofiber loaded Mn (II) and Co (II) ion nanofibers, namely CuMnCo-MOF nanofibers; placing CuMnCo-MOF nano-fibers in a tube furnace for heating to obtain a composite carbon and transition element oxide nano-catalyst;
the weight ratio of the copper nitrate to the manganese nitrate to the cobalt nitrate is 1: 3: 1, the dosage of the copper nitrate is 1.5-2.6 mmol.
2. The method of making composite carbon and transition element oxide nanocatalysts of claim 1, wherein the Cu-MOF nanofibers have the formula [ CuL (H)2O)]nL is aspartic acid H2L (II) ion of L, unit structures of Cu-MOF nanofiber, which are composed of Cu (II) ion centers, L (II) ions and H2And O molecules.
3. The method for preparing composite carbon and transition element oxide nanocatalysts of claim 1, wherein the CuMnCo-MOF nanofibers are composed of Cu-MOF nanofibers with a diameter width of 90-160nm and a length of 400-900um loaded with Co (II) and Mn (II) ions.
4. The method of claim 1, wherein the composite carbon and transition element oxide nanocatalysts are prepared from CuO and MnO as semiconductors2And Co2O3The nano-particles are loaded on the carbon micro-crystals to form the fibrous composite material, the fiber diameter is 80-130nm wide and 300-850 mu m long.
5. The method for preparing composite carbon and transition element oxide nanocatalysts of claim 1, wherein the CuMnCo-MOF nanofibers are heated in a tube furnace under air atmosphere at a heating rate of 3-5 ℃/min to 250-300 ℃, and the temperature is maintained for 1.5-2.5h, and then cooled to room temperature at a cooling rate of 2 ℃/min.
6. The use of the composite carbon and transition element oxide nanocatalyst prepared by the preparation method of claim 1 as an electrolytic water oxygen evolution catalyst.
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| CN108671923B (en) * | 2018-05-10 | 2021-06-29 | 宁波大学 | Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof |
| CN109252180B (en) * | 2018-09-19 | 2021-02-09 | 安徽师范大学 | Ternary MOF nanosheet array material, preparation method and application thereof |
| CN109647407A (en) * | 2019-02-12 | 2019-04-19 | 济南大学 | A kind of preparation method and application based on bimetallic MOF nanocrystalline composite material |
| CN110586191A (en) * | 2019-09-18 | 2019-12-20 | 常州大学 | Oxygen evolution catalyst of CoCu-MOF/SNPC compounded by MOF material |
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