CN109622053B - Preparation method and application of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst - Google Patents
Preparation method and application of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst Download PDFInfo
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- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 40
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
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- 239000008103 glucose Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 8
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- 238000002156 mixing Methods 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
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- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 239000012086 standard solution Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000007853 buffer solution Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 238000011161 development Methods 0.000 description 3
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- -1 sodium nitroferricyanide Chemical compound 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/33—Electric or magnetic properties
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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Abstract
The invention discloses a preparation method of a CuO nano-particle doped Cu-MOF/carbon dot composite catalyst and application of the catalyst in electrocatalysis of room temperature nitrogen reduction, belonging to the technical fields of catalysis technology and nano composite materials. The main step is to add ligand H6L solution and Cu (NO)3)2·3 H2Mixing O and glucose to prepare a raw material mixed solution; heating the raw material mixed solution for 2 days at 90 ℃ to prepare a glucose-doped multi-nitrogen Cu-MOF crystal; and (3) placing the glucose-doped multi-nitrogen Cu-MOF crystal in a tubular furnace in the air atmosphere at 300 ℃ for oxidation-pyrolysis for 2 h to prepare the CuO nano particle-doped Cu-MOF/carbon dot composite catalyst. The catalyst has the advantages of low cost of raw materials for preparation, simple process, good catalytic performance and industrial prospect when used for electrocatalysis of nitrogen gas to ammonia at room temperature.
Description
Technical Field
The invention discloses a preparation method of a CuO nano-particle doped Cu-MOF/carbon dot composite catalyst and application of the catalyst in electrocatalysis of nitrogen at room temperature to reduce ammonia, belonging to the technical fields of catalyst technology and nano composite materials.
Background
NH3Is one of the most important chemicals at present, the annual output of the chemical is at the head of various chemicals, and China synthesizes NH3Large industrial countries, as high energy consuming industries, synthesize NH3Energy consumed by industry accounts for 1-2% of the total amount of the whole world, and NH3The downstream products of (2) are mainly agricultural fertilizers, and other products such as synthetic fibers, explosives, industrial fuels and the like are also important downstream products of the downstream products. Modern synthesis of NH3The industrialization of the technology starts in 1905, and the German chemist Haber proves that the hydrogen and the nitrogen realize NH for the first time under the conditions of the catalyst, the high temperature of 500-3And (4) synthesizing. After more than one hundred years of development, NH is industrially synthesized3The technology makes great progress, for example, the daily capacity of a single set of device is increased from 30 tons to 2500 tons, the reaction pressure of the device is also greatly reduced, and the sources of raw material gases are diversified. However, the ammonia synthesis technology is still a high-energy-consumption industry, and the product CO discharged by the technology is2Is a major greenhouse gas, and therefore, develops low-temperature and low-pressure synthesis technology and finally develops normal-temperature and normal-pressure synthesis of NH3The technology has very important strategic significance. Introduction of electrical energy into ammonia synthesis technology, N stabilization by electrocatalytic cleavage2Three covalent bonds in the molecule, and the preparation technology of the electrocatalyst is the core of the electrochemical nitrogen fixation technology. Although NH has been demonstrated including Ru, Pt, Au catalysts, and the like3But their high cost and limited resources limit their large-scale application, and therefore, the development of inexpensive room temperature N2Reduction to NH3The catalyst has important significance.
Metal-organic frameworks (MOFs) refer to crystalline porous materials with periodic network structures formed by self-assembly of transition metal ions and organic ligands, and the three-dimensional pore structure of the crystalline porous materials comprises two important components: junctions (connectors) and bridges (linkers), typically with metal ions as the junction, are supported by organic ligands to form spatial 3D extensions. Compared with the traditional porous material, the MOFs material has the advantage of being unique, for example, the selection range of raw materials (metal ions and organic coordination) is wide, and the molecular regulation can be carried out by reasonably selecting the metal ions and the organic ligands through the size, the specific surface area, the active sites, the rigidity and the flexibility of the pore channels and the like.
The carbon dots are a nano material which takes carbon as a main element, has the size of less than 10 nm and has a structure containing hydrophilic functional groups such as carboxyl and the like, has the functions of electron transmission and electron acceptor, has excellent conductivity, has the advantages of excellent water solubility, simple synthesis process, easy surface functionalization and the like, and has wide development prospect in the technical fields of biological imaging, drug delivery photoelectric devices, analysis and detection and the like. As a novel carbon nano material, carbon dots can be embedded in gaps of an MOF structure, more and different active sites are exposed and provided, and the transfer of electrons and the diffusion of ions are accelerated, so that the catalytic performance of the carbon dot/MOFs composite material is greatly improved.
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 for preparing a CuO nano particle doped Cu-MOF/carbon dot composite catalyst by taking MOF and glucose as raw materials.
The second technical task of the invention is to provide the application of the catalyst, namely, the catalyst is used for preparing ammonia by electrocatalysis of nitrogen reduction at room temperature, and has good catalytic efficiency and stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. preparation method of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
(1) Preparing a raw material mixture
0.10-0.14 g H6The L ligand is dissolved in 8-12 mL of N, N-dimethylacetamide DMA, 5-12 mL of dimethyl sulfoxide DMSO, and 0.3-0.5 mL of H2Adding 3.5-4.0 mL of HBF with the mass fraction of 40% into a mixed solvent consisting of O4A solution to obtain a clear ligand solution; further adding 0.64-0.70 g of Cu (NO)3)2·3H2Mixing O and 0.2-0.30 g of glucose to obtain a raw material mixed solution;
(2) preparation of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
Heating the raw material mixed solution for 2 days at 90 ℃ to prepare a glucose-doped multi-nitrogen Cu-MOF crystal; and (3) washing the Cu-MOF crystal, and placing the washed Cu-MOF crystal in a tubular furnace in the air atmosphere at 300 ℃ for oxidation-pyrolysis for 2 h to prepare the CuO nano particle doped Cu-MOF/carbon dot composite catalyst.
Said H in step (1)6An L ligand having the structural formula:
the structural unit of the Cu-MOF crystal in the step (2) is [ Cu ]3L(H2O)3]·10H2O.5 DMA is composed of 3 Cu2+1, L6-3 host water molecules, 10 guest water molecules and 5 guest DMA molecules.
2. Application of CuO nano-particle doped Cu-MOF/carbon dot composite catalyst prepared by preparation method in electrocatalysis of nitrogen reduction to ammonia at room temperature
(1) Preparation of working electrode
Dispersing 8 mg of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst in a solution containing 1.5 mL of ethanol and 60 mu L of Nafion, performing ultrasonic treatment for 1h to form a uniform suspension, sucking 10 mu L of the suspension, dripping the suspension on a 4 mm glassy carbon electrode, and airing overnight to prepare a CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst working electrode;
(2) drawing a standard curve
Preparing series NH by adopting ammonium chloride and PBS buffer solution with concentration of 0.1M3A standard solution of (4);
taking 2mL of standard solution, sequentially adding 2mL of NaOH solution with the concentration of 1.0M, 1mL of NaClO with the concentration of 0.05M and 0.2 mL of sodium nitroferricyanide solution with the mass fraction of 1%, quickly shaking for several times, standing for 2 h at 25 ℃, detecting the absorbance peak value of the solution at the 656 nm wavelength by using a UV-vis spectrophotometer, and drawing an absorbance-concentration (A-c) standard curve;
the 1.0M NaOH solution contains 5 mass percent of salicylic acid and sodium citrate;
(3) electrocatalysis of room temperature nitrogen fixation to ammonia
Connecting an H-type two-chamber electrochemical cell on an electrochemical workstation, separating the two chambers by a Nafion 115 proton exchange membrane, adding 30 mL of PBS buffer solution with the concentration of 0.1M into the two chambers, doping CuO nano particles with a Cu-MOF/carbon dot composite catalyst to serve as a working electrode, Ag/AgCl to serve as a reference electrode, a platinum sheet to serve as an auxiliary electrode, and introducing N into the cathode chamber2After 30 min, N was reduced using RHE at-0.2 to-1.0V vs2Fixing nitrogen, taking reaction liquid obtained after 2 hours of catalytic reaction, and analyzing the concentration of ammonia to test the room-temperature nitrogen fixation performance of electrocatalysis;
the method for analyzing the concentration of the ammonia is the same as the step (2), only 2mL of reaction liquid for catalyzing and reacting for 2 h is used for replacing 2mL of standard solution in the step (2), and the yield of the ammonia is calculated according to a standard curve;
the 1.0M NaOH solution contains 5% by weight of salicylic acid and sodium citrate.
When the applied voltage is-0.4V vs RHE, the catalyst is reduced into NH by nitrogen at room temperature3At a rate of 4.5-6.0. mu.gNH3 h−1mg-1The Faraday efficiency is 2.3-3.8%
The beneficial technical effects of the invention are as follows:
(1) the CuO nano particle doped Cu-MOF/carbon dot composite catalyst is prepared based on a convenient two-step method, and firstly, a mixed solution of a ligand, metal ions and a carbon dot precursor glucose raw material is heated for 2 days at 90 ℃ to prepare a glucose doped multi-nitrogen Cu-MOF crystal; secondly, oxidizing and decomposing the glucose-doped multi-nitrogen Cu-MOF crystal for 2 hours at 300 ℃ in an air atmosphere to obtain the glucose-doped multi-nitrogen Cu-MOF crystal; the preparation process is simple, low in cost, easy to operate and easy to industrialize.
(2) The glucose-doped multi-nitrogen Cu-MOF crystal is oxidized and decomposed for 2 h at 300 ℃ in the air atmosphere, the process not only enables partial oxidation and pyrolysis of Cu-MOF to generate CuO nano particles to be loaded on porous multi-nitrogen Cu-MOF, but also enables glucose doped in the multi-nitrogen Cu-MOF crystal to be pyrolyzed in situ to generate carbon dots, namely the CuO nano particle-doped Cu-MOF/carbon dot composite material, and on one hand, the composite material is large in specific surface area and exposes more active sites; in addition, the material is a multi-element composite material consisting of CuO nano particles, carbon dots and Cu-MOF, and all components have synergistic effect, so that the composite material catalyzes N2The activity of reducing the ammonia into ammonia is increased, and the rate of producing ammonia by electrocatalysis at room temperature is higher.
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.
Embodiment 1 preparation method of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
(1) Preparing a raw material mixture
0.10 g H6L ligand was dissolved in a solution of 8 mL of N, N-dimethylacetamide DMA, 5 mL of dimethyl sulfoxide DMSO, and 0.3 mL of H23.5 mL of HBF with the mass fraction of 40 percent is added into the mixed solvent consisting of O4A solution to obtain a clear ligand solution; 0.64 g of Cu (NO) was added continuously3)2·3H2Mixing O and 0.2 g of glucose to obtain a raw material mixed solution;
(2) preparation of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
Heating the raw material mixed solution for 2 days at 90 ℃ to prepare a glucose-doped multi-nitrogen Cu-MOF crystal; and (3) washing the Cu-MOF crystal, and placing the washed Cu-MOF crystal in a tubular furnace in the air atmosphere at 300 ℃ for oxidation-pyrolysis for 2 h to prepare the CuO nano particle doped Cu-MOF/carbon dot composite catalyst.
Embodiment 2 preparation method of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
(1) Preparing a raw material mixture
0.12 g H6L ligand dissolved in 10 mL of N, N-dimethylacetamide DMA, 8.5 mL of dimethyl sulfoxide DMSO, 0.4 mL of H23.7 mL of HBF with the mass fraction of 40 percent is added into the mixed solvent consisting of O4A solution to obtain a clear ligand solution; further addition of 0.68 g of Cu (NO)3)2·3H2O and 0.25 g of glucose are blended to obtain a raw material mixed solution;
(2) preparation of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
Heating the raw material mixed solution for 2 days at 90 ℃ to prepare a glucose-doped multi-nitrogen Cu-MOF crystal; and (3) washing the Cu-MOF crystal, and placing the washed Cu-MOF crystal in a tubular furnace in the air atmosphere at 300 ℃ for oxidation-pyrolysis for 2 h to prepare the CuO nano particle doped Cu-MOF/carbon dot composite catalyst.
Embodiment 3 preparation method of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
(1) Preparing a raw material mixture
0.14 g H6L ligand was dissolved in a mixture of 12 mL of N, N-dimethylacetamide DMA, 12 mL of dimethyl sulfoxide DMSO, and 0.5 mL of H2Adding 4.0 mL of HBF with the mass fraction of 40% into a mixed solvent consisting of O4A solution to obtain a clear ligand solution; further addition of 0.70 g of Cu (NO)3)2·3H2O and 0.30 g of glucose are blended to obtain a raw material mixed solution;
(2) preparation of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
Heating the raw material mixed solution for 2 days at 90 ℃ to prepare a glucose-doped multi-nitrogen Cu-MOF crystal; and (3) washing the Cu-MOF crystal, and placing the washed Cu-MOF crystal in a tubular furnace in the air atmosphere at 300 ℃ for oxidation-pyrolysis for 2 h to prepare the CuO nano particle doped Cu-MOF/carbon dot composite catalyst.
Example 4
H as described in examples 1 to 36An L ligand having the structural formula:
the Cu-MOF crystal is analyzed by an X-ray diffraction pattern, and the structural unit of the Cu-MOF crystal is [ Cu ]3L(H2O)3]·10H2O.5 DMA is composed of 3 Cu2+1, L6-3 host water molecules, 10 guest water molecules and 5 guest DMA molecules.
Example 5
Use of the catalyst prepared in example 1 for electrocatalytic room temperature reduction of nitrogen to ammonia
(1) Preparation of working electrode
Dispersing 8 mg of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst in a solution containing 1.5 mL of ethanol and 60 mu L of Nafion, performing ultrasonic treatment for 1h to form a uniform suspension, sucking 10 mu L of the suspension, dripping the suspension on a 4 mm glassy carbon electrode, and airing overnight to prepare a CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst working electrode;
(2) drawing a standard curve
Preparing series NH by adopting ammonium chloride and PBS buffer solution with concentration of 0.1M3A standard solution of (4);
taking 2mL of standard solution, sequentially adding 2mL of NaOH solution with the concentration of 1.0M, 1mL of NaClO with the concentration of 0.05M and 0.2 mL of sodium nitroferricyanide solution with the mass fraction of 1%, quickly shaking for several times, standing for 2 h at 25 ℃, detecting the absorbance peak value of the solution at the 656 nm wavelength by using a UV-vis spectrophotometer, and drawing an absorbance-concentration (A-c) standard curve;
the 1.0M NaOH solution contains 5 mass percent of salicylic acid and sodium citrate;
(3) electrocatalysis of room temperature nitrogen fixation to ammonia
Connecting an H-type two-chamber electrochemical cell on an electrochemical workstation, separating the two chambers by a Nafion 115 proton exchange membrane, adding 30 mL of PBS buffer solution with the concentration of 0.1M into the two chambers, doping CuO nano particles with a Cu-MOF/carbon dot composite catalyst to serve as a working electrode, Ag/AgCl to serve as a reference electrode, a platinum sheet to serve as an auxiliary electrode, and introducing N into the cathode chamber2After 30 min, N was reduced using RHE at-0.2 to-1.0V vs2Fixing nitrogen, taking reaction liquid obtained after 2 hours of catalytic reaction, and analyzing the concentration of ammonia to test the room-temperature nitrogen fixation performance of electrocatalysis;
the method for analyzing the concentration of the ammonia is the same as the step (2), only 2mL of reaction liquid for catalyzing and reacting for 2 h is used for replacing 2mL of standard solution in the step (2), and the yield of the ammonia is calculated according to a standard curve;
the 1.0M NaOH solution contains 5 mass percent of salicylic acid and sodium citrate;
when the applied voltage is-0.4V vs RHE, the catalyst is reduced into NH by nitrogen at room temperature3At a rate of 4.5. mu.gNH3 h−1mg-1The Faraday efficiency was 2.3%.
Example 6
Example 2 use of the catalyst prepared for electrocatalytic room temperature reduction of nitrogen to ammonia
The procedure is the same as that in example 5, except that the CuO nanoparticle-doped Cu-MOF/carbon dot composite catalyst prepared in example 2 is substituted for the CuO nanoparticle-doped Cu-MOF/carbon dot composite catalyst prepared in example 1, and when the applied voltage is-0.4V vs RHE, the catalyst is reduced to NH with nitrogen at room temperature3At a rate of 6.0. mu.gNH3 h−1mg-1And the Faraday efficiency is 3.8 percent
Example 7
Application of the catalyst prepared in example 3 to electrocatalysis of nitrogen reduction to ammonia at room temperature
The procedure is the same as that of example 5, except that the CuO nanoparticle-doped Cu-MOF/carbon dot composite catalyst prepared in example 3 is substituted for the CuO nanoparticle-doped Cu-MOF/carbon dot composite catalyst prepared in example 1, and when the applied voltage is-0.4V vs RHECatalyst room temperature nitrogen reduction to NH3At a rate of 5.0. mu.gNH3 h−1mg-1The Faraday efficiency was 3.3%.
Claims (3)
1. A preparation method of a CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst is characterized by comprising the following steps:
(1) preparing a raw material mixture
0.10-0.14 g H6The L ligand is dissolved in 8-12 mL of N, N-dimethylacetamide DMA, 5-12 mL of dimethyl sulfoxide DMSO, and 0.3-0.5 mL of H2Adding 3.5-4.0 mL of HBF with the mass fraction of 40% into a mixed solvent consisting of O4A solution to obtain a clear ligand solution; further adding 0.64-0.70 g of Cu (NO)3)2·3H2Mixing O and 0.2-0.30 g of glucose to obtain a raw material mixed solution;
(2) preparation of CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst
Heating the raw material mixed solution for 2 days at 90 ℃ to prepare a glucose-doped multi-nitrogen Cu-MOF crystal; after washing the Cu-MOF crystal, placing the Cu-MOF crystal in a tubular furnace in the air atmosphere at 300 ℃ for oxidation-pyrolysis for 2 h to prepare a CuO nano particle doped Cu-MOF/carbon dot composite catalyst;
said H in step (1)6An L ligand having the structural formula:
2. the preparation method of the CuO nanoparticle-doped Cu-MOF/carbon dot composite catalyst according to claim 1, wherein the structural unit of the Cu-MOF crystal in the step (2) is [ Cu ]3L(H2O)3]·10H2O.5 DMA is composed of 3 Cu2+1, L6-3 host water molecules, 10 guest water molecules and 5 guest DMA molecules.
3. The CuO nanoparticle doped Cu-MOF/carbon dot composite catalyst prepared by the preparation method of claim 1 is used for electrocatalysis of nitrogen reduction to ammonia at room temperature.
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| CN112897526A (en) * | 2021-02-05 | 2021-06-04 | 西南大学 | Preparation method and application of porous carbon dot material based on industrial glucose |
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