CN113289623A - Copper monatomic catalyst and preparation method and application thereof - Google Patents
Copper monatomic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- 150000001345 alkine derivatives Chemical group 0.000 claims abstract description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- VYFYYTLLBUKUHU-UHFFFAOYSA-N Dopamine Natural products NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 6
- -1 dopamine hydrochloride-copper salt-silicon dioxide compound Chemical class 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 238000005691 oxidative coupling reaction Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004375 physisorption Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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Abstract
The invention discloses a copper monatomic catalyst and a preparation method and application thereof. The copper monatomic catalyst prepared by the method is loaded on the nitrogen-doped ordered mesoporous carbon, has a controllable mesoscopic structure, and anchors the copper monatomic through rich nitrogen elements in the mesoporous carbon. The preparation method provided by the invention comprises the following steps: firstly, dopamine hydrochloride and metal copper salt are poured into pores of SBA-15 mesoporous silica by a hard template method, and after high-temperature carbonization, a silica template is removed by NaOH, so that the copper monatomic catalyst can be obtained. The copper monatomic catalyst can effectively catalyze the selective oxidative coupling of terminal alkynes and shows excellent yield and selectivity. The catalyst can be separated by simple centrifugation or filtration and reused. The invention opens up a way for preparing copper monoatomic atoms for catalyzing alkyne coupling reaction.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a novel copper monatomic catalyst with a controllable mesoscopic structure, and a preparation method and application thereof.
Background
The single-atom catalyst is considered as a novel catalyst with great development prospect due to the unique electronic property and the utilization rate of one hundred percent of metal atoms. The mesoporous carbon material has the advantages of surface hydrophobicity, high corrosion resistance, high specific surface area, uniform and adjustable pore diameter, high pore volume, easy surface treatment and the like, and thus, is receiving more and more attention of researchers. However, the conventional carbon-supported monatomic catalyst is often microporous due to its low specific surface area and the large pore size, which limits the contact efficiency and molecular diffusion of reactants and catalytic sites in the catalytic process. Therefore, the use of monatomic catalysts for catalyzing the conversion of organic molecules is greatly limited. The 1,3 conjugated diyne is an important drug intermediate and is a common component in various natural products and organic functional materials. Common methods for synthesizing 1, 3-conjugated diyne are mainly homogeneous catalysis of terminal alkyne coupling, however, a homogeneous system usually requires an excessive amount of ligand to achieve high efficiency, and a cumbersome process is required to separate the product, and the metal catalyst and the ligand cannot be recycled, which greatly increases the production cost. Therefore, it is highly desirable to design a heterogeneous catalyst to achieve efficient synthesis of 1, 3-conjugated diyne and recycling of the catalyst.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a novel copper monatomic catalyst and application thereof in alkyne coupling reaction.
The technical scheme provided by the invention is as follows:
in a first aspect, the present invention provides a method for preparing a copper monatomic catalyst, comprising the steps of:
(1) synthesizing a mesoporous silica template with abundant silicon hydroxyl on the surface;
(2) preparing a precursor solution of a metal copper salt;
(3) adding dopamine hydrochloride into a precursor solution of a metal copper salt, and fully dispersing to obtain a solution A;
(4) adding a mesoporous silica template with rich silicon hydroxyl groups into the solution A, and uniformly stirring to obtain turbid liquid; sealing the turbid liquid, carrying out heat preservation reaction, and drying after the reaction;
(5) and (4) calcining the dopamine hydrochloride-copper salt-silicon dioxide compound obtained in the step (4), removing a silicon dioxide template after calcining, and freeze-drying to obtain the copper monatomic catalyst.
Further, the mesoporous silica template with abundant silicon hydroxyl on the surface comprises SBA-15-OH, MCF-OH, KIT-6-OH, SBA-12-OH, FDU-12-OH, SBA-16-OH and P-SBA-15-OH. Mesoporous silica templates were prepared according to literature reports including SBA-15-OH (J.Am.chem.Soc.1998,120,6024), MCF-OH (J.Am.chem.Soc.1999,121,254-255), KIT-6-OH (chem.Commun.2003,2136-2137), P-SBA-15-OH (chem.Mater.2004,16,4174-4180), FDU-12-OH (J.Am.chem.Soc.2005,127, 10794-10795), SBA-16-OH (Mater.chem.,2006,16,1511-1519) and SBA-12-OH (J.Am.chem.Soc.1998,120, 6024-6036).
Further, the mesoporous silica template with abundant silicon hydroxyl on the surface is prepared by the following method: adding a mixture of silicon dioxide and a surfactant, concentrated nitric acid and a hydrogen peroxide solution into a reaction container, performing reflux reaction, filtering, washing and drying to obtain a template with rich silicon hydroxyl on the surface; the surfactant is P123 or F127.
Further, the metal copper salt precursor solution is obtained by dissolving metal copper salt in an ethanol water solution. According to the physical property of the metal copper salt, a solvent with proper concentration is selected, and the volume content of ethanol in the preferred ethanol water solution is 25-70%. Preferably, the preparation process of the copper nitrate solution is that 10-100 mg of copper nitrate is dissolved in 20-50 g of ethanol-water (the content of ethanol is 10% -90%); the preparation process of the copper acetate solution is that 5-100 mg of copper acetate is dissolved in 20-100 g of ethanol-water (the content of ethanol is 40-70%).
Further, the metallic copper salt includes copper nitrate, copper sulfate, copper chloride, copper acetate and copper acetylacetonate; the volume content of ethanol in the ethanol water solution is 10-90%.
Further, the molar ratio of the metal copper salt precursor solution to the dopamine hydrochloride is 0.1-2: 100. According to the pore volume of different templates, a certain mass of silicon dioxide template is added. The filling ratio of the sum of the volumes of dopamine hydrochloride and metal copper salt to the pore volume of the template is controlled between 10 percent and 100 percent.
Furthermore, the dosage ratio of the mesoporous silica template with abundant silicon hydroxyl groups to the solution A is 0.3-0.9 g:10 mL.
Further, in the step (4), the heat preservation temperature is 40-70 ℃, and the heat preservation reaction time is 2-4 hours for stirring; the drying temperature is 70-90 ℃.
Further, the calcination in the step (5) is carried out in an argon or nitrogen atmosphere, the calcination temperature is 600-1000 ℃, and the calcination time is 2-6 h.
Further, the method for removing the silica template in the step (5) comprises the following steps: and removing the silicon dioxide template by using 0.2-2.0 mol/L NaOH solution at the temperature of room temperature-70 ℃.
In a second aspect, the present invention provides a copper monatomic catalyst produced by the method of the first aspect.
In a third aspect, the invention provides the use of a catalyst of the second aspect for catalyzing the coupling of alkynes, in particular phenylacetylene.
Further, the method for catalyzing phenylacetylene comprises the following steps: placing a certain mass of copper monatomic catalyst in a Schlenk tube, adding a reactant (0.1 mmol-1 mmol of phenylacetylene), adding 0.5-5 times of equivalent of triethylamine and 0.5 mL-2 mL of dichloromethane, sealing the reaction tube, hanging an air balloon, and placing in an oil bath at 30-70 ℃ for reacting for 24-48 h to obtain the 1,3 conjugated diyne.
The invention has the beneficial effects that:
1) the invention mainly utilizes a silicon dioxide template with rich silicon hydroxyl on the surface, dopamine hydrochloride as a carbon source and metallic copper salt as a metal source to prepare the novel copper monatomic catalyst with a mesostructure and high specific surface area.
2) The invention can be extended to different types of mesoporous silica templates, such as SBA-15-OH, MCF-OH, KIT-6-OH, SBA-12-OH, FDU-12-OH, SBA-16-OH and P-SBA-15-OH.
3) The novel copper monatomic catalyst prepared by the method has an ultrahigh specific surface area, a large pore volume and a rich mesoscopic structure.
4) The synthesized novel copper monatomic catalyst with high specific surface area can obviously improve the yield of 1,3 conjugated diyne in the process of catalyzing alkyne coupling reaction.
Drawings
For a further understanding of the invention, reference will now be made in detail to the examples, given by way of illustration of the novel copper monatomic catalyst obtained in accordance with the invention, wherein:
FIGS. 1a, b, c, d, e are respectively an XRD pattern, a nitrogen physisorption pattern, a TEM picture, a HADDF-TEM picture and an X-ray absorption fine structure spectrum of a copper monatomic catalyst having a two-dimensional hexagonal structure of a sample of example 1.
Figure 2 is a drawing of the nitrogen physisorption of the copper monatomic catalyst having a two-dimensional hexagonal structure, sample of example 2.
FIGS. 3a and b are a nitrogen physical adsorption drawing and a TEM picture of a copper monatomic catalyst with a three-dimensional cubic bicontinuous structure of a sample of example 3, respectively.
FIGS. 4a and b are a nitrogen physisorption drawing and a TEM photograph of the copper monatomic catalyst having a spherical structure of the sample of example 4, respectively.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to limit the scope of the present invention.
Example 1
The catalyst was prepared by the following steps:
1) preparing a mesoporous silica SBA-15-OH template: SBA-15-surfactant mixtures were prepared according to the literatureThereafter, 8.0g of the resulting dry silica mixture was dispersed in 120mL of concentrated HNO3(65% by weight) and 40mL of hydrogen peroxide solution (35%). The mixture was then further heated to 80 ℃ and refluxed for 3 hours. (Note! the mixture is very corrosive and the reaction has to be carried out in a fume hood). And finally, filtering, washing and drying to obtain the mesoporous silica template with rich silicon hydroxyl on the surface. The specific surface area of the obtained SBA-15-OH is 810m2G, pore diameter of 10.0nm and pore volume of 1.25cm3/g。
2) 50mg of copper acetate is dissolved in 50ml of ethanol water solution (the volume content of ethanol is 30 percent), and the mixture is stirred and dissolved to form blue precursor solution. Add 1g dopamine hydrochloride and stir well. 0.5g of SBA-15-OH was added and stirred at 50 ℃ for 2 hours and then dried in an oven at 90 ℃ for 12 hours. And transferring the obtained dopamine hydrochloride-copper salt-silicon dioxide compound into a tubular furnace, calcining for 2 hours at 700 ℃ under the condition of argon, and removing the silicon dioxide template by using 2mol/L sodium hydroxide solution at 70 ℃. And centrifuging, washing with water and ethanol, and further drying to obtain the copper monatomic catalyst with the two-dimensional hexagonal structure. The specific surface area is 940m2G, pore diameter of 2.9nm and pore volume of 0.94cm3/g。
FIGS. 1a, b, c, d, e are respectively an XRD pattern, a nitrogen physisorption pattern, a TEM photograph, a HADDF-TEM photograph and an X-ray absorption fine structure spectrum of the copper monatomic catalyst having a two-dimensional hexagonal structure prepared in example 1. The pore size distribution of the material is 2.9nm as can be seen from the nitrogen physical adsorption drawing, the material obtained can be explained to be a two-dimensional hexagonal structure array structure from TEM, and the copper in the material obtained can be explained to exist in a single atom state from HADDF-TEM photos and X-ray absorption fine structure spectrums.
Example 2
The catalyst was prepared by the following steps:
synthesis of the hard template SBA-15-OH was performed as in example 1. 75mg of copper nitrate is dissolved in 50ml of ethanol water solution (the volume content of ethanol is 30 percent), and the mixture is stirred and dissolved to form a blue precursor solution. 0.9g dopamine hydrochloride was added and stirred well. 0.5g of SBA-15-OH was added and stirred at 50 ℃ for 2 hours, thenDried in an oven at 90 ℃ for 12 hours. And transferring the obtained dopamine hydrochloride-copper salt-silicon dioxide compound into a tubular furnace, calcining for 2 hours at 700 ℃ under the condition of argon, and removing the silicon dioxide template by using 2mol/L sodium hydroxide solution at 70 ℃. And centrifuging, washing with water and ethanol, and further drying to obtain the copper monatomic catalyst with the two-dimensional hexagonal structure. The specific surface area is 723m2G, pore diameter of 3.7nm and pore volume of 0.79cm3/g。
Figure 2 is a drawing of the nitrogen physisorption of the copper monatomic catalyst having a two-dimensional hexagonal structure, sample of example 2. It can be seen from FIG. 2 that it has a large specific surface area and a uniform pore size distribution, with a pore size of 3.7 nm.
Example 3
The catalyst was prepared by the following steps:
1) preparation of KIT-6-OH: a KIT-6-surfactant mixture was prepared according to the literature and the resulting dry silica mixture, 8.0g, was then dispersed in 120mL concentrated HNO3(65% by weight) and 40mL of hydrogen peroxide solution (35%). The mixture was then further heated to 80 ℃ and refluxed for 3 hours. (Note! the mixture is very corrosive and the reaction has to be carried out in a fume hood). And finally, filtering, washing and drying to obtain the mesoporous silica template with rich silicon hydroxyl on the surface. The specific surface area of the obtained KIT-6-OH was 780m2G, pore diameter of 10.9nm and pore volume of 1.3cm3/g。
2) 50mg of copper chloride is dissolved in 50ml of ethanol water solution (the volume content of ethanol is 50 percent), and the mixture is stirred and dissolved to form a blue precursor solution. 1.05g dopamine hydrochloride was added and stirred well. 0.5g of KIT-6-OH was added and stirred at 50 ℃ for 2 hours, followed by drying in an oven at 90 ℃ for 12 hours. And transferring the obtained dopamine hydrochloride-copper salt-silicon dioxide compound into a tubular furnace, calcining for 2 hours at 700 ℃ under the condition of argon, and removing the silicon dioxide template by using 2mol/L sodium hydroxide solution at 70 ℃. And centrifuging, washing with water and ethanol, and further drying to obtain the copper monatomic catalyst with the three-dimensional cubic bicontinuous structure. The specific surface area is 658m2G, pore diameter of 3.1nm and pore volume of 0.45cm3/g。
FIGS. 3a and b are a nitrogen physical adsorption drawing and a TEM picture of a copper monatomic catalyst with a three-dimensional cubic bicontinuous structure of a sample of example 3, respectively. It can be seen from FIG. 3a that it has a large specific surface area and a uniform pore size distribution, with a pore size of 3.1 nm. From the TEM photograph, it can be seen that the sample of example 3 is a three-dimensional cubic bicontinuous structure
Example 4
The catalyst was prepared by the following steps:
1) preparation of MCF-OH: MCF-surfactant mixture was prepared according to literature and the resulting dry silica mixture 8.0g was then dispersed in 120mL concentrated HNO3(65% by weight) and 40mL of hydrogen peroxide solution (35%). The mixture was then further heated to 80 ℃ and refluxed for 3 hours. (Note! the mixture is very corrosive and the reaction has to be carried out in a fume hood). And finally, filtering, washing and drying to obtain the mesoporous silica template with rich silicon hydroxyl on the surface. The specific surface area of the obtained MCF-OH is 450m2Per g, pore volume 2.6cm3/g。
2) Dissolving 150mg of copper acetate in 100ml of ethanol water solution (the volume content of ethanol is 50 percent), and stirring to dissolve to form a blue precursor solution. Add 2.5g dopamine hydrochloride and stir well. 0.5g MCF-OH was added and stirred at 50 ℃ for 2 hours and then dried in an oven at 90 ℃ for 12 hours. And transferring the obtained dopamine hydrochloride-copper salt-silicon dioxide compound into a tubular furnace, calcining for 2 hours at 700 ℃ under the condition of argon, and removing the silicon dioxide template by using 2mol/L sodium hydroxide solution at 70 ℃. The spherical copper monatomic catalyst is obtained by centrifugation, water washing and ethanol washing and further drying. The specific surface area is 742m2G, pore diameter of 3.1nm and pore volume of 0.47cm3/g。
FIGS. 4a and b are a nitrogen physisorption drawing and a TEM photograph of the copper monatomic catalyst having a spherical structure of the sample of example 4, respectively. As can be seen from fig. 4: it can be seen that it has a large specific surface area and a relatively uniform pore size distribution, with a pore size of 3.1 nm. From the TEM photographs, it can be seen that the sample of example 4 is a spherical structure.
Application examples
The catalytic reaction was carried out using the catalyst prepared in example 1, with the following steps:
placing a certain mass of copper monatomic catalyst in a Schlenk tube, and adding reactants: 0.1mmol to 1mmol alkyne, then adding 0.5 to 5 times of equivalent triethylamine and 0.5mL to 2mL dichloromethane, sealing the reaction tube, hanging an air balloon, and placing the reaction tube in an oil bath at the temperature of between 30 and 70 ℃ for reaction for 24 to 48 hours to obtain the 1,3 conjugated diyne. The use of the catalytic method is not limited to the coupling of phenylacetylene, and other different kinds of alkyne coupling products can be prepared.
The raw materials of each application example are as follows:
the alkynes of application examples 1 to 5 are in turn
The catalytic reaction parameters and yields of the respective application examples are shown in Table 1.
Table 1 the yield of 1,3 conjugated diynes synthesized using the inventive catalyst example 1 samples catalyzed different terminal alkynes.
As can be seen from Table 1, the catalyst prepared by the method has a good catalytic effect on the coupling of terminal alkynes, and the yield is 85-98%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the copper monatomic catalyst is characterized by comprising the following steps of:
(1) synthesizing a mesoporous silica template with abundant silicon hydroxyl on the surface;
(2) preparing a precursor solution of a metal copper salt;
(3) adding dopamine hydrochloride into a precursor solution of a metal copper salt, and fully dispersing to obtain a solution A;
(4) adding a mesoporous silica template with rich silicon hydroxyl groups into the solution A, and uniformly stirring to obtain turbid liquid; sealing the turbid liquid, carrying out heat preservation reaction, and drying after the reaction;
(5) and (4) calcining the dopamine hydrochloride-copper salt-silicon dioxide compound obtained in the step (4), removing a silicon dioxide template after calcining, and freeze-drying to obtain the copper monatomic catalyst.
2. The method of claim 1, wherein: the mesoporous silica template with rich silicon hydroxyl on the surface comprises SBA-15-OH, MCF-OH, KIT-6-OH, SBA-12-OH, FDU-12-OH, SBA-16-OH and P-SBA-15-OH.
3. The method of claim 1, wherein: the mesoporous silica template with rich silicon hydroxyl on the surface is prepared by the following method: adding a mixture of silicon dioxide and a surfactant, concentrated nitric acid and a hydrogen peroxide solution into a reaction container, performing reflux reaction, filtering, washing and drying to obtain a template with rich silicon hydroxyl on the surface; the surfactant is P123 or F127.
4. The method of claim 1, wherein: the metal copper salt precursor solution is obtained by dissolving metal copper salt in an ethanol water solution.
5. The production method according to claim 3, characterized in that: the metal copper salt comprises copper nitrate, copper sulfate, copper chloride, copper acetate and copper acetylacetonate; the volume content of ethanol in the ethanol water solution is 10-90%.
6. The method of claim 1, wherein: the molar ratio of the metal copper salt precursor solution to the dopamine hydrochloride is 0.1-2: 100.
7. The method of claim 1, wherein: the dosage ratio of the mesoporous silica template with rich silicon hydroxyl groups to the solution A is 0.3g-0.9g:10 mL.
8. The method of claim 1, wherein: the heat preservation temperature in the step (4) is 40-70 ℃, and the heat preservation reaction time is 2-4 hours for stirring; the drying temperature is 70-90 ℃.
9. A copper monatomic catalyst characterized by: prepared by the method of any one of steps 1-8.
10. Use of the copper monatomic catalyst of claim 9 in catalyzing alkyne coupling.
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