CN112403518A - Synthesis of dicyandiamide-modified palladium nano catalyst and application of palladium nano catalyst in catalyzing phenylacetylene semi-hydrogenation - Google Patents
Synthesis of dicyandiamide-modified palladium nano catalyst and application of palladium nano catalyst in catalyzing phenylacetylene semi-hydrogenation Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 50
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 30
- 150000002940 palladium Chemical class 0.000 title claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title claims description 13
- 238000003786 synthesis reaction Methods 0.000 title claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002105 nanoparticle Substances 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 dicyandiamide modified palladium Chemical class 0.000 claims abstract description 22
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000004280 Sodium formate Substances 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 12
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000001308 synthesis method Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 10
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011981 lindlar catalyst Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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Abstract
The invention provides a dicyandiamide-modified palladium nano catalyst and application thereof in catalyzing phenylacetylene semi-hydrogenation. Firstly, dissolving polyvinylpyrrolidone, sodium formate and sodium tetrachloropalladate solution in a thick-wall pressure-resistant bottle containing N, N dimethylformamide or formamide together, then placing the bottle in an oil bath pot, reducing palladium at high temperature, and then centrifugally separating palladium nanoparticles and dissolving the palladium nanoparticles to form a palladium nanoparticle solution; and mixing the palladium nano-particle solution with dicyandiamide and N, N-dimethylformamide, placing the mixture into an oil bath pot, preserving the heat for a certain time at high temperature to obtain a dicyandiamide modified palladium nano-particle solution, then centrifugally separating out dicyandiamide modified palladium nano-particles, and dissolving the dicyandiamide modified palladium nano-particles in ethanol to obtain the dicyandiamide modified palladium nano-catalyst. The dicyandiamide modified palladium nano-catalyst provided by the invention shows good performance in the application of catalyzing acetylene hydrocarbon hydrogenation to prepare olefin, realizes high activity and high selectivity, and is low in price and environment-friendly.
Description
Technical Field
The invention belongs to the field of selective hydrogenation, and particularly relates to synthesis of a dicyandiamide-modified palladium nano catalyst and application of the dicyandiamide-modified palladium nano catalyst in catalyzing phenylacetylene semi-hydrogenation.
Background
The selective hydrogenation of triple-bond alkynes to double-bond alkenes is a very important reaction in chemical production and also has great challenges. Phenylacetylene contained in styrene can affect the quality of olefin, the product performance of olefin synthesis is affected, and the improvement of the selectivity of olefin is the key point of research. Most of the catalytic reactions occur on the surface of the catalyst, the surface structure determines the catalytic property, the change of the surface structure directly influences the capability of the catalyst, and the surface modification of the catalyst is a good strategy. Highly reactive metals are generally selectively protected by organic or inorganic substances, a strategy known as "poisoning of metals". Generally, the poisoning strategy can select organic substances to perform surface modification on metal nanoparticles, so that metal-organic interaction is generated to influence adsorption of reactants or products, thereby realizing improvement of catalyst selectivity.
The Lindlar catalyst is used for catalyzing alkyne to prepare olefin in industry, but the Lindlar catalyst has poor selectivity and low activity, so that the site of an active center is not clear, and the reaction is complex. The pure palladium-loaded catalyst has almost no selectivity, so that the invention generates steric effect and electronic effect by regulating and controlling the ligand structure on the surface of the palladium, thereby improving the selectivity of the catalyst.
Disclosure of Invention
The invention aims to synthesize a dicyandiamide-modified palladium nano catalyst and application thereof in catalyzing phenylacetylene semi-hydrogenation.
In order to achieve the purpose, the invention adopts the technical scheme that:
a synthetic method of a dicyandiamide modified palladium nano-catalyst comprises the following steps:
1) dissolving polyvinylpyrrolidone (PVP), sodium formate and sodium tetrachloropalladate solution together in a thick-wall pressure-resistant bottle containing N, N Dimethylformamide (DMF) or formamide, ultrasonically vibrating to disperse the raw materials, then placing the raw materials in an oil bath pot, reducing palladium nanoparticles by keeping the temperature at high temperature for a certain time, then centrifugally washing, separating the palladium nanoparticles, and dissolving the palladium nanoparticles in N, N dimethylformamide to form a palladium nanoparticle solution;
2) adding the palladium nanoparticle solution, dicyandiamide and N, N-Dimethylformamide (DMF) into a high-pressure bottle, ultrasonically mixing and dispersing, placing the mixture into an oil bath pot, preserving the heat at a high temperature for a certain time to obtain a dicyandiamide modified palladium nanoparticle solution, then centrifugally washing, separating out dicyandiamide modified palladium nanoparticles, and dissolving the dicyandiamide modified palladium nanoparticles in ethanol to obtain a dicyandiamide modified palladium nano catalyst.
In the synthesis method, step 1) sodium formate is used as a reducing agent to reduce Pd nano-particles, meanwhile, the sodium formate is catalyzed by Pd to form sodium carbonate, polyvinylpyrrolidone is added as a dispersing agent, and the Pd nano-particles are synthesized at high temperature and cooled and centrifuged at room temperature to obtain a Pd nano-particle solution; in the step 2), the obtained palladium nanoparticles need to control proper rotating speed in the centrifugal process, and the solvent can be separated from the palladium catalyst by high-speed centrifugation, so that the dicyandiamide-modified palladium nano catalyst is obtained.
Further, in the step 1), the concentration of the sodium tetrachloropalladate solution is 0.2mol/L, and the mass ratio of the polyvinylpyrrolidone, the sodium formate and the sodium tetrachloropalladate solution is 1: 2-2.5: 0.3.
Further, in the step 1), the synthesis temperature is 100-160 ℃, and the heat preservation time is 80-240 min.
Further, in the step 2), the synthesis temperature is 80-120 ℃, and the heat preservation time is 200-240 min.
Further, in the step 2), the dosage ratio of the palladium nanoparticle solution, dicyandiamide and N, N-dimethylformamide is 3 mL: 600 mg: 20 mL.
Further, in step 1) and step 2), the solvent used in the centrifugal washing is at least one of ethanol, acetone, and N, N-dimethylformamide.
Further, in the step 1) and the step 2), the ultrasonic time is 10min to 20min, the temperature during centrifugation is room temperature, the centrifugation rotating speed is 9000r to 12000r, and the centrifugation time is 10min to 20 min.
The dicyandiamide modified palladium nano-catalyst provided by the invention shows good performance in the application of catalyzing acetylene hydrocarbon hydrogenation to prepare olefin, realizes high activity and high selectivity, and is low in price and environment-friendly. For example, catalytic phenylacetylene hemihydrogenation: dissolving dicyandiamide-modified palladium nano-catalyst and phenylacetylene in ethanol, controlling the temperature to be 25-30 ℃ and the hydrogen pressure to be 0.05-0.15 MPa, and carrying out alkyne hydrogenation reaction.
By adopting the technical scheme, the invention provides the palladium catalyst which is simple in synthesis and can effectively improve the selective hydrogenation of phenylacetylene to styrene, the palladium nanoparticles are modified by dicyandiamide, the reaction conditions in the experiment are changed under the regulation and control of a proper molar ratio, the change of the surface structure and the electronic effect of the catalyst is influenced, and the selectivity of the catalyst can be obviously improved when the catalyst catalyzes phenylacetylene. The synthesized dicyandiamide modified palladium nano-catalyst has good dispersibility, shows a good effect when phenylacetylene is selectively hydrogenated into styrene at normal temperature, reaches over 89 percent of selectivity, and is higher than that of a selective hydrogenation catalyst used in the conventional industry. The catalysis has the advantages of easy synthesis, high catalysis efficiency and the like. In addition, the catalyst synthesis method has the advantages of low cost, simple operation, high yield and small environmental pollution.
The invention has the beneficial effects that: the dicyandiamide modified palladium nano-catalyst with high activity, high selectivity and high cycle stability is synthesized by the method. The dicyandiamide modified palladium nano-catalyst is adopted for selective hydrogenation, and the phenylacetylene is subjected to semi-hydrogenation test under the mild condition of fixing H2/0.1MPa at the temperature of 30 ℃, so that the selectivity reaches over 89.4 percent within 100min, and is higher than that of a Lindlar (Lindlar) catalyst adopted in the industry. In the experiment, the palladium nano-catalyst with different modification degrees can be synthesized by controlling the reaction conditions of the synthesis steps and changing the molar ratio of dicyandiamide to palladium, so that the dicyandiamide-modified palladium nano-catalyst with excellent performance is prepared. The catalyst synthesis method has simple steps, can popularize the experiment to the synthesis catalysis of other palladium-based catalysts, and provides theoretical guidance. The chemical reduction method adopted by the invention for preparing the dicyandiamide nano-catalyst has important significance for solving the problem of the actual alkyne semi-hydrogenation at present.
Drawings
FIG. 1 is a transmission electron micrograph of the synthesized palladium nanoparticles.
Fig. 2 is a graph of catalytic performance of the sodium carbonate supported palladium copper nano catalyst prepared in example 1 for preparing styrene by hydrogenation of phenylacetylene, and it can be seen from the graph that the catalyst activity is very high, and the selectivity is more than 89.4% in 100 min.
Detailed Description
The essential matters and advantageous effects of the present invention will be further described in detail with reference to the accompanying drawings and examples
Example 1
Synthetic method and application of dicyandiamide-modified palladium nano-catalyst
1) Preparing 0.2mol/L sodium tetrachloropalladate solution: 1 g of palladium chloride and 0.6592 g of sodium chloride are taken by an electronic balance through weighing paper and dissolved in 32ml of ultrapure water to obtain 0.2mol/L sodium tetrachloropalladate solution, and the solution is put into a refrigerator for refrigeration and preservation for standby.
2) Reduction of Pd particles: taking 30 mg of sodium tetrachloropalladate solution by using a manual pipette, taking 20ml of N, N-dimethylformamide by using a pipette, weighing 100 mg of polyvinylpyrrolidone and 200 mg of sodium formate by using an electronic balance, adding the raw materials into a thick-wall pressure-resistant bottle, ultrasonically mixing for 10-20min for assisting dispersion, then placing the bottle into an oil bath pot, setting the temperature of the oil bath to be 160 ℃ at room temperature, preserving the temperature for 80min, and then cooling to the room temperature. And then adding ethanol and acetone to carry out centrifugal purification for 3-4 times, separating out Pd nanoparticles, dissolving with 9mL of N, N-dimethylformamide to obtain a Pd nanoparticle solution, and putting the Pd nanoparticle solution into a refrigerator for cold storage and preservation for later use.
3) Preparing dicyandiamide modified Pd nano-catalyst: taking 3mL of Pd nanoparticle solution by using a manual pipette, adding 600mg of dicyandiamide and 20mL of N, N-dimethylformamide, completely adding into a dry high-pressure bottle, ultrasonically mixing to assist dispersion, then placing into an oil bath pot, setting the oil bath temperature to be 120 ℃ at room temperature, preserving the temperature for 200min, and then cooling to room temperature. Pouring dicyandiamide modified Pd nano-particles into a centrifugal test tube, adding ethanol and acetone, carrying out centrifugal purification for 3-4 times, separating out dicyandiamide modified Pd nano-catalyst, dissolving the dicyandiamide modified Pd nano-catalyst in the test tube by using ethanol, sticking a label, and placing the test tube in a refrigerator for cold storage and storage for later use.
4) 0.6mL of the synthesized dicyandiamide-modified Pd nano-catalyst was dispersed in 5mL of ethanol, 1mmol of phenylacetylene (commercially available) was added to a dry thick-walled pressure-resistant bottle, a hydrogenation test was performed under a fixed 0.1 MPa/hydrogen pressure and 25 ℃ and the selectivity of the catalyst was evaluated by a gas chromatograph.
Results referring to FIGS. 1-2, it can be seen from FIG. 2 that the catalyst activity is very high with a selectivity of over 89.4% at 100 min.
Example 2
Synthesis method of dicyandiamide-modified palladium nano catalyst
1) Preparing 0.2mol/L sodium tetrachloropalladate solution: the same as in example 1.
2) Reduction of Pd particles: adding 30 mg of sodium tetrachloropalladate solution, 20ml of N, N-dimethylformamide, 100 mg of polyvinylpyrrolidone and 250 mg of sodium formate into a thick-wall pressure-resistant bottle, ultrasonically mixing for 10min to aid dispersion, then placing the mixture into an oil bath pot, setting the temperature of the oil bath to be 100 ℃ at room temperature, preserving the heat for 240min, and then cooling to the room temperature. Adding ethanol and acetone, performing centrifugal purification for 3 times, separating out Pd nanoparticles, and dissolving with 9mL of N, N-dimethylformamide to obtain a Pd nanoparticle solution;
3) preparing dicyandiamide modified Pd nano-catalyst: taking 3mL of Pd nanoparticle solution, adding 720mg of dicyandiamide and 20mL of N, N-dimethylformamide, completely adding into a dry high-pressure bottle, ultrasonically mixing to aid dispersion, then placing into an oil bath pot, setting the oil bath temperature to rise to 80 ℃ at room temperature, preserving the heat for 240min, and then cooling to room temperature. Pouring dicyandiamide modified Pd nano-particles into a centrifugal test tube, adding ethanol and acetone, carrying out centrifugal purification for 3 times, separating out dicyandiamide modified Pd nano-catalyst, dissolving with ethanol, and refrigerating for storage.
Example 3
Synthesis method of dicyandiamide-modified palladium nano catalyst
1) Preparing 0.2mol/L sodium tetrachloropalladate solution: the same as in example 1.
2) Reduction of Pd particles: adding 30 mg of sodium tetrachloropalladate solution, 20ml of N, N-dimethylformamide, 100 mg of polyvinylpyrrolidone and 200 mg of sodium formate into a thick-wall pressure-resistant bottle, ultrasonically mixing for 20min to aid dispersion, placing the mixture into an oil bath pot, setting the temperature of the oil bath to 160 ℃ at room temperature, preserving the heat for 80min, and cooling to room temperature. Adding ethanol and acetone, performing centrifugal purification for 4 times, separating out Pd nanoparticles, and dissolving with 9mL of N, N-dimethylformamide to obtain a Pd nanoparticle solution;
3) preparing dicyandiamide modified Pd nano-catalyst: taking 3mL of Pd nanoparticle solution, adding 700mg of dicyandiamide and 20mL of N, N-dimethylformamide, completely adding into a dry high-pressure bottle, ultrasonically mixing to aid dispersion, then placing into an oil bath pot, setting the oil bath temperature to raise to 120 ℃ at room temperature, preserving the heat for 200min, and then cooling to room temperature. Pouring dicyandiamide modified Pd nano-particles into a centrifugal test tube, adding ethanol and acetone, carrying out centrifugal purification for 4 times, separating out dicyandiamide modified Pd nano-catalyst, dissolving with ethanol, and refrigerating for storage.
Example 4
Synthesis method of dicyandiamide-modified palladium nano catalyst
1) Preparing 0.2mol/L sodium tetrachloropalladate solution: the same as in example 1.
2) Reduction of Pd particles: adding 30 mg of sodium tetrachloropalladate solution, 20ml of N, N-dimethylformamide, 100 mg of polyvinylpyrrolidone and 200 mg of sodium formate into a thick-wall pressure-resistant bottle, ultrasonically mixing for 15min to aid dispersion, then placing the mixture into an oil bath pot, setting the temperature of the oil bath to be 130 ℃ at room temperature, preserving the heat for 160min, and then cooling to the room temperature. Adding ethanol and acetone, performing centrifugal purification for 3 times, separating out Pd nanoparticles, and dissolving with 9mL of N, N-dimethylformamide to obtain a Pd nanoparticle solution;
3) preparing dicyandiamide modified Pd nano-catalyst: taking 4mL of Pd nanoparticle solution, adding 800mg of dicyandiamide and 20mL of N, N-dimethylformamide, completely adding into a dry high-pressure bottle, ultrasonically mixing to aid dispersion, then placing into an oil bath pot, setting the oil bath temperature to rise to 100 ℃ at room temperature, preserving the heat for 220min, and then cooling to room temperature. Pouring dicyandiamide modified Pd nano-particles into a centrifugal test tube, adding ethanol and acetone, carrying out centrifugal purification for 3 times, separating out dicyandiamide modified Pd nano-catalyst, dissolving with ethanol, and refrigerating for storage.
Example 5
Synthesis method of dicyandiamide-modified palladium nano catalyst
1) Preparing 0.2mol/L sodium tetrachloropalladate solution: the same as in example 1.
2) Reduction of Pd particles: adding 30 mg of sodium tetrachloropalladate solution, 20ml of formamide, 100 mg of polyvinylpyrrolidone and 200 mg of sodium formate into a thick-wall pressure-resistant bottle, ultrasonically mixing for 10min to assist dispersion, then placing into an oil bath pot, setting the temperature of the oil bath to be increased to 120 ℃ at room temperature, preserving the temperature for 120min, and then cooling to room temperature. Adding ethanol and acetone, carrying out 3-step centrifugal purification, separating Pd nanoparticles, and dissolving with 9mL of formamide to obtain a Pd nanoparticle solution;
3) preparing dicyandiamide modified Pd nano-catalyst: taking 3mL of Pd nanoparticle solution, adding 600mg of dicyandiamide and 20mL of N, N-dimethylformamide, completely adding into a dry high-pressure bottle, ultrasonically mixing to aid dispersion, then placing into an oil bath pot, setting the temperature of the oil bath to be 150 ℃ at room temperature, preserving the heat for 210min, and then cooling to room temperature. Pouring dicyandiamide modified Pd nano-particles into a centrifugal test tube, adding ethanol and acetone, carrying out centrifugal purification for 3 times, separating out dicyandiamide modified Pd nano-catalyst, dissolving with ethanol, and refrigerating for storage.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A synthetic method of a dicyandiamide modified palladium nano-catalyst is characterized by comprising the following steps:
1) dissolving polyvinylpyrrolidone, sodium formate and sodium tetrachloropalladate solution together in a thick-wall pressure-resistant bottle containing N, N-dimethylformamide or formamide, ultrasonically vibrating to disperse the raw materials, then placing the raw materials in an oil bath pot, reducing palladium nanoparticles by high-temperature heat preservation for a certain time, then centrifugally washing, separating the palladium nanoparticles, and dissolving the palladium nanoparticles in N, N-dimethylformamide to form a palladium nanoparticle solution;
2) adding the palladium nanoparticle solution, dicyandiamide and N, N-dimethylformamide into a high-pressure bottle, ultrasonically mixing and dispersing, placing the mixture into an oil bath pot, preserving the heat at high temperature for a certain time to obtain a dicyandiamide modified palladium nanoparticle solution, then centrifugally washing, separating out dicyandiamide modified palladium nanoparticles, and dissolving the dicyandiamide modified palladium nanoparticles in ethanol to obtain a dicyandiamide modified palladium nano catalyst.
2. The method for synthesizing the dicyandiamide-modified palladium nano-catalyst according to claim 1, wherein in the step 1), the concentration of the sodium tetrachloropalladate solution is 0.2mol/L, and the mass ratio of the polyvinylpyrrolidone, the sodium formate and the sodium tetrachloropalladate solution is 1: 2-2.5: 0.3.
3. The synthesis method of the dicyandiamide-modified palladium nano-catalyst according to claim 1, wherein in the step 1), the synthesis temperature is 100-160 ℃, and the heat preservation time is 80-240 min.
4. The synthesis method of the dicyandiamide-modified palladium nano-catalyst according to claim 1, wherein in the step 2), the synthesis temperature is 80-120 ℃, and the heat preservation time is 200-240 min.
5. The method for synthesizing the dicyandiamide-modified palladium nano-catalyst according to claim 1, wherein in the step 2), the dosage ratio of the palladium nano-particle solution, dicyandiamide and N, N-dimethylformamide is 3 mL: 600 mg: 20 mL.
6. The method for synthesizing the dicyandiamide-modified palladium nanocatalyst according to claim 1, wherein in the step 1) and the step 2), a solvent used for centrifugal washing is at least one of ethanol, acetone and N, N-dimethylformamide.
7. The synthesis method of the dicyandiamide modified palladium nano-catalyst according to claim 1, wherein in the step 1) and the step 2), the ultrasonic time is 10min to 20min, the temperature during centrifugation is room temperature, the centrifugation speed is 9000r to 12000r, and the centrifugation time is 10min to 20 min.
8. Dicyandiamide-modified palladium nanocatalysts obtained according to the synthesis process of any one of claims 1 to 7.
9. The use of the dicyandiamide-modified palladium nanocatalyst of claim 8 in catalyzing the hemihydrogenation of phenylacetylene.
10. Use according to claim 9, characterized in that: dissolving dicyandiamide-modified palladium nano-catalyst and phenylacetylene in ethanol, controlling the temperature to be 25-30 ℃ and the hydrogen pressure to be 0.05-0.15 MPa, and carrying out alkyne hydrogenation reaction.
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