CN107213896A - The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst - Google Patents
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst Download PDFInfo
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- CN107213896A CN107213896A CN201710481112.7A CN201710481112A CN107213896A CN 107213896 A CN107213896 A CN 107213896A CN 201710481112 A CN201710481112 A CN 201710481112A CN 107213896 A CN107213896 A CN 107213896A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 55
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000005119 centrifugation Methods 0.000 claims abstract description 12
- 150000002940 palladium Chemical class 0.000 claims abstract description 12
- 239000000969 carrier Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001499 aryl bromides Chemical class 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- XUHFBOUSHUEAQZ-UHFFFAOYSA-N bromobenzyl cyanide Chemical compound N#CC(Br)C1=CC=CC=C1 XUHFBOUSHUEAQZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- -1 halogenated aryl hydrocarbon Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Optics & Photonics (AREA)
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Abstract
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst, the invention belongs to Suzuki reactions field, and in particular to a kind of preparation method of the catalyst of mesoporous carbon-loaded.The technical problem of the reunion of particle and leakage easily occurs the invention aims to the preparation method of existing loaded catalyst.Method is as follows：Mesoporous carbon carrier is mixed with the palladium salt aqueous solution, then stirring, centrifugation are dried, be laid on supporting boat, is positioned in discharge tube, vacuumized using vavuum pump, be passed through discharge gas, by adjusting reset valve, apply high voltage direct current at electrode two ends, electric discharge is produced.Using the catalyst production of the present invention up to more than 85%.The present invention utilizes glow discharge plasma method, realize in situ preparation of the Pd nano particles in carrier duct, load type palladium nanocatalyst made from the method has higher metal dispersity and stability, and more preferable catalytic activity and recycling are shown in catalysis Suzuki coupling reactions.
Description
Technical field
The invention belongs to Suzuki reactions field, and in particular to a kind of preparation method of the catalyst of mesoporous carbon-loaded.
Background technology
Suzuki coupling reactions are to build one of important reaction of C-C keys, and used palladium catalyst, which can be divided into, homogeneously urges
Agent and heterogeneous catalysis.Homogeneous palladium catalysts have the problem of being difficult to separate and recover, and heterogeneous catalyst can
To realize the recycling of catalyst, at present, the preparation of loaded catalyst mainly realizes Pd by chemical reduction method2+'s
Reduce, but its reduction system need to generally be carried out under liquid phase or hot conditions, easily occurred the reunion of particle and be lost in existing
As.The present invention utilizes glow discharge plasma method, in situ preparation of the Pd nano particles in carrier duct is realized, with change
Method is compared, load type palladium nanocatalyst made from the method have smaller particle size, high metal dispersity, well
Stability, show higher catalytic activity and recycling in catalysis Suzuki coupling reactions.
The content of the invention
Easily occurs reunion and the stream of particle the invention aims to the preparation method of existing loaded catalyst
There is provided a kind of in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst for the technical problem of mistake phenomenon.
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst：
First, the mesoporous carbon carriers of 1g are mixed with 3.8mL-9.4mL concentration for the 0.05mol/L palladium salt aqueous solution, adds and steam
Distilled water, makes mixed system keep 10mL-50mL, at a temperature of 25 DEG C -45 DEG C, stirring, centrifugation, then dries；
2nd, the product of step one is equably laid on supporting boat, be positioned in discharge tube, it is true using vacuum pumping
Sky, is passed through discharge gas, by adjusting reset valve, and it is 60Pa-120Pa to make gas pressure in discharge tube, is applied at electrode two ends
Gas is breakdown in high voltage direct current, discharge tube, triggers glow discharge plasma, in the bar that discharge power is 330W-660W
Under part, discharge 5min-80min, obtained mesoporous carbon-loaded palladium nanocatalyst.
The palladium salt aqueous solution described in step one is Na2PdCl4The aqueous solution, H2PdCl4The aqueous solution or Pd (NO3)2The aqueous solution.
The mesoporous carbon carriers of 1g are mixed with 5.6mL-9mL concentration for the 0.05mol/L palladium salt aqueous solution in step one.
Obtained load type palladium nanocatalyst is applied to the Suzuki coupling reactions of aryl bromide and phenyl boric acid, specifically
Condition is：Catalyst is the load type palladium nanocatalyst of above-mentioned preparation, and halogenated aryl hydrocarbon used can be for parabromoacetophenone, to bromine nitre
Base benzene, parabromotoluene, bromobenzene, to bromobenzylcyanide, para-bromoanisole, o-bromotoluene, m-bromonitrobenzene；Alkali is K2CO3,；It is used molten
Agent is the mixed system of second alcohol and water, and volume ratio is 1:1, cumulative volume is 12mL；30min, catalyst are reacted under the conditions of 60 DEG C
Consumption be the 1 ‰ of aryl bromide, yield is up to more than 85%.
The present invention prepares Pd nano particles by glow discharge plasma original position, it is highly dispersed at carrier duct
It is interior, obtain with less particle size and compared with the load type palladium nanocatalyst of polymolecularity, efficient catalytic aryl bromide
With the Suzuki coupling reactions of phenyl boric acid.
The present invention utilizes glow discharge plasma method, realizes in situ system of the Pd nano particles in carrier duct
Standby, compared with chemical method, load type palladium nanocatalyst made from the method has higher metal dispersity and stability,
More preferable catalytic activity and recycling are shown in catalysis Suzuki coupling reactions.
Brief description of the drawings
A represents P- in the XRD of Fig. 1 mesoporous carbon-loaded palladium nanocatalysts made from embodiment 1 and embodiment 5, figure
PdNPs/CMK-3, b represent PN2- PdNPs/CMK-3, c represent AA-PdNPs/CMK-3；
Fig. 2 is the N of mesoporous carbon-loaded palladium nanocatalyst made from embodiment 1 and embodiment 52In physical absorption figure, figureRepresent mesoporous carbon CMK-3,Mesoporous carbon-loaded palladium nanocatalyst made from embodiment 5 is represented,Represent embodiment
Mesoporous carbon-loaded palladium nanocatalyst made from 1；
In the graph of pore diameter distribution of Fig. 3 mesoporous carbon-loaded palladium nanocatalysts made from embodiment 1 and embodiment 5, figureRepresent mesoporous carbon CMK-3,Mesoporous carbon-loaded palladium nanocatalyst made from embodiment 5 is represented,Represent embodiment
Mesoporous carbon-loaded palladium nanocatalyst made from 1；
Fig. 4 is mesoporous carbon-loaded palladium nanocatalyst PAr-PdNPs/CMK-3 TEM photos；
Fig. 5 is mesoporous carbon-loaded palladium nanocatalyst PN2- PdNPs/CMK-3 TEM photos；
Fig. 6 is mesoporous carbon-loaded palladium nanocatalyst AA-PdNPs/CMK-3 TEM photos；
Fig. 7 is the heat filtering experimental result picture of comparative example 3.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：The in-situ preparation method of the present embodiment mesoporous carbon-loaded palladium nanocatalyst is as follows：
First, the mesoporous carbon carriers of 1g are mixed with 3.8mL-9.4mL concentration for the 0.05mol/L palladium salt aqueous solution, adds and steam
Distilled water, makes mixed system keep 10mL-50mL, at a temperature of 25 DEG C -45 DEG C, stirring, centrifugation, then dries；
2nd, the product of step one is equably laid on supporting boat, be positioned in discharge tube, it is true using vacuum pumping
Sky, is passed through discharge gas, by adjusting reset valve, and it is 60Pa-120Pa to make gas pressure in discharge tube, is applied at electrode two ends
High voltage direct current, under conditions of discharge power is 330W-660W, discharge 5min-80min, and obtained mesoporous carbon-loaded palladium is received
Rice catalyst.
Embodiment two：Present embodiment from palladium salt is water-soluble described in step one unlike embodiment one
Liquid is Na2PdCl4The aqueous solution, H2PdCl4The aqueous solution or Pd (NO3)2The aqueous solution.It is other identical with embodiment one.
Embodiment three：By 1g in step one unlike one of present embodiment and embodiment one or two
Mesoporous carbon carrier is mixed with 5.6mL-9mL concentration for the 0.05mol/L palladium salt aqueous solution.Other and embodiment one or two
One of it is identical.
Embodiment four：By 1g in step one unlike one of present embodiment and embodiment one to three
Mesoporous carbon carrier is mixed with 7.5mL concentration for the 0.05mol/L palladium salt aqueous solution.One of other and embodiment one to three
It is identical.
Embodiment five：35 in step one unlike one of present embodiment and embodiment one to four
At a temperature of DEG C, then stirring, centrifugation are dried.It is other identical with one of embodiment one to four.
Embodiment six：Unlike one of present embodiment and embodiment one to five described in step 2
Discharge gas be Ar or N2.It is other identical with one of embodiment one to five.
Embodiment seven：Make to put in step 2 unlike one of present embodiment and embodiment one to six
Gas pressure is 70Pa-100Pa in fulgurite.It is other identical with one of embodiment one to six.
Embodiment eight：Make to put in step 2 unlike one of present embodiment and embodiment one to seven
Gas pressure is 80Pa in fulgurite.It is other identical with one of embodiment one to seven.
Embodiment nine：Put in step 2 unlike one of present embodiment and embodiment one to eight
Electrical power is the 15min-50min that under conditions of 350W-600W, discharges.It is other identical with one of embodiment one to eight.
Embodiment ten：Put in step 2 unlike one of present embodiment and embodiment one to nine
Electrical power is the 40min that under conditions of 500W, discharges.It is other identical with one of embodiment one to nine.
Effect of the present invention is verified using following embodiments：
Embodiment 1：
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst is as follows：
First, by Na that the mesoporous carbon carriers of 1g and 9.4mL concentration are 0.05mol/L2PdCl4The aqueous solution is mixed, and adds distillation
Water, makes mixed system keep 40mL, at a temperature of 25 DEG C, stirring, centrifugation, then dries；
2nd, the product of 0.1g steps one is equably laid on supporting boat, be positioned in discharge tube, utilize vacuum pumping
Vacuum, is passed through discharge gas Ar, by adjusting reset valve, and it is 100Pa to make gas pressure in discharge tube, applies high at electrode two ends
Direct current is pressed, under conditions of discharge power is 440W, discharge 60min, obtained mesoporous carbon-loaded palladium nanocatalyst (PAr-
PdNPs/CMK-3)。
Embodiment 2：
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst is as follows：
First, by H that the mesoporous carbon carriers of 1g and 7.5mL concentration are 0.05mol/L2PdCl4The aqueous solution is mixed, and adds distilled water,
Mixed system is set to keep 30mL, at a temperature of 40 DEG C, then stirring, centrifugation are dried；
2nd, the product of 0.1g steps one is equably laid on supporting boat, be positioned in discharge tube, utilize vacuum pumping
Vacuum, is passed through discharge gas N2, by adjusting reset valve, it is 60Pa to make gas pressure in discharge tube, applies high at electrode two ends
Direct current is pressed, under conditions of discharge power is 550W, discharge 20min, obtained mesoporous carbon-loaded palladium nanocatalyst.
Embodiment 3：
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst is as follows：
First, by Na that the mesoporous carbon carriers of 1g and 5.6mL concentration are 0.05mol/L2PdCl4The aqueous solution is mixed, and adds distillation
Water, makes mixed system keep 20mL, at a temperature of 35 DEG C, stirring, centrifugation, then dries；
2nd, the product of 0.1g steps one is equably laid on supporting boat, be positioned in discharge tube, utilize vacuum pumping
Vacuum, is passed through discharge gas N2, by adjusting reset valve, it is 80Pa to make gas pressure in discharge tube, applies high at electrode two ends
Direct current is pressed, under conditions of discharge power is 660W, discharge 10min, obtained mesoporous carbon-loaded palladium nanocatalyst (PN2-
PdNPs/CMK-3)。
Embodiment 4：
The in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst is as follows：
First, by Pd (NO that the mesoporous carbon carriers of 1g and 3.8mL concentration are 0.05mol/L3)2The aqueous solution is mixed, and adds distillation
Water, makes mixed system keep 10mL, at a temperature of 30 DEG C, stirring, centrifugation, then dries；
2nd, the product of step one is equably laid on supporting boat, be positioned in discharge tube, it is true using vacuum pumping
Sky, is passed through discharge gas, by adjusting reset valve, and it is 120Pa to make gas pressure in discharge tube, and high straightening is applied at electrode two ends
Stream electricity, under conditions of discharge power is 330W, discharge 80min, obtained mesoporous carbon-loaded palladium nanocatalyst.
Embodiment 5：
Load type palladium nanocatalyst preparation method prepared by chemical method is as follows：
First, by Na that the mesoporous carbon carriers of 1g and 9.4mL concentration are 0.05mol/L2PdCl4The aqueous solution is mixed, and adds distillation
Water, makes mixed system keep 40mL, at a temperature of 25 DEG C, stirring, centrifugation, then dries；
2nd, the product of 0.1g steps one is added in 100mL there-necked flasks, at 60 DEG C, adds 21mL 2mol/L's
After PVP solution, stirring 30min, it is added dropwise after 20mL 0.5mol/L ascorbic acid solution, reaction 2h, obtains chemical legal system
Standby load type palladium nanocatalyst (AA-PdNPs/CMK-3).
Comparative example 1：Embodiment 1, embodiment 3 and the different bromos of load type palladium nanocatalyst catalysis prepared by embodiment 5
The Suzuki coupling reactions of aromatic hydrocarbons and phenyl boric acid：
By 1mmol aryl bromides and 2mmol K2CO3It is added in 100mL there-necked flask, adds 6mL ethanol and 6mL is gone
Ionized water, and the load type palladium nanocatalyst prepared by above-described embodiment 1, embodiment 3 and embodiment 5 is added, addition is
The 1 ‰ of aryl bromide.Reaction system stirs at 40 DEG C, after being completely dissolved, and adds 1.5mmol phenyl boric acids, air atmosphere
Lower reaction 30min.After reaction terminates, 5mL solution is taken out, 5mL 2mol/L NaOH solutions are added, after being well mixed, added
10mL ethyl acetate, stands after being well mixed, upper liquid is taken after layering in surface plate, obtained product carries out liquid chromatogram point
Analysis, as a result such as table 1.
Table 1
As shown in Table 1, Ar or N2Catalyst PAr-PdNPs/CMK-3 and PN made from glow discharge plasma2-
PdNPs/CMK-3, both are catalyzed aryl bromide and the phenyl boric acid reaction of different substrates, and its result is higher than by chemical method
The AA-PdNPs/CMK-3 of preparation.Possible the reason for is, PAr-PdNPs/CMK-3 and PN2- PdNPs/CMK-3 has smaller
Pd nanoparticle sizes, decentralization is high, is more easy to fully contact with substrate.
Comparative example 2：Above-described embodiment 1, embodiment 3 and load type palladium nanocatalyst prepared by embodiment 5 are catalyzed
The use repeatly experiment of Suzuki coupling reactions：
By 10mmol p-Nitrobromobenzenes and 20mmol K2CO3Be added in 250mL there-necked flask, add 60mL ethanol and
60mL deionized waters, and the load type palladium nanocatalyst prepared by above-described embodiment 1 is added, addition is p-Nitrobromobenzene
1‰.Reaction system stirs at 40 DEG C, after being completely dissolved, and adds under 15mmol phenyl boric acids, air atmosphere and reacts 30min.
After reaction terminates, 5mL solution is taken out, 5mL 2mol/L NaOH solutions are added, after being well mixed, 10mL ethyl acetate is added,
Stood after well mixed, upper liquid is taken after layering in surface plate, obtained product carries out liquid-phase chromatographic analysis, as a result such as table 2.
By remaining reaction solution through centrifugation, washing, dry, recovery catalyst, and it is continued to apply into Suzuki idols by above-mentioned steps
Connection reaction.
Table 2
As shown in Table 2, compared with AA-PdNPs/CMK-3 prepared by chemical method, Ar or N2Glow discharge plasma
The catalyst PAr-PdNPs/CMK-3 and PN of preparation2- PdNPs/CMK-3 shows higher recycling；But PAr-
PdNPs/CMK-3 and PN2Both-PdNPs/CMK-3 are compared, and PAr-PdNPs/CMK-3 is recycled 5 times, and yield does not occur
It is decreased obviously, PN2After-PdNPs/CMK-3 is recycled 3 times, yield is declined slightly.This is probably because Ar is as electric discharge gas
Atmosphere, Pd nanoparticle growths are slow, and it is more be distributed in mesoporous carbon duct, be not susceptible to group stronger with carrier intermolecular forces
Poly- leakage, stability is higher.
Comparative example 3：The heat filtering of above-described embodiment 1, embodiment 3 and load type palladium nanocatalyst prepared by embodiment 5
Experiment：
Distinguish in 100mL there-necked flasks, add 6mL ethanol and 6mL deionized waters, and add above-described embodiment 1 and implementation
Load type palladium nanocatalyst prepared by example 5, addition is the 1 ‰ of p-Nitrobromobenzene.Reaction system is stirred at 40 DEG C
After 30min, filter while hot.Obtained filtrate is added in another there-necked flask, is separately added into 1mmol p-Nitrobromobenzenes, 1.5mmol
Phenyl boric acid and 2mmol K2CO3, 30min is reacted at 40 DEG C.After reaction terminates, 5mL solution is taken out, 5mL 2mol/L is added
NaOH solution, after being well mixed, adds 10mL ethyl acetate, is stood after being well mixed, upper liquid is taken after layering in surface plate,
Obtained product carries out liquid-phase chromatographic analysis.
As shown in accompanying drawing 7, Ar or N2Catalyst PAr-PdNPs/CMK-3 and PN prepared by glow discharge plasma2-
PdNPs/CMK-3 heat filtering once after, active component number of dropouts is few, and palladium content is few in filtrate, thus reaction almost do not send out
It is raw.However, AA-PdNPs/CMK-3 prepared by chemical method confirms to occur in that obvious Pd leakages.
Claims (10)
1. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst, it is characterised in that：The mesoporous carbon-loaded palladium nano-catalytic
The in-situ preparation method of agent is as follows：
First, the mesoporous carbon carriers of 1g are mixed with 3.8mL-9.4mL concentration for the 0.05mol/L palladium salt aqueous solution, add distilled water,
Mixed system is set to keep 10mL-50mL, at a temperature of 25 DEG C -45 DEG C, then stirring, centrifugation are dried；
2nd, the product of step one is equably laid on supporting boat, be positioned in discharge tube, vacuumized using vavuum pump, led to
Enter discharge gas, by adjusting reset valve, it is 60Pa-120Pa to make gas pressure in discharge tube, and high straightening is applied at electrode two ends
Stream electricity, under conditions of discharge power is 330W-660W, discharge 5min-80min, obtained mesoporous carbon-loaded palladium nano-catalytic
Agent.
2. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step one
Described in the palladium salt aqueous solution be Na2PdCl4The aqueous solution, H2PdCl4The aqueous solution or Pd (NO3)2The aqueous solution.
3. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step one
It is middle to mix the mesoporous carbon carriers of 1g for the 0.05mol/L palladium salt aqueous solution with 5.6mL-9mL concentration.
4. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step one
It is middle to mix the mesoporous carbon carriers of 1g for the 0.05mol/L palladium salt aqueous solution with 7.5mL concentration.
5. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step one
In at a temperature of 35 DEG C, stirring, centrifugation, then dry.
6. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step 2
Described in discharge gas be Ar or N2。
7. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step 2
In make in discharge tube gas pressure be 70Pa-100Pa.
8. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step 2
In make in discharge tube gas pressure be 80Pa.
9. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step 2
In discharge power be 350W-600W under conditions of, discharge 15min-50min.
10. the in-situ preparation method of mesoporous carbon-loaded palladium nanocatalyst according to claim 1, it is characterised in that：Step
In two under conditions of discharge power is 500W, discharge 40min.
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| CN104368337A (en) * | 2014-10-29 | 2015-02-25 | 温州大学 | Preparation method of precious metal/mesoporous carbon catalyst, catalyst obtained thereby and application of catalyst |
| CN105032408A (en) * | 2015-09-07 | 2015-11-11 | 黑龙江省科学院石油化学研究院 | Preparation method of load type nano catalyst for catalyzing Suzuki coupling reaction |
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| CN104368337A (en) * | 2014-10-29 | 2015-02-25 | 温州大学 | Preparation method of precious metal/mesoporous carbon catalyst, catalyst obtained thereby and application of catalyst |
| CN105032408A (en) * | 2015-09-07 | 2015-11-11 | 黑龙江省科学院石油化学研究院 | Preparation method of load type nano catalyst for catalyzing Suzuki coupling reaction |
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| CN108043393A (en) * | 2017-12-16 | 2018-05-18 | 大连理工大学 | A kind of preparation method and application of carbon material palladium/carbon material catalyst of immobilized Pd nano particle in situ |
| CN108043393B (en) * | 2017-12-16 | 2021-06-01 | 大连理工大学 | Preparation method and application of palladium/carbon material catalyst with palladium nanoparticles immobilized in situ on carbon material |
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