CN108940271A - A kind of titania-silica compound loaded palladium catalyst and the preparation method and application thereof - Google Patents
A kind of titania-silica compound loaded palladium catalyst and the preparation method and application thereof Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- B01J37/16—Reducing
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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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- C07—ORGANIC CHEMISTRY
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- 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
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
Abstract
The invention belongs to palladium catalyst technical fields, and in particular to a kind of titania-silica compound loaded palladium catalyst and the preparation method and application thereof.With graphene oxide Template synthesis silica nanometer piece, titanium dioxide nanoplate is prepared with butyl titanate and hydrofluoric acid hydro-thermal reaction, silica nanometer piece and titanium dioxide nanoplate are passed through into mechanical ball mill again, under shearing force, stable three-dimensional titania-silica compound is formed by Si-O-Ti covalent linkage each other, finally by palladium acetate and ethyl alcohol as maceration extract, using hydrazine hydrate as reducing agent, titania-silica compound loaded palladium catalyst is prepared with method of chemical immersion.The catalyst load efficiency is high, and it is good to be applied to higher its catalytic activity in catalysis Suzuki coupling reaction, high recycling rate, stability.
Description
Technical field
The invention belongs to palladium catalyst technical fields, and in particular to a kind of titania-silica compound supported palladium
Catalyst and the preparation method and application thereof.
Background technique
It is a kind of mode of very important synthesis of organic substance by transition metal-catalyzed C-C coupling reaction, quite extensively
Be applied to various fields, the C-C coupling reaction such as natural medicine, advanced material, polymer, ligand mainly include Suzuki anti-
Answer, Heck reaction, Sonogashira reaction etc..For the Green Chemistry that nowadays everybody generally pursues, in chemical synthesis
In, the principle that we should follow includes highly selective (stereoselectivity, regioselectivity and chemo-selective), reaction condition
Mildly, high yield, easy to operate, low in the pollution of the environment etc..And the Suzuki reaction for meeting these conditions is reacted to Heck
The hot topic of organic synthesis, but the catalyst that both reactions use is generally precious metals palladium catalyst, the change including palladium
The supported palladium of object, complex and some traditional means is closed, but these common palladium catalysts all have expensive, reaction
It is difficult to separate with product after the completion, the disadvantages of environmental pollution is larger.For now, palladium catalyst industrially application still
So it is very limited, and the appearance of load technology, so that this problem has obtained preliminary solution.And it is mainly used for so far
The carrier of loaded palladium catalyst mainly includes polymer, porous carbon material, mesoporous silica gel, molecular sieve and various metals oxidation
Object.And carrying method is broadly divided into physical method and chemical method.Physical method mainly includes infusion process and investment, and chemical
Method mainly has the methods of surface grafting and copolycondensation.Chemical method is compared to physical method, and the palladium catalyst after load is more
Add stabilization, it is not easily to fall off, and its load component be easier to control and load after palladium Particle Distribution it is more uniform, size is more
Adduction is suitable, but its load step is more complicated, needs more operating procedures.Infusion process is prepare palladium catalyst most easy
Method, palladium catalyst prepared by infusion process, active component is mostly distributed in carrier surface, and utilization rate is high, dosage is few, cost
It is low, it is suitable for preparing single, double or more metal-supported catalysts.Influence factor is more during infusion process prepares palladium catalyst,
In mainly have the factors such as the selection of carrier, the configuration of maceration extract, dip time, drying, roasting, reduction.Nano-noble metal catalysis
Agent spreads property-large specific surface area, the surface defect of the unique physical and chemical performance of noble metal and nano material in more, crystal
The combinations such as channel is short, adsorption capacity is strong, show excellent catalytic performance, cause the extensive concern of people.
Patent CN105727992A discloses a kind of system supported hydrogenation catalyst of palladium-nickel, contains palladium, nickel in catalyst,
Mainly contain Al in carrier2O3, it is in terms of 100% by the quality of catalyst, wherein Pd content is 0.02~0.6%；Ni content is 0.04
~3%, which is alloy-type bimetallic catalyst, due to overcoming maceration extract surface tension and solvation effect in preparation side
The adverse effect of palladium-nickel dispersion is coped with, the catalyst of preparation is more conducive to form palladium-nickel alloy, and catalyst has excellent choosing
Selecting property.
Patent CN107824184A discloses a kind of preparation method of support type palladium-gold catalyst, comprising the following steps:
(1) active carbon is immersed in the mixed liquor of gold chloride and sodium tetrachloropallate, then ultrasonic disperse；(2) it filters, filter residue is taken out,
Then it is immersed in sodium hydroxide solution, then hydrazine hydrate solution is added in still aging 50min, be stirred to react；(3) it filters, filter
Slag is washed with deionized, and does not have white precipitate generation when until the silver nitrate solution of 0.1mol/L being added dropwise in cleaning solution, then
Filter residue is dried in vacuo, semi-finished product catalyst is obtained；(4) by semi-finished product catalyst soak in liquor kalii acetici, microwave treatment,
30min is stirred, 40min is then allowed to stand, is filtered, filter residue is dried in vacuo to arrive support type palladium-gold catalyst.The palladium catalyst
High with the load factor of gold, catalytic activity is good, high recycling rate.
Patent CN105478114A discloses a kind of preparation method of the palladium catalyst of ceramic membrane load, the catalyst with
Ceramic membrane is carrier, is modified first using nano-ZnO coating ceramic membrane surface and duct, and active component palladium is then used
Again through hydrazine hydrate reduction catalyst is made in salt solution impregnation.The advantages of the invention, is, by nanoscale palladium catalyst particulate load
In on the ceramic membrane of nano-ZnO coating modification, the binding force between catalyst granules and film is enhanced, the steady of catalyst is improved
It is qualitative, while the problem of catalyst is separated with the subsequent difficulty of product is avoided, it can be widely applied to hydrogenation process.
Patent CN105772080A discloses a kind of tripolite loading palladium catalyst, preparation method and its in catalysis Suzuki
Application in coupling reaction.By natural diatomaceous earth surface and its it is mesoporous present in silicone hydroxyl come with silane coupling agent KH560
It reacts, makes natural diatomaceous earth surface with epoxy group, and by epoxy group and by amino modified triphenylphosphine
Ring-opening reaction makes natural diatomaceous earth become the modified diatomite of triphenylphosphine, then matches by triphenylphosphine and the formation of free palladium
Position effect makes palladium load over celite, becomes reusable effective catalyst.This carrying method has load capacity can
It adjusts, metal dispersity is high, and particle diameter distribution is more uniform, and load process such as is simple and efficient at the excellent results.Carrying out Catalysis experiments
When, newly the yield of bromobenzene and phenyl boric acid coupling reaction can be increased to 95% or more at room temperature by the catalyst that load, and
And after recycling eight times, catalytic activity can still make yield be maintained at 90% or more.
Patent CN105797718A discloses a kind of preparation of the atom dispersion palladium catalyst of heavy load amount.(1) by dioxy
Change titanium to add in water, titanium oxide dispersion is obtained after ultrasonic disperse；(2) it is added in the titanium oxide dispersion obtained by step (1)
After the further ultrasonic disperse of palladium precursor solution, centrifugation, gained pale yellow precipitate is dispersed in water again, obtains predecessor dispersion
Liquid；(3) ultraviolet lighting is carried out to predecessor dispersion liquid obtained by step (2), after being cooled to room temperature, obtains pale yellow precipitate, then clean
It dries afterwards and disperses palladium catalyst to get the atom of heavy load amount, the atom dispersion palladium catalyst of gained heavy load amount is in faint yellow
Powder.Low in cost with strong operability, reaction unit is simple, synthesizes, preparation process condition temperature mild with post-treatment condition
With reaction process cleanliness without any pollution, the advantages that reaction efficiency is high.
Patent CN107746452A discloses a kind of palladium load different-phase catalyst and its system based on micro--mesoporous phenolic resin
Preparation Method.Its preparation step are as follows: polymerize by three (4- aldehyde radical phenyl) phosphines with phenolic hydroxyl-compounds, obtained with bigger serface
And it is rich in micro--mesoporous phenolic resin of hydroxyl and triphenylphosphine, then pass through the complexation reaction of palladium metal and triphenylphosphine, it is prepared into
To the different-phase catalyst of expanded phenol-formaldehyde resin base load palladium metal.The catalyst can be high under nitrogen or air atmosphere in an aqueous medium
The Suzuki coupling reaction of effect catalysis boronic acid compounds and halides, has preparation simply, and catalysis yield is high, catalyst easily recycles
With can Reusability the advantages that.
Summary of the invention
The object of the present invention is to provide a kind of titania-silica compound loaded palladium catalysts and preparation method thereof
With application.With graphene oxide Template synthesis silica nanometer piece, prepared with butyl titanate and hydrofluoric acid hydro-thermal reaction
Titanium dioxide nanoplate, then by silica nanometer piece and titanium dioxide nanoplate by mechanical ball mill, under shearing force,
Stable three-dimensional titania-silica compound is formed by Si-O-Ti covalent linkage each other, finally by acetic acid
Palladium and ethyl alcohol are as maceration extract, and using hydrazine hydrate as reducing agent, it is multiple that titania-silica is prepared with method of chemical immersion
Close object loaded palladium catalyst.The catalyst load efficiency is high, higher applied to its catalytic activity in catalysis Suzuki coupling reaction,
High recycling rate, stability are good.
The technical solution of the present invention is as follows:
A kind of preparation method of titania-silica compound loaded palladium catalyst, comprising the following steps:
(1) graphene oxide is dissolved in n,N-Dimethylformamide (DMF), adds 3- (isobutene acyl-oxygen) propyl
Trimethoxy silane monomer and initiator, are warming up to 60 DEG C~80 DEG C reactions under nitrogen protection, and centrifugation, washing, drying obtain
Ammonium hydroxide is added in the graphene oxide of methoxy silane grafting and is stirred friendship by the graphene oxide of methoxy silane grafting
Connection reaction, obtains suspension, centrifugation, washing, freeze-drying, and then high-temperature calcination obtains silica nanometer piece；
(2) butyl titanate is added in hydrofluoric acid aqueous solution, is stirred evenly, then heat to 150 DEG C~180 DEG C into
Row hydro-thermal reaction, obtains white depositions, and cleaning, drying obtain titanium dioxide nanoplate；
(3) ball milling, silica nanometer piece and two are carried out after mixing silica nanometer piece and titanium dioxide nanoplate
Titanium oxide forms stable three-dimensional titania-silica by Si-O-Ti covalent linkage each other under shearing force
Silicon compound；
(4) titania-silica compound is immersed in the mixed solution of palladium acetate and ethyl alcohol, then ultrasound point
It dissipates, hydrazine hydrate aqueous solution is added and stirs, filter to take filter residue, washing, drying, it is negative to obtain titania-silica compound
Carried palladium catalyst.
Preferably, in step (1) graphene oxide and 3- (isobutene acyl-oxygen) propyl trimethoxy silicane monomer weight
Than for 2~5:1~2.
Preferably, initiator is azodiisobutyronitrile in step (1).
Preferably, the reaction time is 24~30h under nitrogen protection in step (1).
Preferably, the temperature of step (1) high temperature calcining is 650 DEG C~750 DEG C.
Preferably, in step (2) the hydro-thermal reaction time be 12~for 24 hours.
Preferably, speed of agitator is 1600r/min~2000r/min in step (2), and mixing time is 2h~5h.
Preferably, the weight ratio of step (3) silica nanometer piece and titanium dioxide nanoplate is 1~2:2~3.
Preferably, soaking time is 2~3h in step (4), and supersonic frequency is 50HZ~80HZ, ultrasonic time 80min
~120min, mixing time are 40min~60min.
The titania-silica compound loaded palladium catalyst that the above method is prepared.
Application of the above-mentioned titania-silica compound loaded palladium catalyst in catalysis Suzuki coupling reaction.
Beneficial effects of the present invention are as follows:
The present invention is anti-with butyl titanate and hydrofluoric acid hydro-thermal with graphene oxide Template synthesis silica nanometer piece
Titanium dioxide nanoplate should be prepared, then by silica nanometer piece and titanium dioxide nanoplate by mechanical ball mill, in shearing force
Under effect, stable three-dimensional titania-silica compound is formed by Si-O-Ti covalent linkage each other, finally
By palladium acetate and ethyl alcohol as maceration extract, using hydrazine hydrate as reducing agent, titanium dioxide-two is prepared with method of chemical immersion
Silica composite loaded palladium catalyst.The catalyst load efficiency is high, is applied to its catalysis in catalysis Suzuki coupling reaction
Active higher, high recycling rate, stability are good.
Specific embodiment
With reference to embodiment, technical solution of the present invention is described in further detail, but do not constituted pair
Any restrictions of the invention.
Embodiment 1
A kind of preparation method of titania-silica compound loaded palladium catalyst, comprising the following steps:
(1) 3 parts by weight graphene oxides are dissolved in n,N-Dimethylformamide (DMF), add 1.5 parts by weight 3-
The initiator azodiisobutyronitrile of (isobutene acyl-oxygen) propyl trimethoxy silicane monomer and monomer mass 0.03% is protected in nitrogen
It is warming up to 65 DEG C of reactions under shield for 24 hours, is centrifuged under 4500r/min revolving speed, is then washed with DMF, 150 DEG C of dry 1h, obtain methoxy
The ammonium hydroxide that mass concentration is 25%, is added to the graphene oxide of methoxy silane grafting by the graphene oxide of base silane grafting
In be stirred cross-linking reaction, obtain suspension, be centrifuged under 4000r/min revolving speed, be then washed with deionized, be lyophilized, so
The high-temperature calcination 10h at 700 DEG C afterwards, obtains silica nanometer piece；
(2) butyl titanate is added in the hydrofluoric acid aqueous solution that mass concentration is 40%, under the revolving speed of 1800r/min
3h is stirred, 160 DEG C of hydro-thermal reaction 12h is then heated to, obtains white depositions, cleaned with deionized water, 100 DEG C of dry 5h,
Obtain titanium dioxide nanoplate；
(3) 1.5 parts by weight of silica nanometer sheets and 2 parts by weight of titanium dioxide nanometer sheets are mixed, then puts into ball milling
Ball milling 2h in machine, silica nanometer piece and titanium dioxide pass through Si-O-Ti covalent linkage each other under shearing force
Form stable three-dimensional titania-silica compound；
(4) titania-silica compound is immersed in the mixed solution of palladium acetate and ethyl alcohol, impregnates 2h, so
The ultrasonic disperse 100min under 60HZ frequency afterwards is added the hydrazine hydrate aqueous solution that mass concentration is 60% and stirs 50min, filters
Filter residue is taken, is washed with deionized, then dry 3h at 100 DEG C, obtains titania-silica compound load palladium catalysis
Agent.
In the titania-silica compound loaded palladium catalyst Suzuki coupling reaction that the present embodiment is prepared
Application, the specific steps are as follows:
2.5mmol bromobenzene is added in the mono- neck flask of 25mL, be added 3mmol phenyl boric acid, 3mmol K2CO3 and
8mL Isosorbide-5-Nitrae-dioxy six is added in the titania-silica compound loaded palladium catalyst that 30mg the present embodiment is prepared
Ring and 4mL deionized water react 2 hours at 110 DEG C as solvent, reaction system are poured into water, after filtering that screening is dry,
Recycling catalyst waits for next use, after filtrate is extracted with ethyl acetate three times, is dehydrated with magnesium sulfate, after chromatographic column purifies,
Obtained biphenyl yield has reached 92%.
Embodiment 2
A kind of preparation method of titania-silica compound loaded palladium catalyst, comprising the following steps:
(1) 5 parts by weight graphene oxides are dissolved in n,N-Dimethylformamide (DMF), add 2 parts by weight 3-
The initiator azodiisobutyronitrile of (isobutene acyl-oxygen) propyl trimethoxy silicane monomer and monomer mass 0.03% is protected in nitrogen
It is warming up to 60 DEG C of reactions under shield for 24 hours, is centrifuged under 4500r/min revolving speed, is then washed with DMF, 150 DEG C of dry 1h, obtain methoxy
The ammonium hydroxide that mass concentration is 25%, is added to the graphene oxide of methoxy silane grafting by the graphene oxide of base silane grafting
In be stirred cross-linking reaction, obtain suspension, be centrifuged under 4500r/min revolving speed, be then washed with deionized, be lyophilized, so
The high-temperature calcination 8h at 720 DEG C afterwards, obtains silica nanometer piece；
(2) butyl titanate is added in the hydrofluoric acid aqueous solution that mass concentration is 40%, under the revolving speed of 1800r/min
2.5h is stirred, 150 DEG C of hydro-thermal reaction 15h is then heated to, obtains white depositions, cleaned with deionized water, 100 DEG C of dryings
5h obtains titanium dioxide nanoplate；
(3) 2 parts by weight of silica nanometer sheets and 3 parts by weight of titanium dioxide nanometer sheets are mixed, then puts into ball mill
Middle ball milling 4h, silica nanometer piece and titanium dioxide pass through Si-O-Ti covalent linkage shape each other under shearing force
At stable three-dimensional titania-silica compound；
(4) titania-silica compound is immersed in the mixed solution of palladium acetate and ethyl alcohol, impregnates 3h, so
The ultrasonic disperse 90min under 80HZ frequency afterwards is added the hydrazine hydrate aqueous solution that mass concentration is 60% and stirs 45min, filters
Filter residue is taken, is washed with deionized, then dry 5h at 100 DEG C, obtains titania-silica compound load palladium catalysis
Agent.
In the titania-silica compound loaded palladium catalyst Suzuki coupling reaction that the present embodiment is prepared
Application, the specific steps are as follows:
2.5mmol bromobenzene is added in the mono- neck flask of 25mL, be added 3mmol phenyl boric acid, 3mmol Na2CO3 and
8mL Isosorbide-5-Nitrae-dioxy six is added in the titania-silica compound loaded palladium catalyst that 30mg the present embodiment is prepared
Ring and 4mL deionized water react 2 hours at 110 DEG C as solvent, reaction system are poured into water, after filtering that screening is dry,
Recycling catalyst waits for next use, after filtrate is extracted with ethyl acetate three times, is dehydrated with magnesium sulfate, after chromatographic column purifies,
Obtained biphenyl yield has reached 94%.
Embodiment 3
A kind of preparation method of titania-silica compound loaded palladium catalyst, comprising the following steps:
(1) 4 parts by weight graphene oxides are dissolved in n,N-Dimethylformamide (DMF), add 1 parts by weight 3-
The initiator azodiisobutyronitrile of (isobutene acyl-oxygen) propyl trimethoxy silicane monomer and monomer mass 0.03% is protected in nitrogen
It is warming up to 80 DEG C of reaction 30h under shield, is centrifuged under 4500r/min revolving speed, is then washed with DMF, 150 DEG C of dry 1h, obtains methoxy
The ammonium hydroxide that mass concentration is 25%, is added to the graphene oxide of methoxy silane grafting by the graphene oxide of base silane grafting
In be stirred cross-linking reaction, obtain suspension, be centrifuged under 4000r/min revolving speed, be then washed with deionized, be lyophilized, so
The high-temperature calcination 12h at 680 DEG C afterwards, obtains silica nanometer piece；
(2) butyl titanate is added in the hydrofluoric acid aqueous solution that mass concentration is 40%, under the revolving speed of 1800r/min
5h is stirred, 180 DEG C of hydro-thermal reaction 15h is then heated to, obtains white depositions, cleaned with deionized water, 100 DEG C of dry 5h,
Obtain titanium dioxide nanoplate；
(3) 1 parts by weight of silica nanometer sheet and 3 parts by weight of titanium dioxide nanometer sheets are mixed, then puts into ball mill
Middle ball milling 4h, silica nanometer piece and titanium dioxide pass through Si-O-Ti covalent linkage shape each other under shearing force
At stable three-dimensional titania-silica compound；
(4) titania-silica compound is immersed in the mixed solution of palladium acetate and ethyl alcohol, impregnates 2h, so
The ultrasonic disperse 120min under 65HZ frequency afterwards is added the hydrazine hydrate aqueous solution that mass concentration is 60% and stirs 60min, filters
Filter residue is taken, is washed with deionized, then dry 5h at 100 DEG C, obtains titania-silica compound load palladium catalysis
Agent.
In the titania-silica compound loaded palladium catalyst Suzuki coupling reaction that the present embodiment is prepared
Application, the specific steps are as follows:
2.5mmol 4- bromobiphenyl is added in the mono- neck flask of 25mL, 3mmol 4- fluorobenzoic boric acid, 3mmol is added
8mL is added in the titania-silica compound loaded palladium catalyst that Na2CO3 and 30mg the present embodiment is prepared
Isosorbide-5-Nitrae-dioxane and 4mL deionized water are reacted 2 hours at 110 DEG C, reaction system are poured into water, after filtering as solvent
Screening is dry, and recycling catalyst waits for next use, after filtrate is extracted with ethyl acetate three times, is dehydrated with magnesium sulfate, through color
After composing column purification, obtained biphenyl yield has reached 95%.
Embodiment 4
A kind of preparation method of titania-silica compound loaded palladium catalyst, comprising the following steps:
(1) 2 parts by weight graphene oxides are dissolved in n,N-Dimethylformamide (DMF), add 1.5 parts by weight 3-
The initiator azodiisobutyronitrile of (isobutene acyl-oxygen) propyl trimethoxy silicane monomer and monomer mass 0.03% is protected in nitrogen
It is warming up to 70 DEG C of reactions under shield for 24 hours, is centrifuged under 4500r/min revolving speed, is then washed with DMF, 150 DEG C of dry 1h, obtain methoxy
The ammonium hydroxide that mass concentration is 25%, is added to the graphene oxide of methoxy silane grafting by the graphene oxide of base silane grafting
In be stirred cross-linking reaction, obtain suspension, be centrifuged under 4000r/min revolving speed, be then washed with deionized, be lyophilized, so
The high-temperature calcination 12h at 700 DEG C afterwards, obtains silica nanometer piece；
(2) butyl titanate is added in the hydrofluoric acid aqueous solution that mass concentration is 40%, under the revolving speed of 2000r/min
3h is stirred, 180 DEG C of hydro-thermal reaction 20h is then heated to, obtains white depositions, cleaned with deionized water, 100 DEG C of dry 5h,
Obtain titanium dioxide nanoplate；
(3) 2 parts by weight of silica nanometer sheets and 3 parts by weight of titanium dioxide nanometer sheets are mixed, then puts into ball mill
Middle ball milling 2h, silica nanometer piece and titanium dioxide pass through Si-O-Ti covalent linkage shape each other under shearing force
At stable three-dimensional titania-silica compound；
(4) titania-silica compound is immersed in the mixed solution of palladium acetate and ethyl alcohol, impregnates 2.8h,
Then the ultrasonic disperse 110min under 60HZ frequency is added the hydrazine hydrate aqueous solution that mass concentration is 60% and stirs 50min, mistake
Leaching filter residue, is washed with deionized, and then dry 3h at 100 DEG C, obtains titania-silica compound supported palladium and urge
Agent.
In the titania-silica compound loaded palladium catalyst Suzuki coupling reaction that the present embodiment is prepared
Application, the specific steps are as follows:
2.5mmol bromobenzene is added in the mono- neck flask of 25mL, be added 3mmol phenyl boric acid, 3mmol K2CO3 and
8mL Isosorbide-5-Nitrae-dioxy six is added in the titania-silica compound loaded palladium catalyst that 30mg the present embodiment is prepared
Ring and 4mL deionized water react 2 hours at 110 DEG C as solvent, reaction system are poured into water, after filtering that screening is dry,
Recycling catalyst waits for next use, after filtrate is extracted with ethyl acetate three times, is dehydrated with magnesium sulfate, after chromatographic column purifies,
Calculate yield.8 catalyst are back and forth used altogether, and the recycling performance of catalyst is shown in Table 1.
1 catalyst of table reuses performance
| Test number (TN) | It is catalyzed yield | Test number (TN) | It is catalyzed yield |
| 1 | 96 | 5 | 92 |
| 2 | 95 | 6 | 92 |
| 3 | 95 | 7 | 91 |
| 4 | 93 | 8 | 90 |
By titania-silica compound loaded palladium catalyst in above embodiments 1~4 in catalysis Suzuki coupling
Experimental data in reaction is it is found that titania-silica compound loaded palladium catalyst is prepared in the present invention is applied to
It is good to be catalyzed higher its catalytic activity in Suzuki coupling reaction, high recycling rate, stability.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of titania-silica compound loaded palladium catalyst, which is characterized in that including following step
It is rapid:
(1) graphene oxide is dissolved in n,N-Dimethylformamide, adds 3- (isobutene acyl-oxygen) propyl trimethoxy
Silane monomer and initiator, are warming up to 60 DEG C~80 DEG C reactions under nitrogen protection, and centrifugation, washing, drying obtain methoxyl group silicon
Ammonium hydroxide is added in the graphene oxide of methoxy silane grafting and is stirred cross-linking reaction by the graphene oxide of alkane grafting,
Suspension, centrifugation, washing, freeze-drying are obtained, then high-temperature calcination obtains silica nanometer piece；
(2) butyl titanate is added in hydrofluoric acid aqueous solution, is stirred evenly, then heat to 150 DEG C~180 DEG C generation water
Thermal response, obtains white depositions, and cleaning, drying obtain titanium dioxide nanoplate；
(3) ball milling, silica nanometer piece and titanium dioxide are carried out after mixing silica nanometer piece and titanium dioxide nanoplate
Titanium forms stable three-dimensional titania-silica by Si-O-Ti covalent linkage each other under shearing force and answers
Close object；
(4) titania-silica compound is immersed in the mixed solution of palladium acetate and ethyl alcohol, then ultrasonic disperse,
Hydrazine hydrate aqueous solution is added and stirs, filters to take filter residue, washing, drying, obtains titania-silica compound supported palladium
Catalyst.
2. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
Be characterized in that, in step (1) weight ratio of graphene oxide and 3- (isobutene acyl-oxygen) propyl trimethoxy silicane monomer be 2~
5:1~2.
3. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
It is characterized in that, the reaction time is 24~30h under nitrogen protection in step (1), and the initiator is azodiisobutyronitrile.
4. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
It is characterized in that, the temperature of step (1) high temperature calcining is 650 DEG C~750 DEG C.
5. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
Be characterized in that, in step (2) the hydro-thermal reaction time be 12~for 24 hours.
6. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
It is characterized in that, speed of agitator is 1600r/min~2000r/min in step (2), and mixing time is 2h~5h.
7. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
It is characterized in that, the weight ratio of step (3) silica nanometer piece and titanium dioxide nanoplate is 1~2:2~3.
8. a kind of preparation method of titania-silica compound loaded palladium catalyst according to claim 1,
Be characterized in that, in step (4) soaking time be 2~3h, supersonic frequency be 50HZ~80HZ, ultrasonic time be 80min~
120min, mixing time are 40min~60min.
9. the titania-silica compound loaded palladium catalyst that any method is prepared in claim 1 to 8.
10. a kind of titania-silica compound loaded palladium catalyst as claimed in claim 9 is in catalysis Suzuki coupling
Application in reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772310A (en) * | 2019-01-16 | 2019-05-21 | 鲁东大学 | A kind of preparation and its application of mesoporous silicon supported palladium nanocluster catalyst |
| CN113828305A (en) * | 2021-10-11 | 2021-12-24 | 盱眙凹土能源环保材料研发中心 | Preparation method of Pd/attapulgite catalyst for cross-coupling reaction |
| CN114315885A (en) * | 2021-12-28 | 2022-04-12 | 山东金城柯瑞化学有限公司 | Method for catalytically synthesizing methyl 3-hydroxy-4- ((trimethylsilyl) ethynyl) benzoate |
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2018
- 2018-07-04 CN CN201810726688.XA patent/CN108940271A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772310A (en) * | 2019-01-16 | 2019-05-21 | 鲁东大学 | A kind of preparation and its application of mesoporous silicon supported palladium nanocluster catalyst |
| CN113828305A (en) * | 2021-10-11 | 2021-12-24 | 盱眙凹土能源环保材料研发中心 | Preparation method of Pd/attapulgite catalyst for cross-coupling reaction |
| CN114315885A (en) * | 2021-12-28 | 2022-04-12 | 山东金城柯瑞化学有限公司 | Method for catalytically synthesizing methyl 3-hydroxy-4- ((trimethylsilyl) ethynyl) benzoate |
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