CN110479253A - A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde - Google Patents
A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde Download PDFInfo
- Publication number
- CN110479253A CN110479253A CN201910867393.9A CN201910867393A CN110479253A CN 110479253 A CN110479253 A CN 110479253A CN 201910867393 A CN201910867393 A CN 201910867393A CN 110479253 A CN110479253 A CN 110479253A
- Authority
- CN
- China
- Prior art keywords
- nano diamond
- catalyst
- shell structure
- palladium
- benzyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
The invention belongs to catalytic fields, and in particular to a kind of Nano diamond carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde, effective catalytic phenylmethanol aoxidize producing benzaldehyde.Preparation method of the present invention is by making the high defect graphene of fresh Nano diamond Surface Creation in high-temperature calcination, then nitric acid oxidation again, obtain Nano diamond-graphene oxide core-shell structure carbon carrier, and metal Pd is stablized in carbon support by ion-exchange, again through hydrogen reducing, Nano diamond carried palladium catalyst is obtained.Catalyst prepared by the present invention has excellent conversion ratio and selectivity in benzyl alcohol producing benzaldehyde reaction process, and phenmethylol conversion ratio reaches 100%, and benzaldehyde selectively reaches 94%.
Description
Technical field
The invention belongs to catalytic fields, and in particular to a kind of Nano diamond for benzyl alcohol producing benzaldehyde-load palladium is urged
Agent and its preparation method and application, effective catalytic phenylmethanol aoxidize producing benzaldehyde.
Background technique
Benzaldehyde is a kind of important organic chemical industry's intermediate, is widely used in the row such as medicine, plastics, additive, fragrance
Industry.Contain chloride or chloride ion in the benzaldehyde product of traditional chlorination toluene Hydrolyze method production, limits the reality of benzaldehyde
Border application.In addition, conventional method is there are process flow length, product separation is difficult, discharge corrosive gas and debirs etc. are scarce
Point.Oxygen is Green Oxidant, and benzyl alcohol Oxygen Catalytic Oxidation producing benzaldehyde is a kind of green cleaning, environmental-friendly producer
Method.
Currently, the selectivity of the conversion ratio and benzaldehyde that how to improve benzyl alcohol has become benzyl alcohol dioxygen oxidation benzene first
Most challenging one of the research topic of aldehyde reaction.In addition, traditional catalyst also bring post-processing cumbersome, catalyst recycling difficult with
And the problems such as environmental pollution.Therefore, in order to solve these problems, the environment-friendly type that catalytic activity is high, is easily recycled is designed and developed to urge
The emphasis for person's concern that agent is still current research.
Nano diamond has stable chemical property, high heat conductivity and small particle size, big specific surface area
With the characteristics such as fault of construction, through high-temperature calcination, Nano diamond surface produces the graphene of high defect, obtains a nanometer Buddha's warrior attendant
Stone-graphene core-shell structure carbon material.The Nano diamond-graphene core-shell structure is conducive to the transfer of electronics in catalysis reaction,
Be conducive to the evenly dispersed of metal, the active site of abundant exposing metal inhibits the heat of metal nanometre cluster or metal nanoparticle
Mechanics is reunited, therefore is a kind of effective system using Nano diamond-carbon material supported metallic catalyst of graphene core-shell structure
The method of standby high activated catalyst.Based on this, the present invention is from Nano diamond-graphene core-shell structure carbon material, research and development
New Nano diamond-carried palladium catalyst suitable for benzyl alcohol oxidation producing benzaldehyde out has important application value.
Summary of the invention
To solve defect of the existing technology, it is an object of that present invention to provide a kind of receiving for benzyl alcohol producing benzaldehyde
Rice diamond-carried palladium catalyst and preparation method thereof.
For achieving the above object, the invention adopts the following technical scheme:
One aspect of the present invention provides a kind of Nano diamond-carried palladium catalyst, and the catalyst is made in accordance with the following methods
It is standby to obtain:
(1) Nano diamond-graphene core-shell structure carbon material ND@G is prepared；
(2) Nano diamond obtained in step (1)-graphene core-shell structure carbon material ND@G is dispersed in 30~
In 40mL nitric acid, 4~8h of heating stirring in 80~160 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material
Carrier ND@GO；Wherein, Nano diamond concentration in nitric acid is 10mg/mL~15mg/mL；The quality of the nitric acid point
Number is 50%~68%；
(3) Nano diamond obtained in step (2)-graphene core-shell structure carbon material carrier ND@GO is passed through into ultrasound
It is evenly dispersed in solvent；Under stirring conditions, palladium chloride solution is added dropwise, heats 1~4h, filtering drying obtains palladium/receive
Rice diamond-graphene oxide compound precursor object；
(4) by palladium/Nano diamond described in step (3)-graphene oxide compound precursor object, in the mixed of hydrogen and helium
It closes in gas after 100~300 DEG C of 1~2h of reduction are handled to get to Nano diamond carried palladium catalyst Pd/ND@GO.
In above-mentioned technical proposal, specifically, the step (1) is by fresh Nano diamond at 900~1100 DEG C, argon
Atmosphere encloses 1~4h of middle heat preservation.
In above-mentioned technical proposal, specifically, solvent is one of water, ethyl alcohol, acetone in the step (3).
In above-mentioned technical proposal, specifically, palladium chloride solution is that palladium chloride is added drop-wise to containing dilute hydrochloric acid in step (3)
In 2~4mL solvent, wherein the load capacity of palladium is 0.5%~5%；Dilute hydrochloric acid additional amount is 0.05~0.1mL, and dilute hydrochloric acid is added
Concentration be 1.2moL/L.
In above-mentioned technical proposal, specifically, temperature used in step (3) is 50-70 DEG C.
Another aspect of the present invention provides application of the aforementioned catalytic agent in benzyl alcohol producing benzaldehyde.
Third aspect present invention provides a kind of method of benzyl alcohol producing benzaldehyde, the method are as follows: benzyl alcohol, catalysis
Agent, ortho-xylene solvent be added reaction kettle in, be filled with oxygen, under 1~7bar pressure, at 85~125 DEG C react 2.5~
4.5h；The catalyst is aforementioned catalytic agent；The amount ratio of catalyst and benzyl alcohol is 1mL:10-100mg.
The invention has the advantages that: the method for the present invention to handle Nano diamond-graphene core-shell structure carbon materials through nitric acid oxidation
Material, obtains Nano diamond-graphene oxide core-shell structure carbon material, as carrier to load metal palladium, then is carried out hydrogen
Reduction obtains a kind of new Nano diamond-carried palladium catalyst for benzyl alcohol producing benzaldehyde, passes through nitric acid oxidation nanogold
Hard rock-graphene core-shell structure carbon material preparation catalyst, selectivity is strong, has excellent catalytic properties, and product purity is high,
Phenmethylol conversion ratio reaches 100%, and benzaldehyde selectively reaches 94%, and catalyst can be by filtering or being centrifuged recycling.The material
Synthesis technology is simple, does not corrode equipment, pollutes without " three wastes ", using conveniently, has broad application prospects in catalytic field.
Detailed description of the invention
Fig. 1 is the FTIR spectrum figure of 4 catalyst carrier of comparative example and embodiment；
Fig. 2 is the X-ray diffractogram of 4 catalyst of comparative example and embodiment；
Fig. 3 is the transmission electron microscope picture of embodiment 4 and comparative example catalyst；Fig. 3 a, Fig. 3 b be 4 catalyst of embodiment, Fig. 3 c,
3d is comparative example catalyst；
Fig. 4 is the grain size distribution of embodiment 4 and comparative example catalyst；Fig. 4 a is 4 catalyst of embodiment, and Fig. 4 b is comparison
Example catalyst.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit the invention in any way.
Embodiment 1
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 68%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 61.49%, benzaldehyde are selectively 74.83%.
Embodiment 2
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 64%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 81.37%, benzaldehyde are selectively 80.27%.
Embodiment 3
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 60%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 100%, benzaldehyde are selectively 84.83%.
Embodiment 4
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 58%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 100%, benzaldehyde are selectively 94.43%.
Embodiment 5
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 51%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 85.59%, benzaldehyde are selectively 84.19%.
Embodiment 6
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 58%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 100 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 60.15%, benzaldehyde are selectively 68.80%.
Embodiment 7
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 58%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 2.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 80.83%, benzaldehyde are selectively 88.35%.
Embodiment 8
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 58%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 25mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 76.35%, benzaldehyde are selectively 74.70%.
Embodiment 9
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 500mg
In the nitric acid that Nano diamond-graphene core-shell structure carbon material (ND@G) is dispersed in 37mL, mass fraction is 58%, In
Heating stirring 6h in 120 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material carrier (ND@GO)；By 200mg
The Nano diamond of above-mentioned preparation-graphene oxide core-shell structure carbon material carrier (ND@GO) is evenly dispersed in 30mL ethyl alcohol
In solution；Be added dropwise 4mL palladium chloride solution (wherein contain 10mg palladium chloride), 60 DEG C of heating stirring 4h, filtering drying, obtain palladium/
Nano diamond-graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
To get arriving Nano diamond-carried palladium catalyst (Pd/ND@GO) after 300 DEG C of reductase 12 h processing.
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 1bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 9.50%, benzaldehyde are selectively 70.50%.
Comparative example
Fresh Nano diamond powder is put into crucible, crucible is put into tube furnace, argon gas is passed through, with 5 DEG C/
The rate of min rises to 1100 DEG C, keeps the temperature 4h, obtains Nano diamond-graphene core-shell structure carbon material (ND@G)；Take 200mg
The Nano diamond of above-mentioned preparation-graphene core-shell structure carbon material (ND@G) is dispersed in 30mL ethanol solution；It is added dropwise
4mL palladium chloride solution (wherein contains 10mg palladium chloride), and 60 DEG C of heating stirring 4h, filtering drying obtains palladium/Nano diamond-
Graphene oxide compound precursor object；Predecessor is placed in quartz ampoule, in 300 DEG C of reductase 12 h in the gaseous mixture of hydrogen and helium
After processing to get arrive Nano diamond carried palladium catalyst (Pd/ND@G).
1mL benzyl alcohol, 50mg catalyst obtained above, 25mL ortho-xylene solvent are added to 60mL stainless steel high pressure
In reaction kettle, it is filled with 7bar O2, 3.5h is reacted at 115 DEG C.End of reaction is separated by filtration catalyst, and product is through gas phase color
Spectrum analysis, phenmethylol conversion ratio 46%, benzaldehyde are selectively 55%.
Fig. 1 is the FTIR spectrum figure of 4 catalyst carrier ND@GO of comparative example catalyst carrier ND@G and embodiment
Picture, as seen from the figure, Pd/ND@GO is in 1730cm-1There is carbonyl peak in place, illustrates that carrier surface is successfully aoxidized, is conducive to metal
The load of palladium.
Fig. 2 is the X-ray diffraction image of 4 catalyst Pd/ND GO of comparative example catalyst Pd/ND G and embodiment, is sent out in figure
There is the diffractive features peak of Pd in existing catalyst Pd/ND@G, and the diffractive features peak of Pd does not occur in catalyst Pd/ND@GO；Explanation
The crystallinity of Pd is bigger than the crystallinity of Pd on catalyst Pd/ND@GO on catalyst Pd/ND@G, i.e. the Pd grain of catalyst Pd/ND@G
Diameter is bigger than the Pd partial size of catalyst Pd/ND@GO.
It is the transmission electron microscope figure of embodiment 4 catalyst Pd/ND@GO and comparative example catalyst Pd/ND@G in Fig. 3
Picture, Fig. 4 are the particle size distribution map of embodiment 4 catalyst Pd/ND@GO and comparative example catalyst Pd/[email protected] Fig. 3 and Fig. 4
As it can be seen that Pd particle is uniformly dispersed in catalyst support surface, the Pd average grain diameter of Pd/ND@GO is 1.9nm, and the Pd of Pd/ND@G is flat
Equal partial size is 2.5nm.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, anything that does not depart from the technical scheme of the invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (7)
1. a kind of Nano diamond-carried palladium catalyst, which is characterized in that the catalyst is prepared in accordance with the following methods:
(1) Nano diamond-graphene core-shell structure carbon material ND@G is prepared；
(2) Nano diamond-graphene core-shell structure carbon material ND@G prepared in step (1) is dispersed in 30~
In 40mL nitric acid, 4~8h of heating stirring in 80~160 DEG C obtains Nano diamond-graphene oxide core-shell structure carbon material
Carrier ND@GO；Wherein, Nano diamond concentration in nitric acid is 10mg/mL~15mg/mL；The quality of the nitric acid point
Number is 50%~68%；
(3) Nano diamond-graphene core-shell structure carbon material carrier ND@GO prepared in step (2) is equal by ultrasound
Disperse evenly in a solvent；Under stirring conditions, palladium chloride solution is added dropwise, heats 1~4h, filtering drying obtains palladium/nanometer
Diamond-graphene oxide compound precursor object；
(4) by palladium/Nano diamond-graphene oxide compound precursor object prepared in step (3), in the mixed of hydrogen and helium
It closes in gas after 100~300 DEG C of 1~2h of reduction are handled to get to Nano diamond carried palladium catalyst Pd/ND@GO.
2. a kind of Nano diamond-carried palladium catalyst according to claim 1, which is characterized in that the step (1) is will
Fresh Nano diamond keeps the temperature 1~4h at 900~1100 DEG C in argon atmosphere.
3. a kind of Nano diamond-carried palladium catalyst according to claim 1, which is characterized in that solvent is in step (3)
One of water, dehydrated alcohol, acetone.
4. a kind of Nano diamond-carried palladium catalyst according to claim 1, which is characterized in that palladium chloride in step (3)
Solution is added drop-wise to palladium chloride in 2~4mL solvent containing dilute hydrochloric acid, and wherein the load capacity of palladium is 0.5%~5%；Dilute salt
Sour additional amount is 0.05~0.1mL, and the concentration that dilute hydrochloric acid is added is 1.2moL/L.
5. a kind of Nano diamond-carried palladium catalyst according to claim 1, which is characterized in that used in step (3)
Temperature be 50-70 DEG C.
6. application of any one of Claims 1 to 5 catalyst in benzyl alcohol producing benzaldehyde.
7. a kind of method of benzyl alcohol producing benzaldehyde, which is characterized in that the method are as follows: benzyl alcohol, catalyst, ortho-xylene are molten
Agent is added in reaction kettle, is filled with oxygen, and under 1~7bar pressure, 2.5~4.5h is reacted at 85~125 DEG C；The catalyst is
Any one of Claims 1 to 5 catalyst；The amount ratio of catalyst and benzyl alcohol is 1mL:10-100mg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910867393.9A CN110479253A (en) | 2019-09-12 | 2019-09-12 | A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910867393.9A CN110479253A (en) | 2019-09-12 | 2019-09-12 | A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110479253A true CN110479253A (en) | 2019-11-22 |
Family
ID=68557932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910867393.9A Pending CN110479253A (en) | 2019-09-12 | 2019-09-12 | A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110479253A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904556A (en) * | 2022-06-10 | 2022-08-16 | 常州大学 | Preparation method of benzyl alcohol selective oxidation heterogeneous catalyst under solvent-free oxygen condition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307515A (en) * | 2014-09-11 | 2015-01-28 | 闽南师范大学 | Au-Pd/graphene catalyst and preparation method and application thereof |
| CN106466602A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
-
2019
- 2019-09-12 CN CN201910867393.9A patent/CN110479253A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307515A (en) * | 2014-09-11 | 2015-01-28 | 闽南师范大学 | Au-Pd/graphene catalyst and preparation method and application thereof |
| CN106466602A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| YANGMING LIN等: "Fabrication of Nitrogen-Modified Annealed Nanodiamond with Improved Catalytic Activity", 《NANO》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904556A (en) * | 2022-06-10 | 2022-08-16 | 常州大学 | Preparation method of benzyl alcohol selective oxidation heterogeneous catalyst under solvent-free oxygen condition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109326765B (en) | Self-standing electrode and method for manufacturing the same | |
| Yang et al. | Properties of yolk–shell structured Ni@ SiO2 nanocatalyst and its catalytic performance in carbon dioxide reforming of methane to syngas | |
| Pan et al. | Reactions over catalysts confined in carbon nanotubes | |
| Couteau et al. | CVD synthesis of high-purity multiwalled carbon nanotubes using CaCO3 catalyst support for large-scale production | |
| JP2020528499A (en) | Carbon-coated transition metal nanocomposites, their manufacture and applications | |
| Dlamini et al. | Post doped nitrogen-decorated hollow carbon spheres as a support for Co Fischer-Tropsch catalysts | |
| Sushil et al. | Carbon deposition and phase transformations in red mud on exposure to methane | |
| CN1532144A (en) | Method for preparing nano carbon material | |
| CN112452315B (en) | Application of high-temperature sintering-resistant catalyst | |
| Liu et al. | Defect-driven unique stability of Pt/carbon nanotubes for propane dehydrogenation | |
| Zhang et al. | Facile Preparation of Mn+‐Doped (M= Cu, Co, Ni, Mn) Hierarchically Mesoporous CeO2 Nanoparticles with Enhanced Catalytic Activity for CO Oxidation | |
| Hong et al. | Urchin-like CuO microspheres: Synthesis, characterization, and properties | |
| CN112403461B (en) | High-temperature sintering-resistant catalyst and synthesis method thereof | |
| CN106986755B (en) | Method for preparing p-hydroxybenzaldehyde by photocatalysis | |
| CN106587010A (en) | Carbon nanotube material prepared by using carbon-clad metal catalyst and preparation method of carbon nanotube material | |
| JP2012166989A (en) | Graphene laminated nanocarbon, method for producing the same, and catalyst for production of graphene laminated nanocarbon | |
| CN102600878A (en) | Method for preparing TiC-TiO2 core-shell type nanometer material | |
| CN109759041A (en) | A kind of hollow laminated structure titania nanotube catalysis material and preparation method thereof | |
| CN110479253A (en) | A kind of Nano diamond-carried palladium catalyst and its preparation method and application for benzyl alcohol producing benzaldehyde | |
| Wang et al. | Anisotropic growth of one-dimensional carbides in single-walled carbon nanotubes with strong interaction for catalysis | |
| Lorençon et al. | Thermal behavior of carbon nanotubes decorated with gold nanoparticles | |
| JP7071896B2 (en) | A method for continuously producing a self-supporting electrode for a Li-ion battery that does not contain a binder and a current collector by using carbon nanotubes as an additive. | |
| CN110252304B (en) | Iron-based catalyst, preparation method and application thereof, carbon nano tube and preparation method thereof | |
| CN101544365B (en) | Method for preparing hollow carbon nano-cage through iodized thermal treatment | |
| CN108620110B (en) | Vanadium carbide/graphene nanosheet composite material, preparation method and application thereof in hydrogen production through water cracking |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191122 |