CN107497424A - A kind of graphene-based catalyst of supported palladium and preparation method thereof - Google Patents
A kind of graphene-based catalyst of supported palladium and preparation method thereof Download PDFInfo
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- CN107497424A CN107497424A CN201710840972.5A CN201710840972A CN107497424A CN 107497424 A CN107497424 A CN 107497424A CN 201710840972 A CN201710840972 A CN 201710840972A CN 107497424 A CN107497424 A CN 107497424A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 307
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 154
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 66
- 239000010439 graphite Substances 0.000 claims abstract description 66
- 239000000017 hydrogel Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 150000002940 palladium Chemical class 0.000 claims abstract description 31
- 239000004964 aerogel Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000006073 displacement reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- -1 graphite alkene Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000003643 water by type Substances 0.000 description 11
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002352 surface water Substances 0.000 description 8
- 239000000052 vinegar Substances 0.000 description 4
- 235000021419 vinegar Nutrition 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses graphene-based catalyst of a kind of supported palladium and preparation method thereof.Including：It is scattered in graphite oxide is dilute in deionized water, forms the dilute dispersion liquid of graphite oxide；By the dilute dispersion liquid of graphite oxide and palladium salt or palladium salt solution, the graphene hydrogel of supported palladium is made；With the solvent in the graphene hydrogel of deionized water displacement supported palladium for several times, then it is freeze-dried, obtains the graphene aerogel of supported palladium.The present invention uses graphene-supported palladium catalyst, can both utilize the architectural feature of graphene, under the same reaction conditions, reduce the dosage of palladium catalyst, meanwhile the graphene aerogel of the supported palladium of preparation is easy to reclaim, in the industrial production with great production meaning.In addition, making solvent from water in preparation process of the present invention, the use of organic solvent is reduced, so as to reduce pollution of the organic solvent to environment.In addition, preparation technology of the present invention is simple, cost is low.
Description
Technical field
The present invention relates to catalyst field, more particularly to graphene-based catalyst of a kind of supported palladium and preparation method thereof.
Background technology
Palladium catalyst is a kind of using Metal Palladium as main active component, and palladium is carried on into oxidation using the salt of palladium black or palladium
Manufactured various catalyst, it is chemistry and chemical industry using salt such as sodium salt, cadmium salt, lead salts as co-catalyst on the carriers such as aluminium, zeolite
Course of reaction pass through frequently with a kind of catalyst, have catalytic activity high, selectivity is strong, and catalyst is easy to make, and usage amount is few
The features such as.
Palladium catalyst is used to be hydrogenated with the industry, and unsaturated alkenes hydrocarbon, acetylenic hydrocarbon can be made to become saturated alkane;Make insatiable hunger
Become Saturated organic compound with alcohol, aldehyde, ketone, acid；Become solid-state after making the oil hydrogenation of liquid.Reality according to palladium-containing catalyst
Border applicable cases, it can simply be divided into catalytic hydrogenation type, dehydrogenation reaction type and the class of catalysis oxidation type three.Three class is all petrochemical industry
Basic technology, production it is significant.But the market price of palladium metal is 120,000-14 ten thousand/kg at present, Domestic Resources are limited,
Reclaim limited.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of graphene-based catalyst of supported palladium
And preparation method thereof, it is intended to solve existing palladium-containing catalyst, palladium usage amount is big, the problem of being not easy to reclaim.
Technical scheme is as follows：
A kind of preparation method of the graphene-based catalyst of supported palladium, wherein, including：
Step A, it is scattered in graphite oxide is dilute in deionized water, forms the dilute dispersion liquid of graphite oxide；
Step B, by the dilute dispersion liquid of graphite oxide and palladium salt or palladium salt solution, the graphene hydrogel of supported palladium is made；
Step C, with the solvent in the graphene hydrogel of deionized water displacement supported palladium for several times, then it is freeze-dried, is born
Carry the graphene aerogel of palladium.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, the step B is specifically included：
Step B1, palladium salt or palladium salt solution are added in the dilute dispersion liquid of graphite oxide, and stirs, stands, centrifugal drying, obtained
The graphite oxide for obtaining supported palladium is dilute；
Step B2, it is scattered in the graphite oxide of supported palladium is dilute in deionized water, is then placed in reactor and carries out isothermal reaction,
Obtain the graphene hydrogel of supported palladium.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, the step B is specifically included：
Step B1,, the dilute dispersion liquid of graphite oxide be put into reactor carry out isothermal reaction, obtain graphene hydrogel；
Step B2,, graphene hydrogel is positioned in deionized water, while palladium salt is dissolved in organic solvent, forms palladium salt
Solution；
Step B3,, then palladium salt solution is added in the solution of placing graphite alkene hydrogel, and stir, stand, centrifuge
Dry, obtain the graphene hydrogel of supported palladium.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, in the step B, the palladium salt is vinegar
Sour palladium, the palladium salt solution are palladium solution.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, in the step B2, the isothermal reaction
Temperature be 160 ~ 200 DEG C, the time is 10 ~ 14h.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, the step B1,In, the constant temperature is anti-
The temperature answered is 160 ~ 200 DEG C, and the time is 10 ~ 14h.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, the step B2,In, it is described organic molten
Agent is dimethylformamide.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, it is described to use deionization in the step C
Water displacement supported palladium graphene hydrogel in solvent be specially for several times：With the graphene water-setting of deionized water displacement supported palladium
Solvent in glue, water was changed once every 2 ~ 4 hours, replaced 1 ~ 3 day.
The preparation method of the graphene-based catalyst of described supported palladium, wherein, in the step C, at -60 ~ -40 DEG C
It is freeze-dried 46 ~ 50h.
A kind of graphene-based catalyst of supported palladium, wherein, the graphene-based catalyst of the supported palladium is supported palladium
Graphene aerogel, the graphene aerogel of the supported palladium use the graphene-based catalysis of the as above supported palladium described in any one
The preparation method of agent is prepared.
Beneficial effect：The present invention uses graphene-supported palladium catalyst, the architectural feature of graphene can be both utilized, in phase
With the dosage under reaction condition, reducing palladium catalyst, meanwhile, the graphene aerogel of the supported palladium of preparation is easy to reclaim, in work
There is great production meaning in industry production.In addition, the present invention makees solvent from water, the use of organic solvent is reduced, so as to drop
Pollution of the low organic solvent to environment.In addition, the graphene aerogel of the supported palladium is advantageous to progress interface and gathered as carrier
Close.
Brief description of the drawings
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of the graphene-based catalyst of supported palladium of the present invention.
Fig. 2 is the particular flow sheet of step S200 in Fig. 1.
Fig. 3 is another particular flow sheet of step S200 in Fig. 1.
Embodiment
The present invention provides a kind of graphene-based catalyst of supported palladium and preparation method thereof, to make the purpose of the present invention, skill
Art scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that tool described herein
Body embodiment only to explain the present invention, is not intended to limit the present invention.
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of the graphene-based catalyst of supported palladium of the present invention,
As illustrated, it includes：
Step S100, it is scattered in graphite oxide is dilute in deionized water, forms the dilute dispersion liquid of graphite oxide.
The step S100 specifically, be scattered in graphite oxide is dilute in deionized water, and under 300W ultrasonic agitation 10 ~
20min（Such as 15min）, form the dilute dispersion liquid of uniform graphite oxide.
Step S200, by the dilute dispersion liquid of graphite oxide and palladium salt or palladium salt solution, the graphene hydrogel of supported palladium is made.
Preferably, as shown in Fig. 2 the step S200 is specifically included：
Step S201, palladium salt or palladium salt solution are added in the dilute dispersion liquid of graphite oxide, and stir, stand, centrifugal drying,
The graphite oxide for obtaining supported palladium is dilute.
The step S201 is specifically, by palladium salt（Such as palladium）Or palladium salt solution（Such as palladium solution）Add oxidation stone
In the dilute dispersion liquid of ink, preferably palladium salt is added in the dilute dispersion liquid of graphite oxide, and 10 ~ 20min is stirred by ultrasonic under 300W（Such as
15min）To well mixed, 10 ~ 14h of standing（Such as 12h）, centrifugal drying, the graphite oxide for obtaining supported palladium is dilute.
Step S202, be scattered in the graphite oxide of supported palladium is dilute in deionized water, be then placed in reactor carry out it is permanent
Temperature reaction, obtain the graphene hydrogel of supported palladium.
The step S202 is ultrasonic under 300W specifically, be scattered in the graphite oxide of supported palladium is dilute in deionized water
Stir 10 ~ 20min（Such as 15min）, form the dilute dispersion liquid of graphite oxide of uniform supported palladium；Then the dispersion liquid is put into height
Press and isothermal reaction is carried out in hydrothermal reaction kettle, the temperature of the isothermal reaction is 160 ~ 200 DEG C（Such as 180 DEG C）, the time be 10 ~
14h（Such as 12h）, obtain the graphene hydrogel of supported palladium.
Step S300, with the solvent in the graphene hydrogel of deionized water displacement supported palladium for several times, then it is freeze-dried,
Obtain the graphene aerogel of supported palladium.
The step S300 specifically, reaction terminate after, be down to room temperature, carefully pour into the beaker for fill deionized water and put
The solvent changed in the graphene hydrogel of supported palladium, every 2 ~ 4 hours（Such as 3 hours）Change water once, replace 1 ~ 3 day（Such as 2 days）,
Excess surface water is drained, quick-frozen 15 ~ 25min in liquid nitrogen（Such as 20min）, it is then placed in freeze drier at -60 ~ -40 DEG C
46 ~ 50h of lower drying, 48h is preferably dried at -50 DEG C, obtains the graphene aerogel of supported palladium.
The present invention makees solvent from water, the use of organic solvent is reduced, so as to reduce pollution of the organic solvent to environment.Together
The graphene aerogel of Shi Suoshu supported palladiums is the aeroge of three-dimensional network, is easy to recycle and reuse.In addition, the supported palladium
Graphene aerogel as carrier, be advantageous to carry out interfacial polymerization.
Or preferably, as shown in figure 3, the step S200 is specifically included：
Step S201,, the dilute dispersion liquid of graphite oxide be put into reactor carry out isothermal reaction, obtain graphene hydrogel.
The step S201,Specifically, it is anti-that the dilute dispersion liquid of graphite oxide is put into progress constant temperature in high-pressure hydrothermal reaction kettle
Should, the temperature of the isothermal reaction is 160 ~ 200 DEG C（Such as 180 DEG C）, the time is 10 ~ 14h（Such as 12h）, obtain graphene water-setting
Glue.
Step S202,, graphene hydrogel is positioned in deionized water；Palladium salt is dissolved in organic solvent simultaneously, shape
Into palladium salt solution.
The step S202,Specifically, graphene hydrogel is positioned in deionized water；Simultaneously by palladium salt（Such as vinegar
Sour palladium）It is dissolved in a small amount of organic solvent（Such as dimethylformamide）In, form palladium salt solution.
Step S203,, then palladium salt solution is added in the solution of placing graphite alkene hydrogel, and stir, be quiet
Put, centrifugal drying, obtain the graphene hydrogel of supported palladium.
The step S203,Specifically, being then added to palladium salt solution in the solution of placing graphite alkene hydrogel, and stir
Mix uniform, 10 ~ 14h of standing（Such as 12h）, centrifugal drying, obtain the graphene hydrogel of supported palladium.
Graphene aerogel is made by the loaded palladium catalyst in graphene aqueous dispersion liquid in the present invention, is had
There is the graphene aerogel of the supported palladium of catalytic activity.The present invention uses graphene-supported palladium catalyst, can both utilize graphite
The architectural feature of alkene, under the same reaction conditions, reduce the dosage of palladium catalyst；Meanwhile the obtained supported palladium of reaction under high pressure
Graphene aerogel structure is closely knit, is not easy to collapse, and is easy to the recovery of catalyst, is anticipated in the industrial production with great production
Justice.
Solvent is made from water in preparation process of the present invention, reduces the use of organic solvent, so as to reduce organic solvent to ring
The pollution in border.In addition, the graphene aerogel of the supported palladium is advantageous to carry out interfacial polymerization as carrier.It is in addition, of the invention
Preparation technology is simple, and cost is low.
The graphene-based catalyst of a kind of supported palladium of the present invention, it is characterised in that the graphene-based of the supported palladium is urged
Agent is the graphene aerogel of supported palladium, and the graphene aerogel of the supported palladium is using the as above supported palladium described in any one
The preparation method of graphene-based catalyst be prepared.
It should be noted that the invention is not restricted to palladium metal, can also will be cuprous, the metallic catalyst such as platinum is carried on graphene
On aeroge.
Below by embodiment, the present invention is described in detail.
Embodiment 1
The dilute GO of 0.5g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed
The dilute dispersion liquid of uniform graphite oxide.Meanwhile take 50mg palladiums to be added in the dilute dispersion liquid of graphite oxide, it is ultrasonic under 300W
15min, stand 12h.Centrifugal drying, obtain the dilute catalyst of graphite oxide of supported palladium.
The dilute catalyst of graphite oxide of 50mg supported palladium is weighed in 50ml beakers, adds 15ml deionized waters, in
Ultrasonic 15min under 300W, form the dilute dispersion liquid of graphite oxide of uniform supported palladium.Put it into high-pressure hydrothermal reaction kettle,
12h is reacted at 180 DEG C in electric drying oven with forced convection, obtains the graphene hydrogel of supported palladium.
After reaction terminates, room temperature is down to, carefully pours into the beaker for fill deionized water and replaces solvent, was changed every 3 hours
Water once, is replaced 2 days, drains excess surface water, the quick-frozen 20min in liquid nitrogen, is dried 48h at -50 DEG C in freeze drier, is obtained
Obtain the graphene aerogel of supported palladium.
Embodiment 2
The dilute GO of 0.5g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed
The dilute dispersion liquid of uniform graphite oxide.Meanwhile take 50mg palladiums to be dissolved in 1ml dimethylformamides, form uniform acetic acid
Palladium solution.Palladium solution is added in the dilute dispersion liquid of graphite oxide, the ultrasonic 15min under 300W, stands 12h.Centrifugation is dry
It is dry, obtain the dilute catalyst of graphite oxide of supported palladium.
The dilute catalyst of graphite oxide of 50mg supported palladium is weighed in 50ml beakers, adds 15ml deionized waters, in
Ultrasonic 15min under 300W, form the dilute dispersion liquid of graphite oxide of uniform supported palladium.Put it into high-pressure hydrothermal reaction kettle,
12h is reacted at 180 DEG C in electric drying oven with forced convection, obtains the graphene hydrogel of supported palladium.
After reaction terminates, room temperature is down to, carefully pours into the beaker for fill deionized water and replaces solvent, was changed every 3 hours
Water once, is replaced 2 days, drains excess surface water, the quick-frozen 20min in liquid nitrogen, is dried 48h at -50 DEG C in freeze drier, is obtained
Obtain the graphene aerogel of supported palladium.
Embodiment 3
The dilute GO of 0.5g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed
The dilute dispersion liquid of uniform graphite oxide.Meanwhile take 100mg palladiums to be dissolved in 2ml dimethylformamides, form uniform acetic acid
Palladium solution.Palladium solution is added in the dilute dispersion liquid of graphite oxide, the ultrasonic 15min under 300W, stands 12h.Centrifugation is dry
It is dry, obtain the dilute catalyst of graphite oxide of supported palladium.
The dilute catalyst of graphite oxide of 50mg supported palladium is weighed in 50ml beakers, adds 15ml deionized waters, in
Ultrasonic 15min under 300W, form the dilute dispersion liquid of graphite oxide of uniform supported palladium.Put it into high-pressure hydrothermal reaction kettle,
12h is reacted at 180 DEG C in electric drying oven with forced convection, obtains the graphene hydrogel of supported palladium.
After reaction terminates, room temperature is down to, carefully pours into the beaker for fill deionized water and replaces solvent, was changed every 3 hours
Water once, is replaced 2 days, drains excess surface water, the quick-frozen 20min in liquid nitrogen, is dried 48h at -50 DEG C in freeze drier, is obtained
Obtain the graphene aerogel of supported palladium.
Embodiment 4
The dilute GO of 0.5g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed
The dilute dispersion liquid of uniform graphite oxide.Meanwhile take 100mg palladiums to be added in the dilute dispersion liquid of graphite oxide, surpass under 300W
Sound 15min, stand 12h.Centrifugal drying, obtain the dilute catalyst of graphite oxide of supported palladium.
The dilute catalyst of graphite oxide of 100mg supported palladium is weighed in 50ml beakers, adds 15ml deionized waters, in
Ultrasonic 15min under 300W, form the dilute dispersion liquid of graphite oxide of uniform supported palladium.Put it into high-pressure hydrothermal reaction kettle,
12h is reacted at 180 DEG C in electric drying oven with forced convection, obtains the graphene hydrogel of supported palladium.
After reaction terminates, room temperature is down to, carefully pours into the beaker for fill deionized water and replaces solvent, was changed every 3 hours
Water once, is replaced 2 days, drains excess surface water, the quick-frozen 20min in liquid nitrogen, is dried 48h at -50 DEG C in freeze drier, is obtained
Obtain the graphene aerogel of supported palladium.
Embodiment 5
The dilute GO of 0.5g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed
The dilute dispersion liquid of uniform graphite oxide.Put it into high-pressure hydrothermal reaction kettle, reacted in electric drying oven with forced convection at 180 DEG C
12h, obtain graphene hydrogel.Graphene hydrogel is carefully poured into the beaker for filling deionized water, meanwhile, take 50mg vinegar
Sour palladium is dissolved in 1ml dimethylformamides, forms palladium solution, and palladium solution is added to the beaker of graphene hydrogel
In, stand 12h.Centrifugal drying, obtain the graphene hydrogel catalyst of supported palladium.
After reaction terminates, solvent is replaced, water was changed once every 3 hours, replaced 2 days, excess surface water is drained, in liquid nitrogen
Quick-frozen 20min, 48h is dried in freeze drier at -50 DEG C, obtain the graphene aerogel of supported palladium.
Embodiment 6
The dilute GO of 0.5g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed
The dilute dispersion liquid of uniform graphite oxide.Put it into high-pressure hydrothermal reaction kettle, reacted in electric drying oven with forced convection at 180 DEG C
12h, graphene hydrogel is obtained, graphene hydrogel is carefully poured into the beaker for filling deionized water, meanwhile, take 100mg
Palladium is dissolved in 1ml dimethylformamides, forms palladium solution, and palladium solution is added to the burning of graphene hydrogel
In cup, 12h is stood.Centrifugal drying, obtain the graphene hydrogel catalyst of supported palladium.
After reaction terminates, solvent is replaced, water was changed once every 3 hours, replaced 2 days, excess surface water is drained, in liquid nitrogen
Quick-frozen 20min, 48h is dried in freeze drier at -50 DEG C, obtain the graphene aerogel of supported palladium.
Embodiment 7
The dilute GO of 1g graphite oxides is weighed in 100ml beakers, 50ml deionized waters is added, the ultrasonic 15min under 300W, is formed equal
The dilute dispersion liquid of even graphite oxide.Put it into high-pressure hydrothermal reaction kettle, reacted in electric drying oven with forced convection at 180 DEG C
12h, graphene hydrogel is obtained, graphene hydrogel is carefully poured into the beaker for filling deionized water, meanwhile, take 50mg vinegar
Sour palladium is dissolved in 1ml dimethylformamides, forms palladium solution, and palladium solution is added to the beaker of graphene hydrogel
In, stand 12h.Centrifugal drying, obtain the graphene hydrogel catalyst of supported palladium.
After reaction terminates, solvent is replaced, water was changed once every 3 hours, replaced 2 days, excess surface water is drained, in liquid nitrogen
Quick-frozen 20min, 48h is dried in freeze drier at -50 DEG C, obtain the graphene aerogel of supported palladium.
Graphene gel catalyst is loaded using palladium prepared by embodiment 1（PdNPs/GO）A series of c h bond is carried out
Addition reaction is activated, reaction expression sees below formula（1）, the product of specific reaction generation is respectively 3a ~ 3i, its corresponding structural formula and
Corresponding yield is seen below shown in formula respectively.
（1）；
、、、、、、、、。
As can be seen from the above equation, under the conditions of few catalyst amount（0.8mol%）, reached common palladium
The effect of 5mol% dosages, this test prove that the catalyst has high catalytic efficiency, can be significantly reduced precious metal palladium
Dosage.
In summary, graphene-based catalyst of a kind of supported palladium provided by the invention and preparation method thereof, the present invention adopts
With graphene-supported palladium catalyst, the architectural feature of graphene can be both utilized, under the same reaction conditions, reduces palladium catalyst
Dosage, meanwhile, the graphene aerogel of the supported palladium of preparation is easy to reclaim, and is anticipated in the industrial production with great production
Justice.In addition, making solvent from water in preparation process of the present invention, the use of organic solvent is reduced, so as to reduce organic solvent to ring
The pollution in border.In addition, the graphene aerogel of the supported palladium is advantageous to carry out interfacial polymerization as carrier.It is in addition, of the invention
Preparation technology is simple, and cost is low.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
- A kind of 1. preparation method of the graphene-based catalyst of supported palladium, it is characterised in that including：Step A, it is scattered in graphite oxide is dilute in deionized water, forms the dilute dispersion liquid of graphite oxide；Step B, by the dilute dispersion liquid of graphite oxide and palladium salt or palladium salt solution, the graphene hydrogel of supported palladium is made；Step C, with the solvent in the graphene hydrogel of deionized water displacement supported palladium for several times, then it is freeze-dried, is born Carry the graphene aerogel of palladium.
- 2. the preparation method of the graphene-based catalyst of supported palladium according to claim 1, it is characterised in that the step B is specifically included：Step B1, palladium salt or palladium salt solution are added in the dilute dispersion liquid of graphite oxide, and stirs, stands, centrifugal drying, obtained The graphite oxide for obtaining supported palladium is dilute；Step B2, it is scattered in the graphite oxide of supported palladium is dilute in deionized water, is then placed in reactor and carries out isothermal reaction, Obtain the graphene hydrogel of supported palladium.
- 3. the preparation method of the graphene-based catalyst of supported palladium according to claim 1, it is characterised in that the step B is specifically included：Step B1,, the dilute dispersion liquid of graphite oxide be put into reactor carry out isothermal reaction, obtain graphene hydrogel；Step B2,, graphene hydrogel is positioned in deionized water, while palladium salt is dissolved in organic solvent, it is molten to form palladium salt Liquid；Step B3,, then palladium salt solution is added in the solution of placing graphite alkene hydrogel, and stir, stand, centrifuge Dry, obtain the graphene hydrogel of supported palladium.
- 4. the preparation method of the graphene-based catalyst of supported palladium according to claim 1, it is characterised in that the step In B, the palladium salt is palladium, and the palladium salt solution is palladium solution.
- 5. the preparation method of the graphene-based catalyst of supported palladium according to claim 2, it is characterised in that the step In B2, the temperature of the isothermal reaction is 160 ~ 200 DEG C, and the time is 10 ~ 14h.
- 6. the preparation method of the graphene-based catalyst of supported palladium according to claim 3, it is characterised in that the step B1,In, the temperature of the isothermal reaction is 160 ~ 200 DEG C, and the time is 10 ~ 14h.
- 7. the preparation method of the graphene-based catalyst of supported palladium according to claim 3, it is characterised in that the step B2,In, the organic solvent is dimethylformamide.
- 8. the preparation method of the graphene-based catalyst of supported palladium according to claim 1, it is characterised in that the step In C, the solvent in the graphene hydrogel that supported palladium is replaced with deionized water is specially for several times：It is negative with deionized water displacement The solvent in the graphene hydrogel of palladium is carried, water was changed once every 2 ~ 4 hours, is replaced 1 ~ 3 day.
- 9. the preparation method of the graphene-based catalyst of supported palladium according to claim 1, it is characterised in that the step In C, 46 ~ 50h is freeze-dried at -60 ~ -40 DEG C.
- 10. the graphene-based catalyst of a kind of supported palladium, it is characterised in that the graphene-based catalyst of the supported palladium is load The graphene aerogel of palladium, the graphene aerogel of the supported palladium is using the supported palladium as described in any one of claim 1 ~ 9 The preparation method of graphene-based catalyst be prepared.
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| CN108299207A (en) * | 2018-02-12 | 2018-07-20 | 中国科学院化学研究所 | A kind of method of heterogeneous catalytic hydrogenation reduction unsaturated compound |
| CN110860287A (en) * | 2019-11-07 | 2020-03-06 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
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| CN105253879A (en) * | 2015-11-23 | 2016-01-20 | 国家纳米科学中心 | High-porosity functional graphene material as well as preparation method and applications thereof |
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| CN105253879A (en) * | 2015-11-23 | 2016-01-20 | 国家纳米科学中心 | High-porosity functional graphene material as well as preparation method and applications thereof |
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| CN108299207A (en) * | 2018-02-12 | 2018-07-20 | 中国科学院化学研究所 | A kind of method of heterogeneous catalytic hydrogenation reduction unsaturated compound |
| CN110860287A (en) * | 2019-11-07 | 2020-03-06 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
| CN110860287B (en) * | 2019-11-07 | 2022-08-19 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
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