CN107185524A - A kind of preparation method of three-dimensional grapheme noble metal nano catalyst - Google Patents
A kind of preparation method of three-dimensional grapheme noble metal nano catalyst Download PDFInfo
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- CN107185524A CN107185524A CN201710331965.2A CN201710331965A CN107185524A CN 107185524 A CN107185524 A CN 107185524A CN 201710331965 A CN201710331965 A CN 201710331965A CN 107185524 A CN107185524 A CN 107185524A
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 27
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- -1 chlorine palladium acid amide Chemical class 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000499 gel Substances 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 abstract 1
- 239000002082 metal nanoparticle Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000010792 warming Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/42—Platinum
-
- 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
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of three-dimensional grapheme noble metal nano catalyst, following steps are specifically included：Graphene oxide dispersion is crosslinked with noble metal precursor body, a certain amount of crosslinking agent hydro-thermal, is calcined after drying, that is, is obtained three-dimensional grapheme noble metal nano catalyst.The beneficial effects of the invention are as follows：The three-dimensional grapheme noble metal nano catalyst prepared using one kettle way need not add reducing agent, composite structure is stable, noble metal nano particles are dispersed in the surface of graphene, and composite just has broad application prospects in the field such as electro-catalysis, chemical catalysis, energy storage and conversion, bio-sensing.
Description
Technical field
The present invention relates to a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst, belong to material synthesis technology
Field.
Background technology
Noble metal mainly includes the metals such as gold, silver, platinum family (osmium, iridium, platinum, ruthenium, rhodium, palladium), and it is in material, chemical etc.
Field has a wide range of applications.Noble metal itself mostly has very high catalytic activity, can be due to that their amount of storage are very dilute
Lack, thus it is expensive.The activity of noble metal catalyst is affected by many factors, except being influenceed in itself by metal, is gone back and it
The factors such as surface area, porosity and the property of carrier are relevant, want to prepare effective catalyst for this, reduce catalyst cost, its
In active material will realize abundant micronized, increase specific surface area.But noble metal is implemented separately micronized and less held
Easily, on the one hand it is because obtained particle is unstable；The easy reunion of growing up in preparation process of another aspect particle.Conventional at present
Solution is exactly that the active material of catalyst is well dispersed in suitable carrier surface.
Graphene is widely used because its excellent electricity, optics, mechanics and thermal property in Material Field.Stone
Black alkene has the advantages that larger specific surface area, good chemical stability and electric conductivity, theoretically noble metal nano grain
The excellent carrier of son, but because graphenic surface can be very high, easily reunite between two-dimentional graphene sheet layer, greatly reduce it
Actual performance, it is to prevent a kind of effective ways of graphene reunion that two-dimensional graphene is assembled into three-dimensional grapheme.Conventional three
Dimension graphene is typically prepared by freeze-drying, and the three-dimensional grapheme mechanical stability prepared in this way is poor, is met
Structure can cave in after solvent, therefore the performance of composite still be lifted after supported precious metal nano-particle limited.
The content of the invention
For problem present in background technology, the present invention provides a kind of three-dimensional grapheme-noble metal nano catalyst
Preparation method, is made by following step：
1st, the preparation method of a kind of three-dimensional grapheme-noble metal nano catalyst, it is characterised in that preparation process include with
Lower step：
A, by graphene oxide ultrasonic disperse in water, prepare certain density graphene oxide dispersion；Then with it is expensive
Metallic compound, crosslinking agent mixing；The hydro-thermal reaction 12h under certain temperature in hydrothermal reaction kettle, the hydrogel of formation is dried, and is obtained
To xerogel；
B, the xerogel for obtaining step a under argon gas, are calcined under certain temperature, obtain three-dimensional grapheme-noble metal and receive
Rice catalyst.
The concentration of graphene oxide described in above-mentioned steps a is 1-20mg/mL；
Crosslinking agent described in above-mentioned steps a is melamine resin, phenol formaldehyde resin or pollopas；
The mass ratio of graphene oxide and crosslinking agent described in above-mentioned steps a is 1:1~1:10；
The temperature of hydro-thermal reaction described in above-mentioned steps a is 120~180 DEG C；
Precious metal chemical complex described in above-mentioned steps a is chloroplatinic acid, ammonium chloropalladate, gold chloride, silver nitrate, ruthenic chloride；
Calcining heat described in above-mentioned steps b is 550~850 DEG C of heating.
The beneficial effects of the invention are as follows：Three-dimensional grapheme made from the method-noble metal nano catalyst, Stability Analysis of Structures, tool
There is larger specific surface area, nano-particle is uniformly dispersed in graphenic surface, overcome conventional three-dimensional graphene-noble metal nano
Catalyst is easily reunited unstable shortcoming.
Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1:Platinum Nanoparticles prepared by the present invention-three-dimensional graphene composite material transmission electron microscope picture；
Fig. 2:Technique of Nano Pd prepared by the present invention-three-dimensional graphene composite material transmission electron microscope picture；
Fig. 3:Nanogold prepared by the present invention-three-dimensional graphene composite material transmission electron microscope picture；
Fig. 4：Nano Silver prepared by the present invention-three-dimensional graphene composite material transmission electron microscope picture；
Fig. 5：Nanometer ruthenium-three-dimensional graphene composite material transmission electron microscope picture prepared by the present invention.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.It should be understood that these embodiments are intended merely to
The present invention is illustrated, rather than limits the scope of the present invention in any way.
Embodiment 1：
(1) with improvement Hummers methods, the 120mL concentrated sulfuric acids, 13.3mL concentrated phosphoric acids is sequentially added in 500mL containers, is stirred
Mix, 50 DEG C are slowly ramped under water-bath, add 1g graphite powders, 6g potassium permanganate, stir 12h, solution pours into peroxide containing 10mL
On the ice cube for changing hydrogen solution, stirring is cooled to room temperature, filters unreacted solid.Centrifuge washing is dried to neutrality, obtains oxidation stone
Black alkene；
(2) 0.015g GO are weighed, 15mL redistilled waters are added, ultrasonic 2min adds 1mL formaldehyde and 0.35g trimerizations
Cyanamide, 2mL 4mg/mL chloroplatinic acid aqueous solution, is gently mixed；Hydro-thermal reaction 12h at 180 DEG C.By gained solid at 80 DEG C
Dry, obtain the xerogel of crosslinking agent support；
(3) by xerogel, under an argon, tube furnace is first warming up to 300 DEG C with 5 DEG C/min heating rate, then with 10
DEG C/min heating rate is warming up to 550 DEG C, and is incubated 3h, go to take out product afterwards after temperature is down to room temperature, obtain three-dimensional
Graphene-platinum nano catalyst.
Embodiment 2：
(1) the preparation method be the same as Example 1 of graphene oxide.
(2) 0.15g GO are weighed, 30mL redistilled waters are added, ultrasonic 2min adds 1mL formaldehyde and 0.15g phenol,
20mg ammonium chloropalladates, are gently mixed；Hydro-thermal reaction 12h at 160 DEG C.By gained solid in freeze-drying, crosslinking agent support is obtained
Xerogel；
(3) by xerogel, under an argon, tube furnace is first warming up to 300 DEG C with 5 DEG C/min heating rate, then with 10
DEG C/min heating rate is warming up to 650 DEG C, and is incubated 3h, go to take out product afterwards after temperature is down to room temperature, obtain three-dimensional
Graphene-palladium nanocatalyst.
Embodiment 3：
(1) the preparation method be the same as Example 1 of graphene oxide.
(2) 0.15g GO are weighed, 15mL redistilled waters are added, ultrasonic 2min adds 2mL formaldehyde and 0.7g urea,
2mL 4mg/mL aqueous solution of chloraurate, is gently mixed；Hydro-thermal reaction 12h at 140 DEG C.Gained solid is dried at 80 DEG C,
Obtain the xerogel of crosslinking agent support；
(3) by xerogel, under an argon, tube furnace is first warming up to 300 DEG C with 5 DEG C/min heating rate, then with 10
DEG C/min heating rate is warming up to 750 DEG C, and is incubated 3h, go to take out product afterwards after temperature is down to room temperature, obtain three-dimensional
Graphene-gold nano catalyst.
Embodiment 4：
(1) the preparation method be the same as Example 1 of graphene oxide.
(2) 0.3g GO are weighed, 20mL redistilled waters are added, ultrasonic 2min adds 1mL formaldehyde and 0.35g melamines
Amine, 40mg silver nitrates, is gently mixed；Thermal response 12h at 120 DEG C.Gained solid is dried at 80 DEG C, crosslinking agent support is obtained
Xerogel；
(3) xerogel for supporting crosslinking agent, under an argon, tube furnace are first warming up to 5 DEG C/min heating rate
300 DEG C, then 850 DEG C are warming up to 10 DEG C/min heating rate, and 3h is incubated, go to take out after temperature is down to room temperature afterwards and produce
Product, obtain three-dimensional grapheme-silver nanoparticle catalyst.
Embodiment 5：
(4) the preparation method be the same as Example 1 of graphene oxide.
(5) 0.3g GO are weighed, 15mL redistilled waters are added, ultrasonic 2min adds 1mL formaldehyde and 0.35g melamines
Amine, 40mg ruthenic chlorides, is gently mixed；Thermal response 12h at 120 DEG C.Gained solid is dried at 80 DEG C, crosslinking agent support is obtained
Xerogel；
(6) xerogel for supporting crosslinking agent, under an argon, tube furnace are first warming up to 5 DEG C/min heating rate
300 DEG C, then 550 DEG C are warming up to 10 DEG C/min heating rate, and 3h is incubated, go to take out after temperature is down to room temperature afterwards and produce
Product, obtain three-dimensional grapheme-ruthenium nanocatalyst.
Claims (7)
1. the preparation method of a kind of three-dimensional grapheme-noble metal nano catalyst, it is characterised in that preparation process includes following step
Suddenly：
A, by graphene oxide ultrasonic disperse in water, prepare certain density graphene oxide dispersion；Then with noble metal
Compound, crosslinking agent mixing；The hydro-thermal reaction 12h under certain temperature in hydrothermal reaction kettle, the hydrogel of formation is dried, and is done
Gel；
B, the xerogel for obtaining step a under argon gas, are calcined under certain temperature, obtain three-dimensional grapheme-noble metal nano and urge
Agent.
2. a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst according to claim 1, it is characterised in that
The concentration of graphene oxide described in step a is 1-20mg/mL.
3. a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst according to claim 1, it is characterised in that
Crosslinking agent described in step a is melamine resin, phenol formaldehyde resin or Lauxite.
4. a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst according to claim 1, it is characterised in that
The mass ratio of graphene oxide and crosslinking agent described in step a is 1:1~1:10.
5. a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst according to claim 1, it is characterised in that
The temperature of hydro-thermal reaction described in step a is 120~180 DEG C.
6. a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst according to claim 1, it is characterised in that
Precious metal chemical complex described in step a is chloroplatinic acid, chlorine palladium acid amide, gold chloride, silver nitrate, ruthenic chloride.
7. a kind of preparation method of three-dimensional grapheme-noble metal nano catalyst according to claim 1, it is characterised in that
Calcining heat described in step b is 550~850 DEG C of heating.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108144654A (en) * | 2018-01-30 | 2018-06-12 | 常州大学 | A kind of phenolic aldehyde cross-linking method prepares three-dimensional grapheme load nano Pd catalyst and its application in hydrogenation of chloronitrobenzene |
| CN108273378A (en) * | 2018-01-16 | 2018-07-13 | 中山大学 | A kind of graphene/titanium dioxide/silver/magnesium oxide composite material and preparation method thereof |
| CN108636407A (en) * | 2018-05-17 | 2018-10-12 | 江苏大学 | Preparation method based on graphene-supported copper nano-particle |
| CN109225211A (en) * | 2018-10-24 | 2019-01-18 | 常州大学 | A kind of carbon carries the preparation method of ultra-fine Ru nanocrystalline composite material |
| CN109592673A (en) * | 2018-11-07 | 2019-04-09 | 江苏城乡建设职业学院 | A kind of preparation method of graphene oxide-loaded silver-colored palladium composite material |
| CN110624540A (en) * | 2019-10-25 | 2019-12-31 | 辽宁大学 | Novel ruthenium-based self-supporting electro-catalytic material, preparation method thereof and application thereof in electro-catalytic nitrogen reduction for producing ammonia |
| CN111068717A (en) * | 2019-12-10 | 2020-04-28 | 西北大学 | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870460A (en) * | 2016-03-31 | 2016-08-17 | 常州大学 | Preparation method of co-doped graphene gel by bonding of metal and nitrogen |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105870460A (en) * | 2016-03-31 | 2016-08-17 | 常州大学 | Preparation method of co-doped graphene gel by bonding of metal and nitrogen |
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| CN108273378A (en) * | 2018-01-16 | 2018-07-13 | 中山大学 | A kind of graphene/titanium dioxide/silver/magnesium oxide composite material and preparation method thereof |
| CN108144654A (en) * | 2018-01-30 | 2018-06-12 | 常州大学 | A kind of phenolic aldehyde cross-linking method prepares three-dimensional grapheme load nano Pd catalyst and its application in hydrogenation of chloronitrobenzene |
| CN108144654B (en) * | 2018-01-30 | 2020-02-14 | 常州大学 | Three-dimensional graphene-loaded nano Pd catalyst prepared by phenolic crosslinking method and application of catalyst in nitrobenzene hydrogenation |
| CN108636407A (en) * | 2018-05-17 | 2018-10-12 | 江苏大学 | Preparation method based on graphene-supported copper nano-particle |
| CN109225211A (en) * | 2018-10-24 | 2019-01-18 | 常州大学 | A kind of carbon carries the preparation method of ultra-fine Ru nanocrystalline composite material |
| CN109592673A (en) * | 2018-11-07 | 2019-04-09 | 江苏城乡建设职业学院 | A kind of preparation method of graphene oxide-loaded silver-colored palladium composite material |
| CN109592673B (en) * | 2018-11-07 | 2022-01-28 | 江苏城乡建设职业学院 | Preparation method of graphene oxide supported silver-palladium composite material |
| CN110624540A (en) * | 2019-10-25 | 2019-12-31 | 辽宁大学 | Novel ruthenium-based self-supporting electro-catalytic material, preparation method thereof and application thereof in electro-catalytic nitrogen reduction for producing ammonia |
| CN111068717A (en) * | 2019-12-10 | 2020-04-28 | 西北大学 | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof |
| CN111068717B (en) * | 2019-12-10 | 2020-10-30 | 西北大学 | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof |
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