CN105126828B - A kind of porous carbon supported precious metal catalyst and preparation method thereof - Google Patents
A kind of porous carbon supported precious metal catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of porous carbon supported precious metal catalyst and preparation method thereof, the catalyst is made up of porous caged carbon material and the noble metal nano particles being distributed in inside porous caged carbon material.Its preparation method is：1) dispersant solution is added into noble metal nano dispersion liquid, centrifuges and removes supernatant, obtain the noble metal nano particles of surface modification；2) noble metal nano particles of surface modification are mixed with absolute ethyl alcohol, deionized water, ultrasonic disperse is uniform, adds ammoniacal liquor, tetraethyl orthosilicate, obtain noble metal@SiO2Nucleocapsid particles；3) by noble metal@SiO2Nucleocapsid particles are mixed with PS microballoons, carbon-based bottom material, dilution heat of sulfuric acid, ultrasonic disperse is uniform after 120 200 DEG C of reactions, and be fully carbonized, be heat-treated, it is put into after natural cooling in HF solution and handles 10 15h removing silica, is finally washed, drying obtains porous carbon supported precious metal catalyst.
Description
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of porous carbon supported precious metal catalyst and its preparation side
Method.
Background technology
Inorganic porous material is steady with catalytic activity and selectivity height, structure as catalyst and catalyst carrier material
Fixed, technology of preparing is simple, with low cost, post processing is simple, repeatable usability the advantages of, occupy in industrial catalyst application
Very important status, has got a lot of applications in petroleum refining and chemical industry, for example FCC catalyst molecular sieve Y
And ZSM-5.Inorganic porous material is generally used in heterogeneous catalytic system, the course of its catalytic reaction include reactant spread and
The chemical reaction and reaction product of catalyst surface process, reactant in catalyst system and catalyzing are adsorbed onto from the desorption in catalyst
And diffusion process.According to this basic catalytic reaction course, inorganic porous material need to have circulation diffusion it is excellent, urge
Change the attributes such as active and selective high, structure and performance stabilization, usage cycles length, it is existed as catalyst and catalyst carrier
There is irreplaceable advantage in catalytic applications.
Inorganic porous material loaded noble metal catalyst, fully combines the excellent catalytic activity of nano-noble metal, resists
Oxidation and decay resistance, and the excellent circulation diffusion of inorganic porous material, high specific surface area and porosity, duct
The advantages such as the selective catalysis performance of size, cause rapidly the broad interest of catalyst research worker, and become at present
The study hotspot of catalyst technical field.Substantial amounts of nano-noble-metal-loaded type catalyst material is by reported success, for example
Pt/A12O3、Pd/C、Ag/Al2O3、Rh/SiO2、Pt-Pd/Al2O3、Pt-Rh/Al2O3Deng.Existing research shows, loads nanometer
Noble metal type catalyst material has excellent catalytic activity and selectivity, but is typically the surface using porous carrier materials
Prepared by the method loaded, therefore nano-noble metal type catalyst material often has nano active center and is easy to run off, is catalyzed
The problems such as agent stability is poor, greatly shortens its service life, so as to reduce its efficiency used.Therefore, load is improved to receive
The stability and its service life of rice noble metal type catalyst, are the difficult points of current noble metal catalyst research field.
Nano-noble metal is incorporated into the spherical template of three-dimensional ordered polyporous material by this patent, prepares a kind of load single
The inorganic porous catalyst material of scattered nano-noble metal type.
The content of the invention
The technical problems to be solved by the invention are to be lived for above shortcomings in the prior art there is provided one kind catalysis
Property high, the porous carbon supported precious metal catalyst that has good stability and preparation method thereof.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of porous carbon supported precious metal catalyst is provided, the catalyst is by porous caged carbon material and is distributed in porous
Noble metal nano particles composition inside caged carbon material.
By such scheme, the porous caged carbon material has macroporous/mesoporous second hole road structure, and macropore diameter is 250-
700nm, mesoporous pore size is 5-8nm, and the noble metal nano particles particle diameter is 20-50nm.
By such scheme, the noble metal nano particles are that gold nano grain, silver nano-grain, Pt nanoparticle or palladium are received
Rice grain.Noble metal nano particles used of the invention have high catalytic activity and selectivity, and good initial catalyst
Activity and durability.
The preparation method step of the porous carbon supported precious metal catalyst of the present invention is as follows：
1) noble metal nano particles are dispersed in water, obtain noble metal nano dispersion liquid, to the noble metal nano point
Dispersant solution is added in dispersion liquid, wherein noble metal nano particles and dispersant mass ratio are 1:25-60, fully dispersed rear centrifugation
It is separated off the noble metal nano particles that supernatant obtains surface modification；
2) by step 1) noble metal nano particles of gained surface modification mixs with absolute ethyl alcohol, deionized water, ultrasonic to divide
Dissipate and uniformly obtain homogeneous system, a small amount of ammonia spirit, and tetraethyl orthosilicate are added into the homogeneous system, wherein positive silicic acid
Ethyl ester and the noble metal nano particles mass ratio of surface modification are 0.8-1:1,12-24h is stirred, noble metal@SiO are obtained2Nucleocapsid
Particle；
3) by step 2) gained noble metal@SiO2Nucleocapsid particles are mixed with PS microballoons, carbon-based bottom material, dilution heat of sulfuric acid,
Wherein noble metal@SiO2Nucleocapsid particles, PS microballoons and carbon substrate quality of materials ratio are 3:15-20:3, ultrasonic disperse uniformly after
120-200 DEG C of reaction 1-2h, reaction dries product after terminating and fully carbonization obtains inorganic skeleton, then by the nothing after carbonization
Machine thing skeleton is put into tube furnace and is heat-treated, and is put into after natural cooling in HF solution and handles 10-15h removing silica, finally
Washing, drying obtain porous carbon supported precious metal catalyst.
By such scheme, step 1) dispersant be polyvinylpyrrolidone, its molecular weight be 100000-400000；
The dispersant solution concentration is 5-10wt%.
By such scheme, step 3) the PS microsphere average grain diameters are 250-700nm, and particle diameter distribution is uniform.
By such scheme, step 3) the carbon-based bottom material be sucrose；The dilution heat of sulfuric acid concentration is 10wt%.
By such scheme, step 3) carbonization technique is：Be carbonized 8-10h at a temperature of 100 DEG C, then at 160 DEG C of carbonizations
6-8h。
By such scheme, step 3) Technology for Heating Processing is：600-700 DEG C of heating 3-5h under oxygen-free atmosphere.
The present invention forms it into core shell structure, noble metal using noble metal nano particles as core by Silica-coated
Nano particle forms stable surface after PVP surface modifications, improves its compatibility with silica.It is heavy through repeatedly centrifugation
Form sediment, go supernatant liquor to remove the impurity such as unnecessary PVP, it is ensured that silica can be evenly coated at noble metal nano particles top layer shape
Into noble metal@SiO2Nucleocapsid particles, then be dispersed in the mother liquor containing PS microballoons, while adding sucrose is used as carbon
Source, dilution heat of sulfuric acid is used as template and noble metal@SiO as dehydrating agent, PS microballoons2Nucleocapsid particles carry out self assembly in mother liquor
Uniform filling system is formed, the inorganic skeleton that carbonization makes sucrose as carbon source formation catalyst is first passed through, then products therefrom is high
The warm further dehydration of anaerobic processing, PS microsphere volumes drastically shrink carbonization in carbonization and heat treatment process, in catalyst material
Middle formation macroporous structure, is finally handled with HF solution and removed after silica shell, finally gives uniform pattern, performance stabilization, tool
There is the noble metal support type inorganic porous material catalyst of porous cage structure.
The beneficial effects of the present invention are：Catalyst prepared by the present invention has porous cage structure, with outer layer inorganic bone
Frame structure latches noble metal nano activated centre, solve nano active center be easy to run off, poor catalyst stability the problems such as, carry
The high stability in use of catalyst, in addition, the catalyst, which has, mesoporous point between 3-D ordered multiporous structure and big interporal lacuna
Cloth, has bigger specific surface area compared with common large pore material, improves the catalytic performance of the catalyst.
Brief description of the drawings
Fig. 1 is the Au@SiO prepared by the embodiment of the present invention 12Scanning electron microscope (SEM) photograph；
Fig. 2 is the scanning electron microscope (SEM) photograph of porous carbon-Au catalyst prepared by embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of porous carbon-Au catalyst prepared by embodiment 1；
Fig. 4 is the graph of pore diameter distribution of porous carbon-Au catalyst prepared by embodiment 1；
Fig. 5 is the nitrogen Adsorption and desorption isotherms of porous carbon-Au catalyst prepared by embodiment 1；
Fig. 6 is the Wide angle X-ray diffraction figure of porous carbon-Au catalyst prepared by embodiment 1.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Polyvinylpyrrolidone used in the embodiment of the present invention (PVP) molecular weight is 100000-400000.
Embodiment 1
The three-neck flask that will be equipped with 100mL aqueous solution of chloraurate (0.1g/L) is placed in 100 DEG C of oil bath pans, after uniform heating
The above-mentioned sodium citrate solutions of 1.4mL are added dropwise again after instilling 1.4mL sodium citrate aqueous solutions (0.113g/mL), 12min, react
Stopping heating being down to room temperature and obtains the dispersion liquid containing gold nano grain after 1h.3mL PVP are added into gained dispersion liquid water-soluble
Liquid (9.28wt%), after stirring 2 days, centrifuges 30min under 10000r/min rotating speeds, sucks and deionization is added after supernatant liquor
Above-mentioned centrifuge washing step 2 time is repeated after water, ultrasonic disperse 5min, the gold nano grain of surface modification is obtained.
The gold nano grain of the above-mentioned gained surface modifications of 0.01g is mixed simultaneously with 10mL absolute ethyl alcohols, 0.4mL deionized waters
Ultrasonic disperse 10min formation homogeneous systems, add 0.3mL ammonia spirits into the homogeneous system under agitation
(25wt%), 10 μ L tetraethyl orthosilicates, stir 12h and obtain noble metal@SiO at room temperature2Nucleocapsid particles.
By noble metal@SiO2Nucleocapsid particles, PS microballoons (average grain diameter 600nm), sucrose, 10wt% dilution heat of sulfuric acid are with matter
Amount compares 15：100：15：15 ultrasonic disperse 1h react 2h after 120 DEG C, and reaction is sequentially placed into 100 DEG C, in 160 DEG C of baking ovens after terminating
Be carbonized 8h and 6h respectively.The inorganic skeleton obtained after fully carbonization is put into tube furnace again, 700 DEG C under oxygen-free environment
Heat and processing 12h removing silica in HF solution (concentration is 30wt%) is put into after 3h, natural cooling, then be washed with deionized water
Wash and be placed in 60 DEG C of baking ovens being dried to obtain final product porous carbon-Au catalyst.
Fig. 1 is Au@SiO obtained by the present embodiment2Scanning electron microscope (SEM) photograph, as can be seen from the figure obtained Au grain diameters
Homogeneous (particle diameter 20-50nm or so), coated with silica is uniform.Fig. 2 and Fig. 3 is porous carbon-Au catalyst obtained by the present embodiment
Scanning electron microscope (SEM) photograph, as can be seen from the figure porous caged carbon material there is macroporous/mesoporous second hole road structure, macropore diameter is
250-700nm, mesoporous pore size is 5-8nm, and gold grain is dispersed and confinement is inside porous caged carbon material.Fig. 4 and Fig. 5 points
Not Wei porous carbon-Au catalyst obtained by the present embodiment graph of pore diameter distribution and nitrogen Adsorption and desorption isotherms, as can be seen from the figure
There is obvious mesoporous distribution in sample, aperture is 5-8nm.Fig. 6 is the Wide angle X-ray diffraction figure of porous carbon-Au catalyst, and 2 θ are
Bulge at 20 degree, which is shown, unbodied carbon material in sample, 2 θ show the characteristic peak of elemental gold when being 38 degree.
Embodiment 2
The three-neck flask that will be equipped with 100mL aqueous solution of chloraurate (0.1g/L) is placed in 100 DEG C of oil bath pans, after uniform heating
The above-mentioned sodium citrate solutions of 1.6mL are added dropwise again after instilling 1.6mL sodium citrate aqueous solutions (0.113g/mL), 12min, react
Stopping heating being down to room temperature and obtains the dispersion liquid containing gold nano grain after 1h.2.5mL PVP water is added into gained dispersion liquid
Solution (9wt%), after stirring 2 days, centrifuges 30min under 10000r/min rotating speeds, sucks and deionized water is added after supernatant liquor,
Above-mentioned centrifuge washing step 2 time is repeated after ultrasonic disperse 5min, the gold nano grain of surface modification is obtained.
The gold nano grain of the above-mentioned gained surface modifications of 0.01g is mixed simultaneously with 10mL absolute ethyl alcohols, 0.4mL deionized waters
Ultrasonic disperse 10min formation homogeneous systems, add 0.3mL ammonia spirits, the positive silicon of 8ul into the homogeneous system under agitation
Acetoacetic ester, stirs 12h and obtains noble metal@SiO at room temperature2Nucleocapsid particles.
By noble metal@SiO2Nucleocapsid particles, PS microballoons (average grain diameter 500nm), sucrose, 10wt% dilute sulfuric acids are with mass ratio
15：100：15：15 ultrasonic disperse 1h react 1h after 200 DEG C, reaction be sequentially placed into after terminating 100 DEG C, in 160 DEG C of baking ovens respectively
Be carbonized 8h and 6h.The inorganic skeleton obtained after fully carbonization is put into tube furnace again, 700 DEG C of heating under oxygen-free environment
3h removes PS microballoons, is put into after natural cooling in HF solution and handles 12h and remove silica, then is washed with deionized and is placed in
Final product porous carbon-Au catalyst is dried to obtain in 60 DEG C of baking ovens.
Porous carbon-Au catalyst obtained by the present embodiment is tested, it is as a result similar to Example 1.
Embodiment 3
The three-neck flask that will be equipped with 100mL aqueous solution of chloraurate (0.1g/L) is placed in 105 DEG C of oil bath pans, after uniform heating
The above-mentioned sodium citrate solutions of 1.6mL are added dropwise again after instilling 1.6mL sodium citrate aqueous solutions (0.113g/mL), 12min, react
Stopping heating being down to room temperature and obtains the dispersion liquid containing gold nano grain after 1h.3mL PVP are added into gained dispersion liquid water-soluble
Liquid (10wt%), after stirring 2 days, centrifuges 30min under 12000r/min rotating speeds, sucks and deionized water is added after supernatant liquor,
Above-mentioned centrifuge washing step 2 time is repeated after ultrasonic disperse 5min, the gold nano grain of surface modification is obtained.
The gold nano grain of the above-mentioned gained surface modifications of 0.01g is mixed simultaneously with 10mL absolute ethyl alcohols, 0.4mL deionized waters
Ultrasonic disperse 10min formation homogeneous systems, add 0.3mL ammonia spirits, the 8 positive silicon of μ L into the homogeneous system under agitation
Acetoacetic ester, stirs 10h and obtains noble metal@SiO at room temperature2Nucleocapsid particles.By noble metal@SiO2Nucleocapsid particles, PS microballoons are (average
Particle diameter 700nm), sucrose, 10wt% dilute sulfuric acids are with mass ratio 15：100：15：15 ultrasonic disperse 1h react 2h after 160 DEG C, instead
100 DEG C are sequentially placed into after should terminating, be carbonized in 160 DEG C of baking ovens 8h and 6h respectively.The inorganic matter that will be obtained again after fully carbonization
Skeleton is put into tube furnace, and 700 DEG C of heating 3h, which remove to be put into after PS microballoons, natural cooling in HF solution, under oxygen-free environment is handled
10h removes silica, then is washed with deionized and is placed in being dried to obtain final product porous carbon-gold in 60 DEG C of baking ovens and is catalyzed
Agent.
Porous carbon-Au catalyst obtained by the present embodiment is tested, it is as a result similar to Example 1.
Embodiment 4
The three-neck flask that will be equipped with 100mL chloroplatinic acid aqueous solutions (0.1g/L) is placed in 100 DEG C of oil bath pans, after uniform heating
The above-mentioned sodium citrate solutions of 1.4mL are added dropwise again after instilling 1.4mL sodium citrate aqueous solutions (0.113g/mL), 12min, react
Stopping heating being down to room temperature and obtains the dispersion liquid containing Pt nanoparticle after 1h.3mL PVP are added into gained dispersion liquid water-soluble
Liquid (9.28wt%), after stirring 2 days, centrifuges 30min under 10000r/min rotating speeds, sucks and deionization is added after supernatant liquor
Above-mentioned centrifuge washing step 2 time is repeated after water, ultrasonic disperse 5min, the Pt nanoparticle of surface modification is obtained.
The Pt nanoparticle of the above-mentioned gained surface modifications of 0.01g is mixed simultaneously with 10mL absolute ethyl alcohols, 0.4mL deionized waters
Ultrasonic disperse 10min formation homogeneous systems, are adding 0.3mL ammonia spirits, 10 μ L just into the homogeneous system under agitation
Silester, stirs 12h and obtains noble metal@SiO at room temperature2Nucleocapsid particles.By noble metal@SiO2Nucleocapsid particles, PS microballoons are (flat
Equal particle diameter 600nm), sucrose, 10wt% dilute sulfuric acids are with mass ratio 15：100：15：15 ultrasonic disperse 1h react 2h after 150 DEG C,
Reaction is sequentially placed into 100 DEG C after terminating, be carbonized in 160 DEG C of baking ovens 8h and 6h respectively.It is inorganic by what is obtained after fully carbonization again
Thing skeleton is put into tube furnace, and 600 DEG C of heating 5h, which remove to be put into after PS microballoons, natural cooling in HF solution, under oxygen-free environment locates
Manage 12h and remove silica, then be washed with deionized to be placed in being dried to obtain final product porous carbon-platinum in 60 DEG C of baking ovens and urge
Agent.
Porous carbon-platinum catalyst obtained by the present embodiment is tested, it is as a result similar to Example 1.
Embodiment 5
The three-neck flask that will be equipped with 100mL chlorine palladium acid sodium aqueous solution (0.1g/L) 0.14g/L is placed in 100 DEG C of oil bath pans,
The above-mentioned sodium citrates of 1.4mL are added dropwise again after instilling 1.4mL sodium citrate aqueous solutions (0.113g/mL), 12min after uniform heating
Stopping heating being down to room temperature and obtains the dispersion liquid containing palladium nano-particles after solution, reaction 1h.3mL is added into gained dispersion liquid
The PVP aqueous solution (9.28wt%), after stirring 2 days, 30min is centrifuged under 10000r/min rotating speeds, is sucked and is added after supernatant liquor
Above-mentioned centrifuge washing step 2 time is repeated after deionized water, ultrasonic disperse 5min, the palladium nano-particles of surface modification are obtained.
The palladium nano-particles of the above-mentioned gained surface modifications of 0.01g are mixed simultaneously with 10mL absolute ethyl alcohols, 0.4mL deionized waters
Ultrasonic disperse 10min formation homogeneous systems, are adding 0.3mL ammonia spirits, 10 μ L just into the homogeneous system under agitation
Silester, stirs 12h and obtains noble metal@SiO at room temperature2Nucleocapsid particles.By noble metal@SiO2Nucleocapsid particles, PS microballoons are (flat
Equal particle diameter 250nm), sucrose, 10wt% dilute sulfuric acids are with mass ratio 15：100：15：15 ultrasonic disperse 1h react 1h after 200 DEG C,
Reaction is sequentially placed into 100 DEG C after terminating, be carbonized in 160 DEG C of baking ovens 10h and 6h respectively.It is inorganic by what is obtained after fully carbonization again
Thing skeleton is put into tube furnace, and 700 DEG C of heating 3h, which remove to be put into after PS microballoons, natural cooling in HF solution, under oxygen-free environment locates
Manage 12h and remove silica, then be washed with deionized to be placed in being dried to obtain final product porous carbon-palladium in 60 DEG C of baking ovens and urge
Agent.
Porous carbon-palladium catalyst obtained by the present embodiment is tested, it is as a result similar to Example 1.
Claims (9)
1. a kind of porous carbon supported precious metal catalyst, it is characterised in that：The catalyst is by porous caged carbon material and distribution
Noble metal nano particles composition inside porous caged carbon material；
Its preparation methods steps are as follows：
1) noble metal nano dispersion liquid is prepared, dispersant solution, wherein noble metal are added into the noble metal nano dispersion liquid
Nano particle is 1 with dispersant mass ratio:25-60, the fully dispersed rear removing supernatant that centrifuges obtains the expensive of surface modification
Metal nanoparticle；
2) by step 1) gained surface modification noble metal nano particles mixed with absolute ethyl alcohol, deionized water, ultrasonic disperse is equal
It is even to obtain homogeneous system, a small amount of ammonia spirit, and tetraethyl orthosilicate, wherein tetraethyl orthosilicate are added into the homogeneous system
Noble metal nano particles mass ratio with surface modification is 0.8-1:1,12-24h is stirred, noble metal@SiO are obtained2Nucleocapsid particles；
3) by step 2) gained noble metal@SiO2Nucleocapsid particles are mixed with PS microballoons, carbon-based bottom material, dilution heat of sulfuric acid, wherein expensive
Metal@SiO2Nucleocapsid particles, PS microballoons and carbon substrate quality of materials ratio are 3:15-20:3, ultrasonic disperse is uniformly after 120-200
DEG C reaction 1-2h, reaction dries product after terminating and fully carbonization obtains inorganic skeleton, then by the inorganic matter bone after carbonization
Frame is put into tube furnace and is heat-treated, and is put into after natural cooling in HF solution and handles 10-15h removing silica, finally washed, dries
It is dry to obtain porous carbon supported precious metal catalyst.
2. porous carbon supported precious metal catalyst according to claim 1, it is characterised in that：The porous caged carbon material
With macroporous/mesoporous second hole road structure, macropore diameter is 250-700nm, and mesoporous pore size is 5-8nm, the noble metal nano
Grain diameter is 20-50nm.
3. porous carbon supported precious metal catalyst according to claim 1, it is characterised in that：The noble metal nano particles
For gold nano grain, silver nano-grain, Pt nanoparticle or palladium nano-particles.
4. a kind of preparation method of any described porous carbon supported precious metal catalysts of claim 1-3, it is characterised in that step
It is rapid as follows：
1) noble metal nano dispersion liquid is prepared, dispersant solution, wherein noble metal are added into the noble metal nano dispersion liquid
Nano particle is 1 with dispersant mass ratio:25-60, the fully dispersed rear removing supernatant that centrifuges obtains the expensive of surface modification
Metal nanoparticle；
2) by step 1) gained surface modification noble metal nano particles mixed with absolute ethyl alcohol, deionized water, ultrasonic disperse is equal
It is even to obtain homogeneous system, a small amount of ammonia spirit, and tetraethyl orthosilicate, wherein tetraethyl orthosilicate are added into the homogeneous system
Noble metal nano particles mass ratio with surface modification is 0.8-1:1,12-24h is stirred, noble metal@SiO are obtained2Nucleocapsid particles；
3) by step 2) gained noble metal@SiO2Nucleocapsid particles are mixed with PS microballoons, carbon-based bottom material, dilution heat of sulfuric acid, wherein expensive
Metal@SiO2Nucleocapsid particles, PS microballoons and carbon substrate quality of materials ratio are 3:15-20:3, ultrasonic disperse is uniformly after 120-200
DEG C reaction 1-2h, reaction dries product after terminating and fully carbonization obtains inorganic skeleton, then by the inorganic matter bone after carbonization
Frame is put into tube furnace and is heat-treated, and is put into after natural cooling in HF solution and handles 10-15h removing silica, finally washed, dries
It is dry to obtain porous carbon supported precious metal catalyst.
5. the preparation method of porous carbon supported precious metal catalyst according to claim 4, it is characterised in that step 1) institute
Dispersant is stated for polyvinylpyrrolidone, its molecular weight is 100000-400000；The dispersant solution concentration is 5-
10wt%.
6. the preparation method of porous carbon supported precious metal catalyst according to claim 4, it is characterised in that step 3) institute
PS microsphere average grain diameters are stated for 250-700nm, and particle diameter distribution is uniform.
7. the preparation method of porous carbon supported precious metal catalyst according to claim 4, it is characterised in that step 3) institute
Carbon-based bottom material is stated for sucrose；The dilution heat of sulfuric acid concentration is 10wt%.
8. the preparation method of porous carbon supported precious metal catalyst according to claim 4, it is characterised in that step 3) institute
Stating carbonization technique is：Be carbonized 8-10h at a temperature of 100 DEG C, then at 160 DEG C of carbonization 6-8h.
9. the preparation method of porous carbon supported precious metal catalyst according to claim 4, it is characterised in that step 3) institute
Stating Technology for Heating Processing is：600-700 DEG C of heating 3-5h under oxygen-free atmosphere.
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| CN109304464B (en) * | 2018-10-30 | 2021-03-26 | 郑州大学 | Hollow cage-shaped carbon/Ru composite microsphere for hydrogen production by electrolyzing water and preparation method thereof |
| CN111799480B (en) * | 2020-07-02 | 2021-10-29 | 格林美股份有限公司 | Amorphous porous silicon dioxide coated Pt/C catalyst and preparation method thereof |
| CN113275009A (en) * | 2021-05-27 | 2021-08-20 | 安徽艾可蓝环保股份有限公司 | Gas engine tail gas total pollutant purification catalyst and preparation method thereof |
| CN115036522A (en) * | 2022-05-18 | 2022-09-09 | 福州大学 | Method for preparing alloy catalyst for fuel cell in limited area |
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