CN105126828A - Porous carbon load noble metal catalyst and preparation method thereof - Google Patents
Porous carbon load noble metal catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a porous carbon load noble metal catalyst and a preparation method thereof. The catalyst is prepared from porous cage-shaped carbon materials and noble metal nanometer particles distributed in the porous cage-shaped carbon materials. The preparation method of the catalyst includes the steps of firstly, adding a dispersing agent solution to noble metal nanometer dispersion liquid, removing supernate through centrifugal separation, and obtaining surface-decorated noble metal nanometer particles; secondly, mixing the surface-decorated noble metal nanometer particles with absolute ethyl alcohol and deionized water, dispersing the mixture evenly through ultrasonic waves, adding ammonia water and tetraethyl orthosilicate, and obtaining noble metal @SiO2 core-shell particles; thirdly, mixing the noble metal @SiO2 core-shell particles with PS micro-balloons, a carbon substrate material and a dilute sulphuric acid solution, dispersing the mixture evenly through ultrasonic waves to have a reaction at a temperature of 120 DEG C to 200 DEG C, conducting full carbonization and thermal treatment, putting the mixture into an HF solution to be treated for 10 h to 15 h after naturally cooling the mixture so that silicon dioxide can be removed, and finally conducting washing and drying to obtain the porous carbon load noble metal catalyst.
Description
Technical field
The present invention relates to catalyst technical field, be specifically related to a kind of porous carbon supported precious metal catalyst and preparation method thereof.
Background technology
Inorganic porous material is as catalyst and catalyst carrier material, there is catalytic activity and selective height, Stability Analysis of Structures, technology of preparing be simple, with low cost, post processing simple, can the advantage such as reusing, very important status is occupied in industrial catalyst application, get a lot of applications in petroleum refining and chemical industry, such as FCC catalyst molecule sieve Y and ZSM-5.Inorganic porous material is generally used in heterogeneous catalytic system, and the course of its catalytic reaction comprises reactant diffusion and is adsorbed onto chemical reaction in catalyst system and catalyzing of catalyst surface process, reactant and product from the desorption catalyst and diffusion process.The catalytic reaction course basic according to this, inorganic porous material needs to possess the attributes such as circulation diffusion is excellent, catalytic activity and selective height, Structure and Properties is stable, life cycle is long, makes it in catalytic applications, have irreplaceable advantage as catalyst and catalyst carrier.
Inorganic porous material loaded noble metal catalyst, fully combine the catalytic activity of nano-noble metal excellence, anti-oxidant and decay resistance, and the circulation diffusion of inorganic porous material excellence, high specific area and porosity, pore size the advantage such as selective catalysis performance, cause rapidly the broad interest of catalyst research worker, and become the study hotspot of current catalyst technical field.A large amount of nano-noble-metal-loaded type catalyst materials by reported success, such as Pt/A1
2o
3, Pd/C, Ag/Al
2o
3, Rh/SiO
2, Pt-Pd/Al
2o
3, Pt-Rh/Al
2o
3deng.Existing research shows, nano-noble-metal-loaded type catalyst material has excellent catalytic activity and selective, but normally utilize the surface of porous carrier materials to carry out the method preparation of load, therefore often there is the problems such as easily run off in nano active center, poor catalyst stability in nano-noble metal type catalyst material, its service life is shortened greatly, thus reduces its efficiency used.Therefore, improving stability and the service life thereof of nano-noble-metal-loaded type catalyst, is the difficult point of current noble metal catalyst research field.
Nano-noble metal is incorporated in the spherical template of three-dimensional ordered polyporous material by this patent, prepares the inorganic porous catalyst material of a kind of load dispersed nano noble metal type.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provides that a kind of catalytic activity is high, the porous carbon supported precious metal catalyst that has good stability and preparation method thereof.
For solving the problems of the technologies described above, technical scheme provided by the invention is:
There is provided a kind of porous carbon supported precious metal catalyst, described catalyst is made up of porous caged material with carbon element and the noble metal nano particles that is distributed in porous caged material with carbon element inside.
By such scheme, described porous caged material with carbon element has macroporous/mesoporous secondary pore passage structure, and macropore diameter is 250-700nm, and mesoporous pore size is 5-8nm, and described noble metal nano particles particle diameter is 20-50nm.
By such scheme, described noble metal nano particles is gold nano grain, silver nano-grain, Pt nanoparticle or palladium nano-particles.The present invention's noble metal nano particles used has high catalytic activity and selective, and good initial catalytic activity and durability.
Preparation method's step of porous carbon supported precious metal catalyst of the present invention is as follows:
1) noble metal nano particles is scattered in water, obtain noble metal nano dispersion liquid, dispersant solution is added in described noble metal nano dispersion liquid, wherein noble metal nano particles and dispersant mass ratio are 1:25-60, and fully after dispersion, centrifugation removing supernatant obtains the noble metal nano particles of finishing;
2) by step 1) noble metal nano particles of gained finishing mixes with absolute ethyl alcohol, deionized water, ultrasonic disperse evenly obtains homogeneous system, a small amount of ammonia spirit is added in described homogeneous system, and ethyl orthosilicate, wherein the noble metal nano particles mass ratio of ethyl orthosilicate and finishing is 0.8-1:1, stir 12-24h, obtain noble metalSiO
2nucleocapsid particles;
3) by step 2) gained noble metalSiO
2nucleocapsid particles mixes with PS microballoon, carbon substrate material, dilution heat of sulfuric acid, wherein noble metalSiO
2nucleocapsid particles, PS microballoon and carbon substrate quality of materials are than being 3:15-20:3, in 120-200 DEG C of reaction 1-2h after ultrasonic disperse is even, after reaction terminates by product dry and fully carbonization obtain inorganic skeleton, again the inorganic skeleton after carbonization is put into tube furnace heat treatment, naturally put into HF solution after cooling to process 10-15h and remove silica, finally wash, dry and obtain porous carbon supported precious metal catalyst.
By such scheme, step 1) described dispersant is polyvinylpyrrolidone, its molecular weight is 100000-400000; Described dispersant solution concentration is 5-10wt%.
By such scheme, step 3) described PS microsphere average grain diameter is 250-700nm, and even particle size distribution.
By such scheme, step 3) described carbon substrate material is sucrose; Described dilution heat of sulfuric acid concentration is 10wt%.
By such scheme, step 3) described carbonization technique is: carbonization 8-10h at 100 DEG C of temperature, then in 160 DEG C of carbonization 6-8h.
By such scheme, step 3) described Technology for Heating Processing is: 600-700 DEG C of heating 3-5h under oxygen-free atmosphere.
The present invention take noble metal nano particles as core, makes it form nucleocapsid structure by Silica-coated, and noble metal nano particles forms stable surface after PVP finishing, improves the compatibility of itself and silica.Through repeatedly centrifugation, go supernatant liquor to remove the impurity such as unnecessary PVP, guarantee that silica evenly can be coated on noble metal nano particles top layer and form noble metalSiO
2nucleocapsid particles, then be dispersed in the mother liquor containing PS microballoon, add sucrose as carbon source, dilution heat of sulfuric acid is as dehydrating agent, and PS microballoon is as template and noble metalSiO simultaneously
2nucleocapsid particles carries out self assembly and forms uniform filling system in mother liquor, first sucrose is made to form the inorganic skeleton of catalyst as carbon source through carbonization, again the process of products therefrom high temperature anaerobic is dewatered further, in carbonization and heat treatment process, PS microsphere volume sharply shrinks carbonization, macroporous structure is formed in catalyst material, finally by HF solution-treated except after silica shell, finally obtain pattern evenly, stable performance, there is the noble metal support type inorganic porous material catalyst of porous cage structure.
Beneficial effect of the present invention is: catalyst prepared by the present invention has porous cage structure, with outer inorganic skeleton structure latches noble metal nano activated centre, solve the problems such as easily run off in nano active center, poor catalyst stability, improve the stability in use of catalyst, in addition, this catalyst has 3-D ordered multiporous structure and has mesoporous distribution between large interporal lacuna, has larger specific area, improve the catalytic performance of this catalyst compared with common large pore material.
Accompanying drawing explanation
The AuSiO of Fig. 1 prepared by the embodiment of the present invention 1
2scanning electron microscope (SEM) photograph;
The scanning electron microscope (SEM) photograph of the porous carbon-Au catalyst of Fig. 2 prepared by embodiment 1;
The scanning electron microscope (SEM) photograph of the porous carbon-Au catalyst of Fig. 3 prepared by embodiment 1;
The nitrogen Adsorption and desorption isotherms of the porous carbon-Au catalyst of Fig. 4 prepared by embodiment 1;
The graph of pore diameter distribution of the porous carbon-Au catalyst of Fig. 5 prepared by embodiment 1;
The Wide angle X-ray diffraction figure of the porous carbon-Au catalyst of Fig. 6 prepared by embodiment 1.
Detailed description of the invention
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment of the present invention polyvinylpyrrolidone used (PVP) molecular weight is 100000-400000.
Embodiment 1
The three-neck flask that 100mL aqueous solution of chloraurate (0.1g/L) is housed is placed in 100 DEG C of oil bath pans, 1.4mL sodium citrate aqueous solution (0.113g/mL) is instilled after even intensification, the above-mentioned sodium citrate solution of 1.4mL is again dripped, the dispersion liquid stopping heating being down to room temperature after reaction 1h obtaining containing gold nano grain after 12min.The 3mLPVP aqueous solution (9.28wt%) is added in gained dispersion liquid, stir after 2 days, centrifugal 30min under 10000r/min rotating speed, adds deionized water after sucking supernatant liquor, repeat above-mentioned centrifuge washing step 2 time after ultrasonic disperse 5min, obtain the gold nano grain of finishing.
The gold nano grain of above-mentioned for 0.01g gained finishing is mixed also ultrasonic disperse 10min with 10mL absolute ethyl alcohol, 0.4mL deionized water and form homogeneous system, in this homogeneous system, add 0.3mL ammonia spirit (25wt%), 10 μ L ethyl orthosilicates under agitation, stirred at ambient temperature 12h obtains noble metalSiO
2nucleocapsid particles.
By noble metalSiO
2nucleocapsid particles, PS microballoon (average grain diameter 600nm), sucrose, 10wt% dilution heat of sulfuric acid, to react 2h in 120 DEG C after mass ratio 15:100:15:15 ultrasonic disperse 1h, put into 100 DEG C, 160 DEG C baking ovens carbonization 8h and 6h respectively successively after reaction terminates.Again the inorganic skeleton obtained after abundant carbonization is put into tube furnace, 700 DEG C of heating 3h under oxygen-free environment, naturally put into HF solution (concentration is 30wt%) process 12h removing silica after cooling, then spend deionized water and be placed in 60 DEG C of baking oven dryings and obtain end product porous carbon-Au catalyst.
Fig. 1 is the present embodiment gained AuSiO
2scanning electron microscope (SEM) photograph, as can be seen from the figure obtained Au grain diameter homogeneous (particle diameter about 20-50nm), coated with silica is even.Fig. 2 and Fig. 3 is the scanning electron microscope (SEM) photograph of the present embodiment gained porous carbon-Au catalyst, as can be seen from the figure porous caged material with carbon element has macroporous/mesoporous secondary pore passage structure, macropore diameter is 250-700nm, mesoporous pore size is 5-8nm, and gold grain is dispersed and confinement is inner at porous caged material with carbon element.Fig. 4 and Fig. 5 is respectively nitrogen Adsorption and desorption isotherms and the graph of pore diameter distribution of the present embodiment gained porous carbon-Au catalyst, as can be seen from the figure has obvious mesoporous distribution in sample, and aperture is 5-8nm.Fig. 6 is the Wide angle X-ray diffraction figure of porous carbon-Au catalyst, has unbodied material with carbon element, show the characteristic peak of elemental gold when 2 θ are 38 degree in bulge show sample when 2 θ are 20 degree.
Embodiment 2
The three-neck flask that 100mL aqueous solution of chloraurate (0.1g/L) is housed is placed in 100 DEG C of oil bath pans, 1.6mL sodium citrate aqueous solution (0.113g/mL) is instilled after even intensification, the above-mentioned sodium citrate solution of 1.6mL is again dripped, the dispersion liquid stopping heating being down to room temperature after reaction 1h obtaining containing gold nano grain after 12min.The 2.5mLPVP aqueous solution (9wt%) is added in gained dispersion liquid, stir after 2 days, centrifugal 30min under 10000r/min rotating speed, adds deionized water after sucking supernatant liquor, repeat above-mentioned centrifuge washing step 2 time after ultrasonic disperse 5min, obtain the gold nano grain of finishing.
The gold nano grain of above-mentioned for 0.01g gained finishing is mixed also ultrasonic disperse 10min with 10mL absolute ethyl alcohol, 0.4mL deionized water and form homogeneous system, in this homogeneous system, add 0.3mL ammonia spirit, 8ul ethyl orthosilicate under agitation, stirred at ambient temperature 12h obtains noble metalSiO
2nucleocapsid particles.
By noble metalSiO
2nucleocapsid particles, PS microballoon (average grain diameter 500nm), sucrose, 10wt% dilute sulfuric acid, to react 1h in 200 DEG C after mass ratio 15:100:15:15 ultrasonic disperse 1h, put into 100 DEG C, 160 DEG C baking ovens carbonization 8h and 6h respectively successively after reaction terminates.Again the inorganic skeleton obtained after abundant carbonization is put into tube furnace, under oxygen-free environment, 700 DEG C of heating 3h remove PS microballoon, naturally put into HF solution after cooling to process 12h and remove silica, then spend deionized water and be placed in 60 DEG C of baking oven dryings and obtain end product porous carbon-Au catalyst.
Tested by the present embodiment gained porous carbon-Au catalyst, result is similar to embodiment 1.
Embodiment 3
The three-neck flask that 100mL aqueous solution of chloraurate (0.1g/L) is housed is placed in 105 DEG C of oil bath pans, 1.6mL sodium citrate aqueous solution (0.113g/mL) is instilled after even intensification, the above-mentioned sodium citrate solution of 1.6mL is again dripped, the dispersion liquid stopping heating being down to room temperature after reaction 1h obtaining containing gold nano grain after 12min.The 3mLPVP aqueous solution (10wt%) is added in gained dispersion liquid, stir after 2 days, centrifugal 30min under 12000r/min rotating speed, adds deionized water after sucking supernatant liquor, repeat above-mentioned centrifuge washing step 2 time after ultrasonic disperse 5min, obtain the gold nano grain of finishing.
The gold nano grain of above-mentioned for 0.01g gained finishing is mixed also ultrasonic disperse 10min with 10mL absolute ethyl alcohol, 0.4mL deionized water and form homogeneous system, in this homogeneous system, add 0.3mL ammonia spirit, 8 μ L ethyl orthosilicates under agitation, stirred at ambient temperature 10h obtains noble metalSiO
2nucleocapsid particles.By noble metalSiO
2nucleocapsid particles, PS microballoon (average grain diameter 700nm), sucrose, 10wt% dilute sulfuric acid, to react 2h in 160 DEG C after mass ratio 15:100:15:15 ultrasonic disperse 1h, put into 100 DEG C, 160 DEG C baking ovens carbonization 8h and 6h respectively successively after reaction terminates.Again the inorganic skeleton obtained after abundant carbonization is put into tube furnace, under oxygen-free environment, 700 DEG C of heating 3h remove PS microballoon, naturally put into HF solution after cooling to process 10h and remove silica, then spend deionized water and be placed in 60 DEG C of baking oven dryings and obtain end product porous carbon-Au catalyst.
Tested by the present embodiment gained porous carbon-Au catalyst, result is similar to embodiment 1.
Embodiment 4
The three-neck flask that 100mL chloroplatinic acid aqueous solution (0.1g/L) is housed is placed in 100 DEG C of oil bath pans, 1.4mL sodium citrate aqueous solution (0.113g/mL) is instilled after even intensification, the above-mentioned sodium citrate solution of 1.4mL is again dripped, the dispersion liquid stopping heating being down to room temperature after reaction 1h obtaining containing Pt nanoparticle after 12min.The 3mLPVP aqueous solution (9.28wt%) is added in gained dispersion liquid, stir after 2 days, centrifugal 30min under 10000r/min rotating speed, adds deionized water after sucking supernatant liquor, repeat above-mentioned centrifuge washing step 2 time after ultrasonic disperse 5min, obtain the Pt nanoparticle of finishing.
The Pt nanoparticle of above-mentioned for 0.01g gained finishing is mixed also ultrasonic disperse 10min with 10mL absolute ethyl alcohol, 0.4mL deionized water and form homogeneous system, in this homogeneous system, add 0.3mL ammonia spirit, 10 μ L ethyl orthosilicates under agitation, stirred at ambient temperature 12h obtains noble metalSiO
2nucleocapsid particles.By noble metalSiO
2nucleocapsid particles, PS microballoon (average grain diameter 600nm), sucrose, 10wt% dilute sulfuric acid, to react 2h in 150 DEG C after mass ratio 15:100:15:15 ultrasonic disperse 1h, put into 100 DEG C, 160 DEG C baking ovens carbonization 8h and 6h respectively successively after reaction terminates.Again the inorganic skeleton obtained after abundant carbonization is put into tube furnace, under oxygen-free environment, 600 DEG C of heating 5h remove PS microballoon, naturally put into HF solution after cooling to process 12h and remove silica, then spend deionized water and be placed in 60 DEG C of baking oven dryings and obtain end product porous carbon-platinum catalyst.
Tested by the present embodiment gained porous carbon-platinum catalyst, result is similar to embodiment 1.
Embodiment 5
The three-neck flask that 100mL chlorine palladium acid sodium aqueous solution (0.1g/L) 0.14g/L is housed is placed in 100 DEG C of oil bath pans, 1.4mL sodium citrate aqueous solution (0.113g/mL) is instilled after even intensification, the above-mentioned sodium citrate solution of 1.4mL is again dripped, the dispersion liquid stopping heating being down to room temperature after reaction 1h obtaining containing palladium nano-particles after 12min.The 3mLPVP aqueous solution (9.28wt%) is added in gained dispersion liquid, stir after 2 days, centrifugal 30min under 10000r/min rotating speed, adds deionized water after sucking supernatant liquor, repeat above-mentioned centrifuge washing step 2 time after ultrasonic disperse 5min, obtain the palladium nano-particles of finishing.
The palladium nano-particles of above-mentioned for 0.01g gained finishing is mixed also ultrasonic disperse 10min with 10mL absolute ethyl alcohol, 0.4mL deionized water and form homogeneous system, in this homogeneous system, add 0.3mL ammonia spirit, 10 μ L ethyl orthosilicates under agitation, stirred at ambient temperature 12h obtains noble metalSiO
2nucleocapsid particles.By noble metalSiO
2nucleocapsid particles, PS microballoon (average grain diameter 250nm), sucrose, 10wt% dilute sulfuric acid, to react 1h in 200 DEG C after mass ratio 15:100:15:15 ultrasonic disperse 1h, put into 100 DEG C, 160 DEG C baking ovens carbonization 10h and 6h respectively successively after reaction terminates.Again the inorganic skeleton obtained after abundant carbonization is put into tube furnace, under oxygen-free environment, 700 DEG C of heating 3h remove PS microballoon, naturally put into HF solution after cooling to process 12h and remove silica, then spend deionized water and be placed in 60 DEG C of baking oven dryings and obtain end product porous carbon-palladium catalyst.
Tested by the present embodiment gained porous carbon-palladium catalyst, result is similar to embodiment 1.
Claims (9)
1. a porous carbon supported precious metal catalyst, is characterized in that: described catalyst is made up of porous caged material with carbon element and the noble metal nano particles that is distributed in porous caged material with carbon element inside.
2. porous carbon supported precious metal catalyst according to claim 1, it is characterized in that: described porous caged material with carbon element has macroporous/mesoporous secondary pore passage structure, macropore diameter is 250-700nm, and mesoporous pore size is 5-8nm, and described noble metal nano particles particle diameter is 20-50nm.
3. porous carbon supported precious metal catalyst according to claim 1, is characterized in that: described noble metal nano particles is gold nano grain, silver nano-grain, Pt nanoparticle or palladium nano-particles.
4. a preparation method for the arbitrary described porous carbon supported precious metal catalyst of claim 1-3, is characterized in that step is as follows:
1) noble metal nano particles is scattered in water, obtain noble metal nano dispersion liquid, dispersant solution is added in described noble metal nano dispersion liquid, wherein noble metal nano particles and dispersant mass ratio are 1:25-60, and fully after dispersion, centrifugation removing supernatant obtains the noble metal nano particles of finishing;
2) by step 1) noble metal nano particles of gained finishing mixes with absolute ethyl alcohol, deionized water, ultrasonic disperse evenly obtains homogeneous system, a small amount of ammonia spirit is added in described homogeneous system, and ethyl orthosilicate, wherein the noble metal nano particles mass ratio of ethyl orthosilicate and finishing is 0.8-1:1, stir 12-24h, obtain noble metalSiO
2nucleocapsid particles;
3) by step 2) gained noble metalSiO
2nucleocapsid particles mixes with PS microballoon, carbon substrate material, dilution heat of sulfuric acid, wherein noble metalSiO
2nucleocapsid particles, PS microballoon and carbon substrate quality of materials are than being 3:15-20:3, in 120-200 DEG C of reaction 1-2h after ultrasonic disperse is even, after reaction terminates by product dry and fully carbonization obtain inorganic skeleton, again the inorganic skeleton after carbonization is put into tube furnace heat treatment, naturally put into HF solution after cooling to process 10-15h and remove silica, finally wash, dry and obtain porous carbon supported precious metal catalyst.
5. the preparation method of porous carbon supported precious metal catalyst according to claim 4, is characterized in that step 1) described dispersant is polyvinylpyrrolidone, its molecular weight is 100000-400000; Described dispersant solution concentration is 5-10wt%.
6. the preparation method of porous carbon supported precious metal catalyst according to claim 4, is characterized in that step 3) described PS microsphere average grain diameter is 250-700nm, and even particle size distribution.
7. the preparation method of porous carbon supported precious metal catalyst according to claim 4, is characterized in that step 3) described carbon substrate material is sucrose; Described dilution heat of sulfuric acid concentration is 10wt%.
8. the preparation method of porous carbon supported precious metal catalyst according to claim 4, is characterized in that step 3) described carbonization technique is: carbonization 8-10h at 100 DEG C of temperature, then in 160 DEG C of carbonization 6-8h.
9. the preparation method of porous carbon supported precious metal catalyst according to claim 4, is characterized in that step 3) described Technology for Heating Processing is: 600-700 DEG C of heating 3-5h under oxygen-free atmosphere.
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| CN109304464A (en) * | 2018-10-30 | 2019-02-05 | 郑州大学 | A kind of electrolysis aquatic products hydrogen hollow caged carbon/Ru complex microsphere and preparation method thereof |
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| 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 |
| CN116463663A (en) * | 2023-04-19 | 2023-07-21 | 汕头大学 | Nanoparticle material and preparation method and application thereof |
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| CN108845016A (en) * | 2018-06-13 | 2018-11-20 | 信阳师范学院 | A kind of preparation method of L-cysteine self energizing biosensor |
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| 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 |
| CN116463663A (en) * | 2023-04-19 | 2023-07-21 | 汕头大学 | Nanoparticle material and preparation method and application thereof |
| CN116463663B (en) * | 2023-04-19 | 2023-12-12 | 汕头大学 | Nanoparticle material and preparation method and application thereof |
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