CN104923215A - Precious-metal-supported ordered mesoporous alumina material, and synthetic method and application thereof - Google Patents
Precious-metal-supported ordered mesoporous alumina material, and synthetic method and application thereof Download PDFInfo
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Abstract
The invention provides a precious-metal-supported ordered mesoporous alumina material, and a synthetic method and application thereof. The method comprises the following steps: uniformly mixing acid, alcohol and a non-ionic surfactant, then adding hydrophobic precious metal salt and aluminium salt, and carrying out uniform mixing so as to obtain a mixed solution; and maintaining the obtained mixed solution for a period of time at 30 to 60 DEG C so as to volatile a solvent; and carrying out calcination at 300 to 600 DEG C so as to obtain the precious-metal-supported ordered mesoporous alumina material. The precious-metal-supported ordered mesoporous alumina material can be applied in preparation of a catalyst for oxidation reaction of carbon monoxide. According to the invention, the precious-metal-supported ordered mesoporous alumina material is synthesized by a one-step method; the precious metal nanoparticle of the material have high dispersity, high supporting rate, small size and highly-ordered mesopore channel structure in a mesoporous material; and the precious-metal-supported ordered mesoporous alumina material, used as the catalyst for the oxidation reaction of carbon monoxide, has high catalytic activity and heat stability.
Description
Technical field
The present invention relates to a kind of support noble metal ordered mesoporous aluminium oxide material and synthetic method and application, belong to noble metal and support porous material technical field.
Background technology
In mesoporous material, mesopore silicon oxide studies comparatively deep system.Compared to silica, aluminium oxide has some character being better than silica, such as higher hydrolytic stability, stronger acidity, is easier to support different metal species etc., therefore obtains in the field such as catalysis, absorption and applies more widely.Because aluminium oxide has larger specific area, special pore structure and certain acidity, and heat endurance is higher, still remaining on 100m higher than specific area when 800 DEG C
2/ more than g, thus be most widely used at catalytic field, become the most widely used catalyst or catalyst carrier in chemical industry and petroleum industry, played an important role in the course of reaction such as reformation hydrogen production, the purifying of gas phase oil product component, the purification of vehicle exhaust of the cracking of petroleum component, hydrofinishing, hydrodesulfurization, hydrocarbon.But due to alumina system self, the synthetic method of meso-porous alumina is still be not as ripe as mesopore silicon oxide.
Noble metal catalyst has high catalytic activity, the advantage such as high temperature resistant, anti-oxidant, and being the important catalysis material of a class extensive use, is also one of study hotspot in recent years.Be catalyst carrier material with ordered mesoporous material, utilize the confinement effect of mesopore orbit, the growth supporting nano particle can be controlled; On the other hand, because different molecular has difference to the diffusion coefficient in duct, and vestibule is to the transition state Existential Space restriction of catalytic reaction, therefore can realize shape selective catalysis according to the spatial configuration difference etc. of substrate, product and transition state.
The conventional nanoparticle approach that supports in mesopore orbit mainly contains infusion process and grafting.Wherein, infusion process is the most conventional.But the committed step of the synthetic method of this similar " casting " technique is metal oxide precursor supports efficiency in mesopore orbit, and actual conditions are, in dipping process, metal salt solution is more willing to be intended to duct outer surface absorption, capillarity is unique driving force that solution moves in duct simultaneously, if the active force of mesoporous wall and solution is very weak, capillarity also can become very little, cause the filling rate of solution in duct low, nano particle is also not easily dispersed simultaneously.Repeatedly dipping is " nanometer casting " method that method is general repeatedly, but it is loaded down with trivial details consuming time that the problem brought like this is exactly synthesis step, the productive rate of the ordered structure really obtained can not be equal to soft template method, cannot meet extensive synthesis and demand practical further.Another kind of common method is grafting, although grafting can ensure that nano particle enters in duct, needs to find suitable grafting molecule, and supports and need multistep to carry out.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of support noble metal ordered mesoporous aluminium oxide material and synthetic method and application.This synthetic method utilizes hydrophobicity noble metal precursor, one-step synthesis can support the ordered mesoporous aluminium oxide material of noble metal, not need first synthesising mesoporous alumina material, then carried noble metal.
For achieving the above object, the present invention provide firstly a kind of synthetic method supporting the ordered mesoporous aluminium oxide material of noble metal, and it comprises the following steps:
(1), after acid, alcohol, nonionic surface active agent being mixed, add hydrophobicity precious metal salt (as presoma) and aluminium salt (as presoma), after mixing, obtain a mixed solution;
(2) described mixed solution is made to keep a period of time at 30-60 DEG C;
(3) then roasting at 300-600 DEG C, obtains the described ordered mesoporous aluminium oxide material supporting noble metal.
In above-mentioned synthetic method, preferably, described hydrophobicity precious metal salt comprises the combination of one or more in acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate, acetylacetone,2,4-pentanedione silver, golden, the acetylacetone,2,4-pentanedione ruthenium of acetylacetone,2,4-pentanedione and acetylacetone,2,4-pentanedione rhodium etc.; More preferably, described hydrophobicity precious metal salt comprises the combination of one or more in acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate and acetylacetone,2,4-pentanedione silver.
In above-mentioned synthetic method, preferably, described aluminium salt comprises the combination of one or more in aluminum chloride sulphate, aluminum nitrate, aluminium isopropoxide and aluminum sulfate etc.; More preferably, described aluminium salt comprises aluminum nitrate and/or aluminium isopropoxide.
In above-mentioned synthetic method, preferably, described alcohol comprises the combination of one or more in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol and sec-butyl alcohol etc.; More preferably, described alcohol comprises ethanol and/or normal propyl alcohol.
In above-mentioned synthetic method, preferably, described acid comprises the combination of one or more in sulfuric acid, nitric acid, hydrochloric acid, acetic acid and citric acid etc.; More preferably, described acid comprises nitric acid and/or citric acid.Synthetic method of the present invention adopts acid to regulate alcoholic solution, makes it aobvious acid, just can make the alcoholysis slowly of aluminium presoma, be convenient to form mesoporous structure.
In above-mentioned synthetic method, preferably, described nonionic surface active agent comprises triblock copolymer.More preferably, the triblock copolymer adopted comprises the combination of one or more in P123, F127, F68 and Brij-56 etc.; Particularly preferably, described triblock copolymer comprises P123 and/or F127.Synthetic method of the present invention adopts triblock copolymer high molecular surfactant as the template of pore structure.If use the organic molecule of other ionics as template, then because organic molecule itself is smaller, the formwork structure formed is unstable, and the hole wall of induced synthesis is thinner, in the process of roasting, duct easily caves in, and is difficult to obtain the concentrated alumina mesoporous material of high-ratio surface sum pore distribution.
In synthetic method of the present invention, described hydrophobicity precious metal salt, aluminium salt, alcohol, acid and nonionic surface active agent the form of pure material or solution can participate in reaction, and the concentration of its solution can carry out conventional adjustment by those skilled in the art.
In above-mentioned synthetic method, preferably, with the described gross mass supporting the ordered mesoporous aluminium oxide material of noble metal for benchmark, the loading of described noble metal is 0.1-5% (gauge with precious metal simple substance), is more preferably 0.5%-3.5%.
In above-mentioned synthetic method, preferably, with 25mmol aluminium element for benchmark, the consumption of described nonionic surface active agent is 5g-15g.
In above-mentioned synthetic method, preferably, step (1) is: acid, alcohol are mixed with nonionic surface active agent (can agitation as appropriate), under agitation mix with hydrophobicity precious metal salt and aluminium salt again, continue to stir, described hydrophobicity precious metal salt and aluminium salt are dissolved, obtains a mixed solution.More preferably, under agitation mix with hydrophobicity precious metal salt and aluminium salt, the time of then continuing to stir is 5-12 hour.
In above-mentioned synthetic method, preferably, the pH value of the described mixed solution (this mixed solution is the solution after presoma dissolves completely) in step (1) is 1-5.
In above-mentioned synthetic method, the consumption of acid and alcohol can be regulated according to actual conditions by those skilled in the art, as long as the pH value of the mixed solution obtained in the step of making (1) is in the scope of 1-5.
In above-mentioned synthetic method, preferably, step (1) is carried out at 10-30 DEG C.
In above-mentioned synthetic method, the time of volatilization at 30-60 DEG C in step (2), be determine according to the effect of the gel (or dry glue) formed, preferably, the time kept at 30-60 DEG C in step (2) is 12-72 hour.More preferably, step (2) keeps 36-48 hour at 40-50 DEG C.Synthetic method of the present invention adopts 30-60 DEG C (preferably adopting 40-50 DEG C), and volatilize alcohol equal solvent, can be convenient to the formation of meso-hole structure.Preferably, can be transferred in air dry oven by mixed solution, temperature is set as 30-60 DEG C (preferably adopting 40-50 DEG C), carries out the volatilization of alcohol equal solvent with this understanding.
In above-mentioned synthetic method, preferably, in step (3), the time of roasting at 300-600 DEG C is 3-10 hour, to remove nonionic surface active agent template.More preferably, the sintering temperature in step (3) is 400-500 DEG C, and roasting time is 4-8 hour; Particularly preferably, roasting time is 4-6 hour.
The present invention utilizes sol-gel process, using nonionic surface active agent as template, because nonionic surface active agent has two ends hydrophilic radical and middle lipophilic group, the rod-shaped micelle structure with hydrophobic inner core and polarity basic unit can be formed in polar solvent.Now add a certain amount of hydrophobicity noble metal precursor body, due to the solubilization of micella, this hydrophobicity noble metal precursor body is more prone to enter in micella nonpolar hydrophobic kernel.Then add aluminium presoma, then by the slow volatilization of solvent, presoma and surfactant interact and form mesoporous phase.Last roasting removing template, thus one-step synthesis supports the ordered mesoporous aluminium oxide material of noble metal, and do not need first synthesising mesoporous alumina material, then carried noble metal.
On the other hand, present invention also offers a kind of ordered mesoporous aluminium oxide material supporting noble metal, it is preparation-obtained by the above-mentioned synthetic method supporting the ordered mesoporous aluminium oxide material of noble metal.
Support in the ordered mesoporous aluminium oxide material of noble metal above-mentioned, preferably, with the described gross mass supporting the ordered mesoporous aluminium oxide material of noble metal for benchmark, the loading of described noble metal is 0.1-5% (gauge with precious metal simple substance), is more preferably 0.5%-3.5%.
The meso-hole structure high-sequential supporting the ordered mesoporous aluminium oxide material of noble metal provided by the invention.According to the specific embodiment of the present invention, preferably, this specific area supporting the ordered mesoporous aluminium oxide material of noble metal is 100-300m
2/ g, pore volume is 0.1-0.8cm
3/ g, mesoporous pore size is 1-10nm, and the particle diameter of noble metal nano particles is 1-10nm; More preferably, described specific area is 100-200m
2/ g, pore volume is 0.1-0.5cm
3/ g, mesoporous pore size is 3-7nm, and the particle diameter of noble metal nano particles is 2-7nm.
The ordered mesoporous aluminium oxide material supporting noble metal provided by the invention can ensure the high degree of dispersion of noble metal in mesoporous material, what improve noble metal supports rate, and under high loadings, still can keep the mesopore orbit structure of high-sequential, utilize the confinement effect in duct to limit the size of noble metal nano particles simultaneously.
In addition, present invention also offers the application of a kind of above-mentioned ordered mesoporous aluminium oxide material supporting noble metal in the catalyst preparing Oxidation of Carbon Monoxide reaction.
The ordered mesoporous aluminium oxide material supporting noble metal provided by the invention, as the catalyst of Oxidation of Carbon Monoxide reaction, the noble metal prepared with traditional dipping method supports compared with mesoporous aluminum oxide material, the material of this one-step synthesis method has higher catalytic activity and heat endurance, is a kind of catalyst of high thermal stability.
In sum, the present invention adopts one-step synthesis method to support the ordered mesoporous aluminium oxide material of noble metal, the decentralization of noble metal nano particles in mesoporous material of this material is high, the rate that supports is high, noble metal nano particles size is little, and mesopore orbit structure height is orderly, its catalyst as Oxidation of Carbon Monoxide reaction has high catalytic activity and heat endurance.
Accompanying drawing explanation
Fig. 1 is the small angle X-ray diffraction figure supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 1-5.
Fig. 2 is the Wide angle X-ray diffraction figure supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 1-5.
Fig. 3 is the nitrogen adsorption desorption curve supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 1-5.
Fig. 4 is the graph of pore diameter distribution supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 1-5.
Fig. 5 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 1.
Fig. 6 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 2.
Fig. 7 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 3.
Fig. 8 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 4.
Fig. 9 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 5.
Figure 10 is the small angle X-ray diffraction figure supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 6.
Figure 11 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of platinum of embodiment 6.
Figure 12 is the small angle X-ray diffraction figure supporting the ordered mesoporous aluminium oxide material of noble metal of embodiment 7 and 8.
Figure 13 is the nitrogen adsorption desorption curve supporting the ordered mesoporous aluminium oxide material of noble metal of embodiment 7 and 8.
Figure 14 is the graph of pore diameter distribution supporting the ordered mesoporous aluminium oxide material of noble metal of embodiment 7 and 8.
Figure 15 is the transmission electron microscope photo supporting the ordered mesoporous aluminium oxide material of silver of embodiment 7.
Figure 16 is the transmission electron microscope photo of the ordered mesoporous aluminium oxide material of the loaded palladium of embodiment 8.
Figure 17 is the transmission electron microscope photo supporting the mesoporous aluminum oxide material of platinum that in embodiment 9 prepared by infusion process.
Figure 18 is CO conversion ratio in embodiment 10 and temperature relation figure.
Detailed description of the invention
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
In 50mL beaker, add 1.0g non-ionic surface active agent Pluronic P123 and 20mL ethanol, be at room temperature stirred to Pluronic P123 and dissolve.Add 8.4g citric acid, after stirring and dissolving, then add 0.006g acetylacetone,2,4-pentanedione platinum and 3.75g aluminum nitrate, stirred at ambient temperature 10 hours is the longer time even, until all dissolve.Dissolve completely, be transferred to by beaker in air dry oven, uncovered placement, temperature is set as 40 DEG C, carries out solvent volatilization with this understanding.After 48 hours, colloid after being volatilized by solvent takes out, this colloid is transferred in porcelain crucible, be warming up to 400 DEG C, at this temperature, in air atmosphere, roasting removes template in 4 hours, obtain powder-product with agate mortar porphyrize, be the ordered mesoporous aluminium oxide material supporting platinum, the mass percent that in this material, platinum supports is 0.6% (gauge supporting the ordered mesoporous aluminium oxide material of platinum with the amount of platinum simple substance and this is calculated).The little angle XRD of this material is shown in Fig. 1, and wide-angle XRD is shown in Fig. 2; Nitrogen adsorption desorption curve is shown in Fig. 3, and Fig. 4 is shown in by pore-size distribution, and the aperture of this material changes between 4-6nm; Specific area and pore volume are in table 1, and Fig. 5 is shown in by transmission electron microscope (TEM) photo.
Embodiment 2
Identical with embodiment 1 method of operating, difference is the acetylacetone,2,4-pentanedione platinum added is 0.013g, the mass percent 1.3% that platinum supports.The little angle XRD of this material is shown in Fig. 1, and wide-angle XRD is shown in Fig. 2; Nitrogen adsorption desorption curve is shown in Fig. 3, and Fig. 4 is shown in by pore-size distribution, and the aperture of this material changes between 4-6nm; Specific area and pore volume are in table 1, and Fig. 6 is shown in by transmission electron microscope (TEM) photo.
Embodiment 3
Identical with embodiment 1 method of operating, difference is the acetylacetone,2,4-pentanedione platinum added is 0.021g, the mass percent 2.1% that platinum supports.The little angle XRD of this material is shown in Fig. 1, and wide-angle XRD is shown in Fig. 2, and nitrogen adsorption desorption curve is shown in Fig. 3, and Fig. 4 is shown in by pore-size distribution, and the aperture of this material changes between 4-6nm; Specific area and pore volume are in table 1, and Fig. 7 is shown in by transmission electron microscope (TEM) photo.
Embodiment 4
Identical with embodiment 1 method of operating, difference is the acetylacetone,2,4-pentanedione platinum added is 0.03g, the mass percent 3.0% that platinum supports.The little angle XRD of this material is shown in Fig. 1, and wide-angle XRD is shown in Fig. 2; Nitrogen adsorption desorption curve is shown in Fig. 3, and Fig. 4 is shown in by pore-size distribution, and the aperture of this material changes between 4-6nm; Specific area and pore volume are in table 1, and Fig. 8 is shown in by transmission electron microscope (TEM) photo.
Embodiment 5
Identical with embodiment 1 method of operating, difference is the acetylacetone,2,4-pentanedione platinum added is 0.035g, the mass percent 3.5% that platinum supports.The little angle XRD of this material is shown in Fig. 1, and wide-angle XRD is shown in Fig. 2; Nitrogen adsorption desorption curve is shown in Fig. 3, and Fig. 4 is shown in by pore-size distribution, and the aperture of this material changes between 4-6nm; Specific area and pore volume are in table 1, and Fig. 9 is shown in by transmission electron microscope (TEM) photo.
Embodiment 6
Identical with embodiment 1 method of operating, difference changes 8.4g citric acid into 1.5mL red fuming nitric acid (RFNA), and 3.75g aluminum nitrate changes 2.04g aluminium isopropoxide into.The little angle XRD of this material is shown in Figure 10, and Figure 11 is shown in by transmission electron microscope (TEM) photo.
Embodiment 7
Identical with embodiment 1 method of operating, difference 0.006g acetylacetone,2,4-pentanedione platinum is changed into 0.011g acetylacetone,2,4-pentanedione silver, the mass percent 1% that silver supports.The little angle XRD of this material is shown in Figure 12; Nitrogen adsorption desorption curve is shown in Figure 13, and Figure 14 is shown in by pore-size distribution, and the aperture of this material changes between 7-10nm; Specific area and pore volume are in table 1, and Figure 15 is shown in by transmission electron microscope (TEM) photo.
Embodiment 8
Identical with embodiment 1 method of operating, difference changes 0.006g acetylacetone,2,4-pentanedione platinum into 0.016g palladium acetylacetonate, the mass percent 1% that palladium supports.The little angle XRD of this material is shown in Figure 12, and nitrogen adsorption desorption curve is shown in Figure 13, and Figure 14 is shown in by pore-size distribution, and the aperture of this material changes between 7-10nm; Specific area and pore volume are in table 1, and Figure 16 is shown in by transmission electron microscope (TEM) photo.
Embodiment 9
The present embodiment does not add acetylacetone,2,4-pentanedione platinum, and platinum is supported on mesoporous aluminum oxide material by the method for dipping, and concrete grammar is: the H getting 7mL 6.0mmol/L
2ptCl
6solution, as in the flask of 250mL, adds the water of 4.5mL and the methyl alcohol of 40.5mL, and mesoporous aluminum oxide material, react after 3 hours, solid absolute ethyl alcohol and deionized water are repeatedly washed, centrifugation must precipitate, then dry in 100 DEG C of baking ovens, last 300 DEG C of roastings 2 hours.The mass percent 1.4% that platinum supports.The specific area of this material and pore volume are in table 1, and Figure 17 is shown in by transmission electron microscope (TEM) photo.As apparent from Figure 17 can, this material mesoporous unordered.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Specific area (m 2/g) | 113 | 130 | 160 | 165 | 147 | 120 | 142 | 100 | 156 |
| Pore volume (cm 3/g) | 0.208 | 0.213 | 0.324 | 0.410 | 0.301 | 0.240 | 0.296 | 0.193 | 0.310 |
Embodiment 10
CO catalytic oxidation is tested: material embodiment 2 and embodiment 9 prepared 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C roastings 1 hour, then respectively gets 25mg respectively, respectively with 4g quartz sand Homogeneous phase mixing, is placed on and is of a size of in the stainless steel tube of 1 × 60cm.It is the CO of the 1% and O of 20% that reaction gas consists of mass fraction
2, take He as Balance Air.After reaction, gas composition utilizes gas chromatography to detect, and the CO conversion ratio obtained and the graph of a relation of temperature are shown in Figure 18.As seen from Figure 18, the material of embodiment 2 is as catalyst, and its catalytic activity and heat endurance are apparently higher than the material of embodiment 9.
As can be seen from the above-described embodiment, the present invention adopts one-step synthesis method to support the ordered mesoporous aluminium oxide material of noble metal, the decentralization of noble metal nano particles in mesoporous material of this material is high, the rate that supports is high, noble metal nano particles size is little, and mesopore orbit structure height is orderly, its catalyst as Oxidation of Carbon Monoxide reaction has high catalytic activity and heat endurance.
Claims (9)
1. support a synthetic method for the ordered mesoporous aluminium oxide material of noble metal, it comprises the following steps:
(1) after acid, alcohol, nonionic surface active agent being mixed, add hydrophobicity precious metal salt and aluminium salt, after mixing, obtain a mixed solution;
(2) described mixed solution is made to keep a period of time at 30-60 DEG C;
(3) then roasting at 300-600 DEG C, obtains the described ordered mesoporous aluminium oxide material supporting noble metal.
2. synthetic method according to claim 1, wherein, described aluminium salt comprises the combination of one or more in aluminum chloride sulphate, aluminum nitrate, aluminium isopropoxide and aluminum sulfate; Preferably, described aluminium salt comprises aluminum nitrate and/or aluminium isopropoxide;
Described hydrophobicity precious metal salt comprises the combination of one or more in acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate, acetylacetone,2,4-pentanedione silver, golden, the acetylacetone,2,4-pentanedione ruthenium of acetylacetone,2,4-pentanedione and acetylacetone,2,4-pentanedione rhodium; Preferably, described hydrophobicity precious metal salt comprises the combination of one or more in acetylacetone,2,4-pentanedione platinum, palladium acetylacetonate and acetylacetone,2,4-pentanedione silver;
Described alcohol comprises the combination of one or more in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol and sec-butyl alcohol; Preferably, described alcohol comprises ethanol and/or normal propyl alcohol;
Described acid comprises the combination of one or more in sulfuric acid, nitric acid, hydrochloric acid, acetic acid and citric acid; Preferably, described acid comprises nitric acid and/or citric acid;
Described nonionic surface active agent comprises triblock copolymer; Preferably, the triblock copolymer adopted comprises the combination of one or more in P123, F127, F68 and Brij-56; More preferably, described triblock copolymer comprises P123 and/or F127.
3. synthetic method according to claim 1, wherein, the pH value of the described mixed solution in step (1) is 1-5; Step (1) is carried out at 10-30 DEG C.
4. synthetic method according to claim 1, wherein, the time kept at 30-60 DEG C in step (2) is 12-72 hour; Preferably, step (2) keeps 36-48 hour at 40-50 DEG C.
5. synthetic method according to claim 1, wherein, in step (3), the time of roasting at 300-600 DEG C is 3-10 hour; Preferably, the sintering temperature in step (3) is 400-500 DEG C, and roasting time is 4-8 hour; More preferably, roasting time is 4-6 hour.
6. support an ordered mesoporous aluminium oxide material for noble metal, it is preparation-obtained by the synthetic method supporting the ordered mesoporous aluminium oxide material of noble metal described in any one of claim 1-5.
7. the ordered mesoporous aluminium oxide material supporting noble metal according to claim 6, wherein, with the described gross mass supporting the ordered mesoporous aluminium oxide material of noble metal for benchmark, the loading of described noble metal is 0.1-5%, is preferably 0.5%-3.5%.
8. the ordered mesoporous aluminium oxide material supporting noble metal according to claim 6, its specific area is 100-300m
2/ g, pore volume is 0.1-0.8cm
3/ g, mesoporous pore size is 1-10nm, and the particle diameter of noble metal nano particles is 1-10nm; Preferably, described specific area is 100-200m
2/ g, pore volume is 0.1-0.5cm
3/ g, mesoporous pore size is 3-7nm, and the particle diameter of noble metal nano particles is 2-7nm.
9. the application of the ordered mesoporous aluminium oxide material supporting noble metal described in an any one of claim 6-8 in the catalyst preparing Oxidation of Carbon Monoxide reaction.
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| CN114871426A (en) * | 2022-05-20 | 2022-08-09 | 爱科美材料科技(南通)有限公司 | Mesoporous alumina in-situ coated nano-silver material, preparation method and application |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080090118A1 (en) * | 2006-08-23 | 2008-04-17 | Leonid Gorobinskiy | Catalyst for oxidizing carbon monoxide for reformer used in fuel cell, method for preparing the same, and fuel cell system comprising the same |
| CN101579635A (en) * | 2009-06-18 | 2009-11-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Room temperature catalytic oxidation carbon monoxide catalyst and preparation method thereof |
| CN102424411A (en) * | 2011-09-15 | 2012-04-25 | 暨南大学 | Preparation method for ordered mesoporous gamma-Al2O3 |
| CN104588020A (en) * | 2014-12-17 | 2015-05-06 | 中国人民解放军防化学院 | Preparation method of ordered mesoporous alumina supported metal catalyst |
-
2015
- 2015-05-07 CN CN201510229476.7A patent/CN104923215B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080090118A1 (en) * | 2006-08-23 | 2008-04-17 | Leonid Gorobinskiy | Catalyst for oxidizing carbon monoxide for reformer used in fuel cell, method for preparing the same, and fuel cell system comprising the same |
| CN101579635A (en) * | 2009-06-18 | 2009-11-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Room temperature catalytic oxidation carbon monoxide catalyst and preparation method thereof |
| CN102424411A (en) * | 2011-09-15 | 2012-04-25 | 暨南大学 | Preparation method for ordered mesoporous gamma-Al2O3 |
| CN104588020A (en) * | 2014-12-17 | 2015-05-06 | 中国人民解放军防化学院 | Preparation method of ordered mesoporous alumina supported metal catalyst |
Non-Patent Citations (1)
| Title |
|---|
| ZHEN-XING LI ET AL.: ""A facil route to ordered mesoporous-alumina-supported catalysts,and their catalytic activities for CO oxidation"", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
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