CN104707597B - Metal nanowire network/mesoporous silica core-shell structure catalyst preparation method - Google Patents
Metal nanowire network/mesoporous silica core-shell structure catalyst preparation method Download PDFInfo
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Abstract
The present invention relates to a preparation method, structure characteristics and applications of a metal nanowire network/mesoporous silica core-shell structure catalyst. The preparation method comprises: dissolving a surfactant in a hydrophobic solvent, adding a metal salt aqueous solution and a reducing agent, finally adding an orthosilicate compound, transferring to a stainless steel reaction kettle to crystallize, and carrying out washing, drying and calcining to obtain the metal nanowire network/mesoporous silica core-shell structure catalyst. With the preparation method of the present invention, the metal nanowire network catalyst having different metal composition and different mesoporous silica thicknesses can be obtained, the method has characteristics of simple operation, rapid reaction, easy surfactant removing, good stability, and easy synthesis amplifying, and the prepared nanometer catalyst can be used for the fields of petrochemical industry, pollution control, fuel cells and the like.
Description
Technical field
The invention belongs to petrochemical industry, pollution control and fuel cell field, and in particular to a kind of wire screen/mesoporous two
The preparation method of silicon oxide catalyst with core-casing structure, architectural feature and application.
Background technology
Metallic catalyst is in traditional petrochemical industry（Catalytic reforming）, the field such as pollution control and fuel cell have very wide
General application.But easily there is the aggregation of granule and inactivate in this kind of catalyst, therefore this kind of catalysis under the conditions of real reaction
Agent stability is generally poor.For this problem, domestic and international scientific research personnel has carried out many fruitful works in this field
Make.
Summer etc. utilizes electrostatic spinning technique, and styroflex is prepared first, and supports Pt nanoparticle on its surface,
Again in its superficial growth CeO2, finally polystyrene is removed, obtain a series of Pt nanoparticles and supported in CeO2Nanofiber
Internal metallic platinum catalyst.And show more excellent stability in subsequent CO oxidation reactions（K.Yoon;
Y.Yang;Y.N.Xia.et al.Angew.Chem.Int.Ed.2012,51,10089-10092）.
Stair et al. prepares Pd/Al first with infusion process2O3Catalyst, recycles ald（ALD）Technology
Certain thickness porous Al is deposited on the surface of Pd granules2O3.Just because of porous Al2O3Protection, this catalyst is in ethane
Oxidative dehydrogenation in show extremely strong carbon accumulation resisting ability.Therefore, with common Pd/Al2O3Catalyst is compared and shown
More excellent stability（J.L.Lu,B.S.Fu;P.S.Stair.Et al.Science.2012,335,1205-1208）.
In sum, said method improves to a certain extent the stability of catalyst, but remains preparation
Step is complicated, it is difficult to the problems such as large-scale commercial applications are combined to.It is necessary to develop new synthetic method.For the problems referred to above, this
It is bright to develop a kind of preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst.The method is simple to operate,
It is easy to amplify, the Pt base agent surfactants of preparation are easily removed, with preferable catalytic stability.Can be applicable to oil
The fields such as work, pollution control, fuel cell.
The content of the invention
It is an object of the invention to provide a kind of high stability metal nano gauze/meso-porous silica core-shell structured catalysis
The preparation method of agent, the method is simple to operate, is swift in response, short preparation period, is suitable to large-scale production, and surfactant is easy to
Remove.Outer layer mesoporous silicon oxide thickness is adjustable in prepared multimetal reforming catalyst, gauze narrow size distribution.
The invention provides a kind of preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst, tool
Body step is：Surfactant is dissolved in hydrophobicity solvent, metal precursor aqueous solution is added, is stirred at 15-30 DEG C
30-180 minutes, stand, point liquid goes eliminating water phase, by 2-50 times of surplus solution dilute, in the stirring for being more than 400 revs/min
Under speed, water-soluble reducing agent or its aqueous solution are added, reacted more than 4 minutes；Add alkaline solution that system pH is adjusted to into 8-
12, positive compound of silicate class is added, continue to react more than 0.1 hour at 20-80 DEG C, it is transferred to in politef
In the stainless steel cauldron of lining, crystallization more than 1 hour, obtains series metal and receives after scrubbed, dry, roasting at 30-200 DEG C
Rice noodle net/meso-porous silica core-shell structure catalyst.
The preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, the table
Molar concentration of the face activating agent in hydrophobicity solvent is 0.01-10000mmol/L, and surfactant is cetyl trimethyl
Ammonium bromide, octadecyl trimethyl ammonium chloride, dodecylbenzene sodium sulfonate, sodium cetanesulfonate, potassium stearate, oleoyl are more
Contracting amino acid sodium, sodium dodecyl aminopropionitrile, sodium lauryl sulfate, Pluronic F-127 lauroyl ether, lauric acid Sorbitan
Alcohol ester, oleic acid diethyl amide, dodecyldimethylammonium hydroxide inner salt, dodecyldimethylamine base sulfoethyl glycine betaine, stearic acid, oil
One or more mixture in amine, Oleic acid, alkyl polyoxyethylene ether class compound.
The preparation method of the metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, institute
Hydrophobicity solvent is stated for toluene, dimethylbenzene, normal hexane, hexamethylene, Ketohexamethylene, carbon tetrachloride, chloroform, methylisobutylketone, acetic acid
The mixture of one or two or more kinds in isopropyl ester or their derivant.
The preparation method of the metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, institute
The molar concentration for stating metal precursor aqueous solution is 0.1-5000mmol/L, and metal precursor is platinum compounds, ruthenium compound, rhodium
Compound, palladium compound, silver compound, rhenium compound, osmium compound, iridic compound, gold compound, iron compound, cobalt chemical combination
One or two or more kinds mixture in thing, nickel compound, copper compound.
The preparation method of the metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, institute
Platinum compounds is stated for the mixture of one or two or more kinds in chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite；
The ruthenium compound is the mixture of one or two or more kinds in ruthenium trichloride, ruthenium hydrochloride, ruthenium hydrochloride salt；
The rhodium compound is the mixing of one or two or more kinds in rhodium chloride, rhodium sulfate, the acid of chlorine rhodium, chlorine rhodate
Thing；
The palladium compound is the mixture of one or two or more kinds in palladium chloride, tetrachloro-palladium acid salt, palladium sulfate；
The silver compound is silver nitrate；
The rhenium compound is the mixture of one or two or more kinds in rhenium pentachloride, perrhenic acid, perrhenate；
The osmium compound is the mixture of one or two or more kinds in osmium tetrachloride, chlorine osmic acid, chloro-osmate；
The iridic compound is the mixture of one or two or more kinds in iridic chloride, chloro-iridic acid, chloroiridate；
The gold compound is the mixture of one or two or more kinds in Auric chloride., gold chloride, chloroaurate；
The iron compound is one in ferric chloride, iron, iron sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate
Kind or more than two kinds of mixture；
The cobalt compound is the mixing of one or two or more kinds in cobalt dichloride, cobaltic chloride, cobalt nitrate, cobaltous sulfate
Thing；
The nickel compound is the mixture of one or two or more kinds in Nickel dichloride., nickel sulfate, nickel nitrate；
The copper compound be it is a kind of in copper chloride, Cu-lyt., copper sulfate, cuprous sulfate, copper nitrate, cuprous nitrate or
More than two kinds of mixture.
The preparation method of the metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, institute
The molar concentration for stating water-soluble reducing agent is 0.5-5000mmol/L, and water-soluble reducing agent is formaldehyde, formic acid, lithium borohydride, boron
It is sodium hydride, potassium borohydride, methanol, ethanol, polyhydric alcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, anti-bad
The mixture of one or two or more kinds in hematic acid or their derivant.
The preparation method of the metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, institute
Alkaline solution is stated for ammonia, ethylenediamine, n-butylamine, sodium hydroxide, potassium hydroxide, Lithium hydrate, tetraethyl ammonium hydroxide, 4 third
One or more mixture in base ammonium hydroxide.
The preparation method of the metal nano gauze/meso-porous silica core-shell structure catalyst that the present invention is provided, institute
Positive compound of silicate class is stated for methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or their derivant
In the mixture of one or two or more kinds.
Present invention also offers metal nano gauze/meso-porous silica core-shell structured catalysis that methods described is prepared
Agent, the architectural feature of the catalyst is：Pattern is in nanowire mesh structure, a diameter of 1-30nm of wire screen itself, diameter chi
Very little to be distributed as 5-20%, in 5-500nm, the meso-porous titanium dioxide silicon thickness of outer layer is 0.1-15nm to length.
The present invention prepare metal nano gauze/meso-porous silica core-shell structure catalyst can be used for petrochemical industry,
The fields such as pollution control, fuel cell.
Compared with the metallic catalyst preparation method reported, the present invention has advantages below：
a）Using the template function of soft template, and different reaction conditions, can be with the mesoporous dioxy of effective control outer layer
The thickness of SiClx.
b）Due to the protection of meso-porous titanium dioxide silicon layer, nanowire mesh is not susceptible to aggregation, improves catalytic reaction process
Stability.On the premise of rail network structure pattern is not affected, the surfactant for being used can be removed by the method for roasting.
c）Low temperature synthesis, it is simple to operate, be swift in response and easily amplify, be suitable to commercially produce.
Description of the drawings
The sample synthetic route schematic diagram of Fig. 1 embodiments 1；
Fig. 2 embodiments 1 prepare the transmission electron microscope of sample（TEM）Photo；
Fig. 3 comparative examples 1 prepare the transmission electron microscope of sample（TEM）Photo；
Fig. 4 embodiments 5 prepare the transmission electron microscope of sample（TEM）Photo；
Fig. 5 embodiments 13 prepare the transmission electron microscope of sample（TEM）Photo；
Fig. 6 embodiments 14 prepare the course Electronic Speculum of sample（TEM）.
Specific embodiment
Embodiment 1：
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to poly- four
In the stainless steel cauldron of fluorothene liner, crystallization 72 hours at 100 DEG C obtain metal nano after scrubbed, dry, roasting
Gauze/meso-porous silica core-shell structure catalyst.
The synthesis schematic diagram of the method is as shown in Figure 1.
Such as Fig. 2, with not plus compared with tetraethyl orthosilicate sample, the diameter of rail network structure has increased to 3nm by original 2nm,
Show in the superficial growth 0.5nm of gauze thick silicon dioxide layer.
Comparative example 1：According to the method for embodiment 1, tetraethyl orthosilicate and ammonia are added without during the course of the reaction.
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under the conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reacts 5 minutes, scrubbed,
It is dried, obtains metal nano rail network structure catalyst.
Such as Fig. 3, when not adding tetraethyl orthosilicate, common Pt nanowires net diameter is in 2nm or so.
Embodiment 2：Kinds of surfactants
The sodium cetanesulfonate of 115.35mg is dissolved in 10mL chloroforms, adds the 20mmol/L's of 10mL
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, add 90mL go from
Sub- water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reacts 5 minutes, finally adds
Enter ammonia and pH value is adjusted to into 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to polytetrafluoro
In the stainless steel cauldron of ethylene liner, crystallization 72 hours at 100 DEG C obtain metal nanometer line after scrubbed, dry, roasting
Net/meso-porous silica core-shell structure catalyst.
Embodiment 3：Hydrophobicity solvent species
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL toluene, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to poly- four
In the stainless steel cauldron of fluorothene liner, crystallization 72 hours at 100 DEG C obtain metal nano after scrubbed, dry, roasting
Gauze/meso-porous silica core-shell structure catalyst.
Embodiment 4：Metal front bulk concentration
The cetyl trimethylammonium bromide of 1.46g is dissolved in 10mL chloroforms, adds the 200mmol/L's of 10mL
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, add 90mL go from
Sub- water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reacts 5 minutes, finally adds
Enter ammonia and pH value is adjusted to into 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to polytetrafluoro
In the stainless steel cauldron of ethylene liner, crystallization 72 hours is scrubbed, dry at 100 DEG C, obtain metal nanometer line after roasting
Net/meso-porous silica core-shell structure catalyst.
Embodiment 5：Metal precursor species（Palladium）
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PdCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to poly- four
In the stainless steel cauldron of fluorothene liner, crystallization 72 hours at 100 DEG C obtain metal nano after scrubbed, dry, roasting
Gauze/meso-porous silica core-shell structure catalyst.
Such as Fig. 4, the palladium gauze diameter of itself is in 17nm or so, and the silicon dioxide layer thickness of outer layer covers is that 13nm is left
It is right.
Embodiment 6：Metal precursor species（Platinum, palladium）
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/ of 7.5mL is added
The K of L2PtCl4Aqueous solution, the K of the 20mmol/L of 2.5mL2PdCl4Aqueous solution, stirring reaction 2 hours, quiet under the conditions of 25 DEG C
Put, point liquid removes upper strata aqueous phase, adds the deionized water of 90mL, under conditions of 1600 revs/min, add 10mL's
The NaBH of 300mmol/L4Aqueous solution, reacts 5 minutes, is eventually adding ammonia and pH value is adjusted to into the positive silicic acid second of 10, and 144 μ L
Ester, reacts 1 hour under the conditions of 35 DEG C, is transferred to in teflon-lined stainless steel cauldron, brilliant at 100 DEG C
Change 72 hours, metal nano gauze/meso-porous silica core-shell structure catalyst is obtained after scrubbed, dry, roasting.
Embodiment 7：Metal precursor species（Platinum, palladium, iridium）
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 6mL is added
K2PtCl4Aqueous solution, the K of the 20mmol/L of 2mL2PdCl4Aqueous solution, the Na of the 20mmol/L of 2mL2IrCl4Aqueous solution, 25
Stirring reaction 2 hours under the conditions of DEG C, stand, and point liquid removes upper strata aqueous phase, the deionized water of 90mL is added, at 1600 revs/min
Under conditions of clock, the NaBH of the 300mmol/L of 10mL is added4Aqueous solution, reacts 5 minutes, is eventually adding ammonia and adjusts pH value
To 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, it is transferred to teflon-lined rustless steel
In reactor, crystallization 72 hours at 100 DEG C obtain metal nano gauze/mesoporous silicon oxide after scrubbed, dry, roasting
Catalyst with core-casing structure.
Embodiment 8：Metal precursor species（Platinum, palladium, ruthenium）
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 6mL is added
K2PtCl4Aqueous solution, the K of the 20mmol/L of 2mL2PdCl4Aqueous solution, the K of the 10mmol/L of 2mL2RuCl5Aqueous solution, 25
Stirring reaction 2 hours under the conditions of DEG C, stand, and point liquid removes upper strata aqueous phase, the deionized water of 90mL is added, at 1600 revs/min
Under conditions of clock, the NaBH of the 300mmol/L of 10mL is added4Aqueous solution, reacts 5 minutes, is eventually adding ammonia and adjusts pH value
To 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, it is transferred to teflon-lined rustless steel
In reactor, crystallization 72 hours at 100 DEG C obtain metal nano gauze/mesoporous silicon oxide after scrubbed, dry, roasting
Catalyst with core-casing structure.
Embodiment 9：Metal precursor species（Platinum, palladium, gold）
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 6mL is added
K2PtCl4Aqueous solution, the K of the 20mmol/L of 2mL2PdCl4Aqueous solution, the NaAuCl of the 10mmol/L of 2mL4Aqueous solution, 25
Stirring reaction 2 hours under the conditions of DEG C, stand, and point liquid removes upper strata aqueous phase, the deionized water of 90mL is added, at 1600 revs/min
Under conditions of clock, the NaBH of the 300mmol/L of 10mL is added4Aqueous solution, reacts 5 minutes, is eventually adding ammonia and adjusts pH value
To 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, it is transferred to teflon-lined rustless steel
In reactor, crystallization 72 hours at 100 DEG C obtain metal nano gauze/mesoporous silicon oxide after scrubbed, dry, roasting
Catalyst with core-casing structure.
Embodiment 10：Reducing agent species
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the LiBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into 10, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to poly- four
In the stainless steel cauldron of fluorothene liner, crystallization 72 hours at 100 DEG C obtain metal nano after scrubbed, dry, roasting
Gauze/meso-porous silica core-shell structure catalyst.
Embodiment 11：Silicon source species
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into 10, and 144 μ L methyl silicates, react 1 hour under the conditions of 35 DEG C, be transferred to poly- four
In the stainless steel cauldron of fluorothene liner, crystallization 72 hours at 100 DEG C obtain metal nano after scrubbed, dry, roasting
Gauze/meso-porous silica core-shell structure catalyst.
Embodiment 12：Alkaline solution species
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add sodium hydroxide that pH value is adjusted to into 12, and 144 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to and carry
In teflon-lined stainless steel cauldron, crystallization 72 hours at 100 DEG C obtain metal after scrubbed, dry, roasting
Nanowire mesh/meso-porous silica core-shell structure catalyst.
Embodiment 13：Silicon source quantity
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into the positive esters of silicon acis of 10, and 288 μ L, react 1 hour under the conditions of 35 DEG C, be transferred to polytetrafluoro
In the stainless steel cauldron of ethylene liner, crystallization 72 hours at 100 DEG C obtain metal nanometer line after scrubbed, dry, roasting
Net/meso-porous silica core-shell structure catalyst.
Such as Fig. 5, further increase the amount of tetraethyl orthosilicate, the silicon dioxide layer thickness on gauze surface also increases therewith, line
Net diameter shows the 3nm thick silicon dioxide layer of superficial growth in gauze in 8nm or so.
Embodiment 14：Silicon source quantity
The cetyl trimethylammonium bromide of 145.78mg is dissolved in 10mL chloroforms, the 20mmol/L of 10mL is added
K2PtCl4Aqueous solution, stirring reaction 2 hours under the conditions of 25 DEG C stand, and point liquid removes upper strata aqueous phase, adds going for 90mL
Ionized water, under conditions of 1600 revs/min, adds the NaBH of the 300mmol/L of 10mL4Aqueous solution, reaction 5 minutes, finally
Add ammonia that pH value is adjusted to into 10, and 72 μ L tetraethyl orthosilicates, react 1 hour under the conditions of 35 DEG C, be transferred to poly- four
In the stainless steel cauldron of fluorothene liner, crystallization 72 hours at 100 DEG C obtain metal nano after scrubbed, dry, roasting
Gauze/meso-porous silica core-shell structure catalyst.
Such as Fig. 6, the amount of tetraethyl orthosilicate is reduced to after the half of embodiment 1, has also obtained outer layer and be surrounded by silicon dioxide
Pt nanowires web frame.
Close with embodiment 1, what embodiment 2-4 and embodiment 6-12 were obtained is also the platinum nanometer that outer layer is surrounded by silicon dioxide
Rail network structure.The simply thickness of the size of nanowire mesh and outer layer silicon dioxide difference.
Claims (8)
1. a kind of preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst, it is characterised in that：By surface
Activating agent is dissolved in hydrophobicity solvent, adds metal precursor aqueous solution, is stirred 30-180 minutes at 15-30 DEG C, is stood,
Point liquid goes eliminating water phase, by 2-50 times of surplus solution dilute, under the mixing speed more than 400 revs/min, addition water solublity
Reducing agent or its aqueous solution, react more than 4 minutes；Add alkaline solution that system pH is adjusted to into 8-12, add positive silicate class
Compound, continues to react more than 0.1 hour at 20-80 DEG C, is transferred to teflon-lined stainless steel cauldron
Interior, the crystallization more than 72 hours at 100 DEG C obtains series metal nanowire mesh/meso-porous titanium dioxide after scrubbed, dry, roasting
Silicon catalyst with core-casing structure；The metal precursor is platinum compounds, ruthenium compound, rhodium compound, palladium compound, patina conjunction
In thing, rhenium compound, osmium compound, iridic compound, gold compound, iron compound, cobalt compound, nickel compound, copper compound
The mixture of one or two or more kinds.
2., according to the preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst described in claim 1, it is special
Levy and be：The surfactant is cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, detergent alkylate sulphur
Contracting amino acid sodium, sodium dodecyl aminopropionitrile, lauryl sulfate more than sour sodium, sodium cetanesulfonate, potassium stearate, oleoyl
Sodium, Pluronic F-127 lauroyl ether, lauric acid sorbitan ester, oleic acid diethyl amide, dodecyldimethylammonium hydroxide inner salt,
One kind or two in dodecyldimethylamine base sulfoethyl glycine betaine, stearic acid, oleyl amine, Oleic acid, alkyl polyoxyethylene ether class compound
Plant the mixture of the above；Molar concentration of the surfactant in hydrophobicity solvent is 0.01-10000mmol/L.
3., according to the preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst described in claim 1, it is special
Levy and be：The hydrophobicity solvent is that toluene, dimethylbenzene, normal hexane, hexamethylene, Ketohexamethylene, carbon tetrachloride, chloroform, methyl are different
The mixture of one or two or more kinds in butanone, isopropyl acetate.
4., according to the preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst described in claim 1, it is special
Levy and be：The molar concentration of the metal precursor aqueous solution is 0.1-5000mmol/L；
The platinum compounds is the mixing of one or two or more kinds in chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite
Thing；
The ruthenium compound is the mixture of one or two or more kinds in ruthenium trichloride, ruthenium hydrochloride, ruthenium hydrochloride salt；
The rhodium compound is the mixture of one or two or more kinds in rhodium chloride, rhodium sulfate, the acid of chlorine rhodium, chlorine rhodate；
The palladium compound is the mixture of one or two or more kinds in palladium chloride, tetrachloro-palladium acid salt, palladium sulfate；
The silver compound is silver nitrate；
The rhenium compound is the mixture of one or two or more kinds in rhenium pentachloride, perrhenic acid, perrhenate；
The osmium compound is the mixture of one or two or more kinds in osmium tetrachloride, chlorine osmic acid, chloro-osmate；
The iridic compound is the mixture of one or two or more kinds in iridic chloride, chloro-iridic acid, chloroiridate；
The gold compound is the mixture of one or two or more kinds in Auric chloride., gold chloride, chloroaurate；
The iron compound be it is a kind of in ferric chloride, iron, iron sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate or
More than two kinds of mixture；
The cobalt compound is the mixture of one or two or more kinds in cobalt dichloride, cobaltic chloride, cobalt nitrate, cobaltous sulfate；
The nickel compound is the mixture of one or two or more kinds in Nickel dichloride., nickel sulfate, nickel nitrate；
The copper compound is a kind of in copper chloride, Cu-lyt., copper sulfate, cuprous sulfate, copper nitrate, cuprous nitrate or two kinds
Mixture above.
5., according to the preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst described in claim 1, it is special
Levy and be：The reducing agent is formaldehyde, formic acid, lithium borohydride, sodium borohydride, potassium borohydride, methanol, ethanol, polyhydric alcohol, hydration
One or more mixture in hydrazine, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid；Reducing agent exists
Molar concentration is 0.5-5000mmol/L in reaction system.
6., according to the preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst described in claim 1, it is special
Levy and be：The alkaline solution is ammonia, ethylenediamine, n-butylamine, sodium hydroxide, potassium hydroxide, Lithium hydrate, tetraethyl hydrogen-oxygen
Change ammonium, one or more mixture in TPAOH.
7., according to the preparation method of metal nano gauze/meso-porous silica core-shell structure catalyst described in claim 1, it is special
Levy and be：The positive compound of silicate class is one in methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate
Kind or more than two kinds of mixture.
8. the metal nano gauze/meso-porous silica core-shell structure catalyst for preparing according to claim 1 methods described,
Can be used for petrochemical industry, pollution control and fuel cell field.
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