CN104785251A - Synthesis method and application of nanoreactor with multi-silver core/hollow mesoporous silica yolk shell structure - Google Patents
Synthesis method and application of nanoreactor with multi-silver core/hollow mesoporous silica yolk shell structure Download PDFInfo
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- CN104785251A CN104785251A CN201510178118.8A CN201510178118A CN104785251A CN 104785251 A CN104785251 A CN 104785251A CN 201510178118 A CN201510178118 A CN 201510178118A CN 104785251 A CN104785251 A CN 104785251A
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Abstract
The invention discloses a synthesis method and application of a nanoreactor with a multi-silver core/hollow mesoporous silica yolk shell structure. The synthesis method comprises the following steps: firstly, synthesizing hollow mesoporous silica through etching by utilizing the structural difference of solid silica and mesoporous silica; then, synthesizing silver nanoparticles in inner cavities of hollow mesoporous silica spheres in an alcohol-containing solution; further, crushing the silver nanoparticles inside the hollow mesoporous silica through a laser irradiation technology. The nanoreactor is applied to the catalytic reaction, the mesoporous shell has the quick mass transfer effect, and the multi-precious metal inner cover provides an abundant catalytic activity center, so that the catalytic efficiency is improved, and the stability of a catalyst is improved.
Description
Technical field
The present invention relates to a kind of synthetic technology of nano-reactor, particularly relate to synthetic method and the application thereof of a kind of many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor.
Background technology
The catalytic performance of noble metal nano particles excellence is proven in multinomial catalyst system and catalyzing reactions such as () oxidation, reduction, addition and polymerizations, and starts to show up prominently in existing Industrial Catalysis.But because the surface energy that noble metal nano particles is high, make noble metal nano particles polymerization (or fusion) in course of reaction and active reduction causes reaction efficiency to reduce; In order to address this problem, thinking that noble metal nano particles and inorganic matter are combined with each other is carried out, its by the catalyst normal form extensively approved as palladium/carbon.Along with selling well of core/shell structure, large quantities of nanocatalyst is synthesized out; In view of the Contact of feature catalyst granules of this structure and then the problem of fusion have been overcome, but because the coated raising making insufficient exposure of catalytic site but also limit catalytic efficiency of densification of outer shell.On this basis, noble metal nano particles being coated on synthesis thinking that mesoporous material inside forms a kind of nano-reactor of " small bell " structure (also known as yolk shell structure) is carried out; This design that catalyst and body are not only separated but also are connected by mesoporous shell be have received good effect in catalytic reaction, simultaneously also by further modifying catalysis reaction of high order afterwards to shell mesoporous material.In recent years, prepare the nano-reactor of this structure multiple by hard template method (after first core shell process), but all can only obtain the yolk shell structure of monokaryon, there is no the report of nucleosynthesis multinuclear yolk shell structural nano reactor after the first shell of a step at present.
Summary of the invention
The object of this invention is to provide and a kind of there is many galactic nucleus, outer mesoporous shell, embedded silica network, the synthetic method of the much higher galactic nucleus of catalytic performance/hollow mesoporous silicon oxide yolk shell structural nano reactor and application thereof.
The object of the invention is to be achieved through the following technical solutions:
The synthetic method of many galactic nucleus of the present invention/hollow mesoporous silicon oxide yolk shell structural nano reactor, comprises step:
A, first prepare monodispersed hollow mesoporous silica spheres;
Introduce silver nano-grain in B, the hollow mesoporous silica spheres that then obtains in steps A and form many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor;
C, silver nano-grain further by the many galactic nucleus obtained in laser irradiation technology breaking up step B/hollow mesoporous silicon oxide yolk shell structural nano inside reactor.
The application of above-mentioned many galactic nucleus of the present invention/hollow mesoporous silicon oxide yolk shell structural nano reactor, this nano-reactor is used for the conversion of catalysis and organic pollution.
As seen from the above technical solution provided by the invention, the synthetic method of many galactic nucleus that the embodiment of the present invention provides/hollow mesoporous silicon oxide yolk shell structural nano reactor and application thereof, monodispersed hollow mesoporous silicon oxide is obtained owing to first utilizing architectural difference etching method, then to inverse composition silver nano-grain in its inner chamber, the silver nano-grain size further in the effect lower inner cavity of laser irradiation reduces, quantity increases; The space obstacle that outer field mesoporous silicon oxide is conducive to the turnover of reactant and product, the residual network of internal oxidation silicon is formed is conducive to stable silver nano-grain, inner space provides a homogeneous reaction environment.The present invention has successfully synthesized the yolk shell structural nano reactor of many galactic nucleus, and by laser, set material irradiation is further reduced to the size of silver nano-grain, improves its catalytic performance.
Accompanying drawing explanation
Fig. 1 a is after using improvement in the embodiment of the present invention
the field emission scanning electron microscope photo of the solid silica dioxide granule of method synthesis, its smooth surface, size uniformity (~ 180nm);
Fig. 1 b and Fig. 1 c is at ethyl orthosilicate (TEOS) and C in the embodiment of the present invention
18the Flied emission surface sweeping electromicroscopic photograph of TMS cohydrolysis after the silica that the coated one deck of the silica particles shown in Fig. 1 a is mesoporous and projection photo (perforating agent C
18tMS removes), the particle diameter after coated is increased to ~ 230nm, coated thickness ~ 25nm;
Fig. 1 d and Fig. 1 e is surface sweeping Electronic Speculum after using sodium carbonate to etch the silica/mesoporous silica particles after coated in a heated condition in the embodiment of the present invention and projection electromicroscopic photograph;
Fig. 2 a and Fig. 2 b is the BET phenogram of the hollow mesoporous silicon oxide obtained in the embodiment of the present invention: Fig. 2 a is N
2-adsorption/desorption curve, Fig. 2 b is the mesoporous pore size distribution of BJH method simulation;
Fig. 3 a and Fig. 3 b is the Size Distribution introducing the many galactic nucleus after silver nano-grain/hollow projection electromicroscopic photograph of mesoporous silicon oxide yolk shell structural nano reactor and the silver nano-grain of its correspondence in the embodiment of the present invention in hollow mesoporous silica spheres; Fig. 3 c and Fig. 3 d is the Size Distribution to silver nano-grain in the transmission electron microscope photo after the many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor laser irradiation introduced after galactic nucleus and its inner chamber in the embodiment of the present invention; Fig. 3 e is that the component mapping of nano-reactor schemes;
Fig. 4 is the UV-vis absorption spectra of many galactic nucleus before and after laser irradiation/hollow mesoporous silicon oxide yolk shell structural nano reactor; Absorb peak width before laser irradiation, absworption peak center is at 422nm place; After laser irradiation, absworption peak narrows, and absworption peak center moves on to 406nm place;
Fig. 5 a to Fig. 5 c uses ultraviolet-visible light (Uv-vis) the absorption spectra relation over time of many galactic nucleus of preparation/hollow mesoporous silicon oxide yolk shell structural nano reactor catalytic reduction 4-nitrophenol under sodium borohydride makees reducing agent in the embodiment of the present invention: Fig. 5 a is that the UV-vis absorption spectra of the catalytic reaction of directly obtained many galactic nucleus/hollow mesoporous silicon oxide yolk shell structure is schemed over time, Fig. 5 b is that the UV-vis absorption spectra of the catalytic reaction of many galactic nucleus/hollow mesoporous silicon oxide yolk shell structure after laser irradiation is schemed over time, Fig. 5 c is that the UV-vis absorption spectra of the Argent grain catalytic reaction under condition of equivalent suitable with predose Argent grain size of synthesis is schemed over time, Fig. 5 d is the catalytic rate in Fig. 5 a, Fig. 5 b and Fig. 5 c: I corresponding diagram 5a, II corresponding diagram 5b, III corresponding diagram 5c.
Detailed description of the invention
To be described in further detail the embodiment of the present invention below.
The synthetic method of many galactic nucleus of the present invention/hollow mesoporous silicon oxide yolk shell structural nano reactor, its preferably detailed description of the invention comprise step:
A, first prepare monodispersed hollow mesoporous silica spheres;
Introduce silver nano-grain in B, the hollow mesoporous silica spheres that then obtains in steps A and form many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor;
C, silver nano-grain further by the many galactic nucleus obtained in laser irradiation technology breaking up step B/hollow mesoporous silicon oxide yolk shell structural nano inside reactor.
Described steps A comprises:
First the ammoniacal liquor of 71.4mL absolute ethyl alcohol, 10mL deionized water, 3.14mL and 6mL TEOS are mixed, at 30 DEG C, reaction obtains the solid silica dioxide granule of particle diameter ~ 180nm for 4 hours;
Add 70mL absolute ethyl alcohol and the dilution of 5mL deionized water again, add covering liquid by syringe pump to reaction system: 1.6mL C18TMS+4mL TEOS+8mL absolute ethyl alcohol, obtains the nucleocapsid structure of solid silica/mesoporous silicon oxide;
Solid silica/the mesoporous silica particles of the nucleocapsid structure obtained is dispersed in the sodium carbonate liquor of 0.4M, under the condition of 50 DEG C of water-baths, etches 5 ~ 10h, obtain bell type and hollow mesoporous silica particles;
Centrifugal under 12000rpm, wash repeatedly post-drying.
Described step B comprises:
Weigh the hollow mesoporous silicon oxide 20mg synthesized in steps A, add 30mL methyl alcohol and fully disperse, after stirring half an hour, add the liquor argenti nitratis ophthalmicus of 500uL 1M;
Afterwards wherein with the methanol solution (5mL of syringe pump instillation NaI, 0.1M), then in reaction system, instill the methanol solution (5mL, 0.01M) of hydroquinones, reaction 10h obtains many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor later;
Dry in 50 DEG C of vacuum drying ovens after centrifuge washing.
Described step C comprises:
Take the nano-reactor that obtains in 2.5mg step B and be dispersed in the countless ethanol of 10mL, under moderate-speed mixer, being placed on irradiation 10min under the laser of unfocused wavelength 532nm, pulse energy 80mJ;
By irradiated sample centrifugal and washing repeatedly, dry in 50 DEG C of vacuum drying ovens.
Use absolute ethyl alcohol as solvent, and regulate the content of the inner silver of nano-reactor.
The application of above-mentioned many galactic nucleus of the present invention/hollow mesoporous silicon oxide yolk shell structural nano reactor, its preferably detailed description of the invention be:
This nano-reactor is used for the conversion of catalysis and organic pollution.Its catalytic performance is evaluated specifically for catalytic model reaction (reduction 4-nitrophenol).
Described nano-reactor is separated from reaction system and reuses after washing.
The present invention has effectively prepared the yolk shell structural nano reactor of many galactic nucleus/hollow mesoporous silicon oxide by the synthesis thinking of core after first shell, the specific area that silver nano-grain is large, hangs key make it have high catalytic activity without surface ligand and a large amount of surfaces; Outer field hollow mesoporous silicon oxide forms a homogeneous internal-response environment silver nano-grain that also protection is inner, reaction substrate and product can diffuse into out nano-reactor by the mesoporous of its surface, and the physical barrier that the network of silica of its internal residual is formed can prevent from merging mutually between nano particle growing up and inactivation; Nano-reactor reduces the size of its inner silver nano-grain further by laser irradiation; This nano-reactor (before and after laser irradiation) can catalytic reduction 4-nitrophenol be the reaction of PAP under sodium borohydride does the prerequisite of reducing agent, and after laser irradiation, its catalytic performance is further improved.The simple effective method of this synthesis of nano reactor provided by the invention can provide a kind of approach for the synthesis of novel nano catalyst, greatly will improve the result of use of nanocatalyst and expand its scope of application.
Specific embodiment:
First monodispersed hollow mesoporous silica spheres is prepared, then in hollow mesoporous silica spheres, introduce silver nano-grain form many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor, the technology further by laser irradiation smashes the silver nano-grain of nano-reactor inside.The concrete operation step of this preparation method is as follows:
One, hollow mesoporous silica spheres is prepared
1.
solid silica (the s-SiO of method synthesis
2) nano particle: measure absolute ethyl alcohol 71.4mL, deionized water 10mL and 3.14mL ammoniacal liquor join in 100mL volumetric flask, ethyl orthosilicate (TEOS) 6mL is added stir 0.5h under 30 DEG C of water bath condition after, terminate after reaction 4h, obtain the solid silica of average grain diameter ~ 180nm (Fig. 1 a);
2. the coated solid silica of mesoporous silicon oxide: add 70mL absolute ethyl alcohol and the dilution of 5mL deionized water in the solid silica system of milky of synthesis, by covering liquid (the 1.6mL C be pre-mixed
18tMS+4mL TEOS+10mL absolute ethyl alcohol) instill reaction system with syringe pump with the speed of 10mL/h, after complete reaction 4h to be injected by product centrifugal and with deionized water and absolute ethanol washing repeatedly, then dry in 50 DEG C of baking ovens and obtain solid silica/mesoporous silicon oxide (s-SiO
2@m-SiO
2) nucleocapsid structure (Fig. 1 b and Fig. 1 c);
3. etch the solid silica/mesoporous silicon oxide (s-SiO of synthesis in " 2 "
2@m-SiO
2) nucleocapsid structure: by the solid silica/mesoporous silicon oxide sample dispersion of 1/4 in the sodium carbonate liquor of 100mL 0.4M, in 50 DEG C of water-baths, etch 10h, centrifugal and with deionized water and absolute ethanol washing repeatedly post-drying obtain the hollow mesoporous silicon oxide (Fig. 1 d and Fig. 1 e) of wall thickness ~ 25nm, diameter ~ 230nm.
Two, after first shell, core method synthesizes many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor
The hollow mesoporous silicon oxide (20mg) of synthesis is dispersed in the methyl alcohol of 30mL, adds the AgNO of 500uL 1M
3rapid stirring 30min after solution; Then the NaI of 0.0824g is dissolved in the methyl alcohol of 5mL, with syringe pump with the speed of 5mL/h instillation reaction, in reaction, after being added dropwise to complete, instills the methanol solution of 5mL 0.0550g hydroquinones again with the speed of 2.5mL/h.5min is left standstill after reaction 10h, general for upper strata green solution poured out centrifugal after the Argent grain not entering hollow mesoporous silicon oxide inside is deposited in reaction container bottom and wash repeatedly by absolute ethyl alcohol and deionized water, after drying in the vacuum drying oven of 50 DEG C, obtaining many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor.Fig. 3 a, 3b are depicted as many galactic nucleus/hollow architectural feature of mesoporous silicon oxide yolk shell structural nano reactor and the Size Distribution (average-size 20.03nm) of inner silver nano-grain.
Three, the silver nano-grain of nano-reactor inside is smashed in laser irradiation
2.5mg nano-reactor is dispersed in 10mL absolute ethyl alcohol, with the laser of the unfocused wavelength 532nm of Nd:YAG laser instrument with frequency 20Hz pulse duration 7ns, irradiation 10min under bundle spot energy 80mJ restraints the condition of spot 10mm; By centrifugal for irradiation afterproduct and with absolute ethanol washing repeatedly, in the vacuum drying oven of 50 DEG C dry after obtain inner nanoparticle size reduce nano-reactor.Fig. 3 c, 3d are depicted as the Size Distribution (average-size 7.34nm) of inner silver nano-grain after the architectural feature of the nano-reactor after laser irradiation and irradiation.
As shown in Figure 3 e, the nano-reactor of prepared yolk shell structure confirms to be made up of silver, silicon, oxygen element by element mapping, confirms further to have synthesized silver nano-grain in meso-porous hollow silica inner chamber.
Be the nitrogen adsorption-desorption curve of hollow mesoporous silicon oxide as shown in Figure 2 a, its feature meets the IV type thermoisopleth that H3 type returns stagnant ring.Illustration in Fig. 2 b to be drawn the pore size distribution curve that BJH (Barrett-Joyner-Halenda) method simulates by desorption, and wherein the peak of 9.3 to about 12.2nm shows that major bore size is 9.3 to 12.2nm.The pore volume of BET specific surface area and sample is respectively 61.34m
2g
-1, 0.182cm
3g
-1.Large aperture contributes to reactant and product improves catalytic performance by diffusion turnover reactor inner chamber.
Nano-reactor sample light-metering after predose is absorbed, before laser irradiation, the UV peak of sample is more widened, the center of its absworption peak is at 422nm place, and the refraction of the size of the absworption peak of this broadening and the red shift of absworption peak and inside reactor silver nano-grain, distribution and outer hollow mesoporous silicon oxide is consistent; After laser irradiation, the UV peak of sample narrows, and the position at central absorbent peak is at 406nm place, and the narrowing of this absworption peak, absworption peak meet (see Fig. 4) to the movement of short wavelength and the reduction of the inner silver nano-grain size of nano-reactor.
4-nitrophenol is reduced under using the sample before and after laser irradiation to do the condition of reducing agent at sodium borohydride as catalyst, Fig. 5 a, Fig. 5 b are depicted as the light absorption-time absorption spectra of the front/rear nano-reactor catalysis of irradiation, and Fig. 5 c is the light absorption-time absorption spectra of the silver nano-grain catalysis suitable with inner silver nano-grain (predose) size of nano-reactor used as a comparison; Obtain its reaction rate constant to the catalytic result in Fig. 5 a, 5b and 5c by the linear fit of pseudo-first-order model to be respectively: k
iI (after nano-reactor-irradiation)=1.082min
-1>k
i (nano-reactor-predose)=0.3832min
-1>k
iII (silver nano-grain)=0.1036min
- 1, show the catalytic performance of the excellence after nano-reactor and laser irradiation.
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (8)
1. a synthetic method for galactic nucleus more than/hollow mesoporous silicon oxide yolk shell structural nano reactor, is characterized in that, comprise step:
A, first prepare monodispersed hollow mesoporous silica spheres;
Introduce silver nano-grain in B, the hollow mesoporous silica spheres that then obtains in steps A and form many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor;
C, silver nano-grain further by the many galactic nucleus obtained in laser irradiation technology breaking up step B/hollow mesoporous silicon oxide yolk shell structural nano inside reactor.
2. the synthetic method of many galactic nucleus according to claim 1/hollow mesoporous silicon oxide yolk shell structural nano reactor, it is characterized in that, described steps A comprises:
First the ammoniacal liquor of 71.4mL absolute ethyl alcohol, 10mL deionized water, 3.14mL and 6mL TEOS are mixed, at 30 DEG C, reaction obtains the solid silica dioxide granule of particle diameter ~ 180nm for 4 hours;
Add 70mL absolute ethyl alcohol and the dilution of 5mL deionized water again, add covering liquid by syringe pump to reaction system: 1.6mL C18TMS+4mL TEOS+8mL absolute ethyl alcohol, obtains the nucleocapsid structure of solid silica/mesoporous silicon oxide;
Solid silica/the mesoporous silica particles of the nucleocapsid structure obtained is dispersed in the sodium carbonate liquor of 0.4M, under the condition of 50 DEG C of water-baths, etches 5 ~ 10h, obtain bell type and hollow mesoporous silica particles;
Centrifugal under 12000rpm, wash repeatedly post-drying.
3. the synthetic method of many galactic nucleus according to claim 2/hollow mesoporous silicon oxide yolk shell structural nano reactor, it is characterized in that, described step B comprises:
Weigh the hollow mesoporous silicon oxide 20mg synthesized in steps A, add 30mL methyl alcohol and fully disperse, after stirring half an hour, add the liquor argenti nitratis ophthalmicus of 500uL 1M;
Instill the methanol solution of the NaI of 5mL, 0.1M afterwards wherein with syringe pump, in reaction system, then drip the methanol solution of the hydroquinones of 5mL, 0.01M, reaction 10h obtains many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor later;
Dry in 50 DEG C of vacuum drying ovens after centrifuge washing.
4. the synthetic method of many galactic nucleus according to claim 3/hollow mesoporous silicon oxide yolk shell structural nano reactor, it is characterized in that, described step C comprises:
Take the nano-reactor that obtains in 2.5mg step B and be dispersed in the countless ethanol of 10mL, under moderate-speed mixer, being placed on irradiation 10min under the laser of unfocused wavelength 532nm, pulse energy 80mJ;
By irradiated sample centrifugal and washing repeatedly, drying in 50 DEG C of vacuum drying ovens.
5. the synthetic method of many galactic nucleus according to claim 3/hollow mesoporous silicon oxide yolk shell structural nano reactor, is characterized in that, uses absolute ethyl alcohol as solvent, and regulates the content of the inner silver of nano-reactor.
6. an application for the many galactic nucleus described in any one of claim 1 to 5/hollow mesoporous silicon oxide yolk shell structural nano reactor, is characterized in that, this nano-reactor is used for the conversion of catalysis and organic pollution.
7. the application of many galactic nucleus according to claim 6/hollow mesoporous silicon oxide yolk shell structural nano reactor, is characterized in that, this nano-reactor, for reducing the reaction of 4-nitrophenol catalytic model, evaluates its catalytic performance.
8. the application of many galactic nucleus according to claim 7/hollow mesoporous silicon oxide yolk shell structural nano reactor, is characterized in that, is separated by described nano-reactor and reuses after washing from reaction system.
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Citations (4)
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| CN102198929A (en) * | 2010-03-22 | 2011-09-28 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof |
| CN102786061A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| WO2013117192A1 (en) * | 2012-02-08 | 2013-08-15 | Studiengesellschaft Kohle Mbh | Use of mesoporous graphite particles for electrochemical applications |
| CN103611928A (en) * | 2013-12-05 | 2014-03-05 | 东北大学 | Ag and Ag-composite nanometer particles and laser control synthetic method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198929A (en) * | 2010-03-22 | 2011-09-28 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof |
| WO2013117192A1 (en) * | 2012-02-08 | 2013-08-15 | Studiengesellschaft Kohle Mbh | Use of mesoporous graphite particles for electrochemical applications |
| CN102786061A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| CN103611928A (en) * | 2013-12-05 | 2014-03-05 | 东北大学 | Ag and Ag-composite nanometer particles and laser control synthetic method thereof |
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