CN104492430A - Novel method for synthesizing nano-hollow silicon sphere supported noble metal catalyst by micro-emulsion method - Google Patents
Novel method for synthesizing nano-hollow silicon sphere supported noble metal catalyst by micro-emulsion method Download PDFInfo
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Abstract
The invention provides a method for synthesizing a nano-hollow silicon sphere supported noble metal catalyst by a micro-emulsion method. The method comprises the following steps: slowly adding a surfactant A into a solvent B to form a solution C; adding a co-surfactant D into the solution C to form a solution E; uniformly mixing a silicate compound F and a saline reagent G to form a precursor solution, and dropwise adding the precursor solution into the solution E to form a solution H; dropwise adding deionized water into the solution H to form a solution I; dropwise adding ammonia water into the solution I to form a solution J so as to form an organic SiO2(o) sphere; adding a silicate compound K into the solution J to form a solution M so as to form a SiO2(o)@SiO2(i) structure; adding a precipitant N into the solution M, standing to obtain precipitate, washing for 1-2 times with O, and dispersing into the deionized water to form a solution P; etching the SiO2(o) layer by a hydrofluoric acid aqueous solution to obtain an SiO2 hollow sphere, centrifugally washing, and drying; reducing the SiO2 hollow sphere into an Si hollow sphere by magnesium powder; supporting noble metal particles Q to the Si hollow sphere to obtain the nano-hollow silicon sphere supported noble metal effective photo-catalyst, and centrifugally drying.
Description
Technical field
The invention belongs to technology field, particularly relate to a kind of method of novel microemulsion liquid method synthesis of nano hollow silicon ball supported precious metal catalyst.
Background technology
The development of the energy to human society is most important.When fossil energy is by approach exhaustion, extremely urgent to the research of novel renewable energy.Hydrogen Energy, it is as secondary energy sources, have clean, efficient, safe, can store, the plurality of advantages such as can to transport, generally be it is believed that it is a kind of free of contamination green energy resource of optimal new century, therefore received the great attention of various countries.Since Tokyo Univ Japan in 1972 two professor reported first TiO
2the possibility of Single Crystalline Electrodes photocatalytic hydrogen production by water decomposition, opens the research road utilizing solar photolysis water hydrogen.The key of photolysis water hydrogen is the selection of catalyst, and now increasing people have aimed at eye at nanocatalyst, nano material be often referred at least in a dimension size 2 to the material in 100nm interval.At this yardstick, the specific area of material is very large, can be with and become discrete energy levels, often depend on its shape and have electricity mutually distinct with body, chemistry, optics, magnetics and mechanical property.
Because titanium dioxide has the features such as the nontoxic and low cost of stable chemical nature, anti-light burn into, be subject to common concern in the field such as opto-electronic conversion and photocatalysis therefore at present.But, TiO
2be wide band gap semiconducter, can only absorb limited ultraviolet light, and photo-generate electron-hole is to easy compound, photo-quantum efficiency is low, limits its application in photoelectrocatalysis field.Therefore, exploitation has the nano-photocatalyst of visible ray effect and expands the vital task that its application is current photocatalysis research.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of nano-photocatalyst with visible ray effect.
In order to solve the problem, the invention discloses a kind of method of novel microemulsion liquid method synthesis of nano hollow silicon ball supported precious metal catalyst, comprising:
1-10ml surfactant A is slowly added in 20-50ml solvent B, forms solution C, stirred at ambient temperature 1-10min;
1-10ml cosurfactant D is added in described solution C, forms solution E, stirred at ambient temperature 1-10min;
0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G is mixed formation precursor solution, is slowly added drop-wise in described solution E, form Solution H, stirred at ambient temperature 1-5min;
0.3-3ml deionized water is added drop-wise in described Solution H with the speed of 0.5-1ml/min, forms solution I, stirring at room temperature 1-10min;
Be added drop-wise in described solution I by 0.03-0.3ml ammoniacal liquor with the speed of 0.5-1ml/min, form solution J, stirred at ambient temperature 3-5h, forms organic SiO
2(o) ball;
Be added in described solution J by 0.01-1.5ml silicon salt compound K, form solution M, stirred at ambient temperature 20-30h, forms inorganic SiO
2coated organic SiO
2the SiO of ball
2(o)@SiO
2(i) structure;
Be added in described solution M by 10-100ml precipitating reagent N, standing 10-30min is precipitated, and cleans 1-2 time, be distributed in deionized water and form solution P with solvent O;
The SiO in described solution P is etched with the hydrofluoric acid aqueous solution that 0.5-5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10-30min, obtains SiO
2hollow ball, eccentric cleaning, dry 8-12h at 70-90 DEG C;
By SiO described in 10-100mg
2hollow ball and the mixing of 5-80mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, react 1-10h under the condition of 500-1000 DEG C, described SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
By Si hollow ball load 10-50mg noble metal Q described in 10-100mg, obtain nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.
Preferably, described surfactant A is that polyethylene glycol is to isooctyl phenyl ether, 1,1,3,3-polyglycol ether, NPE, OPEO, high-carbon fatty alcohol polyoxyethylene ether or polyoxyethylene carboxylate.
Preferably described solvent B is n-hexane, cyclohexane, pentane, normal butane or normal octane.
Preferably described cosurfactant D is ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-octanol, sec-n-octyl alcohol or n nonylphenol.
Preferably described silicon salt compound F is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate.
Preferably described silane reagent G is trim,ethylchlorosilane, HMDS, 1,2-bis-(trimethyl oxygen base is silica-based) hexane, hexa methyl oxy disilicane, tert-butyl chloro-silicane, tri isopropyl chlorosilane, dimethyldiacetoxy silane, di-t-butyl dichlorosilane, trimethyl hydroxyethylammonium silane or methyldiphenyl base ethoxy silane.
Preferably described silicon salt compound K is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate.
Preferably described precipitating reagent N is acetone, diacetyl, acetylacetone,2,4-pentanedione or propiophenone.
Preferably described solvent O is methyl alcohol, ethanol or propyl alcohol.
Preferably described noble metal Q is gold, silver, platinum or palladium.
Compared with prior art, the present invention includes following advantage:
The invention provides a kind of method of novel microemulsion liquid method synthesis of nano hollow silicon ball supported precious metal catalyst, comprise and 1-10ml surfactant A is slowly added in solvent B, form solution C, stirred at ambient temperature 1-10min; And then 1-10ml cosurfactant D adds in above-mentioned solution C, and form solution E, stirring at room temperature 1-10min, now defines a microemulsion system; Next 0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G is mixed formation precursor solution, be slowly added drop-wise in above-mentioned solution E, form Solution H, stirring at room temperature 1-5min; 0.3-3ml deionized water is added drop-wise in Solution H with the speed of 0.5-1ml/min, forms solution I, stirring at room temperature 1-10min; Be added drop-wise in solution I by 0.03-0.3ml ammoniacal liquor with the speed of 0.5-1ml/min, form solution J, stirring at room temperature 3-5h, forms organic SiO
2(o) ball; Be added in solution J by 0.01-1.5ml silicon salt compound K, form solution M, stirring at room temperature 20-30h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure; Be added in solution M by 10-100ml precipitating reagent N, standing 10-30min is precipitated, and cleans 1-2 time, be distributed in deionized water and form solution P with solvent O; The SiO in described solution P is etched with the hydrofluoric acid aqueous solution that 0.5-5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10-30min, obtains SiO
2hollow ball, eccentric cleaning, dry 8-12h at 70-90 DEG C; By 10-100mgSiO
2hollow ball and the mixing of 5-80mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, react 1-10h under the condition of 500-1000 DEG C, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder; By 10-100mgSi hollow ball load 10-50mg noble metal Q, obtain nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.By the embodiment of the present invention, the hydrolysis of Different Silicon salt compound is adopted to obtain the SiO of different structure first
2nuclear shell ball, then utilizes hf etching to fall nexine SiO
2thus obtain SiO
2hollow ball, then reduce SiO with Mg
2obtain nano Si hollow ball, finally carried noble metal particle on nano Si hollow ball, obtain nano-hollow silicon ball carried noble metal effective catalyst.
Hollow-core construction prepared by the method for a kind of microemulsion method synthesis of nano hollow silicon ball supported precious metal catalyst that the present invention proposes can increase specific area, and then fully contacts with water thus greatly improve reaction rate; Small size noble-metal-supported to nano-hollow silicon ball will can realize the synergic catalytic effect of noble metal and silicon, the nano-hollow silicon ball of high-specific surface area also serves the effect of well dispersion noble metal, stop small sized metallic particle agglomeration, the final catalytic performance improving catalyst.Remain the series of properties such as strong optical scattering and plasma resonance of nano-metal particle simultaneously, have broad application prospects.Further, the method technique simple, convenient operation, environmental friendliness, low input high production.
Accompanying drawing explanation
Fig. 1 is the flow chart of a kind of novel microemulsion liquid method synthesis of nano hollow silicon ball carried noble metal efficient catalytic agent method of the embodiment of the present invention;
Fig. 2 is the method schematic diagram of a kind of novel microemulsion liquid method synthesis of nano hollow silicon ball carried noble metal effective catalyst of the embodiment of the present invention;
Fig. 3 is the XRD figure of the silicon hollow ball (SiHS) that the embodiment of the present invention 4 is synthesized;
Fig. 4 a and 4b is the TEM figure of silver-colored load hollow silicon ball (Ag-SiHS) effective catalyst that the embodiment of the present invention 4 is synthesized;
Fig. 5 is the EDX spectrogram of silver-colored load hollow silicon ball (Ag-SiHS) effective catalyst that the embodiment of the present invention 4 is synthesized;
Fig. 6 is the silicon hollow ball (SiHS) of the embodiment of the present invention 4 synthesis and the photodissociation aquatic products hydrogen figure of silver-colored load hollow silicon ball (Ag-SiHS) effective catalyst.
Detailed description of the invention
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, and below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Give the flow chart of the method for a kind of novel microemulsion liquid method synthesis of nano hollow silicon ball carried noble metal effective catalyst of the embodiment of the present invention see Fig. 1, comprising:
Step 101,1-10ml surfactant A is slowly added in above-mentioned solution B, forms solution C, stirred at ambient temperature 1-10min; 1-10ml cosurfactant D is added in described solution C, forms solution E, stirring at room temperature 1-10min; 0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G is mixed formation precursor solution, is slowly added drop-wise in described solution E, form Solution H, stirred at ambient temperature 1-5min; 0.3-3ml deionized water is added drop-wise in described Solution H with the speed of 0.5-1ml/min, forms solution I stirring at room temperature 1-10min; Be added drop-wise in described solution I by 0.03-0.3ml ammoniacal liquor with the speed of 0.5-1ml/min, form solution J, stirred at ambient temperature 3-5h, forms organic SiO
2(o) ball.
The silicon materials that the embodiment of the present invention adopts have earth rich reserves, the feature such as with low cost, and silicon is a kind of low bandgap material simultaneously, therefore has visible light-responded characteristic, greatly can improve light utilization efficiency; Can carry out noble metal compound to silicon, acceleration electronics is separated with hole, namely reduces the compound of electron-hole pair, realizes the synergic catalytic effect of noble metal and silicon, therefore have broad application prospects simultaneously.
In the embodiment of the present invention, adopt described surfactant A be polyethylene glycol to isooctyl phenyl ether, 1,1,3,3-polyglycol ether, NPE, OPEO, high-carbon fatty alcohol polyoxyethylene ether or polyoxyethylene carboxylate, concrete scope is 1-10ml; Described solvent B is n-hexane, cyclohexane, pentane, normal butane or normal octane, and concrete scope is 10-50ml; Described cosurfactant D is ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-octanol, sec-n-octyl alcohol or n nonylphenol, and concrete scope is 1-10ml; Described silicon salt compound F is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate, and concrete scope is 0.05-0.5ml; Described silane reagent G is trim,ethylchlorosilane, HMDS, 1,2-bis-(trimethyl oxygen base is silica-based) hexane, hexa methyl oxy disilicane, tert-butyl chloro-silicane, tri isopropyl chlorosilane, dimethyldiacetoxy silane, di-t-butyl dichlorosilane, trimethyl hydroxyethylammonium silane, methyldiphenyl base ethoxy silane or octadecyl trimethyl TMOS, concrete scope is 5-50ul.
Step 102, be added in described solution J by 0.01-1.5ml silicon salt compound K, form solution M, stirred at ambient temperature 20-30h, forms inorganic SiO
2coated organic SiO
2the SiO of ball
2(o)@SiO
2(i) structure;
Described silicon salt compound K is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate, tetraethyl orthosilicate, and concrete scope is 0.01-1.5ml.
Step 103, be added in described solution M by 10-100ml precipitating reagent N, standing 10-30min is precipitated, and cleans 1-2 time, be distributed in deionized water and form solution P with solvent O; The SiO in described solution P is etched with the hydrofluoric acid aqueous solution that 0.5-5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10-30min, obtains SiO
2hollow ball, eccentric cleaning, dry 8-12h at 70-90 DEG C.
Described precipitating reagent N is acetone, diacetyl, acetylacetone,2,4-pentanedione, propiophenone, and concrete scope is 10-100ml; Described O is methyl alcohol, ethanol, propyl alcohol.
Step 104, by SiO described in 10-100mg
2hollow ball and the mixing of 5-80mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, react under the condition of 500-1000 DEG C, 1-10h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
Step 105, by hollow ball load 10-50mg noble metal Q described in 10-100mgSi, obtain nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.
Described noble metal Q is Au Ag Pt Pd.
Fig. 2 is the method schematic diagram of a kind of novel microemulsion liquid method synthesis of nano hollow silicon ball supported precious metal catalyst of the embodiment of the present invention, and building-up process comprises: SiO
2(o) particles → SiO
2(o)@SiO
2(i) particles → SiO
2hS particles → SiHS particles → M-SiHS particles.
Core idea of the present invention is, utilizes Different Silicon salt compound to be hydrolyzed the SiO obtaining different structure
2nuclear shell ball, then utilizes hf etching to fall nexine SiO
2thus obtain SiO
2hollow ball, then reduce SiO with Mg
2obtain nano Si hollow ball; finally carried noble metal particle on nano Si hollow ball; obtain nano-hollow silicon ball carried noble metal effective catalyst; the advantages such as the nanocatalyst of this space confinement had both had that light absorption range is wide, specific area large, concerted catalysis, protection small sized metallic particle are not easily reunited; remain the series of properties such as strong optical scattering and plasma resonance of nano-metal particle simultaneously, have broad application prospects.Further, the method technique simple, convenient operation, environmental friendliness, low input high production.
In order to make those skilled in the art understand the present invention better, be described below by way of the method for specific embodiment to novel microemulsion liquid method synthesis of nano hollow silicon ball carried noble metal effective catalyst of the present invention.
Embodiment 1
(1) 1ml OPEO is slowly added in 20ml n-hexane, stirred at ambient temperature 1min; 1ml n-butanol is added in above-mentioned solution, stirring at room temperature 1min, now define a microemulsion system; 0.3ml butyl silicate and 30ul octadecyl trimethyl TMOS are mixed formation precursor solution, is slowly added drop-wise in above-mentioned solution, stirring at room temperature 3min; 3ml deionized water is added drop-wise in above-mentioned solution with the speed of 0.5ml/min, stirring at room temperature 10min; 0.03ml ammoniacal liquor is added drop-wise in above-mentioned solution with the speed of 0.5ml/min, stirring at room temperature 5h, forms organic SiO
2(o) ball.
(2) 0.8ml butyl silicate is added in above-mentioned solution, stirring at room temperature 25h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure.
(3) be added in above-mentioned solution by 50ml diacetyl, standing 20min is precipitated, and with ethanol purge 1 time, is distributed in deionized water; With the hydrofluoric acid aqueous solution etching SiO that 3ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 25min, obtains SiO
2hollow ball, eccentric cleaning, dry 10h at 80 DEG C.
(4) by 100mgSiO
2hollow ball and the mixing of 80mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 1000 DEG C, 1h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
(5) by 100mgSi hollow ball load 50mgAu particle, nano-hollow silicon ball gold-supported particle efficient photochemical catalyst is obtained, centrifugal drying.
Embodiment 2
(1) 10ml high-carbon fatty alcohol polyoxyethylene ether is slowly added in 50ml n-hexane, stirred at ambient temperature 10min; 10ml n-octyl alcohol is added in above-mentioned solution, stirring at room temperature 10min, now define a microemulsion system; 0.3ml silester and 30ul hexa methyl oxy disilicane are mixed formation precursor solution, is slowly added drop-wise in above-mentioned solution, stirring at room temperature 3min; 1.5ml deionized water is added drop-wise in above-mentioned solution with the speed of 0.75ml/min, stirring at room temperature 5min; 0.15ml ammoniacal liquor is added drop-wise in above-mentioned solution with the speed of 0.75ml/min, stirring at room temperature 4h, forms organic SiO
2(o) ball;
(2) 0.8ml silester is added in above-mentioned solution, stirring at room temperature 25h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure;
(3) be added in above-mentioned solution by 50ml acetone, standing 20min is precipitated, and by washed with methanol 1 time, is distributed in deionized water; With the hydrofluoric acid aqueous solution etching SiO that 2.5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 20min, obtains SiO
2hollow ball, eccentric cleaning, dry 9h at 80 DEG C.
(4) by 10mgSiO
2hollow ball and the mixing of 5mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 500 DEG C, 5h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
(5) by 10mgSi hollow ball load 10mgAu particle, nano-hollow silicon ball gold-supported particle efficient photochemical catalyst is obtained, centrifugal drying.
Embodiment 3
(1) 5ml polyethylene glycol is slowly added in 50ml n-hexane to isooctyl phenyl ether, stirred at ambient temperature 5min; 5ml isooctanol is added in above-mentioned solution, stirring at room temperature 5min, now define a microemulsion system; 0.05ml silicic acid propyl ester and 5ul methyldiphenyl base ethoxy silane mixture are evenly formed precursor solution, is slowly added drop-wise in above-mentioned solution, stirring at room temperature 1min; 0.3ml deionized water is added drop-wise in above-mentioned solution with the speed of 0.5ml/min, stirring at room temperature 1min; 0.3ml ammoniacal liquor is added drop-wise in above-mentioned solution with the speed of 1ml/min, stirring at room temperature 5h, forms organic SiO
2(o) ball;
(2) 0.01ml silicic acid propyl ester is added in above-mentioned solution, stirring at room temperature 20h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure;
(3) be added in above-mentioned solution by 10ml propiophenone, standing 10min is precipitated, and with ethanol purge 2 times, is distributed in deionized water; With the hydrofluoric acid aqueous solution etching SiO that 0.5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10min, obtains SiO
2hollow ball, eccentric cleaning, dry 12h at 70 DEG C.
(4) by 10mgSiO
2hollow ball and the mixing of 5mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 500 DEG C, 10h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
(5) by 10mgSi hollow ball load 10mgPt particle, nano-hollow silicon ball loaded with platinum particles high efficiency photocatalyst is obtained, centrifugal drying.
Embodiment 4
(1) 3ml NPE is slowly added in 50ml n-hexane, stirred at ambient temperature 2min; 3ml n-hexyl alcohol is added in above-mentioned solution, stirring at room temperature 5min, now define a microemulsion system; Positive for 0.25ml quanmethyl silicate and 25ul dimethyldiacetoxy silane mixture are evenly formed precursor solution, is slowly added drop-wise in above-mentioned solution, stirring at room temperature 2min; 0.9ml deionized water is added drop-wise in above-mentioned solution with the speed of 1ml/min, stirring at room temperature 5min; 0.1ml ammoniacal liquor is added drop-wise in above-mentioned solution with the speed of 1ml/min, stirring at room temperature 3h, forms organic SiO
2(o) ball;
(2) positive for 0.3ml quanmethyl silicate is added in above-mentioned solution, stirring at room temperature 20h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure;
(3) be added in above-mentioned solution by 50ml diacetyl, standing 10min is precipitated, and by washed with methanol 1 time, is distributed in deionized water; With the hydrofluoric acid aqueous solution etching SiO that 3ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10min, obtains SiO
2hollow ball, eccentric cleaning, dry 10h at 90 DEG C.
(4) by 30mgSiO
2hollow ball and the mixing of 25mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 950 DEG C, 4h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
(5) by 10mgSi hollow ball load 5mgAg particle, nano-hollow silicon ball load silver particles high efficiency photocatalyst is obtained, centrifugal drying.
Fig. 3 is the XRD figure of the silicon hollow ball (SiHS) that the embodiment of the present invention 4 is synthesized, 2 θ=28.4470 in XRD collection of illustrative plates, 47.3110 and 56.1320 diffraction maximum corresponding consistent with the PDF#65-1060 standard card of simple substance Si, sharply and the assorted peak of diffraction maximum occurs, illustrates that product crystallinity is good.
Fig. 4 a and 4b is the TEM figure of silver-colored load hollow silicon ball (Ag-SiHS) effective catalyst that the embodiment of the present invention 4 is synthesized, as can be seen from the figure most of hollow silicon ball remains the integrality of structure, product cut size is comparatively homogeneous, Average Particle Diameters is about 200nm, and the uniform load of silver nano-grain is on the surface of hollow silicon ball simultaneously.
Fig. 5 is the EDX spectrogram of silver-colored load hollow silicon ball (Ag-SiHS) effective catalyst that the embodiment of the present invention 4 is synthesized, existence two obvious peaks can be seen from books, corresponding Si and Ag element respectively, this is indicated as simple silver-colored load hollow silicon ball, there are not other elements.
Fig. 6 is the silicon hollow ball (SiHS) of the embodiment of the present invention 4 synthesis and the photodissociation aquatic products hydrogen figure of silver-colored load hollow silicon ball (Ag-SiHS) effective catalyst, as can be seen from scheming us, the average hydrogen-producing speed of SiHS is 0.392mmol/g/h, and the average hydrogen-producing speed of Ag-SiHS is 1.378mmol/g/h, through silver-colored load hollow silicon ball, improve its hydrogen-producing speed greatly.
Embodiment 5
(1) by 5ml polyethylene glycol in the slow 50ml n-hexane of isooctyl phenyl ether, stirred at ambient temperature 5min; 5ml isoamyl alcohol is added in above-mentioned solution, stirring at room temperature 5min, now define a microemulsion system; 0.5ml tetraethyl orthosilicate and 50ul methyldiphenyl base ethoxy silane mixture are evenly formed precursor solution, is slowly added drop-wise in above-mentioned solution, stirring at room temperature 5min; 3ml deionized water is added drop-wise in above-mentioned solution with the speed of 1ml/min, stirring at room temperature 10min; 2ml ammoniacal liquor is added drop-wise in above-mentioned solution with the speed of 0.8ml/min, stirring at room temperature 4h, forms organic SiO
2(o) ball;
(2) 1.5ml tetraethyl orthosilicate is added in above-mentioned solution, stirring at room temperature 30h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure;
(3) be added in above-mentioned solution by 100ml acetone, standing 30min is precipitated, and with ethanol purge 1 time, is distributed in deionized water; With the hydrofluoric acid aqueous solution etching SiO that 5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 30min, obtains SiO
2hollow ball, eccentric cleaning, dry 12h at 90 DEG C.
(4) by 50mgSiO
2hollow ball and the mixing of 40mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 750 DEG C, 6h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
(5) by 50mgSi hollow ball load 25mgPd particle, nano-hollow silicon ball supported palladium particle efficient photochemical catalyst is obtained, centrifugal drying.
Embodiment 6
(1) 2ml polyoxyethylene carboxylate is slowly added in 50ml n-hexane, stirred at ambient temperature 1min; 2ml n-octyl alcohol is added in above-mentioned solution, stirring at room temperature 3min, now define a microemulsion system; 0.15ml methyl silicate and 15ul octadecyl trimethyl TMOS are mixed formation precursor solution, is slowly added drop-wise in above-mentioned solution, stirring at room temperature 2min; 0.8ml deionized water is added drop-wise in above-mentioned solution with the speed of 1ml/min, stirring at room temperature 5min; 0.2ml ammoniacal liquor is added drop-wise in above-mentioned solution with the speed of 2ml/min, stirring at room temperature 2h, forms organic SiO
2(o) ball;
(2) 0.2ml methyl silicate is added in above-mentioned solution, stirring at room temperature 20h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure;
(3) be added in above-mentioned solution by 50ml acetone, standing 10min is precipitated, and with ethanol purge 1 time, is distributed in deionized water; With the hydrofluoric acid aqueous solution etching SiO that 2.5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10min, obtains SiO
2hollow ball, eccentric cleaning, dry 12h at 50 DEG C.
(4) by 30mgSiO
2hollow ball and the mixing of 25mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 500 DEG C, 10h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
(5) by 10mgSi hollow ball load 10mgPd particle, nano-hollow silicon ball supported palladium particle efficient photochemical catalyst is obtained, centrifugal drying.
The invention provides a kind of method of novel microemulsion liquid method synthesis of nano hollow silicon ball carried noble metal effective catalyst, 1-10ml surfactant A is slowly added in 20-50ml solution B, form solution C, stirred at ambient temperature 1-10min; And then 1-10ml cosurfactant D adds in above-mentioned solution C, and form solution E, stirring at room temperature 1-10min, now defines a microemulsion system; Next 0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G is mixed formation precursor solution, be slowly added drop-wise in above-mentioned solution E, form Solution H, stirring at room temperature 1-5min; 0.3-3ml deionized water is added drop-wise in Solution H with the speed of 0.5-1ml/min, forms solution I stirring at room temperature 1-10min; Be added drop-wise in solution I by 0.03-0.3ml ammoniacal liquor with the speed of 0.5-1ml/min, form solution J, stirring at room temperature 3-5h, forms organic SiO
2(o) ball; Be added in solution J by 0.01-1.5ml silicon salt compound K, form solution M, stirring at room temperature 20-30h, forms inorganic SiO
2coated organic SiO
2the structure of ball and SiO
2(o)@SiO
2(i) structure; Be added in solution M by 10-100ml precipitating reagent N, standing 10-30min is precipitated, and cleans 1-2 time, be distributed in deionized water and form solution P with solvent O; The SiO in described solution P is etched with the hydrofluoric acid aqueous solution that 0.5-5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10-30min, obtains SiO
2hollow ball, eccentric cleaning, dry 8-12h at 70-90 DEG C.By 10-100mgSiO
2hollow ball and the mixing of 5-80mg magnesium powder, grinding, puts into containing 5%H
2ar atmosphere under tube furnace in, 500-1000 DEG C, 1-10h, SiO
2hollow ball is reduced into Si hollow ball by magnesium powder; By 10-100mgSi hollow ball load 10-50mg noble metal Q, obtain nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.By the embodiment of the present invention, the hydrolysis of Different Silicon salt compound is adopted to obtain the SiO of different structure first
2nuclear shell ball, then utilizes hf etching to fall nexine SiO
2thus obtain SiO
2hollow ball, then reduce SiO with Mg
2obtain nano Si hollow ball; finally carried noble metal particle on nano Si hollow ball; obtain nano-hollow silicon ball carried noble metal effective catalyst; the nanocatalyst of this space confinement had both had the advantages such as specific area is large, protection small sized metallic particle is not easily reunited; remain the series of properties such as strong optical scattering and plasma resonance of nano-metal particle simultaneously, have broad application prospects.Further, the method technique simple, convenient operation, environmental friendliness, low input high production.
For embodiment of the method, in order to simple description, therefore it is all expressed as a series of combination of actions, but those skilled in the art should know, the present invention is not by the restriction of described sequence of movement, because according to the present invention, some step can adopt other order or carry out simultaneously.Secondly, those skilled in the art also should know, the embodiment described in description all belongs to preferred embodiment, and involved action and parts might not be that the present invention is necessary.
Above the method for a kind of novel microemulsion liquid method synthesis of nano hollow silicon ball supported precious metal catalyst provided by the present invention is described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (10)
1. a method for novel microemulsion liquid method synthesis of nano hollow silicon ball supported precious metal catalyst, is characterized in that, comprising:
1-10ml surfactant A is slowly added in 20-50ml solvent B, forms solution C, stirred at ambient temperature 1-10min;
1-10ml cosurfactant D is added in described solution C, forms solution E, stirred at ambient temperature 1-10min;
0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G is mixed formation precursor solution, is slowly added drop-wise in described solution E, form Solution H, stirred at ambient temperature 1-5min;
0.3-3ml deionized water is added drop-wise in described Solution H with the speed of 0.5-1ml/min, forms solution I, stirring at room temperature 1-10min;
Be added drop-wise in described solution I by 0.03-0.3ml ammoniacal liquor with the speed of 0.5-1ml/min, form solution J, stirred at ambient temperature 3-5h, forms organic SiO
2(o) ball;
Be added in described solution J by 0.01-1.5ml silicon salt compound K, form solution M, stirred at ambient temperature 20-30h, forms inorganic SiO
2coated organic SiO
2the SiO of ball
2(o)@SiO
2(i) structure;
Be added in described solution M by 10-100ml precipitating reagent N, standing 10-30min is precipitated, and cleans 1-2 time, be distributed in deionized water and form solution P with solvent O;
The SiO in described solution P is etched with the hydrofluoric acid aqueous solution that 0.5-5ml mass concentration is 10%
2(o)@SiO
2siO in (i) structure
2o () layer, reaction 10-30min, obtains SiO
2hollow ball, eccentric cleaning, dry 8-12h at 70-90 DEG C;
By SiO described in 10-100mg
2hollow ball and the mixing of 5-80mg magnesium powder, grinding, puts into the tube furnace under the Ar atmosphere containing 5%H2, reacts 1-10h under the condition of 500-1000 DEG C, described SiO
2hollow ball is reduced into Si hollow ball by magnesium powder;
By Si hollow ball load 10-50mg noble metal Q described in 10-100mg, obtain nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.
2. the method for claim 1, it is characterized in that, described surfactant A be polyethylene glycol to isooctyl phenyl ether, 1,1,3,3-polyglycol ether, NPE, OPEO, high-carbon fatty alcohol polyoxyethylene ether or polyoxyethylene carboxylate.
3. the method for claim 1, is characterized in that, described solvent B is n-hexane, cyclohexane, pentane, normal butane or normal octane.
4. the method for claim 1, is characterized in that, described cosurfactant D is ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-octanol, sec-n-octyl alcohol or n nonylphenol.
5. the method for claim 1, is characterized in that, described silicon salt compound F is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate.
6. the method for claim 1, it is characterized in that, described silane reagent G is trim,ethylchlorosilane, HMDS, 1,2-bis-(trimethyl oxygen base is silica-based) hexane, hexa methyl oxy disilicane, tert-butyl chloro-silicane, tri isopropyl chlorosilane, dimethyldiacetoxy silane, di-t-butyl dichlorosilane, trimethyl hydroxyethylammonium silane or methyldiphenyl base ethoxy silane.
7. the method for claim 1, is characterized in that, described silicon salt compound K is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate.
8. the method for claim 1, is characterized in that, described precipitating reagent N is acetone, diacetyl, acetylacetone,2,4-pentanedione or propiophenone.
9. the method for claim 1, is characterized in that, described solvent O is methyl alcohol, ethanol or propyl alcohol.
10. the method for claim 1, is characterized in that, described noble metal Q is gold, silver, platinum or palladium.
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| CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| WO2011156895A2 (en) * | 2010-06-14 | 2011-12-22 | National Research Council Of Canada | Magnetic nanoparticles and uses thereof |
| CN102874823A (en) * | 2012-10-24 | 2013-01-16 | 南开大学 | Method for preparing silicon dioxide hollow microspheres with uniform shape by taking pollen grains as biological template |
| CN103803556A (en) * | 2012-11-05 | 2014-05-21 | 中国科学院大连化学物理研究所 | Organic modified hydrophobic nano silica hollow ball and preparation method thereof |
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| CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| WO2011156895A2 (en) * | 2010-06-14 | 2011-12-22 | National Research Council Of Canada | Magnetic nanoparticles and uses thereof |
| CN102874823A (en) * | 2012-10-24 | 2013-01-16 | 南开大学 | Method for preparing silicon dioxide hollow microspheres with uniform shape by taking pollen grains as biological template |
| CN103803556A (en) * | 2012-11-05 | 2014-05-21 | 中国科学院大连化学物理研究所 | Organic modified hydrophobic nano silica hollow ball and preparation method thereof |
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| CN112062919A (en) * | 2020-09-11 | 2020-12-11 | 华东理工大学 | Preparation method and application method of phenolic resin with hollow shell structure |
| CN112062919B (en) * | 2020-09-11 | 2022-08-30 | 华东理工大学 | Preparation method and application method of phenolic resin with hollow shell structure |
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