CN104492430B - The method of novel microemulsion liquid method synthesis nano-hollow silicon ball supported precious metal catalyst - Google Patents
The method of novel microemulsion liquid method synthesis nano-hollow silicon ball supported precious metal catalyst Download PDFInfo
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Abstract
The method that the invention provides a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball supported precious metal catalyst, including surfactant A being added slowly in solvent B, forms solution C；Cosurfactant D is added in solution C and form solution E；Silicon salt compound F and silane reagent G mix homogeneously are formed precursor solution, is added drop-wise in solution E form Solution H；It is added drop-wise to deionized water in Solution H form solution I；It is added drop-wise to ammonia in solution I form solution J, forms organic SiO2(o) ball；Silicon salt compound K is added in solution J forms solution M and forms SiO2(o)@SiO2(i) structure；It is added to precipitant N in solution M stand and is precipitated, clean 12 times with O and be distributed in deionized water form solution P；SiO is etched with hydrofluoric acid aqueous solution2O () layer obtains SiO2Hollow ball, eccentric cleaning, it is dried；By SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；By Si hollow ball carried noble metal particle Q, obtain nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.
Description
Technical field
The invention belongs to Technology field, particularly relate to a kind of novel microemulsion liquid method synthesis nanometer empty
The method of heart silicon ball supported precious metal catalyst.
Background technology
The energy is most important to the development of human society.Situation that will be depleted in fossil energy
Under, the research to novel renewable energy is extremely urgent.Hydrogen Energy, it has as secondary energy sources
Cleaning, efficiently, safety, can store, the plurality of advantages such as can transport, the most generally be it is believed that and be
A kind of free of contamination green energy resource of optimal new century, has therefore suffered from the great attention of various countries.
Since two professor's reported first TiO of Tokyo Univ Japan in 19722Single Crystalline Electrodes photochemical catalyzing
The probability of hydrogen manufacturing, opens the research road utilizing solar photolysis water hydrogen.Photolysis water hydrogen
It is crucial that the selection of catalyst, the most increasing people have aimed at eye at nanocatalyst,
Nano material be often referred at least in a dimension size at 2 to 100nm interval materials.At this
Individual yardstick, the specific surface area of material is very big, can become discrete energy levels by band, tend to rely on its shape
There is electricity mutually distinct with body, chemistry, optics, magnetics and mechanical property.
Owing to titanium dioxide has that stable chemical nature, anti-light burn into be nontoxic and the feature such as low cost,
Therefore common concern is had been subjected in the field such as opto-electronic conversion and photocatalysis at present.But, TiO2It is
Wide band gap semiconducter, can only absorb limited ultraviolet light, and photo-generate electron-hole is to the most compound, light
Quantum efficiency is low, limits its application in photoelectrocatalysis field.Therefore, exploitation has visible ray
The nano-photocatalyst of effect also expands the vital task that its application is current photocatalysis research.
Summary of the invention
The technical problem to be solved is to provide a kind of nanometer light with visible ray effect and urges
Agent.
In order to solve the problems referred to above, the invention discloses a kind of novel microemulsion liquid method synthesis nano-hollow silicon
The method of ball supported precious metal catalyst, including:
1-10ml surfactant A is added slowly in 20-50ml solvent B, forms solution C, room
1-10min is stirred under temperature；
1-10ml cosurfactant D is added in described solution C, form solution E, stir under room temperature
Mix 1-10min；
0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G mix homogeneously are formed presoma molten
Liquid, is slowly dropped in described solution E, forms Solution H, stirs 1-5min under room temperature；
0.3-3ml deionized water is added drop-wise in described Solution H with the speed of 0.5-1ml/min, is formed
Solution I, is stirred at room temperature 1-10min；
0.03-0.3ml ammonia is added drop-wise in described solution I with the speed of 0.5-1ml/min, forms solution
J, stirs 3-5h, forms organic SiO under room temperature2(o) ball；
0.01-1.5ml silicon salt compound K is added in described solution J, forms solution M, stir under room temperature
Mix 20-30h, form inorganic SiO2It is coated with organic SiO2The SiO of ball2(o)@SiO2(i) structure；
10-100ml precipitant N is added in described solution M, stands 10-30min and be precipitated,
Clean 1-2 time with solvent O, be distributed in deionized water form solution P；
Etch in described solution P with the hydrofluoric acid aqueous solution that 0.5-5ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 10-30min, obtains SiO2Hollow ball, from
The heart cleans, and is dried 8-12h at 70-90 DEG C；
By SiO described in 10-100mg2Hollow ball and the mixing of 5-80mg magnesium powder, grind, put into containing 5%H2
Ar atmosphere under tube furnace in, under conditions of 500-1000 DEG C react 1-10h, described SiO2Hollow ball
It 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-poly-second two
Alcohol ether, NPE, OPEO, high-carbon fatty alcohol polyoxyethylene ether or fat
Fat acid polyoxyethylene ester.
The most described solvent B is normal hexane, hexamethylene, pentane, normal butane or normal octane.
The most described cosurfactant D be ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol,
N-amyl alcohol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-capryl alcohol, sec-n-octyl alcohol or n nonylphenol.
The most described silicon salt compound F is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, just
Butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate.
The most described silane reagent G is trim,ethylchlorosilane, hexamethyldisiloxane, 1,2-bis-(three
Methyl epoxide is silica-based) hexane, hexa methyl oxy disilicane, tert-butyl chloro-silicane, triisopropyl chlorine
Silane, dimethyldiacetoxy silane, di-t-butyl dichlorosilane, trimethyl hydroxyethylammonium silane or
Methyldiphenyl base ethoxy silane.
The most described silicon salt compound K is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, just
Butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate.
The most described precipitant N is acetone, diacetyl, acetylacetone,2,4-pentanedione or propiophenone.
The most described solvent O is methanol, ethanol or propanol.
The most described noble metal Q is gold, silver, platinum or palladium.
Compared with prior art, the present invention includes advantages below:
The invention provides a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball supported precious metal catalyst
Method, be added slowly in solvent B including by 1-10ml surfactant A, formed solution C, room
1-10min is stirred under temperature；And then during 1-10ml cosurfactant D adds above-mentioned solution C, shape
Become solution E, 1-10min is stirred at room temperature, now defines a microemulsion system；Next will
0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G mix homogeneously form precursor solution, slow
Slowly it is added drop-wise in above-mentioned solution E, forms Solution H, 1-5min is stirred at room temperature；By 0.3-3ml deionization
Water is added drop-wise in Solution H with the speed of 0.5-1ml/min, forms solution I, 1-10min is stirred at room temperature；
0.03-0.3ml ammonia is added drop-wise in solution I with the speed of 0.5-1ml/min, forms solution J, room temperature
Stirring 3-5h, forms organic SiO2(o) ball；0.01-1.5ml silicon salt compound K is added in solution J,
Form solution M, 20-30h is stirred at room temperature, forms inorganic SiO2It is coated with organic SiO2The structure of ball is i.e.
SiO2(o)@SiO2(i) structure；10-100ml precipitant N is added in solution M, stands 10-30min
It is precipitated, cleans 1-2 time with solvent O, be distributed in deionized water form solution P；Use 0.5-5ml
Mass concentration is the SiO in the hydrofluoric acid aqueous solution described solution P of etching of 10%2(o)@SiO2In (i) structure
SiO2O () layer, reacts 10-30min, obtains SiO2Hollow ball, eccentric cleaning, it is dried at 70-90 DEG C
8-12h；By 10-100mgSiO2Hollow ball and the mixing of 5-80mg magnesium powder, grind, put into containing 5%H2
Ar atmosphere under tube furnace in, under conditions of 500-1000 DEG C react 1-10h, SiO2Hollow ball is by magnesium
Powder is reduced into Si hollow ball；10-100mgSi hollow ball is loaded 10-50mg noble metal Q,
To nano-hollow silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.By the embodiment of the present invention,
Different silicon salt compound hydrolysis is used to obtain the SiO of different structure first2Nuclear shell ball, then utilizes hydrogen
Fluoric acid etches away nexine SiO2Thus obtain SiO2Hollow ball, then reduce SiO with Mg2Obtain nanometer
Si hollow ball, finally carried noble metal particle on nano Si hollow ball, obtain nano-hollow silicon ball
Carried noble metal effective catalyst.
The side of a kind of microemulsion method synthesis nano-hollow silicon ball supported precious metal catalyst that the present invention proposes
Hollow-core construction prepared by method can increase specific surface area, and then and water carry out being fully contacted thus significantly
Improve reaction rate；Small size noble-metal-supported can be realized noble metal on nano-hollow silicon ball
With the synergic catalytic effect of silicon, the nano-hollow silicon ball of high-specific surface area also acts well dispersion
The effect of noble metal, stops small sized metallic particle agglomeration, the final catalytic performance improving catalyst.
Remain the series of properties such as the strong optical scattering of nano-metal particle and plasma resonance, tool simultaneously
Have broad application prospects.Further, the method technique is simple, convenient to operate, environmental friendliness, low
Put into high production.
Accompanying drawing explanation
Fig. 1 is your gold a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball of the embodiment of the present invention loads
Belong to the flow chart of efficient catalytic agent method；
Fig. 2 is your gold a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball of the embodiment of the present invention loads
Belong to the method schematic diagram of effective catalyst；
Fig. 3 is the XRD figure of the silicon hollow ball (SiHS) of the embodiment of the present invention 4 synthesis；
Fig. 4 a and 4b is that silver load hollow silicon ball (Ag-SiHS) of the embodiment of the present invention 4 synthesis is efficient
The TEM figure of catalyst；
Fig. 5 is silver load hollow silicon ball (Ag-SiHS) effective catalyst of the embodiment of the present invention 4 synthesis
EDX spectrogram；
Fig. 6 is silicon hollow ball (SiHS) and the silver load hollow silicon ball of the embodiment of the present invention 4 synthesis
(Ag-SiHS) the photodissociation Aquatic product hydrogen figure of effective catalyst.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with
The present invention is further detailed explanation for the drawings and specific embodiments.
Experimental technique described in following embodiment, if no special instructions, is conventional method；Institute
State reagent and material, if no special instructions, the most commercially obtain.
See Fig. 1 give the embodiment of the present invention a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball bear
The flow chart of the method for supported noble metal effective catalyst, including:
Step 101,1-10ml surfactant A is added slowly in above-mentioned solution B, forms solution
C, stirs 1-10min under room temperature；1-10ml cosurfactant D is added in described solution C, shape
Become solution E, 1-10min is stirred at room temperature；0.05-0.5ml silicon salt compound F and 5-50ul silane are tried
Agent G mix homogeneously forms precursor solution, is slowly dropped in described solution E, forms Solution H,
1-5min is stirred under room temperature；0.3-3ml deionized water is added drop-wise to described molten with the speed of 0.5-1ml/min
In liquid H, form solution I and 1-10min is stirred at room temperature；By 0.03-0.3ml ammonia with 0.5-1ml/min's
Speed is added drop-wise in described solution I, forms solution J, stirs 3-5h, form organic SiO under room temperature2(o)
Ball.
The silicon materials that the embodiment of the present invention uses have earth rich reserves, the feature such as with low cost,
Silicon is a kind of low bandgap material simultaneously, therefore has visible light-responded characteristic, is greatly improved light
Utilization rate；Silicon can carry out noble metal be combined simultaneously, accelerate electronics and the separation in hole, i.e. subtract
Being combined of few electron-hole pair, it is achieved noble metal and the synergic catalytic effect of silicon, therefore has wide
Application prospect.
In the embodiment of the present invention, the described surfactant A of employing is that Polyethylene Glycol is to isooctyl phenyl
Ether, 1,1,3,3-polyglycol ether, NPE, OPEO, high carbocyclic aliphatic
Polyoxyethylenated alcohol or polyoxyethylene carboxylate, concrete scope is 1-10ml；Described solvent B is just
Hexane, hexamethylene, pentane, normal butane or normal octane, specifically in the range of 10-50ml；Described help table
Face activating agent D be ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol,
1-hexanol, 2-hexanol, 1-capryl alcohol, sec-n-octyl alcohol or n nonylphenol, concrete scope is 1-10ml；Described silicon
Salt compound F is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive silicic acid
Four methyl ester or tetraethyl orthosilicate, concrete scope is 0.05-0.5ml；Described silane reagent G is trimethyl
Chlorosilane, hexamethyldisiloxane, 1,2-bis-(trimethyl epoxide is silica-based) hexane, hexamethyl oxygen two silicon
Alkane, tert-butyl chloro-silicane, tri isopropyl chlorosilane, dimethyldiacetoxy silane, two uncles
Butyl dichlorosilane, trimethyl hydroxyethylammonium silane, methyldiphenyl base ethoxy silane or octadecyl three
Methyl TMOS, concrete scope is 5-50ul.
Step 102,0.01-1.5ml silicon salt compound K is added in described solution J, forms solution M,
Stir 20-30h under room temperature, form inorganic SiO2It is coated with organic SiO2The SiO of ball2(o)@SiO2(i) structure；
Described silicon salt compound K is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, positive silicic acid fourth
Ester, positive quanmethyl silicate, tetraethyl orthosilicate, concrete scope is 0.01-1.5ml.
Step 103,10-100ml precipitant N is added in described solution M, stands 10-30min and obtain
To precipitation, clean 1-2 time with solvent O, be distributed in deionized water form solution P；Use 0.5-5ml
Mass concentration is the SiO in the hydrofluoric acid aqueous solution described solution P of etching of 10%2(o)@SiO2In (i) structure
SiO2O () layer, reacts 10-30min, obtains SiO2Hollow ball, eccentric cleaning, it is dried at 70-90 DEG C
8-12h。
Described precipitant N is acetone, diacetyl, acetylacetone,2,4-pentanedione, propiophenone, and concrete scope is 10-100ml；
Described O is methanol, ethanol, propanol.
Step 104, by SiO described in 10-100mg2Hollow ball and the mixing of 5-80mg magnesium powder, grind, put
Enter containing 5%H2Ar atmosphere under tube furnace in, under conditions of 500-1000 DEG C react, 1-10h, SiO2
Hollow ball is reduced into Si hollow ball by magnesium powder；
Step 105, by described in 10-100mgSi hollow ball load 10-50mg noble metal Q, 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 your gold a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball of the embodiment of the present invention loads
The method schematic diagram of metal catalyst, building-up process includes: SiO2(o)particles→SiO2(o)@SiO2(i)
particles→SiO2HS particles→SiHS particles→M-SiHS particles。
The core idea of the present invention is, utilizes different silicon salt compound hydrolysis to obtain different structure
SiO2Nuclear shell ball, then utilizes hf etching to fall nexine SiO2Thus obtain SiO2Hollow ball, then
SiO is reduced with Mg2Obtain nano Si hollow ball, finally carried noble metal on nano Si hollow ball
Particle, obtains nano-hollow silicon ball carried noble metal effective catalyst, the nanometer of this space confinement
Catalyst had both had that light absorption range width, specific surface area be big, concerted catalysis, protection small sized metallic
Grain is difficult to the advantages such as reunion, remains the strong optical scattering of nano-metal particle with plasma altogether simultaneously
The series of properties such as shake, and has broad application prospects.Further, the method technique is simple, be easy to
Operation, environmental friendliness, low input high production.
In order to make those skilled in the art be more fully understood that the present invention, below by way of specific embodiment to this
The method of the novel microemulsion liquid method synthesis nano-hollow silicon ball carried noble metal effective catalyst of invention is carried out
Explanation.
Embodiment 1
(1) 1ml OPEO is added slowly in 20ml normal hexane, stirs under room temperature
1min；1ml n-butyl alcohol is added in above-mentioned solution, 1min is stirred at room temperature, now define one micro-
Emulsion system；0.3ml butyl silicate and 30ul octadecyl trimethyl TMOS mix homogeneously are formed
Precursor solution, is slowly dropped in above-mentioned solution, 3min is stirred at room temperature；By 3ml deionized water with
The speed of 0.5ml/min is added drop-wise in above-mentioned solution, and 10min is stirred at room temperature；By 0.03ml ammonia with
The speed of 0.5ml/min is added drop-wise in above-mentioned solution, and 5h is stirred at room temperature, and forms organic SiO2(o) ball.
(2) 0.8ml butyl silicate is added in above-mentioned solution, 25h is stirred at room temperature, form inorganic SiO2
It is coated with organic SiO2The structure of ball i.e. SiO2(o)@SiO2(i) structure.
(3) 50ml diacetyl is added in above-mentioned solution, stands 20min and be precipitated, clear with ethanol
Wash 1 time, be distributed in deionized water；By the hydrofluoric acid aqueous solution etching that 3ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 25min, obtains SiO2Hollow ball is centrifugal clear
Wash, at 80 DEG C, be dried 10h.
(4) by 100mgSiO2Hollow ball and the mixing of 80mg magnesium powder, grind, put into containing 5%H2's
In tube furnace under Ar atmosphere, 1000 DEG C, 1h, SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；
(5) 100mgSi hollow ball is loaded 50mgAu particle, obtain nano-hollow silicon ball gold-supported
Particle efficient photocatalyst, centrifugal drying.
Embodiment 2
(1) 10ml high-carbon fatty alcohol polyoxyethylene ether is added slowly in 50ml normal hexane, under room temperature
Stirring 10min；10ml n-octyl alcohol is added in above-mentioned solution, 10min is stirred at room temperature, now defines
One microemulsion system；Before 0.3ml silester and 30ul hexa methyl oxy disilicane mix homogeneously are formed
Drive liquid solution, be slowly dropped in above-mentioned solution, 3min is stirred at room temperature；By 1.5ml deionized water with
The speed of 0.75ml/min is added drop-wise in above-mentioned solution, and 5min is stirred at room temperature；By 0.15ml ammonia with
The speed of 0.75ml/min is added drop-wise in above-mentioned solution, and 4h is stirred at room temperature, and forms organic SiO2(o) ball；
(2) 0.8ml silester is added in above-mentioned solution, 25h is stirred at room temperature, form inorganic SiO2
It is coated with organic SiO2The structure of ball i.e. SiO2(o)@SiO2(i) structure；
(3) 50ml acetone is added in above-mentioned solution, stands 20min and be precipitated, clean with methanol
1 time, it is distributed in deionized water；By the hydrofluoric acid aqueous solution etching that 2.5ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 20min, obtains SiO2Hollow ball is centrifugal clear
Wash, at 80 DEG C, be dried 9h.
(4) by 10mgSiO2Hollow ball and the mixing of 5mg magnesium powder, grind, put into containing 5%H2Ar
In tube furnace under atmosphere, 500 DEG C, 5h, SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；
(5) 10mgSi hollow ball is loaded 10mgAu particle, obtain nano-hollow silicon ball load goldc grains
Sub-high efficiency photocatalyst, centrifugal drying.
Embodiment 3
(1) isooctyl phenyl ether is added slowly in 50ml normal hexane by 5ml Polyethylene Glycol, under room temperature
Stirring 5min；5ml isooctanol is added in above-mentioned solution, 5min is stirred at room temperature, now defines one
Individual microemulsion system；By 0.05ml silicic acid propyl ester and the 5ul methyldiphenyl base uniform shape of ethoxy silane mixture
Become precursor solution, be slowly dropped in above-mentioned solution, 1min is stirred at room temperature；By 0.3ml deionized water
It is added drop-wise in above-mentioned solution with the speed of 0.5ml/min, 1min is stirred at room temperature；By 0.3ml ammonia with
The speed of 1ml/min is added drop-wise in above-mentioned solution, and 5h is stirred at room temperature, and forms organic SiO2(o) ball；
(2) 0.01ml silicic acid propyl ester is added in above-mentioned solution, 20h is stirred at room temperature, form inorganic SiO2
It is coated with organic SiO2The structure of ball i.e. SiO2(o)@SiO2(i) structure；
(3) 10ml propiophenone is added in above-mentioned solution, stands 10min and be precipitated, clear with ethanol
Wash 2 times, be distributed in deionized water；By the hydrofluoric acid aqueous solution etching that 0.5ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 10min, obtains SiO2Hollow ball is centrifugal clear
Wash, at 70 DEG C, be dried 12h.
(4) by 10mgSiO2Hollow ball and the mixing of 5mg magnesium powder, grind, put into containing 5%H2Ar
In tube furnace under atmosphere, 500 DEG C, 10h, SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；
(5) 10mgSi hollow ball is loaded 10mgPt particle, obtain nano-hollow silicon ball load platinum grain
Sub-high efficiency photocatalyst, centrifugal drying.
Embodiment 4
(1) 3ml NPE is added slowly in 50ml normal hexane, under room temperature, stirs 2min；
3ml hexanol is added in above-mentioned solution, 5min is stirred at room temperature, now defines an Emulsions
System；Before positive for 0.25ml quanmethyl silicate and 25ul dimethyldiacetoxy silane mixture are formed uniformly
Drive liquid solution, be slowly dropped in above-mentioned solution, 2min is stirred at room temperature；By 0.9ml deionized water with
The speed of 1ml/min is added drop-wise in above-mentioned solution, and 5min is stirred at room temperature；By 0.1ml ammonia with 1ml/min
Speed be added drop-wise in above-mentioned solution, 3h is stirred at room temperature, forms organic SiO2(o) ball；
(2) positive for 0.3ml quanmethyl silicate is added in above-mentioned solution, 20h is stirred at room temperature, form inorganic SiO2
It is coated with organic SiO2The structure of ball i.e. SiO2(o)@SiO2(i) structure；
(3) 50ml diacetyl is added in above-mentioned solution, stands 10min and be precipitated, clear with methanol
Wash 1 time, be distributed in deionized water；By the hydrofluoric acid aqueous solution etching that 3ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 10min, obtains SiO2Hollow ball is centrifugal clear
Wash, at 90 DEG C, be dried 10h.
(4) by 30mgSiO2Hollow ball and the mixing of 25mg magnesium powder, grind, put into containing 5%H2Ar
In tube furnace under atmosphere, 950 DEG C, 4h, SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；
(5) 10mgSi hollow ball is loaded 5mgAg particle, obtain nano-hollow silicon ball load silver granuel
Sub-high efficiency photocatalyst, centrifugal drying.
Fig. 3 is the XRD figure of the silicon hollow ball (SiHS) of the embodiment of the present invention 4 synthesis, and XRD figure is composed
In 2 θ=28.4470,47.3110 and the PDF#65-1060 mark of diffraction maximum and simple substance Si of 56.1320
Quasi-card is corresponding consistent, and diffraction maximum is sharp-pointed and does not has miscellaneous peak to occur, illustrates that product crystallinity is good.
Fig. 4 a and 4b is that silver load hollow silicon ball (Ag-SiHS) of the embodiment of the present invention 4 synthesis is efficient
The TEM figure of catalyst, the most most of hollow silicon balls remain the integrity of structure,
Product cut size is the most homogeneous, and Average Particle Diameters is about 200nm, and silver nano-grain loads uniformly simultaneously
Surface at hollow silicon ball.
Fig. 5 is silver load hollow silicon ball (Ag-SiHS) effective catalyst of the embodiment of the present invention 4 synthesis
EDX spectrogram, from books it can be seen that there are two obvious peaks, the most corresponding Si and Ag element,
This is shown to be simple silver and loads hollow silicon ball, there are not other elements.
Fig. 6 is silicon hollow ball (SiHS) and the silver load hollow silicon ball of the embodiment of the present invention 4 synthesis
(Ag-SiHS) the photodissociation Aquatic product hydrogen figure of effective catalyst, by figure it will be seen that the average of SiHS produces
Hydrogen speed is 0.392mmol/g/h, and the average hydrogen-producing speed of Ag-SiHS is 1.378mmol/g/h, warp
Cross silver load hollow silicon ball, be greatly improved its hydrogen-producing speed.
Embodiment 5
(1) by slow to isooctyl phenyl ether for 5ml Polyethylene Glycol 50ml normal hexane, stir under room temperature
5min；5ml isoamyl alcohol is added in above-mentioned solution, 5min is stirred at room temperature, now define one micro-
Emulsion system；By 0.5ml tetraethyl orthosilicate and the 50ul methyldiphenyl base uniform shape of ethoxy silane mixture
Become precursor solution, be slowly dropped in above-mentioned solution, 5min is stirred at room temperature；By 3ml deionized water
It is added drop-wise in above-mentioned solution with the speed of 1ml/min, 10min is stirred at room temperature；By 2ml ammonia with
The speed of 0.8ml/min is added drop-wise in above-mentioned solution, and 4h is stirred at room temperature, and forms organic SiO2(o) ball；
(2) 1.5ml tetraethyl orthosilicate is added in above-mentioned solution, 30h is stirred at room temperature, formed inorganic
SiO2It is coated with organic SiO2The structure of ball i.e. SiO2(o)@SiO2(i) structure；
(3) 100ml acetone is added in above-mentioned solution, stands 30min and be precipitated, clear with ethanol
Wash 1 time, be distributed in deionized water；By the hydrofluoric acid aqueous solution etching that 5ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 30min, obtains SiO2Hollow ball is centrifugal clear
Wash, at 90 DEG C, be dried 12h.
(4) by 50mgSiO2Hollow ball and the mixing of 40mg magnesium powder, grind, put into containing 5%H2Ar
In tube furnace under atmosphere, 750 DEG C, 6h, SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；
(5) 50mgSi hollow ball is loaded 25mgPd particle, obtain nano-hollow silicon ball supported palladium grain
Sub-high efficiency photocatalyst, centrifugal drying.
Embodiment 6
(1) 2ml polyoxyethylene carboxylate is added slowly in 50ml normal hexane, stirs under room temperature
1min；2ml n-octyl alcohol is added in above-mentioned solution, 3min is stirred at room temperature, now define one micro-
Emulsion system；By 0.15ml methyl silicate and 15ul octadecyl trimethyl TMOS mix homogeneously shape
Become precursor solution, be slowly dropped in above-mentioned solution, 2min is stirred at room temperature；By 0.8ml deionized water
It is added drop-wise in above-mentioned solution with the speed of 1ml/min, 5min is stirred at room temperature；By 0.2ml ammonia with
The speed of 2ml/min is added drop-wise in above-mentioned solution, and 2h is stirred at room temperature, and forms organic SiO2(o) ball；
(2) 0.2ml methyl silicate is added in above-mentioned solution, 20h is stirred at room temperature, form inorganic SiO2
It is coated with organic SiO2The structure of ball i.e. SiO2(o)@SiO2(i) structure；
(3) 50ml acetone is added in above-mentioned solution, stands 10min and be precipitated, use ethanol purge
1 time, it is distributed in deionized water；By the hydrofluoric acid aqueous solution etching that 2.5ml mass concentration is 10%
SiO2(o)@SiO2SiO in (i) structure2O () layer, reacts 10min, obtains SiO2Hollow ball is centrifugal clear
Wash, at 50 DEG C, be dried 12h.
(4) by 30mgSiO2Hollow ball and the mixing of 25mg magnesium powder, grind, put into containing 5%H2Ar
In tube furnace under atmosphere, 500 DEG C, 10h, SiO2Hollow ball is reduced into Si hollow ball by magnesium powder；
(5) 10mgSi hollow ball is loaded 10mgPd particle, obtain nano-hollow silicon ball supported palladium grain
Sub-high efficiency photocatalyst, centrifugal drying.
The invention provides a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball carried noble metal efficiently to urge
The method of agent, is added slowly to 1-10ml surfactant A in 20-50ml solution B, is formed molten
Liquid C, stirs 1-10min under room temperature；And then 1-10ml cosurfactant D adds above-mentioned solution C
In, form solution E, 1-10min is stirred at room temperature, now defines a microemulsion system；Next
0.05-0.5ml silicon salt compound F and 5-50ul silane reagent G mix homogeneously are formed precursor solution,
It is slowly dropped in above-mentioned solution E, forms Solution H, 1-5min is stirred at room temperature；0.3-3ml is gone from
Sub-water is added drop-wise in Solution H with the speed of 0.5-1ml/min, forms solution I and 1-10min is stirred at room temperature；
0.03-0.3ml ammonia is added drop-wise in solution I with the speed of 0.5-1ml/min, forms solution J, room temperature
Stirring 3-5h, forms organic SiO2(o) ball；0.01-1.5ml silicon salt compound K is added in solution J,
Form solution M, 20-30h is stirred at room temperature, forms inorganic SiO2It is coated with organic SiO2The structure of ball is i.e.
SiO2(o)@SiO2(i) structure；10-100ml precipitant N is added in solution M, stands 10-30min
It is precipitated, cleans 1-2 time with solvent O, be distributed in deionized water form solution P；Use 0.5-5ml
Mass concentration is the SiO in the hydrofluoric acid aqueous solution described solution P of etching of 10%2(o)@SiO2In (i) structure
SiO2O () layer, reacts 10-30min, obtains SiO2Hollow ball, eccentric cleaning, it is dried at 70-90 DEG C
8-12h.By 10-100mgSiO2Hollow ball and the mixing of 5-80mg magnesium powder, grind, put into containing 5%H2
Ar atmosphere under tube furnace in, 500-1000 DEG C, 1-10h, SiO2Hollow ball is reduced into Si by magnesium powder
Hollow ball；10-100mgSi hollow ball is loaded 10-50mg noble metal Q, obtains nano-hollow
Silicon ball carried noble metal high efficiency photocatalyst, centrifugal drying.By the embodiment of the present invention, use first
Different silicon salt compound hydrolysis obtain the SiO of different structure2Nuclear shell ball, then utilizes hf etching
Fall nexine SiO2Thus obtain SiO2Hollow ball, then reduce SiO with Mg2Obtain nano Si hollow
Ball, finally carried noble metal particle on nano Si hollow ball, obtain the load of nano-hollow silicon ball expensive
Metal effective catalyst, the nanocatalyst of this space confinement had both had that specific surface area is big, protection
Small sized metallic granule is difficult to the advantages such as reunion, and the high light simultaneously remaining nano-metal particle dissipates
Penetrate and the series of properties such as plasma resonance, have broad application prospects.Further, the method work
Skill is simple, convenient to operate, environmental friendliness, low input high production.
For embodiment of the method, in order to be briefly described, 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 limited by described sequence of movement,
Because according to the present invention, some step can use other order or carry out simultaneously.Secondly, originally
Skilled person also should know, embodiment described in this description belongs to preferred embodiment,
Necessary to involved action and the parts not necessarily present invention.
Above your gold a kind of novel microemulsion liquid method synthesis nano-hollow silicon ball provided by the present invention is loaded
The method of metal catalyst is described in detail, the specific case principle to the present invention used herein
And embodiment is set forth, the explanation of above example is only intended to help to understand the present invention's
Method and core concept thereof；Simultaneously for one of ordinary skill in the art, according to the present invention's
Thought, the most all will change, in sum, and this theory
Bright book content should not be construed as limitation of the present invention.
Claims (1)
1. the method for a microemulsion method synthesis nano-hollow silicon ball supported precious metal catalyst, it is characterised in that including:
By 1-
10mL surfactant A is added slowly to 20-
In 50mL solvent B, form solution C, under room temperature, stir 1-10min；
By 1-
10mL cosurfactant D adds in described solution C, forms solution E, stirs 1-10min under room temperature；
By 0.05-0.
5mL silicon salt compound F and 5-
50
μ L silane reagent G mix homogeneously forms precursor solution, is slowly dropped in described solution E, forms Solution H, stirs 1-5min under room temperature；
By 0.3-
3mL deionized water is with 0.5-1m
The speed of L/min is added drop-wise in described Solution H, forms solution I, 1-10min is stirred at room temperature；
By 0.03-0.
3mL ammonia is with 0.5-
The speed of 1mL/min is added drop-wise in described solution I, forms solution J, stirs 3-5h, form organic SiO under room temperature2(o) ball；
By 0.01-1.
5mL silicon salt compound K is added in described solution J, forms solution M, stirs 20-30h, form inorganic SiO under room temperature2It is coated with organic SiO2The SiO of ball2(o)@SiO2(i) structure；
By 10-
100mL precipitant N is added in described solution M, stands 10-30min and is precipitated, cleans 1-2 time with solvent O, is distributed in deionized water form solution P；
Use 0.5-
5mL mass concentration is the SiO in the hydrofluoric acid aqueous solution described solution P of etching of 10%2(o)@SiO2SiO in (i) structure2O () layer, reacts 10-30min, obtains SiO2Hollow ball, eccentric cleaning, it is dried 8-12h at 70-90 DEG C；
By SiO described in 10-100mg2Hollow ball and the mixing of 5-80mg magnesium powder, grind, put into containing 5%H2Ar atmosphere under tube furnace in, under conditions of 500-1000 DEG C react 1-10h, described SiO2Hollow 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；
Wherein, 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；
Described solvent B is normal hexane, hexamethylene, pentane, normal butane or normal octane；
Described cosurfactant D is ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-capryl alcohol, sec-n-octyl alcohol or n nonylphenol；
Described silicon salt compound F is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate；
Described silane reagent G is trim,ethylchlorosilane, hexamethyldisiloxane, 1,2-bis-(trimethyl epoxide 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；
Described silicon salt compound K is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, positive quanmethyl silicate or tetraethyl orthosilicate；
Described precipitant N is acetone, diacetyl, acetylacetone,2,4-pentanedione or propiophenone；
Described solvent O is methanol, ethanol or propanol；
Described noble metal Q is gold, silver, platinum or palladium.
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| 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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| 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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