CN105289595B - A kind of preparation method and application of the golden silica Janus structure nano particles with high catalysis characteristics - Google Patents
A kind of preparation method and application of the golden silica Janus structure nano particles with high catalysis characteristics Download PDFInfo
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Abstract
A kind of preparation method and application of the golden silica Janus structure nano particles with high catalysis characteristics, the present invention relates to golden silica Janus structure nano particles and its preparation method and application.The invention solves the problems that prior art can make the gold surface of uncoated silica cover thick and heavy part macromolecular, so as to significantly reduce the catalytic activity of golden silica Janus structure nano particles, it is unsuitable for the problem of Industrial Catalysis is applied.Golden silica Janus structure nano particles with high catalysis characteristics are that uviol lamp is irradiated, centrifuges and obtained after water washing to golden silica Janus structure nano particle ethanol waters.Method：First, the reaction system of the golden nanometer particle containing double part claddings is prepared；2nd, the golden silica Janus structure nano particle aqueous solution is prepared；3rd, uv light irradiation.Using：For p-nitrophenol to be reduced into para-aminophenol in organic reaction.
Description
Technical field
The present invention relates to gold-silica Janus structure nano particles and its preparation method and application.
Background technology
Since Gennes mentions Janus structured particles emphatically first in the prize-winning speech of its Nobel, this structure just exists
Received significant attention in material science.In general, Janus structured particles refer to while having two different functionalized surfaces
Or two kinds of components with different physico-chemical properties are combined in same particle structure.The a variety of functions of Janus structural integrities in
One, therefore have good application prospect in fields such as optics, catalysis, sensing and biomarkers.Gold-silica Janus knots
Structure nano-particle is the more class that wherein attracts attention, and the silica of part cladding can effectively prevent golden nanometer particle
Aggregation and poisoning, but the existing technology for preparing gold-silica Janus structure nano particles can make the gold of uncoated silica
Surface covers thick and heavy part macromolecular, so as to significantly reduce the catalytic activity of gold-silica Janus structure nano particles, no
Suitable for Industrial Catalysis application.
The content of the invention
The invention solves the problems that the existing technology for preparing gold-silica Janus structure nano particles can make uncoated oxidation
The gold surface of silicon covers thick and heavy part macromolecular, so that the catalysis for significantly reducing gold-silica Janus structure nano particles is lived
Property, it is unsuitable for the problem of Industrial Catalysis is applied, and a kind of gold with high catalysis characteristics-silica Janus structure nanos are provided
Particle and its preparation method and application.
A kind of gold with high catalysis characteristics-silica Janus structure nano particles, gold-oxygen with high catalysis characteristics
SiClx Janus structure nano particles be uviol lamp gold-silica Janus structure nano particle ethanol waters are irradiated,
Centrifuge and obtained after water washing.
A kind of preparation method of gold with high catalysis characteristics-silica Janus structure nano particles, be specifically according to
What lower step was carried out：
First, particle diameter is mixed for 2 nanometers~100 nanometers of golden nanometer particle with water, it is 10 to obtain concentration-4Mmol/L~
10-3The mmol/L golden nanometer particle aqueous solution, the golden nanometer particle aqueous solution is added dropwise in alcohols solvent, reaction system is obtained,
Then in the case where rotating speed is 50rpm~400rpm stirring conditions, with concentration it is by the solution A that concentration is 1mmol/L~10mmol/L
0.2mmol/L~5mmol/L B solution is added dropwise in reaction system, after completion of dropping, by reaction system rotating speed be 50rpm
Under~400rpm, 1min~10min is stirred, then 10min~60min is stirred in the case where rotating speed is 50rpm~400rpm again, obtains
To the reaction system of the golden nanometer particle coated containing double parts；
Described particle diameter is that 2 nanometers~100 nanometers of golden nanometer particle is that the synthesis of sodium citrate cladding process is obtained；
Described solution A is 4- mercaptophenylacetic acids/ethanol solution or 4- mercaptobenzoic acids/ethanol solution, described B solution
For the polyacrylic acid aqueous solution；
The described golden nanometer particle aqueous solution and the volume ratio of alcohols solvent are 1:(1~10)；
The described golden nanometer particle aqueous solution and the volume ratio of solution A are 1:(0.01~0.1)；
The described golden nanometer particle aqueous solution and the volume ratio of B solution are 1:(0.01~0.1)；
2nd, in the case where rotating speed is 20rpm~200rpm, add into the reaction system of the golden nanometer particle coated containing double parts
Enter the tetraethyl orthosilicate aqueous solution that concentration is 1mmol/L~30mmol/L and the ammoniacal liquor that mass percent is 10%~50%, stir
8h~24h is mixed, separation simultaneously water washing 3 times~6 times is then centrifuged for, obtains gold-silica Janus structure nano particle solution, will
Gold-silica Janus structure nano particle solution is dispersed in water, and obtains gold-silica Janus structure nano particles water-soluble
Liquid；
The reaction system and the volume ratio of the tetraethyl orthosilicate aqueous solution of the described golden nanometer particle containing double part claddings
For 1:(0.1~1)；
The described reaction system of the golden nanometer particle coated containing double parts and the volume ratio of ammoniacal liquor is 1:(0.01~
0.1)；
The volume ratio of described gold-silica Janus structure nano particles solution and water is 1:(1~10)；
3rd, under conditions of ultrasonic power is 100W~500W, by gold-silica Janus structure nano particle aqueous solution
Mixed with ethanol and ultrasound 1min~30min, obtain gold-silica Janus structure nano particle ethanol waters, then turned
Speed be 50rpm~400rpm under, using power for 0.1W~1000W uviol lamp to gold-silica Janus structure nano particles
Ethanol water is irradiated, and irradiates 1min~1000min, under conditions of ultrasonic power is 100W~500W, after irradiation
Gold-silica Janus ultrasonically treated 1min~100min of structure nano particle ethanol water, be then centrifuged for separating and wash
Wash 3 times~6 times, be finally distributed to water it is standby in, obtain the gold with high catalysis characteristics-silica Janus structure nano particles；
Described uviol lamp for one kind in wavelength 200nm~400nm ultraviolet light in single wavelength and continuous wavelength or
Two kinds of combination；
The volume ratio of described gold-silica Janus structure nano particles aqueous solution and ethanol is 1:(1~20).
The application of a kind of gold with high catalysis characteristics-silica Janus structure nano particles, with high catalysis characteristics
Gold-silica Janus structure nano particles are used to p-nitrophenol is reduced into para-aminophenol, catalysis time in organic reaction
For 6 minutes~8 minutes, catalytic rate was up to 0.26min-1~0.39min-1, it is specifically what is carried out according to the following steps：
For the p-nitrophenol aqueous solution and sodium borohydride aqueous solution are added dropwise into water, it is well mixed, being then added dropwise has height
The gold of the catalysis characteristics-silica Janus structure nano particle aqueous solution；
The described p-nitrophenol aqueous solution and the volume ratio of sodium borohydride aqueous solution are 1:1；Described p-nitrophenol
The concentration ratio of the aqueous solution and sodium borohydride aqueous solution is 1:100；The described p-nitrophenol aqueous solution and the volume ratio of water are 1:
60；The described p-nitrophenol aqueous solution and gold-silica Janus structure nano particle aqueous solution with high catalysis characteristics
Volume ratio is 1:2；The described p-nitrophenol aqueous solution and the gold with high catalysis characteristics-silica Janus structure nanos grain
The concentration ratio of the sub- aqueous solution is 1:0.2.
The beneficial effects of the invention are as follows：(1) catalysis characteristics of gold-silica Janus structure nano particles is significantly increased, is had
Beneficial to industrial applications；In the reduction reaction for carrying out nitrophenol, under the same conditions, gold-silica Janus knots before illumination
The complete catalysis time of structure nano-particle is 10 minutes, and the part for coating gold surface half after illumination comes off, exposed part gold
Surface, improved the complete catalysis time of Janus structure nano particles to 6 minutes.And either illumination whether, Janus gold-oxygen
Catalytic rate (the 0.24min before illumination of SiClx-1With 0.39min after illumination-1) it is above now widely used nucleocapsid structure
Gold-silicon oxide catalyst (0.16min-1), and it can be found that Janus structure nano particles after illumination before and after contrasting illumination
Catalytic rate improve 1.6 times.Although the catalytic rate of Janus structures gold-silica after illumination is urged with simple gold nano
Speed (the 0.34min of agent-1) close, but the recycling of four kinds of catalyst of contrast, it can be found that gold nano catalyst
Recyclability is very bad, and the catalytic efficiency of Janus structures gold-silica loss very little, this outstanding repeatable utilization
Property is especially advantageous for industrial applications.
(2) method is simple, controllability is good, beneficial to large-scale production.
The present invention is used for a kind of gold with high catalysis characteristics-silica Janus structure nano particles and preparation method thereof
And application.
Brief description of the drawings
Fig. 1 is the transmission electricity of the gold with high catalysis characteristics-silica Janus structure nano particles prepared by embodiment one
Mirror figure；
Fig. 2 is that gold-silica Janus structure nano particles before ultraviolet light irradiation prepared by the step 2 of embodiment one are urged
The UV-vis for changing organic reaction absorbs spectrogram；
Fig. 3 is that the catalysis of the gold with high catalysis characteristics-silica Janus structure nano particles prepared by embodiment one has
The UV-vis of machine reaction absorbs spectrogram；
Fig. 4 is catalytic rate comparison diagram, and 1 is simple Au catalyst, 2 be embodiment one prepare there is high catalysis characteristics
Gold-silica Janus structure nano particles, 3 be gold-silica before ultraviolet light irradiation prepared by the step 2 of embodiment one
Janus structure nano particles, 4 be gold-silicon oxide nanoparticle of nucleocapsid structure；
Fig. 5 is circulation catalytic efficiency comparison diagram, and 1 is circulation primary, and 2 is circulate twice, and 3 be circulation three times, and a is simple golden
Catalyst, b be nucleocapsid structure gold-silicon oxide nanoparticle, c be the step 2 of embodiment one prepare ultraviolet light irradiation before
Gold-silica Janus structure nano particles, d is the gold with high catalysis characteristics-silica Janus knots prepared by embodiment one
Structure nano-particle.
Embodiment
Technical solution of the present invention is not limited to the embodiment of act set forth below, in addition to each embodiment it
Between any combination.
Embodiment one：A kind of gold with high catalysis characteristics-silica Janus structures described in present embodiment
Nano-particle is that uviol lamp is irradiated, centrifuged and washed to gold-silica Janus structure nano particle ethanol waters
Obtained after washing.
The beneficial effect of present embodiment is：(1) catalysis for significantly increasing gold-silica Janus structure nano particles is special
Property, be conducive to industrial applications；In the reduction reaction for carrying out nitrophenol, under the same conditions, gold-silica before illumination
The complete catalysis time of Janus structure nano particles is 10 minutes, and the part for coating gold surface half after illumination comes off, exposed
Part gold surface, improved the complete catalysis time of Janus structure nano particles to 6 minutes.And either illumination whether, Janus
Gold-silica catalytic rate (0.24min before illumination-1With 0.39min after illumination-1) be above now widely used core-
The gold of shell structure-silicon oxide catalyst (0.16min-1), and it can be found that the Janus structures after illumination are received before and after contrasting illumination
The catalytic rate of rice corpuscles improves 1.6 times.Although the catalytic rate of Janus structures gold-silica after illumination and simple gold
Speed (the 0.34min of nanocatalyst-1) close, but the recycling of four kinds of catalyst of contrast, it can be found that gold nano is urged
The recyclability of agent is very bad, and the catalytic efficiency of Janus structures gold-silica loss very little, and this outstanding weighs
Multiple usability is especially advantageous for industrial applications.
(2) method is simple, controllability is good, beneficial to large-scale production.
Embodiment two：Present embodiment from unlike embodiment one：Described gold-silica
Janus structure nano particle ethanol waters are specifically prepared according to the following steps：First, it is 2 nanometers~100 nanometers by particle diameter
Golden nanometer particle is mixed with water, and it is 10 to obtain concentration-4Mmol/L~10-3The mmol/L golden nanometer particle aqueous solution, by gold nano
The particle aqueous solution is added dropwise in alcohols solvent, obtains reaction system, then in the case where rotating speed is 50rpm~400rpm stirring conditions,
The B solution that the solution A for being 1mmol/L~10mmol/L by concentration is 0.2mmol/L~5mmol/L with concentration is added dropwise to reactant
In system, after completion of dropping, by reaction system in the case where rotating speed is 50rpm~400rpm, 1min~10min is stirred, is then being turned again
Speed obtains the reactant of the golden nanometer particle containing double parts claddings under 50rpm~400rpm, to stir 10min~60min
System；Described particle diameter is that 2 nanometers~100 nanometers of golden nanometer particle is that the synthesis of sodium citrate cladding process is obtained；Described A is molten
Liquid is 4- mercaptophenylacetic acids/ethanol solution or 4- mercaptobenzoic acids/ethanol solution, and described B solution is the polyacrylic acid aqueous solution；
The described golden nanometer particle aqueous solution and the volume ratio of alcohols solvent are 1:(1~10)；The described golden nanometer particle aqueous solution and A
The volume ratio of solution is 1:(0.01~0.1)；The described golden nanometer particle aqueous solution and the volume ratio of B solution are 1:(0.01~
0.1)；
2nd, in the case where rotating speed is 20rpm~200rpm, add into the reaction system of the golden nanometer particle coated containing double parts
Enter the tetraethyl orthosilicate aqueous solution that concentration is 1mmol/L~30mmol/L and the ammoniacal liquor that mass percent is 10%~50%, stir
8h~24h is mixed, separation simultaneously water washing 3 times~6 times is then centrifuged for, obtains gold-silica Janus structure nano particle solution, will
Gold-silica Janus structure nano particle solution is dispersed in water, and obtains gold-silica Janus structure nano particles water-soluble
Liquid；The described reaction system of golden nanometer particle containing double part claddings and the volume ratio of the tetraethyl orthosilicate aqueous solution is 1:
(0.1~1)；The described reaction system of the golden nanometer particle coated containing double parts and the volume ratio of ammoniacal liquor is 1:(0.01~
0.1)；The volume ratio of described gold-silica Janus structure nano particles solution and water is 1:(1~10)；
3rd, under conditions of ultrasonic power is 100W~500W, by gold-silica Janus structure nano particle aqueous solution
Mixed with ethanol and ultrasound 1min~30min, obtain gold-silica Janus structure nano particle ethanol waters；Described
The volume ratio of gold-silica Janus structure nano particles aqueous solution and ethanol is 1:(1~20).Other and embodiment
One is identical.
Embodiment three：Unlike one of present embodiment and embodiment one or two：Described is ultraviolet
Lamp is obtained after being irradiated to gold-silica Janus structure nano particle ethanol waters, is specifically to carry out according to the following steps：
In the case where rotating speed is 50rpm~400rpm, using the uviol lamp that power is 0.1W~1000W to gold-silica Janus structure nanos
Particle ethanol water is irradiated, and irradiates 1min~1000min, under conditions of ultrasonic power is 100W~500W, by spoke
Gold-silica Janus ultrasonically treated 1min~100min of structure nano particle ethanol water according to after, are then centrifuged for separation simultaneously
Water washing 3 times~6 times, be finally distributed to water it is standby in, obtain the gold with high catalysis characteristics-silica Janus structure nanos
Particle；
Described uviol lamp for one kind in wavelength 200nm~400nm ultraviolet light in single wavelength and continuous wavelength or
Two kinds of combination.It is other identical with embodiment one or two.
Embodiment four：A kind of gold with high catalysis characteristics-silica Janus structures described in present embodiment
The preparation method of nano-particle, is specifically followed the steps below：
First, particle diameter is mixed for 2 nanometers~100 nanometers of golden nanometer particle with water, it is 10 to obtain concentration-4Mmol/L~
10-3The mmol/L golden nanometer particle aqueous solution, the golden nanometer particle aqueous solution is added dropwise in alcohols solvent, reaction system is obtained,
Then in the case where rotating speed is 50rpm~400rpm stirring conditions, with concentration it is by the solution A that concentration is 1mmol/L~10mmol/L
0.2mmol/L~5mmol/L B solution is added dropwise in reaction system, after completion of dropping, by reaction system rotating speed be 50rpm
Under~400rpm, 1min~10min is stirred, then 10min~60min is stirred in the case where rotating speed is 50rpm~400rpm again, obtains
To the reaction system of the golden nanometer particle coated containing double parts；
Described particle diameter is that 2 nanometers~100 nanometers of golden nanometer particle is that the synthesis of sodium citrate cladding process is obtained；
Described solution A is 4- mercaptophenylacetic acids/ethanol solution or 4- mercaptobenzoic acids/ethanol solution, described B solution
For the polyacrylic acid aqueous solution；
The described golden nanometer particle aqueous solution and the volume ratio of alcohols solvent are 1:(1~10)；
The described golden nanometer particle aqueous solution and the volume ratio of solution A are 1:(0.01~0.1)；
The described golden nanometer particle aqueous solution and the volume ratio of B solution are 1:(0.01~0.1)；
2nd, in the case where rotating speed is 20rpm~200rpm, add into the reaction system of the golden nanometer particle coated containing double parts
Enter the tetraethyl orthosilicate aqueous solution that concentration is 1mmol/L~30mmol/L and the ammoniacal liquor that mass percent is 10%~50%, stir
8h~24h is mixed, separation simultaneously water washing 3 times~6 times is then centrifuged for, obtains gold-silica Janus structure nano particle solution, will
Gold-silica Janus structure nano particle solution is dispersed in water, and obtains gold-silica Janus structure nano particles water-soluble
Liquid；
The reaction system and the volume ratio of the tetraethyl orthosilicate aqueous solution of the described golden nanometer particle containing double part claddings
For 1:(0.1~1)；
The described reaction system of the golden nanometer particle coated containing double parts and the volume ratio of ammoniacal liquor is 1:(0.01~
0.1)；
The volume ratio of described gold-silica Janus structure nano particles solution and water is 1:(1~10)；
3rd, under conditions of ultrasonic power is 100W~500W, by gold-silica Janus structure nano particle aqueous solution
Mixed with ethanol and ultrasound 1min~30min, obtain gold-silica Janus structure nano particle ethanol waters, then turned
Speed be 50rpm~400rpm under, using power for 0.1W~1000W uviol lamp to gold-silica Janus structure nano particles
Ethanol water is irradiated, and irradiates 1min~1000min, under conditions of ultrasonic power is 100W~500W, after irradiation
Gold-silica Janus ultrasonically treated 1min~100min of structure nano particle ethanol water, be then centrifuged for separating and wash
Wash 3 times~6 times, be finally distributed to water it is standby in, obtain the gold with high catalysis characteristics-silica Janus structure nano particles；
Described uviol lamp for one kind in wavelength 200nm~400nm ultraviolet light in single wavelength and continuous wavelength or
Two kinds of combination；
The volume ratio of described gold-silica Janus structure nano particles aqueous solution and ethanol is 1:(1~20).
The beneficial effect of present embodiment is：(1) catalysis for significantly increasing gold-silica Janus structure nano particles is special
Property, be conducive to industrial applications；In the reduction reaction for carrying out nitrophenol, under the same conditions, gold-silica before illumination
The complete catalysis time of Janus structure nano particles is 10 minutes, and the part for coating gold surface half after illumination comes off, exposed
Part gold surface, improved the complete catalysis time of Janus structure nano particles to 6 minutes.And either illumination whether, Janus
Gold-silica catalytic rate (0.24min before illumination-1With 0.39min after illumination-1) be above now widely used core-
The gold of shell structure-silicon oxide catalyst (0.16min-1), and it can be found that the Janus structures after illumination are received before and after contrasting illumination
The catalytic rate of rice corpuscles improves 1.6 times.Although the catalytic rate of Janus structures gold-silica after illumination and simple gold
Speed (the 0.34min of nanocatalyst-1) close, but the recycling of four kinds of catalyst of contrast, it can be found that gold nano is urged
The recyclability of agent is very bad, and the catalytic efficiency of Janus structures gold-silica loss very little, and this outstanding weighs
Multiple usability is especially advantageous for industrial applications.
(2) method is simple, controllability is good, beneficial to large-scale production.
Embodiment five：Present embodiment from unlike embodiment four：Alcohols described in step one
Solvent is isopropanol, methanol or ethanol.It is other identical with embodiment four.
Embodiment six：Unlike one of present embodiment and embodiment four or five：Institute in step one
The polyacrylic acid molecular weight stated is 1000Da~100000Da.It is other identical with embodiment four or five.
Embodiment seven：Unlike one of present embodiment and embodiment four to six：Will in step one
Particle diameter mixes for 50 nanometers of golden nanometer particle with water, and it is 5.8 × 10 to obtain concentration-4The mmol/L golden nanometer particle aqueous solution.
It is other identical with embodiment four to six.
Embodiment eight：Unlike one of present embodiment and embodiment four to seven：In step one so
Afterwards in the case where rotating speed is 50rpm~400rpm stirring conditions, the solution A and concentration for being 5mmol/L by concentration are 0.645mmol/L's
B solution is added dropwise in reaction system.It is other identical with embodiment four to seven.
Embodiment nine：Unlike one of present embodiment and embodiment four to eight：In step 2
Rotating speed is under 20rpm~200rpm, addition concentration is into the reaction system of the golden nanometer particle coated containing double parts
The 8.9mmol/L tetraethyl orthosilicate aqueous solution and mass percent is 30% ammoniacal liquor, stirs 8h~24h.Other and specific reality
Apply mode four to eight identical.
Embodiment ten：A kind of application of gold with high catalysis characteristics-silica Janus structure nano particles,
Gold with high catalysis characteristics-silica Janus structure nano particles are used in organic reaction p-nitrophenol being reduced to pair
Amino-phenol, catalysis time is 6 minutes~8 minutes, and catalytic rate is up to 0.26min-1~0.39min-1, specifically by following
What step was carried out：
For the p-nitrophenol aqueous solution and sodium borohydride aqueous solution are added dropwise into water, it is well mixed, being then added dropwise has height
The gold of the catalysis characteristics-silica Janus structure nano particle aqueous solution；
The described p-nitrophenol aqueous solution and the volume ratio of sodium borohydride aqueous solution are 1:1；Described p-nitrophenol
The concentration ratio of the aqueous solution and sodium borohydride aqueous solution is 1:100；The described p-nitrophenol aqueous solution and the volume ratio of water are 1:
60；The described p-nitrophenol aqueous solution and gold-silica Janus structure nano particle aqueous solution with high catalysis characteristics
Volume ratio is 1:2；The described p-nitrophenol aqueous solution and the gold with high catalysis characteristics-silica Janus structure nanos grain
The concentration ratio of the sub- aqueous solution is 1:0.2.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：
A kind of preparation method of gold with high catalysis characteristics-silica Janus structure nano particles is according to the following steps
Carry out：
First, particle diameter is mixed for 50 nanometers of golden nanometer particle with water, it is 5.8 × 10 to obtain concentration-4Mmol/L Jenner
The rice corpuscles aqueous solution, the 2.5mL golden nanometer particle aqueous solution is added dropwise in 12.5mL isopropanols, reaction system, Ran Hou is obtained
Rotating speed be 200rpm stirring conditions under, be by 0.1mL concentration 5mmol/L 4- mercaptophenylacetic acids/ethanol solution and 0.1mL concentration
The 0.645mmol/L polyacrylic acid aqueous solution is added dropwise in reaction system, after completion of dropping, is in rotating speed by reaction system
Under 300rpm, 5min is stirred, then 30min is stirred in the case where rotating speed is 200rpm again, the gold nano containing double part claddings is obtained
The reaction system of particle；
Described particle diameter is that 50 nanometers of golden nanometer particle is that the synthesis of sodium citrate cladding process is obtained；
2nd, in the case where rotating speed is 200rpm, add into the reaction system of the 15.2mL golden nanometer particles for containing double part claddings
Enter the tetraethyl orthosilicate aqueous solution that 3mL concentration is 8.9mmol/L and the ammoniacal liquor that 0.45mL mass percents are 30%, stir 12h,
Separation simultaneously water washing 3 times are then centrifuged for, gold-silica Janus structure nano particle solution are obtained, by 0.9mL gold-silica
Janus structure nano particle solution is dispersed in 1mL water, obtains gold-silica Janus structure nano particle aqueous solution；
3rd, ultrasonic power be 100W under conditions of, by 1mL gold-silica Janus structure nano particles aqueous solution with
The mixing of 10mL ethanol and ultrasound 5min, obtain gold-silica Janus structure nano particle ethanol waters, are then in rotating speed
Under 300rpm, using wavelength be 365nm, power be 10W uviol lamp to gold-silica Janus structure nano particle ethanol waters
Solution is irradiated, and irradiates 60min, under conditions of ultrasonic power is 100W, by the gold after irradiation-silica Janus structures
The ultrasonically treated 5min of nano-particle ethanol water, is then centrifuged for separation simultaneously water washing 3 times, is finally distributed in 1mL water, obtains
Gold with high catalysis characteristics-silica Janus structure nano particles.
Fig. 1 is the transmission electricity of the gold with high catalysis characteristics-silica Janus structure nano particles prepared by embodiment one
Mirror figure；As seen from the figure, the material that the present embodiment method is prepared is used to carry out half cladding shape to golden nanometer particle for silica
Into gold-silica Janus structure nano particles.
To the gold with high catalysis characteristics-silica Janus structure nano particles manufactured in the present embodiment and step 2 system
Gold before standby ultraviolet light irradiation-silica Janus structure nano particles carry out the reduction reaction of nitrophenol, specifically by with
What lower process was carried out：In 3mL water, the p-nitrophenol aqueous solution 0.05mL and concentration that dropwise addition concentration is 1mg/g are 100mg/g
Sodium borohydride aqueous solution 0.05mL, be well mixed, 0.1mL concentration manufactured in the present embodiment is added dropwise has height for 0.2mg/g
Concentration prepared by the gold of catalysis characteristics-silica Janus structure nano particles aqueous solution or 0.1mL step 2 is 0.2mg/g's
Gold-silica Janus structure nano particle aqueous solution before ultraviolet light irradiation, every two minutes test mixing solution it is ultraviolet-
Visible absorption spectra, test wavelength scope is 200nm~600nm, and test result is as shown in Fig. 2 to 5.Fig. 2 is the step of embodiment one
The UV-vis of the catalysis organic reaction of gold-silica Janus structure nano particles before rapid two ultraviolet light irradiations prepared absorbs
Spectrogram；Fig. 3 is that the catalysis of the gold with high catalysis characteristics-silica Janus structure nano particles prepared by embodiment one is organic
The UV-vis of reaction absorbs spectrogram；As seen from the figure, under the same conditions, the gold before illumination-silica Janus structure nano particles
Complete catalysis time be 10 minutes, and the part for coating gold surface half after illumination comes off, exposed part gold surface, improves
The complete catalysis time of Janus structure nano particles was to 6 minutes.
Fig. 4 is catalytic rate comparison diagram, and 1 is simple Au catalyst, 2 be embodiment one prepare there is high catalysis characteristics
Gold-silica Janus structure nano particles, 3 be gold-silica before ultraviolet light irradiation prepared by the step 2 of embodiment one
Janus structure nano particles, 4 be gold-silicon oxide nanoparticle of nucleocapsid structure；
Gold-silicon oxide nanoparticle of described nucleocapsid structure can according to W.Stober, A.Fink and E.Bohn,
J.Colloid and Interface Sci., 1968,26,62, prepared.As seen from the figure, by simple Au catalyst,
The catalytic rate contrast of gold-silica Janus structure catalysts before and after gold-silica catalyst with core-casing structure and illumination can be with
It was found that, either whether illumination to be, the catalytic rate of Janus gold-silica (0.24min before illumination-1With 0.39min after illumination-1) it is above gold-silicon oxide catalyst (0.16min of now widely used nucleocapsid structure-1), and can before and after contrasting illumination
To find, the catalytic rate of the Janus structure nano particles after illumination improves 1.6 times.
Fig. 5 is circulation catalytic efficiency comparison diagram, and 1 is circulation primary, and 2 is circulate twice, and 3 be circulation three times, and a is simple golden
Catalyst, b be nucleocapsid structure gold-silicon oxide nanoparticle, c be the step 2 of embodiment one prepare ultraviolet light irradiation before
Gold-silica Janus structure nano particles, d is the gold with high catalysis characteristics-silica Janus knots prepared by embodiment one
Structure nano-particle.Although the speed of the catalytic rate of Janus structures gold-silica after illumination and simple gold nano catalyst
(0.34min-1) close, but the recycling of four kinds of catalyst of contrast, it can be found that the recyclability of gold nano catalyst is non-
It is often bad, and the catalytic efficiency of Janus structures gold-silica loses very little, this outstanding repeatable usability is especially advantageous for
Industrial applications.
Embodiment two：Present embodiment from unlike embodiment one：Using wavelength it is that 285nm, power are in step 3
10W uviol lamp is irradiated to gold-silica Janus structure nano particle ethanol waters, irradiates 60min.It is other with it is real
Apply example one identical.
To the gold with high catalysis characteristics-silica Janus structure nano particles manufactured in the present embodiment and step 2 system
Gold before standby ultraviolet light irradiation-silica Janus structure nano particles carry out the reduction reaction of nitrophenol, specifically by with
What lower process was carried out：In 3mL water, the p-nitrophenol aqueous solution 0.05mL and concentration that dropwise addition concentration is 1mg/g are 100mg/g
Sodium borohydride aqueous solution 0.05mL, be well mixed, 0.1mL concentration manufactured in the present embodiment is added dropwise has height for 0.2mg/g
The gold of the catalysis characteristics-silica Janus structure nano particle aqueous solution, every the ultraviolet-visible of two minutes test mixing solution
Absorption spectrum, test wavelength scope is 200nm~600nm.The part for coating gold surface half after illumination comes off, exposed part gold
Surface, improves the complete catalysis time of Janus structure nano particles to 6 minutes, catalytic rate is 0.29min-1。
Embodiment three：Present embodiment from unlike embodiment one：In step 3 using ultra-violet (UV) band all-wave length 200nm~
400nm, power irradiate for 10W uviol lamp to gold-silica Janus structure nano particle ethanol waters, irradiate
60min.It is other identical with embodiment one.
To the gold with high catalysis characteristics-silica Janus structure nano particles manufactured in the present embodiment and step 2 system
Gold before standby ultraviolet light irradiation-silica Janus structure nano particles carry out the reduction reaction of nitrophenol, specifically by with
What lower process was carried out：In 3mL water, the p-nitrophenol aqueous solution 0.05mL and concentration that dropwise addition concentration is 1mg/g are 100mg/g
Sodium borohydride aqueous solution 0.05mL, be well mixed, 0.1mL concentration manufactured in the present embodiment is added dropwise has height for 0.2mg/g
The gold of the catalysis characteristics-silica Janus structure nano particle aqueous solution, every the ultraviolet-visible of two minutes test mixing solution
Absorption spectrum, test wavelength scope is 200nm~600nm.The part for coating gold surface half after illumination comes off, exposed part gold
Surface, improves the complete catalysis time of Janus structure nano particles to 6 minutes, catalytic rate is 0.34min-1。
Example IV：Present embodiment from unlike embodiment one：Using wavelength it is that 365nm, power are in step 3
10W uviol lamp is irradiated to gold-silica Janus structure nano particle ethanol waters, irradiates 120min.It is other with it is real
Apply example one identical.
To the gold with high catalysis characteristics-silica Janus structure nano particles manufactured in the present embodiment and step 2 system
Gold before standby ultraviolet light irradiation-silica Janus structure nano particles carry out the reduction reaction of nitrophenol, specifically by with
What lower process was carried out：In 3mL water, the p-nitrophenol aqueous solution 0.05mL and concentration that dropwise addition concentration is 1mg/g are 100mg/g
Sodium borohydride aqueous solution 0.05mL, be well mixed, 0.1mL concentration manufactured in the present embodiment is added dropwise has height for 0.2mg/g
The gold of the catalysis characteristics-silica Janus structure nano particle aqueous solution, every the ultraviolet-visible of two minutes test mixing solution
Absorption spectrum, test wavelength scope is 200nm~600nm.The part for coating gold surface half after illumination comes off, exposed part gold
Surface, improves the complete catalysis time of Janus structure nano particles to 8 minutes, catalytic rate is 0.26min-1。
Embodiment five：Present embodiment from unlike embodiment one：Using wavelength it is that 365nm, power are in step 3
50W uviol lamp is irradiated to gold-silica Janus structure nano particle ethanol waters, irradiates 60min.It is other with it is real
Apply example one identical.
To the gold with high catalysis characteristics-silica Janus structure nano particles manufactured in the present embodiment and step 2 system
Gold before standby ultraviolet light irradiation-silica Janus structure nano particles carry out the reduction reaction of nitrophenol, specifically by with
What lower process was carried out：In 3mL water, the p-nitrophenol aqueous solution 0.05mL and concentration that dropwise addition concentration is 1mg/g are 100mg/g
Sodium borohydride aqueous solution 0.05mL, be well mixed, 0.1mL concentration manufactured in the present embodiment is added dropwise has height for 0.2mg/g
The gold of the catalysis characteristics-silica Janus structure nano particle aqueous solution, every the ultraviolet-visible of two minutes test mixing solution
Absorption spectrum, test wavelength scope is 200nm~600nm.The part for coating gold surface half after illumination comes off, exposed part gold
Surface, improves the complete catalysis time of Janus structure nano particles to 8 minutes, catalytic rate is 0.29min-1。
Claims (7)
1. the preparation method of a kind of gold with high catalysis characteristics-silica Janus structure nano particles, it is characterised in that it is
Carry out according to the following steps：
First, particle diameter is mixed for 2 nanometers~100 nanometers of golden nanometer particle with water, it is 10 to obtain concentration-4Mmol/L~10- 3The mmol/L golden nanometer particle aqueous solution, the golden nanometer particle aqueous solution is added dropwise in alcohols solvent, obtains reaction system, so
Afterwards in the case where rotating speed is 50rpm~400rpm stirring conditions, with concentration it is by the solution A that concentration is 1mmol/L~10mmol/L
0.2mmol/L~5mmol/L B solution is added dropwise in reaction system, after completion of dropping, by reaction system rotating speed be 50rpm
Under~400rpm, 1min~10min is stirred, then 10min~60min is stirred in the case where rotating speed is 50rpm~400rpm again, obtains
To the reaction system of the golden nanometer particle coated containing double parts；
Described particle diameter is that 2 nanometers~100 nanometers of golden nanometer particle is that the synthesis of sodium citrate cladding process is obtained；
Described solution A is 4- mercaptophenylacetic acids/ethanol solution or 4- mercaptobenzoic acids/ethanol solution, and described B solution is poly-
Acrylic acid aqueous solution；
The described golden nanometer particle aqueous solution and the volume ratio of alcohols solvent are 1:(1~10)；
The described golden nanometer particle aqueous solution and the volume ratio of solution A are 1:(0.01~0.1)；
The described golden nanometer particle aqueous solution and the volume ratio of B solution are 1:(0.01~0.1)；
2nd, in the case where rotating speed is 20rpm~200rpm, added into the reaction system of the golden nanometer particle coated containing double parts dense
The ammoniacal liquor that the tetraethyl orthosilicate aqueous solution and mass percent that degree is 1mmol/L~30mmol/L are 10%~50%, stirs 8h
~24h, is then centrifuged for separation simultaneously water washing 3 times~6 times, gold-silica Janus structure nano particle solution is obtained, by gold-oxygen
SiClx Janus structure nano particle solution is dispersed in water, and obtains gold-silica Janus structure nano particle aqueous solution；
The described reaction system of golden nanometer particle containing double part claddings and the volume ratio of the tetraethyl orthosilicate aqueous solution is 1:
(0.1~1)；
The described reaction system of the golden nanometer particle coated containing double parts and the volume ratio of ammoniacal liquor is 1:(0.01~0.1)；
The volume ratio of described gold-silica Janus structure nano particles solution and water is 1:(1~10)；
3rd, under conditions of ultrasonic power is 100W~500W, by gold-silica Janus structure nano particles aqueous solution and second
Alcohol mixing and ultrasound 1min~30min, obtain gold-silica Janus structure nano particle ethanol waters, are then in rotating speed
Under 50rpm~400rpm, using the uviol lamp that power is 0.1W~1000W to gold-silica Janus structure nano particle ethanol
The aqueous solution is irradiated, irradiate 1min~1000min, ultrasonic power be 100W~500W under conditions of, by the gold after irradiation-
The silica Janus ultrasonically treated 1min~100min of structure nano particle ethanol water, are then centrifuged for separation simultaneously water washing 3 times
~6 times, be finally distributed to water it is standby in, obtain the gold with high catalysis characteristics-silica Janus structure nano particles；
Described uviol lamp is one or both of single wavelength and continuous wavelength in wavelength 200nm~400nm ultraviolet light
Combination；
The volume ratio of described gold-silica Janus structure nano particles aqueous solution and ethanol is 1:(1~20).
2. a kind of preparation of gold with high catalysis characteristics-silica Janus structure nano particles according to claim 1
Method, it is characterised in that the alcohols solvent described in step one is isopropanol, methanol or ethanol.
3. a kind of preparation of gold with high catalysis characteristics-silica Janus structure nano particles according to claim 1
Method, it is characterised in that the polyacrylic acid molecular weight described in step one is 1000Da~100000Da.
4. a kind of preparation of gold with high catalysis characteristics-silica Janus structure nano particles according to claim 1
Method, it is characterised in that mix particle diameter with water for 50 nanometers of golden nanometer particle in step one, it is 5.8 × 10 to obtain concentration- 4The mmol/L golden nanometer particle aqueous solution.
5. a kind of preparation of gold with high catalysis characteristics-silica Janus structure nano particles according to claim 1
Method, it is characterised in that in step one and then in the case where rotating speed is 50rpm~400rpm stirring conditions, by the A that concentration is 5mmol/L
Solution is added dropwise in reaction system with concentration for 0.645mmol/L B solution.
6. a kind of preparation of gold with high catalysis characteristics-silica Janus structure nano particles according to claim 1
Method, it is characterised in that in step 2 in the case where rotating speed is 20rpm~200rpm, to the golden nanometer particle coated containing double parts
The tetraethyl orthosilicate aqueous solution that concentration is 8.9mmol/L and the ammoniacal liquor that mass percent is 30%, stirring are added in reaction system
8h~24h.
7. the gold with high catalysis characteristics prepared by preparation method as claimed in claim 1-silica Janus structure nanos grain
The application of son, it is characterised in that the gold with high catalysis characteristics-silica Janus structure nano particles are used in organic reaction will
P-nitrophenol is reduced to para-aminophenol, and catalysis time is 6 minutes~8 minutes, and catalytic rate is up to 0.26min-1~
0.39min-1, it is specifically what is carried out according to the following steps：
For the p-nitrophenol aqueous solution and sodium borohydride aqueous solution are added dropwise into water, it is well mixed, being then added dropwise has high catalysis
The gold of the characteristic-silica Janus structure nano particle aqueous solution；
The described p-nitrophenol aqueous solution and the volume ratio of sodium borohydride aqueous solution are 1:1；Described p-nitrophenol is water-soluble
The concentration ratio of liquid and sodium borohydride aqueous solution is 1:100；The described p-nitrophenol aqueous solution and the volume ratio of water are 1:60；Institute
The volume of the p-nitrophenol aqueous solution stated and gold-silica Janus structure nano particle aqueous solution with high catalysis characteristics
Than for 1:2；The described p-nitrophenol aqueous solution and gold-silica Janus structure nano particle water with high catalysis characteristics
The concentration ratio of solution is 1:0.2.
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