CN106670497B - Temperature sensitive nano material and its preparation method and application - Google Patents
Temperature sensitive nano material and its preparation method and application Download PDFInfo
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- CN106670497B CN106670497B CN201510954811.XA CN201510954811A CN106670497B CN 106670497 B CN106670497 B CN 106670497B CN 201510954811 A CN201510954811 A CN 201510954811A CN 106670497 B CN106670497 B CN 106670497B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
- G01K11/14—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of inorganic materials
Abstract
The invention discloses a kind of temperature sensitive nano materials and its preparation method and application.The temperature sensitive nano material is mainly by gold nanorods coated with silver core-shell structure particles, can be under the conditions of set temperature by the oxidant of the silver-colored shell sections oxidation in the gold nanorods coated with silver core-shell structure particles, it can be under the conditions of set temperature by Ag+It restores and re-forms the reducing agent of the silver-colored shell in the gold nanorods coated with silver core-shell structure particles and dispersed system that at least one solvent is mixed to form.Temperature sensitive nano material provided by the invention can be used for recycling measuring temperature, and can determine whether temperature by observing its color, simplify using difficulty; its preparation process is simple simultaneously; it can be carried out in mild condition, such as atmospheric environment at room temperature, without high temperature and pressure, gas shield etc.; raw material is cheap and easy to get; it is safe and non-toxic, it is environmental-friendly, it is pollution-free; it is of low cost, it is suitable for large-scale use.
Description
Technical field
The present invention relates to a kind of temperature monitoring material, more particularly to a kind of temperature sensitive nano material and preparation method thereof
And application, belong to field of nanometer material technology.
Background technology
Since unique local of noble metal nano particles etc. is from primitive characteristic, in optical device, electrochemical device and urge
There is prodigious application prospect in the fields such as change.Composition metal nano particle is since various metals are in terms of promoting molecule absorption and activation
Synergistic effect make its show than monometallic update and diversification physicochemical properties, such as magnetism, superconductivity, shape remember
Recall effect, catalytic activity, hydrogen storage ability and temperature susceplibility etc..
Composition metal nano particle has different from the equal from primitive property of monometallic component.Such as in the outer of gold nanorods
Bread covers certain thickness silver-colored shell, can generate the equal from primitive resonance of four different modes, and show different formants.Altogether
Shake peak variation macro manifestations be colloidal solution color variation, may determine that GOLD FROM PLATING SOLUTION nanometer using chromogenic reaction in this way
The thickness of stick coated with silver nucleocapsid structure shell.
Nano material answering in terms of temperature sensing based on composite noble metal nanorod surfaces etc. from primitive resonant check
With a hot spot for being current field of nanometer material technology research.How gold nanorods coated with silver nuclear shell structured nano pimpled rubber is synthesized
Body, and be current when business from primitive characteristic using stronger surface of gold nanorods coated with silver nuclear shell structured nano structure etc.
It is anxious.There are some researchers to utilize gold nanorods coated with silver nuclear shell structured nano particle reaction system and temperature and time recently
Dependence, the composition metal nano particle temperature for being successfully realized the record to food storing situation, but wherein applying
Sensing technology, in temperature and time sensing is all disposable, not can be recycled.
Invention content
The main purpose of the present invention is to provide a kind of temperature sensitive nano material and its preparation method and application, with gram
Take the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of temperature sensitive nano material is provided in some embodiments, it is mainly to coat galactic nucleus by gold nanorods
Shell structure granules, can be under the conditions of set temperature by the silver-colored shell sections in the gold nanorods coated with silver core-shell structure particles
The oxidant of oxidation, can be under the conditions of set temperature by Ag+It restores and re-forms the gold nanorods coated with silver nucleocapsid knot
The dispersed system that the reducing agent and at least one solvent of silver-colored shell in structure particle are mixed to form.
Further, the oxidant includes peroxide, such as is preferably hydrogen peroxide.
Further, the reducing agent includes ascorbic acid.
Further, the set temperature condition refers to the condition that temperature range is room temperature to 46 DEG C, in the temperature range
Interior, with the raising of temperature, the color of the temperature sensitive nano material is changed into green by pink, and with temperature
It reduces, the color of the temperature sensitive nano material is changed into pink by green.
A kind of method preparing the temperature sensitive nano material is provided in some embodiments comprising：
The dispersion of gold nanorods coated with silver core-shell structure particles is provided,
The dispersion is fully reacted at room temperature after evenly mixing with reducing agent and oxidant, it is quick to obtain the temperature
The nano material of sense.
A kind of temperature sensitive applications to nanostructures is provided in some embodiments, such as in reagent preparation
Application in box, temperature monitoring device.
A kind of temperature sensing method is provided in some embodiments comprising：By the temperature sensitive nano material
In environment to be monitored, by observing the color change of the temperature sensitive nano material, and realize to environment temperature
Monitoring.
Compared with prior art, the present invention at least has the following advantages that：Utilize silver in gold nanorods coated with silver nucleocapsid structure
The thickness of shell can vary with temperature, and the growth of silver-colored shell also has the characteristic of cycling deposition in entire solution system,
A kind of temperature sensitive nano material can be used for recycling measuring temperature is proposed, and by observing the temperature sensitive nanometer
The color of material can determine whether temperature, simplify using difficulty, and the preparation process of the temperature sensitive nano material is simple,
It can be carried out in mild condition, such as atmospheric environment at room temperature, without high temperature and pressure, gas shield etc., raw material is inexpensively easy
, it is safe and non-toxic, it is environmental-friendly, it is pollution-free, it is of low cost, it is suitable for large-scale use.
Description of the drawings
Fig. 1 a are a kind of transmission electron microscope picture of the gold nanorods prepared using crystal seed growth method in the embodiment of the present invention 1；
Fig. 1 b are a kind of transmission electron microscope picture of gold nanorods coated with silver Core-shell Structure Nanoparticles in the embodiment of the present invention 1；
Fig. 2 a are that a kind of gold nanorods coated with silver Core-shell Structure Nanoparticles surface silver is aoxidized in the embodiment of the present invention 2
Transmission electron microscope picture；
A kind of transmission in Fig. 2 b embodiment of the present invention 1 in gold nanorods coated with silver Core-shell Structure Nanoparticles growth course
Electron microscope；
Fig. 3 is in the embodiment of the present invention 3 in different environment temperatures, and a kind of the ultraviolet of temperature sensitive nano material can
The most peak position at strong resonance peak is with temperature almost linear variation diagram in light-exposed spectrum；
Fig. 4 a are a kind of uv-vis spectra that temperature sensitive nano material changes over time in the embodiment of the present invention 3
Figure；
Fig. 4 b are the most strong resonance in a kind of ultravioletvisible absorption of temperature sensitive nano material in the embodiment of the present invention 3
The circulation change figure of peak at any time.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution will be described in more detail as follows.
A kind of temperature sensitive nano material is provided in one embodiment of the present of invention (it is quick to be also regarded as a kind of temperature
Feel liquid), it be mainly by gold nanorods coated with silver core-shell structure particles, can be under the conditions of set temperature by the gold nano
The oxidant of silver-colored shell sections oxidation in stick coated with silver core-shell structure particles, can be under the conditions of set temperature by Ag+Reduction
And the reducing agent of the silver-colored shell in the gold nanorods coated with silver core-shell structure particles is re-formed, and at least one solvent is mixed
Close the dispersed system formed.In some embodiments, the oxidant may be selected from but not limited to peroxide, such as can
Preferably hydrogen peroxide.
In some embodiments, the reducing agent may be selected from but not limited to ascorbic acid.
In some embodiments, the molar ratio of the gold nanorods coated with silver core-shell structure particles and oxidant is preferably
0.5×10-8:1~3.17 × 10-8:1。
In some embodiments, the molar ratio of the oxidant and reducing agent is 6:1~30:1.
In some embodiments, the initial concentration of oxidant is preferably in the temperature sensitive nano material
0.0315mol/L~0.158mol/L.
In some embodiments, the length of gold nanorods is preferably in the gold nanorods coated with silver core-shell structure particles
60~120nm, diameter are preferably 10~40nm, and draw ratio is preferably 2~4；
And/or the thickness of silver-colored shell is preferably 5~10nm in the gold nanorods coated with silver core-shell structure particles.
In some embodiments, the set temperature condition refers to the condition that temperature range is room temperature to 46 DEG C, at this
In temperature range, with the raising of temperature, the color of the temperature sensitive nano material is changed into green by pink, and with
The reduction of temperature, the color of the temperature sensitive nano material is changed into pink by green.
In some embodiments, the solvent is preferably from water, but can also be the mixing of water and other secondary solvents
Object.
In some embodiments, the temperature sensitive nano material also may include surfactant (such as hexadecane
Base trimethyl ammonium chloride CTAC), alkaline matter (such as NaOH) etc..
A kind of method preparing the temperature sensitive nano material is provided in one embodiment of the present of invention, is wrapped
It includes：
The dispersion of gold nanorods coated with silver core-shell structure particles is provided,
The dispersion is fully reacted at room temperature after evenly mixing with reducing agent and oxidant, it is quick to obtain the temperature
The nano material of sense.
In some embodiments, the preparation method includes：The greeny dispersion and oxidant is uniform
It is stood at room temperature after mixing, until mixed liquor is changed into pink by green, obtains the temperature sensitive nano material.
In some more specific embodiment, the preparation method includes：
It is prepared using cetyl trimethylammonium bromide as the gold nanorods colloidal solution of stabilizer using crystal seed method；
The cetyl trimethyl bromination in the gold nanorods colloidal solution is substituted with hexadecyltrimethylammonium chloride
Ammonium adds soluble silver salt and reducing agent, fully obtains the gold nanorods coated with silver core-shell structure particles after reaction.
Further, the soluble silver salt is preferably silver nitrate, but not limited to this.
Further, the reducing agent is preferably ascorbic acid, but not limited to this.
In one more specifically case study on implementation, the preparation method can specifically include following steps：
(1) using cetyl trimethylammonium bromide as stabilizer, gold nanorods are prepared using crystal seed method；
(2) gold nanorods prepared are washed with the centrifugation of the speed of 3000~4000g twice, it is extra in growth-promoting media to remove
Ingredient finally concentrates about 5~10 times, and gold nanorods are dispersed in the hexadecyltrimethylammonium chloride solution of concentration about 0.1M
In；
(3) solution of the gold nanorods of above-mentioned concentration is taken, the hexadecane of concentration about 0.2M is sequentially added after about 100 times of dilution
Base trimethyl ammonium chloride, the silver nitrate and concentration about 0.1M ascorbic acid of concentration about 0.01M, is then heated to 45~60 DEG C
It is kept for 4~5 hours, gold nanorods solution, silver nitrate solution and ascorbic acid solution volume ratio are 2:2:1；
(4) hydrogen peroxide of mass fraction about 30%, mixed solution and hydrogen peroxide are added into step (3) obtained mixed solution
Volume ratio be about 50:1.Then by whole system it is packaged after, wait for the color of solution to become pink by green, in this way it
After solution is placed on different temperatures afterwards, solution can show different colours, and with gradually rising for temperature, solution colour is gradually by powder
Red becomes green.
A kind of kit is provided in one embodiment of the present of invention comprising the temperature sensitive nano material.
A kind of temperature monitoring device is provided in one embodiment of the present of invention comprising the temperature sensitive nanometer
Material.
A kind of temperature sensing method is provided in one embodiment of the present of invention comprising：It will be described temperature sensitive
Nano material, the kit or the temperature monitoring device are set in environment to be monitored, by observing the temperature
The color change of sensitive nano material, and realize the monitoring to environment temperature.
A kind of temperature sensitive nano material provided by the invention can be considered as gold nanorods coated with silver nuclear shell structured nano
The mixed solution of particle, oxidant (such as hydrogen peroxide) and reducing agent (such as ascorbic acid), at room temperature this GOLD FROM PLATING SOLUTION receive
Rice stick shell silver is aoxidized, oxidant in solution, reducing agent and Ag+Certain stabilising system is formed, after temperature rise, solution
In Ag+It being reduced and is coated on gold nanorods, and under condition of different temperatures, gold nanorods surface silver shell thickness is different,
So that the position from resonance absorbing peak such as golden coated with silver core-shell particles surface is different, macro manifestations are mixed solution in different rings
Different colours are shown in the temperature of border；When the temperature of environment is restored to room temperature, gold nanorods surface silver shell is aoxidized, solution
Color restPoses.Therefore, measuring temperature can be recycled using the temperature sensitive nano material system, and by molten
The color of liquid judges temperature, simplifies using difficulty.
The present invention utilizes in gold nanorods coated with silver nucleocapsid structure, and the thickness of silver-colored shell can vary with temperature and whole
Also the characteristic with cycling deposition, proposition can be used for recycling the temperature of measuring temperature for the growth of silver-colored shell in a solution system
Sensitive nano material, application process is simple, and testing result is intuitive, meanwhile, preparation process is simple, mild condition, in room
It can be carried out in atmospheric environment under temperature, be not necessarily to high temperature and pressure, gas shield etc., while activity can be used mild, nontoxic
Ascorbic acid need not use the very strong reducing agent of reproducibility, and common hydrogen peroxide can be used as oxygen as reducing agent
Agent, it is environmental-friendly in whole preparation process, it is pollution-free, it is of low cost, it is suitable for large-scale use.
Technical scheme of the present invention is further described below in conjunction with several embodiments and attached drawing.
Embodiment 1：
(1) bibliography (such as J.AM.CHEM.SOC.2010,132,4806-4814) is prepared using crystal seed growth method
The transmission electron microscope picture of gold nanorods, pattern is as shown in Figure 1a；
(2) take the gold nanorods that the cetyl trimethylammonium bromide that crystal seed method is grown in 10mL steps (1) is stablized (longitudinal
Plasmon absorption wavelength is 730nm), 4000g, centrifugation in 25 minutes is twice.Then the hexadecane of a concentration of 0.1M of 0.87mL is added
Base trimethyl ammonium chloride aqueous dispersion；
(3) gold nanorods after taking 0.1mL to concentrate, add the hexadecyltrimethylammonium chloride of a concentration of 0.2M of 1mL to disperse,
And 8.54mL ultra-pure waters are added.Then the silver nitrate aqueous solution 0.1mL of a concentration of 0.01M is added, is eventually adding a concentration of 0.1M
Aqueous ascorbic acid 0.0525mL.The temperature of solution is heated to 45-60 DEG C to be kept for 4-5 hours, obtains green solution, i.e.,
Gold nanorods coated with silver nuclear shell structured nano particle colloid.At the end of gold nanorods coated with silver nuclear shell structured nano granular grows
Transmission electron microscope picture it is as shown in Figure 1 b.Fig. 2 b are the transmission in gold nanorods coated with silver nuclear shell structured nano particle growth process
Electron microscopic picture.
Embodiment 2：
(1) gold nanorods coated with silver nuclear shell structured nano particle and hydrogen peroxide colloid mixture green solution 1mL are taken, is added
The hydrogen peroxide solution that 0.02mL mass fractions are 30%.
(2) mixed solution is placed under room temperature (20 DEG C~25 DEG C) environment, is stood after a certain period of time, the color of solution is gradual
Become pink from green, i.e., (transmission electron microscope picture is such as by oxidation for gold nanorods coated with silver nuclear shell structured nano particle surface silver
Shown in Fig. 2 a).
(3) above-mentioned pink solution is placed in different temperature, after a period of time it is observed that in different temperature
Under solution show different colours, as temperature is increased to 46 DEG C or so from room temperature, the color of solution gradually becomes from pink
Bottle green.As shown in figure 3, mixed solution is placed in different environment temperatures, most strong resonance in the uv-vis spectra of solution
The peak position at peak changes with temperature almost linear.
Embodiment 3：
(1) gold nanorods coated with silver nuclear shell structured nano particle and hydrogen peroxide mixed colloidal solution are in a certain environment temperature
After middle stabilization, bottle green no longer changes.It, can be apparent after a period of time by temperature chromophoric solution being placed in room temperature again
The color of solution is observed by green before and changes back to pink.
(2) after the temperature of solution returns to room temperature, the color of solution also return before pink.Then again by the solution
Be placed in different temperature environments, after a certain period of time, the color of solution changes back to green, and different temperature again, display from
Light green color is to bottle-green different colours.
(3) when this solution returns once again to room temperature, the color of solution also return before pink.This solution is repeated
(2) experiment in 3 times, all obtains identical result.It can see on ultraviolet-visible spectrogram as shown in Figs. 4 a-b, this is molten
Liquid repeatedly uses, the most strong resonance peak position circulation change in the ultravioletvisible absorption of solution, and wherein Fig. 4 a are at any time
The ultraviolet-visible spectrogram of variation, Fig. 4 b are the circulation change of most strong resonance peak at any time in the ultravioletvisible absorption of solution
Figure.
In conclusion using the method for the present invention, it can be under the conditions of environmental-friendly, comparatively gentle, with simple controllable
Operation synthesizes gold nanorods coated with silver nuclear shell structured nano particle.Obtained gold nanorods coated with silver nucleocapsid structure is synthesized to receive
Rice grain and the mixed solution of hydrogen peroxide composition have good temperature sensing performance, and have the characteristics that be recycled for multiple times.Most
It is important that cost is relatively low compared with the existing technology, it is very easy to be widely popularized and industrialization production.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, it is all within the thought and principle of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of temperature sensitive nano material, it is characterised in that it be mainly by gold nanorods coated with silver core-shell structure particles,
It can be under the conditions of set temperature by the oxidation of the silver-colored shell sections oxidation in the gold nanorods coated with silver core-shell structure particles
Agent, can be under the conditions of set temperature by Ag+It restores and re-forms in the gold nanorods coated with silver core-shell structure particles
The dispersed system that the reducing agent of silver-colored shell and at least one solvent are mixed to form.
2. temperature sensitive nano material according to claim 1, it is characterised in that：The oxidant includes peroxidating
Object, the peroxide include hydrogen peroxide；And/or the reducing agent includes ascorbic acid；And/or the solvent includes
Water.
3. temperature sensitive nano material according to claim 1, it is characterised in that：
The molar ratio of the gold nanorods coated with silver core-shell structure particles and oxidant is 0.5 × 10-8:1~3.17 × 10-8:1；
And/or the molar ratio of the oxidant and reducing agent is 6:1~30:1；
And/or in the dispersed system oxidant initial concentration ranging from 0.0315mol/L~0.158mol/L；
And/or in the gold nanorods coated with silver core-shell structure particles gold nanorods length be 60~120nm, a diameter of 10
~40nm, draw ratio are 2~4；
And/or the thickness of silver-colored shell is 5~10nm in the gold nanorods coated with silver core-shell structure particles.
4. temperature sensitive nano material according to claim 1, it is characterised in that：The set temperature condition refers to temperature
The condition of degree ranging from room temperature to 46 DEG C, within this temperature range, with the raising of temperature, the temperature sensitive nano material
Color green is changed by pink, and with the reduction of temperature, the color of the temperature sensitive nano material is by green
It is changed into pink.
5. the preparation method of temperature sensitive nano material as described in any one of claim 1-4, it is characterised in that including：
The dispersion of gold nanorods coated with silver core-shell structure particles is provided,
The dispersion is fully reacted at room temperature after evenly mixing with reducing agent and oxidant, is obtained described temperature sensitive
Nano material.
6. preparation method according to claim 5, it is characterised in that including：By the greeny dispersion and oxidant
It stands at room temperature after evenly mixing, until mixed liquor is changed into pink by green, obtains the temperature sensitive nano material.
7. preparation method according to claim 5, it is characterised in that including：
It is prepared using cetyl trimethylammonium bromide as the gold nanorods colloidal solution of stabilizer using crystal seed method；
The cetyl trimethylammonium bromide in the gold nanorods colloidal solution is substituted with hexadecyltrimethylammonium chloride, then
Soluble silver salt and reducing agent is added, fully obtains the gold nanorods coated with silver core-shell structure particles after reaction.
8. preparation method according to claim 7, it is characterised in that：The soluble silver salt includes silver nitrate；And/or
The reducing agent includes ascorbic acid.
9. a kind of kit or temperature monitoring device, it is characterised in that quick including the temperature described in any one of claim 1-4
The nano material of sense.
10. a kind of temperature sensing method, it is characterised in that including：It will be temperature sensitive described in any one of claim 1-4
Kit or temperature monitoring device described in nano material or claim 9 are set in environment to be monitored, described in observation
The color change of temperature sensitive nano material, and realize the monitoring to environment temperature.
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| CN104759617A (en) * | 2015-04-02 | 2015-07-08 | 东华大学 | Light/temperature double responsiveness hybrid microgel of silver-loaded nanoparticles and preparation method thereof |
| CN104826656A (en) * | 2015-04-30 | 2015-08-12 | 天津大学 | Temperature sensitive graphene-based gold-platinum core-shell bimetallic catalyst and preparation method thereof |
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|---|---|---|---|---|
| JPH11140436A (en) * | 1997-11-07 | 1999-05-25 | Matsushita Electric Ind Co Ltd | Heat-sensitive coloring material and its production |
| CN101130883A (en) * | 2006-08-22 | 2008-02-27 | 国家纳米科学中心 | Rectangular bimetallic nano rod with gold nucleus and palladium shell and method for making the same |
| US8033715B2 (en) * | 2007-11-08 | 2011-10-11 | Illinois Institute Of Technology | Nanoparticle based thermal history indicators |
| CN102286185A (en) * | 2011-06-29 | 2011-12-21 | 天津大学 | Temperature sensitive composite gold nano particles and preparation method and catalytic application thereof |
| CN104007080A (en) * | 2014-06-13 | 2014-08-27 | 福州大学 | Alkaline phosphatase analytical method based on long gold nanorod silver shell |
| CN104759617A (en) * | 2015-04-02 | 2015-07-08 | 东华大学 | Light/temperature double responsiveness hybrid microgel of silver-loaded nanoparticles and preparation method thereof |
| CN104826656A (en) * | 2015-04-30 | 2015-08-12 | 天津大学 | Temperature sensitive graphene-based gold-platinum core-shell bimetallic catalyst and preparation method thereof |
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