CN106735295B - A kind of two-dimensional layer Au nanometer sheet material and preparation method thereof - Google Patents
A kind of two-dimensional layer Au nanometer sheet material and preparation method thereof Download PDFInfo
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- CN106735295B CN106735295B CN201611140572.5A CN201611140572A CN106735295B CN 106735295 B CN106735295 B CN 106735295B CN 201611140572 A CN201611140572 A CN 201611140572A CN 106735295 B CN106735295 B CN 106735295B
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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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0551—Flake form nanoparticles
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
Abstract
The present invention provides a kind of two-dimensional layer Au nanometer sheet materials and preparation method thereof, include the following steps：Silicon wafer is immersed in sodium citrate ethyl alcohol colloidal sol, the silicon substrate with sodium citrate film is obtained by the method for liquid deposition；The silicon substrate with sodium citrate film is reacted with the ethanol solution of gold chloride, after reaction, silicon substrate and Au nanometer sheet are separated, two-dimensional layer Au nanometer sheet material can be obtained.The preparation method of two-dimensional layer Au nanometer sheet material provided herein, pass through liquid phase deposition, obtain sodium citrate film, and gold chloride is restored in this film surface, Au nanometer sheet is prepared, there is many advantages, such as simple process, single step reaction is completed, reaction temperature is low, reaction condition is simple, at low cost.The advantages that prepared two-dimensional layer Au nanometer sheet, active strong, good dispersion, thickness uniformly, easily shift, size and shape are controllable, size range can cover nanometer to Centimeter Level.
Description
Technical field
The present invention relates to nano metal materials to prepare manufacturing technology field, receives in particular to a kind of two-dimensional layer Au
Rice sheet material and preparation method thereof.
Background technique
Au is considered chemical property stabilization within a very long time, lacks catalytic activity, and has good anti-oxidant
Property and corrosion resistance, be often used to make various jewellery and artwork Ornament, it is deep to be liked by people.But when the size of Au reduces
When to Nano grade, many novel physicochemical characteristics that stock size can not show can be showed.Such as：Nanometer Au particle exists
There is very high catalytic activity under low temperature, surface Raman scattered signal etc. can greatly be enhanced.Therefore research Au nano material
Preparation method, and how simply and effectively to control the size and pattern etc. of its growth, have important practical significance and answer
With value.
It is a kind of side commonly used at present using reduction of sodium citrate gold chloride in existing Au nano material preparation process
Method.This method has process simple, at low cost, generates the advantages that Au granular mass is good.However, directly utilizing reduction of sodium citrate
Gold chloride, obtained product is Au nano particle, rather than Au nanometer sheet.And utilizing dimethyl sulfoxide is reducing agent, although can
Small size Au nanometer sheet is prepared, but preparation process needs to be added a large amount of dispersing agent and stabilizer, is prepared into simultaneously
This also increased compared with reduction of sodium citrate method.The addition of dispersing agent and stabilizer is bound to so that subsequent removal, purification process become
Obtain sufficiently complex, these dispersing agents and the remaining catalytic activity that will also largely effect on generation Au nano material of stabilizer, optics
Performance etc..Sastry et al. (Ambarish Sanyal and Murali Sastry, Gold nanosheets via
reduction of aqueous chloroaurate ions by anthracene anions bound to a
Liquid-liquid interface, Chem.Commun., 11 (2003) 1236) utilize the chloroform reduction chlorine gold containing anthracene
A kind of mixture of nanometer sheet containing Au has been prepared in acid, and this method uses 4 hours of ultraviolet light, and preparation efficiency is low and makes
Standby process is complicated, and obtained product is mixture, and the content of Au nanometer sheet is not high.Ekgasit et al. (Supeera
Nootchanat,Chuchaat Thammacharoen,Boonrat Lohwongwatana and Sanong Ekgasit,
Formation of large H2O2-reduced gold nanosheets via starch-induced two-
Dimensional oriented attachment, RSC Adv., 3 (2013) 3707) utilize hydrogen peroxide (H2O2) and hydroboration
Sodium (NaBH4) it is used as reducing agent, starch is stabilizer, and gold chloride provides Jin Yuan, the Au nanometer sheet of large area has been prepared, but
It is that this method equally has the shortcomings that preparation flow is complicated, preparation efficiency is low, needs to add stabilizer.
In addition, the preparation process of Au nanometer sheet requires hot environment in the prior art, usual reaction temperature will reach 90
DEG C, or even be heated to boil.However, pyroreaction condition is one of the principal element for causing nanoparticle to be reunited, it should as far as possible
It avoids.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of two-dimensional layer Au nanometer sheet material, existing to solve
In the method for preparing nanometer Au material, preparation flow is complicated, preparation efficiency is low, need to add stabilizer or reaction temperature is excessively high
The disadvantages of, the preparation method of the two-dimensional layer Au nanometer sheet material obtains sodium citrate film by liquid phase deposition,
And two-dimensional layer Au nanometer sheet is prepared in this film surface reduction gold chloride, there is simple process, single step reaction to complete, is anti-
Answer that temperature is low, reaction condition is simple, at low cost, easy transfer, does not need addition stabilizer and many advantages, such as protective agent.
The preparation method that the second object of the present invention is to provide two-dimensional layer Au nanometer sheet material described in one kind is made
Standby two-dimensional layer Au nanometer sheet material, this method two-dimensional layer Au nanometer sheet material, active strong, good dispersion, thickness
Uniformly, the advantages that size and shape are controllable, size range can cover nanometer to the two-dimensional layer Au nanometer sheet of Centimeter Level.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of preparation method of two-dimensional layer Au nanometer sheet material, includes the following steps：
Silicon wafer is immersed in sodium citrate ethyl alcohol colloidal sol, sodium citrate film is obtained by the method for liquid deposition
Silicon substrate；
The silicon substrate for having sodium citrate film is reacted with the ethanol solution of gold chloride, after reaction, silicon is served as a contrast
Bottom and Au nanometer sheet are separated, and two-dimensional layer Au nanometer sheet material can be obtained.
The preparation method of two-dimensional layer Au nanometer sheet material provided herein, using sodium citrate as reducing agent,
It can simplify process, preparation cost be effectively reduced.For other opposite reducing agents, ethyl alcohol has lower surface tension and pole
Property, while ethyl alcohol has lower fusing point (- 114 DEG C) relative to water, is a kind of excellent organic dispersing agent.Also, use second
Alcohol prepares Au nanometer sheet as solvent, can be the case where not adding protective agent and stabilizer, and low temperature environment, which is prepared, to be had
Dispersed two-dimensional layer Au nanometer sheet high, activity is strong, size is controllable.It therefore is precursor liquid using sodium citrate ethyl alcohol colloidal sol,
Sodium citrate film is prepared by liquid deposition, the film surface restore gold chloride, may be implemented do not add it is any
Under the premise of protective agent and stabilizer, low temperature synthesis has the two-dimensional layer Au nanometer sheet that dispersibility is high, activity is strong.Meanwhile because
It can be effectively controlled by related physical, chemical parameters during adjusting liquid deposition for the size of sodium citrate film,
So the also available effective regulation of the size for the two-dimensional layer Au nanometer sheet being prepared.This method have simple process,
Single step reaction complete, reaction temperature is low, reaction condition is simple, it is at low cost, do not need addition stabilizer and protective agent etc. it is many excellent
Point.
Preferably, the preparation method of the sodium citrate ethyl alcohol colloidal sol, specifically includes following steps：
It will be dissolved in the water under trisodium citrate dihydrate heating condition, after mixing evenly, obtain the water-soluble of sodium citrate
Liquid；, the aqueous solution of sodium citrate is instilled in dehydrated alcohol under the revolving speed greater than 1000rpm, it is molten to obtain sodium citrate ethyl alcohol
Sol solution；Sodium citrate ethyl alcohol sol solution is subjected to centrifugal treating, sodium citrate ethyl alcohol colloidal sol is obtained after centrifugation；
It is furthermore preferred that the temperature of the heating is 45~60 DEG C；
It is furthermore preferred that the time of the stirring is 15~25 minutes；
It is furthermore preferred that the mass concentration of the aqueous solution of the sodium citrate is 60%~70%, even more preferably, institute
The volume ratio of the aqueous solution and the dehydrated alcohol of stating sodium citrate is 1：(200~500).
The preparation of sodium citrate ethyl alcohol colloidal sol is the presoma of the sodium citrate film of silicon substrate, in stirring at a high speed, acutely
It mixes down, the aqueous solution of sodium citrate is added drop-wise in dehydrated alcohol with dropper.Generally, sodium citrate is configured in a heated state
At aqueous solution, 60%~70%, which ensure that in preparation process mass concentration, the stabilization of sodium citrate ethyl alcohol colloidal sol
Property.Preferably, within the scope of above-mentioned mass concentration, the aqueous solution of sodium citrate and the volume ratio of dehydrated alcohol are 1：(200~
500), in about every 100mL dehydrated alcohol, the aqueous solution of 0.2~0.5mL sodium citrate is added dropwise, according to the dropper of 3mL, about 8~
12 drops.The time stirred in preparation process is 15~25 minutes, and the aqueous solution for being conducive to sodium citrate uniformly divides in dehydrated alcohol
It dissipates, forms stable sodium citrate ethyl alcohol colloidal sol.In addition, because sodium citrate is dissolved in water, the lemon being prepared
When sour sodium ethyl alcohol colloidal sol, using dehydrated alcohol, market purchase is 95% alcoholic solution, uses prior art preparation to be anhydrous
Ethyl alcohol.
Preferably, the process of the centrifugation, specifically includes following steps：
The sodium citrate ethyl alcohol sol solution is centrifuged 10~14 minutes under 6000~8000rpm revolving speed, after filtering
Precipitating is dispersed in dehydrated alcohol, then is centrifuged 10~14 minutes under 4000~5000rpm revolving speed, isolated sodium citrate
Ethyl alcohol colloidal sol.
The size for the sodium citrate sol particle being prepared can be regulated and controled by the revolving speed of control centrifugation.It is different twice
After the centrifugal treating of revolving speed, filtering, the unprecipitated sodium citrate ethyl alcohol colloidal sol of the milky extracted.
Preferably, the cleaning method of the silicon wafer, specifically includes following steps：
After silicon wafer is first used the concentrated sulfuric acid-hydrogen peroxide system digestion at 100~120 DEG C, then ammonia is used at 30~80 DEG C
Water-hydrogen peroxide system digestion, is finally cleaned by ultrasonic with acetone, the silicon wafer after being cleaned；
It is furthermore preferred that the time of the digestion is 10~20 minutes twice.
Silicon wafer is adequately cleaned, it is uniformly complete with the sodium citrate film for guaranteeing that it is formed above, and then guarantee
Obtained Au piece property is complete, thickness is uniform, good dispersion.The concentrated sulfuric acid-hydrogen peroxide cleans silicon wafer, to solve silicon wafer table
The remaining organic impurities in face (mainly being brought by cutting fluid and home roll).Ammonium hydroxide be in order to eliminate the impurity of silicon wafer and cutting abrasive material,
Hydrogen peroxide is in order to which the nubbin of cutting fluid is rinsed well, and acetone can help its volatilization.
Preferably, the time of the immersion is 10~14 hours.
The process of immersion is the principle using liquid deposition.Show to form sodium citrate film in silicon wafer.Because of citric acid
Sodium is dissolved in water, so the sodium citrate film being prepared will avoid contacting with water, using ethyl alcohol as solution, destroys film
Integrality.
Preferably, the mass concentration of the ethanol solution of the gold chloride is 0.20~0.25%.
In the application, reacted using gold chloride in sodium citrate film, and then obtain the Au piece of specific shape.Chlorine gold
The concentration of acid embodies the effective ion quantity that interface participates in reaction, controls the concentration of gold chloride, can effectively control reaction
Speed, obtains that thickness is uniform, the complete Au nanometer sheet of shape.
Preferably, the temperature of the reaction is 20~50 DEG C, and the time of reaction is 4~12 hours；
It is furthermore preferred that the temperature of the reaction is 25~40 DEG C, the time of reaction is 6~8 hours；
It is further preferred that the temperature of the reaction is 25~30 DEG C, the time of reaction is 5~6 hours.
The preparation method of two-dimensional layer Au nanometer sheet material provided herein, the requirement of reaction temperature condition is not harsh,
30 DEG C or so can react, and the reaction time is short, are suitble to produce in enormous quantities and be widely applied.
Preferably, described separation is carried out to silicon substrate and Au nanometer sheet to be operated using the method for ultrasonic vibration, it is more excellent
Choosing, the time of the ultrasonic vibration is 1~5 minute, and the time of the further preferred ultrasonic vibration is 2~3 minutes.
Ultrasonic vibration sinks to the bottom Au nanometer sheet with silicon to separate, do not destroy the integrality of Au nanometer sheet.
Two-dimensional layer Au nanometer sheet material prepared by the preparation method of two-dimensional layer Au nanometer sheet material as described above.
Preferably, the two-dimensional layer Au nanometer sheet material is the side N shape, wherein N >=3.
Prepared two-dimensional layer Au nanometer sheet material, with good dispersion, thickness is uniform, size and shape are controllable etc.
Advantage, size range cover nanometer to micron-sized two-dimensional layer Au nanometer sheet.It is more to be often made as triangle, hexagon etc.
Side shape, controlled shape, size are controllable.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of two-dimensional layer Au nanometer sheet material provided herein obtains lemon by liquid phase deposition
Lemon acid sodium film, and two-dimensional layer Au nanometer sheet is prepared in this film surface reduction gold chloride, there is simple process, a step
Many advantages, such as reaction is completed, reaction temperature is low, reaction condition is simple, at low cost.
(2) preparation method of two-dimensional layer Au nanometer sheet material provided herein, using sodium citrate as reduction
Agent can simplify preparation process, preparation cost is effectively reduced, do not add protective agent and stabilizer.
(3) Au nanometers of two-dimensional layer prepared by the preparation method of two-dimensional layer Au nanometer sheet material provided herein
The advantages that sheet material, active strong, good dispersion, thickness are uniformly, size and shape are controllable, size range covers nanometer
To the two-dimensional layer Au nanometer sheet of Centimeter Level.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the method flow diagram provided by the embodiments of the present application for preparing two-dimensional layer Au nanometer sheet；
Fig. 2 is polygon Au nanometer sheet TEM photo provided by the embodiment of the present application 1；
Fig. 3 is polygon Au nanometer sheet TEM photo provided by the embodiment of the present application 2；
Fig. 4 is hexagon Au nanometer sheet TEM photo provided by the embodiment of the present application 3；
Fig. 5 is triangle Au nanometer sheet TEM photo provided by the embodiment of the present application 4；
Fig. 6 is the TEM diffractional lattice of triangle Au nanometer sheet monocrystalline provided by the embodiment of the present application.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
Fig. 1 is the flow chart of Au nanometers of piece preparation methods of two-dimensional layer provided by the embodiment of the present application 1-4, specific implementation
Example method is as shown in embodiment 1-4.
Embodiment 1
The method of the Au nanometer sheet for preparing polygon provided herein, specifically includes following steps：
(1), sodium citrate colloidal sol is prepared
(a), under the conditions of 50 DEG C, by 40g (Na3C6H5O7·2H2O) it is dissolved in 20mL aqueous solution that (mass percent is
66.7%) it, is sufficiently stirred after twenty minutes, obtains sodium citrate aqueous solution, it is spare；
(b), 100mL dehydrated alcohol is prepared with beaker, is vigorously stirred with magnetic stirring apparatus, low whipping speed is greater than
Under the conditions of 1000rpm, instill about 8 drop (0.2ml) the step of (a) in sodium citrate aqueous solution, sodium citrate second is prepared
Alcosol solution, is repeated 2 times, and obtains amounting to 200ml sodium citrate ethyl alcohol sol solution；
(c), the 200ml sodium citrate ethyl alcohol sol solution in step (b) is passed through into centrifugal treating, first turned in 6000rpm
Speed lower centrifugation 12 minute, precipitating is dispersed in dehydrated alcohol after filtering, then is centrifuged 12 minutes under 4000rpm revolving speed, is filtered,
Obtain milky sodium citrate ethyl alcohol colloidal sol.
(2), sodium citrate film is prepared
(d), polygon silicon wafer is taken, after silicon wafer is first used the concentrated sulfuric acid-hydrogen peroxide system digestion 15 minutes at 120 DEG C, then
Ammonium hydroxide-hydrogen peroxide system digestion 15 minutes is used at 30 DEG C, is finally cleaned by ultrasonic with acetone, the silicon after being cleaned
Piece；
(e), it by the silicon wafer after cleaning in step (d), is immersed in sodium citrate ethyl alcohol colloidal sol obtained in step (1),
It is standing and soaking 12 hours, obtains the silicon substrate with sodium citrate film.
(3), Au nanometer sheet is prepared
(f), by HAuCl4·4H2O is dissolved in dehydrated alcohol, prepares the chlorauric acid solution that mass percent is 0.21%：
(g), the silicon substrate that sodium citrate film is had obtained in step (2) is placed in the gold chloride of step (f) preparation
It is reacted at 30 DEG C in solution 6 hours, after reaction, silicon is sunk to the bottom as in ethanol solution, ultrasonic vibration 1 minute, that is, is existed
Polygon Au nanometer sheet material is obtained in ethanol solution.
Embodiment 2
The method of the Au nanometer sheet for preparing polygon provided herein, specifically includes following steps：
(1), sodium citrate colloidal sol is prepared
(a), under the conditions of 45 DEG C, by Na3C6H5O7·2H2O is dissolved in 20mL aqueous solution, after being sufficiently stirred 15 minutes,
The sodium citrate aqueous solution that mass percent is 60% is prepared, it is spare；
(b), 100mL dehydrated alcohol is prepared with beaker, is vigorously stirred with magnetic stirring apparatus, low whipping speed is greater than
Under the conditions of 1000rpm, instill about 12 drop (0.5ml) the step of (a) in sodium citrate aqueous solution, sodium citrate second is prepared
Alcosol solution, is repeated 2 times, and obtains amounting to 200ml sodium citrate ethyl alcohol sol solution；
(c), the 200ml sodium citrate ethyl alcohol sol solution in step (b) is passed through into centrifugal treating, first turned in 8000rpm
Speed lower centrifugation 10 minute, precipitating is dispersed in dehydrated alcohol after filtering, then is centrifuged 10 minutes under 5000rpm revolving speed, is filtered,
Obtain milky sodium citrate ethyl alcohol colloidal sol.
(2), sodium citrate film is prepared
(d), polygon silicon wafer is taken, silicon wafer is first used into the concentrated sulfuric acid-hydrogen peroxide system digestion after twenty minutes at 100 DEG C, then
Ammonium hydroxide-hydrogen peroxide system digestion 10 minutes is used at 80 DEG C, is finally cleaned by ultrasonic with acetone, the silicon after being cleaned
Piece；
(e), it by the silicon wafer after cleaning in step (d), is immersed in sodium citrate ethyl alcohol colloidal sol obtained in step (1),
It is standing and soaking 14 hours, obtains the silicon substrate with sodium citrate film.
(3), Au nanometer sheet is prepared
(f), by HAuCl4·4H2O is dissolved in dehydrated alcohol, prepares the chlorauric acid solution that mass percent is 0.20%：
(g), the silicon substrate that sodium citrate film is had obtained in step (2) is placed in the gold chloride of step (f) preparation
It is reacted at 20 DEG C in solution 12 hours, after reaction, silicon is sunk to the bottom as in ethanol solution, ultrasonic vibration 3 minutes, that is, is existed
Polygon Au nanometer sheet material is obtained in ethanol solution.
Embodiment 3
The method of the Au nanometer sheet for preparing hexagon provided herein, specifically includes following steps：
(1), sodium citrate colloidal sol is prepared
(a), under the conditions of 60 DEG C, by Na3C6H5O7·2H2O is dissolved in 20mL aqueous solution, after being sufficiently stirred 25 minutes,
The sodium citrate aqueous solution that mass percent is 70% is prepared, it is spare；
(b), 100mL dehydrated alcohol is prepared with beaker, is vigorously stirred with magnetic stirring apparatus, low whipping speed is greater than
Under the conditions of 1000rpm, instill about 10 drop (0.3ml) the step of (a) in sodium citrate aqueous solution, sodium citrate second is prepared
Alcosol solution, is repeated 2 times, and obtains amounting to 200ml sodium citrate ethyl alcohol sol solution；
(c), the 200ml sodium citrate ethyl alcohol sol solution in step (b) is passed through into centrifugal treating, first turned in 6000rpm
Speed lower centrifugation 10 minute, precipitating is dispersed in dehydrated alcohol after filtering, then is centrifuged 10 minutes under 4000rpm revolving speed, is filtered,
Obtain milky sodium citrate ethyl alcohol colloidal sol.
(2), sodium citrate film is prepared
(d), hexagon silicon wafer is taken, silicon wafer is first used into the concentrated sulfuric acid-hydrogen peroxide system digestion after ten minutes at 120 DEG C, then
Ammonium hydroxide-hydrogen peroxide system digestion 20 minutes is used at 50 DEG C, is finally cleaned by ultrasonic with acetone, the silicon after being cleaned
Piece；
(e), it by the silicon wafer after cleaning in step (d), is immersed in sodium citrate ethyl alcohol colloidal sol obtained in step (1),
It is standing and soaking 10 hours, obtains the silicon substrate with sodium citrate film.
(3), Au nanometer sheet is prepared
(f), by HAuCl4·4H2O is dissolved in dehydrated alcohol, prepares the chlorauric acid solution that mass percent is 0.25%：
(g), the silicon substrate that sodium citrate film is had obtained in step (2) is placed in the gold chloride of step (f) preparation
It is reacted at 50 DEG C in solution 4 hours, after reaction, silicon is sunk to the bottom as in ethanol solution, ultrasonic vibration 5 minutes, that is, is existed
Six shape Au nanometer sheet material is obtained in ethanol solution.
Embodiment 4
The method of the Au nanometer sheet for preparing triangle provided herein, specifically includes following steps：
(1), sodium citrate colloidal sol is prepared
(a), under the conditions of 55 DEG C, by Na3C6H5O7·2H2O is dissolved in 20mL aqueous solution, is sufficiently stirred after twenty minutes,
The sodium citrate aqueous solution that mass percent is 65% is prepared, it is spare；
(b), with the step (b) in embodiment 1；
(c), with the step (c) in embodiment 1.
(2), sodium citrate film is prepared
(d), with the step (d) in embodiment 1；
(e), with the step (e) in embodiment 1.
(3), Au nanometer sheet is prepared
(f), by HAuCl4·4H2O is dissolved in dehydrated alcohol, prepares the chlorauric acid solution that mass percent is 0.22%：
(g), the silicon substrate that sodium citrate film is had obtained in step (2) is placed in the gold chloride of step (f) preparation
It is reacted at 40 DEG C in solution 6 hours, after reaction, silicon is sunk to the bottom as in ethanol solution, ultrasonic vibration 2 minutes, that is, is existed
Triangle Au nanometer sheet material is obtained in ethanol solution.
Experimental example electron lens (TEM) test
TEM test is carried out to Au nanometer sheet material provided by the embodiment of the present application 1-4, test result is as shown in Figure 2-5.
The experimental results showed that the preparation method of two-dimensional layer Au nanometer sheet material provided herein, prepared to obtain
Au nanometer sheet good dispersion, thickness uniformly, size and shape it is controllable.Fig. 6 is the TEM diffractional lattice of Au nanometer sheet monocrystalline,
The result shows that the two-dimensional layer Au nanometer sheet of synthesis is monocrystalline, there is diffraction spot good symmetry to illustrate to synthesize Au nanometer sheet
Defect it is seldom, diffraction spot completely illustrates face-centered cubic (fcc) lattice structure of Au.
In conclusion the preparation method of two-dimensional layer Au nanometer sheet material provided herein, by liquid phase deposition,
Sodium citrate film is obtained, and two-dimensional layer Au nanometer sheet is prepared in this film surface reduction gold chloride, there is technique letter
Many advantages, such as single, single step reaction is completed, reaction temperature is low, reaction condition is simple, at low cost.Prepared two-dimensional layer Au receives
Rice sheet material, active strong, good dispersion, the advantages that thickness is uniform, size and shape are controllable, size range covers nanometer
To micron-sized two-dimensional layer Au nanometer sheet.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that the above various embodiments is only used
To illustrate technical solution of the present invention, rather than its limitations；Those skilled in the art should understand that：Without departing substantially from this hair
It in the case where bright spirit and scope, is possible to modify the technical solutions described in the foregoing embodiments, or to wherein
Some or all of technical characteristic is equivalently replaced；And these are modified or replaceed, and do not make the essence of corresponding technical solution
It departs from the scope of the technical solutions of the embodiments of the present invention；It is, therefore, intended that in the following claims including belonging to the present invention
All these substitutions and modifications in range.
Claims (15)
1. a kind of preparation method of two-dimensional layer Au nanometer sheet material, which is characterized in that include the following steps：
Silicon wafer is immersed in sodium citrate ethyl alcohol colloidal sol, the silicon with sodium citrate film is obtained by the method for liquid deposition
Substrate；
The silicon substrate with sodium citrate film is reacted with the ethanol solution of gold chloride, after reaction, to silicon substrate
It is separated with Au nanometer sheet, two-dimensional layer Au nanometer sheet material can be obtained；
The mass concentration of the ethanol solution of the gold chloride is 0.20~0.25%；
The temperature of the reaction is 20~50 DEG C, and the time of reaction is 4~12 hours；
It is described separation is carried out to silicon substrate and Au nanometer sheet to be operated using the method for ultrasonic vibration, the ultrasonic vibration when
Between be 1~5 minute.
2. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 1, which is characterized in that the citric acid
The preparation method of sodium ethyl alcohol colloidal sol, specifically includes following steps：
It will be dissolved in the water under sodium citrate heating condition, after mixing evenly, obtain the aqueous solution of sodium citrate；By sodium citrate
Aqueous solution greater than 1000rpm revolving speed under instill dehydrated alcohol in, obtain sodium citrate ethyl alcohol sol solution；By citric acid
Sodium ethyl alcohol sol solution carries out centrifugal treating, and sodium citrate ethyl alcohol colloidal sol is obtained after centrifugation.
3. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 2, which is characterized in that the heating
Temperature is 45~60 DEG C.
4. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 2, which is characterized in that the stirring
Time is 15~25 minutes.
5. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 2, which is characterized in that the citric acid
The mass concentration of the aqueous solution of sodium is 60%~70%.
6. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 2, which is characterized in that the citric acid
The volume ratio of the aqueous solution of sodium and the dehydrated alcohol is 1：(200~500).
7. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 2, which is characterized in that the centrifugation
Process specifically includes following steps：
The sodium citrate ethyl alcohol sol solution is centrifuged 10~14 minutes under 6000~8000rpm revolving speed, will be sunk after filtering
Shallow lake is dispersed in dehydrated alcohol, then is centrifuged 10~14 minutes under 4000~5000rpm revolving speed, isolated sodium citrate ethyl alcohol
Colloidal sol.
8. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 1, which is characterized in that the silicon wafer
Cleaning method specifically includes following steps：
By silicon wafer first with after the concentrated sulfuric acid-hydrogen peroxide system digestion at 100~120 DEG C, then at 30~80 DEG C it is bis- using ammonium hydroxide-
Oxygen aqueous systems digestion, is finally cleaned by ultrasonic with acetone, the silicon wafer after being cleaned.
9. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 8, which is characterized in that the leaching twice
The time boiled is 10~20 minutes.
10. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 1, which is characterized in that the immersion
Time be 10~14 hours.
11. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 1, which is characterized in that the reaction
Temperature be 25~40 DEG C, time of reaction is 6~8 hours.
12. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 1, which is characterized in that the reaction
Temperature be 25~30 DEG C, time of reaction is 5~6 hours.
13. the preparation method of two-dimensional layer Au nanometer sheet material according to claim 1, which is characterized in that the ultrasound
The time of concussion is 2~3 minutes.
14. two dimension prepared by the preparation method of -13 described in any item two-dimensional layer Au nanometer sheet materials according to claim 1
Stratiform Au nanometer sheet material.
15. two-dimensional layer Au nanometer sheet material according to claim 14, which is characterized in that described two-dimensional layer Au nanometers
Sheet material is the side N shape, wherein N >=3.
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