CN102921961A - Method for producing metallic nanomaterials through femtosecond lasers - Google Patents

Method for producing metallic nanomaterials through femtosecond lasers Download PDF

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Publication number
CN102921961A
CN102921961A CN2012105022794A CN201210502279A CN102921961A CN 102921961 A CN102921961 A CN 102921961A CN 2012105022794 A CN2012105022794 A CN 2012105022794A CN 201210502279 A CN201210502279 A CN 201210502279A CN 102921961 A CN102921961 A CN 102921961A
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laser
nano material
metal nano
potassium
material according
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CN102921961B (en
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袭锴
王远
王力
蒋天行
詹鹏
樊亚仙
贾叙东
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Nanjing University
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Abstract

The invention discloses a method for producing metallic nanomaterials through femtosecond lasers. According to the method, the lasers are used for directly irradiating metallic salt solution, thus obtaining the metallic nanomaterials with different shapes, wherein the time for laser irradiation is 1-3600 seconds, the average power of the incoming lasers is 5mW-400mW, and the concentration of the metallic salt solution is 1m mol/L-1mol/L. The method is simple and convenient, and does not need any reducing agent or surface active agent; and moreover, reaction conditions are simple and easy to control and are environment-friendly. The shapes and sizes of the produced metallic nanomaterials can be controlled, and the produced metallic nanomaterials can be applied to the fields of catalysis, electrochemistry, surface raman reinforcement or biomedicines and the like.

Description

A kind of femtosecond laser prepares the method for metal nano material
Technical field
The present invention relates to the metal nano material technical field, be specifically related to the method that a kind of femtosecond laser prepares metal nano material.
Background technology
Along with the development of nearly decades, nano science has become one of scientific research field of current hot topic.And metal nanoparticle becomes the emphasis of nano science research owing to character such as its distinctive skin effect, small-size effect, macro quanta tunnel effects.Corresponding metal nano material has been applied to the numerous areas such as bio-sensing, catalysis, electronics industry, optics.The current existing multiple method for preparing metal nano material is such as vapor phase method, chemical precipitation method, sol-gel process, chemical reduction method, heat drop solution, photoreduction met hod etc.Wherein photo-reduction ratio juris is the character that part metals has surface plasma body resonant vibration, can be under the visible region light absorbing energy.When having a certain specific light source that the solution that contains metal ion is shone, metal ion can be reduced.If control suitable reaction condition, just can access the metal nano material of different-shape and size.Compare with additive method, photoreduction met hod has simple to operate, reaction temperature and etc. advantage, therefore also become a kind of common method of preparation metal nano material.
Reported at present to prepare metal nano material with photoreduction met hod mainly be the aqueous solution that contains metal ion with UV-irradiation, obtain metal nano material.Also there is report to shine the liquor argenti nitratis ophthalmicus that contains reducing agent with the diode lights that can regulate optical wavelength, obtains the silver nano material of different-shape.But these light sources are because light intensity is lower, and the irradiation time that often needs to grow just can react completely very.If use the laser illumination that energy density is high, directionality is good, then can just can make the metal ion reduction within a short period of time, prepare metal nano material.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the purpose of this invention is to provide the method that a kind of femtosecond laser prepares metal nano material, it is had simple to operate, consuming time shorter, environmental friendliness, the characteristics such as pattern and size are controlled.Prepared metal nano material can be used for the fields such as catalysis, electrochemistry, surface Raman enhancement or biomedicine.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
A kind of femtosecond laser prepares the method for metal nano material: directly shine with the laser alignment metal salt solution, obtain the metal nano material of different-shape; Wherein, the time of Ear Mucosa Treated by He Ne Laser Irradiation is 1 ~ 3600s, and the mean power of incident laser is 5 ~ 400mW, and the concentration of metal salt solution is 1mmol/L ~ 1mol/L.
Described slaine comprises silver nitrate, silver acetate, gold chloride, sodium chloraurate, potassium chloroaurate, auribromohydric acid, sodium terabomoaurate, gold potassium bromide, iodo-auric acid, Potassium Tetraiodoaurate, chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate, bromoplatinic acid, potassium bromoplatinate, potassium bromoplatinate, platinic sulfate, platinum nitrate, copper sulphate, copper nitrate, copper chloride, copper bromide, and any molar mixture of gold chloride and chloroplatinic acid.
The solvent of described metal salt solution comprises water, methyl alcohol, ethanol, ethylene glycol, propane diols, glycerine, oxolane, DMF, DMAc, and, the mixing of the arbitrary volume ratio of one or more among water and methyl alcohol, ethanol, ethylene glycol, propane diols, glycerine, oxolane, DMF, the DMAc.
The concentration of described metal salt solution is preferably 10 ~ 100mmol/L.
The time of described Ear Mucosa Treated by He Ne Laser Irradiation, be preferably 600 ~ 1200s.
The mean power of described incident laser is preferably 20 ~ 50mW.
Described Ear Mucosa Treated by He Ne Laser Irradiation sample has rays pass through lens to focus on rear irradiation and direct irradiation dual mode.
Used light source is femto-second laser among the present invention, and the laser of its generation has the advantages that the pulse duration is short, peak power is high.In the situation that gross output is less, femto-second laser also can provide enough energy for the chemical reaction that some needs very high-energy could occur.And therefore femtosecond laser gross output and little can not cause material to be burnt.
Beneficial effect: compared with prior art, advantage of the present invention comprises: the present invention adopts above-mentioned process, and is simple and convenient, need not to add any reducing agent or surfactant, and reaction condition is simple and easy to control, environmental friendliness.Prepared metal nano material pattern and size are controlled, can be applicable to the fields such as catalysis, electrochemistry, surface Raman enhancement or biomedicine.
Description of drawings
Fig. 1 is that femtosecond laser prepares metal nano material experiment index path;
Fig. 2 is AgNO 3The transmission electron microscope photo of the nano particle that forms behind the process Ear Mucosa Treated by He Ne Laser Irradiation;
Fig. 3 is the transmission electron microscope photo that chlorauric acid solution passes through the nanometer rods that forms behind the Ear Mucosa Treated by He Ne Laser Irradiation;
Fig. 4 is the transmission electron microscope photo that chlorauric acid solution passes through the hexagonal nanosheet that forms behind the Ear Mucosa Treated by He Ne Laser Irradiation;
Fig. 5 is the transmission electron microscope photo that gold chloride and chloroplatinic acid mixed solution pass through the nanometer rods that forms behind the Ear Mucosa Treated by He Ne Laser Irradiation;
The specific embodiment
The present invention is described further below in conjunction with specific embodiment.
Embodiment 1
As shown in Figure 1, used laser instrument is the Legend Elite femto-second laser of Coherent company.Debugging laser makes the light path of laser aim at the plane of incidence of sample cell.Use the lens on light line focus, the position of focus is at the center of sample cell inside.Then the power with laser transfers to 20mW, and the silver nitrate aqueous solution of the 10mmol/L for preparing is added in the sample cell, shines after leaving standstill 5min again.Behind the irradiation 600s, sample is detected.AgNO 3Through the nano particle that forms behind the Ear Mucosa Treated by He Ne Laser Irradiation, as shown in Figure 2.
Embodiment 2
Replace silver nitrate with silver acetate, other conditions are with embodiment 1.
Embodiment 3
Debugging laser takes off lens, the hot spot of laser is aimed at the plane of incidence of sample cell.Then the power with laser transfers to 400mW, and the chlorauric acid solution of the 1mmol/L for preparing is added in the sample cell, shines after leaving standstill 5min again.Behind the irradiation 1s, sample is detected.The nanometer rods of gold chloride through forming behind the Ear Mucosa Treated by He Ne Laser Irradiation, as shown in Figure 3.After shining 2 min, sample is detected.The hexagonal nanosheet of chlorauric acid solution through forming behind the Ear Mucosa Treated by He Ne Laser Irradiation, as shown in Figure 4.
Embodiment 4
Replace gold chloride with sodium chloraurate, potassium chloroaurate, auribromohydric acid, sodium terabomoaurate, gold potassium bromide, iodo-auric acid, Potassium Tetraiodoaurate respectively, other conditions are with embodiment 3.
Embodiment 5
Debugging laser makes the light path of laser aim at the plane of incidence of sample cell.Use the lens on light line focus, the position of focus is at the center of sample cell.Then the power with laser transfers to 50mW, and the copper sulfate solution of the 1mol/L for preparing is added in the sample cell, shines after leaving standstill 5min again.Behind the irradiation 1200s, sample is detected.
Embodiment 6
Replace copper sulphate with copper nitrate, copper chloride, copper bromide respectively, other conditions are with embodiment 5.
Embodiment 7
Debugging laser makes the light path of laser aim at the plane of incidence of sample cell.Use the lens on light line focus, the position of focus is at the center of sample cell.Then the power with laser transfers to 5mW, and the gold chloride of the total concentration 100mmol/L for preparing and the aqueous solution of chloroplatinic acid mol ratio 1:1 are added in the sample cell, shines after leaving standstill 5min again.Behind the irradiation 3600s, sample is detected.Gold chloride and the chloroplatinic acid mixed solution nanometer rods through forming behind the Ear Mucosa Treated by He Ne Laser Irradiation, as shown in Figure 5.
Embodiment 8
Replace gold chloride with sodium chloraurate, potassium chloroaurate, auribromohydric acid, sodium terabomoaurate, gold potassium bromide, iodo-auric acid, Potassium Tetraiodoaurate respectively, replace chloroplatinic acid with platinic sodium chloride, potassium chloroplatinate, bromoplatinic acid, potassium bromoplatinate, potassium bromoplatinate, platinic sulfate, platinum nitrate respectively simultaneously, the two kinds of samples in front and back can be corresponding arbitrarily, and (other conditions are with embodiment 7.
Embodiment 9
Replace water among the embodiment 1 to 8 with the mixed solvent of methyl alcohol, ethanol, ethylene glycol, propane diols, glycerine, oxolane, DMF, DMAc or water and above-mentioned solvent arbitrary volume ratio, other conditions are with embodiment 1 to 8.

Claims (7)

1. a femtosecond laser prepares the method for metal nano material, it is characterized in that: directly shine with the laser alignment metal salt solution, obtain the metal nano material of different-shape; Wherein, the time of Ear Mucosa Treated by He Ne Laser Irradiation is 1 ~ 3600s, and the mean power of incident laser is 5 ~ 400mW, and the concentration of metal salt solution is 1mmol/L ~ 1mol/L.
2. the method for preparing metal nano material according to claims 1 described femtosecond laser, it is characterized in that: described slaine comprises silver nitrate, silver acetate, gold chloride, sodium chloraurate, potassium chloroaurate, auribromohydric acid, sodium terabomoaurate, gold potassium bromide, iodo-auric acid, Potassium Tetraiodoaurate, chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate, bromoplatinic acid, potassium bromoplatinate, potassium bromoplatinate, platinic sulfate, platinum nitrate, copper sulphate, copper nitrate, copper chloride, copper bromide, and any molar mixture of gold chloride and chloroplatinic acid.
3. the method for preparing metal nano material according to claims 1 described femtosecond laser, it is characterized in that: the solvent of described metal salt solution comprises water, methyl alcohol, ethanol, ethylene glycol, propane diols, glycerine, oxolane, DMF, DMAc, and, the mixing of the arbitrary volume ratio of one or more among water and methyl alcohol, ethanol, ethylene glycol, propane diols, glycerine, oxolane, DMF, the DMAc.
4. prepare the method for metal nano material according to claims 1 described femtosecond laser, it is characterized in that: the concentration of described metal salt solution is 10 ~ 100mmol/L.
5. prepare the method for metal nano material according to claims 1 described femtosecond laser, it is characterized in that: the time of described Ear Mucosa Treated by He Ne Laser Irradiation is 600 ~ 1200s.
6. prepare the method for metal nano material according to claims 1 described femtosecond laser, it is characterized in that: irradiation and two kinds of methods of direct irradiation after the method for described Ear Mucosa Treated by He Ne Laser Irradiation sample has rays pass through lens to focus on.
7. prepare the method for metal nano material according to claims 1 described femtosecond laser, it is characterized in that: the mean power of described incident laser is 20 ~ 50mW.
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CN103341635A (en) * 2013-06-21 2013-10-09 中国计量学院 Method using laser to generate hydrated electrons to prepare gold nanometer particles
CN104625422A (en) * 2014-12-29 2015-05-20 北京理工大学 Method for assisting metal processing based on electronic dynamic control of ethanol solution
CN105834434A (en) * 2016-04-27 2016-08-10 广东工业大学 Chemical laser compound preparation method for copper micro-nano particles controllable in particle size distribution
CN107538017A (en) * 2017-08-21 2018-01-05 北京理工大学 A kind of method that light induced electron reduction prepares metal dithionite molybdenum composite construction
CN108057406A (en) * 2017-12-14 2018-05-22 中国科学院长春光学精密机械与物理研究所 A kind of phthalocyanin nano material and preparation method thereof
CN109837531A (en) * 2017-11-27 2019-06-04 重庆科技学院 Gold nano triangle piece preparation method with surface-enhanced Raman effects
CN110125431A (en) * 2019-04-04 2019-08-16 华南师范大学 A method of gold nanosphere is prepared based on Rayleigh unstability
CN110280776A (en) * 2019-04-15 2019-09-27 清华大学 Gold nanorods enhancing shaping methods and its system based on intra two-pulse laser
CN112658275A (en) * 2020-12-02 2021-04-16 山东大学 Method for preparing ruthenium-iridium nano alloy by using laser irradiation acoustic suspension liquid drop
US11110448B1 (en) * 2019-09-18 2021-09-07 Tsinghua University Method for preparing gold nanorods having high catalytic activity by using femtosecond laser
CN113547130A (en) * 2021-07-12 2021-10-26 杭州苏铂科技有限公司 Laser-assisted functionalized gold nano-star preparation method
CN114734051A (en) * 2022-04-21 2022-07-12 中国科学院合肥物质科学研究院 Method for in-situ preparation of ultra-small precious metal and non-precious metal alloy on carbon carrier

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Cited By (19)

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CN103341635A (en) * 2013-06-21 2013-10-09 中国计量学院 Method using laser to generate hydrated electrons to prepare gold nanometer particles
CN103341635B (en) * 2013-06-21 2016-06-22 中国计量学院 A kind of method preparing nanogold particle by laser generation aqueous electron
CN104625422A (en) * 2014-12-29 2015-05-20 北京理工大学 Method for assisting metal processing based on electronic dynamic control of ethanol solution
CN104625422B (en) * 2014-12-29 2016-08-24 北京理工大学 Based on dynamic control ethanol solution assistant metal processing method
CN105834434A (en) * 2016-04-27 2016-08-10 广东工业大学 Chemical laser compound preparation method for copper micro-nano particles controllable in particle size distribution
CN105834434B (en) * 2016-04-27 2017-12-05 广东工业大学 A kind of chemical laser composite preparation process of the controllable copper micro-nano particle of particle diameter distribution
CN107538017A (en) * 2017-08-21 2018-01-05 北京理工大学 A kind of method that light induced electron reduction prepares metal dithionite molybdenum composite construction
CN107538017B (en) * 2017-08-21 2020-04-21 北京理工大学 Method for preparing metal-molybdenum disulfide composite structure by photo-generated electronic reduction
CN109837531A (en) * 2017-11-27 2019-06-04 重庆科技学院 Gold nano triangle piece preparation method with surface-enhanced Raman effects
CN108057406A (en) * 2017-12-14 2018-05-22 中国科学院长春光学精密机械与物理研究所 A kind of phthalocyanin nano material and preparation method thereof
CN110125431A (en) * 2019-04-04 2019-08-16 华南师范大学 A method of gold nanosphere is prepared based on Rayleigh unstability
CN110280776A (en) * 2019-04-15 2019-09-27 清华大学 Gold nanorods enhancing shaping methods and its system based on intra two-pulse laser
US11110448B1 (en) * 2019-09-18 2021-09-07 Tsinghua University Method for preparing gold nanorods having high catalytic activity by using femtosecond laser
CN112658275A (en) * 2020-12-02 2021-04-16 山东大学 Method for preparing ruthenium-iridium nano alloy by using laser irradiation acoustic suspension liquid drop
CN112658275B (en) * 2020-12-02 2022-03-29 山东大学 Method for preparing ruthenium-iridium nano alloy by using laser irradiation acoustic suspension liquid drop
WO2022116380A1 (en) * 2020-12-02 2022-06-09 山东大学 Method for preparing ruthenium iridium nano alloy by means of laser irradiation and acoustic suspension of droplets
CN113547130A (en) * 2021-07-12 2021-10-26 杭州苏铂科技有限公司 Laser-assisted functionalized gold nano-star preparation method
CN114734051A (en) * 2022-04-21 2022-07-12 中国科学院合肥物质科学研究院 Method for in-situ preparation of ultra-small precious metal and non-precious metal alloy on carbon carrier
CN114734051B (en) * 2022-04-21 2024-04-26 中国科学院合肥物质科学研究院 Method for in-situ preparation of ultra-small-size noble metal non-noble metal alloy on carbon carrier

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