CN103803632A - Preparation method of carbon-coated photothermal conversion nano material - Google Patents
Preparation method of carbon-coated photothermal conversion nano material Download PDFInfo
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- CN103803632A CN103803632A CN201410070626.XA CN201410070626A CN103803632A CN 103803632 A CN103803632 A CN 103803632A CN 201410070626 A CN201410070626 A CN 201410070626A CN 103803632 A CN103803632 A CN 103803632A
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Abstract
The invention discloses a preparation method of a carbon-coated photothermal conversion nano material. The preparation method comprises the following steps: 1, adding a surfactant and a distilled water solution of Na2S.9H2O in a distilled water solution of CuCl2.2H2O, heating to 80-90 DEG C after stirring at a room temperature for 5 minutes, obtaining a product after stirring for 20-30 minutes, then centrifugally separating and washing for multiple times by using the distilled water and a methanol solution, and naturally drying, thereby obtaining organic matter ligand coated CuS nano particles; 2, diluting the organic matter ligand coated CuS nano particles by adopting a distilled water solution, after ultrasonically dispersing, pouring in a hydrothermal reaction kettle, reacting at a high temperature of 195-215 DEG C for 4-6 hours, centrifugally separating and washing for multiple times by using the distilled water and the methanol solution, and naturally drying, thereby obtaining the carbon coated CuS nano particles. According to a carbon coated layer prepared by adopting the preparation method, the biotoxicity of the CuS is effectively reduced, the biocompatibility and the photothermal conversion efficiency are increased, the nano particles can be prevented from aggregating and being oxidized, the stability is improved, the preparation process is simple, and the carbon-coated photothermal conversion nano material can be used for photothermal therapy.
Description
Technical field
The invention belongs to photo-thermal conversion nano material preparing technical field, relate to a kind of photo-thermal conversion nano compound material, specifically, relate to a kind of preparation method of the coated photo-thermal conversion nano material of carbon with near-infrared absorption function and photo-thermal conversion performance.
Background technology
Photo-thermal conversion nano material is that one can absorb near infrared light, maybe can produce with transition the new function material of heat by plasma resonance.As a new study hotspot, Chinese scholars is devoted to the synthetic of this material, it has purposes extremely widely at biomedical aspect, as medicament slow release, photo-thermal therapy and medical imaging etc., the research of association area also has greater advance, as: the Zheng Nan of Xiamen University peak teach problem group is prepared a kind of novel nano palladium material of blueness, realizes photothermal, can directly apply to the near infrared light heat cure of tumour.Advanced Materials periodical report: nanometer gold shell material can be heat energy by near-infrared laser light energy conversion, and high-efficiency low-toxicity kills tumour cell.
Cupric sulfide, as a kind of important transient metal sulfide, is the multi-functional synthetic materials that a kind of chemical stability is good.Nano level CuS particle diameter is little, specific surface area is large, has good optical absorption, can be used for photo-thermal therapy etc.In the time that medium temperature is elevated to 42 ℃, cancer cells just can be killed effectively, therefore metal Nano structure material note people is transported to the nanostructure with targeting in tumour in tumour or by intravenous injection, again by laser radiation tumor locus, just can effectively destroy tumor tissues, and very little to healthy tissues wound around.It is reported, by ligand exchange (ACS nanometer (Nano), 2011,5,9761-9771), the CuS nano particle of preparing efficiently solves the problem of its biocompatibility, but toxicity is large, and complicated process of preparation, has limited its biologic applications.Therefore, explore a kind of CuS nano composite material of exploitation, when thering is high light thermal conversion efficiency, effectively reduce bio-toxicity, significant at biomedical sector.
Summary of the invention
The object of the invention is to overcome above existing technological deficiency, develop a kind of photo-thermal conversion nano compound material, that is: the coated CuS photo-thermal conversion nano material of carbon, it has higher near-infrared absorption function and photo-thermal conversion efficiency, and has effectively reduced bio-toxicity.
For achieving the above object, the invention provides the preparation method of the coated photo-thermal conversion nano material of a kind of carbon, the method comprises following steps:
Step 1, the CuS nano particle that precipitator method synthesis of organic substance part is coated: to CuCl
22H
2in the distilled water solution of O, add tensio-active agent and Na
2s9H
2the distilled water solution of O, at room temperature stirs after 5 minutes and is warming up to 80-90 ℃, stirs after 20-30 minute and obtains product, then, with distilled water and methanol solution centrifugation washing several, after seasoning, obtains the coated CuS nano particle of organism part;
Step 2, hydrothermal synthesis of carbon is coated CuS nano particle: the coated CuS nano particle of organism part that adopts the distilled water solution dilution step 1 of sodium sulphite to obtain, after ultrasonic dispersion, pour in hydrothermal reaction kettle, pyroreaction 4 ~ 6 hours at 195 ~ 215 ℃, with distilled water and methanol solution centrifugation washing several, after seasoning, obtain the coated CuS nano particle of carbon again.
The preparation method of the above-mentioned coated photo-thermal conversion nano material of carbon, wherein, more than any one in described tensio-active agent employing sodium dimercaptosuccinate, glucose.Wherein, sodium dimercaptosuccinate is reacted and makes with sodium hydroxide by dimercaptosuccinic acid (DMSA).
The preparation method of the above-mentioned coated photo-thermal conversion nano material of carbon, wherein, in step 1, described tensio-active agent and CuCl
22H
2the mol ratio of O is 4-7:1, is preferably 5:1; The mol ratio of Cu and S element is 1:1 ~ 2.
The preparation method of the above-mentioned coated photo-thermal conversion nano material of carbon, wherein, in step 2, the coated CuS nano particle of organism part that dilution step 1 obtains is to adopt in distilled water solution to contain sodium sulphite; Further, the pH value of described sodium sulfide solution is 11-12.5; Be preferably 12.This sodium sulfide solution pH value is weakly alkaline, the coated CuS of DMSA is disperseed in solution more even, prevents the reunion of nano particle in carbonization process.
The present invention has used tensio-active agent in preparation process, after tensio-active agent adds, chemical reaction has occurred in solution, has formed the coated CuS nano particle of organism part; In hydrothermal reaction process, the at high temperature carbonization of coated organic ligand, be coated one deck carbon at spherical CuS nano grain surface, thereby be converted to the coated CuS of carbon, effectively reduce the bio-toxicity of CuS, improved its biocompatibility, photo-thermal conversion efficiency, and can prevent nanoparticle agglomerates, improve stability etc.Moreover, carbon coating layer has also reduced the size of particle, has solved a difficult problem for nanoparticle agglomerates, and prevents the oxidation of nano particle, has improved stability.The coated CuS nano material of this carbon has higher near-infrared absorption performance and photo-thermal conversion efficiency, and biocompatibility is also fine, and preparation technology is simple, can be used for photo-thermal therapy etc.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the coated CuS nano material of the carbon prepared of the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the coated CuS nano material of the carbon prepared of the embodiment of the present invention 1.
Fig. 3 is the uv-visible absorption spectra figure of the coated CuS nano material of the carbon prepared of the embodiment of the present invention 1.
Fig. 4 is that carbon prepared by the embodiment of the present invention 1 is coated the heating curve figure of CuS nano material under 808nm laser radiation.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is further described.
Embodiment 1
In beaker, add CuCl
22H
2o (0.17g, 1mmol), and with the dissolving of 1000ml distilled water, constantly stir and obtain light blue solution.Again by DMSA (0.9 g, 5mmol), NaOH (0.4 g, 10mmol), Na
2s9H
2o (0.24g, 1mmol) add successively in 10ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, being warming up to 85 ℃, magnetic agitation obtains deep green product for 25 minutes, with after distilled water and methanol solution centrifugation for several times, obtain the coated CuS nano particle of DMSA.Above-mentioned particle is joined in the 35ml sodium sulfide solution of pH=12, after ultrasonic dispersion, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 6 hours at 210 ℃, finally use distilled water and methanol solution centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
The high-resolution-ration transmission electric-lens (TEM) of the coated CuS nano particle of this carbon is schemed as shown in Figure 1, the coated CuS nano particle of carbon presents obvious globose nucleus shell structure, carbon coating layer thickness is about 1.6nm, this structure has effectively improved photo-thermal conversion efficiency and the stability of CuS nano particle, and has reduced its bio-toxicity.
As shown in Figure 2, the CuS standard spectrum collection of illustrative plates of (101), (102), (103), (006), (108) and (116) diffraction crystal face and hexagonal structure is wherein substantially identical for the XRD spectra of the coated CuS nano particle of this carbon.In addition, do not observe as Cu
2the existence of the impurity peaks such as S, CuO and S, but slightly weaken because the nanometer of CuS crystal causes diffraction peak intensity, and there is relative broadening phenomenon.On the whole, the coated CuS nano particle of carbon still has higher purity and crystallinity.
As shown in Figure 3, the coated CuS nano particle of carbon has stronger absorption peak to the uv-visible absorption spectra figure of the coated CuS nano particle of this carbon near near-infrared region 920nm and 1070nm, illustrates that it has good near-infrared absorption performance.
The heating curve figure of the coated CuS nano particle of this carbon under 808nm laser radiation as shown in Figure 4, under 808nm laser radiation, the coated CuS nano particle of carbon has raise approximately 23 ℃ after 600 seconds, have higher photo-thermal conversion efficiency, and the temperature of control group distilled water does not change substantially.The concrete testing method of this heating curve figure is: with power be 1W/cm
2wavelength 808nm laser irradiation device irradiate respectively and fill the coated CuS nano particle of 1ml distilled water and the 2mg carbon quartz container of (disperseing with 1ml distilled water), strength of current is 1.14A, irradiation time is 600 seconds, the temperature value that record raises respectively.
Embodiment 2
In beaker, add CuCl
22H
2o (0.25g, 1.5mmol), and with the dissolving of 1000ml distilled water, constantly stir and obtain light blue solution.Again by DMSA (1.25g, 7mmol), NaOH (0.4 g, 10mmol), Na
2s9H
2o (0.36g, 1.5mmol) add successively in 10ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, being warming up to 90 ℃, magnetic agitation obtains deep green product for 20 minutes, with after distilled water and methanol solution centrifugation for several times, obtain the coated CuS nano particle of DMSA.Above-mentioned particle is joined in the 35ml sodium sulfide solution of pH=11, after ultrasonic dispersion, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 5 hours at 210 ℃, finally use distilled water and methanol solution centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
Embodiment 3
In beaker, add CuCl
22H
2o (0.08g, 0.5mmol), and with the dissolving of 500ml distilled water, constantly stir and obtain light blue solution.Again by DMSA (0.45g, 2.5mmol), NaOH (0.2g, 5mmol), Na
2s9H
2o (0.12g, 0.5mmol) add successively in 5ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, being warming up to 85 ℃, magnetic agitation obtains deep green product for 20 minutes, with after distilled water and methanol solution centrifugation for several times, obtain the coated CuS nano particle of DMSA.Above-mentioned particle is joined in the 35ml sodium sulfide solution of pH=12.5, after ultrasonic dispersion, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 5 hours at 210 ℃, finally use distilled water and methanol solution centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
Embodiment 4
In beaker, add CuCl
22H
2o (0.17g, 1mmol), and with the dissolving of 1000ml distilled water, constantly stir and obtain light blue solution.Again by glucose (1.25g, 7mmol) and Na
2s9H
2o (0.24g, 1mmol) add successively in 10ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, being warming up to 90 ℃, magnetic agitation obtains deep green product for 20 minutes, with after distilled water centrifugation for several times, obtain the coated CuS nano particle of glucose.Dissolve above-mentioned particle with distilled water, pour the hydrothermal reaction kettle of 50ml after ultrasonic dispersion into, pyroreaction 5 hours at 190 ℃, finally uses distilled water centrifugation for several times, after seasoning, obtains the coated CuS nano particle of carbon.
The coated CuS nano particle of carbon of embodiment 2-4 also obtains respectively TEM, XRD, uv-visible absorption spectra figure and the heating curve figure under 808nm laser radiation, and its result is all similar with Fig. 1-4 respectively.
To sum up, the coated CuS nano particle of carbon provided by the invention has reduced the bio-toxicity of CuS effectively, has improved its biocompatibility, photo-thermal conversion efficiency, and can prevent nanoparticle agglomerates, improve stability.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.Read after foregoing those skilled in the art, for multiple modification of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. a preparation method for the coated photo-thermal conversion nano material of carbon, is characterized in that, the method comprises following steps:
Step 1, the CuS nano particle that precipitator method synthesis of organic substance part is coated: to CuCl
22H
2in the distilled water solution of O, add tensio-active agent and Na
2s9H
2the distilled water solution of O, at room temperature stirs after 5 minutes and is warming up to 80-90 ℃, stirs after 20-30 minute and obtains product, then, with distilled water and methanol solution centrifugation washing several, after seasoning, obtains the coated CuS nano particle of organism part;
Step 2, hydrothermal synthesis of carbon is coated CuS nano particle: the coated CuS nano particle of organism part that adopts distilled water solution dilution step 1 to obtain, after ultrasonic dispersion, pour in hydrothermal reaction kettle, pyroreaction 4 ~ 6 hours at 195 ~ 215 ℃, with distilled water and methanol solution centrifugation washing several, after seasoning, obtain the coated CuS nano particle of carbon again.
2. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 1, is characterized in that, more than any one in described tensio-active agent employing sodium dimercaptosuccinate, glucose.
3. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 2, is characterized in that, described sodium dimercaptosuccinate is reacted and makes with sodium hydroxide by dimercaptosuccinic acid.
4. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 1, is characterized in that, in step 1, and described tensio-active agent and CuCl
22H
2the mol ratio of O is 4 ~ 7:1; The mol ratio of Cu and S element is 1:1 ~ 2.
5. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 4, is characterized in that, in step 1, and described tensio-active agent and CuCl
22H
2the mol ratio of O is 4.5 ~ 6.5:1.
6. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 5, is characterized in that, in step 1, and described tensio-active agent and CuCl
22H
2the mol ratio of O is 5:1.
7. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 1, is characterized in that, in step 2, the coated CuS nano particle of organism part that dilution step 1 obtains is to adopt in distilled water solution to contain sodium sulphite.
8. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 7, is characterized in that, in step 2, the pH value of described sodium sulfide solution is 11 ~ 12.5.
9. the preparation method of the coated photo-thermal conversion nano material of carbon as claimed in claim 8, is characterized in that, in step 2, the pH value of described sodium sulfide solution is 12.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036179A (en) * | 2015-04-29 | 2015-11-11 | 金华职业技术学院 | Method of preparing CdS nano particles through room-temperature solid-phase reaction |
| CN110156066A (en) * | 2019-05-06 | 2019-08-23 | 上海应用技术大学 | A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy |
| CN110713203A (en) * | 2019-11-20 | 2020-01-21 | 南京信息工程大学 | CuS/carbon black composite photothermal conversion material and preparation method thereof |
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| CN102219251A (en) * | 2011-03-30 | 2011-10-19 | 东华大学 | Copper sulfide superstructure and its application in improving near infrared thermal conversion efficiency |
| CN102612486A (en) * | 2009-11-25 | 2012-07-25 | E·I·内穆尔杜邦公司 | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
| CN103121705A (en) * | 2012-12-14 | 2013-05-29 | 深圳先进技术研究院 | Preparation method of CuS nanoparticles, product and application thereof |
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2014
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Patent Citations (3)
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| CN102612486A (en) * | 2009-11-25 | 2012-07-25 | E·I·内穆尔杜邦公司 | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
| CN102219251A (en) * | 2011-03-30 | 2011-10-19 | 东华大学 | Copper sulfide superstructure and its application in improving near infrared thermal conversion efficiency |
| CN103121705A (en) * | 2012-12-14 | 2013-05-29 | 深圳先进技术研究院 | Preparation method of CuS nanoparticles, product and application thereof |
Non-Patent Citations (1)
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| GUANG-YI CHEN ET AL.: "Synthesis, Characterization, and Formation Mechanism of Copper Sulfide-Core/Carbon-Sheath Cables by a Simple Hydrothermal Route", 《CRYSTAL GROWTH & DESIGN》, vol. 8, no. 7, 29 May 2008 (2008-05-29), pages 2137 - 2143 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036179A (en) * | 2015-04-29 | 2015-11-11 | 金华职业技术学院 | Method of preparing CdS nano particles through room-temperature solid-phase reaction |
| CN110156066A (en) * | 2019-05-06 | 2019-08-23 | 上海应用技术大学 | A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy |
| CN110713203A (en) * | 2019-11-20 | 2020-01-21 | 南京信息工程大学 | CuS/carbon black composite photothermal conversion material and preparation method thereof |
| CN110713203B (en) * | 2019-11-20 | 2022-07-08 | 南京信息工程大学 | CuS/carbon black composite photothermal conversion material and preparation method thereof |
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Inventor after: Li Xiaofeng Inventor after: Zhang Yingjie Inventor after: An Yan Inventor after: Tao Fujun Inventor after: Dong Lihua Inventor after: Yin Yansheng Inventor before: Zhang Yingjie Inventor before: Li Xiaofeng Inventor before: An Yan Inventor before: Tao Fujun Inventor before: Dong Lihua Inventor before: Yin Yansheng |
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