CN107572592B - One kind being suitable for light activated optothermal material of near-infrared and preparation method thereof - Google Patents
One kind being suitable for light activated optothermal material of near-infrared and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of CuFeS2Preparation method, comprising the following steps: (1) press chemical formula CuFeS2The molar percentage of middle each element weighs reaction raw materials；(2) cuprous halide is added in solvent, stirs simultaneously heat de-airing；(3) after being passed through inert gas shielding, sulphur powder is added and stirs evenly, heating reaction after the completion, is cooled to room temperature；(4) divalent iron salt and lauryl mercaptan are added, simultaneously heat de-airing is stirred；(5) it is passed through inert gas shielding, then heating reaction, after the completion, is cooled to room temperature；The CuFeS that the present invention is prepared2Nanometer sheet has very strong absorption in the whole region of near-infrared, and it is a kind of good light thermit powder, the great potential in the photo-thermal therapy of the following cancer that photothermal conversion efficiency is high.
Description
Technical field
The invention belongs to technical field of nano material, in particular to it is a kind of suitable for near-infrared excitation optothermal material and its
Preparation method.
Background technique
In recent years, with the development of laser and infrared technique, the research in relation to near-infrared material is increasingly rapid, especially exists
Absorption, fluorescence and light sensitive characteristic of near-infrared etc..By the mechanism of action, nearly near infrared absorption material can be divided by infra-red material
Material, 3 major class of near infrared emission material and near-infrared fluorescent material.Near infrared absorption material is due to the property such as its excellent light, electricity, magnetic
Can, it has a wide range of applications in many technical fields, such as lasing safety, optical filtering heat insulating coat, optical recording storage, the sun
Energy battery, biological detection and therapeutic treatment etc..In terms of therapeutic treatment, the photo-thermal therapy Cancer Treatment Regimens emerging as one kind,
Since its is at low cost, Small side effects, the high-efficient extensive concern for causing people.Photo-thermal therapy is to absorb light using optothermal material
It can be converted into thermal energy, to kill cancer cell.Because light stimulus response has good spatial and temporal resolution and watt level is adjustable,
Therefore the treatment of cancer efficiently controlled under specific time, space can be realized.Near infrared light has more preferable for ultraviolet light
Internal penetration depth and higher biological safety.With the fast development of modern science and technology, the demand of this kind of material can also be got over
Come it is bigger, the exploitation of near-infrared material be concentrated mainly on the new material of exploitation function admirable and explore it is easy, effectively may be used
The synthetic method of industrialized production.Near infrared absorption material can be mainly divided into inorganic and organic two major classes, and inorganic is inhaled mostly
Receipts wave-length coverage is wide, and good to photo-thermal equistability, organic refers mainly to organic dyestuff, usually poor to tolerances such as photo-thermal, holds
It is degradable to lose effect, and color is very deep, but its absorption intensity is high, wave crest is narrow and easy to control, also receives significant attention.It is inorganic close
Infrared absorbing material is nano material mostly, these nano materials can because of its surface plasmon resonance absorption, it is general have compared with
Good photoelectric properties.Studying more inorganic absorbent materials at present mainly has metal oxide, metal sulfide and nano metal.
Metal sulfide has extraordinary near-infrared absorption characteristic, in thermoelectricity material due to that can generate energy band transition
Material, nonlinear optical material etc. have a good application prospect.It is introduced second on the basis of unit metal sulfide
Metal ion forms multi-element metal sulfide powders, can usually form cubic spinel structure AB after introducing second of metal2X4
Or yellow copper structure ABX2, there is preferable stability, therefore there is good practicability.When the metal sulfide being developed into
Particle size is much smaller than visible wavelength, it is expected to obtain higher visible light transmittance rate.Nano-powder is doped to gel or high polymer
In, it can be prepared into the optical thin film with unique absorption characteristic and be applied in solar heat shielding device.Related multi-element metal
The preparation method of sulfide mainly has hydrothermal synthesis method, coprecipitation, microemulsion method etc..The multi-element metal sulphur being prepared at present
The excitation light power density that compound photothermal conversion efficiency is low, light thermal property is unstable, uses is excessively high.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide it is a kind of suitable for near-infrared excitation optothermal material and
Preparation method.
Above-mentioned purpose is achieved through the following technical solutions:
A kind of CuFeS2Preparation method, comprising the following steps:
(1) chemical formula CuFeS is pressed2The molar percentage of middle each element weighs reaction raw materials；
(2) cuprous halide is added in solvent, stirs simultaneously heat de-airing；
(3) after being passed through inert gas shielding, sulphur powder is added and stirs evenly, heating reaction after the completion, is cooled to room temperature；
(4) divalent iron salt and lauryl mercaptan are added, simultaneously heat de-airing is stirred；
(5) it is passed through inert gas shielding, then heating reaction, after the completion, is cooled to room temperature.
The lauryl mercaptan being added in the present invention is to maintenance CuFeS2The integrality of nanometer chip architecture plays an important role, and ten
Two mercaptan can be combined with copper atom, to protect nanometer sheet surface.If being added without lauryl mercaptan in the present invention, and use other
Sulphur-containing substance (such as CuS) be used as template, also can be to CuFeS2Transformation, but particle that can be small with formation, while etching is received
The edge of rice piece, this is because the active edge of nanometer sheet can be reacted with the copper in solution phase quickly.Therefore, in the present invention preferably
Lauryl mercaptan is added.
Preferably, the cuprous halide includes at least one of CuI, CuCl and CuBr.
Preferably, the sulphur powder is dissolved in solvent by pretreatment, sulphur powder can be made to be dissolved in by ultrasonic treatment molten
In agent, sulphur powder can also be made to be dissolved in solvent by heating, heating temperature is 80-160 DEG C.Wherein, the amount of solvent is enough sulphur
Powder dissolution, it is further preferred that every 1mmol sulphur powder is dissolved in 1-10mL solvent.
Preferably, the solvent in step (2) may be the same or different with solvent used in dissolution sulphur powder；More preferably
Ground, solvent used in the solvent and dissolution sulphur powder in step (2) is oleyl amine.
Preferably, every 0.4mmol cuprous halide is dissolved in 3-20mL solvent in step (2).
Preferably, step (2) and (4) middle temperature heated are 80-160 DEG C.
Preferably, step (2) and (4) middle time to deaerate are 5-60min.
Preferably, the divalent iron salt is selected from FeCl2、Fe(NO3)2、Fe(CH3COO)2With acetylacetone,2,4-pentanedione ferrous iron at least
It is a kind of.
Preferably, the inert gas includes at least one of nitrogen, argon gas.
Preferably, the temperature of step (3) heating reaction is 100-160 DEG C, time 1-8h.
Preferably, the temperature of step (5) heating reaction is 220-310 DEG C, time 1-8h.
The present invention also provides one kind to be suitable for the light activated optothermal material of near-infrared, is prepared for the above method
CuFeS2。
Beneficial effects of the present invention
1, the CuFeS that preparation method obtains through the invention2Nanometer sheet has very strong suction in the whole region of near-infrared
It receives, it can be achieved that a variety of different wave length near infrared light excitation responses；
2 compare with common optothermal material CuS, and due under near-infrared laser, there are valence band to sky in the 3d track of iron
Intermediate Gray electron transition, the electrons for being energized into Intermediate Gray release heat in the form of radiationless, so as to avoid conduction band is arrived
Electron transmission loss, the nanometer CuFeS that the present invention is prepared2Photothermal conversion efficiency improve by about one time；
3, preparation method raw material sources provided by the present invention are abundant, preparation method is simple, low in cost, are prepared
CuFeS2Thermal stability and chemical stability are high, the great potential in the photo-thermal therapy of the following cancer.
Detailed description of the invention
Fig. 1 is the CuFeS that embodiment 1 is prepared2XRD diffracting spectrum；
Fig. 2 is the CuFeS that embodiment 1 is prepared2Ultraviolet-visible absorption spectroscopy figure；
Fig. 3 is the CuFeS that embodiment 1 is prepared2Transmission electron microscope picture；
Fig. 4 is the CuFeS that embodiment 1 is prepared2In 808nm near infrared light (1w/cm2) under irradiation, temperature at any time
Change curve；
Fig. 5 is the CuFeS that embodiment 2 is prepared2Transmission electron microscope picture；
Fig. 6 is the CuFeS that embodiment 3 is prepared2Transmission electron microscope picture.
Specific embodiment
The present invention is described in more detail With reference to embodiment, but the present invention is not limited to these embodiment party
Formula.
Embodiment 1
(1) it weighs 0.0762 gram of CuI to be added in 10 milliliters of oleyl amines, 120 DEG C is heated under stirring, nitrogen is passed through after degassing
0.0320 gram of sulphur powder is added in protection, injection, and wherein sulphur powder is dissolved in 2 milliliters of oleyl amines by ultrasound, is reacted under conditions of 120 DEG C
After 6 hours, it is cooled to room temperature；
(2) 0.1016 gram of acetylacetone,2,4-pentanedione ferrous iron is added, 1 milliliter of lauryl mercaptan is heated to 120 DEG C under stirring, lead to after degassing
Enter nitrogen protection, after being then heated to 260 DEG C, reaction 6 hours, is cooled to room temperature, obtains CuFeS2。
The sample being prepared is characterized by X-ray diffraction, it is as a result as shown in Figure 1, bright as we can see from the figure
Aobvious CuFeS2Characteristic peak illustrates that the product being prepared is CuFeS2.Sample is carried out by uv-visible absorption spectra again
Test, as a result as shown in Fig. 2, it can be seen from the figure that CuFeS2Nanometer sheet, which shows to compose entirely, to be absorbed, and is had near infrared region
Long upper uphill slope illustrates that sample has very strong absorption, it can be achieved that a variety of different wave length near infrared light excitation responses near infrared region.
Fig. 3 is the transmission electron microscope picture of this example sample, it can be seen that nanometer sheet is in approximate six side's shapes, opposite side size about 110nm, monodispersity
Well.Fig. 4 is this example sample in 808nm near infrared light (1w/cm2) under irradiation, temperature variation curve at any time, it can be seen that
Sample continues heat release under the irradiation of near infrared light, illustrates that sample has good photo-thermal effect.The present invention using CuS as template,
CuFeS is synthesized by the method that ionic portions replace2Nanometer sheet, for the most common CuS optothermal material, photo-thermal turns
Change improved efficiency by about one time, this is primarily due under near-infrared laser, and there are valence band to empty centre in the 3d track of iron
The electron transition of band, the electrons for being energized into Intermediate Gray release heat in the form of radiationless, so as to avoid the electronics for arriving conduction band
Transmitting loss.
Embodiment 2
(1) it weighs 0.0574 gram of CuBr to be added in 10 milliliters of oleyl amines, 120 DEG C is heated under stirring, nitrogen is passed through after degassing
0.0320 gram of sulphur powder is added in gas shielded, injection, and wherein sulphur powder is dissolved in 2 milliliters of oleyl amines by ultrasound, anti-under conditions of 120 DEG C
After answering 6 hours, it is cooled to room temperature.
(2) 0.1016 gram of acetylacetone,2,4-pentanedione ferrous iron is added, 1 milliliter of lauryl mercaptan is heated to 120 DEG C under stirring, lead to after degassing
Enter nitrogen protection, after being then heated to 260 DEG C, reaction 6 hours, is cooled to room temperature, obtains CuFeS2。
Fig. 5 is the CuFeS that this example is prepared2Transmission electron microscope picture, it can be seen that nanometer sheet is in approximate six side's shapes, right
Side size about 100nm, monodispersity are good.
Embodiment 3
(1) it weighs 0.0396 gram of CuCl to be added in 10 milliliters of oleyl amines, 120 DEG C is heated under stirring, nitrogen is passed through after degassing
0.0320 gram of sulphur powder is added in gas shielded, injection, and wherein sulphur powder is dissolved in 2 milliliters of oleyl amines by ultrasound, anti-under conditions of 120 DEG C
After answering 6 hours, it is cooled to room temperature.
(2) 0.1016 gram of acetylacetone,2,4-pentanedione ferrous iron is added, 1 milliliter of lauryl mercaptan is heated to 120 DEG C under stirring, lead to after degassing
Enter nitrogen protection, after being then heated to 260 DEG C, reaction 6 hours, is cooled to room temperature, obtains CuFeS2。
Fig. 6 is the CuFeS that this example is prepared2Transmission electron microscope picture, it can be seen that nanometer sheet is in approximate six side's shapes, right
Side size about 100nm, monodispersity are good.
Embodiment 4
(1) it weighs 0.0762 gram of CuI to be added in 10 milliliters of oleyl amines, 120 DEG C is heated under stirring, nitrogen is passed through after degassing
0.0320 gram of sulphur powder is added in protection, injection, and wherein sulphur powder is dissolved in 2 milliliters of oleyl amines by ultrasound, is reacted under conditions of 120 DEG C
After 6 hours, it is cooled to room temperature.
(2) 0.0507 gram of frerrous chloride is added, 1 milliliter of lauryl mercaptan is heated to 120 DEG C, nitrogen is passed through after degassing under stirring
Gas shielded is cooled to room temperature after being then heated to 260 DEG C, reaction 6 hours, obtains CuFeS2。
Embodiment 5
(1) it weighs 0.0762 gram of CuI to be added in 10 milliliters of oleyl amines, 120 DEG C is heated under stirring, nitrogen is passed through after degassing
0.0320 gram of sulphur powder is added in protection, injection, and wherein sulphur powder is dissolved in 2 milliliters of oleyl amines by ultrasound, is reacted under conditions of 120 DEG C
After 6 hours, it is cooled to room temperature.
(2) 0.0719 gram of ferrous nitrate is added, 1 milliliter of lauryl mercaptan is heated to 120 DEG C, nitrogen is passed through after degassing under stirring
Gas shielded is cooled to room temperature after being then heated to 260 DEG C, reaction 6 hours, obtains CuFeS2。
Embodiment 6
(1) it weighs 0.0762 gram of CuI to be added in 10 milliliters of oleyl amines, 120 DEG C is heated under stirring, nitrogen is passed through after degassing
0.0320 gram of sulphur powder is added in protection, injection, and wherein sulphur powder is dissolved in 2 milliliters of oleyl amines by ultrasound, is reacted under conditions of 120 DEG C
After 6 hours, it is cooled to room temperature.
(2) 0.0696 gram of ferrous nitrate is added, 1 milliliter of lauryl mercaptan is heated to 120 DEG C, nitrogen is passed through after degassing under stirring
Gas shielded is cooled to room temperature after being then heated to 260 DEG C, reaction 6 hours, obtains CuFeS2。
Obviously, above-described embodiment is only intended to clearly illustrate made preferred embodiments, not to the limit of embodiment
It is fixed.For those of ordinary skill in the art, it can also make on the basis of the above description other various forms of
Variation changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this obvious
Change or changes still within the protection scope of the invention.
Claims (4)
1. a kind of CuFeS2Preparation method, which comprises the following steps:
(1) chemical formula CuFeS is pressed2The molar percentage of middle each element weighs reaction raw materials；
(2) cuprous halide is added in solvent, stirs simultaneously heat de-airing；
(3) after being passed through inert gas shielding, sulphur powder is added and stirs evenly, heating reaction after the completion, is cooled to room temperature；
(4) divalent iron salt and lauryl mercaptan are added, simultaneously heat de-airing is stirred；
(5) it is passed through inert gas shielding, then heating reaction, after the completion, is cooled to room temperature；
Gained CuFeS2For six side's shape nanometer sheets, opposite side is having a size of 100nm or 110nm；
The cuprous halide includes at least one of CuI, CuCl and CuBr；
The solvent is oleyl amine；
The temperature heated in step (2) and (4) is 80-160 DEG C, and the time of degassing is 5-60min；Step (3) heating reaction
Temperature is 100-160 DEG C, time 1-8h；The temperature of step (5) heating reaction is 220-310 DEG C, time 1-8h.
2. a kind of CuFeS according to claim 12Preparation method, which is characterized in that the sulphur powder, will by pretreatment
It is dissolved in solvent.
3. a kind of CuFeS according to claim 12Preparation method, which is characterized in that the divalent iron salt is selected from
FeCl2、Fe(NO3)2、Fe(CH3COO)2At least one of with acetylacetone,2,4-pentanedione ferrous iron.
4. a kind of CuFeS according to claim 12Preparation method, which is characterized in that the inert gas include nitrogen,
At least one of argon gas.
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| CN104362343A (en) * | 2014-11-21 | 2015-02-18 | 厦门大学 | Preparation method and application of one-dimensional rod-like CuFeS2 compound |
| CN104402063A (en) * | 2014-11-10 | 2015-03-11 | 武汉理工大学 | Rapid preparation method of high performance CuFeS2 thermoelectric material |
| CN105154060A (en) * | 2015-07-21 | 2015-12-16 | 东华大学 | Preparation method for three-element copper-iron-sulfur (CuFeS2) fluorescent quantum dot with magnetic property by aqueous-phase synthesis |
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|---|---|---|---|---|
| CN104402063A (en) * | 2014-11-10 | 2015-03-11 | 武汉理工大学 | Rapid preparation method of high performance CuFeS2 thermoelectric material |
| CN104362343A (en) * | 2014-11-21 | 2015-02-18 | 厦门大学 | Preparation method and application of one-dimensional rod-like CuFeS2 compound |
| CN105154060A (en) * | 2015-07-21 | 2015-12-16 | 东华大学 | Preparation method for three-element copper-iron-sulfur (CuFeS2) fluorescent quantum dot with magnetic property by aqueous-phase synthesis |
Non-Patent Citations (1)
| Title |
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