CN109453374B - A kind of tellurium-cuprous sulfide heterojunction composite material and its preparation method and use - Google Patents
A kind of tellurium-cuprous sulfide heterojunction composite material and its preparation method and use Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
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- 239000011593 sulfur Substances 0.000 claims abstract description 9
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- 150000001880 copper compounds Chemical class 0.000 claims abstract description 7
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims 1
- 238000007626 photothermal therapy Methods 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 1
- 238000013170 computed tomography imaging Methods 0.000 abstract 1
- -1 fully stir Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 210000004881 tumor cell Anatomy 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 101100494769 Mus musculus Cts8 gene Proteins 0.000 description 3
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- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
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- 101150110592 CTS1 gene Proteins 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 101000722224 Homo sapiens Deleted in esophageal cancer 1 Proteins 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940124597 therapeutic agent Drugs 0.000 description 2
- 101150089509 Cts7 gene Proteins 0.000 description 1
- 241000243774 Trichinella Species 0.000 description 1
- 241001053383 Trichopilus Species 0.000 description 1
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract
本发明涉及一种碲‑硫化亚铜异质结复合材料及其制备方法和用途，所述方法包括如下步骤：(1)：将铜化合物与二甲基二硫代氨基甲酸钠加入无水乙醇中，充分搅拌，抽滤烘干得到硫铜源前驱体；硫碲源前驱体购买所得；(2)：将含硫铋源前驱体和硫铜源前驱体加入到有机溶剂中，充分搅拌，混合均匀，得到前驱反应液；(3)：将所述前驱反应液进行两段式微波加热恒温反应，得到前面所述结构的碲‑硫化亚铜异质结复合材料。所述制备方法通过特定的工艺步骤与工艺参数的选择，从而得到了具有优良的光热性能和光热效应的碲‑硫化亚铜异质结复合材料，可将其用于CT造影和光热治疗领域，具有良好的应用前景。
The invention relates to a tellurium-cuprous sulfide heterojunction composite material and a preparation method and application thereof. The method comprises the following steps: (1): adding a copper compound and sodium dimethyldithiocarbamate into anhydrous ethanol , fully stirred, suction filtered and dried to obtain the sulfur-copper source precursor; the sulfur-tellurium source precursor was purchased; (2): add the sulfur-containing bismuth source precursor and the sulfur-copper source precursor into the organic solvent, fully stir, and mix uniform, to obtain a precursor reaction solution; (3): subjecting the precursor reaction solution to a two-stage microwave heating constant temperature reaction to obtain the tellurium-cuprous sulfide heterojunction composite material with the aforementioned structure. The preparation method obtains a tellurium-cuprous sulfide heterojunction composite material with excellent photothermal performance and photothermal effect through the selection of specific process steps and process parameters, which can be used in the fields of CT imaging and photothermal therapy , has a good application prospect.
Description
Technical Field
The invention relates to the field of inorganic semiconductor materials and photothermal therapy technology, and particularly provides a tellurium-based semiconductor sulfide heterojunction composite material and a preparation method and application thereof, and more particularly provides a tellurium-cuprous sulfide heterojunction composite material and a preparation method and application thereof.
Background
Since the twenty-first century, the industrialization process is accelerated, the incidence of malignant tumors with extremely high death rate is on the rise along with the deterioration of the environment, the existing treatment mode is limited, the treatment effect is not obvious, the treatment process has great side effect on the human body, and the development of a novel treatment mode with small side effect and good treatment effect is urgent.
It was found that tumor cells died at temperatures approaching 42 ℃. The currently used heat treatment modes such as ultrasound, radio frequency, microwave and the like can kill tumor cells and damage surrounding normal tissues. Photothermal therapy is being developed as a novel therapeutic means to overcome the above problems. The working mechanism is as follows: enrichment of tumor cells in material with photothermal conversion effect, irradiating affected area with near infrared light (harmless to human body) to generate local high temperature to kill tumor cells; the near infrared light has extremely strong tissue penetration capability, and the mediated heat can only be transmitted to the tumor in a targeted way, so that the normal tissue can not be damaged in the treatment process.
Since the new century, with the development of nanoscience and technology, photothermal therapeutics based on nanomaterials have attracted the attention of many researchers at home and abroad, and the most studied at present are noble metals (Au, Ag, Pt, etc.) with a nano-morphological structure, which have excellent photothermal conversion performance. Secondly, sulfide inorganic nano-materials, wherein sulfide of copper is proved to have good photo-thermal conversion performance, such as Cu with the diameter of about 15 nm synthesized by Tian et al9S5The power of the nanocrystalline is 0.51W/cm2The temperature of the material is raised to 13 ℃ after 980 nm laser irradiation for 7 min, the mass concentration of the used solution is 40 mug/mL, and the sulfide of visible copper has potential application value in the field of photo-thermal treatment, but the accurate position of the tumor cell in the body is difficult to determine by a single photo-thermal agent, so that the tumor treatment is difficult.
The Te element is an environment-friendly element, has very low toxicity, has very high photothermal conversion performance and has wide application prospect in the field of photothermal therapy.
Based on the above, the excellent photo-thermal therapeutic agent with photo-thermal property can be realized by synthesizing the copper sulfide and tellurium composite material, and tumor cells are killed by local high temperature through the photo-thermal property, so that the photo-thermal therapeutic agent has great potential application value in the photo-thermal treatment field.
Disclosure of Invention
The invention provides a preparation method of a tellurium-cuprous sulfide heterojunction composite material, aiming at overcoming the defects of the prior art, and the method can be used for preparing the tellurium-cuprous sulfide heterojunction composite material with excellent optical performance.
The second purpose of the invention is to provide a tellurium-cuprous sulfide heterojunction composite material which has excellent photo-thermal performance and photo-thermal effect.
The third purpose of the invention is to provide a method for measuring the photothermal effect by using the tellurium-cuprous sulfide heterojunction composite material.
In order to realize the first purpose, the technical scheme of the invention is as follows:
a preparation method of a tellurium-cuprous sulfide heterojunction composite material comprises the following steps:
(1): adding a copper compound and sodium dimethyldithiocarbamate into absolute ethyl alcohol, fully stirring at the temperature of 10-30 ℃, and performing suction filtration and drying to obtain a copper sulfide source precursor;
(2): adding a sulfur tellurium source precursor and a sulfur copper source precursor into an organic solvent, fully stirring, and uniformly mixing to obtain a precursor reaction solution;
(3): carrying out two-stage microwave heating constant-temperature reaction on the precursor reaction solution to obtain a tellurium-cuprous sulfide heterojunction composite material;
the molar ratio of the copper compound to the sodium dimethyldithiocarbamate in the step (1) is 1:1-3, and the most preferable ratio is 1: 2;
the molar ratio of the sulfur copper source precursor to the sulfur tellurium source precursor is 1-5:3, preferably 2: 3;
in the preparation method of the invention, the copper compound in the step (1) is any one or a mixture of any more of copper sulfate, copper nitrate and copper chloride;
in the preparation method, the sulfur tellurium source precursor in the step (1) is one or a mixture of any more of tellurium oxide, sodium tellurite and tellurium dimethyldithiocarbamate, preferably tellurium dimethyldithiocarbamate;
in the preparation method of the present invention, the organic solvent in step (1) is any one of ethylene glycol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP), and most preferably ethylene glycol.
In the preparation method of the invention, the specific content of the step (3) is as follows:
s1: heating the precursor reaction solution obtained in the step S2 from room temperature to 90 ℃ under the ultrasonic stirring power of 200W, wherein the process needs 3-5min to obtain a first reaction solution;
s2: continuously heating the first reaction liquid to 170-190 ℃ under the ultrasonic stirring power of 200W, wherein the process needs 8-10min, and keeping the temperature for 3-6 min to obtain a second reaction liquid;
s3: and naturally cooling the second reaction solution to room temperature, centrifuging at the centrifugal speed of 18000 rpm for 4-6 minutes, washing the obtained precipitate with absolute ethyl alcohol and deionized water for 2-3 times respectively, and then drying in vacuum to obtain the tellurium-cuprous sulfide heterojunction composite material.
It is further configured that, in step S2, the first reaction solution is continuously heated to 150-.
It is further configured that, in step S1, the obtained precursor reaction solution is heated from room temperature to 90 ℃ under the ultrasonic stirring power of 200W, and the process takes 3-5min, and most preferably 4 min.
As described above, the invention provides a preparation method of a tellurium-cuprous sulfide heterojunction composite material, and the preparation method has the advantages that when the preparation method is adopted, the tellurium-cuprous sulfide heterojunction composite material with a specific appearance can be obtained, and when certain process parameters such as raw material dosage ratio, microwave power, constant temperature and the like are changed, the photothermal conversion composite material with the shape cannot be obtained.
In order to achieve the second purpose of the invention, the technical scheme is as follows:
the tellurium-cuprous sulfide heterojunction composite material is obtained by the preparation method. The invention has the beneficial effects that: the tellurium-cuprous sulfide heterojunction composite material has excellent photo-thermal performance due to the structural morphology characteristic that the caterpillar-shaped structure is adopted, so that the tellurium-cuprous sulfide heterojunction composite material can be applied to the field of photo-thermal treatment and has a good application prospect.
In order to achieve the third purpose, the technical scheme of the invention is as follows:
a method for measuring a tellurium-cuprous sulfide heterojunction composite material applied to a photo-thermal effect is specifically as follows: preparing the tellurium-cuprous sulfide heterojunction composite material as claimed in claim 6 into solutions with different mass concentrations by using high-purity water, irradiating the solutions under 808nm near-infrared laser, and measuring the relation between the temperature change and the time.
The mass concentration of the tellurium-cuprous sulfide heterojunction composite material prepared in the method is 5-100 mug/mL.
The laser power of 808nm near-infrared laser used in the method is 0.72W/cm2。
In the method, the dosage of the tellurium-cuprous sulfide heterojunction composite material solution irradiated under 808nm near-infrared laser is 1 mL.
The invention has the beneficial effects that: the obtained tellurium-cuprous sulfide heterojunction composite material with specific morphology can quickly raise the temperature of a solution under the irradiation of 808nm near-infrared laser, has excellent photo-thermal performance, and has great potential application value in the photo-thermal treatment field.
Drawings
FIG. 1 Scanning Electron Micrograph (SEM) of CTS1 of example 1;
FIG. 2 Transmission Electron Micrograph (TEM) and local High Resolution Transmission Electron Micrograph (HRTEM) of CTS1 of example 1;
FIG. 3 energy spectrum (EDX) of CTS1 from example 1;
FIG. 4X-ray diffraction Pattern (XRD) of CTS1 of example 1;
FIG. 5X-ray photoelectron Spectroscopy (XPS) of CTS1 of example 1;
FIG. 6 SEM images of CTS2 of example 2, CTS3 of example 3 and CTS1 of example 1;
FIG. 7 shows the growth process of the Te-cuprous sulfide heterojunction composite material obtained in the two-stage microwave heating isothermal reaction of the embodiment 1 of the present invention, which is performed in the step of increasing the temperature of the first reaction solution to 135-180 ℃ along with the heating of the first reaction solution in the reaction step S3-2;
FIG. 8 is a graph of the temperature change versus time for different mass concentrations of CTS1 from example 1 under 808nm laser irradiation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
S1: respectively adding 0.1 moL of copper nitrate and 0.2 moL of sodium dimethyldithiocarbamate into absolute ethyl alcohol, fully stirring, standing for 24 hours, and performing suction filtration and drying to obtain copper dimethyldithiocarbamate; tellurium dimethyldithiocarbamate is commercially available;
s2: adding copper dimethyldithiocarbamate (Cu (DMDC)) into proper amount of organic solvent ethylene glycol in a molar ratio of 2:32) And Tellurium Dimethyldithiocarbamate (TDEC), fully stirring by an ultrasonic cleaner, wherein the process needs 10-20 min, and uniformly mixing to obtain a precursor reaction solution;
s3: carrying out two-stage microwave heating constant-temperature reaction on the precursor reaction solution to obtain the tellurium-cuprous sulfide heterojunction composite material, which specifically comprises the following steps:
s3-1: heating the precursor reaction solution obtained in the step S2 from room temperature to 90 ℃ under the ultrasonic stirring power of 200W, wherein the process needs 4 min to obtain a first reaction solution;
s3-2: continuously heating the first reaction liquid to 180 ℃ under the ultrasonic stirring power of 200W, wherein the process needs 9 min, and keeping the temperature for 5min to obtain a second reaction liquid;
s3-3: and naturally cooling the second reaction solution to room temperature, centrifuging at the centrifugal speed of 18000 rpm for 5 minutes, washing the obtained precipitate with absolute ethyl alcohol and deionized water respectively for 3 times, and then drying in vacuum to obtain the telium-cuprous sulfide heterojunction composite material with the trichopilus structure, which is named as CTS 1.
EXAMPLES 2-3 examination of the amount ratio of raw materials
Except that copper dimethyldithiocarbamate (Cu (DMDC)) was used in step S1 in different molar ratios as shown in Table 1 below2) And Tellurium Dimethyldithiocarbamate (TDEC), the other operations being the same as in example 1, thus carrying out examples 2-3, the ratios of the raw materials used and the nomenclature of the composite materials are given in table 1 below.
EXAMPLES 4-6 examination of ultrasonic agitation Power
Examples 4 to 6: examples 4-6 were carried out using the same ultrasonic agitation power and composite material nomenclature as set forth in Table 2 below, except that the ultrasonic agitation power shown in Table 2 below was used in steps S3-2 and S3-3, which were the same as example 1.
EXAMPLES 7-10 two-stage microwave heating endpoint temperature examination
Examples 7 to 10: examples 7-10 were performed using the same procedure as example 1 except that the endpoint temperatures shown in Table 3 below were used in step S3-2, and the endpoints and composite designations used are given in Table 3 below.
EXAMPLES 11-13 inspection of two-stage microwave heating end-point constant temperature time
Examples 11 to 13: examples 11-13 were carried out using the same procedure as example 1 except that the endpoint thermostating times shown in Table 4 below were used in step S3-3, and the endpoints and composite nomenclature used are set forth in Table 4 below.
EXAMPLES 14-15 two-stage microwave heating Rate examination
Example 14: example 14 was conducted by following the same procedure as in example 1 except that the time required for heating the first reaction liquid to 180 ℃ was changed to 16min in step S3-2, i.e., the heating rate was 5 ℃/min, and the resulting material was named CTS 14.
Example 15: example 15 was conducted in the same manner as in example 1 except that in step S3-2, the time required for heating the first reaction liquid to 180 ℃ was changed to 6min, i.e., the heating rate was 15 ℃/min, and the resulting material was named CTS 15.
Microscopic characterization
The caterpillar tellurium-cuprous sulfide heterojunction composite material obtained in the example 1 is subjected to microscopic characterization by various different means, and the result is as follows:
1. as can be seen from the Scanning Electron Microscope (SEM) image with low magnification in figure 1, the tellurium-cuprous sulfide heterojunction composite material has uniform appearance and novel structure, is a caterpillar-shaped heterojunction, and has the diameter width of 300-400 nm and the branch length of 1-3 μm.
2. It can be seen from the Transmission Electron Micrograph (TEM) of fig. 2 that there are caterpillar-like heterojunctions, in which very clear lattice fringes are visible from the high-resolution transmission electron microscope (HRTEM), the width of which is predominantly 0.313 nm, corresponding to the (101) crystal plane of Te, respectively.
3. The energy spectrum (EDX) test of fig. 3 shows that: the sample contains three elements of Cu, Te and S, which indicates that the prepared caterpillar-shaped composite material contains three elements of Cu, Te and S.
4. As can be seen from the X-ray diffraction pattern (XRD) of FIG. 4, as a (TDEC) sulfur tellurium source and (Cu (DMDC))2) In the XRD diffraction pattern of the sample obtained from the sulfur-copper source, the diffraction peak with heart-shaped marks is the diffraction peak of Te (101), and the rest is mainly corresponding to Cu2Diffraction peak of S.
5. As can be seen from the X-ray photoelectron spectroscopy (XPS) of figure 5,with a sulfur tellurium source (TDEC) and a sulfur copper source (Cu (DMDC)2) The obtained sample is combined with other characterization modes to obtain the state that Te in the material exists in 0, +2 and +4 valence states, and Cu exists in Cu2The form of S exists.
6. FIGS. 6(a) - (c) are SEM images of CTS2 of example 2, CTS3 of example 3 and CTS1 of example 1, respectively, and it can be seen that the molar ratio of the CuS/Te as a raw material has a decisive influence on the morphology of the final product, and only when the molar ratio of the CuS/Te is 2:3, the best morphology of the Trichinella is produced.
7. Fig. 7 is a growth process of the caterpillar-shaped tellurium-cuprous sulfide heterojunction optical composite material obtained along with the change of the reaction temperature during the two-stage microwave heating isothermal reaction in the embodiment 1 of the present invention, wherein the corresponding temperatures in each figure are as follows: (a) the method comprises the following steps 135 deg.C; (b) the method comprises the following steps 145 ℃; (c) the method comprises the following steps 150 ℃; (d) the method comprises the following steps 160 ℃; (e) the method comprises the following steps 170 ℃; (f) the method comprises the following steps 180 ℃ is carried out.
8. Fig. 8 is a graph of mass concentration and temperature rise change obtained by photo-thermal effect test of the caterpillar tellurium-cuprous sulfide heterojunction light composite material obtained in example 1 of the invention, and it can be seen from the graph that the material has excellent photo-thermal effect, and the temperature change and the concentration have a nearly linear relationship.
Therefore, the caterpillar tellurium-cuprous sulfide heterojunction optical composite material has excellent photo-thermal performance and has great potential application value in the field of photo-thermal treatment.
Characterization of the composite materials obtained in the other examples
1. SEM characterization of CTS4-CTS6 shows that the CTS4-CTS6 is in a caterpillar-like similar structure, but the morphological regularity is inferior to that of CTS 1.
2. The SEM characterization of the CTS7-CTS10 shows that the CTS7 and the CTS8 do not generate caterpillar-shaped morphology structures and have large-block precursor assemblies, the CTS9 and the CTS10 are caterpillar-shaped morphology structures, the CTS9 morphology rules are poor, and the CTS10 and the CTS1 have basically the same morphology.
3. SEM characterization of CTS11-CTS13 shows that bulk precursor assemblies exist in CTS11, which shows incomplete reaction, and CTS12 and CTS13 have basically the same morphology as CTS1, but the reaction time is preferably short.
4. The SEM characterization of the CTS14-CTS15 shows that large precursor assemblies exist in the CTS14, the morphology of the CTS14 is different from that of caterpillar, and the CTS15 and the CTS1 have basically the same morphology, but the reaction time is preferably short.
Test of photothermal conversion Property
1. The caterpillar tellurium-cuprous sulfide heterojunction light composite material obtained in the example 1 is used for photo-thermal conversion, and the specific treatment method comprises the following steps:
the tellurium-cuprous sulfide heterojunction composite material is dispersed into high-purity water to be prepared into 0 mu g/mL, 10 mu g/mL, 25 mu g/mL, 50 mu g/mL, 100 mu g/mL and 200 mu g/mL respectively, the prepared solution is sucked into 1mL and added into a quartz cuvette (3 mL), and the temperature change is recorded by using 808nm laser for 10min irradiation.
The diagram of the relationship between laser irradiation and temperature change of the tellurium-cuprous sulfide heterojunction composite material prepared in the embodiment 1 of the invention is shown in the attached figure 8, under the mass concentration of 50 mu g/mL, the temperature rise of the tellurium-cuprous sulfide heterojunction composite material after 10min of laser irradiation is higher than that of pure water by about 12.5 ℃, and is higher than most of photothermal conversion materials, and meanwhile, the temperature change and the concentration have a nearly linear relationship, so that the tellurium-cuprous sulfide heterojunction composite material has excellent photothermal performance.
In summary, it can be seen from all the above embodiments that the preparation method of the invention obtains the caterpillar-shaped tellurium-cuprous sulfide heterojunction composite material with a unique morphology through the synergistic combination and coordination of specific process steps, process parameters and the like, and has a good photo-thermal effect.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (9)
1. The preparation method of the tellurium-cuprous sulfide heterojunction composite material is characterized by comprising the following steps of:
(1): adding a copper compound and sodium dimethyldithiocarbamate into absolute ethyl alcohol, fully stirring at the temperature of 10-25 ℃, and performing suction filtration and drying to obtain a copper sulfide source precursor;
(2): adding a sulfur tellurium source precursor and a sulfur copper source precursor into an organic solvent, fully stirring, and uniformly mixing to obtain a precursor reaction solution;
(3): carrying out two-stage microwave heating constant-temperature reaction on the precursor reaction solution to obtain a tellurium-cuprous sulfide heterojunction composite material;
the molar ratio of the copper compound to the sodium dimethyldithiocarbamate in the step (1) is 1: 1-3; the molar ratio of the sulfur copper source precursor to the sulfur tellurium source precursor is 2: 3;
the step (3) is specifically as follows:
s1: heating the precursor reaction solution obtained in the step (2) from room temperature to 90 ℃ under the ultrasonic stirring power of 200W, wherein the process needs 3-5min to obtain a first reaction solution;
s2: continuously heating the first reaction liquid to 180-190 ℃ under the ultrasonic stirring power of 200W, wherein the process needs 8-9 min, and keeping the temperature for 3-5min to obtain a second reaction liquid;
s3: and naturally cooling the second reaction solution to room temperature, centrifuging at the centrifugal speed of 18000 rpm for 4-6 minutes, washing the obtained precipitate with absolute ethyl alcohol and deionized water for 2-3 times respectively, and then drying in vacuum to obtain the tellurium-cuprous sulfide heterojunction composite material.
2. The method of claim 1, wherein: in the step (1), the copper compound is any one or a mixture of any more of copper sulfate, copper nitrate and copper chloride.
3. The method of claim 1, wherein: in the step (2), the sulfur tellurium source precursor is any one or a mixture of any more of tellurium oxide, sodium tellurite and tellurium dimethyldithiocarbamate.
4. The method of claim 1, wherein: in the step (2), the organic solvent is any one of ethylene glycol, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
5. A tellurium-cuprous sulfide heterojunction composite material obtained by the preparation method according to any one of claims 1-4.
6. The method for measuring the application of the tellurium-cuprous sulfide heterojunction composite material to the photo-thermal effect, which is characterized in that: the method specifically comprises the following steps: preparing the tellurium-cuprous sulfide heterojunction composite material as claimed in claim 5 into solutions with different mass concentrations by using high-purity water, irradiating the solutions under 808nm near-infrared laser, and measuring the relation between the temperature change and the time.
7. The measurement method according to claim 6, characterized in that: the mass concentration of the prepared tellurium-cuprous sulfide heterojunction composite material is 5-100 mug/mL.
8. The method of any of claims 6-7, wherein: the laser power of the 808nm near-infrared laser is 0.72W/cm2。
9. The method of any of claims 6-7, wherein: the dosage of the tellurium-cuprous sulfide heterojunction composite material solution irradiated under 808nm near-infrared laser is 1 mL.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106994184A (en) * | 2017-03-31 | 2017-08-01 | 温州大学 | A kind of vulcanized lead tellurium composite, preparation method and its usage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106924734A (en) * | 2017-03-31 | 2017-07-07 | 温州大学 | A kind of bismuth sulfide cuprous sulfide heterojunction composite of sea urchin shape structure and its preparation method and application |
| CN106994184A (en) * | 2017-03-31 | 2017-08-01 | 温州大学 | A kind of vulcanized lead tellurium composite, preparation method and its usage |
Non-Patent Citations (2)
| Title |
|---|
| "Multifunctional Cu2−xTe Nanocubes Mediated Combination Therapy for Multi-Drug Resistant MDA MB 453";Aby Cheruvathoor Poulose et al;《Scientific Reports》;20161024;第6卷;第1-13页 * |
| "新型硫化铅基纳米材料的液相微波法可控制备与应用研究";郑皓源;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20160215(第02期);第B020-432页 * |
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