CN113233495B - CdS nano ring and preparation method and application thereof, cdS composite membrane and preparation method and application thereof - Google Patents
CdS nano ring and preparation method and application thereof, cdS composite membrane and preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J35/39—Photocatalytic properties
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Abstract
The invention provides a CdS nano ring, a preparation method and application thereof, a CdS composite membrane, a preparation method and application thereof, wherein after coordination by using a coordination agent, S generated by hydrolysis of thiourea under microwave radiation is combined 2‑ Preparing CdS nano-rings, crosslinking sodium carboxymethylcellulose and sodium alginate to form a transparent hydrogel biomembrane as a matrix, dispersing CdS in the matrix, and loading to prepare the CdS composite membrane. Compared with the prior art, the method has the advantages of simple equipment, simple and convenient operation, nontoxic and environment-friendly reaction reagents, no need of using a surfactant, lower synthesis temperature and shorter reaction time, and the prepared CdS nano-ring has better degradation effect on various dyes under the irradiation of visible light; the matrix used for the photocatalyst loading is green and environment-friendly, the formed hydrogel is colorless and transparent, and the loaded composite film has good repeated degradation effect on various dyes under the irradiation of visible light.
Description
Technical Field
The invention belongs to the technical field of nano material preparation and loading, and particularly relates to a CdS nano ring, a preparation method and application thereof, a CdS composite membrane and a preparation method and application thereof.
Background
CdS is a group II-VI direct band gap semiconductor material, the band gap is 2.4eV, and the CdS is an excellent photocatalytic material. As the organic dye can generate OH under the excitation of visible light and degrade the organic dye, the organic dye can be widely applied to the treatment of organic sewage.
The performance of the nano material has close relation with the structure, and CdS with different morphologies such as quantum dots, nanowires and hollow microspheres have different degradation performances on organic dyes. The nano ring is a nano material with a special structure, and the existing annular cavity can increase the interface area and the sites of the photocatalytic reaction, thereby being beneficial to improving the efficiency of the photocatalytic reaction. However, previous synthesis of CdS nanorings typically employed solvothermal or chemical bath methods. In the solvothermal method, expensive surfactants such as 1, 12-dodecyl diamine, 1, 8-octanediamine, 1, 6-hexamethylenediamine and the like are required to be added, and the reaction is required to be carried out for 4-48 hours at 150-200 ℃; in the chemical bath method, the reaction is required to be carried out in a water bath at 60 ℃ for 1h, and the generated morphology is not uniform. Therefore, there is a need for a simple, economical way of preparing CdS nanorings with high photocatalytic degradation capability.
In addition, the prepared CdS nano-ring powder is easy to agglomerate and adhere to degraded molecules, so that the CdS nano-ring powder is difficult to separate and has low recycling rate; and CdS has unstable chemical property, S 2- Is easy to oxidize to generate serious photo-corrosion, and not only can dissolve out harmful Cd 2+ But also can make the catalyst reutilization inefficiency. In order to improve the recycling efficiency of the CdS nano ring and reduce heavy metal pollution caused by photo-corrosion, a certain matrix is often selected to perform catalyst immobilization treatment, so that the problems of catalyst separation, recovery and recycling can be solved, and the phenomenon of nanoparticle aggregation can be avoided. The common fixed matrix materials are mostly inorganic materials, such as CdS is loaded on a perlite carrier, wrapped in a zeolite cavity or loaded on porous zirconium titanium phosphate, and the mesoporous and microporous materials have large specific surface area, uniform pore diameter and easily controlled pore size, so that the photo-corrosion resistance of the CdS is obviously improved, and the phenomenon of reduced photo-catalytic activity caused by loading is avoided. However, inorganic materials have a fatal defect that they block a part of incident light from reaching the surface of the catalyst, so that light energy is not fully utilized.
Disclosure of Invention
The invention aims to provide a CdS nano-ring and a preparation method thereof, and the Cd nano-ring is coordinated by using a complexing agent 2+ After that, the processing unit is configured to,and S generated by hydrolysis of thiourea under microwave radiation 2- The preparation method of the CdS nano-ring is low in temperature, rapid and free of surfactant, and solves the problems that in the prior art, complex surfactant, higher temperature and longer reaction time are needed in the CdS nano-ring synthesis process.
The invention also aims to provide an application of the CdS nano-ring in the field of photocatalytic degradation.
The invention further aims to provide a CdS composite membrane and a preparation method thereof, wherein sodium carboxymethyl cellulose and sodium alginate are used as matrixes, cdS nano-rings are dispersed in the matrixes, and the CdS composite membrane is prepared by loading.
The final object of the invention is to provide an application of the CdS composite film in the field of photocatalytic degradation.
The specific technical scheme of the invention is as follows:
the preparation method of the CdS nano ring specifically comprises the following steps:
the cadmium salt solution is regulated to be alkaline, then a sulfur source is added, and the mixture is stirred uniformly; and carrying out microwave reaction on the obtained mixed solution to obtain the CdS nano ring.
The solvent of the cadmium salt solution is distilled water;
the cadmium salt is soluble cadmium salt; the cadmium salt is Cd (NO) 3 ) 2 Or CdCl 2 ；
The sulfur source is thiourea;
the alkaline is regulated to be an ammonia solution, and the ammonia solution is hydrazine hydrate; the thiourea is adjusted to be alkaline so as to be beneficial to hydrolysis of the thiourea in an alkaline solution; the hydrazine hydrate can not only regulate the solution to be alkaline, but also provide coordination group-NH 2 ；
The alkaline adjustment means that the pH is adjusted to 10.8-11.5, and a sulfur source is added, preferably 11.0;
the concentration of the cadmium salt solution is 8-12mmol/L, preferably 10mmol/L; the sulfur source is 1.5-6 times, preferably 3 times, the amount of the cadmium salt substance;
the power of the microwave reaction is 200-800W, preferably 800W; the reaction temperature is 70-90 ℃, preferably 80 ℃; the reaction time is 5-40min, preferably 20min.
After the microwave reaction is finished, centrifuging at 6000-10000rpm for 5-10min, washing the obtained product with distilled water and absolute ethyl alcohol for three times, and vacuum drying at 60 ℃ for 4-6h to obtain the CdS nano ring.
The CdS nano ring provided by the invention is prepared by adopting the method, the prepared CdS is in a hollow annular structure, and the diameter of the ring is 100-200nm; the ring cavity is 50-100nm, and the CdS nano ring is assembled by nano particles with the diameter of 5-8 nm.
The preparation method of the CdS nano-ring of the invention comprises the steps of 2+ with-NH containing a coordinating group 2 After coordination of hydrazine hydrate, thiourea is combined, S generated by hydrolysis of thiourea in alkaline solution 2- Forming CdS crystal nucleus and further assembling into ring under the action of microwave. The microwaves can be directly combined with the molecules of the reaction mixture, which is favorable for homogeneous phase formation in the reaction process, so that the nano-rings with uniform size and shape distribution can be formed. In particular, the microwave reaction can realize rapid temperature rise in a short time, which is beneficial to improving the reaction efficiency.
The application of the CdS nano ring provided by the invention is used for photocatalytic degradation of dye.
The CdS composite membrane provided by the invention is prepared by adopting the CdS nano ring, and the specific preparation method comprises the following steps:
1) Dispersing CdS nano-rings in water;
2) Dispersing the hydrogel material in CdS dispersion liquid, and uniformly stirring to obtain film liquid;
3) Cooling the membrane liquid to form a membrane, and transferring the membrane to CaCl 2 Soaking in water solution, taking out, washing, and freeze drying to obtain CdS composite film.
In the step 1), the CdS nano-rings are dispersed in water, and the concentration is 10-30mg/mL, preferably 20mg/mL;
in the step 2), the mass ratio of the hydrogel material to the CdS nano-ring is 3:1-3:3, preferably 3:2;
the hydrogel material is a mixture of sodium carboxymethyl cellulose and sodium alginate;
the weight ratio of the sodium carboxymethyl cellulose to the sodium alginate is 1:4-4:2, and can be 1:4, 1:2, 2:3, 1:1, 3:2 or 4:2, preferably 1:2;
the step 3) is specifically as follows: transferring 1-3mL, preferably 2mL, of membrane solution into a culture dish with diameter of 3.5cm to form a composite membrane with thickness of 2.8-3.2mm, and freezing at-8deg.C to-12deg.C for 12-24 hr in a refrigerator.
CaCl as described in step 3) 2 The mass percentage concentration of the aqueous solution is 5%; by Ca 2+ Coordinates with groups such as-COOH, -OH and the like contained in the hydrogel material to increase the hardness of the film and improve the stability of the film.
In step 3), the freeze-formed film is directly transferred to 5% CaCl 2 Completely soaking in the solution for at least 12 hr, taking out, and washing the membrane surface with distilled water at normal temperature to remove CaCl adhered to the membrane surface 2 And transferring the aqueous solution into a low-temperature freeze dryer, and freeze-drying at-30 ℃ to-70 ℃ to obtain the CdS composite membrane.
The CdS composite film provided by the invention is prepared by adopting the method.
According to the preparation method of the composite membrane, the transparent hydrogel biomembrane is formed by crosslinking sodium carboxymethylcellulose containing groups such as-COOH, -OH and the like and sodium alginate as a matrix, so that the light transmittance can be remarkably improved, and the loss of light energy caused by taking an opaque inorganic material as a carrier is avoided. On the other hand, the hydrogel with a three-dimensional network structure formed by crosslinking a plurality of hydrophilic groups such as-COOH, -OH and the like can absorb a large amount of water, and provides a good environment for photocatalytic degradation reaction in aqueous solution; and the catalyst also has high thermal stability, and is beneficial to regulating and controlling photocatalytic degradation reaction in a variable temperature range.
The application of the CdS composite film provided by the invention is used for photocatalytic degradation, and is especially used for repeated degradation of dye.
Compared with the prior art, the photocatalyst preparation method has the advantages that equipment used for preparing the photocatalyst is simple (mainly a microwave synthesizer), the operation is simple and convenient, most of reaction reagents are nontoxic and environment-friendly, a surfactant is not needed, the synthesis temperature is low, the reaction time is short, and the prepared CdS nano-ring has a good degradation effect on various dyes under irradiation of visible light; the matrix used for the photocatalyst loading is green and environment-friendly, the formed hydrogel is colorless and transparent, and the loaded composite film has good repeated degradation effect on various dyes under the irradiation of visible light.
Drawings
FIG. 1 is SEM (a) and XRD (b) images of CdS nanorings prepared in example 1;
FIG. 2 is a TEM image of CdS nanorings prepared in example 1;
FIG. 3 is an XPS chart of the CdS nanoring prepared in example 1;
FIG. 4 shows the UV-visible absorption spectra (a) and N of the CdS nanoring prepared in example 1 2 Adsorption and desorption isotherms (b), wherein the insert in fig. 4 a is the CdS optical band gap calculated by the direct band gap method, and the insert in fig. 4 b is the BHJ plot;
FIG. 5 is a graph of the photodegradation of methyl blue (a), rhodamine B (B), and malachite green (c) for the CdS nanoring prepared in example 1;
FIG. 6 is a SEM image of the CdS composite film (a) and the original film (b) prepared in example 1, and a TG (c) image of the CdS composite film and the original film;
FIG. 7 is a graph showing the contact angle between the CdS composite film (a) prepared in example 1 and the original film (b);
FIG. 8 is a graph showing repeated photodegradation of methyl blue (a), rhodamine B (B) and malachite green (c) for the CdS composite film prepared in example 1;
FIG. 9 is an SEM image of the CdS produced in example 2;
FIG. 10 is an SEM image of the CdS produced in example 3;
FIG. 11 is an SEM image of the CdS produced in example 4;
FIG. 12 is an SEM image of the CdS produced in comparative example 1;
FIG. 13 is an SEM image of the CdS produced in comparative example 2;
FIG. 14 is an SEM image of the prepared CdS of comparative example 3.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The preparation method of the CdS nano ring specifically comprises the following steps: adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration is 0.01mol/L, then the pH is regulated to 11.0 by hydrazine hydrate, and Cd (NO) is added 3 ) 2 ·4H 2 Thiourea with the quantity of O substance being three times that of the O substance is evenly mixed to obtain a mixed solution, then the mixed solution is transferred into a microwave reactor, the reaction time is 20min at the reaction power of 800W and the reaction temperature of 80 ℃, the obtained product is centrifuged at 10000rpm for 5min, the obtained product is firstly washed three times by distilled water and then is washed three times by absolute ethyl alcohol, and the CdS nano-ring is obtained by drying in a vacuum oven at 60 ℃.
The method for preparing the CdS composite film by utilizing the CdS nano ring specifically comprises the following steps: adding 60mg of CdS nano-ring into 3mL of water, fully dispersing, adding a mixture of 30mg of sodium carboxymethylcellulose and 60mg of sodium alginate into the dispersion, continuously stirring for at least 12 hours to form uniform membrane liquid, pouring 2mL of membrane liquid into a culture dish with the diameter of 3.5cm, and freezing in a refrigerator at the temperature of minus 10 ℃ for 24 hours. The frozen film was completely immersed in 5% CaCl 2 Soaking the membrane in the solution for 12 hr, taking out, clamping with forceps, and washing the membrane surface with distilled water at normal temperature to remove CaCl adhered to the membrane surface 2 And transferring the aqueous solution into a low-temperature freeze dryer, and freeze-drying at-70 ℃ to obtain the complete composite membrane.
The morphology structure of the CdS nano-ring prepared in the example 1 is shown in fig. 1, a in fig. 1 is an SEM photograph of CdS, and the synthesized CdS is in a hollow annular structure with the size of about 100nm; in fig. 1 b is the XRD result of CdS, and the synthesized CdS is a zinc blende structure in cubic phase, consistent with standard PDF card 10-0454. TEM results (FIG. 2) further confirm that the synthesized CdS is hollow ring structure with a ring diameter of 100nm and a ring cavity of 50nm (FIG. 2 a); the nanoring is assembled from nanoparticles with a size of 5-8nm (b in fig. 2); the lattice plane spacing is 0.33nm and 0.21nm, corresponding to the (111) and (220) crystal planes of the sphalerite crystal phase, respectively (c in fig. 2); area selection electricityThe sub-diffraction is a polycrystalline ring structure, and the diffraction rings correspond to the (111), (220) and (311) crystal planes (d in fig. 2). As shown in FIG. 3, XPS of CdS nanoring, it can be seen from the figure that it contains Cd, S, C, O and other elements (a in FIG. 3); cleavage of Cd3d to Cd3d 5/2 (412eV),Cd3d 3/2 (405.2 eV), the difference in cleavage energy was 6.8eV (b in FIG. 3), indicating that Cd exists in the form of Cd (II); s2p cleavage into S2p 3/2 (161.5 eV) and S2p 1/2 (162.6 eV), the difference in cleavage energy was 1.1eV (c in FIG. 3), indicating the presence of sulfide. Thus, the product formed was demonstrated to be CdS. The test of the element ratio in XPS shows that Cd: the S atomic ratio is 1:1.05.
The property of CdS is shown in FIG. 4, wherein a in FIG. 4 is an ultraviolet-visible absorption spectrum, which shows that CdS has good absorption in the visible light region, shoulder appears at 532nm, and the optical band gap is calculated to be 2.25eV by a direct band gap method (an illustration in FIG. 4); n (N) 2 Adsorption and desorption isotherm test for characterizing porosity and specific surface area of materials, as seen in fig. 4 b, it shows an i-type isotherm with a hysteresis loop from 0.8 to 1.0P 0 P, average CdS pore diameter of 52nm, and specific surface area of 44.1673m were obtained from BJH chart (b insert in FIG. 4) 2 And/g, the sample has mesoporous pores and larger specific surface area.
FIG. 5 is a graph of the photodegradation of CdS nanorings versus different dyes. The photodegradation experiment is carried out according to the following steps: 30mg of the synthesized CdS nanoring was suspended in 50mL of a methyl blue (concentration: 100 mg/L) solution or a RhB (concentration: 60 mg/L) solution or a malachite green (concentration: 80 mg/L) solution, respectively. Stirring and ultrasonic treatment are carried out for 10 minutes to obtain a homogeneous solution. At intervals 3mL of the suspension was removed from the system, centrifuged to remove CdS particles and the maximum absorbance change of methyl blue (λ=588 nm) or RhB (λ=554 nm) or malachite green (λ=617 nm) was detected with an uv-vis spectrophotometer. The absorbance value (C) of a specific reaction time system is shown on the abscissa t ) Absorbance of the system before unreacted (C 0 ) Is plotted on the ordinate. Before photodegradation, the suspension is placed in the dark for 60min to reach adsorption and desorption equilibrium, and the photoreaction is carried out under AM1.5 sunlight emitted by a 300W xenon lamp provided with a CUT420 optical filter, and the absorption is carried outThe attachment and degradation rates are determined by the reaction under dark and light (C 0 -C t )/C 0 Obtained. The distance between the xenon lamp and the reaction tank is 10cm, and the intensity is about 220mW/cm 2 . To prevent the temperature from rising, the system is cooled with circulating water. As can be seen from fig. 5 a, the degradation rate of the CdS nano ring to methyl blue under 120min of illumination is 86.97% (the adsorption rate of dark reaction for 60min is 49.02%); in FIG. 5, B is a photodegradation curve of CdS nanoring to rhodamine B, and the degradation rate under illumination for 120min is 91.38% (the adsorption rate for dark reaction for 60min is 5.48%); in FIG. 5c is a photodegradation curve of CdS nanoring versus malachite green, the degradation rate under light irradiation for 120min was 98.80% (dark reaction 60min adsorption rate was 26.55%). Obviously, three dyes basically reach adsorption equilibrium within about 20-30min in the dark reaction, and decompose rapidly after illumination, which shows that the CdS nano-ring has excellent photocatalytic degradation capability for various organic dyes.
SEM of the CdS composite film prepared in example 1 is shown in FIG. 6 a, compared with a flat original film (shown in FIG. 6 b, wherein the original film is prepared by dissolving a mixture of 30mg sodium carboxymethylcellulose and 60mg sodium alginate in 3mL water to form a uniform film solution, pouring 2mL of the film solution into a culture dish with a diameter of 3.5cm, freezing in a refrigerator at-10deg.C for 24h, completely immersing the frozen film in 5% CaCl 2 Taking out the solution after 12 hours, fully flushing the surface of the membrane with water, and then transferring the membrane to a low-temperature freeze dryer at the temperature of-70 ℃ for freeze drying to obtain the catalyst CdS, wherein the surface of the composite membrane is convex and uneven, and a colloidal matrix formed by the membrane wraps the catalyst CdS; in fig. 6 c is a TG plot of the composite film, the stability of the composite film is significantly increased compared to the original film, which is thermally unstable, due to the reduced relative mass of the organics. Fig. 7 a is a graph of contact angle of the composite film, and the contact angle of the CdS composite film is obviously reduced to 30.08 ° compared with the contact angle of the original film of 41.77 ° (b in fig. 7), which indicates that the composite film has stronger hydrophilicity.
FIG. 8 is a graph showing absorbance change curves for three-fold degradation of different dyes by a composite membrane. The photodegradation experiment is carried out according to the following steps: the prepared composite membrane is respectively placed in 50mL of methyl blue solution (100 mg/L) or RhB solution (60 mg/L) or malachite greenIn a hollow basket in solution (80 mg/L) to ensure adequate contact of the membrane with the dye. A certain amount of degradation solution was taken at intervals, and the change in the maximum absorbance of methyl blue (λ=588 nm) or RhB (λ=554 nm) or malachite green (λ=617 nm) was detected with an ultraviolet-visible spectrophotometer. The absorbance value (C) of a specific reaction time system is shown on the abscissa t ) Absorbance of the system before unreacted (C 0 ) Is plotted on the ordinate. Before photodegradation, it was placed in the dark for 60min to reach adsorption and desorption equilibrium, the photoreaction was performed under AM1.5 sunlight from a 300W xenon lamp equipped with a CUT420 filter, and the adsorption and degradation rates were determined by the adsorption and degradation rates under dark and photoreaction (C 0 -C t )/C 0 Obtained. The distance between the xenon lamp and the reaction tank is 10cm, and the intensity is about 220mW/cm 2 . To prevent the temperature from rising, the system is cooled with circulating water. After each photodegradation is finished, the composite membrane is placed in distilled water to be soaked for 5-6 hours so as to remove dye molecules adsorbed on the surface, and after the excessive moisture on the surface is absorbed by filter paper, photocatalytic degradation reaction is performed again. In FIG. 8, a is a graph of degrading methyl blue, and the three degradation rates under light irradiation are 99.58%, 96.98% and 90.58%, respectively (the adsorption rates in dark reaction for 60min are 6.25%, 6.07% and 4.29%, respectively); in the graph of fig. 8, the degradation rates of B for rhodamine B under light irradiation are 69.14%, 64.40% and 64.40%, respectively (the adsorption rates for dark reaction for 60min are 18.61%, 10.13% and 5.87%, respectively); in FIG. 8, c is a graph showing the degradation rate of malachite green, which was 87.71%, 82.32% and 74.85% for three times under light (adsorption rates of 5.38%, 4.19% and 5.47% for dark reaction 60min, respectively). Obviously, after repeated degradation of a plurality of dyes, the degradation effect of the composite film is reduced slightly, which indicates that the composite film has good reusability and universality for degradation of a plurality of dyes.
Example 2
The preparation method of the CdS nano ring specifically comprises the following steps: adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration is 0.012mol/L, then the pH is adjusted to 11.0 by hydrazine hydrate, and Cd (NO) is added 3 ) 2 ·4H 2 Thiourea in three times the amount of O substance and mixingAfter homogenization, a mixed solution is obtained, the mixed solution is transferred into a microwave reactor, the reaction time is 20min at the reaction power of 800W and the reaction temperature of 80 ℃, the obtained product is centrifuged at 10000rpm for 5min, distilled water and absolute ethyl alcohol are used for three times, and the CdS nano-ring is obtained after drying in a vacuum oven at 60 ℃.
Example 3
The preparation method of the CdS nano ring specifically comprises the following steps: adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration is 0.01mol/L, then the pH is regulated to 11.0 by hydrazine hydrate, and Cd (NO) is added 3 ) 2 ·4H 2 Thiourea with the quantity of O substance being three times that of the O substance is evenly mixed to obtain a mixed solution, the mixed solution is transferred into a microwave reactor, the reaction time is 20min at the reaction power of 200W and the reaction temperature of 80 ℃, the obtained product is centrifuged at 10000rpm for 5min, distilled water and absolute ethyl alcohol are used for washing three times respectively, and the CdS nano-ring is obtained after drying in a vacuum oven at 60 ℃.
Example 4
The preparation method of the CdS nano ring specifically comprises the following steps: adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration is 0.01mol/L, then the pH is regulated to 11.0 by hydrazine hydrate, and Cd (NO) is added 3 ) 2 ·4H 2 Thiourea with the quantity of O substance being three times that of the O substance is evenly mixed to obtain a mixed solution, the mixed solution is transferred into a microwave reactor, the reaction time is 20min at the reaction power of 800W and the reaction temperature of 70 ℃, the obtained product is centrifuged at 10000rpm for 5min, distilled water and absolute ethyl alcohol are used for washing three times respectively, and the CdS nano-ring is obtained after drying in a vacuum oven at 60 ℃.
FIG. 9 is an SEM image of CdS nanoring prepared in example 2 using 0.012mol/L cadmium salt and three times the amount of thiourea, the product being a hollow ring structure assembled from nanoparticles, the ring diameter being about 200nm, the annulus diameter being about 100nm; FIG. 10 is an SEM image of a CdS nanoring prepared by a 200W microwave reaction in example 3, the product being a hollow ring structure assembled from nanoparticles, the ring diameter being 100-150nm, the ring cavity diameter being 50-100nm; FIG. 11 is an SEM image of CdS nanorings prepared at 70deg.C in example 4, and the product was mostly hollow ring-shaped structures assembled by nanoparticles, the diameter of the rings was around 100nm, the diameter of the ring cavity was around 50nm, but there were still a small number of chain-like structures that were not completely ring-shaped. It can be seen that the ring can be formed when the reactant concentration, microwave power, reaction temperature, etc. are varied over a range, with the differences of ring integrity, ring diameter size, and annulus size.
Comparative example 1
The preparation of the CdS material specifically comprises the following steps:
adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration was 0.01mol/L, then the pH was adjusted to 11.0 with triethanolamine, and Cd (NO) 3 ) 2 ·4H 2 Thiourea with the quantity of O substance being three times that of the O substance is evenly mixed to obtain a mixed solution, and the mixed solution is transferred into a microwave reactor, and the reaction time is 20min at the reaction power of 800W and the reaction temperature of 80 ℃. And centrifuging the obtained product at 10000rpm for 5min, washing with distilled water and absolute ethyl alcohol for three times respectively, and drying in a vacuum oven at 60 ℃ for 6h to obtain the CdS nanomaterial.
Comparative example 2
The preparation of the CdS material specifically comprises the following steps:
adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration is 0.01mol/L, then the pH is regulated to 11.0 by hydrazine hydrate, and Cd (NO) is added 3 ) 2 ·4H 2 Thioacetamide with the amount of O substance being three times that of the thioacetamide is uniformly mixed to obtain a mixed solution, and the mixed solution is transferred into a microwave reactor, and the reaction time is 20min at the reaction power of 800W and the reaction temperature of 80 ℃. And centrifuging the obtained product at 10000rpm for 5min, washing with distilled water and absolute ethyl alcohol for three times respectively, and drying in a vacuum oven at 60 ℃ for 6h to obtain the CdS nanomaterial.
Comparative example 3
The preparation of the CdS material specifically comprises the following steps:
adding a certain amount of Cd (NO) into the aqueous solution 3 ) 2 ·4H 2 O, cd is caused to 2+ The concentration is 0.01mol/L, then the pH is regulated to 11.0 by hydrazine hydrate, and Cd (NO) is added 3 ) 2 ·4H 2 Thiourea, three times the amount of O substance, was mixed uniformly to obtain a mixed solution, which was transferred to an autoclave, and reacted at a reaction temperature of 80℃for 20 minutes. And centrifuging the obtained product at 10000rpm for 5min, washing with distilled water and absolute ethyl alcohol for three times respectively, and drying in a vacuum oven at 60 ℃ for 6h to obtain the CdS nanomaterial.
FIG. 12 is an SEM image of a synthesized CdS using triethanolamine as a pH adjustor, the product was in the form of independent particles, and the size was about 20nm, and could not form a ring shape; FIG. 13 is an SEM image of a synthesized CdS using thioacetamide as a sulfur source, the product being layered and not being cyclic; FIG. 14 is an SEM image of CdS synthesized by solvothermal reaction, and the product is in the form of independent particles with a size of about 40-50nm, and the product is mostly randomly piled up, and a small amount of product is connected into a chain structure, so that the product can hardly form a ring shape. It can be seen that when the pH adjustor, the sulfur source, the reaction system, and the like are changed, the cyclic structure cannot be formed.
In general, the nanoring formation process goes through a series of processes. Hydrazine hydrate contains two amino groups and can be used for preparing Cd 2+ Strongly coordinated and then combined with thiourea to form an intermediate complex, S generated by hydrolysis of thiourea in an alkaline solution 2- And forming CdS crystal nucleus, and decomposing to form homogeneous nanometer ring structure under microwave heating condition. When the complexing agent becomes triethanolamine, the ring cannot be formed due to the reduction of the complexing ability; when the sulfur source is changed into thioacetamide, the hydrolysis in alkaline solution is not favored; when the reaction mode is changed into solvothermal, the requirement of homogeneous reaction cannot be met, and therefore, a uniform nano-ring structure cannot be formed.
Claims (4)
1. The preparation method of the CdS nano ring is characterized by specifically comprising the following steps:
regulating the pH value of the cadmium salt solution to 10.8-11.5 by adopting hydrazine hydrate, adding thiourea as a sulfur source, and uniformly stirring; carrying out microwave reaction on the obtained mixed solution to obtain CdS nano-rings;
the power of the microwave reaction is 200-800W, the reaction temperature is 70-90 ℃, and the reaction time is 5-40 min;
the prepared CdS is in a hollow annular structure, and the diameter of the ring is 100-150 nm; the ring cavity is 50-100nm, and the CdS nano-ring is assembled by nano-particles with the diameter of 5-8 nm.
2. The method according to claim 1, wherein the concentration of the cadmium salt solution is 8-12mmol/L, and the sulfur source is 1.5-6 times the amount of the cadmium salt substance.
3. The preparation method of the CdS composite film is characterized in that the CdS nano-ring prepared by the preparation method of claim 1 is prepared, and the preparation method of the specific CdS composite film comprises the following steps:
1) Dispersing CdS nano-rings in water;
2) Dispersing the hydrogel material in CdS dispersion liquid, and uniformly stirring to obtain film liquid;
3) Cooling the membrane liquid to form a membrane, and transferring the membrane to CaCl 2 Soaking in aqueous solution, taking out, washing, and freeze drying to obtain CdS composite membrane;
the preparation method of the CdS nano ring comprises the following steps:
regulating the pH value of the cadmium salt solution to 10.8-11.5 by adopting hydrazine hydrate, adding thiourea as a sulfur source, and uniformly stirring; carrying out microwave reaction on the obtained mixed solution to obtain CdS nano-rings; the power of the microwave reaction is 200-800W, the reaction temperature is 70-90 ℃, and the reaction time is 5-40 min;
the prepared CdS is in a hollow annular structure, and the diameter of the ring is 100-150 nm; the ring cavity is 50-100nm, and the CdS nano-ring is assembled by nano-particles with the diameter of 5-8 nm.
4. The preparation method of the CdS composite film is characterized in that the CdS nano-ring prepared by the preparation method of claim 2 is prepared, and the preparation method of the specific CdS composite film comprises the following steps:
1) Dispersing CdS nano-rings in water;
2) Dispersing the hydrogel material in CdS dispersion liquid, and uniformly stirring to obtain film liquid;
3) Cooling the membrane liquid to form a membrane, and transferring the membrane to CaCl 2 Soaking in aqueous solution, taking out, washing, and freeze drying to obtain CdS composite membrane;
the preparation method of the CdS nano ring comprises the following steps: regulating the pH value of the cadmium salt solution to 10.8-11.5 by adopting hydrazine hydrate, adding thiourea as a sulfur source, and uniformly stirring; carrying out microwave reaction on the obtained mixed solution to obtain CdS nano-rings; the power of the microwave reaction is 200-800W, the reaction temperature is 70-90 ℃, and the reaction time is 5-40 min; the concentration of the cadmium salt solution is 8-12mmol/L, and the sulfur source is 1.5-6 times of the amount of the cadmium salt substance;
the prepared CdS is in a hollow annular structure, and the diameter of the ring is 100-150 nm; the ring cavity is 50-100nm, and the CdS nano-ring is assembled by nano-particles with the diameter of 5-8 nm.
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