CN108586469B - Method for inhibiting photo-corrosion of cadmium sulfide - Google Patents
Method for inhibiting photo-corrosion of cadmium sulfide Download PDFInfo
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- CN108586469B CN108586469B CN201810226328.3A CN201810226328A CN108586469B CN 108586469 B CN108586469 B CN 108586469B CN 201810226328 A CN201810226328 A CN 201810226328A CN 108586469 B CN108586469 B CN 108586469B
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 80
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 7
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 41
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 16
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- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 description 2
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- IARNVKSBRPYBMQ-UHFFFAOYSA-N COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 IARNVKSBRPYBMQ-UHFFFAOYSA-N 0.000 description 1
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- OISMQLUZKQIKII-UHFFFAOYSA-L dichlorocadmium;hydrate Chemical compound O.[Cl-].[Cl-].[Cd+2] OISMQLUZKQIKII-UHFFFAOYSA-L 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- B82—NANOTECHNOLOGY
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Abstract
本发明公开了一种抑制硫化镉光腐蚀的方法，包括在硫化镉的表面修饰锌四酰肼基苯基卟啉，所述锌四酰肼基苯基卟啉可通过羰基锚固在硫化镉的表面。锌四酰肼基苯基卟啉的引入，降低了硫化镉纳米片光生电子‑空穴的复合，抑制了硫化镉光腐蚀的发生，加速了其光生电子的迁移速率，使其具有良好的光电性能，可作为一种优良的光电材料用于构建多巴胺光电化学传感器。The invention discloses a method for inhibiting the photocorrosion of cadmium sulfide. surface. The introduction of zinc tetrahydrazide phenyl porphyrin reduces the recombination of photogenerated electron-holes in cadmium sulfide nanosheets, inhibits the occurrence of photocorrosion of cadmium sulfide, accelerates the migration rate of photogenerated electrons, and makes it have good optoelectronic properties. It can be used as an excellent optoelectronic material for the construction of dopamine photoelectrochemical sensors.
Description
Technical Field
The invention relates to a method for inhibiting photo-corrosion of cadmium sulfide.
Background
With the rapid development of industry and the mass combustion of fossil fuels, the problems of environmental pollution and energy shortage faced by human beings are increasingly highlighted. The direct discharge of various pollutants into the agricultural environment not only affects the agricultural production, but also affects the health of human beings. Meanwhile, the large consumption of fossil fuels also brings about an increasingly severe energy crisis. Solar energy has been of interest to many researchers as an ideal, efficient, renewable energy source, and scientists have invested a great deal of work in the preparation and use of photosensitizing materials.
Cadmium sulfide is a direct band gap n-type inorganic semiconductor material in II-VI main groups, and the forbidden band width is 2.42 eV. The solar cell has special optical and electrical properties, so that the solar cell is more and more concerned by broad students, and is widely applied to the fields of novel solar cells, photocatalysis, photoelectric conversion, photoluminescence and the like. However, pure cadmium sulfide is very susceptible to photo-corrosion under long-term illumination, which results in unstable photoelectric properties. The existing research shows that the photoelectric property of the cadmium sulfide nanosheet is higher than that of one-dimensional nanoparticles and two-dimensional nanorods.
Disclosure of Invention
The present invention is directed to a method for inhibiting photo-corrosion of cadmium sulfide in light of the above background art.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for inhibiting photo-corrosion of cadmium sulfide comprises modifying zinc tetrahydrohydrazide phenyl porphyrin on the surface of cadmium sulfide.
Preferably, the zinc tetrahydrohydrazide phenyl porphyrin is anchored to the surface of the cadmium sulfide through a carbonyl group.
Preferably, the mass ratio of the zinc tetrahydrohydrazide phenyl porphyrin to the cadmium sulfide is (1-4): 10.
Preferably, the process of modification comprises: cadmium sulfide and zinc tetrahydrazide phenyl porphyrin are mixed and reacted in an organic solvent.
More preferably, the organic solvent is N, N-dimethylformamide.
A cadmium sulfide/zinc tetrahydrohydrazide phenyl porphyrin composite material, wherein the zinc tetrahydrohydrazide phenyl porphyrin is anchored on the surface of the cadmium sulfide through carbonyl.
Preferably, the cadmium sulfide is cadmium sulfide nanosheets.
Preferably, the preparation process of the cadmium sulfide nanosheet comprises: and reacting cadmium chloride and sulfur by using diethylenetriamine as a solvent through a solvothermal method to obtain the cadmium sulfide nanosheet.
More preferably, the reaction temperature is 80 ℃, and the molar ratio of the cadmium chloride to the sulfur is 1 (6-7).
Zinc tetrahydrohydrazide phenyl porphyrin is a p-type organic semiconductor, cadmium sulfide nanosheets are used as an n-type semiconductor, the p-n heterojunction can be formed by compounding the zinc tetrahydrohydrazide phenyl porphyrin and the cadmium sulfide, and the HOMO of the zinc tetrahydrohydrazide phenyl porphyrin is well matched with the LOMO orbit and the valence band and conduction band of the cadmium sulfide in energy level, so that the introduction of the zinc tetrahydrohydrazide phenyl porphyrin is beneficial to the injection of electrons under the excitation of light, the compounding of photo-generated electrons and hole pairs is reduced, the photo-corrosion of the cadmium sulfide is inhibited, the migration rate of the photo-generated electrons is accelerated, the zinc tetrahydrohydrazide phenyl porphyrin has good photoelectric properties, and the zinc tetrahydrohydrazide phenyl porphyrin can be used as an excellent photoelectric material for detecting dopamine.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a diagram of zinc tetrahydrohydrazide phenyl porphyrin (ZnTHPP) of the present invention1H-NMR spectrum.
FIG. 2 is a scanning electron microscope image of CdS NSs/ZnTHPP composite material.
FIG. 3 shows X-ray powder diffraction patterns of CdS NSs and CdS NSs/ZnTHPP composite materials.
FIG. 4 is a UV-VIS spectrum of CdS NSs, ZnTHPP, CdS NSs/ZnTHPP composite material.
FIG. 5 is a Fourier infrared spectrum of CdS NSs, ZnTHPP and CdS NSs/ZnTHPP composite material.
FIG. 6 is an i-t curve diagram of CdS NSs and CdS NSs/ZnTHPP composite material.
FIG. 7 is a graph of photocurrent response of CdS NSs/ZnTHPP composite material to dopamine with different concentrations and calibration curve.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
1) Preparation of cadmium sulfide nanosheets (CdS NSs): 0.073g of 2.5 g of cadmium chloride hydrate and 0.064g of sublimed sulfur were added to 12mL of diethylenetriamine, stirred at room temperature for 1 hour, and the resulting yellowish green suspension was transferred to a polytetrafluoroethylene reaction vessel (20mL) and heated at 80 ℃ for 48 hours. After naturally cooling to room temperature, a pale yellow precipitate was collected by centrifugation and washed three times with ethanol/water (V: V ═ 1: 1). The obtained pale yellow powder was dried in an oven at 60 ℃ for 24 h.
2) Synthesis of Zinc Tetrahydrazino phenyl porphyrin
a, synthesis of 5,10,15, 20-tetra (4-carbomethoxy) phenyl porphyrin: the pyrrole and the propionic acid are newly distilled under reduced pressure. In a 500 mL three-necked flask, 7.5g (45mmol) of methyl p-formylbenzoate and 200mL of propionic acid were charged, magnetically stirred and heated to 128 ℃ and 3.1mL (45mmol) of pyrrole was dissolved in 10mL of propionic acid, and added dropwise and slowly to the propionic acid solution (about 10min) using a constant pressure dropping funnel, and reacted for about 1.5 hours. Stopping heating, when the temperature of a reaction system is reduced to be below 80 ℃, adding 200mL of absolute ethyl alcohol under the condition of full stirring, putting the reaction system into a refrigerator for cooling overnight, carrying out suction filtration to obtain a purple black crude product, washing the crude product for a plurality of times by using secondary water and absolute ethyl alcohol respectively, carrying out vacuum drying at 40 ℃, carrying out silica gel chromatographic column separation on the crude product, and after removing a first green color band by using dichloromethane as an eluent, using dichloromethane: and (3) taking acetic acid ethyl acetate II 20:1 as an eluent, collecting a purple first color band, and performing spin drying to obtain a bright purple product.
b.5,10,15, 20-tetra (4-carboximoyl) phenyl zinc porphyrin: 0.5g (0.59mmol) of 5,10,15, 20-tetrakis (4-carboxymethylester) phenylporphyrin was dissolved in 40mL of chloroform with stirring, and then a 20mL methanol solution containing 1.036g (2.36mmol) of zinc acetate was added to the solution, and the mixture was refluxed at 65 ℃ for 2 hours. After the reaction was completed, water was added for multiple extractions to remove unreacted salts, the organic phase was collected and spin-dried, and a magenta solid was collected.
c, synthesis of 5,10,15, 20-tetra (4-benzoyl hydrazine) based zinc porphyrin (namely zinc tetrahydrohydrazide based phenyl porphyrin): 5,10,15, 20-tetrakis (4-carboxymethylester) phenylzinc porphyrin (0.5mmol,0.4560g) was dissolved in 40mL of chloroform with stirring, 25mL of 80% hydrazine hydrate was dissolved in 100mL of ethanol, the two solutions were mixed with stirring, and the mixture was refluxed at 75 ℃ for 24 h. After the reaction is finished, rotary evaporation and concentration are carried out, a proper amount of distilled water is added, a large amount of green precipitate is separated out, suction filtration is carried out, and the filter cake is washed by water and a small amount of trichloromethane for a plurality of times. Drying at constant temperature of 80 ℃, and collecting dark green products.
3) Cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material: weighing 20mg of cadmium sulfide nanosheet prepared in the step 1), adding 20mL of DMF, performing ultrasonic treatment for 1h to form a suspension, adding 2mg of zinc tetrahydrohydrazide phenyl porphyrin prepared in the step 2), performing ultrasonic treatment for 30min, and stirring at room temperature for 24h at the rotation speed of 700 rpm. And (3) obtaining a product through centrifugal separation, washing the product for a plurality of times by using absolute ethyl alcohol, and drying the product for 6 hours at the temperature of 60 ℃ to obtain the cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin nanocomposite.
4) Photoelectric detection of the cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material on dopamine: weighing 10mg 3) of the cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material, adding the cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material into 10mL of distilled water, ultrasonically forming suspension with the concentration of 1mg/mL, dropwise adding the suspension onto cleaned ITO conductive glass by a dropping coating method, and naturally drying. The three-electrode system is used as a working electrode to test the photocurrent response of the three-electrode system in dopamine solutions with different concentrations.
FIG. 1 is a diagram of zinc tetrahydrohydrazide phenyl porphyrin (ZnTHPP) of the present invention1An H-NMR spectrum of the mixture is shown,1H-NMR(CD3SOCD3,600MHz)δ(ppm):10.10(s,4H,hydrazide-NH),8.76(s,8H,β-H),8.23(t,16H,Ar-H),4.66(brs,8H,NH2) The structure is as follows:
FIG. 2 is a scanning electron microscope image of the CdS NSs/ZnTHPP composite material of the present invention, which shows that the synthesized cadmium sulfide is a lamellar structure and the surface of the cadmium sulfide is loaded with porphyrin.
FIG. 3 shows X-ray powder diffraction of CdS NSs and CdS NSs/ZnTHPP composite materials of the invention, wherein the X-ray powder diffraction angles of 24.8, 26.6, 28.2, 43.7, 47.9 and 51.8 degrees are characteristic peaks of X-ray diffraction of cadmium sulfide nanosheets, and it can be seen that the introduction of porphyrin does not destroy the crystal form of the cadmium sulfide nanosheets.
FIG. 4 is a diagram of the UV-VIS spectrum of the CdS NSs, ZnTHPP and CdS NSs/ZnTHPP composite material of the present invention, which shows that the light absorption range and intensity of cadmium sulfide are increased by the introduction of porphyrin.
FIG. 5 shows the Fourier infrared spectrum of CdS NSs, ZnTHPP and CdS NSs/ZnTHPP composite material of the present invention, from which it can be seen that after being loaded with cadmium sulfide nanosheets, zinc tetrahydrohydrazide phenyl porphyrin is 1650cm-1The intensity of the characteristic peak of the C ═ O bond in the acylhydrazone structure is obviously weakened, and the fact that porphyrin is anchored on the cadmium sulfide nanosheet through carbonyl is proved.
FIG. 6 is an i-t curve diagram of the CdS NSs and CdS NSs/ZnTHPP composite material of the present invention. The test was carried out on a CHI900 electrochemical workstation using a phosphate buffer solution at pH 7, a bias of-0.3V and a light switch time of 10 seconds, using a three-electrode system. As can be seen from FIG. 6, the photocurrent of pure cadmium sulfide decreases sharply due to photo-corrosion, and the photocurrent of the composite material becomes stable after porphyrin is introduced.
Fig. 7 is a graph of photocurrent response of the CdS NSs/ZnTHPP composite material of the present invention to dopamine with different concentrations and calibration curve, and it is seen from the graph that, within a certain concentration range, the photocurrent of the composite material increases linearly with the increase of the dopamine concentration.
The synthesis of zinc tetrahydrohydrazide phenyl porphyrin can also be referred to as the literature, "meso-tetra (4-hydrazidophenyl) porphyrin and metal complexes thereof covalently and non-covalently modify multi-walled carbon nanotubes", advanced chemical academy of schools, 2010, volume 31, phase 4, p 696-702.
Example 2
1) Cadmium sulfide nanosheets were prepared as in example 1.
2) Zinc tetrahydrohydrazide phenyl porphyrin was prepared as in example 1.
3) Cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material: weighing 20mg of cadmium sulfide nanosheet, adding 20mL of DMF, performing ultrasound for 1h to form a suspension, then adding 4mg of zinc tetrahydrohydrazide phenyl porphyrin, continuing ultrasound for 30min, and then stirring for 24h at room temperature at the rotating speed of 700 rpm. The product was isolated by centrifugation, washed several times with absolute ethanol and dried at 60 ℃ for 6 h.
Example 3
1) Cadmium sulfide nanosheets were prepared as in example 1.
2) Zinc tetrahydrohydrazide phenyl porphyrin was prepared as in example 1.
3) Cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material: weighing 20mg of cadmium sulfide nanosheet, adding 20mL of DMF, performing ultrasound for 1h to form a suspension, then adding 6mg of zinc tetrahydrohydrazide phenyl porphyrin, continuing ultrasound for 30min, and then stirring for 24h at room temperature at the rotating speed of 700 rpm. The product was isolated by centrifugation, washed several times with absolute ethanol and dried at 60 ℃ for 6 h.
Example 4
1) Cadmium sulfide nanosheets were prepared as in example 1.
2) Zinc tetrahydrohydrazide phenyl porphyrin was prepared as in example 1.
3) Cadmium sulfide nanosheet/zinc tetrahydrohydrazide phenyl porphyrin composite material: weighing 20mg of cadmium sulfide nanosheet, adding 20mL of DMF, performing ultrasound for 1h to form a suspension, then adding 8mg of zinc tetrahydrohydrazide phenyl porphyrin, continuing ultrasound for 30min, and then stirring for 24h at room temperature at the rotating speed of 700 rpm. The product was isolated by centrifugation, washed several times with absolute ethanol and dried at 60 ℃ for 6 h.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for inhibiting photo-corrosion of cadmium sulfide comprises modifying zinc tetrahydrohydrazide phenyl porphyrin on the surface of cadmium sulfide;
the structure of the zinc tetrahydrohydrazide phenyl porphyrin is as follows:
2. the method of claim 1, wherein: the zinc tetrahydrohydrazide phenyl porphyrin is anchored on the surface of cadmium sulfide through carbonyl.
3. The method of claim 1, wherein: the mass ratio of the zinc tetrahydrohydrazide phenyl porphyrin to the cadmium sulfide is (1-4): 10.
4. The method of claim 1, wherein the modifying comprises: cadmium sulfide and zinc tetrahydrazide phenyl porphyrin are mixed and reacted in an organic solvent.
5. The method of claim 4, wherein: the organic solvent is N, N-dimethylformamide.
6. A cadmium sulfide/zinc tetrahydrohydrazide phenyl porphyrin composite material, wherein the zinc tetrahydrohydrazide phenyl porphyrin is anchored on the surface of the cadmium sulfide through carbonyl;
the structure of the zinc tetrahydrohydrazide phenyl porphyrin is as follows:
7. the composite material of claim 6, wherein: the cadmium sulfide is a cadmium sulfide nanosheet.
8. The composite material of claim 7, wherein the cadmium sulfide nanosheets are obtained by a solvothermal reaction of cadmium chloride and sulfur with diethylenetriamine as a solvent.
9. The composite material of claim 8, wherein: the reaction temperature is 80 ℃, and the molar ratio of cadmium chloride to sulfur is 1 (6-7).
10. Use of the composite of claim 6 for detecting dopamine.
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