CN114849737B - Flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst and application thereof - Google Patents
Flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst and application thereof Download PDFInfo
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 56
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002096 quantum dot Substances 0.000 title claims abstract description 34
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052946 acanthite Inorganic materials 0.000 title claims abstract description 32
- 229940056910 silver sulfide Drugs 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical class [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000008021 deposition Effects 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 7
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
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- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/04—Sulfides
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Abstract
Preparation method of flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalystAnd the application thereof, which belongs to the technical field of photocatalysis, wherein the photocatalysis material is silver sulfide quantum dots which are adsorbed on flower-shaped cadmium sulfide nano sheets by deposition, and the specific process comprises the following steps: 1) Preparing flower-shaped cadmium sulfide nano-sheets by using an oil bath method; 2) Preparing silver sulfide quantum dots by an oil bath method; 3) Adding flower-like cadmium sulfide nano-sheets and silver sulfide quantum dots into absolute ethyl alcohol, stirring for 24 hours, and evaporating to dryness; 4) Washing the product with absolute ethyl alcohol, and drying to obtain the flower-like cadmium sulfide/silver sulfide composite photocatalytic material. When the flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalytic material is applied to photocatalytic carbon dioxide reduction, the CO generation rate of the material reaches 16.6 mu mol g under the irradiation of visible light ‑1 ·h ‑1 Has potential application prospect in the field of photocatalytic carbon dioxide reduction.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and in particular relates to a flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst capable of efficiently and selectively photocatalytic reduction of carbon dioxide and application thereof
Background
Conventional fossil energy is a non-renewable energy source, and combustion of fossil energy produces a large amount of carbon dioxide (CO 2 ) The carbon circulation balance in the nature is broken. In recent years, the rising photocatalysis technology utilizes solar energy to excite semiconductor photocatalysis material to generate photo-generated electron-hole so as to induce oxidation-reduction reaction to convert CO 2 Conversion to storable hydrocarbon fuels, e.g. methane (CH) 4 ) Methanol (CH) 3 OH), is considered to be the most promising CO 2 One of the transformation paths has great research value.
CdS is used as a II-VI group direct band gap semiconductor material, the forbidden band width is only 2.4eV, and the corresponding intrinsic light absorption band edge is 517nm, so that the CdS has good sunlight absorption performance and energy level structure, and can perform photocatalysis reaction in visible light and even near infrared light regions. However, the electron-hole pair recombination rate in the single cadmium sulfide is high, the density of photo-generated carriers is low, separation and transfer of photo-generated electrons and holes are hindered, and the photo-catalytic activity is low.
Therefore, how to solve the problems of fast combination of photo-generated electrons and low light absorption efficiency is an important research meaning for designing and synthesizing the high-efficiency cadmium sulfide photocatalyst so as to further improve the photocatalytic performance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst, aiming at the problems existing in the background technology, and the photocatalyst can effectively solve the problems of rapid composite and unsatisfactory light absorption of single cadmium sulfide photo-generated electrons and improve the yield of CO.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst is a composite material formed by silver sulfide quantum dots and flower-shaped cadmium sulfide nano sheets, wherein the silver sulfide quantum dots are spherical, and the diameter is 5-10 nm; the cadmium sulfide nano sheet is rectangular, the thickness is 3-5 nm, the diameter of a flower-shaped structure formed by the cadmium sulfide nano sheet is 150-200 nm, and the height is 20-40 nm; the mass ratio of the silver sulfide quantum dots to the cadmium sulfide is 1:20.
The preparation method of the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst comprises the following steps:
s1, uniformly dissolving 5mmol of sodium citrate in 50mL of deionized water, then adding 10mL of 0.3mol/L cadmium chloride into a mixed solution, stirring for 20 minutes, sequentially dripping 5mL of ammonia water (25-28 wt%) and 10mL of 0.9mol/L thiourea into the solution, transferring the uniform orange suspension into an oil bath pot, maintaining the temperature at 60 ℃ for 3 hours, centrifuging to collect generated orange precipitate after reaction cooling, washing the orange precipitate with deionized water and ethanol for several times, and then drying the orange precipitate in an oven at 60 ℃ for more than 12 hours;
s2, preparing silver sulfide quantum dots by an oil bath method: into a three-necked flask, 10mL of Ethylene Glycol (EG) was charged and N was introduced 2 30min to completely remove air in the system, continuously injecting N above the liquid during the whole reaction process 2 Heating to 110 ℃, sequentially adding 0.05mol of silver nitrate and 0.1mL of 3-mercaptopropionic acid, heating to 145 ℃ after the reactants are uniformly mixed, preserving heat for 15 minutes, gradually changing the reaction liquid from clear and transparent to wine red during the period, finally changing the reaction liquid to black brown, cooling the solution to room temperature to obtain a sample, and finally precipitating the quantum dots by adding deionized water, centrifuging and washing with deionized water and ethanol;
s3, preparing a flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst: 0.2g of CdS nano-sheet and 0.01g of Ag are mixed 2 S quantum dots are added into 20mL of ethanol, stirred for 2h, and the mixed solution is transferred into a 60 ℃ oven for 24h until the ethanol is completely volatilized.
The flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst is prepared by the preparation method.
Compared with the prior art, the invention has the following remarkable advantages:
(1) Compared with other noble metal catalysts and traditional photocatalysts, the flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst prepared by the invention has a flower-like structure formed by stacking 2D lamellar structures, thereby obtaining larger specific surface area and increasing CO 2 The contact area increases the reaction rate.
(2) According to the invention, by introducing silver sulfide quantum dots, the visible light absorption range of cadmium sulfide is widened, the electron transfer impedance is reduced, the electron transfer is promoted, meanwhile, silver sulfide is taken as an electron acceptor, and photo-generated electrons generated in the process of reacting illumination are promoted to further separate photo-generated electron pairs, so that the photocatalytic activity of the material is improved.
(3) The flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst prepared by the invention can be applied to illumination of CO 2 The reduction and CO yield are high, and the popularization and application have great advantages.
Drawings
Fig. 1 a is a Scanning Electron Microscope (SEM) picture of the flower-shaped cadmium sulfide/silver sulfide quantum dot prepared in experimental example 1, and b is a Transmission Electron Microscope (TEM) picture of the flower-shaped cadmium sulfide/silver sulfide quantum dot prepared in experimental example 1;
FIG. 2 is a high-power transmission electron microscope (HRTEM) photograph of flower-like cadmium sulfide/silver sulfide quantum dots prepared in experimental example 1 of the present invention;
FIG. 3 is an XRD diffraction pattern of the material prepared in example 1, comparative example 1, and comparative example 4 according to the present invention;
FIG. 4 shows the diffuse reflection spectra of UV-visible light of the materials prepared in Experimental example 1, comparative example 1, example 2, example 3, and example 4;
FIG. 5 is a graph showing the comparison of the production rates of photocatalytic carbon dioxide reduction under visible light irradiation of the materials prepared in Experimental example 1, comparative example 1, example 2, example 3, and example 4.
Detailed Description
The invention will be further illustrated by the following specific examples. It should be understood that the examples are presented for the purpose of further illustrating the invention and are not to be construed as limiting the scope of the invention in any way.
Example 1
Preparing flower-shaped cadmium sulfide nano-sheets by an oil bath method: 5mmol of sodium citrate is uniformly dissolved in 50mL of deionized water, then 10mL of 0.3mol/L cadmium chloride is added into the mixed solution, after stirring for 20 minutes, 5mL of ammonia water (25-28 wt%) and 10mL of 0.9mol/L thiourea are sequentially added into the solution in a dropwise manner, then the uniform orange suspension is transferred into an oil bath pot, the oil bath is kept at 60 ℃ for 3 hours, after the reaction is cooled, the generated orange precipitate is centrifugally collected, washed with deionized water and ethanol for a plurality of times, and then dried in an oven at 60 ℃ for more than 12 hours.
Preparing silver sulfide quantum dots by an oil bath method: into a three-necked flask, 10mL of Ethylene Glycol (EG) was charged and N was introduced 2 For 30min to completely remove air in the system, and continuously injecting N above the liquid during the whole reaction process 2 Heated to 110℃and 0.05mol of silver nitrate and 0.1mL of 3-mercaptopropionic acid were added sequentially. After the reactants are uniformly mixed, the temperature is raised to 145 ℃, the temperature is kept for 15 minutes, and during the period, the reaction solution is gradually clear and transparentAnd turns to wine red and finally to black brown. Then, the solution was cooled to room temperature to obtain a sample. Finally, the quantum dots were precipitated by adding deionized water, centrifugation, and washing with deionized water and ethanol.
Preparing flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst by deposition and adsorption: 0.2g of CdS nano-sheet and 0.01g of Ag are mixed 2 S quantum dots were added to 20mL ethanol and stirred for 2h. And transferring the mixed solution into a 60 ℃ oven for 24 hours until the ethanol is completely volatilized, and obtaining the product, namely the flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst.
Comparative example 1
In order to verify the improvement of the performance of the flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst relative to flower-like cadmium sulfide, compared with experimental example 1, steps 2 and 3 are omitted, the flower-like cadmium sulfide nano-sheet obtained in the step 1 is directly carried out, and the obtained product is marked as CAO.
Comparative example 2
The preparation method in this comparative example is the same as that of experimental example 1, except that the mass of the silver sulfide quantum dot added in step 3 of this comparative example is 2% of the theoretical mass of the flower-like cadmium sulfide, and the remaining conditions are unchanged.
Comparative example 3
The preparation method in this comparative example is the same as that of experimental example 1, except that the mass of the silver sulfide quantum dot added in step 3 of this comparative example is 8% of the theoretical mass of the flower-like cadmium sulfide, and the remaining conditions are unchanged.
Comparative example 4
The preparation method in this comparative example is the same as that of experimental example 1, except that the mass of the silver sulfide quantum dot added in step 3 of this comparative example is 10% of the theoretical mass of the flower-like cadmium sulfide, and the remaining conditions are unchanged.
The materials obtained in the above experimental example 1, comparative examples 1, 2, 3 and 4 were subjected to a photocatalytic reduction carbon dioxide activity test, and the specific steps are as follows:
(1) Dissolving 30mg of a sample in 4mL of ethanol and performing ultrasonic dispersion to obtain a uniform solution;
(2) Uniformly dispersing the solution in a shallow tray, then putting the shallow tray into an oven, and drying the shallow tray into a film shape at 60 ℃;
(3) Placing the tray at the bottom of a glass reactor of a photocatalysis online analysis system (Perfect Light Labsolar A), dripping 0.5mL deionized water on the tray, and sealing the reactor by using vacuum grease;
(4) Vacuumizing the reactor, then introducing carbon dioxide, setting the circulation time to be 30min, and performing a circulation test for about 4 hours; the pressure of the system is kept at 70-80 Kpa, and a 300W xenon lamp is used as a light source for carrying out photocatalytic reduction on CO 2 And (5) experiment. The products of the carbon dioxide photo-reduction were detected by gas chromatography.
Fig. 1 a is a Scanning Electron Microscope (SEM) picture of the flower-shaped cadmium sulfide/silver sulfide quantum dot prepared in experimental example 1, and b is a Transmission Electron Microscope (TEM) picture of the flower-shaped cadmium sulfide/silver sulfide quantum dot prepared in experimental example 1; it can be seen that the silver sulfide quantum dots were successfully loaded on the cadmium sulfide nanoplatelets.
FIG. 2 is a high-power transmission electron microscope (HRTEM) photograph of flower-like cadmium sulfide/silver sulfide quantum dots prepared in experimental example 1 of the present invention; the lattice fringes of cadmium sulfide and silver sulfide quantum dots can be seen, wherein the 0.36nm lattice fringes correspond to the (111) crystal plane of cadmium sulfide and the 0.24nm lattice fringes correspond to the (200) crystal plane of silver sulfide quantum dots.
FIG. 3 is an XRD diffraction pattern of the material prepared in example 1, comparative example 1, and comparative example 4 according to the present invention; it can be seen that silver sulfide quantum dots in the composite material are successfully loaded on flower-shaped cadmium sulfide quantum dots.
FIG. 4 shows the diffuse reflection spectra of UV-visible light of the materials prepared in Experimental example 1, comparative example 1, example 2, example 3, and example 4; it can be seen that the introduction of the silver sulfide quantum dots widens the visible light absorption range and reduces the forbidden bandwidth.
FIG. 5 is a graph showing the comparison of the production rates of photocatalytic carbon dioxide reduction under visible light irradiation of the materials prepared in experimental examples 1, comparative examples 1, 2, example 3 and example 4; as can be seen, the CO production rate of CA5 reached 16.6. Mu. Mol. G -1 ·h -1 The reduction efficiency of CA0 and CA10 is far exceeded, and the superiority of the material prepared by the invention is reflected.
It should be noted that the above-described embodiments provide a more complete understanding of the present invention to those skilled in the art, but do not limit the present invention in any way. Accordingly, it will be understood by those skilled in the art that the present invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and technical essence of the invention are included in the protection scope of the invention patent.
Claims (2)
1. The application of the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst is characterized in that the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst is applied to photocatalytic reduction of carbon dioxide;
the preparation method of the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst comprises the steps of preparing flower-shaped cadmium sulfide nano sheets and silver sulfide quantum dots by an oil bath method, and then assembling the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst by utilizing deposition and adsorption;
the method specifically comprises the following steps:
step 1, preparing flower-like cadmium sulfide nano sheets,
uniformly dissolving 5mmol of sodium citrate in 50mL of deionized water, adding 10mL of 0.3mol/L cadmium chloride into the mixed solution, stirring for 20min, sequentially dripping 5mL ammonia water and 10mL of 0.9mol/L thiourea into the solution, transferring the uniform orange suspension into an oil bath pot, maintaining the temperature at 60 ℃ for 3h, centrifuging to collect generated orange precipitate after cooling, washing the orange precipitate with deionized water and ethanol for several times, and drying the orange precipitate in an oven at 60 ℃ for more than 12 h;
step 2, preparing silver sulfide quantum dots,
adding 10mL of Ethylene Glycol (EG) into a three-neck flask, introducing nitrogen for 30min to completely remove air in the system, continuously injecting nitrogen above the liquid in the whole reaction process, heating to 110 ℃, sequentially adding 0.05mol of silver nitrate and 0.1mL of 3-mercaptopropionic acid, heating to 145 ℃ after the reactants are uniformly mixed, preserving heat for 15min, gradually changing the reaction liquid from clear and transparent to reddish-white and finally changing the reaction liquid to black brown, cooling the solution to room temperature, adding deionized water and centrifuging, and washing the obtained product with deionized water and ethanol;
step 3, preparing a flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst,
adding 0.2g of CdS nano-sheet and 0.01 and g of Ag2S quantum dot into 20mL of ethanol, stirring for 2h, transferring the mixed solution into a 60 ℃ oven for 24h until the ethanol is completely volatilized, and obtaining the product which is the flower-like cadmium sulfide/silver sulfide quantum dot composite photocatalyst.
2. The application of the flower-shaped cadmium sulfide/silver sulfide quantum dot composite photocatalyst is characterized in that the concentration of ammonia water in the step 1 is 25-28 wt%.
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