CN114308075B - Efficient and stable visible light photocatalyst and preparation method thereof - Google Patents
Efficient and stable visible light photocatalyst and preparation method thereof Download PDFInfo
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- CN114308075B CN114308075B CN202111440951.7A CN202111440951A CN114308075B CN 114308075 B CN114308075 B CN 114308075B CN 202111440951 A CN202111440951 A CN 202111440951A CN 114308075 B CN114308075 B CN 114308075B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a high-efficiency stable visible light photocatalyst, which mainly comprises CdS, carbon and transition metals Fe, co and Ni. The invention also discloses a preparation method, which comprises the steps of firstly dispersing CdS nanocrystalline and glucose in ultrapure water in an ultrasonic manner, and carrying out hydrothermal reaction for several hours to obtain carbon-coated CdS nanocrystalline; then one or more of transition metal elements Fe, co and Ni are deposited on the surface of the carbon coating layer in situ by adopting a light deposition method, and then the product is ultrasonically cleaned and centrifugally separated; finally sintering under the protection of inert atmosphere to obtain the final product. The composite photocatalyst material prepared by the method has excellent photocatalytic performance in the visible light spectrum range and stable physical and chemical properties. The deposition of the transition metal element not only can optimize the photocatalytic hydrogen evolution effect of the prepared catalyst, but also can promote the graphitization of surface carbon, thereby further improving the transmission efficiency of the photogenerated carriers.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a high-efficiency stable visible light photocatalyst and a preparation method thereof.
Background
The photocatalytic water splitting hydrogen production technology is one of ideal ways for producing green hydrogen, is a most challenging scientific technology, and has great practical significance for solving the future environmental energy crisis. CdS is an excellent visible light photocatalyst. However, the use of intrinsic CdS is greatly limited by the high recombination efficiency of photo-generated electron-hole pairs, yi Guangshi, and the like. Related studies have shown that carbon materials can improve the photocatalytic performance of CdS and can enhance the optical stability of CdS. However, amorphous carbon is not as capable of transporting carriers as graphitic carbon due to the lack of conjugated structure. Therefore, the use of graphitic carbon to improve the photocatalytic activity of CdS is a desirable option.
Based on the prior related literature reports and patents, most of the materials are composite materials of graphite carbon and CdS prepared by adopting a chemical adsorption or physical blending mode. In the materials prepared by the methods, the graphite and CdS are not firmly contacted, so that the improvement of the photocatalytic performance is not obvious, and the problems can be solved by adopting an in-situ preparation method. However, the graphitization temperature of carbon is close to 3000 ℃, whereas the decomposition temperature of CdS is only around 650 ℃, so that in situ formation of a graphitic carbon coating on the CdS surface is almost impossible. Therefore, from the aspect of reducing the graphitization temperature of the carbon, the transition metal element is adopted to reduce the graphitization temperature of the carbon, so that the composite nano material of transition metal-graphite carbon-CdS is prepared.
Disclosure of Invention
The invention aims to: the invention aims to provide a high-efficiency stable visible light photocatalyst and a preparation method thereof.
The technical scheme is as follows: the composite photocatalyst with visible light photocatalytic activity comprises CdS, carbon and one or more of transition metal elements Fe, co and Ni; the mass ratio of the CdS nanocrystalline to the glucose is kept between 5 and 0.1; the thickness of the carbonization layer coated on the CdS nanocrystalline surface is 1-20 nm; the mass percentage of the deposited transition element accounting for CdS is kept between 0.1% and 10%.
The preparation method of the composite photocatalyst with visible light photocatalytic activity comprises the following steps:
(1) Ultrasonically dispersing CdS nanocrystals and glucose in ultrapure water, and then performing hydrothermal reaction to obtain CdS nanocrystals uniformly coated with carbon;
(2) Uniformly dispersing one or more of transition metal elements Fe, co and Ni on the surface of the carbon coating layer by adopting a photodecomposition method, ultrasonically cleaning, separating out a product, and vacuum drying;
(3) And (3) placing the dried sample in a tube furnace, and sintering for 1-10h at 300-800 ℃ under the protection of inert gas to obtain a final product.
Further, in the step (1), the hydrothermal reaction temperature is 140-200 ℃ and the hydrothermal reaction time is 6-12h.
Further, in the step (2), the specific steps of the photo-deposition are as follows:
(11) Firstly, ultrasonically dispersing the CdS nanocrystalline coated with carbon prepared in the step (1) into a mixed solution of water and methanol, and then adding a salt solution of Fe, co and Ni into the solution;
(12) Turning on a light source under the condition of continuous stirring, and continuously illuminating for 3-24 hours;
(13) Repeatedly cleaning the solid precipitate for several times by using ultrapure water under the condition of ultrasonic until the solution does not contain salt;
(14) The washed product was placed in a vacuum drying oven and dried in vacuum.
Further, in the step (11), in the mixed salt solution, the molar ratio between the metal elements is 1:1.
further, in the step (12), the wavelength of the light source is larger than 400nm, and the power of the light source is between 50 and 500W.
Further, in the step (14), the temperature of the vacuum drying is 70-80 ℃ and the drying time is 24-30h.
Further, in the step (3), the specific steps of high-temperature sintering are as follows:
(31) And (3) placing the dried product in the step (14) into a corundum crucible, placing the corundum crucible into a tube furnace, continuously introducing inert gas, and sintering for 1-10h at the temperature of 300-800 ℃.
According to the invention, a layer of carbon is uniformly coated on the surface of the CdS nanocrystal by adopting a hydrothermal method, so that a protective shield is acted, the CdS is prevented from being directly irradiated by a light source, the photo-etching behavior of the CdS is inhibited, and the separation of photo-generated electron hole pairs is accelerated; and then the hydrogen evolution performance of the carbon layer is improved by depositing transition metal elements, and meanwhile, transition from the carbon layer to graphitization is induced. The test shows that the composite photocatalyst has excellent visible light catalytic performance, and the quantum efficiency at 420nm wavelength is over 20%. The test of photochemical stability also shows that the stability of the composite photocatalyst is greatly improved, and the photocatalytic performance is not obviously reduced after repeated test for 50 hours.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
1. the process flow is simple, no complex equipment is needed, and the raw material cost is low;
2. the coating thickness of the carbonization layer can be controlled by adjusting the mass ratio of CdS nanocrystalline to glucose;
3. the invention innovatively utilizes one or more of transition metal elements Fe, co and Ni to improve the structure of the carbon layer, and provides more photocatalytic hydrogen evolution active sites;
4. the coating of the outer carbon can improve the photochemical stability of the inner core CdS nanocrystalline.
5. The photocatalytic performance can be optimized by adjusting the mass percentage of the transition element to CdS.
6. Synergistic catalysis among the metal elements can be improved by adding one or more of transition metal elements Fe, co and Ni;
7. the composite photocatalyst material prepared by the method is stable in physical and chemical properties and has good catalytic activity under the condition of visible light.
Drawings
FIG. 1 is a TEM image of a nanocomposite prepared according to the scheme of example 1 as a photocatalyst;
FIG. 2 is a TEM contrast of a photocatalyst prepared according to the example 1 protocol and the example 2 protocol;
fig. 3 is a graph comparing the spectra of the RAMAN of the photocatalysts prepared according to the schemes of example 1 and example 5.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
Firstly, 1.0g of CdS nanocrystalline and 1.0g of glucose are dispersed in 80ml of ultrapure water by ultrasonic, after ultrasonic treatment for 30min, the mixture is placed in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and the mixture is reacted for 6h at 160 ℃ in a blast drying box. The product obtained by the hydrothermal reaction was ultrasonically washed with ethanol and ultrapure water respectively for 3 times, and dried in vacuum at 70℃for 12 hours. Then, 0.5g of the dried sample was weighed and dispersed in a mixed solution of methanol and water by ultrasonic treatment for 30min, followed by adding a solution containing 0.13g of FeCl 3 After stirring for 10min, applying light (100W LED light with the light source wavelength in the range of 400-800 nm), keeping the light irradiation for 6 hours, after the light deposition is finished, gradually deepening the solution, filtering the product until no chloride ions exist in the filtrate, and vacuum drying the separated product at 70 ℃ for 12 hours; finally, the dried sample in the last step is put into a tube furnace, vacuumized, and sintered for 3 hours at 500 ℃ by introducing high-purity Ar gas. After sintering, the Fe-C-CdS composite photocatalyst is obtained. As shown in fig. 1, the core-shell structure is very obvious, and a layer of graphite is uniformly coated on the surface of CdS.
Example 2
First, 1.0g of CdS nanocrystals and 2.0g of glucose were ultrasonically dispersed in 80ml of ultrapure water, superbAfter 30min, the mixture is placed in a polytetrafluoroethylene-lined hydrothermal reaction kettle and reacted for 6h at 160 ℃ in a blast drying box. The product obtained by the hydrothermal reaction was ultrasonically washed with ethanol and ultrapure water respectively for 3 times, and dried in vacuum at 70℃for 12 hours. Then, 0.5g of the dried sample was weighed and dispersed in a mixed solution of methanol and water by ultrasonic treatment for 30min, followed by adding a solution containing 0.13g of FeCl 3 After stirring for 10min, applying light (100W LED light with the light source wavelength in the range of 400-800 nm), keeping the light irradiation for 6 hours, after the light deposition is finished, gradually deepening the solution, filtering the product until no chloride ions exist in the filtrate, and vacuum drying the separated product at 70 ℃ for 12 hours; finally, the dried sample in the last step is put into a tube furnace, vacuumized, and sintered for 3 hours at 500 ℃ by introducing high-purity Ar gas. After sintering, the Fe-C-CdS composite photocatalyst is obtained.
Example 2 was followed by the procedure of example 1, except that the mass ratio of CdS to glucose was 1:2, whereas in the preparation of example 1, the mass ratio of CdS to glucose was 1:1. as shown in fig. 2, the core-shell structure features are clear, and the thickness of the graphite layer coated on the CdS surface has a significant difference.
Example 3
Firstly, 1.0g of CdS nanocrystalline and 1.0g of glucose are dispersed in 80ml of ultrapure water by ultrasonic, after ultrasonic treatment for 30min, the mixture is placed in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and the mixture is reacted for 6h at 160 ℃ in a blast drying box. The product obtained by the hydrothermal reaction was ultrasonically washed with ethanol and ultrapure water respectively for 3 times, and dried in vacuum at 70℃for 12 hours. Then, 0.5g of the dried sample was weighed and dispersed in a mixed solution of methanol and water by ultrasonic treatment for 30min, followed by adding a solution containing 0.13g of FeCl 3 And 0.1g NiCl 2 After stirring for 10min, applying light (100W LED light with the light source wavelength in the range of 400-800 nm), keeping the light for 6 hours, gradually deepening the solution after the light deposition is finished, separating and filtering the product until no chloride ions exist in the filtrate, and vacuum drying the separated product at 70 ℃ for 12 hours; finally, the dried sample in the last step is put into a tube furnace, vacuumized and introduced with high purityAr gas, sintering at 500 ℃ for 3 hours. After sintering, the Fe-Ni-C-CdS composite photocatalyst is obtained.
According to the method of example 1, two transition metal elements of Fe and Ni were simultaneously deposited, unlike example 3, and only Fe was deposited during the preparation of example 1.
Example 4
Firstly, 1.0g of CdS nanocrystalline and 1.0g of glucose are dispersed in 80ml of ultrapure water by ultrasonic, after ultrasonic treatment for 30min, the mixture is placed in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and the mixture is reacted for 6h at 160 ℃ in a blast drying box. The product obtained by the hydrothermal reaction was ultrasonically washed with ethanol and ultrapure water respectively for 3 times, and dried in vacuum at 70℃for 12 hours. Then, 0.5g of the dried sample was weighed and dispersed in a mixed solution of methanol and water by ultrasonic treatment for 30min, followed by adding a solution containing 0.13g of FeCl 3 、0.11gCoCl 2 And 0.1g NiCl 2 After stirring for 10min, applying light (100W LED light with the light source wavelength in the range of 400-800 nm), keeping the light for 6 hours, gradually deepening the solution after the light deposition is finished, separating and filtering the product until no chloride ions exist in the filtrate, and vacuum drying the separated product at 70 ℃ for 12 hours; finally, the dried sample in the last step is put into a tube furnace, vacuumized, and sintered for 3 hours at 500 ℃ by introducing high-purity Ar gas. After sintering, the Fe-C-CdS composite photocatalyst is obtained.
According to the method of example 1, three transition metal elements of Fe, co and Ni were simultaneously deposited, whereas only Fe was deposited during the preparation of example 1.
Example 5
Firstly, 1.0g of CdS nanocrystalline and 1.0g of glucose are dispersed in 80ml of ultrapure water by ultrasonic, after ultrasonic treatment for 30min, the mixture is placed in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and the mixture is reacted for 6h at 160 ℃ in a blast drying box. The product obtained by the hydrothermal reaction was ultrasonically washed with ethanol and ultrapure water respectively for 3 times, and dried in vacuum at 70℃for 12 hours. Then, 0.5g of the dried sample was weighed and dispersed in a mixed solution of methanol and water by ultrasonic treatment for 30min, followed by adding a solution containing 0.13g of FeCl 3 Is used for the preparation of a solution of (a),stirring for 10min, applying light (100W LED light with light source wavelength in 400-800 nm), keeping the light for 6 hr, gradually deepening solution after light deposition, separating, filtering the product until no chloride ion exists in the filtrate, and vacuum drying the separated product at 70deg.C for 12 hr; finally, the dried sample in the last step is put into a tube furnace, vacuumized, and high-purity Ar gas is introduced, and sintered for 3 hours at 600 ℃. After sintering, the Fe-C-CdS composite photocatalyst is obtained.
According to the method of example 1, example 5 is different in that the sintering temperature of the final step is 600℃and in the preparation of example 1, the sintering temperature of the final step is 500 ℃. As shown in fig. 3, the graphitization degree of the material surface coating layer is significantly improved after different heat treatments.
Claims (6)
1. The high-efficiency stable visible light photocatalyst is characterized by comprising one or more of CdS, carbon and transition metal elements Fe, co and Ni; the carbon is prepared by hydrothermal carbonization of an organic matter and uniformly coats the surface of CdS, and the thickness of the carbon is 1-20 nm; the transition metal elements Fe, co and Ni are deposited on the surface of the carbonization layer in situ by a photo-deposition method, and the mass ratio of the load is 1% -5%.
2. The method for preparing the high-efficiency stable visible light photocatalyst according to claim 1, comprising the following steps:
(1) Ultrasonically dispersing CdS nanocrystals and glucose in ultrapure water, and then performing hydrothermal reaction to obtain CdS nanocrystals uniformly coated with carbon;
(2) Uniformly dispersing one or more of transition metal elements Fe, co and Ni on the surface of the carbon coating layer by adopting a photodecomposition method, ultrasonically cleaning, separating out a product, and vacuum drying;
(3) And (3) placing the dried sample in a tube furnace, and sintering for 1-10 hours at 300-800 ℃ under the protection of inert gas to obtain a final product.
3. The method for preparing a high-efficiency stable visible light photocatalyst according to claim 2, wherein in the step (1), the mass ratio of the CdS nanocrystals to the glucose is kept between 5 and 0.1, the carbon coating layer is carbonized by an organic matter at high temperature and high pressure, and the organic matter is glucose.
4. The method for preparing the efficient and stable visible light photocatalyst according to claim 2, wherein in the step (1), the ultrasonic dispersion time is 10-60 min; the hydrothermal reaction time is between 6 and 12 hours; the temperature of the hydrothermal reaction is 140-200 ℃.
5. The method for preparing the high-efficiency stable visible light photocatalyst according to claim 2, wherein in the step (2), the mass percentage of the deposited transition element to the CdS is kept between 0.1% and 10%; one or more of Fe, co and Ni are selected for deposition or Co-deposition; the time of the photo-deposition is 3-24 hours.
6. The method for preparing a high-efficiency stable visible light photocatalyst according to claim 2, wherein in the step (3), the sintering temperature is 300-800 ℃ and the sintering time is 1-10h.
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| CN102941045A (en) * | 2012-11-16 | 2013-02-27 | 浙江师范大学 | Method for preparing multiple nano-composite balls with uniform size and CdS-C core-shell structures shaped like trivalvular flowers |
| CN108745382A (en) * | 2018-06-27 | 2018-11-06 | 福州大学 | A kind of preparation method and applications of the CdS visible light catalysts of NiCd double non-noble metals modification |
| CN109158114A (en) * | 2018-07-26 | 2019-01-08 | 福建农林大学 | A kind of method that one-step method prepares CdS@C composite photo-catalyst |
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