CN116273060A - Preparation method and application of zinc cadmium sulfide and titanium carbide composite photocatalyst - Google Patents
Preparation method and application of zinc cadmium sulfide and titanium carbide composite photocatalyst Download PDFInfo
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- CN116273060A CN116273060A CN202310189779.5A CN202310189779A CN116273060A CN 116273060 A CN116273060 A CN 116273060A CN 202310189779 A CN202310189779 A CN 202310189779A CN 116273060 A CN116273060 A CN 116273060A
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- titanium carbide
- cadmium sulfide
- composite photocatalyst
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- zinc cadmium
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 239000012265 solid product Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- -1 uniformly stirred Chemical compound 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 description 22
- 239000010936 titanium Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000013606 potato chips Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/006—Compounds containing, besides cadmium, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
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Abstract
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a preparation method and application of a zinc cadmium sulfide and titanium carbide composite photocatalyst. The prepared zinc cadmium sulfide/titanium carbide composite photocatalyst shows good water hydrogen production performance by photocatalytic decomposition. The preparation method is simple and convenient to operate, the preparation conditions are well controlled, and the prepared zinc cadmium sulfide and titanium carbide composite photocatalyst has good photocatalytic hydrogen production activity and stability and has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalysis nano materials, and particularly relates to a preparation method and application of a zinc cadmium sulfide and titanium carbide composite photocatalyst.
Background
In the last decades, the problems of energy depletion and environmental pollution have become a global focus of attention. In order to solve the problems of fossil fuel consumption and serious environmental pollution associated with combustion, it has become urgent to develop a clean energy source that is efficient, sustainable, inexpensive and safe. Among renewable energy sources, solar light energy is attracting attention with advantages of abundant resources, low cost, easy availability, cleanliness, harmlessness, environmental friendliness, etc., and it can substantially satisfy the demands of human survival and development, thereby people are devoted to applying solar energy to daily production. The method for preparing hydrogen by photocatalytic water splitting through semiconductor materials is a very environment-friendly method for obtaining hydrogen by taking water as a raw material and solar energy as a driving force, and is considered as a promising strategy for converting solar energy into hydrogen energy. Among the semiconductor photocatalysts currently studied, a zinc cadmium sulfide (CZS) solid solution having a visible light absorption characteristic is widely used in the field of photocatalysis by virtue of a narrow band gap width (about 2.4 eV) and high photocatalytic activity. However, due to their inherent drawbacks, zinc cadmium sulfide has limited further applications, particularly low specific surface area, fast photo-generated charge recombination rates, and hole-induced self-corrosion.
Transition metal carbides or nitrides (MXene) are a novel class of two-dimensional laminates composed of transition metals and carbon or nitrogen and having the formula M n+1 X n (where M is a transition metal element and X is C or N, n=1, 2 or 3) shaped like a stack of potato chips or accordion. Due to its typical layered structure andthe catalyst has excellent electronic performance, can be used as a catalyst promoter for compounding other photocatalytic materials so as to enhance the separation of photo-generated charges and inhibit the rapid compounding of the charges, and finally converts solar energy into chemical energy. A variety of MXene materials have been successfully synthesized to date, including Ti 3 C 2 、Ti 2 C. TiNbC, and the like.
In order to effectively change the inherent defects of zinc sulfide and cadmium sulfide and improve the photocatalytic performance of the zinc sulfide and cadmium sulfide, the invention aims to prepare a proper material to be compounded with the zinc sulfide and cadmium sulfide and improve the photocatalytic performance of the zinc sulfide and cadmium sulfide.
Disclosure of Invention
Aiming at the problems in the background technology, the invention aims to provide a preparation method and application of a zinc cadmium sulfide and titanium carbide composite photocatalyst, the preparation method is simple and easy to implement, the preparation conditions are easy to control, and the prepared zinc cadmium sulfide and titanium carbide composite photocatalyst has good activity of decomposing water into hydrogen by photocatalysis and has a certain application prospect.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the zinc cadmium sulfide and titanium carbide composite photocatalyst comprises the steps of dissolving cadmium nitrate tetrahydrate, zinc nitrate hexahydrate and thiourea in ethylenediamine and deionized water, and uniformly stirring; then adding titanium carbide into the mixture to obtain suspension; the suspension is hydrothermally treated for 12 to 13 hours in a stainless steel autoclave of polytetrafluoroethylene at 170 to 180 ℃, solid products are centrifugally separated, and then the solid products are washed for a plurality of times by deionized water and absolute ethyl alcohol, and the solid products are dried at 80 ℃ to prepare the zinc cadmium sulfide and titanium carbide composite photocatalyst.
Further, the mole ratio of the tetrahydrated cadmium nitrate, the hexahydrated zinc nitrate and the thiourea is 10-20: 5-15: 65-85; preferably, the molar ratio of the cadmium nitrate tetrahydrate, the zinc nitrate hexahydrate and the thiourea is 15:10:75; wherein the volume ratio of ethylenediamine to deionized water is 2:1.
Further, the concentration of titanium carbide in the suspension is 0.17-0.5 mg/ml; the loading mass of the titanium carbide in the zinc cadmium sulfide and titanium carbide composite photocatalyst is 1.7% -5.0%; preferably, the titanium carbide has a load mass of 3.3% in the zinc cadmium sulfide and titanium carbide composite photocatalyst.
Further, the invention also comprises a preparation method of the titanium carbide: dispersing lithium fluoride in 9-10 mol/L hydrochloric acid solution, uniformly stirring the mixture, adding titanium aluminum carbide powder, and putting the obtained mixture into an oil bath pot at 80-90 ℃ for stirring reaction until the reaction is complete; after the suspension is cooled to room temperature, centrifuging and washing with deionized water until the pH of the mixture reaches 6-7, and drying at 80 ℃; and dispersing the prepared powder in deionized water for ultrasonic treatment, centrifugally collecting black titanium carbide, and drying at 80 ℃.
Further, in the method for producing titanium carbide, the mass ratio of lithium fluoride to titanium aluminum carbide is 1 to 1.1:1, preferably 1:1.
Further, in the method for preparing titanium carbide, the stirring speed in the stirring reaction is 200r/min, and the stirring time is 23-24 hours. Too long stirring time can lead to excessive etching, too short stirring time can lead to insufficient etching, and the accordion-shaped multilayer stacked titanium carbide is difficult to obtain.
Further, in the preparation method of titanium carbide, after the suspension is cooled to room temperature, the suspension is centrifuged and washed by deionized water until the pH of the mixture reaches 6-7, and the mixture is kept weakly acidic to neutral. The weak acid or neutrality is maintained by deionized water washing, so that a small amount of residual salt ions can be prevented from continuing to react and the stability of the titanium carbide can be maintained.
Further, in the preparation method of the titanium carbide, an ice-water bath is adopted for ultrasonic treatment, the temperature is strictly controlled at about 0 ℃, and the high-temperature oxidation of the titanium carbide is avoided.
Furthermore, the ultrasonic power of ultrasonic treatment is 360W, the ultrasonic frequency is 40KHz, and the ultrasonic time is 60-70 minutes, so that the high-temperature oxidation of titanium carbide is further avoided.
The invention provides an application of a zinc cadmium sulfide and titanium carbide composite photocatalyst in photocatalytic decomposition of water to produce hydrogen.
Compared with the prior art, the invention has the technical principle and beneficial effects that:
1. among the numerous MXene materials, ti 3 C 2 MXene has a large number of hydrophilic groups on its surfaceThe water-absorbing material has good water absorption, a two-dimensional lamellar atomic structure and adjustable physical properties, and the surface of the material is provided with a plurality of metal sites, so that more reactive sites can be provided. The titanium carbide material selected by the invention has high light collecting efficiency, excellent conductivity and structural stability, simple preparation and high economic benefit.
2. The invention firstly synthesizes titanium carbide by adopting a solvothermal method, zinc cadmium sulfide is loaded on the titanium carbide by in-situ growth, and the zinc cadmium sulfide and titanium carbide composite photocatalyst is obtained by hydrothermal reaction. Cd (cadmium sulfide) 1-x Zn x The S nano solid solution has S vacancy, heterogeneous junction and twin crystal homogeneous junction, effectively promotes carrier separation, strengthens S 2- Adsorption on the catalyst surface. The titanium carbide is used as a cocatalyst to form a heterojunction with the zinc cadmium sulfide, so that electron hole transfer is accelerated, and photocatalysis performance is enhanced.
3. The preparation method is simple and easy to implement, the preparation conditions are easy to control, and the prepared zinc cadmium sulfide and titanium carbide composite photocatalyst has good hydrogen evolution activity and has a certain application prospect.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of zinc cadmium sulfide and titanium carbide composite photocatalysts with different contents prepared in examples 1-3 and comparative example 1 of the present invention;
FIG. 2 is a fluorescence emission spectrum of the zinc cadmium sulfide and titanium carbide composite photocatalyst prepared in example 2 of the present invention;
FIG. 3 is a band gap diagram of a zinc cadmium sulfide and titanium carbide composite photocatalyst prepared in example 2 of the present invention;
FIG. 4 is a graph showing the hydrogen production activity rates of the zinc cadmium sulfide and titanium carbide composite catalysts prepared in examples 1 to 3 and comparative example 1 according to the present invention;
FIG. 5 is a cycle chart of the photocatalysis experiment of the zinc cadmium sulfide and titanium carbide composite catalyst prepared in the embodiment 2 of the invention.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are intended to illustrate the invention and not to limit it further.
Example 1
(1) Preparation of titanium carbide: 1g of lithium fluoride was dispersed in 20ml of a 9mol/L hydrochloric acid solution, and the mixture was stirred for 10 minutes to obtain a uniform mixture. Subsequently, 1g of titanium aluminum carbide powder was immersed in a lithium fluoride/hydrochloric acid solution which had been stirred uniformly, and the obtained mixture was put into an oil bath at 80℃for stirring for 24 hours, after the suspension was cooled to room temperature, centrifuged and washed with deionized water until the pH of the mixture reached 6, dried overnight in an oven at 80℃for 12 hours, and the prepared powder was further sonicated in deionized water for 1 hour, centrifuged at 3500 rpm for 30 minutes to collect black titanium carbide, and dried overnight in an oven at 80℃for 12 hours.
(2) Zinc cadmium sulfide and titanium carbide composite photocatalyst (Cd) 0.6 Zn 0.4 S/Ti 3 C 2 -5 mg) preparation: 0.555g of cadmium nitrate tetrahydrate (1.8 mmol), 0.357g of zinc nitrate hexahydrate (1.2 mmol) and 0.685g of thiourea (9 mmol) were dissolved in ethylenediamine (20 ml) and deionized water (10 ml). Then adding 5mg of titanium carbide into the mixture, carrying out hydrothermal treatment on the suspension in a stainless steel autoclave of 100ml of polytetrafluoroethylene at 180 ℃ for 12 hours, centrifugally separating a solid product, washing the solid product with deionized water and absolute ethyl alcohol (volume ratio is 1:1) for several times, and then drying the solid product at 80 ℃ overnight to obtain the zinc cadmium sulfide and titanium carbide composite photocatalyst (Cd) containing 5mg of titanium carbide 0.6 Zn 0.4 S/Ti 3 C 2 -5 mg) of titanium carbide, the loading of which in the zinc cadmium sulfide and titanium carbide composite photocatalyst is 1.7%.
Example 2
(1) Preparation of titanium carbide: as in example 1.
(2) Zinc cadmium sulfide and titanium carbide composite photocatalyst (Cd) 0.6 Zn 0.4 S/Ti 3 C 2 -10 mg) preparation: 0.555g of cadmium nitrate tetrahydrate (1.8 mmol), 0.357g of zinc nitrate hexahydrate (1.2 mmol) and 0.685g of thiourea (9 mmol) were dissolved in ethylenediamine (20 ml) and deionized water (10 ml). Subsequently, another 10mg of titanium carbide was added to the mixture, and the suspension was stirred in a stainless steel autoclave of 100ml of polytetrafluoroethylene at 180 DEG CHydrothermally treating for 12 hours, centrifugally separating a solid product, washing the solid product with deionized water and absolute ethyl alcohol (volume ratio is 1:1) for several times, and then drying the solid product at 80 ℃ overnight to obtain the zinc cadmium sulfide and titanium carbide composite photocatalyst (Cd) containing 10mg of titanium carbide 0.6 Zn 0.4 S/Ti 3 C 2 -10 mg) of titanium carbide, and the loading of the titanium carbide in the zinc cadmium sulfide and titanium carbide composite photocatalyst is 3.3 percent.
Example 3
(1) Preparation of titanium carbide: as in example 1.
(2) Zinc cadmium sulfide and titanium carbide composite photocatalyst (Cd) 0.6 Zn 0.4 S/Ti 3 C 2 -15 mg) of preparation: 0.555g of cadmium nitrate tetrahydrate (1.8 mmol), 0.357g of zinc nitrate hexahydrate (1.2 mmol) and 0.685g of thiourea (9 mmol) were dissolved in ethylenediamine (20 ml) and deionized water (10 ml). Then adding 15mg of titanium carbide into the mixture, carrying out hydrothermal treatment on the suspension in a stainless steel autoclave of 100ml of polytetrafluoroethylene for 12 hours at the temperature of 180 ℃, centrifugally separating a solid product, washing the solid product with deionized water and absolute ethyl alcohol (volume ratio is 1:1) for several times, and then drying the solid product at the temperature of 80 ℃ overnight to obtain the zinc cadmium sulfide and titanium carbide composite photocatalyst (Cd) containing 15mg of titanium carbide 0.6 Zn 0.4 S/Ti 3 C 2 15 mg) of titanium carbide, and the loading of the titanium carbide in the zinc cadmium sulfide and titanium carbide composite photocatalyst is 5.0 percent.
Comparative example 1
Cadmium zinc sulfide (Cd) 0.6 Zn 0.4 S) preparation:
0.555g of cadmium nitrate tetrahydrate (1.8 mmol), 0.357g of zinc nitrate hexahydrate (1.2 mmol) and 0.685g of thiourea (9 mmol) were dissolved in ethylenediamine (20 ml) and deionized water (10 ml). The suspension was hydrothermally treated in a stainless steel autoclave of 100ml polytetrafluoroethylene at 180℃for 12 hours, the solid product was separated by centrifugation, washed several times with deionized water and absolute ethanol (volume ratio 1:1) and then dried overnight at 80 ℃.
Titanium carbide alone has no catalytic activity.
TC, cd prepared in examples 1 to 3 0.6 Zn 0.4 S/Ti 3 C 2 Visible light catalyst and Cd prepared in comparative example 1 0.6 Zn 0.4 S is analyzed by Japanese science D/max2500PC autorotation X-ray diffractometer, wherein X-ray is Cu target
The voltage is 40kV, the current is 100mA, the step size is 0.02 DEG, and the scanning range is 10 DEG-80 deg. As shown in FIG. 1, the synthesis of the zinc cadmium sulfide and titanium carbide composite photocatalyst is also verified by the peak shapes at the (002), (010) and (110) positions in the composite structure.
Cd in example 2 was observed using a Cary Eclipse fluorescence spectrophotometer 0.6 Zn 0.4 S/Ti 3 C 2 The fluorescence spectrum of the 10mg photocatalyst is shown in FIG. 2. As can be seen from the spectral diagram of FIG. 2, pure Cd 0.6 Zn 0.4 S showed a higher fluorescence intensity at an excitation wavelength of 480nm, indicating Cd 0.6 Zn 0.4 The charges in the S semiconductors are easily recombined and their lifetime is short during the photocatalytic reaction. However, cd 0.6 Zn 0.4 S/Ti 3 C 2 The hybridization of-10 mg greatly reduces the fluorescence intensity of the photocatalyst, and the fluorescence intensity of the composite material is greatly reduced, probably because the titanium carbide nano-sheet with excellent conductivity provides a rapid channel for the transfer and migration of the photon-generated carrier in the acceleration composite material, and the photocatalytic performance is improved. In the present embodiment, ti is introduced 3 C 2 After that, cd 0.6 Zn 0.4 S/Ti 3 C 2 Fluorescent intensity of-10 mg compared with Cd in comparative example 1 0.6 Zn 0.4 S was reduced, indicating Cd 0.6 Zn 0.4 S and Ti 3 C 2 After the heterojunction is formed, the recombination of photo-generated electron hole pairs in ZIS is effectively inhibited, and the separation of photo-generated electron-hole pairs is effectively promoted, so that the service life of electrons is prolonged, and the photocatalytic efficiency of the composite photocatalyst is enhanced.
Measurement of Cd in example 2 using UV-3600 ultraviolet-visible diffuse reflectance spectroscopy 0.6 Zn 0.4 S/Ti 3 C 2 The band gap diagram of the-10 mg photocatalyst is shown in FIG. 3Shown. As can be seen from the band gap diagram of FIG. 3, the present embodiment introduces Ti 3 C 2 After that, cd 0.6 Zn 0.4 S/Ti 3 C 2 Band gap width of-10 mg compared with Cd in comparative example 1 0.6 Zn 0.4 S, the light capturing capability of the composite material is higher than that of pure Cd 0.6 Zn 0.4 S is stronger, the band gap is narrower, and the photocatalytic performance is better.
Cd prepared in examples 1 to 3 0.6 Zn 0.4 S/Ti 3 C 2 As a photocatalyst to decompose the aqueous hydrogen. The hydrogen evolution rate was determined by a closed Pyrex reactor with a top PL SSXE300/300 ultraviolet xenon lamp (300W, simulating 400-760nm visible). First, 1.37g of Na was taken 2 S and 1.58gNa 2 SO 3 Dissolved in 50mL of water, and then 10mg of the catalyst was dispersed in the above solution by ultrasonic treatment. After transferring the suspension to the Pyrex reactor, air above the liquid level and in the solution was removed by purging with argon for 30 minutes. 500. Mu.L of the mixed gas was taken every 30 minutes, reacted for 3 hours, and the hydrogen content was measured by GC-7900 gas chromatography. As can be seen from FIG. 4, the zinc cadmium sulfide and titanium carbide composite photocatalyst of example 2 has a hydrogen production rate of 103.9mmolg under the condition of light irradiation -1 h -1 The hydrogen production rate of example 1 was 87.3 mmolgs -1 h -1 The hydrogen production rate of example 3 was 67.7 mmolgs -1 h -1 All higher than that of comparative example 1 by 45.5 mmolgs -1 h -1 It can be seen that the introduction of titanium carbide can obviously improve the hydrogen production rate of the photocatalyst, and the content of titanium carbide has obvious influence on the photocatalytic activity; therefore, in the preferred embodiment 2, the zinc cadmium sulfide and titanium carbide composite photocatalyst with the titanium carbide content of 10mg is selected.
In order to verify the stability of the zinc cadmium sulfide and titanium carbide composite photocatalyst prepared by the invention, a photocatalytic cycle experiment was performed on the zinc cadmium sulfide and titanium carbide composite catalyst prepared by example 2. The experimental result is shown in fig. 5, and the catalyst has high catalytic activity after four times of circulation, which shows that the prepared zinc cadmium sulfide and titanium carbide composite photocatalyst has good stability.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description.
Claims (9)
1. The preparation method of the zinc cadmium sulfide and titanium carbide composite photocatalyst is characterized in that cadmium nitrate tetrahydrate, zinc nitrate hexahydrate and thiourea are dissolved in ethylenediamine and deionized water, uniformly stirred, and titanium carbide is added to obtain suspension; and carrying out hydrothermal treatment on the suspension in an autoclave at 170-180 ℃ for 12-13 hours, and carrying out centrifugal separation on a solid product, washing and drying to obtain the zinc cadmium sulfide and titanium carbide composite photocatalyst.
2. The method for preparing the zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 1, wherein the molar ratio of the cadmium nitrate tetrahydrate to the zinc nitrate hexahydrate to the thiourea is 10-20: 5-15: 65 to 85.
3. The method for preparing a zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 1, wherein the concentration of titanium carbide in the suspension is 0.17-0.5 mg/ml.
4. The method for preparing the zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 1, wherein the titanium carbide has a load mass of 1.7% -5% in the zinc cadmium sulfide and titanium carbide composite photocatalyst.
5. The method for preparing the zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 1, wherein the method for preparing the titanium carbide comprises the following steps: dispersing lithium fluoride in 9-10 mol/L hydrochloric acid solution, uniformly stirring the mixture, adding titanium aluminum carbide powder, and putting the obtained mixture into an oil bath pot at 80-90 ℃ for stirring reaction until the reaction is complete; after the suspension is cooled to room temperature, centrifuging and washing with deionized water until the pH of the mixture reaches 6-7, and drying at 80 ℃; dispersing the prepared powder in deionized water for ultrasonic treatment, centrifugally collecting black titanium carbide, and drying at 80 ℃; wherein the mass ratio of the lithium fluoride to the titanium aluminum carbide is 1-1.1:1.
6. The method for preparing a zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 5, wherein the stirring speed in the stirring reaction is 200r/min, and the stirring time is 23-24 hours.
7. The method for preparing the zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 5, wherein the ultrasonic treatment is performed in an ice-water bath at 0 ℃.
8. The method for preparing the zinc cadmium sulfide and titanium carbide composite photocatalyst according to claim 7, wherein the ultrasonic power of the ultrasonic treatment is 360W, the ultrasonic frequency is 40KHz, and the ultrasonic time is 60-70 minutes.
9. The application of the zinc cadmium sulfide and titanium carbide composite photocatalyst prepared by the method of claim 1 is characterized in that the application of the zinc cadmium sulfide and titanium carbide composite photocatalyst in photocatalytic decomposition of water to produce hydrogen.
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