CN111203238A - Z-shaped MoS2/CaTiO3Heterojunction and preparation method and application thereof - Google Patents
Z-shaped MoS2/CaTiO3Heterojunction and preparation method and application thereof Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 64
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 63
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910002971 CaTiO3 Inorganic materials 0.000 claims abstract description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002077 nanosphere Substances 0.000 claims description 12
- 239000011941 photocatalyst Substances 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000011575 calcium Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007723 transport mechanism Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015667 MoO4 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- 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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- 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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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Abstract
The invention belongs to the technical field of semiconductor material preparation, and particularly relates to Z-shaped MoS2/CaTiO3Heterojunction and preparation method and application thereof. Ca (NO) is added to the calcium-containing material3)2·4H2Dispersing O in deionized water, adding tetrabutyl titanate into the solution dropwise after first magnetic stirring, adding sodium hydroxide into the solution, and adding MoS after second magnetic stirring2Dispersing in the above solution, stirring, transferring the obtained mixture into stainless steel autoclave with polytetrafluoroethylene as lining, reacting under autogenous pressure to obtain precipitate, centrifuging and washing the precipitate with ethanol and deionized water, and drying to obtain MoS with Z-type electron transport mechanism2/CaTiO3A heterojunction. The invention has high-efficiency activity in the aspect of photocatalytic hydrogen production, simple process and reactionLow cost, convenient batch production and environmental-friendly requirement.
Description
Technical Field
The invention belongs to the technical field of semiconductor material preparation, and particularly relates to Z-shaped MoS2/CaTiO3Heterojunction, preparation method and application thereof, and macroporous multilayer hollow CaTiO constructed by using morphology control method3CubeAnd MoS2The Z-type electron transport mechanism of the nanosphere is used for research on hydrogen production by photocatalytic water decomposition.
Background
In the society which is green, efficient and sustainable as the theme of the world, clean energy promotes prosperity and development. Hydrogen energy is emerging as a highly efficient, clean, storable, transportable and sustainable "zero-carbon" energy source in every country. At present, the subsidiary local Changshan of the energy supply Bureau of China points out on the 24 th world energy conference: "China will continue to advance energy structure adjustments. The strategic direction of green and low carbon is always adhered to, the consumption proportion of clean energy is improved, and the existing main energy, namely fossil energy, is gradually replaced. It is expected that in 2020, the non-fossil energy consumption will be improved to 15%, and further to about 20% by 2030. Therefore, the positive promotion of the innovation and the development of the hydrogen energy has important significance for China and even the world. In recent years, the traditional hydrogen production method mainly produces hydrogen from fossil fuel, but the traditional hydrogen production method has the problems of low fuel utilization rate, serious pollution, high energy consumption and the like in the application process. Based on this, the solar photocatalytic water splitting hydrogen production technology utilizes the advantages of solar energy and hydrogen energy to meet the requirements of high efficiency, cleanness, sustainability and the like in practical application. The photocatalyst plays a decisive role as a main active substance in a hydrogen production system by photocatalytic water decomposition. Therefore, excellent photocatalysts are the target we are looking for: the appropriate valence conduction band position can better absorb and utilize sunlight, the separation efficiency of photogenerated electron and hole is excellent, the recombination rate of carriers is lower, the mobility of photogenerated electrons is stronger, more reactive sites are provided, and more redox reaction centers are provided. Therefore, the discovery of the photocatalyst which can widen the light absorption range, enhance the charge separation efficiency, improve the oxidation-reduction active site and improve the light stability has a decisive influence on the improvement of the photocatalytic hydrogen production performance.
In recent years, CaTiO3One of the most important perovskites is the photocatalytic water splitting process for producing H, because of its extremely flexible structure and good compatibility with other semiconductors2Exhibit excellent photocatalysisAnd (4) performance is improved. But due to the single CaTiO3The recombination rate of the photo-generated electron-hole pairs is high, so that the photocatalytic activity is reduced. Therefore, a heterostructure strategy was applied to CaTiO3Combination with other semiconductor materials to improve CaTiO3The photocatalytic performance has important significance. MoS2Due to the characteristics of good photocatalytic performance, low cost, safety, no toxicity and the like, the photocatalyst gradually draws the attention of researchers in the field of photocatalysis. In this sense, MoS2The semiconductor being of CaTiO3The combination forms a good partner of the heterostructure, and because the band structure is well matched, the carrier can be effectively separated, which is beneficial to improving the performance of photocatalytic hydrogen production. To date there is no MoS2Nanosphere and macroporous multi-shell hollow CaTiO3The preparation of the cubic composite Z-type heterojunction and the application of photocatalysis are reported.
Disclosure of Invention
The invention aims to provide a simple and quick Z-shaped MoS2/CaTiO3The method for synthesizing the heterojunction material comprises the steps of synthesizing macroporous multilayer hollow CaTiO by using calcium nitrate tetrahydrate, tetrabutyl titanate, sodium hydroxide, sodium molybdate dihydrate and thiourea as raw materials and utilizing a morphology control method3Cube and MoS2MoS of Z-type electron transport mechanism of nanosphere2/CaTiO3A heterojunction material.
The invention provides a MoS of a Z-shaped electronic transmission mechanism2/CaTiO3The preparation method of the heterojunction material is characterized by comprising the following steps of:
step 1: MoS2Preparation of nanospheres
First, Na is added2MoO4·2H2Dispersing O and PVP (K-30) in deionized water, adding thiourea after first magnetic stirring, transferring the obtained mixture into a stainless steel high-pressure kettle with a polytetrafluoroethylene lining after second magnetic stirring, and reacting under autogenous pressure to obtain a precipitate; centrifugally washing the precipitate with ethanol and deionized water, and drying to obtain MoS2Nanospheres.
The Na is2MoO4·2H2The mass ratio of O to PVP (K-30) was 1.613: 1.
The time for two times of magnetic stirring is 60 min.
The reaction temperature under the autogenous pressure is 180 ℃, and the reaction time is 36 h.
The drying temperature is 60 ℃, and the drying time is 12 h.
Step 2: MoS of Z-type electron transport mechanism2/CaTiO3Preparation of heterojunctions
First, Ca (NO) is added3)2·4H2Dispersing O in deionized water, adding tetrabutyl titanate into the solution dropwise after first magnetic stirring, adding sodium hydroxide into the solution, and adding MoS after second magnetic stirring2Dispersing in the above solution, stirring, transferring the obtained mixture into stainless steel autoclave with polytetrafluoroethylene as lining, reacting under autogenous pressure to obtain precipitate, centrifuging and washing the precipitate with ethanol and deionized water, and drying to obtain MoS with Z-type electron transport mechanism2/CaTiO3A heterojunction.
The Ca (NO)3)2·4H2The ratio of O, tetrabutyl titanate and sodium hydroxide is 10 mmol: 3.4 mL: 0.02 mol.
The time of the first magnetic stirring is 60min, and the time of the second magnetic stirring is 30 min.
The reaction temperature under the autogenous pressure is 200 ℃, and the reaction time is 24 h.
The MoS2/CaTiO3In the heterojunction, MoS2With CaTiO3The mass ratio of (A) to (B) is 0.005:1-0.05: 1; the preferred ratio is 0.01: 1.
the drying temperature is 60 ℃, and the drying time is 12 h.
Advantageous effects
MoS for synthesizing Z-shaped electronic transmission mechanism by utilizing morphology control method2/CaTiO3The heterojunction shows excellent photocatalytic activity in the photocatalytic hydrogen production process; first, a multi-shelled hollow CaTiO3The cube can provide more reactive sites, reduce the recombination of charge-hole pairs and improve the lightThe structural stability of the catalyst enhances the light absorption and utilization capacity of the catalyst; second, MoS2The nanosphere has the advantages of high reaction activity, low surface potential energy, rich earth components and the like; secondly, the multi-shell hollow CaTiO3Cube and MoS2The Z-type electron transmission mechanism formed by the nanospheres greatly promotes the transmission of photo-generated electrons, so that the hydrogen production performance of photocatalytic water decomposition is improved. Thirdly, the photocatalyst is prepared by a simple template-free hydrothermal method, so that the photocatalyst has unique advantages in production and application. The invention has high-efficiency activity in the aspect of photocatalytic hydrogen production, simple process and low reaction cost, is convenient for batch production and meets the environment-friendly requirement.
Drawings
FIG. 1 is a scanning image (SEM), a transmission image (TEM), a high resolution image (HRTEM) and an EDSmappings image of a sample prepared according to the present invention, wherein the SEM image (a) is a CaTiO image3SEM picture (b) is MoS2SEM picture (c) is MoS2/CaTiO3Heterojunction, TEM image (d) CaTiO3TEM image (e) is MoS2/CaTiO3Heterojunction, HRTEM image (f) MoS2/CaTiO3Heterojunction, EDSmappings diagram (g) MoS2/CaTiO3A heterojunction. MoS can be found from SEM, TEM, HRTEM and EDS maps2Nanospheres have been successfully prepared in multi-shelled hollow CaTiO3On the cube.
FIG. 2 is an X-ray diffraction pattern (XRD) and a Raman pattern (Raman) of a sample prepared according to the present invention, wherein (a) is an XRD pattern from 10 to 80 DEG and (b) is an XRD pattern from 50cm-1To 950cm-1From the results of XRD and Raman tests, it can be seen that pure CaTiO has been successfully prepared3，MoS2And MoS2/CaTiO3A heterojunction.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) of a sample prepared according to the present invention, wherein panel (a) is an XPS total spectrum, panel (b) is an XPS of Ca 2p, panel (c) is an XPS of Ti 2p, panel (d) is an XPS of O1S, panel (e) is an XPS of Mo 3d, and panel (f) is an XPS of S2 p; the test results show that the prepared samples contain the elements Ca, Ti, O, Mo, S and are in contact with CaTiO3XPS spectra (FIGS. 3b-d) comparison, MoS2/CaTiO3The Ca 2p, Ti 2p and O1s states of the heterojunction move to the high energy direction, indicating that MoS2/CaTiO3The electron density of the heterojunction is low. At the same time, MoS2/CaTiO3Mo 3d and S2p (FIGS. 3e, f) of the heterojunctions transferred to a low energy region (high electron density) compared to molybdenum disulfide, indicating that electron transport is from CaTiO3Transfer to MoS2This indicates that XPS spectra show that it possesses all the elements of the synthesized sample and synthesizes Z-type MoS2/CaTiO3A heterojunction.
FIG. 4 shows MoS2，MoS2/CaTiO3-0.5％,MoS2/CaTiO3-1％,MoS2/CaTiO3-3％and MoS2/CaTiO3-5% and CaTiO3The efficiency-time relationship diagram of the photocatalyst for photocatalytic hydrogen production under visible light is shown in fig. 4 (a); FIG. (b) shows the hydrogen production efficiency; graph (c) is a cycle performance graph; graph (d) is quantum efficiency; as can be seen from the figure, MoS2/CaTiO3The-1% heterojunction has excellent photocatalytic hydrogen production efficiency of 622.14 mu mol h-1g-1Respectively being a monomer CaTiO3And MoS23.11 times and 35.03 times of the total amount of the components, which shows that the Z-type electron transport mechanism greatly improves the photocatalytic hydrogen production performance.
Detailed Description
Example 1
The method comprises the following steps: MoS2Preparation of nanospheres
First, 2mmol of Na2MoO4·2H2O and 0.3g PVP (K-30) were dispersed in 80ml of deionized water, stirred for 60min under strong magnetic force, and 10mmol of thiourea was added to gradually form a uniform slurry. After stirring for 1 hour, the resulting mixture was transferred to a 100ml stainless steel autoclave lined with polytetrafluoroethylene and maintained at 180 ℃ under autogenous pressure for 36 hours. Centrifugally washing the precipitate with ethanol and deionized water, and finally drying at 60 ℃ for 12h to obtain MoS2Nanospheres.
Example 2
The method comprises the following steps: z-shaped MoS2/CaTiO3Preparation of heterojunctions
Firstly, 1 is mixed0mmol Ca(NO3)2·4H2O was dispersed in 30mL of deionized water. After a first magnetic stirring for 60min, 3.4ml of tetrabutyl titanate was added dropwise to the above solution, followed by the addition of 0.02mol of sodium hydroxide thereto, and after a second magnetic stirring for 30min, MoS was added2Dispersed in the above solution, stirred for 30min, and the resulting mixture was transferred to a 50 ml stainless steel autoclave lined with polytetrafluoroethylene and reacted at 200 ℃ under autogenous pressure for 24 hours. Centrifugally washing the precipitate with ethanol and deionized water, and drying at 60 ℃ for 12h to obtain Z-shaped MoS2/CaTiO3A heterojunction.
Further, in the composite material, MoS2With CaTiO3The mass ratio of (A) to (B) is 0.005: 1.
Further, the label is MoS2/CaTiO3-0.5％。
Example 3
The method comprises the following steps: z-shaped MoS2/CaTiO3Preparation of heterojunctions
First, 10mmol Ca (NO) was added3)2·4H2O was dispersed in 30mL of deionized water. After a first magnetic stirring for 60min, 3.4ml of tetrabutyl titanate was added dropwise to the above solution, followed by the addition of 0.02mol of sodium hydroxide thereto, and after a second magnetic stirring for 30min, MoS was added2Dispersed in the above solution, stirred for 30min, and the resulting mixture was transferred to a 50 ml stainless steel autoclave lined with polytetrafluoroethylene and reacted at 200 ℃ under autogenous pressure for 24 hours. Centrifugally washing the precipitate with ethanol and deionized water, and drying at 60 ℃ for 12h to obtain Z-shaped MoS2/CaTiO3A heterojunction.
Further, in the composite material, MoS2With CaTiO3The mass ratio of (A) to (B) is 0.01: 1.
Further, the label is MoS2/CaTiO3-1％。
Example 4
The method comprises the following steps: z-shaped MoS2/CaTiO3Preparation of heterojunctions
First, 10mmol Ca (NO) was added3)2·4H2O was dispersed in 30mL of deionized water. First magnetic stirring 60After min, 3.4ml tetrabutyl titanate was added dropwise to the above solution, followed by 0.02mol sodium hydroxide, and after a second magnetic stirring for 30min, MoS was added2Dispersed in the above solution, stirred for 30min, and the resulting mixture was transferred to a 50 ml stainless steel autoclave lined with polytetrafluoroethylene and reacted at 200 ℃ under autogenous pressure for 24 hours. Centrifugally washing the precipitate with ethanol and deionized water, and drying at 60 ℃ for 12h to obtain Z-shaped MoS2/CaTiO3A heterojunction.
Further, in the composite material, MoS2With CaTiO3The mass ratio of (A) to (B) is 0.03: 1.
Further, the label is MoS2/CaTiO3-3％。
Example 5
The method comprises the following steps: z-shaped MoS2/CaTiO3Preparation of heterojunctions
First, 10mmol Ca (NO) was added3)2·4H2O was dispersed in 30mL of deionized water. After a first magnetic stirring for 60min, 3.4ml of tetrabutyl titanate was added dropwise to the above solution, followed by the addition of 0.02mol of sodium hydroxide thereto, and after a second magnetic stirring for 30min, MoS was added2Dispersed in the above solution, stirred for 30min, and the resulting mixture was transferred to a 50 ml stainless steel autoclave lined with polytetrafluoroethylene and reacted at 200 ℃ under autogenous pressure for 24 hours. Centrifugally washing the precipitate with ethanol and deionized water, and drying at 60 ℃ for 12h to obtain Z-shaped MoS2/CaTiO3A heterojunction.
Further, in the composite material, MoS2With CaTiO3The mass ratio of (A) to (B) is 0.05: 1.
Further, the label is MoS2/CaTiO3-5％。
Example 6
The method comprises the following steps: preparation of hollow CaTiO3Cube
First, 10mmol Ca (NO) was added3)2·4H2O was dispersed in 30mL of deionized water. After the first magnetic stirring for 60min, 3.4ml of tetrabutyl titanate was added dropwise to the above solution, followed by charging 0.02mol of sodium hydroxide thereto, and stirring under continuous magnetic forceAfter stirring for 1 hour, the resulting mixture was transferred to a 50 ml stainless steel autoclave lined with polytetrafluoroethylene and reacted at 200 ℃ under autogenous pressure for 24 hours. Centrifugally washing the precipitate with ethanol and deionized water, and drying at 60 ℃ for 12h to obtain multi-shell hollow CaTiO3A cube.
Example 7
MoS prepared by the above method2，MoS2/CaTiO3-0.5％,MoS2/CaTiO3-1％,MoS2/CaTiO3-3％andMoS2/CaTiO3-5% and CaTiO3The samples were subjected to the following photocatalytic water splitting hydrogen production experiments, respectively:
step 1: experimental preparation phase
0.05g of the catalyst is respectively weighed and added into 100ml of VC (0.3mol/L) solution, and the mixture is subjected to ultrasonic treatment for 5min to be used.
Step 2: experimental process stage
And (3) putting the sample obtained in the step (1) into a photocatalytic hydrogen production device, and vacuumizing for 30min to remove the influence of air. And turning on a light source to perform photocatalytic hydrogen production reaction.
And step 3: experimental testing phase
The generated hydrogen was detected by on-line gas chromatography (GC-7900) with nitrogen as the carrier gas and plotted in fig. 4.
Claims (8)
- Z-shaped MoS2/CaTiO3Method for preparing a heterojunction, said Z-type MoS2/CaTiO3The heterojunction is made of macroporous multilayer hollow CaTiO3Cube and MoS2Of nanospheres, MoS2Nanosphere in multi-shell hollow CaTiO3Cubic, characterized in that Ca (NO) is added3)2·4H2Dispersing O in deionized water, adding tetrabutyl titanate into the solution dropwise after first magnetic stirring, adding sodium hydroxide into the solution, and adding MoS after second magnetic stirring2Dispersing in the above solution, stirring, transferring the obtained mixture into stainless steel autoclave with polytetrafluoroethylene lining, reacting under autogenous pressure to obtain precipitate, centrifuging the precipitate with ethanol and deionized waterWashing and drying to obtain MoS with Z-shaped electronic transmission mechanism2/CaTiO3A heterojunction.
- 2. The Z-MoS of claim 12/CaTiO3A method for preparing a heterojunction, characterized in that said Ca (NO) is3)2·4H2The ratio of O, tetrabutyl titanate and sodium hydroxide is 10 mmol: 3.4 mL: 0.02 mol.
- 3. The Z-MoS of claim 12/CaTiO3The preparation method of the heterojunction is characterized in that the time of the first magnetic stirring is 60min, and the time of the second magnetic stirring is 30 min.
- 4. The Z-MoS of claim 12/CaTiO3The preparation method of the heterojunction is characterized in that the reaction temperature under the autogenous pressure is 200 ℃ and the reaction time is 24 hours.
- 5. The Z-MoS of claim 12/CaTiO3Method for preparing a heterojunction, characterized in that said MoS2/CaTiO3In the heterojunction, MoS2With CaTiO3The mass ratio of (A) to (B) is 0.005:1-0.05: 1.
- 6. The Z-MoS of claim 52/CaTiO3A method for preparing a heterojunction, characterized in that MoS2With CaTiO3Is 0.01: 1.
- 7. the Z-MoS of claim 12/CaTiO3The preparation method of the heterojunction is characterized in that the drying temperature is 60 ℃ and the drying time is 12 h.
- 8. MoS prepared by the method of any of claims 1-72/CaTiO3The heterojunction is characterized by being used as a photocatalyst for photocatalytic decomposition of water to prepare hydrogen.
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| CN112387292A (en) * | 2020-08-24 | 2021-02-23 | 江苏大学 | Quantum dot modified multi-shell CaTiO3Cube, preparation method and application |
| CN112786870A (en) * | 2021-02-10 | 2021-05-11 | 广西师范大学 | Polypyrrole coated MoS2/C composite material and preparation method thereof |
| CN114177899A (en) * | 2021-10-25 | 2022-03-15 | 江苏大学 | Multi-shell CaTiO3Cube, preparation method and application |
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| CN112387292A (en) * | 2020-08-24 | 2021-02-23 | 江苏大学 | Quantum dot modified multi-shell CaTiO3Cube, preparation method and application |
| CN112387292B (en) * | 2020-08-24 | 2023-07-18 | 江苏大学 | Quantum dot modified multishell CaTiO 3 Cube, preparation method and application |
| CN112786870A (en) * | 2021-02-10 | 2021-05-11 | 广西师范大学 | Polypyrrole coated MoS2/C composite material and preparation method thereof |
| CN114177899A (en) * | 2021-10-25 | 2022-03-15 | 江苏大学 | Multi-shell CaTiO3Cube, preparation method and application |
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