CN117244566A - Photocatalyst 1T/2H MoSe 2 ZIS and method for the production thereof - Google Patents
Photocatalyst 1T/2H MoSe 2 ZIS and method for the production thereof Download PDFInfo
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- 229910016001 MoSe Inorganic materials 0.000 title claims abstract description 91
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 25
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- 239000000843 powder Substances 0.000 claims abstract description 14
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
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- 230000008569 process Effects 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000009830 intercalation Methods 0.000 abstract description 11
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- 230000033228 biological regulation Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 6
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- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- 238000006053 organic reaction Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 12
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000006136 alcoholysis reaction Methods 0.000 description 6
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- 230000008859 change Effects 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- 230000001276 controlling effect Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
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- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 230000001506 immunosuppresive effect Effects 0.000 description 1
- 239000003018 immunosuppressive agent Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a photocatalyst 1T/2H MoSe 2 ZIS and a preparation method thereof, which relate to the technical field of semiconductor photocatalysis and comprise the following steps: step 1, preparing a ZIS photocatalyst; step 2, taking ZIS photocatalyst prepared in step 1 and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Adding the mixture into an organic solvent containing an amide group according to the molar ratio of (0.60-1.20) (0.05-0.15) (0.10-0.30) for stirring and adsorbing. Step 3, transferring the solution obtained in the step 2 into a high-pressure reaction kettle, maintaining the temperature at 140-210 ℃ for 12-48H, separating precipitate, cleaning the precipitate, and drying to obtain the MoSe loaded with 1T phase and 2H phase 2 ZIS of (2). The invention cooperates with temperature regulation and in-situ intercalation to improve MoSe 2 The phase conversion rate is increased, the 1T phase stability is enhanced, and a new thought and approach are provided for designing and developing novel high-efficiency visible light catalytic synthesis organic reaction.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalysis, and particularly relates to a photocatalyst 1T/2H MoSe 2 /ZIS and its preparation method.
Background
Beta-alkoxy alcohols have been widely used in the production of immunosuppressive and antitumor drugs as an important class of organic solvents and important precursors for organic synthesis. Compared with the traditional thermal reaction system, the photocatalytic organic synthesis reaction condition is mild, has good regioselectivity on target products, can directly convert solar energy into chemical energy, and provides a sustainable development path for the production of fine chemicals. Although photocatalysis has been developed in the epoxide alcoholysis field, the existing photocatalysis system still has the problems of high manufacturing cost, narrow photoresponse range, poor photoinduced charge carrier separation efficiency and the like. In recent years, indium zinc sulfide (ZIS) has been proved to be a very promising photocatalyst because of its suitable forbidden bandwidth, good photocatalytic activity and chemical stability. While the zinc acid sites on the ZIS surface achieve epoxide adsorption and efficient polarization. Research shows that ZIS has higher catalytic activity in photocatalytic organic synthesis, photocatalytic decomposition, hydrolysis hydrogen production and photocatalytic degradation of organic pollutants, and has better photochemical stability compared with binary metal sulfide. However, the photogenerated charges of a single ZIS are easily recombined, and the quantum efficiency is relatively low. Therefore, the ZIS needs to be modified to improve its photocatalytic performance.
In general, the heterojunction is constructed on the surface of the photocatalyst by coupling different materials, so that the problem of rapid photo-generated electron-hole recombination can be effectively inhibited. In recent years, S-type heterostructures have become one of the most effective strategies for achieving efficient photocatalysis. To build an S-type heterostructure, the primary precondition is to match the band structure, where the conduction band of one semiconductor should be as close as possible to the valence band of the other semiconductor. MoSe is reported 2 The conduction band potential of (about-0.45 eV) is lower than the conduction band of ZIS but very close to its valence band (0.99 eV), indicating MoSe 2 The photogenerated electrons in the conduction band are likely to recombine with the photogenerated holes in the ZIS valence band according to the S-scheme route. MoSe is based on the arrangement of Se atoms 2 There are mainly two phases, including the most stable 2H phase and the metallic 1T phase. In recent years, it has been found that although MoSe in the 2H phase 2 MoSe with excellent intrinsic photocatalytic activity but metallic 1T phase 2 It appears to exhibit better properties, including richer substrates and edge reaction sites, as well as excellent electron conductivity.
However, to date, moSe due to the 1T phase 2 High energy of formation, direct synthesis of pure 1T-MoSe 2 Still very difficult. In view of this, from 2H-MoSe 2 To 1T-MoSe 2 The inverse phase transformation of (2) is of great interest, but the degree of phase transformation (2 H.fwdarw.1T) is still at a low level. Thus, a controllable strategy is explored to realize the slave 2H-MoSe 2 To 1T-MoSe 2 Is very critical. At present, various strategies have been proposed to achieve 2 H.fwdarw.1T phase transitions, including temperature regulation, ion intercalation (e.g. Li+, T-butyllithium), and elemental doping, among others. Temperature regulation: the 1T and 2H phase contents are controlled by injecting thermal activation energy in the solvothermal process, i.e. changing the solvothermal temperature. The low temperature is responsible for the formation of the 1T phase, which, due to its thermodynamically metastable nature, is easily transformed into the 2H phase above 200 ℃. Chemical stripping and electrochemical lithium intercalation liquid ammonia assisted lithiation: adding blocky organic lithium in the preparation process to prepare MoSe 2 The powder is peeled into monolayer nano-sheets. However, these modification strategies also suffer from drawbacks such as chemical stripping, electrochemical lithium intercalation and liquid ammonia-assisted lithiation, which can promote MoSe 2 Phase changes, defects can also be introduced resulting in the exposure of more active sites. But the phase of the techniqueThe conversion rate is low, and the doping and embedding only stay on the surface, so the phase conversion rate is not high; the temperature control method can also promote MoSe 2 Phase transition, but 1T phase MoSe generated by temperature regulation 2 Thermodynamically unstable, and reverse phase transformation easily occurs.
Disclosure of Invention
For the MoSe described above 2 The invention provides a photocatalyst and a preparation method thereof, which have the problems of low phase conversion rate of 2H-1T and reverse phase transformation. Promoting MoSe through temperature regulation 2 Phase transition occurs while intercalation of the amide group-containing compound causes MoSe to occur 2 The interlayer spacing expansion accelerates the adsorption of reactive intermediate species and the desorption of beta-alkoxy alcohol, and the compound containing amide group inserted in situ can be used as a stabilizer to inhibit 1T phase MoSe 2 The reverse phase change occurs. 1T/2H MoSe 2 The catalyst is loaded on ZIS to form an S-shaped heterojunction structure, so as to generate the composite photocatalyst.
In order to achieve the above purpose, the following technical scheme is adopted:
the invention provides a photocatalyst 1T/2H MoSe 2 A method of preparing/ZIS comprising the steps of:
step 1, preparing a ZIS photocatalyst;
step 2, taking ZIS photocatalyst prepared in step 1 and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Adding (0.60-1.20) 0.05-0.15 (0.10-0.30) 0.10-0.30 into an organic solvent containing amide groups, stirring and adsorbing, wherein NaBH is introduced 4 Is used for reducing Se powder.
Step 3, transferring the solution obtained in the step 2 into a high-pressure reaction kettle, maintaining the temperature at 140-210 ℃ for 12-48H, separating precipitate, cleaning the precipitate, and drying to obtain the MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
Further, the method for preparing the ZIS photocatalyst in the step 1 is as follows: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving (1.0-2.0) and (5.0-7.0) into deionized water according to the molar ratio of (0.5-1.5)And heating the precursor solution to react at 70-120 ℃ for 1.5-3.0 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing with absolute ethyl alcohol and deionized water, and drying in a vacuum oven overnight at 60-80 ℃.
Further, the organic solvent containing an amide group in step 2 is N, N-Dimethylformamide (DMF).
Further, in step 2, ZIS photocatalyst prepared in step 1 is dispersed in an organic solvent containing amide groups, and ZIS and Na are added 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the mixture into the organic solvent containing the amide groups according to the molar ratio of 0.90:0.10:0.20:0.20, and stirring for adsorption.
Further, in the step 3, the lining of the high-pressure reaction kettle is polytetrafluoroethylene.
Further, the reaction temperature in the autoclave in step 3 was 200 ℃.
Further, the precipitate obtained in the step 3 is separated and washed with deionized water and ethanol.
The invention also provides a photocatalyst 1T/2H MoSe 2 ZIS, obtainable by a process according to any one of the preceding claims.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention promotes MoSe by temperature regulation 2 Realizes 2H-1T phase change, improves 1T phase conversion rate, and solves the problem of directly synthesizing pure 1T-MoSe 2 Is difficult to be carried out.
(2) In the preparation of MoSe 2 In the process of (2), adding an organic solvent containing an amide group, and intercalating the compound containing the amide group to obtain MoSe 2 The expansion of the interlayer spacing accelerates the adsorption of reactive species in the middle of the reaction and the desorption of the product beta-alkoxy alcohol, while the in situ intercalated amide group-containing compound is reacted with MoSe 2 There is a bonding action, so that the compound containing amide groups can effectively inhibit 1T phase MoSe as a stabilizer 2 The reverse phase change occurs, and the 1T phase MoSe generated by temperature regulation is effectively solved 2 And the thermodynamic instability.
(3) 1T/2H MoSe to expand the interlayer 2 The oxidation-reduction capability of the material is optimized to a greater extent by coupling with ZIS to form the S-type heterojunction photocatalytic composite material.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the indium zinc sulfide photocatalyst (ZIS) prepared in example 1;
FIG. 2 is a 1T/2H MoSe prepared in example 1 2 Scanning Electron Microscope (SEM) image of/ZIS photocatalyst (MS/ZIS);
FIG. 3 is a Transmission Electron Microscope (TEM) image of the sulfur indium zinc photocatalyst (ZIS) prepared in example 1;
FIG. 4 is a partially enlarged view of a Transmission Electron Microscope (TEM) image of the sulfur indium zinc photocatalyst (ZIS) prepared in example 1;
FIG. 5 is a 1T/2H MoSe prepared in example 1 2 Transmission Electron Microscope (TEM) image of/ZIS photocatalyst (MS/ZIS);
FIG. 6a is a 1T/2H MoSe prepared in example 1 2 A partial magnified view of a Transmission Electron Microscope (TEM) image of a/ZIS photocatalyst (MS/ZIS);
FIG. 6b is an enlarged view of portion b of FIG. 6 a;
FIG. 6c is an enlarged view of portion c of FIG. 6 a; FIG. 7 is a schematic diagram of a 1T/2H MoSe photocatalyst (ZIS) prepared in example 1 2 (200 MS) and 1T/2H MoSe 2 XRD spectra of/ZIS photocatalyst (200 MS/ZIS);
fig. 8 is a raman spectrum of MS prepared at different solvothermal temperatures.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown.
The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
In view of direct synthesis of pure 1T-MoSe 2 Still very difficult, from 2H-MoSe 2 To 1T-MoSe 2 The degree of reverse phase transformation of (a) is still limited to a low level, and various strategies have been proposed in the prior art to achieve 2H to 1T phase transformation, including temperature regulation, ion intercalation (e.g., li+, T-butyllithium), element doping, and the like, but each method has a number of drawbacks. For example, temperature regulation: generated 1T phase MoSe 2 Thermodynamically unstable, and easily undergoes reverse phase transition; chemical stripping, electrochemical lithium intercalation and liquid ammonia assisted lithiation: introducing defects results in exposure of more active sites and phase inversion is not high.
Therefore, the photocatalyst 1T/2H MoSe provided by the embodiment of the invention 2 ZIS and method for preparing same, by temperature control to promote MoSe 2 Phase transition occurs while intercalation of the amide group-containing compound causes MoSe to occur 2 The interlayer spacing expansion accelerates the adsorption of reactive intermediate species and the desorption of beta-alkoxy alcohol, and the compound containing amide group inserted in situ can be used as a stabilizer to inhibit 1T phase MoSe 2 The reverse phase change occurs. 1T/2H MoSe 2 The catalyst is loaded on ZIS to form an S-shaped heterojunction structure, so as to generate the composite photocatalyst.
Specifically, the method comprises the following steps:
step 1, preparing a ZIS photocatalyst;
step 2, taking the ZIS photocatalyst prepared in the step 1, dispersing in an organic solvent containing amide groups, and adding Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Is also added into an organic solvent containing amide groups for stirring and adsorption.
Step 3, step 2Transferring the obtained solution into a high-pressure reaction kettle, performing high-temperature reaction, separating to obtain precipitate after the reaction is finished, cleaning, and drying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
The method for preparing the ZIS photocatalyst in the step 1 is as follows: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving (1.0-2.0) and (5.0-7.0) into 40ml of deionized water according to the molar ratio of (0.5-1.5) to form a precursor solution, heating the precursor solution to react at the temperature of 70-120 ℃ for 1.5-3.0 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing with absolute ethyl alcohol and deionized water, drying in a vacuum oven overnight at the temperature of 60-80 ℃.
In step 1, the precursor solution is heated to generate a heating reaction, and may be heated by an oil bath.
In step 2, ZIS photocatalyst prepared in step 1 and Na were taken 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Adding the mixture into an organic solvent containing an amide group according to the molar ratio of (0.60-1.20) (0.05-0.15) (0.10-0.30) for stirring and adsorbing.
Further, in step 2, ZIS photocatalyst is dispersed in an amide group-containing organic solvent such as DMF as an organic N group-containing macromolecule, and DMF can be added in MoSe due to its large steric hindrance and layering effect 2 Embedding during formation, resulting in MoSe 2 The interlayer spacing is enlarged, thereby exposing more basal surface and edge active sites, and the organic solvent containing the amide group can be ethylenediamine, octylamine and the like. Promotion of MoSe due to heating 2 2H- & gt1T is subjected to phase change to generate 1T-phase MoSe 2 Thermodynamically unstable, easily undergoing reverse phase transformation, and further, intercalation of DMF to MoSe 2 Adsorption of active species in interlayer spacing expansion reaction and desorption of beta-alkoxy alcohol as product, and DMF inserted in situ can be used as stabilizer to inhibit 1T phase MoSe 2 The reverse phase change occurs.
And in the step 3, transferring the solution obtained in the step 2 into a high-pressure reaction kettle for reaction. When the reaction occurs, the reactant is gasified, and the pressure in the container is increased, so that the high-temperature reaction can be safely carried out by the high-pressure reaction kettle. The high-pressure reaction kettle is selected to be lined with polytetrafluoroethylene.
In step 3, transferring the solution obtained in step 2 into a high-pressure reaction kettle, maintaining at 140-210 deg.C for 12-48 hr, separating precipitate, cleaning the precipitate, and drying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
In step 3, deionized water and ethanol may be selected for cleaning the precipitate obtained by separation.
The invention also provides a photocatalyst 1T/2H MoSe 2 ZIS, obtainable by a process according to any one of the preceding claims. By coupling MoSe at the surface of ZIS 2 And a heterostructure is constructed, so that the problem of fast photo-generated electron-hole recombination is effectively inhibited, and the photocatalysis performance is improved.
The invention also provides the following specific examples to illustrate the preparation process in detail:
example 1
(1) Preparation of ZIS photocatalyst: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving the mixture into 40ml of deionized water according to the molar ratio of 1.0:1.5:6.0 to form a precursor solution, heating the precursor solution to react at the reaction temperature of 95 ℃ for 2.5 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing the reaction product with absolute ethyl alcohol and deionized water, and drying the reaction product in a vacuum oven overnight at the temperature of 70 ℃.
(2) Dispersing ZIS photocatalyst prepared in (1) in DMF solution, and mixing ZIS and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the mixture into the DMF solution according to the molar ratio of 0.90:0.10:0.20:0.20, and stirring for adsorption.
(3) Transferring the solution into a high-pressure reaction kettle with polytetrafluoroethylene lining, maintaining at 200deg.C for 48 hr, centrifuging to obtain precipitate, washing the precipitate with deionized water and ethanol, and dryingDrying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
Example 2
(1) Preparation of ZIS photocatalyst: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving the mixture into 40ml of deionized water according to the molar ratio of 0.5:1.0:5.0 to form a precursor solution, heating the precursor solution to react at the reaction temperature of 90 ℃ for 1.5 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing the reaction product with absolute ethyl alcohol and deionized water, and drying the reaction product in a vacuum oven overnight at the temperature of 70 ℃.
(2) Dispersing ZIS photocatalyst prepared in (1) in DMF solution, and mixing ZIS and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the mixture into the DMF solution according to the molar ratio of 0.60:0.05:0.10:0.10, and stirring for adsorption.
(3) Transferring the solution into a high-pressure reaction kettle with polytetrafluoroethylene lining, maintaining at 190 deg.C for 36 hr, centrifuging to obtain precipitate, washing the precipitate with deionized water and ethanol, and drying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
Example 3
(1) Preparation of ZIS photocatalyst: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving the mixture into 40ml of deionized water according to the molar ratio of 1.5:2.0:7.0 to form a precursor solution, heating the precursor solution to react at the reaction temperature of 100 ℃ for 3 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing the reaction product with absolute ethyl alcohol and deionized water, and drying the reaction product in a vacuum oven overnight at the temperature of 70 ℃.
(2) Dispersing ZIS photocatalyst prepared in (1) in DMF solution, and mixing ZIS and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the components into the DMF solution according to the molar ratio of 1.20:0.15:0.30:0.30, and stirring for adsorption.
(3) Transferring the solution into a high-pressure reaction kettle with polytetrafluoroethylene lining, and maintaining at 210 ℃ for 48hCentrifugally separating to obtain precipitate, washing the precipitate with deionized water and ethanol, and drying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
Example 4
(1) Preparation of ZIS photocatalyst: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving the mixture into 40ml of deionized water according to the molar ratio of 1.0:1.5:6.0 to form a precursor solution, heating the precursor solution to react at the reaction temperature of 95 ℃ for 2.5 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing the reaction product with absolute ethyl alcohol and deionized water, and drying the reaction product in a vacuum oven overnight at the temperature of 70 ℃.
(2) Dispersing ZIS photocatalyst prepared in (1) in DMF solution, and mixing ZIS and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the mixture into the DMF solution according to the molar ratio of 0.90:0.10:0.20:0.20, and stirring for adsorption.
(3) Transferring the solution into a high-pressure reaction kettle with polytetrafluoroethylene lining, maintaining at 190 deg.C for 48 hr, centrifuging to obtain precipitate, washing the precipitate with deionized water and ethanol, and drying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
Example 5
(1) Preparation of ZIS photocatalyst: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving the mixture into 40ml of deionized water according to the molar ratio of 1.0:1.5:6.0 to form a precursor solution, heating the precursor solution to react at the reaction temperature of 95 ℃ for 2.5 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing the reaction product with absolute ethyl alcohol and deionized water, and drying the reaction product in a vacuum oven overnight at the temperature of 70 ℃.
(2) Dispersing ZIS photocatalyst prepared in (1) in DMF solution, and mixing ZIS and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the mixture into the DMF solution according to the molar ratio of 0.90:0.10:0.20:0.20, and stirring for adsorption.
(3) Transferring the above solutionPutting into high-pressure reactor with polytetrafluoroethylene lining, maintaining at 210 deg.C for 48 hr, centrifuging to obtain precipitate, washing the precipitate with deionized water and ethanol, and drying to obtain MoSe loaded with 1T phase and 2H phase 2 ZIS of (2). The invention also performs performance tests on the above embodiments:
fig. 1 is a Scanning Electron Microscope (SEM) image of the zinc indium sulfide photocatalyst (ZIS) prepared in example 1. As can be seen from the figure, the zinc indium sulfide photocatalyst prepared by using the oil bath is of a nanoflower structure and consists of a large number of stacked nano sheets.
FIG. 2 is a 1T/2H MoSe prepared in example 1 2 Scanning Electron Microscope (SEM) image of photocatalyst (MS/ZIS). As can be seen from the figure, 1T/2H MoSe 2 ZIS having a similar morphology, again petaloid morphology, suggests that the nanoflower structure of ZIS was not altered by solvothermal treatment.
Fig. 3 is a Transmission Electron Microscope (TEM) image of the zinc indium sulfide photocatalyst (ZIS) prepared in example 1. As can be seen from the figure, the pure ZIS photocatalyst sample is formed by stacking a large number of two-dimensional nano-sheets, the two-dimensional nano-sheets have clear and complete lattice fringes (see fig. 4), and the lattice spacing of 0.32nm corresponds to the (102) crystal face of the ZIS crystal phase structure, so that the hexagonal crystal phase structure of the ZIS photocatalyst prepared by the oil bath is further proved.
FIG. 5 is a 1T/2H MoSe prepared in example 1 2 Transmission Electron Microscope (TEM) image of photocatalyst (MS/ZIS). The composite material after solvothermal treatment is still in a lamellar structure, and MoSe can be clearly seen 2 And also has a lamellar structure and is tightly combined with ZIS nano sheets. See FIG. 6a,1T/2H MoSe 2 The (002) crystal face of FIG. 6b is an enlarged view of the portion b of FIG. 6a showing MoSe more clearly 2 Lattice expansion occurs, which is caused by DMF molecular intercalation. Fig. 6c is an enlarged view of fig. 6a at c, and it can also be seen that ZIS and 1T/2H phase MS are tightly coupled together.
FIG. 7 is a schematic diagram of a 1T/2H MoSe photocatalyst (ZIS) prepared in example 1 2 (200 MS) and 1T/2H MoSe 2 ZIS photocatalyst (200M)S/ZIS). As can be seen from the figure, the characteristic diffraction peaks of the ZIS photocatalyst prepared by using the oil bath correspond to ZIS (JCPDS card No. 72-0773) of hexagonal phase, respectively, indicating that the oil bath can prepare and obtain a pure hexagonal phase ZIS structure; while the characteristic diffraction peak of ZIS is not changed obviously after further treatment by solvothermal treatment, which is probably MoSe 2 Too low a content of (C) so that no MoSe is observed 2 Is a characteristic diffraction peak of (2); the crystallinity of the 200MS photocatalyst prepared at a solvothermal temperature of 200℃was poor, and the characteristic diffraction peak portions thereof correspond to the 2H phase and the 1T phase, indicating that a mixed phase MoSe was obtained at 200 ℃ 2 Structure is as follows.
Furthermore, the invention also compares the conversion rate of the photocatalytic alcoholysis styrene oxide reaction of the MS/ZIS composite photocatalyst obtained at different temperatures, and the result is as follows:
the preparation temperatures in the autoclave in examples 1, 4 and 5 were 200℃and 190℃and 210℃respectively, and the other reaction conditions were the same to prepare 1T/2H MoSe respectively 2 Composite photocatalyst/ZIS (MS/ZIS). The table above shows the 1T/2H MoSe prepared at different preparation temperatures in a high-pressure reactor 2 Data on the performance of the photocatalytic alcoholysis styrene oxide with light irradiation of the composite photocatalyst (MS/ZIS)/ZIS. As can be seen from the table, when the preparation temperature is not higher than 200 ℃, the photocatalytic alcoholysis oxidation capability of the composite material MS/ZIS is increased along with the increase of the preparation temperature, when the preparation temperature is higher than 200 ℃, the photocatalytic alcoholysis oxidation capability of the composite material MS/ZIS is reduced along with the increase of the preparation temperature, and when the preparation temperature is 200 ℃, the photocatalytic alcoholysis oxidation capability of the composite material MS/ZIS is strongest, and the oxidation conversion rate is 93.25%. The performance test result shows that the ZIS sample subjected to solvothermal treatment is loaded with 1T/2H MoSe 2 After the structure, the photocatalytic oxidation performance of ZIS and MS can be improved, and the fact that the heterojunction formed by loading another material is an effective modification means for improving the photocatalytic activity of ZIS is also demonstrated.
FIG. 8 is a graph of different solvothermal temperaturesThe raman spectrum of MS was obtained at the same temperature, and it can be seen from the figure that as the solvothermal temperature was increased, the content of 1T phase MS increased and then decreased, and when the temperature reached 400 ℃, the 1T phase MS was completely converted into 2H phase. Therefore, the crystal phase content of MS can be controllably regulated by regulating and controlling the solvothermal temperature, thereby regulating and controlling MoSe 2 Solvothermal temperature control of 1T phase MoSe 2 The content in the composite material further improves the photocatalytic activity of the composite material.
Based on the above, it is preferable to keep at 200℃for 12-48 hours, separate the precipitate, wash the precipitate and then dry it, and then obtain a 1T phase and 2H phase MoSe loaded 2 The higher the 1T phase content in ZIS, the higher the conversion.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. Photocatalyst 1T/2H MoSe 2 The preparation method of/ZIS is characterized by comprising the following steps:
step 1, preparing a ZIS photocatalyst;
step 2, taking ZIS photocatalyst prepared in step 1 and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Adding (0.60-1.20) 0.05-0.15 (0.10-0.30) 0.10-0.30 into an organic solvent containing an amide group according to a molar ratio, stirring and adsorbing;
step 3, transferring the solution obtained in the step 2 into a high-pressure reaction kettle, maintaining the temperature at 140-210 ℃ for 12-48H, separating precipitate, cleaning the precipitate, and drying to obtain the MoSe loaded with 1T phase and 2H phase 2 ZIS of (2).
2. The photocatalyst 1T/2H MoSe according to claim 1 2 A preparation method of/ZIS, which is characterized in that the preparation method of ZIS photocatalyst in step 1 comprises the following steps: znCl 2 、In(NO 3 ) 3 And CH (CH) 3 CSNH 2 Sequentially dissolving (1.0-2.0) and (5.0-7.0) into deionized water according to the molar ratio of (0.5-1.5) to form a precursor solution, heating the precursor solution to react at the reaction temperature of 70-120 ℃ for 1.5-3.0 hours, cooling to room temperature after the reaction is finished, filtering and collecting a reaction product, washing with absolute ethyl alcohol and deionized water, and drying in a vacuum oven overnight at the temperature of 60-80 ℃.
3. The photocatalyst 1T/2H MoSe according to claim 1 2 The preparation method of/ZIS is characterized in that the organic solvent containing amide groups in the step 2 is DMF.
4. The photocatalyst 1T/2H MoSe according to claim 1 2 A process for preparing/ZIS, which comprises, in step 2, dispersing ZIS photocatalyst prepared in step 1 in an organic solvent containing an amide group to obtain ZIS and Na 2 MoO 4 ·2H 2 O, se powder and NaBH 4 Sequentially adding the mixture into the organic solvent containing the amide groups according to the molar ratio of 0.90:0.10:0.20:0.20, and stirring for adsorption.
5. The photocatalyst 1T/2H MoSe according to claim 1 2 The preparation method of/ZIS is characterized in that the lining of the high-pressure reaction kettle in the step 3 is polytetrafluoroethylene.
6. The photocatalyst 1T/2H MoSe according to claim 1 2 The preparation method of/ZIS is characterized in that the reaction temperature in the high-pressure reaction kettle in the step 3 is 200 ℃.
7. The photocatalyst 1T/2H MoSe according to claim 1 2 The preparation method of/ZIS is characterized in that the precipitate separated in the step 3 is washed with deionized water and ethanol.
8. Photocatalyst 1T/2H MoSe 2 ZIS, characterized in that it is obtainable by a process according to any one of claims 1 to 7.
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