CN114534785B - MoS 2 @COF-Ph composite material and preparation method and application thereof - Google Patents
MoS 2 @COF-Ph composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 title description 4
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 7
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
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- 238000013508 migration Methods 0.000 abstract description 5
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- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract 2
- 239000002077 nanosphere Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000004098 Tetracycline Substances 0.000 description 11
- 229960002180 tetracycline Drugs 0.000 description 11
- 229930101283 tetracycline Natural products 0.000 description 11
- 235000019364 tetracycline Nutrition 0.000 description 11
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 10
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
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- 239000003344 environmental pollutant Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
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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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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention belongs to the technical field of photocatalysts, and discloses a MoS 2 @COF-Ph composite material and preparation method and application thereof. The MoS 2 The preparation method of the @ COF-Ph composite material comprises the following steps: preparing COF-Ph by taking cyanuric chloride and p-phenylenediamine as raw materials through hydrothermal method; thioacetamide and sodium molybdate are taken as sulfur sources and molybdenum sources, and are uniformly mixed with COF-Ph to carry out hydrothermal reaction. In the obtained composite material, moS 2 And a heterojunction is formed between the photo-active material and the COF-Ph through coordination bonds, a transfer channel is provided for migration of electrons and holes, the photo-generated electron-hole recombination rate is reduced, the composite material has high photocatalytic activity, and the composite material has good stability, simple preparation process and low cost, so that the photo-active material has good application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and in particular relates to a coincidence material MoS based on a multi-nitrogen covalent organic framework 2 @COF-Ph, a preparation method thereof and application thereof in sewage treatment and photocatalytic hydrogen production.
Background
At present, since the semiconductor photocatalyst has remarkable potential in solving ecological and environmental problems by using solar energy, it has been widely used for the water decomposition and treatment of various environmental pollutants. Molybdenum disulfide (MoS) 2 ) The preparation is simple, the content is rich, the specific surface area is large, the photoelectric chemical property is unique, the band gap energy (1.2-1.9 eV) is adjustable, and the preparation method hasHigh carrier mobility and excellent light absorption properties are used in photocatalytic degradation technology. However, the practical application of molybdenum disulfide in photocatalytic wastewater treatment is limited by factors such as high site density and high photoinduced carrier recombination rate.
Covalent Organic Frameworks (COFs) are a class of polymers with high crystallinity and porosity, organic building blocks with defined pore structures and highly tunable optoelectronic properties, with organic building block motifs bonded by covalent bonds. Although the COFs material has the characteristics of higher thermal stability, higher chemical stability, larger specific surface area, tunable porosity, modifiable framework and the like, the photocatalytic performance of the COFs material is not obvious.
Thus, COFs material is combined with MoS 2 Compounding for degrading water pollutants and solving environmental problems is becoming interesting, and researches show that the structure of COFs materials and MoS 2 The combination mode has important influence on the catalytic performance of the composite material.
Disclosure of Invention
The object of the present invention is to provide a COFS material and MoS 2 Composite material of composition for modifying MoS 2 The semiconductor has the defect of low photocatalytic activity, and the obtained composite material has high catalytic activity in the aspects of degradation of pollutants and hydrogen production by photolysis of water.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a MoS 2 @COF-Ph composite material in which MoS 2 Heterojunction is formed between the COF-Ph and the composite material through coordination bond, and the mass percentage of the COF-Ph in the composite material is 14-40%.
The invention also provides a method for preparing the MoS 2 A method of @ COF-Ph composite comprising the steps of:
s1, preparing COF-Ph by taking cyanuric chloride and p-phenylenediamine as raw materials through hydrothermal method;
s2, dissolving thioacetamide and sodium molybdate in water, adding oxalic acid and the COF-Ph prepared in the step S1, uniformly mixing, transferring into an autoclave for hydrothermal reaction, filtering and drying after the reaction is finished to obtain the productMoS 2 @cof-Ph composite material.
Preferably, step S1 is specifically:
s11, mixing 1, 4-dioxane, mesitylene and acetic acid to be used as a mixed solvent;
s12, dissolving cyanuric chloride in the mixed solvent in S11, introducing Ar, adding p-phenylenediamine, uniformly mixing, transferring into a reaction kettle for hydrothermal reaction, and washing and drying the product to obtain the COF-Ph.
More preferably, the volume ratio of the 1, 4-dioxane, mesitylene and acetic acid in the step S11 is 3-5:3-5:1.
More preferably, the molar ratio of cyanuric chloride to p-phenylenediamine in step S12 is from 0.5 to 1.5:1.
More preferably, the reaction temperature of the hydrothermal reaction in step S12 is 100 to 120 ℃ and the reaction time is 24 to 36 hours.
Preferably, the mass ratio of thioacetamide to sodium molybdate in the step S2 is 2-3:1.
Preferably, the hydrothermal reaction process in step S2 specifically includes: heating to 100-150 ℃ from room temperature according to the heating rate of 4-8 ℃/min, and then preserving heat for 18-24 h.
The MoS provided by the invention 2 The @ COF-Ph composite material has high photocatalytic activity, can be used for degrading pollutants and producing hydrogen by photocatalytic pyrolysis, and has a good application effect.
The beneficial effects of the invention are as follows:
COF-Ph is supported on MoS by hydrothermal method 2 On COF-Ph and MoS 2 The heterojunction is formed through coordination bonds, a transfer channel is provided for the migration of electrons and holes, the migration rate of the photogenerated electrons on the surface of the material is effectively improved, the separation of photogenerated carriers is promoted, the photon-hole recombination probability is reduced, and the photocatalysis performance of the composite material is remarkably improved. Furthermore, moS 2 Ratio of @ COF-Ph composite to MoS 2 The material has larger specific surface area and obviously enhanced light absorption capacity, so that the material can better utilize light energy, thereby promoting photocatalytic activity.
The preparation process of the invention is to produceThe novel Z-shaped MoS can be obtained by a simple hydrothermal method with low cost, easy operation and sufficient raw material sources 2 @cof-Ph composite material.
Experiments of photocatalytic degradation of TC and hydrogen production by pyrolysis prove that the MoS prepared by the invention 2 The @ COF-Ph heterojunction not only has better photocatalytic performance, but also has high material stability and great potential in practical application.
Drawings
FIG. 1 shows a composite material and pure MoS prepared according to the present invention 2 A contrast map of the surface morphology of COF-P;
FIG. 2 shows a composite material and pure MoS prepared according to the present invention 2 XRD contrast pattern of COF-P;
FIG. 3 is a BET spectrum of a composite material prepared according to the present invention;
FIG. 4 shows a composite material and pure MoS prepared according to the present invention 2 Solid ultraviolet visible diffuse reflectance spectra of COF-Ph;
FIG. 5 shows a composite material and pure MoS prepared according to the present invention 2 XPS full spectrum of COF-Ph;
FIG. 6 shows a composite material and pure MoS prepared according to the present invention 2 XPS contrast spectrograms of each element of COF-Ph;
FIG. 7 shows a composite material and pure MoS prepared according to the present invention 2 Electrical impedance spectra of COF-Ph;
FIG. 8 shows a composite material and pure MoS prepared according to the present invention 2 Photo current response plot of COF-Ph;
FIG. 9 shows a composite material and pure MoS prepared according to the present invention 2 A TC graph (left graph) of COF-Ph photocatalytic degradation and a first order kinetics graph (right graph) of degradation;
FIG. 10 is a MoS of an embodiment of the present invention 2 @COF-Ph 0.25 Stability profile during successive multiple degradation of TC;
FIG. 11 shows a composite material and pure MoS prepared according to the present invention 2 A comparison graph of the photocatalytic hydrogen production capacity of COF-Ph;
FIG. 12 shows MoS prepared according to the present invention 2 /COF-Ph 0.25 In photocatalytic hydrogen productionA stability characterization graph;
FIG. 13 is a graph of photocatalytic mechanism analysis for a composite material prepared according to the present invention.
Detailed Description
The present invention will be further described with reference to the drawings and examples, which are only for more clearly illustrating the technical solution of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1
MoS 2 The preparation of the @ COF-Ph composite material comprises the following steps:
(1) Preparation of COF-Ph
1, 4-Dioxahexacyclic ring (C) 4 H 8 O 2 ) Mesitylene (C) 9 H 12 ) And acetic acid (CH) 3 COOH) according to the volume ratio of 5:5:1 to obtain a mixed solution. Then the cyanuric chloride (C) 3 Cl 3 N 3 0.05 g) of the above-mentioned mixed solution was dissolved, ar was introduced, and p-phenylenediamine (C) was added 6 H 8 N 2 0.044 g), and the mass ratio of cyanuric chloride to p-phenylenediamine in the reaction system is 0.65:1. Transferring into a reaction kettle, keeping the temperature at 120 ℃, performing hydrothermal reaction for 35 hours, washing with hot absolute ethyl alcohol (EtOH) for 2 times, and drying to obtain the COF-Ph.
(2) Preparation of composite materials
With thioacetamide (C) 2 H 5 NS,0.4 g) and sodium molybdate (NaMoO 4 ·2H 2 O,0.2 g) as sulfur source and molybdenum source, dissolved in 60mL deionized water, and added with oxalic acid (H) after ultrasonic mixing evenly 2 C 2 O 4 0.5g of excess oxalic acid is decomposed in the hydrothermal process, no residue is generated, the pH value of the final product is adjusted (the pH value is 4-6), a certain amount of COF-Ph prepared in the step (1) is added, the uniform solution is obtained by stirring, the uniform solution is transferred into a stainless steel-lined autoclave, and the reaction is carried out for 22 hours at 150 ℃. After the reaction, naturally cooling to room temperature, collecting black precipitate, continuously washing with deionized water and ethanol (EtOH) for 10min, and drying at 60deg.C for 6 hr to obtain black powder (MoS) 2 @cof-Ph composite material.
Changing the addition amount of COF-Ph in the step (2), and recording the products as MoS respectively 2 @COF-Ph 0.14 、MoS 2 @COF-Ph 0.25 And MoS 2 @COF-Ph 0.4 0.14, 0.25 and 0.40 represent the percentage of COF-Ph in the composite material as 14wt%, 25wt% and 40wt%, respectively.
Comparative example 1
Preparation of COF-Ph was carried out in the same manner as in step (1) of example 1.
Comparative example 2
MoS 2 The nanometer material is prepared with thioacetamide and sodium molybdate as sulfur source and molybdenum source and NaMoO as main material 4 ·2H 2 O (0.20 g,0.83 mmol) and C 2 H 5 NS (0.40 g,5.3 mmol) was dissolved in 60mL deionized water. H is then added to the solution 2 C 2 O 4 (0.50 g,5.6 mmol) to adjust the pH of the solution. After magnetic stirring for 30 minutes, transferring into a polytetrafluoroethylene hydrothermal reaction kettle, heating at 150 ℃ for 22 hours, naturally cooling to room temperature, collecting black precipitate, and washing with deionized water and ethanol for 3 times. Finally, the mixture was dried in a vacuum oven at 60℃for 10 hours to obtain a black powder.
Samples prepared in examples and comparative examples were tested by the following analysis:
(1) surface topography characterization
Scanning electron microscope images (SEM) were taken under an acceleration voltage of 15kV by a Zeiss Gemini SEM300 microscope, and transmission electron microscope images (TEM) and high resolution transmission electron microscope images (HRTEM) were obtained by measurement under an acceleration voltage of 200kV using a JEOL JEM 2000 microscope.
In FIG. 1 a and b are each pure MoS 2 SEM and TEM images of nanospheres, from which MoS can be seen 2 The nanospheres have rough surfaces, show a nanosphere, have uniform size distribution and have a diameter size of about 200nm. As can be seen from the further enlarged image in FIG. 1 c, the lighter colored locations in the image are COF-Ph, showing a sharp outline, while the darker colored areas are MoS 2 The nanospheres are more obvious in shape. Contrast pure MoS 2 Nanospheres and synthesized MoS 2 @COF-Ph 0.25 In the form of the composite material, the loaded molybdenum sulfide nanospheres are wrapped by COF-Ph, the color is darker, and the light-colored area is the COF-Ph. All of the above results indicate that COF-Ph is in MoS 2 The nano sphere surface completes the loading process, and MoS is prepared by hydrothermal synthesis 2 @COF-Ph 0.25 Sample composites are possible.
(2) XRD characterization
The powder X-ray diffraction (PXRD) characterization results are shown in figure 2. For pure MoS 2 The nanospheres exhibit diffraction peaks at 2θ=16.5°, 32.8 ° and 57.2 °, corresponding to MoS, respectively 2 (002), (100) and (110), notably 2θ=16.5° in MoS 2 The broad nature of the major diffraction peaks in nanospheres suggests the presence of stacked layered structures. Whereas for COF-Ph powder X-ray diffraction (PXRD) analysis, there is a distinct peak at 2θ=17.5° that can correspond to the in-plane reflection (200) plane; although there is no long-range order in all COF-Ph, two broad reflections occur at 24.8 ° and 25.2 °, from the reflective (110) face of the COF-Ph crystal. In MoS 2 Obvious diffraction peaks appear at the positions of 21.0 degrees and 31.5 degrees of the composite material obtained after the COF-Ph is introduced on the nanospheres, and the peaks correspond to the diffraction peak angles of the pure-state COF-Ph and are in high coincidence, so that the composite material simultaneously comprises the two pure-state materials. This further verifies nanosphere MoS 2 Successful hydrothermal recombination with COF-Ph.
(3) Analysis of specific surface area
FIG. 3 shows MoS 2 @COF-Ph 0.14 Can find COF-Ph to be wrapped in MoS 2 After the above, the specific surface area is effectively improved, which indicates that the light energy can be better utilized and the photocatalytic activity is promoted.
(4) Ultraviolet visible diffuse reflectance spectroscopy
As shown in FIG. 4, the pure MoS 2 The nanospheres show strong absorption spectrum at 300-400 nm, namely have strong light absorption capacity in the ultraviolet region; for pure COF-Ph, a strong absorption band can be detected around 700nm, which is a coordination field absorption band caused by hexahedron with N as the center in pure COF-PhThe absorption in the visible region; moS (MoS) 2 @COF-Ph 0.25 The composite material has an absorption edge at 700nm, which is close to pure COF-Ph; but unlike pure form COF-Ph, moS 2 @COF-Ph 0.25 The composite material has enhanced visible light absorption in the range of 350-400 nm, indicating that heterojunction formation can promote light absorption.
(5) Photoelectron spectroscopy characterization
As shown in fig. 5 to 6, the main elements and chemical states of the material surface were studied by X-ray photoelectron spectroscopy (XPS).
FIG. 5 is a full spectrum of XPS showing the MoS of the composite material 2 @COF-Ph 0.25 Mainly comprises four elements of Mo, S, N and C, and pure MoS 2 @COF-Ph 0.25 The nanospheres contain two elements, mo and S, while the pure COF-Ph mainly contains two elements, N and C.
FIG. 6 shows a pure MoS 2 Nanospheres, pure COF-Ph and MoS 2 @COF-Ph 0.25 XPS fine spectral characterization of the corresponding elements Mo3d, S2 p, C1S and N1S. Most importantly, as shown in FIG. 6 (d), in MoS 2 @COF-Ph 0.25 In the photocatalyst, the N1s region can be curve-fitted to two peaks with binding energies of 399.0eV and 400.4eV, respectively, while the peak at 399.0eV corresponds to sp 2 The peak at 400.4eV shifted significantly to higher binding energies, indicating Mo, when hybridized aromatic nitrogen was bound to carbon atoms (C-n=c) 2+ Coordination with N results in a decrease in electron cloud density of N, further proving MoS 2 And the COF-Ph forms heterojunction through coordination bond, provides a transfer channel for migration of electrons and holes, promotes separation of photon-generated carriers, and improves photocatalysis performance.
(6) Electrochemical AC impedance and instantaneous photocurrent response test
In order to understand the intrinsic electronic and optoelectronic properties of the material, the interfacial charge transfer resistance and the separation of photogenerated electron-hole pairs are described by electrochemical alternating current impedance (EIS) and instantaneous photocurrent response curves.
As shown in fig. 7, EIS nyquist arc radii for all materials appear as: moS (MoS) 2 @COF-Ph 0.25 <MoS 2 @COF-Ph 0.4 <MoS 2 @COF-Ph 0.14 <MoS 2 <Sequence of COF-Ph. The results show that the pure MoS 2 The combination of the COF-Ph can effectively improve the electron transmission efficiency, which means that the composite material has faster charge transmission capacity, namely, the load of the COF-Ph can effectively improve the migration rate of photo-generated electrons on the surface of the material.
Meanwhile, FIG. 8 shows MoS 2 @COF-Ph 0.25 The photocurrent response intensity of (2) is obviously strongest in all composite materials, shows the best photoelectron-hole separation efficiency, and the capability of photon-generated carriers is obviously better than that of pure MoS 2 And pure COF-Ph. This result indicates MoS 2 The heterostructure between the composite material and the COF-Ph can quickly separate photo-generated carriers, improve the interface electron transfer process, and provide powerful evidence for the optimal catalytic activity of the composite material in a photocatalysis experiment.
(7) Degradation capability of different materials to pollutants
Determination of MoS in sunlight using Tetracycline (TC) as a simulated contaminant 2 Photocatalytic activity of COF-Ph and composites (both 30 mg).
As can be seen from the left plot in fig. 9, the content of TC decreases over time, indicating that TC is subject to continuous photocatalytic degradation. In all composites, moS 2 @COF-Ph 0.25 The degradation rate of TC is highest, and the degradation rate reaches 98.4% within 90 min. MoS (MoS) 2 @COF-Ph 0.14 And MoS 2 @COF-Ph 0.4 The degradation rate to TC is 79.45% and 75% respectively, which are higher than pure MoS 2 And pure COF-Ph. This illustrates MoS 2 The catalytic degradation activity of the composite material formed by the composite material and the COF-Ph on TC is enhanced to different degrees, and further proves that MoS 2 @COF-Ph 0.25 The composite material has excellent photodegradation capability.
As shown in the right diagram of FIG. 9, moS 2 @COF-Ph 0.25 (0.02372min -1 ) Exhibit maximum k values in all materials, respectively compared to pure MoS 2 Nanospheres (0.01575 min) -1 ) And pure state COF-Ph(0.00357min -1 ) About 1.51 times and 6.64 times higher. The experimental results show that in pure state MoS 2 The introduction of COF-Ph on the nanospheres is beneficial to the photogeneration of the carrier, thereby obviously improving the photocatalytic activity.
With MoS2@COF-Ph 0.25 For example, the stability and reusability of the composite material in degrading contaminants were further verified, and the results indicate that: the photocatalyst showed substantially no change in the TC degradation rate during the reaction after each degradation (as in fig. 10 a); and the structure of the composite material before and after four cycle reactions is analyzed through a PXRD map (as shown in b in fig. 10), which shows that the composite material has no obvious transformation in the reaction process. Therefore, the MoS2@COF-Ph composite material prepared by the method has good photocatalytic stability and structural stability.
(8) Photocatalytic hydrogen production capability analysis of different materials
The results of the photocatalytic hydrogen production and the hydrogen production rate of different materials under the sunlight for 4 hours are shown in FIG. 11, moS 2 @COF-Ph 0.25 The highest speed of the photocatalytic hydrogen production can reach 7251.9 mu mol g -1 ·h -1 ；MoS 2 @COF-Ph 0.14 And MoS 2 @COF-Ph 0.4 The rates of (2) are 3775.3. Mu. Mol. G, respectively -1 ·h -1 And 5455.9. Mu. Mol.g -1 ·h -1 . And MoS 2 With COF-Ph 0.4 The rates of (2) are 1406.6. Mu. Mol. G, respectively -1 ·h -1 And 46.3. Mu. Mol g -1 ·h -1 。
Taking MoS 2 @COF-Ph 0.25 The photocatalytic hydrogen production cycle experiment was performed, and after each experiment was completed, the material was washed and dried, and then continued to enter the next cycle, and the result is shown in fig. 12.
In conclusion, the photocatalytic mechanism analysis of the composite material is shown in fig. 13, and the composite material prepared by the invention forms a type II heterojunction, so that the photocatalytic activity is improved. In addition, experiments prove that the performance of the composite material has no obvious difference in the preparation process parameter range provided by the invention.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (7)
1. MoS (MoS) 2 The preparation method of the composite material is characterized by comprising the following steps of:
s1, preparing COF-Ph by using cyanuric chloride and p-phenylenediamine as raw materials through a hydrothermal method;
s2, dissolving thioacetamide and sodium molybdate in water, adding oxalic acid and the COF-Ph prepared in the step S1, uniformly mixing, transferring into an autoclave for hydrothermal reaction, filtering and drying after the reaction is finished to obtain MoS 2 A @ COF-Ph composite;
in the material, moS 2 Heterojunction is formed between the COF-Ph and the composite material through coordination bonds, and the mass percentage of the COF-Ph in the composite material is 14-40%;
in the step S2, the mass ratio of the thioacetamide to the sodium molybdate is 2-3:1, and the hydrothermal reaction process specifically comprises the following steps: and (3) heating the mixture to 100-150 ℃ from room temperature according to a heating rate of 4-8 ℃/min, and then preserving heat for 18-24 hours, wherein the oxalic acid is used for adjusting the pH value to 4-6.
2. MoS according to claim 1 2 The @ COF-Ph composite material is characterized in that the step S1 is specifically as follows:
s11, taking a mixed solution of 1, 4-dioxane, mesitylene and acetic acid as a solvent;
and S12, dissolving cyanuric chloride in the solvent in the step S11, introducing Ar, adding p-phenylenediamine, uniformly mixing, transferring into a reaction kettle for hydrothermal reaction, and washing and drying the product to obtain the COF-Ph.
3. MoS according to claim 2 2 The @ COF-Ph composite material is characterized in that the volume ratio of the 1, 4-dioxane, the mesitylene and the acetic acid in the step S11 is 3-5:3-5:1.
4. MoS according to claim 2 2 The composite material @ COF-Ph is characterized in that the molar ratio of cyanuric chloride to p-phenylenediamine in the step S12 is 0.5-1.5:1.
5. MoS according to claim 2 2 The composite material @ COF-Ph is characterized in that the reaction temperature of the hydrothermal reaction in the step S12 is 100-120 ℃ and the reaction time is 24-36 h.
6. The MoS according to any one of claims 1 to 5 2 Use of the @ COF-Ph composite in contaminant degradation.
7. The MoS according to any one of claims 1 to 5 2 Application of the @ COF-Ph composite material in photocatalytic water production hydrogen.
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