CN116078439A - Two-dimensional material modified zirconium-based catalyst and preparation method and application thereof - Google Patents
Two-dimensional material modified zirconium-based catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
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- 238000002360 preparation method Methods 0.000 title abstract description 12
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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Abstract
The invention relates to a photocatalysis material, in particular to a two-dimensional material modified zirconium-based catalyst, a preparation method and application thereof, wherein the catalyst is obtained by taking a zirconium-based metal organic framework material as a substrate and loading a two-dimensional material; the two-dimensional material is titanium niobate nanometer sheet. The method comprises the following steps: s1: completely dissolving a zirconium source and an organic ligand in a solvent to obtain a first mixed solution; s2: adding the two-dimensional material into a solvent, and stirring to obtain a second mixed solution; s3: transferring the first mixed solution and the second mixed solution into a reaction kettle to react to obtain a reaction product; s4: washing and drying the reaction product to obtain the two-dimensional material modified zirconium-based catalyst, compared with the prior art, the methodZirconium-based metal organic framework material is taken as a substrate, and modified by titanium niobate nano-sheet two-dimensional material for photocatalytic reduction of CO 2 So as to reduce the catalytic cost and improve the photocatalytic reduction of CO 2 Performance objectives.
Description
Technical Field
The invention relates to a photocatalytic material, in particular to a two-dimensional material modified zirconium-based catalyst, and a preparation method and application thereof.
Background
CO in the atmosphere 2 The concentration increases year by year, which causes global greenhouse effect and destroys ecological environment. CO can be continuously produced by means of light energy by using photocatalyst 2 Reduction to valuable high value fuels, e.g. CO, CH 4 And the like, and can reduce the problems of environmental pollution and exhaustion of fossil fuel.
The zirconium-based metal organic framework material has the advantages of high thermal stability, large specific surface area, adjustable structure and function and the like, so that the zirconium-based metal organic framework material can reduce CO in photocatalysis 2 The field has attracted considerable attention. However, due to the problems of easy recombination of photo-generated carriers, low reduction efficiency and the like of the zirconium-based metal-organic framework material, the method limits the reduction of CO in photocatalysis 2 Practical application in the field.
Recent researches show that the supported catalyst promoter improves the low separation efficiency of photo-generated electrons and holes of the zirconium-based metal organic framework material, improves the light absorption and realizes the effective photocatalytic reduction of CO 2 One of the simplest and most efficient methods. Noble metals have proven to be an excellent promoter, but noble metals have the defects of high price, scarce resources and the like, so that the noble metals are supported as the promoter to improve the light absorption performance of the zirconium-based metal organic framework material, which cannot be produced in a large scale, and the practical application of the zirconium-based metal organic framework material is hindered. Therefore, a search for a kind of a material is requiredThe cocatalyst which can strengthen the zirconium-based metal organic framework material is also required to reduce the production cost on the premise of ensuring high performance.
Disclosure of Invention
The invention aims to solve at least one of the problems and provide a two-dimensional material modified zirconium-based catalyst, a preparation method and application thereof, wherein the catalyst takes a zirconium-based organic framework material as a substrate, modifies by loading titanium niobate nano-sheet two-dimensional material, improves the specific surface area of the material, and is used for photocatalytic reduction of CO 2 So as to reduce the catalytic cost and improve the photocatalytic reduction of CO 2 Performance objectives.
The aim of the invention is achieved by the following technical scheme:
the invention discloses a two-dimensional material modified zirconium-based catalyst, which is obtained by taking a zirconium-based metal organic framework material as a substrate and loading a two-dimensional material, wherein the two-dimensional material is titanium niobate nano-sheets.
The titanic niobate nano-sheet is a semiconductor nano-sheet two-dimensional material with excellent photoelectric characteristics, has high stability, low cost, high anisotropism and excellent solid acid property, and can effectively separate photogenerated carriers by in-situ loading the titanic niobate nano-sheet on a zirconium-based metal organic framework material, thereby improving the transfer efficiency of the photogenerated carriers and further improving the photocatalytic reduction of CO 2 And at the same time, the cost is reduced.
Preferably, the mass ratio of the two-dimensional material to the zirconium-based metal organic framework material is 0.1wt% to 20wt%.
More preferably, the mass ratio of the two-dimensional material to the zirconium-based metal organic framework material is 0.5wt% to 7wt%.
In a second aspect, the invention discloses a method for preparing a two-dimensional material modified zirconium-based catalyst as described in any one of the preceding claims, comprising the steps of:
s1: completely dissolving a zirconium source and an organic ligand in a solvent to obtain a first mixed solution;
s2: adding the two-dimensional material into a solvent, and fully stirring to obtain a second mixed solution;
s3: transferring the first mixed solution obtained in the step S1 and the second mixed solution obtained in the step S2 into a reaction kettle to react to obtain a reaction product;
s4: and (3) washing and drying the reaction product obtained in the step (S3) to obtain the two-dimensional material modified zirconium-based catalyst.
Preferably, in step S1, the zirconium source is one or more of zirconium silicate, zirconium chloride, zirconium oxychloride and zirconium oxide; the organic ligand is one or more of isophthalic acid, trimesic acid, 1,2,3, 4-butane tetracarboxylic acid, terephthalic acid, 2, 5-dihydroxyterephthalic acid, trimellitic acid, succinic acid and oxalic acid; the mass ratio of the zirconium source to the organic ligand is 1:0.7-1:2.6.
Preferably, in step S1 and step S2, the solvent is one or more of water, methanol, ethanol, ethylene glycol, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in step S3, the reaction temperature is 80-180 ℃ and the reaction time is 8-24h.
Preferably, in step S4, the drying temperature is 15-70 ℃ and the drying time is 5-10h.
The invention discloses an application of the two-dimensional material modified zirconium-based catalyst in photocatalytic reduction of greenhouse gases.
Preferably, the greenhouse gas is CO 2 。
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the catalyst has mild reaction conditions, easily obtained raw materials and easily controlled process; meanwhile, the catalyst has the advantages of high separation efficiency of photo-generated carriers, high photo-catalytic activity and good repeatability. Photocatalytic reduction of CO by optimizing the loading of two-dimensional materials 2 The CO production was 10 times that of the pure zirconium-based catalyst. Thus, two-dimensional material modified zirconium-based catalysts for photocatalytic reduction of CO 2 Has wide application prospect in the aspect.
2. Two-dimensional materials of the inventionModified zirconium-based catalyst for photocatalytic reduction of CO 2 Shows very good performance and has very good stability, namely, the catalyst of the invention can react with CO under the condition of normal temperature and normal pressure 2 Has high activity.
3. The invention has the advantages of easily obtained raw materials, simple operation, low cost and good repeatability, and is beneficial to the popularization and application of the technology.
Drawings
FIG. 1 is a transmission electron microscope image of the catalyst prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the catalysts prepared in examples 1-5 and comparative example 1;
FIG. 3 is a photoluminescence spectrum of the catalyst prepared in example 1 and comparative example 1;
FIG. 4 shows the photocatalytic reduction of CO by the catalysts prepared in examples 1-5 and comparative example 1 2 CO production plot of (c).
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The invention relates to a preparation method and application of a composite photocatalyst of a two-dimensional material titanium niobate loaded zirconium-based metal organic framework material, wherein the composite photocatalyst takes the zirconium-based metal organic framework material as a carrier, and a two-dimensional material titanium niobate nano sheet is loaded on the zirconium-based metal organic framework material; wherein the loading amount of the two-dimensional material titanium niobate nano plates in the composite material is 0.1wt percent to 20wt percent.
The chemicals and instruments used in the examples below are all commercially available.
Example 1
The preferred preparation method of the two-dimensional material modified zirconium-based catalyst with 3 weight percent of titanic niobate nano-sheet loading in the embodiment comprises the following steps:
step S1, zirconium chloride and terephthalic acid are mixed according to the following ratio of 1:1 is completely dissolved in N, N-dimethylformamide to obtain a mixed solution;
step S2, adding 50mg of titanic niobic acid into N, N-dimethylformamide, and stirring for 1h to obtain a mixed solution;
s3, transferring the mixed solution of S1 and S2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 20 hours at 120 ℃ to obtain a reaction product;
and S4, washing the reaction product obtained in the step S3 with water and drying to obtain the 3wt% titanium niobate modified zirconium-based catalyst. Wherein the mass ratio of the zirconium-based metal organic framework material to the titanium niobate is 100:3, and the name is UTi-3.
Example 2
The preferred preparation method of the two-dimensional material modified zirconium-based catalyst with 0.5 weight percent of titanic niobate nano-sheet loading in the embodiment comprises the following steps:
steps S1 and S3 are the same as in example 1.
Step S2, adding 8.3mg of titanic niobic acid into N, N-dimethylformamide, and stirring for 1h to obtain a mixed solution;
and S4, washing the reaction product obtained in the step S3 with water and drying to obtain the 0.5wt% titanium niobate modified zirconium-based catalyst. Wherein the mass ratio of the zirconium-based metal organic framework material to the titanium niobate is 100:0.5, and the name is UTi-0.05.
Example 3
The preferred preparation method of the two-dimensional material modified zirconium-based catalyst with the titanic niobate nano-sheet loading of 1 weight percent comprises the following steps:
steps S1 and S3 are the same as in example 1.
Step S2, adding 16.6mg of titanic niobic acid into N, N-dimethylformamide, and stirring for 1h to obtain a mixed solution;
and S4, washing the reaction product obtained in the step S3 with water and drying to obtain the 1wt% titanium niobate modified zirconium-based catalyst. Wherein the mass ratio of the zirconium-based metal organic framework material to the titanium niobate is 100:1, and the name is UTi-1.
Example 4
The preferred preparation method of the two-dimensional material modified zirconium-based catalyst with 5 weight percent of titanic niobate nano-sheet loading is provided in the embodiment, and comprises the following steps:
steps S1 and S3 are the same as in example 1.
Step S2, adding 83.3mg of titanic niobic acid into N, N-dimethylformamide, and stirring for 1h to obtain a mixed solution;
and S4, washing the reaction product obtained in the step S3 with water and drying to obtain the 5wt% titanium niobate modified zirconium-based catalyst. Wherein the mass ratio of the zirconium-based metal organic framework material to the titanium niobate is 100:5, and the name is UTi-5.
Example 5
The preferred preparation method of the two-dimensional material modified zirconium-based catalyst with the titanic niobate nano-sheet loading of 7 weight percent comprises the following steps:
steps S1 and S3 are the same as in example 1.
Step S2, adding 116.6mg of titanic niobic acid into N, N-dimethylformamide, and stirring for 1h to obtain a mixed solution;
and S4, washing the reaction product obtained in the step S3 with water, drying, washing with water and drying to obtain the 7wt% titanium niobate modified zirconium-based catalyst. Wherein the mass ratio of the zirconium-based metal organic framework material to the titanium niobate is 100:7, and the name is UTi-7.
Comparative example 1
The comparative example is a method for preparing a non-supported zirconium-based catalyst comprising the steps of:
0.205g of terephthalic acid was weighed and dissolved in 10mL of N, N-dimethylformamide solution, a proper amount of acetic acid was added dropwise thereto, stirring was performed, and at the same time, 0.318g of zirconium chloride was dissolved in 10mL of N, N-dimethylformamide solution. The two solutions were mixed homogeneously and transferred to an autoclave containing teflon and reacted in an oven at 120 ℃ for 20h. After cooling to room temperature, the obtained product was centrifuged, washed and dried for 8 hours to obtain an unsupported zirconium-based metal organic framework catalyst designated UiO-66.
Characterization of the properties:
the photocatalysts prepared in examples 1-5 and comparative example 1 of the present invention were taken for characterization, and specifically include:
1. UTi-3 projection electron microscope characterization
Specifically, FIG. 1 shows a projection electron microscope image of the UTi-3 composite photocatalyst prepared according to example 1. The projection electron microscope of FIG. 1 (a) shows that UiO-66 is uniformly deposited on the surface of the titanium niobate nano-sheet, and a dense contact interface is formed between the UiO-66 and the titanium niobate nano-sheet; FIG. 1 (b) shows 0.33nm of lattice fringes from a high power electron microscope, consistent with the lattice spacing of the corresponding crystal planes of titanium niobate on a standard card. This corresponds to the face of the titanium niobate nanosheet (200).
2. X-ray diffraction characterization of UiO-66 and different titanium niobate nanoplatelets supported zirconium-based catalysts
Specifically, FIG. 2 clearly shows the X-ray diffraction (XRD) characterization of UiO-66 and the different titanium niobate nanoplatelets supported zirconium-based catalysts prepared in examples 1-5 and comparative example 1. It can be seen that all XRD results exhibited similar patterns with characteristic peaks for UiO-66, and that the characteristic peaks for UiO-66 gradually decreased as the loading of the titanium niobate nanoplatelets increased.
3. Photoluminescence spectral characterization of UiO-66 and UTi-3
Specifically, FIG. 3 shows photoluminescence spectra of UTi-3 prepared according to example 1 and comparative example 1, and it can be seen that the photoluminescence spectrum of UTi-3 has the lowest intensity, indicating that the separation efficiency of photo-generated carriers of the UTi-3 photocatalyst is the highest.
4. Specific surface area of UiO-66 and different titanium niobate nanoplatelets supported zirconium-based catalysts
Specifically, table 1 shows specific surface areas and pore size results for UiO-66 and different titanium niobate nanoplatelets supported zirconium-based catalysts prepared according to examples 1-5 and comparative example 1. It can be seen that the surface area of the zirconium-based catalyst loaded with the titanium niobate nanosheet two-dimensional material is compared with that of pure UiO-66 (847 m 2 ·g -1 ) Greatly improves the specific surface area of UTi-3 to 1027m 2 ·g -1 . Meanwhile, after the titanic niobate nano-sheet two-dimensional material is loaded, the pore diameter is converted into a micropore structure (pore diameter is 1.4 nm) and a mesoporous structure (pore diameter is 12.4 nm). Mesoporous structure and larger specific surface area are more beneficial to CO 2 Molecules are adsorbed on the active site of the zirconium-based catalyst of the titanium niobate nano-sheet-loaded two-dimensional material, thereby improving the photocatalytic reduction of CO 2 Is not limited to the above-described embodiments.
TABLE 1 specific surface area and pore size results for the catalysts prepared in examples 1-5 and comparative example 1
| Sample of | Specific surface area (m) 2 ·g -1 ) | Total pore volume (cm) 3 ·g -1 ) | Aperture (nm) |
| UiO-66 | 847 | 1.08 | 1.4 |
| UTi-0.5 | 879 | 1.07 | 1.4/12.4 |
| UTi-1 | 915 | 1.02 | 1.4/12.4 |
| UTi-3 | 1027 | 1.07 | 1.4/12.4 |
| UTi-5 | 955 | 1.07 | 1.4/12.4 |
| UTi-7 | 860 | 0.96 | 1.4/12.4 |
Application example
The specific application method comprises the following steps: a certain amount of zirconium-based catalyst modified by two-dimensional materials is subjected to photocatalytic reduction of CO in a reaction device consisting of a kettle body, a lining, a kettle cover, a control system, a stirring system, a heating system, a light source, a box body and the like 2 . Wherein the inner liner is polytetrafluoroethylene material with a capacity of 150mL. A sealing gasket is arranged between the two kettle covers, and the kettle covers are sealed into a whole through bolts and nuts. The rotor in the lining makes the catalyst in the solution uniformly mixed and fully adsorb CO through the stirring system 2 And (3) gas. CO 2 The inlet and outlet gas concentrations of (2) are detected by gas chromatograph on-line analysis.
This application is based on examples 1-5 and comparative example 1, the prepared catalyst being used as a photocatalyst for the photocatalytic reduction of CO 2 The method specifically comprises the following steps:
step S1, weighing 10mg of photocatalyst and adding the photocatalyst into a photocatalytic reactor;
step S2, adding 2.5mL of 10wt% triethanolamine aqueous solution into the photocatalytic reactor;
step S3, continuously introducing CO into the photocatalytic reactor 2 The gas was irradiated for 1h with a 300W xenon lamp as a light source to reduce CO 2 。
Referring to fig. 4, it can be seen that the photocatalytic activity is improved under the condition that a two-dimensional material modified zirconium-based catalyst is used as a photocatalyst and triethanolamine is used as an electron sacrificial agent. UTi-3 has the best by optimizing the loading of the titanium niobate nanosheet two-dimensional materialPhotocatalytic activity of photocatalytic reduction of CO 2 The CO production was about 10 times higher than that of pure UiO-66. From this, it can be seen that the two-dimensional material-modified zirconium-based catalyst prepared in the embodiment of the invention has the function of photocatalytic reduction of CO 2 The activity of producing CO is higher, and CO can be produced without any photosensitizer 2 Reducing to CO.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A two-dimensional material modified zirconium-based catalyst is characterized in that the catalyst is obtained by taking a zirconium-based metal organic framework material as a substrate and loading a two-dimensional material; the two-dimensional material is titanium niobate nanometer sheet.
2. The two-dimensional material modified zirconium-based catalyst according to claim 1, wherein the mass ratio of the two-dimensional material to the zirconium-based metal organic framework material is 0.1wt% to 20wt%.
3. The two-dimensional material modified zirconium-based catalyst according to claim 2, wherein the mass ratio of the two-dimensional material to the zirconium-based metal organic framework material is 0.5wt% to 7wt%.
4. A method of preparing the two-dimensional material modified zirconium-based catalyst of any one of claims 1-3, comprising the steps of:
s1: completely dissolving a zirconium source and an organic ligand in a solvent to obtain a first mixed solution;
s2: adding the two-dimensional material into a solvent, and stirring to obtain a second mixed solution;
s3: transferring the first mixed solution obtained in the step S1 and the second mixed solution obtained in the step S2 into a reaction kettle to react to obtain a reaction product;
s4: and (3) washing and drying the reaction product obtained in the step (S3) to obtain the two-dimensional material modified zirconium-based catalyst.
5. The method for preparing a two-dimensional material modified zirconium-based catalyst according to claim 4, wherein in the step S1, the zirconium source is one or more of zirconium silicate, zirconium chloride, zirconium oxychloride and zirconium oxide; the organic ligand is one or more of isophthalic acid, trimesic acid, 1,2,3, 4-butane tetracarboxylic acid, terephthalic acid, 2, 5-dihydroxyterephthalic acid, trimellitic acid, succinic acid and oxalic acid; the mass ratio of the zirconium source to the organic ligand is 1:0.7-1:2.6.
6. The method for preparing a two-dimensional material modified zirconium-based catalyst according to claim 4, wherein the solvent in the step S1 and the step S2 is one or more of water, methanol, ethanol, ethylene glycol, N-dimethylformamide and N, N-dimethylacetamide.
7. The method for preparing a two-dimensional material modified zirconium-based catalyst according to claim 4, wherein in the step S3, the reaction temperature is 80-180 ℃ and the reaction time is 8-24h.
8. The method for preparing a two-dimensional material modified zirconium-based catalyst according to claim 4, wherein in the step S4, the drying temperature is 15-70 ℃ and the drying time is 5-10h.
9. Use of a two-dimensional material modified zirconium-based catalyst according to any one of claims 1-3 for photocatalytic reduction of greenhouse gases.
10. The use of a two-dimensional material modified zirconium-based catalyst according to claim 9, wherein the greenhouse gas is CO 2 。
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