CN111135868A - MOF/nanometer β -Ga2O3Preparation method of composite film - Google Patents
MOF/nanometer β -Ga2O3Preparation method of composite film Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 151
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 83
- 239000010703 silicon Substances 0.000 claims abstract description 83
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 34
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
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- 238000007664 blowing Methods 0.000 claims description 10
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- 238000001914 filtration Methods 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
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- 238000002203 pretreatment Methods 0.000 claims description 9
- 238000009736 wetting Methods 0.000 claims description 7
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- -1 acetyl propyl Chemical group 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
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- 238000000643 oven drying Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 63
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 description 9
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- 239000001294 propane Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/766—Dehydrogenation of -CH-CH- or -C=C- to -C=C- or -C-C- triple bond species
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a preparation method of an MOF/nanometer β -Ga2O3 composite film, which relates to the technical field of new materials and comprises the following steps of preparing nanometer β -Ga2O3Preparation of MOF/Nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, adding into mixed solution of DMF/polyethylene glycol at a volume ratio of 1:1 to obtain liquid crystal, pretreating silicon wafer, oven drying, moistening with DMF vapor, soaking the polished surface in the liquid crystal for 5-10min, heating to 100 deg.C at a certain speed, maintaining for 5-10h, taking out to obtain silicon wafer with crystal seed layer adsorbed on surface, and mixing with β -Ga nanoparticles2O3Copper nitrate trihydrate and 1, 4-naphthalenedicarboxylic acidAnd (2) placing acid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed crystal layer into the reaction liquid, placing the reaction kettle into a microwave reactor, heating to 130 ℃, reacting for 30-50min, naturally cooling to room temperature, placing for 20-50min, taking out the silicon wafer, washing and drying with DMF (dimethyl formamide), and scraping the film.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to MOF/nanometer β -Ga2O3A preparation method of the composite film.
Background
Metal Organic Frameworks (MOFs) are a new type of porous framework material that is self-assembled from metal ions and organic ligands. Compared with other traditional porous materials such as activated carbon, silica gel, molecular sieves and the like, the MOFs material has the main structural characteristics of huge specific surface area, ultrahigh porosity, adjustable pore size, modifiable functional groups and the like, so that the MOFs material has wide application in the fields of gas adsorption and separation, catalysis and the like. However, some of the disadvantages of MOFs materials themselves limit more applications. Firstly, part of MOFs materials have poor chemical stability and are easy to collapse; secondly, the MOFs crystalline materials prepared by the traditional synthesis method generally exist in powder form and have weak mechanical strength.
The MOFs material and a series of functional materials are combined to construct the metal organic framework composite material, so that the problem of poor chemical stability of the MOFs material can be solved, the characteristics of the MOFs material such as high porosity, large specific surface area and the like and the excellent characteristics of other functional materials such as optics, electricity, magnetism, catalysis and the like can be integrated, and even a new function which is not possessed by a single material is generated through a synergistic effect between the two materials. The composite material is expected to have better application prospect in the fields of gas adsorption, separation and storage, multi-phase catalysis, chemical sensing, biomedicine and the like.
The patent publication No. CN108147678A discloses a preparation method of MOFs-derived NiO electrochromic film, which comprises the following steps: dissolving PTA and nickel salt in N, N-dimethylformamide DMF, and dropwise adding deionized water to obtain PTA-Ni-MOFs precursor solution; placing the pretreated FTO glass in a precursor solution for hydrothermal reaction, cooling, cleaning, and vacuum drying to obtain the FTO glass with the PTA-Ni-MOFs film attached to the surface; and carrying out heat treatment to obtain the MOFs derived NiO electrochromic film. The preparation method is simple and convenient, and can be used for large-scale production; the obtained MOFs-derived NiO film material has a perfect pore structure and high-efficiency and stable electrochromic performance, and has important application value in the fields of electronic display, building curtain walls, intelligent home and the like.
The patent with publication number CN104117290B discloses a preparation method of MOFs tubular hybrid membrane for separating aromatic hydrocarbon/alkane, belonging to the technical field of membrane separation. The method comprises the following steps: preparing MOFs particles by a solvent thermal method; preparing MOFs/polymer membrane liquid by adopting a blending method, performing ultrasonic dispersion, and standing for defoaming; compounding MOFs/polymers on the outer surface of the ceramic porous membrane modified by the silane coupling agent by a dynamic pressurization method to form a membrane separation layer; and drying the hybrid membrane at 30-120 ℃ for 0.1-4 h, and enhancing the stability of the separation layer. The invention provides a preparation method of a novel MOFs hybrid membrane for separating aromatic hydrocarbon/alkane, the process is simple, and the prepared hybrid membrane has good pervaporation performance and greatly improved mechanical strength.
At present, no MOF/nanometer β -Ga is available2O3Related reports of composite films.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides MOF/nanometer β -Ga2O3A preparation method of a composite film.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
(1) sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadecene under the nitrogen atmosphere, blowing nitrogen into the mixed solution at room temperature for deoxidation for 5-10min, heating to 120-140 ℃ for reaction for 30-50min, continuing to heat to 280-300 ℃ for reaction for 15-30min, controlling the cooling speed to be 10-15 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying by ethanol to obtain the nano β -Ga2O3；
(2) Mixing nanometer β -Ga2O3Placing copper nitrate trihydrate and 1, 4-naphthalenedicarboxylic acid into a reaction kettle, adding deionized water, stirring and mixing uniformly, placing the reaction kettle into a microwave reactor, heating to 160-Then cooling to room temperature, standing for 20-30h, filtering, washing solid materials with water, washing with DMF (dimethyl formamide) and ethanol, drying at 40-60 ℃ to obtain MOF/nano β -Ga2O3A composite crystal;
(3) mixing MOF/nano β -Ga2O3Grinding the composite crystal, adding the ground composite crystal into a mixed solution with a volume ratio of DMF/polyethylene glycol of 1:1 to obtain a liquid crystal, pretreating a silicon wafer, drying, wetting with DMF steam, immersing the polished surface into the liquid crystal for 5-10min, taking out, heating to 100 ℃ at a certain speed, keeping the temperature for 5-10h, taking out, and obtaining the silicon wafer with the surface adsorbed with the seed crystal layer;
(4) mixing nanometer β -Ga2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed crystal layer into reaction liquid, putting the reaction kettle into a microwave reactor, heating to 130 ℃, reacting for 30-50min, naturally cooling to room temperature, standing for 20-50min, taking out the silicon wafer, washing with DMF (dimethyl formamide) for drying, and scraping a film.
Preferably, the flow rate of nitrogen during deoxygenation in step (1) is 3 to 8 m/s.
Preferably, the nano β -Ga in the step (2)2O3The mass ratio of the nitric acid to the copper nitrate trihydrate is 1: 20-50.
Preferably, the power of the microwave reaction in the step (2) is 200-.
Preferably, in the step (2), the solid material is washed by water for 3 times, DMF for 3 times and ethanol for 3 times.
Preferably, in step (3), the MOF/nano β -Ga2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1: 8-12.
Preferably, the silicon wafer pretreatment method in the step (3) comprises the following steps: soaking the silicon wafer in hydrofluoric acid with a certain concentration for 5min, washing with deionized water for 5min, and soaking in deionized water for 10 min.
Preferably, the temperature rising speed in the step (3) is 1-5 ℃/min.
Preferably, the power of the microwave reaction in step (4) is 200W.
Preferably, the drying temperature in step (4) is less than or equal to 40 ℃.
(III) advantageous effects
The invention provides a MOF/nanometer β -Ga2O3The preparation method of the composite film has the following beneficial effects:
the nanometer β -Ga prepared by the method of the invention2O3The surface is rich in active groups, and Cu (OH) (1, 4-NDC). 2H generated by the reaction of copper nitrate trihydrate and 1, 4-naphthalene diacid2O can be adsorbed at nanometer β -Ga in the growth process2O3The surface of the catalyst forms a core-shell structure, residual solvent micromolecules occupy pore channels of the core-shell structure in the synthesis and cleaning processes, a persistent pore structure can be left after drying, the catalytic activity can be correspondingly improved, and in addition, the nano β -Ga is controlled2O3The thickness of the core-shell structure can be controlled by the mass proportion of the nano-crystalline copper nitrate to the copper nitrate trihydrate, and the nano-crystalline copper nitrate is controlled by β -Ga2O3The mass ratio of the obtained core-shell structure to the copper nitrate trihydrate is 1:20-50, the obtained core-shell structure has the highest catalytic activity, in addition, a process of firstly preparing a seed crystal layer and then carrying out secondary adsorption growth is adopted, and the obtained MOF/nanometer β -Ga is obtained2O3The composite film is uniform and compact, the continuous process is high, the gaps among crystals are small, and the catalytic dehydrogenation experiment proves that the MOF/nano β -Ga prepared by the invention2O3The composite film has good catalytic performance, the conversion rate of propane and the selectivity of propylene at the initial reaction stage (10min) reach 45.1 percent and 96.1 percent respectively, and are greatly higher than β -Ga2O3The catalyst has low catalytic activity reduction with time, and the propylene selectivity is well maintained.
Drawings
FIG. 1 is a SEM photograph of the surface of a seed layer on a silicon wafer;
FIG. 2 is an SEM image of a cross-section of a seed layer on a silicon wafer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 6m/s into the mixed solution at room temperature for deoxygenation for 8min, heating to 130 ℃ for reaction for 40min, then continuing heating to 290 ℃ for reaction for 20min, controlling the cooling speed to be 13 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying by ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:40), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 165 ℃, reacting for 40min, naturally cooling to room temperature with the microwave reaction power of 200W, standing for 25h, filtering, washing solid materials with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 45 ℃ to obtain MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:10), the silicon wafer is pretreated and dried (the pretreatment method of the silicon wafer comprises the steps of soaking the silicon wafer in hydrofluoric acid with certain concentration for 5min, then washing the silicon wafer with deionized water for 5min, then soaking the silicon wafer in deionized water for 10min), wetting the silicon wafer with DMF steam, soaking the polished surface in liquid crystal for 8min, taking out the silicon wafer, heating the silicon wafer to 100 ℃ at the speed of 4 ℃/min, keeping the temperature for 6h, taking out the silicon wafer with a crystal seed layer adsorbed on the surface, and then adding β -Ga2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, and then adding the mixtureImmersing the silicon wafer seed crystal layer into the reaction liquid, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 40min, naturally cooling to room temperature, standing for 30min, taking out the silicon wafer, washing with DMF, drying at 30 ℃, and scraping the film.
Example 2:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 3m/s into the mixed solution at room temperature for deoxygenation for 10min, heating to 120 ℃ for reaction for 50min, then continuously heating to 280 ℃ for reaction for 30min, controlling the cooling speed to be 10 ℃/min, slowly cooling to room temperature, adding ethyl acetate, performing ultrasonic oscillation for 10min, centrifuging, performing ultrasonic oscillation for 10min on solid acetone, centrifuging, finally cleaning and drying by using ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:50), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 180 ℃, reacting for 30min, the power of the microwave reaction is 400W, naturally cooling to room temperature, standing for 25h, filtering, washing the solid material with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 50 ℃ to obtain the MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:8), the silicon wafer is pretreated and dried (the pretreatment method of the silicon wafer comprises the steps of soaking the silicon wafer in hydrofluoric acid with certain concentration for 5min, then washing the silicon wafer with deionized water for 5min, then soaking the silicon wafer in deionized water for 10min), wetting the silicon wafer with DMF steam, soaking the polished surface in liquid crystal for 10min, taking out the silicon wafer, heating the silicon wafer to 100 ℃ at the speed of 1 ℃/min, keeping the temperature for 6h, taking out the silicon wafer with a crystal seed layer adsorbed on the surface, and then adding β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in the reactionAdding deionized water into a kettle, stirring and mixing uniformly, immersing the silicon wafer seed layer into the reaction solution, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 30min, naturally cooling to room temperature, standing for 40min, taking out the silicon wafer, washing with DMF (dimethyl formamide) at 25 ℃, drying, and scraping the film.
Example 3:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 6m/s into the mixed solution at room temperature for deoxygenation for 8min, heating to 120 ℃ for reaction for 35min, then continuing heating to 300 ℃ for reaction for 20min, controlling the cooling speed to be 10 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying by ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:30), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 165 ℃, reacting for 30min, naturally cooling to room temperature with the microwave reaction power of 200W, standing for 25h, filtering, washing solid materials with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 55 ℃ to obtain MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:10), the silicon wafer is pretreated and dried (the pretreatment method of the silicon wafer comprises the steps of soaking the silicon wafer in hydrofluoric acid with certain concentration for 5min, then washing the silicon wafer with deionized water for 5min, then soaking the silicon wafer in deionized water for 10min), wetting the silicon wafer with DMF steam, soaking the polished surface in liquid crystal for 5min, taking out the silicon wafer, heating the silicon wafer to 100 ℃ at the speed of 1 ℃/min, keeping the temperature for 10h, taking out the silicon wafer with a crystal seed layer adsorbed on the surface, and then adding β -Ga2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed layer into a reaction solution, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 30min, naturally cooling to room temperature, standing for 50min, taking out the silicon wafer, washing with DMF, drying at 25 ℃, and scraping a film.
Example 4:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 3m/s into the mixed solution at room temperature for deoxygenation for 5min, heating to 120 ℃ for reaction for 30min, then continuing to heat to 280 ℃ for reaction for 15min, controlling the cooling speed to be 10 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying by ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:20), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 160 ℃, reacting for 30min, naturally cooling to room temperature, standing for 20h, filtering, washing solid materials with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 40 ℃ to obtain MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:8), and the silicon wafer is pretreated and then dried (the pretreatment method of the silicon wafer is as follows: soaking silicon wafer in hydrofluoric acid of certain concentration for 5min, washing with deionized water for 5min, soaking in deionized water for 10min), moistening with DMF vapor, soaking the polished surface in liquid crystal for 5min, taking out, heating to 100 deg.C at 1 deg.C/min, and maintaining for 5hTaking out to obtain silicon wafer with crystal seed layer adsorbed on surface, and mixing nanometer β -Ga solution2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed crystal layer into reaction liquid, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 30min, naturally cooling to room temperature, standing for 20min, taking out the silicon wafer, washing with DMF (dimethyl formamide) at 25 ℃, drying, and scraping a film.
Example 5:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadecene under the nitrogen atmosphere, blowing nitrogen with the flow rate of 8m/s into the mixed solution at room temperature for deoxygenation for 10min, heating to 140 ℃ for reaction for 50min, continuing heating to 300 ℃ for reaction for 30min, controlling the cooling speed to be 15 ℃/min, slowly cooling to room temperature, adding ethyl acetate, performing ultrasonic oscillation for 10min, centrifuging, performing ultrasonic oscillation for 10min with solid acetone, finally cleaning and drying with ethanol to obtain nanometer β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:50), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 180 ℃, reacting for 50min, the power of the microwave reaction is 400W, naturally cooling to room temperature, standing for 30h, filtering, washing the solid material with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 60 ℃ to obtain MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:12), and the silicon wafer is pretreated and dried (the pretreatment method of the silicon wafer is as follows: soaking silicon wafer in hydrofluoric acid with certain concentration for 5min, washing with deionized water for 5min, soaking in deionized water for 10min), moistening with DMF vapor, and soaking the polished surface in the solutionTaking out from the liquid crystal for 10min, heating to 100 deg.C at a speed of 5 deg.C/min, maintaining for 10h to obtain silicon wafer with seed crystal layer adsorbed on surface, and mixing with nanometer β -Ga powder2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed layer into a reaction solution, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 50min, naturally cooling to room temperature, standing for 50min, taking out the silicon wafer, washing with DMF, drying at 40 ℃, and scraping a film.
Example 6:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 8m/s into the mixed solution at room temperature for deoxygenation for 5min, heating to 140 ℃ for reaction for 30min, then continuing heating to 300 ℃ for reaction for 15min, controlling the cooling speed to be 10-15 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying by ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to the copper nitrate trihydrate is 1:50), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 160 ℃, reacting for 30min, naturally cooling to room temperature with the microwave reaction power of 200W, standing for 20h, filtering, washing the solid material with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 40 ℃ to obtain the MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:8), and the silicon wafer is pretreated and then dried (the pretreatment method of the silicon wafer is as follows: soaking silicon wafer in hydrofluoric acid with certain concentration for 5min, washing with deionized water for 5min, and washing with deionized waterSoaking in deionized water for 10min), wetting with DMF vapor, soaking the polished surface in liquid crystal for 10min, heating to 100 deg.C at 5 deg.C/min, maintaining for 8h to obtain silicon wafer with crystal seed layer adsorbed on the surface, and soaking nanometer β -Ga powder in the solution2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed layer into a reaction solution, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 40min, naturally cooling to room temperature, standing for 40min, taking out the silicon wafer, washing with DMF, drying at 35 ℃, and scraping a film.
Example 7:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 5m/s into the mixed solution at room temperature for deoxygenation for 6min, heating to 125 ℃ for reaction for 30min, then continuing heating to 280 ℃ for reaction for 20min, controlling the cooling speed to be 10 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying by ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:20), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 165 ℃, reacting for 30min, naturally cooling to room temperature, standing for 25h, filtering, washing solid materials with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 40 ℃ to obtain MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:10), and the silicon wafer is pretreated and then dried (the pretreatment method of the silicon wafer is as follows: using silicon wafersSoaking in hydrofluoric acid of certain concentration for 5min, washing with deionized water for 5min, soaking in deionized water for 10min), moistening with DMF vapor, soaking the polished surface in liquid crystal for 5min, heating to 100 deg.C at 1 deg.C/min, maintaining for 5 hr, taking out to obtain silicon wafer with crystal seed layer adsorbed on the surface, and preparing into nanometer β -Ga oxide film2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed crystal layer into reaction liquid, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 30min, naturally cooling to room temperature, standing for 20min, taking out the silicon wafer, washing with DMF (dimethyl formamide) at 25 ℃, drying, and scraping a film.
Example 8:
MOF/nanometer β -Ga2O3The preparation method of the composite film comprises the following steps:
under the nitrogen atmosphere, sequentially adding gallium acetylacetonate, lauryl alcohol, oleylamine and oleic acid into octadiene, blowing nitrogen with the flow rate of 8m/s into the mixed solution at room temperature for deoxygenation for 10min, heating to 135 ℃ for reaction for 40min, then continuously heating to 285 ℃ for reaction for 20min, controlling the cooling speed to be 10 ℃/min, slowly cooling to room temperature, adding ethyl acetate, performing ultrasonic oscillation for 10min, centrifuging, performing ultrasonic oscillation for 10min on solid acetone, centrifuging, finally cleaning and drying by using ethanol to obtain nano β -Ga2O3Prepared from nanometer β -Ga2O3Copper nitrate trihydrate and 1, 4-naphthalene diacid are placed in a reaction kettle (nanometer β -Ga)2O3The mass ratio of the raw materials to copper nitrate trihydrate is 1:50), adding deionized water, stirring and mixing uniformly, putting the reaction kettle into a microwave reactor, heating to 165 ℃, reacting for 50min, naturally cooling to room temperature with the microwave reaction power of 200W, standing for 20h, filtering, washing solid materials with water for 3 times, washing with DMF for 3 times, washing with ethanol for 3 times, and drying at 40 ℃ to obtain MOF/nano β -Ga2O3Composite crystal prepared from MOF/nanometer β -Ga2O3Grinding the composite crystal, and adding into a mixed solution of DMF/polyethylene glycol with a volume ratio of 1:1 to obtain a liquid crystal (MOF/nanometer β -Ga)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1:8), mixingPre-treating silicon wafer, drying (the pre-treating method comprises soaking the silicon wafer in hydrofluoric acid with a certain concentration for 5min, washing with deionized water for 5min, soaking in deionized water for 10min), wetting with DMF vapor, soaking the polished surface in liquid crystal for 10min, taking out, heating to 100 deg.C at 4 deg.C/min, maintaining the temperature for 6h to obtain silicon wafer with crystal seed layer adsorbed on the surface, and drying the silicon wafer with β -Ga oxide nanoparticles2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed layer into a reaction solution, putting the reaction kettle into a microwave reactor, heating to 130 ℃ with the microwave reaction power of 200W, reacting for 35min, naturally cooling to room temperature, standing for 20min, taking out the silicon wafer, washing with DMF, drying at 40 ℃, and scraping a film.
And (3) testing catalytic dehydrogenation performance:
the MOF/nanometer β -Ga prepared in the invention example 12O3Composite film with β -Ga2O3Catalyst comparative testing on flow reactor (β -Ga)2O3The catalyst is prepared according to the literature Roy r, Hill v.c., osbmne.f. j.am.chem.soc]1952,74: 719-722), the dehydrogenation reaction gas composition is: v (C)3H8)：V(N2)＝1:39；
Wherein the propane conversion is (amount of propane converted/total propane feed) x 100%
Propylene selectivity (amount of converted product/stoichiometric number of the product)/(amount of converted propane) × 100%
The results of comparison of propane conversions at 10min, 120min, 240min, and 480min are shown in Table 1 below:
table 1:
the propylene selectivity comparison results of 10min, 120min, 240min and 480min are shown in the following table 2:
table 2:
MOF/Nano β -Ga prepared by the present invention, as shown in tables 1 and 22O3The composite film has good catalytic performance, the conversion rate of propane and the selectivity of propylene at the initial reaction stage (10min) reach 45.1 percent and 96.1 percent respectively, and are greatly higher than β -Ga2O3The catalyst has low catalytic activity reduction with time, and the propylene selectivity is well maintained.
It is noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. MOF/nanometer β -Ga2O3The preparation method of the composite film is characterized by comprising the following steps:
(1) under the nitrogen atmosphere, the acetyl propyl is sequentially addedAdding gallium ketone, lauryl alcohol, oleylamine and oleic acid into octadecene, blowing nitrogen into the mixed solution at room temperature for deoxidation for 5-10min, heating to 140 ℃ for reaction for 30-50min, continuing to heat to 300 ℃ for reaction for 15-30min, controlling the cooling speed to be 10-15 ℃/min, slowly cooling to room temperature, adding ethyl acetate for ultrasonic oscillation for 10min, centrifuging, ultrasonically oscillating solid acetone for 10min, centrifuging, finally cleaning and drying ethanol to obtain nanometer β -Ga2O3；
(2) Mixing nanometer β -Ga2O3Placing copper nitrate trihydrate and 1, 4-naphthalenedicarboxylic acid into a reaction kettle, adding deionized water, stirring and mixing uniformly, placing the reaction kettle into a microwave reactor, heating to 160-180 ℃, reacting for 30-50min, naturally cooling to room temperature, placing for 20-30h, filtering, washing solid materials with water, washing with DMF (dimethyl formamide), washing with ethanol, and drying at 40-60 ℃ to obtain MOF/nano β -Ga2O3A composite crystal;
(3) mixing MOF/nano β -Ga2O3Grinding the composite crystal, adding the ground composite crystal into a mixed solution with a volume ratio of DMF/polyethylene glycol of 1:1 to obtain a liquid crystal, pretreating a silicon wafer, drying, wetting with DMF steam, immersing the polished surface into the liquid crystal for 5-10min, taking out, heating to 100 ℃ at a certain speed, preserving heat for 5-10h, and taking out to obtain the silicon wafer with the surface adsorbed with the seed crystal layer;
(4) mixing nanometer β -Ga2O3Putting copper nitrate trihydrate and 1, 4-naphthalene diacid into a reaction kettle, adding deionized water, stirring and mixing uniformly, immersing the silicon wafer seed crystal layer into reaction liquid, putting the reaction kettle into a microwave reactor, heating to 130 ℃, reacting for 30-50min, naturally cooling to room temperature, standing for 20-50min, taking out the silicon wafer, washing and drying with DMF, and scraping a film.
2. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the nitrogen flow rate is 3-8m/s during deoxygenation in the step (1).
3. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the nano-step in the step (2)Rice β -Ga2O3The mass ratio of the nitric acid to the copper nitrate trihydrate is 1: 20-50.
4. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the power of the microwave reaction in the step (2) is 200-400W.
5. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the solid material in the step (2) is washed by water for 3 times, DMF for 3 times and ethanol for 3 times.
6. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that MOF/nanometer β -Ga in the step (3)2O3The mass ratio of the composite crystal to the DMF/polyethylene glycol mixed solution is 1: 8-12.
7. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the silicon wafer pretreatment method in the step (3) comprises the following steps: soaking the silicon wafer in hydrofluoric acid with a certain concentration for 5min, washing the silicon wafer with deionized water for 5min, and soaking the silicon wafer in deionized water for 10 min.
8. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the temperature rise speed in the step (3) is 1-5 ℃/min.
9. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the power of the microwave reaction in the step (4) is 200W.
10. The MOF/Nano β -Ga of claim 12O3The preparation method of the composite film is characterized in that the drying temperature in the step (4) is less than or equal to 40 ℃.
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