CN114408970A - Preparation method of hollow mesoporous carbon-doped gallium sesquioxide nanospheres and product thereof - Google Patents
Preparation method of hollow mesoporous carbon-doped gallium sesquioxide nanospheres and product thereof Download PDFInfo
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- CN114408970A CN114408970A CN202210088162.XA CN202210088162A CN114408970A CN 114408970 A CN114408970 A CN 114408970A CN 202210088162 A CN202210088162 A CN 202210088162A CN 114408970 A CN114408970 A CN 114408970A
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 115
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004793 Polystyrene Substances 0.000 claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920002223 polystyrene Polymers 0.000 claims abstract description 30
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229940044658 gallium nitrate Drugs 0.000 claims abstract description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
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- 239000002245 particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 241000157855 Cinchona Species 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000006293 aldehyde allylation reaction Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
- 150000003147 proline derivatives Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical group [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QGLVEAGMVUQOJP-UHFFFAOYSA-N prop-2-enylboronic acid Chemical compound OB(O)CC=C QGLVEAGMVUQOJP-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J35/51—Spheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a preparation method of hollow mesoporous carbon-doped gallium sesquioxide nanospheres and a product thereof, belonging to the technical field of preparation of inorganic/metal hybrid materials. The invention mainly utilizes a hydrothermal method to enable polystyrene/acrylic acid nanospheres and gallium nitrate to react under the action of a surfactant (sodium dodecyl benzene sulfonate), and then the hollow mesoporous carbon-doped gallium trioxide nanospheres are obtained by high-temperature calcination. The preparation method is simple and easy to operate, and is suitable for industrial mass production of the carbon-doped gallium trioxide nanospheres with hollow mesopores. The invention is madeThe crystal form of the prepared hollow mesoporous carbon-doped gallium sesquioxide nanosphere is beta-Ga2O3The hollow mesoporous nanospheres are spherical (the diameter is 600-800 nm, the hollow inner diameter of the hollow mesoporous nanospheres is 200-300 nm, and the pore diameter is distributed between 2-6 nm), and have the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet absorption capacity and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of gallium sesquioxide nanospheres, and relates to a preparation method of hollow mesoporous carbon-doped gallium sesquioxide nanospheres and a product thereof.
Background
Hollow microspheres have unique characteristics such as small density, large specific surface area, good thermal stability and surface permeability, and large internal space, and thus have been receiving increasing attention and research.
The nano carbon doped gallium trioxide as a novel inorganic fine chemical product has the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet absorption capacity and the like, and can be widely appliedThe method is widely applied to the engineering fields of pigment adsorption, micro-substance storage and transportation, catalyst loading and the like, and plays more and more roles in production and life. Wherein beta-Ga2O3The nano gallium sesquioxide has excellent catalytic performance, and is well applied to the fields of wastewater treatment, air purification, antibiosis and the like. The nano-material is used as a new nano-material in the field of catalysis and environmental management, has the characteristics of biological non-toxicity, high catalytic activity, high physical and chemical stability, no secondary pollution and the like, can degrade organic pollutants in the environment, and can remove nitrogen oxides and sulfides in the atmosphere through oxidation.
However, the existing nanocarbon-doped gallium trioxide still has the defect of low catalytic performance, so that the nano structure of the nanocarbon-doped gallium trioxide needs to be further improved, the catalytic performance of the nanocarbon-doped gallium trioxide is improved, and a certain promotion effect is achieved for realizing low-cost and high-efficiency immobilized catalysis application.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing carbon-doped gallium sesquioxide nanospheres with hollow mesoporous structure; the second purpose of the invention is to provide carbon-doped gallium sesquioxide nanospheres with hollow mesoporous; the invention also aims to provide application of the carbon-doped gallium sesquioxide nanospheres with hollow mesoporous in pigment adsorption or catalyst loading.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of carbon-doped gallium sesquioxide nanospheres with hollow mesopores comprises the following steps:
(1) adding an aqueous solution containing polystyrene/acrylic acid nanospheres (PS/AA) into a container containing potassium nitrate and a surfactant (sodium dodecyl benzene sulfonate) under an inert gas atmosphere, heating to 70-90 ℃, and stirring for 18-24 hours to obtain a mixed solution;
(2) and placing the mixed solution into a reaction kettle, reacting at 100-120 ℃ for 12-15 h to obtain a white powdery solid, centrifugally cleaning, drying, and calcining at 600-1000 ℃ for 2-5 h in a nitrogen atmosphere to obtain the carbon-doped gallium trioxide nanospheres with the hollow mesopores.
Preferably, in the step (1), the aqueous solution containing polystyrene/acrylic acid nanospheres (PS/AA) is specifically: adding polystyrene/acrylic acid nanospheres (PS/AA) into the water solution subjected to pre-ultrasonic treatment, and stirring to uniformly disperse the polystyrene/acrylic acid nanospheres;
the inert gas is one or two of nitrogen or argon.
Further preferably, the molar volume ratio of the polystyrene/acrylic acid nanospheres (PS/AA) to the water is 0.2-0.5: 100-600, and the mol: mL.
Preferably, in the step (1), the molar mass ratio of the polystyrene/acrylic acid nanospheres (PS/AA), the gallium nitrate and the surfactant (sodium dodecyl benzene sulfonate) is 1.5-2: 1-1.2: 2-5, and the mol is mol: g.
Preferably, in the step (2), the inner lining of the reaction kettle is made of polytetrafluoroethylene.
Preferably, in the step (2), the centrifugal washing is specifically: and repeatedly washing the white powdery solid with acetone under a centrifugal state, and then repeatedly washing with absolute ethyl alcohol.
Preferably, in the step (2), the drying is specifically drying at 800 ℃ for 2h under a nitrogen atmosphere.
2. The carbon-doped gallium sesquioxide nanospheres with hollow mesopores prepared by the preparation method are provided.
Preferably, the diameter of the nanosphere is 600-800 nm, the hollow inner diameter of the hollow mesoporous nanosphere is 200-300 nm, and the pore diameter of the nanosphere is 2-6 nm.
3. The carbon-doped gallium sesquioxide nanospheres with the hollow mesopores are applied to pigment adsorption or catalyst loading (such as quinine, proline derivatives and the like).
Preferably, the pigment is methyl orange or dimethyl blue.
Preferably, the catalyst is cinchona-alkaloid or proline derivatives.
The invention has the beneficial effects that:
1. the invention provides a preparation method of hollow mesoporous carbon-doped gallium sesquioxide nanospheres, which mainly comprises the steps of reacting polystyrene/acrylic acid nanospheres (PS/AA) and gallium nitrate under the action of a surfactant (sodium dodecyl benzene sulfonate) by using a hydrothermal method, and then calcining at high temperature to obtain the hollow mesoporous carbon-doped gallium sesquioxide nanospheres. The preparation method is simple and easy to operate, and is suitable for industrial preparation of the carbon-doped gallium trioxide nanospheres with hollow mesopores.
2. The invention also discloses a hollow mesoporous carbon-doped gallium sesquioxide nanosphere, and the crystal form of the hollow mesoporous carbon-doped gallium sesquioxide nanosphere prepared by the invention is beta-Ga2O3The hollow mesopores in the shape of spheres (the diameter is 600-800 nm, the hollow diameter of the nanospheres is 200-300 nm, the pore diameter is distributed between 2-6 nm), and the hollow mesopores have the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet absorption capacity and the like, and are widely applied to the engineering fields of pigment adsorption, micro-substance storage and transportation, catalyst loading and the like.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an SEM image of hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in the example, wherein the addition amounts of gallium nitrate in a, b, c, and d are 0.025mol, 0.05mol, 0.1mol, and 0.0125mol, respectively, of the hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in the example;
fig. 2 is a TEM spectrum of the carbon-doped digallium trioxide nanospheres of hollow mesopores prepared in example 1;
FIG. 3 is a hollow core prepared in example 3The pore diameter distribution diagram of the mesoporous carbon-doped gallium sesquioxide nanospheres is shown, wherein the concentration of polystyrene/acrylic acid nanospheres (PS/AA) in the water solution containing the polystyrene/acrylic acid nanospheres (PS/AA) added in the preparation process of the hollow mesoporous carbon-doped gallium sesquioxide nanospheres in a, b, c and d is 0.05 mol.L-1、0.1mol·L-1、0.2mol·L-1、0.8mol·L-1；
Fig. 4 is an XRD spectrum of the carbon-doped gallium trioxide nanospheres of hollow mesopores prepared in example 1;
fig. 5 is a uv-vis absorption spectrum of the carbon-doped digallium trioxide nanospheres of hollow mesopores prepared in example 1;
FIG. 6 shows the adsorption of the hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in example 1 with the common hollow carbon spheres loaded with the chiral catalyst cinchona alkaloid derivative (CD-NH)2) A comparative graph of (a).
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
A carbon-doped gallium sesquioxide nanosphere with hollow mesopores is prepared by the following preparation method:
(1) adding 24.4g (0.2mol) of polystyrene/acrylic acid nanosphere (PS/AA) into 100mL of pre-ultrasonic deionized water, and stirring to uniformly disperse the polystyrene/acrylic acid nanosphere (PS/AA) to obtain an aqueous solution containing the polystyrene/acrylic acid nanosphere (PS/AA);
(2) placing 16g (0.1mol) of gallium nitrate and 0.2g of surfactant (sodium dodecyl benzene sulfonate) in a 250ml three-necked bottle, vacuumizing, introducing nitrogen for replacement, and replacing for three times;
(3) adding the water solution containing the polystyrene/acrylic acid nanospheres (PS/AA) in the step (1) into the three-necked bottle filled with the nitrogen atmosphere in the step (2), heating to 70 ℃, and stirring at the rotating speed of 500rpm for 24 hours to obtain a mixed solution;
(4) transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into a drying oven with the temperature of 110 ℃, reacting for 12 hours at constant temperature to obtain white powdery solid, continuously transferring the white powdery solid into a centrifuge tube, cleaning for 3 times by using acetone, cleaning for 3 times by using absolute ethyl alcohol to obtain a white solid product, and then drying for 4 hours at constant temperature in the drying oven with the temperature of 80 ℃ to obtain a reaction precursor Ga (NO)3)3.5H2And O, placing the precursor in a muffle furnace after grinding, and calcining for 2h at 800 ℃ in a nitrogen atmosphere to obtain black powder solid, namely the carbon-doped gallium sesquioxide nanospheres with the hollow mesopores.
Example 2
The method and conditions are the same as those in example 1 except that 0.05mol, 0.025mol and 0.0125mol of gallium nitrate added in example 1 are respectively changed, and products formed by the reaction of gallium nitrate with different contents are obtained.
Example 3
The method and conditions for preparing the polystyrene/acrylic acid nanospheres (PS/AA) added in the aqueous solution containing the polystyrene/acrylic acid nanospheres (PS/AA) added in example 1 were the same as those of example 1 except that 0.2mol of the polystyrene/acrylic acid nanospheres (PS/AA) was changed to 0.05mol, 0.1mol, 0.4mol and 0.8mol, and thus products formed by the reaction of the polystyrene/acrylic acid nanospheres (PS/AA) with different contents were obtained.
Example 4
The calcination temperatures of 800 c in example 1 were modified to 600 c and 1000 c, and the remaining preparation methods and conditions were the same as in example 1, to obtain products formed by the reaction at different calcination temperatures.
Fig. 1 is an SEM image of carbon-doped gallium sesquioxide nanospheres of hollow mesopores prepared in example, wherein the addition amounts of gallium nitrate in a, b, c, d were 0.025mol, 0.05mol, 0.1mol, and 0.0125mol, respectively, of the carbon-doped gallium sesquioxide nanospheres of hollow mesopores prepared in example. As can be seen from FIG. 1, when the addition amount of gallium nitrate is 0025mol, the average particle size of the prepared carbon-doped gallium sesquioxide nanospheres with hollow mesopores is about 300-500 nm, but the surface of the nanospheres is uneven, the nanospheres have different shapes, and the particle sizes are basically inconsistent; when the addition amount of gallium nitrate is 0.05mol, the average particle size of the prepared hollow mesoporous carbon-doped gallium sesquioxide nanospheres is 400-600 nm, the nanospheres are basically uniform in shape, but part of the nanospheres are irregular in shape; when the addition amount of gallium nitrate is 0.1mol, the average particle size of the prepared hollow mesoporous carbon-doped gallium sesquioxide nanospheres is about 600-800 nm, the particle size range is relatively average, and the particle shapes are uniformly in a standard spherical shape; when the addition amount of the gallium nitrate is 0.0125mol, the average particle size of the prepared hollow mesoporous carbon-doped gallium oxide nanospheres is about 200-700 nm, the nanospheres are amorphous in shape, and the particle sizes are different and have larger difference.
Fig. 2 is a TEM spectrum of the carbon-doped digallium trioxide nanospheres of hollow mesopores prepared in example 1. As can be seen from FIG. 2, the hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in example 1 have a hollow diameter of 200-300 nm.
FIG. 3 is a graph showing a distribution of pore diameters of carbon-doped trigallium trioxide nanospheres having hollow mesopores prepared in example 3, wherein the concentration of polystyrene/acrylic acid nanospheres (PS/AA) in the aqueous solution containing polystyrene/acrylic acid nanospheres (PS/AA) added during the preparation of the carbon-doped trigallium trioxide nanospheres having hollow mesopores in a, b, c, d is 0.05 mol. L-1、0.1mol·L-1、0.2mol·L-1、0.8mol·L-1. As can be seen from FIG. 3, in the process of preparing the carbon-doped gallium sesquioxide nanospheres having the hollow mesoporous structure, when the polystyrene/acrylic acid nanospheres (PS/AA) are added at a concentration of 0.05 mol. L-1When the preparation method is used, the aperture of the prepared hollow mesoporous carbon-doped gallium sesquioxide nanospheres is within the range of 3-10 nm, and the distribution is relatively dispersed; when the concentration of the added polystyrene/acrylic acid nanosphere (PS/AA) is 0.1 mol.L-1When the preparation method is used, the aperture of the prepared hollow mesoporous carbon-doped gallium sesquioxide nanospheres is within the range of 2-8 nm, and the distribution is relatively dispersed;when the concentration of the added polystyrene/acrylic acid nanosphere (PS/AA) is 0.2 mol.L-1Then, the aperture of the prepared hollow mesoporous carbon-doped gallium sesquioxide nanosphere is within the range of 2-6 nm; when the concentration of the added polystyrene/acrylic acid nanosphere (PS/AA) is 0.8 mol.L-1When the nanospheres are prepared, almost no mesopores are distributed.
Fig. 4 is an XRD spectrum of the carbon-doped digallium trioxide nanospheres of hollow mesopores prepared in example 1. As can be seen from fig. 4, the XRD pattern of the carbon-doped digallium trioxide nanospheres with hollow mesopores prepared in example 1 is consistent with that of the standard card.
Fig. 5 is a uv-vis absorption spectrum of the carbon-doped digallium trioxide nanospheres with hollow mesopores prepared in example 1. As can be seen from fig. 5, the carbon-doped gallium sesquioxide nanospheres with hollow mesopores prepared in example 1 have low absorbance in the visible light range with the wavelength of 400-800 nm, and have low utilization rate of visible light; and the absorbance is higher in the ultraviolet light range with the wavelength range of 200-400 nm, which indicates that the carbon-doped gallium sesquioxide nanospheres with hollow mesopores prepared in the embodiment 1 have higher utilization rate on the ultraviolet light with the wavelength range of 200-400 nm.
FIG. 6 shows the adsorption of the hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in example 1 with the common hollow carbon spheres loaded with the chiral catalyst cinchona alkaloid derivative (CD-NH)2) A comparative graph of (a). As can be seen from FIG. 6, the hollow mesoporous carbon-doped digallium trioxide nanospheres prepared in example 1 are directed to a cinchona alkaloid derivative (CD-NH)2) The highest load can reach 14.2 percent, while the common hollow carbon spheres can be used for the quinine derivative (CD-NH)2) The loading amount of the carbon-doped gallium sesquioxide nanospheres can only reach 3.9% after 96 hours, because the hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in the example 1 change the pore distribution of the original carbon spheres, so that the loading amount is improved.
Likewise, the hollow mesoporous carbon-doped gallium sesquioxide nanospheres prepared in example 2, example 3 and example 4 were subjected to ultraviolet-visible absorption spectrum and chiral catalyst cinchona alkaloid derivative (CD-NH)2) The results of the load amount test of (2) were the same as those of example 1The test results were the same.
TABLE 1 content of N element before and after adsorption of catalyst by carbon-doped gallium trioxide nanospheres
Because of the catalyst CD-NH2Contains N element, so the carbon-doped gallium trioxide nanospheres after adsorbing the catalyst can be calculated by measuring the content of the N element through element analysis (table 1). 0.01mmol/g before adsorption is blank error, and the content of nitrogen after adsorption is increased to 0.72mmol/g, which indicates that the catalyst is successfully adsorbed.
Catalyzing aldehyde allylation reaction by using carbon-doped gallium trioxide nanospheres adsorbing a catalyst: the catalyst (1.39g,1mmol) was added to the reaction tube, and the tube was evacuated and purged with argon three times. A solution of freshly distilled toluene (1mL) was added, placed in a low temperature reactor at-30 ℃ and added benzaldehyde (21.2mg, 0.2mmol, 1.0eq) and allylboronic acid pinacol ester (40.3mg, 0.24mmol, 1.2eq) for 6 h. Purification by silica gel column chromatography [ PE/EA (v/v) ═ 10:1] gave a colorless liquid (28.0mg, yield 96%, 96% ee). And the substrate is expanded to obtain better yield and selectivity, which is shown in table 2.
TABLE 2 catalysis of aldehyde allylation reaction by carbon-doped digallium trioxide nanosphere adsorption catalyst
In summary, the invention provides a preparation method of carbon-doped gallium sesquioxide nanospheres with hollow mesopores, which mainly utilizes a hydrothermal method to ensure thatPolystyrene/acrylic acid nanospheres (PS/AA) and gallium nitrate react under the action of a surfactant (sodium dodecyl benzene sulfonate), and then the hollow mesoporous carbon-doped gallium trioxide nanospheres are obtained by high-temperature calcination. The preparation method is simple and easy to operate, and is suitable for industrial preparation of the carbon-doped gallium trioxide nanospheres with hollow mesopores. In addition, the invention also discloses a carbon-doped gallium sesquioxide nanosphere with hollow mesopores, and the crystal form of the carbon-doped gallium sesquioxide nanosphere with hollow mesopores prepared by the invention is beta-Ga2O3The hollow mesopores in the shape of spheres (the diameter is 600-800 nm, the hollow diameter of the nanospheres is 200-300 nm, and the pore diameter is distributed between 2-6 nm), has the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet absorption capacity and the like, and is widely applied to the engineering fields of pigment adsorption, micro-material storage and transportation, catalyst loading and the like.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of carbon-doped gallium sesquioxide nanospheres with hollow mesopores is characterized by comprising the following steps:
(1) adding an aqueous solution containing polystyrene/acrylic acid nanospheres (PS/AA) into a container containing potassium nitrate and a surfactant (sodium dodecyl benzene sulfonate) under an inert gas atmosphere, heating to 70-90 ℃, and stirring for 18-24 hours to obtain a mixed solution;
(2) and placing the mixed solution into a reaction kettle, reacting at 100-120 ℃ for 12-15 h to obtain a white powdery solid, centrifugally cleaning, drying, and calcining at 600-1000 ℃ for 2-5 h in a nitrogen atmosphere to obtain the carbon-doped gallium trioxide nanospheres with the hollow mesopores.
2. The method according to claim 1, wherein in step (1), the aqueous solution containing polystyrene/acrylic nanospheres (PS/AA) is specifically: adding polystyrene/acrylic acid nanospheres (PS/AA) into the water solution subjected to pre-ultrasonic treatment, and stirring to uniformly disperse the polystyrene/acrylic acid nanospheres;
the inert gas is one or two of nitrogen or argon.
3. The preparation method of claim 2, wherein the molar volume ratio of the polystyrene/acrylic acid nanospheres (PS/AA) to the water is 0.2-0.5: 100-600, mol: mL.
4. The preparation method according to claim 1, wherein in the step (1), the molar mass ratio of the polystyrene/acrylic acid nanospheres (PS/AA), the gallium nitrate and the surfactant (sodium dodecyl benzene sulfonate) is 1.5-2: 1-1.2: 2-5, and the molar ratio is mol: g.
5. The method according to claim 1, wherein in the step (2), the inner lining of the reaction kettle is polytetrafluoroethylene.
6. The preparation method according to claim 1, wherein in the step (2), the centrifugal washing is specifically: and repeatedly washing the white powdery solid with acetone under a centrifugal state, and then repeatedly washing with absolute ethyl alcohol.
7. The method according to claim 1, wherein in the step (2), the drying is performed for 2 hours at 800 ℃ under a nitrogen atmosphere.
8. The carbon-doped gallium sesquioxide nanospheres with hollow mesopores prepared by the preparation method according to any one of claims 1 to 1.
9. The hollow mesoporous carbon-doped gallium sesquioxide nanosphere according to claim 8, wherein the diameter of the nanosphere is 600-800 nm, the hollow inner diameter of the hollow mesoporous nanosphere is 200-300 nm, and the pore diameter of the nanosphere is 2-6 nm.
10. The use of the carbon-doped gallium sesquioxide nanospheres with hollow mesopores as claimed in any one of claims 8 to 9 for pigment adsorption or catalyst loading.
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