CN114408970B - Preparation method of hollow mesoporous carbon-doped gallium trioxide nanospheres and product thereof - Google Patents
Preparation method of hollow mesoporous carbon-doped gallium trioxide nanospheres and product thereof Download PDFInfo
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- CN114408970B CN114408970B CN202210088162.XA CN202210088162A CN114408970B CN 114408970 B CN114408970 B CN 114408970B CN 202210088162 A CN202210088162 A CN 202210088162A CN 114408970 B CN114408970 B CN 114408970B
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 110
- 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 72
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004793 Polystyrene Substances 0.000 claims abstract description 54
- 229920002223 polystyrene Polymers 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000049 pigment Substances 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
- 238000000034 method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 238000005406 washing Methods 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 5
- 229910005191 Ga 2 O 3 Inorganic materials 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 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 235000021513 Cinchona Nutrition 0.000 description 7
- 241000157855 Cinchona Species 0.000 description 7
- 150000003797 alkaloid derivatives Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910021392 nanocarbon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction 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
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003147 proline derivatives Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000006293 aldehyde allylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 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
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a hollow mesoporous carbon-doped gallium trioxide nanosphere and a product thereof, belonging to the technical field of preparation of inorganic/metal hybrid materials. The invention mainly utilizes a hydrothermal method to lead polystyrene/acrylic 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 through high-temperature calcination. The preparation method of the invention is simple and easy to operate, and is suitable for industrialized mass production of hollow mesoporous carbon-doped gallium trioxide nanospheres. The crystal form of the hollow mesoporous carbon doped gallium trioxide nanospheres prepared by the invention is beta-Ga 2 O 3 The hollow mesoporous has spherical shape (the diameter is 600-800 nm, the hollow inner diameter of the hollow mesoporous nanospheres is 200-300 nm, the pore diameter is distributed between 2-6 nm), and the hollow mesoporous nanospheres have the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet absorption capability and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of gallium trioxide nanospheres, and relates to a preparation method of a hollow mesoporous carbon-doped gallium trioxide nanosphere 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, hollow microspheres are receiving increasing attention and research.
The nano carbon doped gallium oxide is used 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 ray absorption capability and the like, can be widely applied to the engineering fields of pigment adsorption, micro substance storage and transportation, catalyst loading and the like, and plays an increasing role in production and life. Wherein beta-Ga 2 O 3 Nano gallium oxide with excellent propertiesThe catalytic performance is well applied in the fields of wastewater treatment, air purification, antibiosis and the like. As an emerging nano material in the catalytic field and the environmental treatment field, the nano material has the characteristics of biological non-toxicity, high catalytic activity, high physical and chemical stability, no secondary pollution and the like, not only can degrade organic pollutants in the environment, but also can remove nitrogen oxides and sulfides in the atmosphere through oxidation.
However, the existing nano carbon doped gallium trioxide still has the defect of lower catalytic performance, so that the nano structure of the nano carbon doped gallium trioxide needs to be further improved, the catalytic performance of the nano carbon doped gallium trioxide is improved, and a certain promotion effect is achieved for realizing low-cost and high-efficiency immobilized catalytic application.
Disclosure of Invention
Therefore, one of the purposes of the present invention is to provide a method for preparing hollow mesoporous carbon doped gallium oxide nanospheres; the second purpose of the invention is to provide a hollow mesoporous carbon-doped gallium oxide nanosphere; the invention further aims to provide an application of the hollow mesoporous carbon-doped gallium oxide nanospheres in pigment adsorption or catalyst loading.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. the preparation method of the hollow mesoporous carbon-doped gallium trioxide nanospheres comprises the following steps:
(1) Adding an aqueous solution containing polystyrene/acrylic nanospheres (PS/AA) into a container containing potassium nitrate and a surfactant (sodium dodecyl benzene sulfonate) in an inert gas atmosphere, heating to 70-90 ℃ and stirring for 18-24 hours to obtain a mixed solution;
(2) And (3) placing the mixed solution into a reaction kettle, reacting for 12-15 hours at 100-120 ℃ to obtain white powdery solid, centrifugally cleaning, drying, and calcining for 2-5 hours at 600-1000 ℃ in a nitrogen atmosphere to obtain the hollow mesoporous carbon-doped gallium trioxide nanospheres.
Preferably, in the step (1), the aqueous solution containing polystyrene/acrylic nanospheres (PS/AA) is specifically: adding polystyrene/acrylic acid nanospheres (PS/AA) into the pre-ultrasonic aqueous solution, and stirring to uniformly disperse the polystyrene/acrylic acid nanospheres;
the inert gas is any one or two of nitrogen and argon.
Further preferably, the molar volume ratio of the polystyrene/acrylic nanospheres (PS/AA) to water is 0.2-0.5:100-600, mol/mL.
Preferably, in the step (1), the molar mass ratio of the polystyrene/acrylic 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:g is the same as the molar mass ratio of the polystyrene/acrylic nanospheres (PS/AA).
Preferably, in the step (2), the lining of the reaction kettle is polytetrafluoroethylene.
Preferably, in the step (2), the centrifugal cleaning specifically includes: and repeatedly cleaning the white powdery solid with acetone under a centrifugal state, and then repeatedly cleaning with absolute ethyl alcohol.
Preferably, in step (2), the drying is specifically performed under a nitrogen atmosphere at 800 ℃ for 2 hours.
2. The hollow mesoporous carbon doped gallium oxide nanospheres prepared by the preparation method are prepared.
Preferably, the diameter of the nanospheres is 600-800 nm, the hollow inner diameter of the hollow mesoporous nanospheres is 200-300 nm, and the aperture of the nanospheres is 2-6 nm.
3. The hollow mesoporous carbon-doped gallium trioxide nanospheres are applied to pigment adsorption or supported catalysts (such as cinchona alkaloid, proline derivatives and the like).
Preferably, the pigment is methyl orange or dimethyl blue.
Preferably, the catalyst is cinchona alkaloid or proline derivative.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a hollow mesoporous carbon-doped gallium trioxide nanosphere, which mainly comprises the steps of reacting polystyrene/acrylic acid nanospheres (PS/AA) with gallium nitrate under the action of a surfactant (sodium dodecyl benzene sulfonate) by a hydrothermal method, and then calcining at a high temperature to obtain the hollow mesoporous carbon-doped gallium trioxide nanosphere. The preparation method of the invention is simple and easy to operate, and is suitable for the industrialized preparation of the hollow mesoporous carbon-doped gallium trioxide nanospheres.
2. The invention also discloses a hollow mesoporous carbon-doped gallium trioxide nanosphere, and the crystal form of the hollow mesoporous carbon-doped gallium trioxide nanosphere prepared by the invention is beta-Ga 2 O 3 The hollow mesoporous has spherical morphology (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 mesoporous has the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet light absorption capability and the like, and is widely applied to the engineering fields of pigment absorption, 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 objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an SEM image of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in examples, wherein the addition amount of gallium nitrate in a, b, c, d is 0.025mol, 0.05mol, 0.1mol and 0.0125mol, respectively;
FIG. 2 is a TEM spectrum of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1;
FIG. 3 is a graph showing the pore size distribution of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 3, wherein water containing polystyrene/acrylic nanospheres (PS/AA) was added during the preparation of the hollow mesoporous carbon-doped gallium trioxide nanospheres in a, b, c, dThe concentration of polystyrene/acrylic acid nanospheres (PS/AA) in the solution was 0.05 mol.L -1 、0.1mol·L -1 、0.2mol·L -1 、0.8mol·L -1 ；
FIG. 4 is an XRD pattern of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1;
FIG. 5 is an ultraviolet-visible absorption spectrum of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1;
FIG. 6 shows the adsorption of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1 with a common hollow carbon sphere to support a chiral catalyst cinchona alkaloid derivative (CD-NH) 2 ) Is a comparison of the figures.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
The hollow mesoporous carbon doped gallium trioxide nanospheres are prepared according to the following preparation method:
(1) Adding 24.4g (0.2 mol) of polystyrene/acrylic acid nanospheres (PS/AA) into 100mL of deionized water subjected to presonic treatment, and stirring to uniformly disperse the polystyrene/acrylic acid nanospheres (PS/AA) to obtain an aqueous solution containing the polystyrene/acrylic acid nanospheres (PS/AA);
(2) 16g (0.1 mol) of gallium nitrate and 0.2g of surfactant (sodium dodecyl benzene sulfonate) are taken and placed in a three-necked bottle of 250ml, and after vacuumizing, nitrogen is introduced for replacement for three times;
(3) Adding the aqueous solution containing the polystyrene/acrylic 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 500rpm for 24 hours to obtain a mixed solution;
(4) Transferring the mixed solution into a reaction kettle with polytetrafluoroethylene lining, transferring the reaction kettle into a baking oven with the temperature of 110 ℃ for constant-temperature reaction for 12 hours to obtain white powdery solid, continuously transferring into a centrifuge tube, washing with acetone for 3 times, washing with absolute ethyl alcohol for 3 times to obtain a white solid product, and then placing into a baking oven with the temperature of 80 ℃ for constant-temperature drying for 4 hours to obtain a reaction precursor Ga (NO 3 ) 3 .5H 2 And O, placing the precursor in a muffle furnace after grinding, and calcining for 2 hours in a nitrogen atmosphere at 800 ℃ to obtain black powder solid, namely the hollow mesoporous carbon-doped gallium trioxide nanospheres.
Example 2
The gallium nitrate added in example 1 was modified to 0.05mol, 0.025mol and 0.0125mol, respectively, and the other preparation methods and conditions were the same as in example 1, to obtain the products formed by the reaction of gallium nitrate with different contents.
Example 3
The preparation method and conditions were the same as in example 1 except that 0.2mol polystyrene/acrylic nanospheres (PS/AA) added to the aqueous solution containing polystyrene/acrylic nanospheres (PS/AA) added in example 1 were modified to 0.05mol, 0.1mol, 0.4mol, and 0.8mol, to obtain products having different contents of polystyrene/acrylic nanospheres (PS/AA) involved in the reaction.
Example 4
The calcination temperatures of 800℃in example 1 were modified to 600℃and 1000℃and the rest of the preparation method and conditions were the same as in example 1, to obtain the products formed by the reaction at different calcination temperatures.
Fig. 1 is an SEM image of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in examples, in which the added amounts of gallium nitrate in a, b, c, d were 0.025mol, 0.05mol, 0.1mol and 0.0125mol, respectively. As can be seen from fig. 1, when the addition amount of gallium nitrate is 0025mol, the average particle size of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared is about 300-500 nm, but the surface of the hollow mesoporous carbon-doped gallium trioxide nanospheres is rugged, different in shape and basically inconsistent in particle size; when the adding amount of gallium nitrate is 0.05mol, the average grain diameter of the prepared hollow mesoporous carbon doped gallium oxide nanospheres is 400-600 nm, the shape is basically uniform, but partial nanospheres still have irregular shapes; when the adding amount of gallium nitrate is 0.1mol, the average particle size of the prepared hollow mesoporous carbon-doped gallium oxide nanospheres is about 600-800 nm, the particle size range is relatively average, and the particle shapes are uniform and form standard spheres; when the adding amount of gallium nitrate is 0.0125mol, the average grain diameter of the prepared hollow mesoporous carbon doped gallium oxide nanospheres is about 200-700 nm, the shape is amorphous, and the grain diameters are different in size and have larger difference.
Fig. 2 is a TEM image of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1. As can be seen from fig. 2, the hollow diameter of the prepared hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1 is 200-300 nm.
FIG. 3 is a graph showing the pore size distribution of hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 3, wherein the concentration of polystyrene/acrylic nanospheres (PS/AA) in an aqueous solution containing polystyrene/acrylic nanospheres (PS/AA) added during the preparation of hollow mesoporous carbon-doped gallium trioxide nanospheres in a, b, c, d was 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 hollow mesoporous carbon-doped gallium trioxide nanospheres, when the concentration of the added polystyrene/acrylic nanospheres (PS/AA) is 0.05 mol.L -1 When the pore diameter of the prepared hollow mesoporous carbon doped gallium oxide nanospheres is in the range of 3-10 nm, the distribution is more dispersed; when the concentration of the added polystyrene/acrylic acid nanospheres (PS/AA) is 0.1 mol.L -1 When the pore diameter of the prepared hollow mesoporous carbon doped gallium oxide nanospheres is in the range of 2-8 nm, the distribution is more dispersed; when the concentration of the added polystyrene/acrylic acid nanospheres (PS/AA) is 0.2 mol.L -1 When the hollow mesoporous carbon doped gallium oxide nanospheres are prepared, the aperture of the hollow mesoporous carbon doped gallium oxide nanospheres is in the range of 2-6 nm; when polystyrene/propylene is addedThe concentration of the acid nanospheres (PS/AA) is 0.8mol.L -1 In the process, almost no mesoporous distribution exists in the preparation of nanospheres.
Fig. 4 is an XRD pattern of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1. As can be seen from fig. 4, the XRD pattern of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1 was consistent with that of the standard card.
Fig. 5 is an ultraviolet-visible absorption spectrum of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1. As can be seen from fig. 5, the absorbance of the hollow mesoporous carbon-doped gallium oxide nanospheres prepared in example 1 in the visible light range with the wavelength of 400-800 nm is not high, and the utilization rate of visible light is low; and in the ultraviolet light range with the wavelength range of 200-400 nm, the absorbance is higher, which indicates that the hollow mesoporous carbon-doped gallium trioxide nanospheres 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 trioxide nanospheres prepared in example 1 with a common hollow carbon sphere to support a chiral catalyst cinchona alkaloid derivative (CD-NH) 2 ) Is a comparison of the figures. As can be seen from fig. 6, the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1 were specific for cinchona alkaloid derivatives (CD-NH 2 ) The highest loading of the catalyst can reach 14.2%, and the common hollow carbon sphere is used for preparing cinchona alkaloid derivatives (CD-NH) 2 ) The loading amount of the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 1 can only reach 3.9% after 96 hours, because the pore distribution of the original carbon spheres is changed, and the loading amount is improved.
Likewise, the hollow mesoporous carbon-doped gallium trioxide nanospheres prepared in example 2, example 3 and example 4 were subjected to ultraviolet-visible absorption spectrogram and chiral catalyst cinchona alkaloid derivative (CD-NH) 2 ) The results remain the same as the test results of example 1.
TABLE 1N content before and after carbon doped Digallium trioxide nanosphere adsorption catalyst
Because of the catalyst CD-NH 2 The carbon doped gallium trioxide nanospheres after adsorbing the catalyst can be calculated by measuring the content of the N element by elemental analysis (table 1). And the blank error is 0.01mmol/g before adsorption, and the nitrogen content after adsorption is increased to 0.72mmol/g in a surging manner, so that the catalyst is successfully adsorbed.
Catalytic aldehyde allylation reaction with carbon doped gallium trioxide nanospheres adsorbing catalyst: catalyst (1.39 g,1 mmol) was added to the reaction tube and the tube was evacuated and purged with argon for three substitutions. A solution of freshly distilled toluene (1 mL) was placed in a low temperature reactor at-30℃and benzaldehyde (21.2 mg,0.2mmol,1.0 eq) and pinacol allylborate (40.3 mg,0.24mmol,1.2 eq) were added and reacted for 6h. Purification by silica gel column chromatography [ PE/EA (v/v) =10:1 ] gave a colorless liquid (28.0 mg, yield 96%,96% ee). And the substrate is expanded to obtain better yield and selectivity, as shown in Table 2.
TABLE 2 carbon doped Digallium trioxide nanosphere adsorption catalyst for catalyzing Aldolylating reactions
In summary, the invention provides a preparation method of hollow mesoporous carbon doped gallium trioxide nanospheres, which mainly utilizes a hydrothermal method to enable polystyrene/acrylic nanospheres (PS/AA) to react with gallium nitrate under the action of a surfactant (sodium dodecyl benzene sulfonate), and then the hollow mesoporous carbon doped gallium trioxide nanospheres are obtained through high-temperature calcination. The invention is thatThe preparation method is simple, easy to operate and suitable for the industrialized preparation of the hollow mesoporous carbon-doped gallium trioxide nanospheres. In addition, the invention also discloses a hollow mesoporous carbon-doped gallium trioxide nanosphere, and the crystal form of the hollow mesoporous carbon-doped gallium trioxide nanosphere prepared by the invention is beta-Ga 2 O 3 The hollow mesoporous has spherical morphology (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 mesoporous has the unique properties of large specific surface area, high surface activity, good light absorption performance, strong ultraviolet absorption capability and the like, and is widely applied to the engineering fields of pigment absorption, micro-substance storage and transportation, catalyst loading and the like.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the hollow mesoporous carbon-doped gallium trioxide nanospheres is characterized by comprising the following steps of:
(1) Adding an aqueous solution containing polystyrene/acrylic nanospheres into a container containing potassium nitrate and sodium dodecyl benzene sulfonate under the atmosphere of inert gas, heating to 70-90 ℃ and stirring for 18-24 hours to obtain a mixed solution;
(2) And (3) placing the mixed solution into a reaction kettle, reacting for 12-15 hours at 100-120 ℃ to obtain white powdery solid, centrifugally cleaning, drying, and calcining for 2-5 hours at 600-1000 ℃ in a nitrogen atmosphere to obtain the hollow mesoporous carbon-doped gallium trioxide nanospheres.
2. The preparation method according to claim 1, wherein in the step (1), the aqueous solution containing polystyrene/acrylic nanospheres is specifically: adding polystyrene/acrylic acid nanospheres into the pre-ultrasonic aqueous solution, and stirring to uniformly disperse the polystyrene/acrylic acid nanospheres;
the inert gas is any one or two of nitrogen and argon.
3. The preparation method according to claim 2, wherein the molar volume ratio of the polystyrene/acrylic nanospheres to 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 nanospheres, gallium nitrate and sodium dodecyl benzene sulfonate is 1.5-2:1-1.2:2-5, and mol:mol:g.
5. The method according to claim 1, wherein in the step (2), the lining of the reaction vessel is polytetrafluoroethylene.
6. The method according to claim 1, wherein in the step (2), the centrifugal washing is specifically: and repeatedly cleaning the white powdery solid with acetone under a centrifugal state, and then repeatedly cleaning with absolute ethyl alcohol.
7. The method according to claim 1, wherein in step (2), the drying is performed in particular under a nitrogen atmosphere at 80 ℃ for 2 hours.
8. The hollow mesoporous carbon-doped gallium oxide nanospheres prepared by the preparation method according to any one of claims 1 to 7.
9. The hollow mesoporous carbon doped gallium trioxide 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. Use of the hollow mesoporous carbon-doped gallium oxide nanospheres according to any one of claims 8 to 9 in pigment adsorption or supported catalysts.
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