CN110354835A - Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application - Google Patents
Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application Download PDFInfo
- Publication number
- CN110354835A CN110354835A CN201910562676.2A CN201910562676A CN110354835A CN 110354835 A CN110354835 A CN 110354835A CN 201910562676 A CN201910562676 A CN 201910562676A CN 110354835 A CN110354835 A CN 110354835A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- hollow sphere
- graphene
- silicon dioxide
- nanometer silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 147
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 193
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 95
- 239000002245 particle Substances 0.000 claims abstract description 76
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 67
- 239000006185 dispersion Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 230000000694 effects Effects 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000011246 composite particle Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 83
- 239000004408 titanium dioxide Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 30
- 239000011941 photocatalyst Substances 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- -1 amine compound Chemical class 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000005083 Zinc sulfide Substances 0.000 claims description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- AVBGNFCMKJOFIN-UHFFFAOYSA-N triethylammonium acetate Chemical compound CC(O)=O.CCN(CC)CC AVBGNFCMKJOFIN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims 1
- 229960002050 hydrofluoric acid Drugs 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 14
- 238000013019 agitation Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 241000209094 Oryza Species 0.000 description 11
- 235000007164 Oryza sativa Nutrition 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 235000009566 rice Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000000969 carrier Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007821 HATU Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000013495 cobalt Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AOSAZXDTNNHFSC-UHFFFAOYSA-L [O-]C(C([O-])=O)=O.N.O.[Ti+4] Chemical compound [O-]C(C([O-])=O)=O.N.O.[Ti+4] AOSAZXDTNNHFSC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- MRSOZKFBMQILFT-UHFFFAOYSA-L diazanium;oxalate;titanium(2+) Chemical compound [NH4+].[NH4+].[Ti+2].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O MRSOZKFBMQILFT-UHFFFAOYSA-L 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/23—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to photochemical catalyst field, a kind of hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application are disclosed.Preparation method includes: the spray-dried composite particles for obtaining graphene oxide and coating aminated nano silica of aqueous liquid dispersion that 1) will contain aminated nanometer silicon dioxide particle and graphene oxide；2) it is performed etching using the composite particles that acid coats aminated nano silica to the graphene oxide that step 1) obtains, removes the aminated nanometer silicon dioxide particle in composite particles, obtain hollow sphere graphene oxide carrier.Carrier provided by the invention has three-dimensional hollow spherical structure, can be improved mass transfer velocity, and guarantees that catalyst activity particle receives light irradiation to greatest extent, further improves catalyst performance.
Description
Technical field
The invention belongs to photochemical catalyst fields, and in particular to a kind of hollow sphere graphene oxide carrier, hollow sphere graphene
Carrier, photochemical catalyst and application.
Background technique
Titanium dioxide is a kind of widely used semiconductor light-catalyst, and performance is stablized, and environmental-friendly, forbidden band is wider
(3.0eV or so), the hole on electronics and valence band in conduction have very strong oxidationreduction ability, and degradable major part has
Machine pollutant.But it can only absorb ultraviolet light, and UV energy only accounts for the 5% of solar energy, therefore limit it and individually play
Effectiveness needs to carry out it modification of various modes, generally comprises titanium dioxide body mutually modified and support modification.
Graphene is for one kind by carbon atom with sp2The honeycomb flat film that hybrid form is formed, be it is a kind of only one
The quasi- two-dimensional material of atomic layer level thickness does monoatomic layer graphite so being called, and is that presently found thin and strong degree is maximum, conduction is led
A kind of strongest novel nano-material of hot property.For graphene Theory Conductivity up to 106S/cm, theoretical specific surface area is reachable
2630m2/ g is a kind of ideal carrier material.
A large number of studies show that the performance of titanium dioxide can be greatly improved in the introducing of graphene, it is mainly reflected in four aspects:
1, graphene is as electron acceptor, can rapid dispersion light induced electron, inhibit the compound of light induced electron and hole；2, graphene conduct
Carrier, energy physical absorption organic pollutant, reduces response path；3, graphene can make titanium dioxide and graphite as photosensitizer
The composite material band gap of alkene reduces, and is responded in visible-range, improves the photocatalysis efficiency of titanium dioxide；4, graphene
High surface area so that titanium dioxide granule more dispersed, refined, improve reactivity.
But there are still more problems, for example, inevitably occurring to tire out layer by layer since graphene carrier is planar structure
Long-pending phenomenon, the catalyst granules in lower layer can not see light, cause its performance that cannot play, simultaneous reactions object and product
For Two dimensional mass transfer, process is slow, limits the maximum of catalyst performance and plays.
Therefore, the performance for giving full play to photochemical catalyst is a technical problem to be solved urgently.
Summary of the invention
The purpose of the invention is to overcome reaction mass transfer speed existing for photochemical catalyst in the prior art slow and light
The poor problem of catalytic efficiency performance provides a kind of hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst
And application, the hollow sphere graphene oxide carrier, hollow sphere graphene carrier have three-dimensional hollow spherical structure, can be realized 360 °
Reaction mass transfer, while the spherical structure of carrier can guarantee catalyst activity particle receive to greatest extent light irradiation, into
One step improves the service efficiency of catalyst.
To achieve the goals above, first aspect present invention provides a kind of preparation side of hollow sphere graphene oxide carrier
Method, this method comprises:
1) it obtains the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide is spray-dried
Graphene oxide coats the composite particles of aminated nanometer silicon dioxide particle；
2) composite particles of aminated nanometer silicon dioxide particle are coated to the graphene oxide that step 1) obtains using acid
It performs etching, removes the aminated nanometer silicon dioxide particle in composite particles, obtain hollow sphere graphene oxide carrier.
Preferably, the amido in the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide
The content for changing nanometer silicon dioxide particle is 0.5-10wt%.
Preferably, the oxidation in the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide
The content of graphene is 0.05-5wt%.
Preferably, in step 1), by aminated nanometer silicon dioxide particle aqueous liquid dispersion and aqueous point of graphene oxide
Dispersion liquid be mixed to get described in contain aminated nanometer silicon dioxide particle and graphene oxide aqueous liquid dispersion.
Preferably, the aminated nanometer silicon dioxide particle by by nanometer silicon dioxide particle and amine compound into
Row haptoreaction and obtain.
Preferably, the amine compound is selected from N- methanediamine, ethylenediamine, N, N- dimethyl cyclohexyl amine, methylamine, benzene
One of amine, cyclohexylamine, hexamethylene diamine, ethylamine hydrochloride and acetate triethylamine are a variety of.
Preferably, the partial size of the nanometer silicon dioxide particle is 0.01-1 μm.
Preferably, in the haptoreaction of the nanometer silicon dioxide particle and amine compound, amine compound and nanometer
The mass ratio of silica dioxide granule is 1:(5-20).
Preferably, the solvent in the aminated nanometer silicon dioxide particle aqueous liquid dispersion be selected from water, methanol, ethyl alcohol,
Isopropanol, ethylene glycol, n-butanol, glycerine, N,N-dimethylformamide, tetrahydrofuran or N-Methyl pyrrolidone.
Preferably, the acid is hydrofluoric acid.
Second aspect, the present invention provides the hollow sphere graphene oxide carriers as made from method of the invention.
The third aspect, the present invention provides a kind of hollow sphere graphene carriers, by the way that hollow sphere of the invention is aoxidized stone
Black alkene carrier obtains the hollow sphere graphene carrier through hydrothermal reduction.
Preferably, it is 100-300 DEG C that the condition of the hydrothermal reduction, which includes: reaction temperature, reaction time 120-
720min。
Fourth aspect, the present invention provides a kind of photochemical catalyst, the photochemical catalyst includes hollow sphere graphite of the invention
Alkene carrier and the photocatalyst activity component being supported on hollow sphere graphene carrier.
Preferably, the mass ratio of the photocatalyst activity component and graphene is 1:(0.05-9.9).
Preferably, the photocatalyst activity group be divided into titanium dioxide, zinc oxide, cobaltosic oxide, di-iron trioxide,
One of platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide are a variety of.
Preferably, the photocatalyst activity group is divided into titanium dioxide.
5th aspect, the present invention provides a kind of preparation methods of photochemical catalyst, by hollow sphere graphite oxide of the invention
Alkene carrier and catalyst activity component are made through hydrothermal reduction.
Preferably, it is 100-300 DEG C that the condition of the hydrothermal reduction, which includes: reaction temperature, reaction time 120-
720min。
Preferably, the photocatalyst activity group be divided into titanium dioxide, zinc oxide, cobaltosic oxide, di-iron trioxide,
One of platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide are a variety of.
Preferably, the photocatalyst activity group be divided into titanium dioxide, zinc oxide, cobaltosic oxide, di-iron trioxide,
Platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide presoma.
Preferably, the photocatalyst activity group is divided into titanium dioxide.
Preferably, the presoma of the titanium dioxide is butyl titanate, titanium sulfate, titanium trichloride, titanium tetrachloride, oxalic acid
Oxygen titanium ammonium, titanium tetrafluoride or Titanium Nitrate.
6th aspect, the present invention provides hollow sphere graphene carriers of the invention to prepare the application in photochemical catalyst.
Hollow sphere graphene oxide carrier provided by the invention, hollow sphere graphene carrier have three-dimensional hollow spherical structure,
It can be realized 360 ° of reaction mass transfer, while the spherical structure of carrier can guarantee that catalyst activity particle receives to greatest extent
Light irradiation, further improves the service efficiency of catalyst.
Specifically, the present invention have it is following the utility model has the advantages that
1, the present invention realizes graphene oxide to the cladding of nanometer silicon dioxide particle using spray drying, and efficiency is higher,
And covered effect is good, the particle dispersion of generation is good, is suitable for mass production；
2, the present invention is overcome photochemical catalyst and is received light by the way of the graphene-supported titanium dioxide of three-dimensional hollow sphere
The problem that photocatalysis efficiency caused by scarce capacity is low and mass transfer velocity is slow, significantly improves the catalytic effect of photochemical catalyst.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the preparation method schematic diagram of hollow sphere graphene oxide carrier；
Fig. 2 is the electromicroscopic photograph of the clad structure of the nano silica and graphene oxide in the embodiment of the present application 1；
Fig. 3 is the electromicroscopic photograph of the hollow ball structure in the embodiment of the present application 1；
Fig. 4 is the catalytic effect schematic diagram of the catalyst of the embodiment of the present application 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As shown in Figure 1, in a first aspect, the present invention provides a kind of preparation method of hollow sphere graphene oxide carrier, the party
Method includes:
1) it obtains the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide is spray-dried
Graphene oxide coats the composite particles of aminated nanometer silicon dioxide particle；
2) composite particles of aminated nanometer silicon dioxide particle are coated to the graphene oxide that step 1) obtains using acid
It performs etching, removes the aminated nanometer silicon dioxide particle in composite particles, obtain hollow sphere graphene oxide carrier.
The present invention is by being prepared into three-dimensional hollow spherical structure for carrier, to realize 360 ° of reaction in the photocatalytic process
Mass transfer, and guarantee that catalyst activity particle receives light to the maximum extent and irradiates using the spherical structure of carrier, and then improve
The service efficiency of catalyst.
In the method for the invention, in order to guarantee obtain three-dimensional hollow sphere structural intergrity, it is preferable that it is described to contain amine
The content of aminated nanometer silicon dioxide particle in the aqueous liquid dispersion of base nanometer silicon dioxide particle and graphene oxide
For 0.5-10wt%；It is highly preferred that the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide
In aminated nanometer silicon dioxide particle content be 0.5-5wt%.
In the method for the invention, in order to guarantee obtain three-dimensional hollow sphere structural intergrity, it is preferable that it is described to contain amine
The content of graphene oxide in the aqueous liquid dispersion of base nanometer silicon dioxide particle and graphene oxide is 0.05-5wt%；
It is highly preferred that the graphene oxide in the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide
Content be 0.5-3wt%.
In the method for the invention, it is preferable that in step 1), by aminated nanometer silicon dioxide particle aqueous liquid dispersion and
Graphene oxide aqueous liquid dispersion be mixed to get described in containing aminated nanometer silicon dioxide particle and graphene oxide
Aqueous liquid dispersion.
In the method for the invention, it is preferable that the aminated nanometer silicon dioxide particle by by particle with it is aminated
Object is closed to carry out haptoreaction and obtain.
For above-mentioned amine compound, there is no particular limitation, can be realized amido introducing nano silica,
In the method for the invention, it is preferable that the amine compound be selected from N- methanediamine, ethylenediamine, N, N- dimethyl cyclohexyl amine,
One of methylamine, aniline, cyclohexylamine, hexamethylene diamine, ethylamine hydrochloride and acetate triethylamine are a variety of.
For above-mentioned nanometer silicon dioxide particle, there is no particular limitation, in order to further ensure obtained hollow balloon borne
The performance of body, it is preferable that the partial size of the nanometer silicon dioxide particle is 0.01-1 μm；It is highly preferred that the nanometer titanium dioxide
The partial size of silicon particle is 0.05-0.5 μm.
For the solvent in above-mentioned aqueous liquid dispersion, there is no particular limitation, can be realized aminated nano silica
Grain is evenly dispersed, in the method for the invention, it is preferable that the solvent in the aqueous liquid dispersion is selected from water, methanol, second
In alcohol, isopropanol, ethylene glycol, n-butanol, glycerine, N,N-dimethylformamide, tetrahydrofuran and N-Methyl pyrrolidone
It is one or more；It is highly preferred that the solvent in the aqueous liquid dispersion is water.
Process of the present invention it is preferred in the haptoreaction of ground, the nanometer silicon dioxide particle and amine compound, amine
The mass ratio of based compound and nanometer silicon dioxide particle is 1:(5-20)；It is highly preferred that the nanometer silicon dioxide particle with
In the haptoreaction of amine compound, the mass ratio of amine compound and nanometer silicon dioxide particle is 1:(10-20).
Preferably, the haptoreaction of the nanometer silicon dioxide particle and amine compound in the presence of aqueous solvent into
Row, the aqueous solvent are selected from methanol, ethyl alcohol, isopropanol, ethylene glycol, n-butanol, glycerine, n,N-Dimethylformamide, four
One of hydrogen furans and N-Methyl pyrrolidone are a variety of；It is highly preferred that the aqueous solvent is n,N-Dimethylformamide.
For above-mentioned steps 2) in acid be not particularly limited, can in wet etching common various acid,
In the method for invention, it is preferable that the acid is hydrofluoric acid.
For the concentration of above-mentioned acid, also there is no particular limitation, can be realized the aminated nanometer two in removal composite particles
Silicon oxide particle, in the method for the invention, it is preferable that the concentration of the acid is 5-15wt%.
Second aspect, the present invention provides the hollow sphere graphene oxide carriers as made from method of the invention.
The third aspect, the present invention provides a kind of hollow sphere graphene carriers, by the way that hollow sphere of the invention is aoxidized stone
Black alkene carrier obtains the hollow sphere graphene carrier through hydrothermal reduction.
In the present invention, it is preferred to it is 100-300 DEG C that the condition of the hydrothermal reduction, which includes: reaction temperature, the reaction time
For 120-720min；It is highly preferred that it is 120-250 DEG C that the condition of the hydrothermal reduction, which includes: reaction temperature, the reaction time is
150-450min。
Fourth aspect, the present invention provides a kind of photochemical catalyst, the photochemical catalyst includes hollow sphere graphite of the invention
Alkene carrier and the photocatalyst activity component being supported on hollow sphere graphene carrier.
In the present invention, it is preferred to which the mass ratio of the photocatalyst activity component and graphene is 1:(0.05-9.9)；
It is highly preferred that the mass ratio of the photocatalyst activity component and graphene is 1:(0.1-9).
In the present invention, it is preferred to which the photocatalyst activity group is divided into titanium dioxide, zinc oxide, cobaltosic oxide, three
Aoxidize one of two iron, platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide or a variety of.
In the present invention, it is preferred to which the photocatalyst activity group is divided into titanium dioxide.
5th aspect, the present invention provides a kind of preparation methods of photochemical catalyst, by hollow sphere graphite oxide of the invention
Alkene carrier and catalyst activity component are made through hydrothermal reduction.
In the method for the invention, it is preferable that the condition of the hydrothermal reduction includes: that reaction temperature is 100-300 DEG C, instead
It is 120-720min between seasonable；It is highly preferred that it is 120-250 DEG C, when reaction that the condition of the hydrothermal reduction, which includes: reaction temperature,
Between be 150-450min.
In the method for the invention, it is preferable that the photocatalyst activity group is divided into titanium dioxide, zinc oxide, four oxidations
One of three cobalts, di-iron trioxide, platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide are a variety of.
In the method for the invention, it is preferable that the photocatalyst activity group is divided into titanium dioxide, zinc oxide, four oxidations
Three cobalts, di-iron trioxide, platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide presoma.
In the method for the invention, it is preferable that the photocatalyst activity group is divided into titanium dioxide.
In the method for the invention, it is preferable that the presoma of the titanium dioxide is butyl titanate, titanium sulfate, trichlorine
Change titanium, titanium tetrachloride, ammonium titanyl oxalate, titanium tetrafluoride or Titanium Nitrate.
6th aspect, the present invention provides hollow sphere graphene carriers of the invention to prepare the application in photochemical catalyst.
The present invention will be described in detail by way of examples below.It is unless otherwise instructed, used in following embodiment
Each material can be commercially available, and unless otherwise instructed, method used is the conventional method of this field.
Following nano graphite powders used in the examples, D50 < 50nm, Aladdin
Cell disruptor ultrasound: model JY98-IIIN, the new sesame in Ningbo
Spray dryer: model B-90, Japan's step are rugged
Embodiment 1
Step 1 prepares aminated nanometer silicon dioxide particle dispersion liquid
Taking 0.5g average grain diameter is the nanometer silicon dioxide particle of 200nm, is dispersed in 500ml N, N- dimethyl methyl
In amide (DMF), 0.05g ethylenediamine is added after ultrasonic disperse, continues ultrasonic machine and disperses 1 hour, 2mg HATU is added, will react
Container is transferred to 60 DEG C of water-baths and after the continuous reaction of reflux environment relaying 6 hour, is centrifugated product, and with after ethanol washing 6 times
Vacuum drying 12 hours at 50 DEG C, obtain aminated nanometer silicon dioxide particle.
By aminated nanometer silicon dioxide particle 0.5g ultrasonic disperse in 100ml water, forms the aminated of 0.5wt% and receive
Rice silica aqueous dispersion.
Step 2 prepares graphene oxide aqueous liquid dispersion
Graphene oxide is prepared using Hummers method is improved
Reaction vessel is placed in ice-water bath after taking 4g nano graphite powder and 3g sodium nitrate to mix, under magnetic stirring plus
Enter the 200ml concentrated sulfuric acid, be sufficiently mixed uniformly, then point 5 addition 25g potassium hyperchlorates and 15g potassium permanganate, control temperature does not surpass
20 DEG C are crossed, after stirring a period of time, reaction vessel is placed under room temperature (25 DEG C), continues stirring and continues for 24 hours.Under agitation
It is slowly added to 300ml deionized water, temperature is controlled at 98 DEG C, and after stirring 120min, the hydrogen peroxide of 100ml 30%, reaction is added
After sixty minutes, it is washed with 5wt%HCl solution and deionized water until separating liquid is in neutrality, then by filtration product at 90 DEG C
Vacuum drying.
Above-mentioned filtration product 0.5g is dispersed in 500ml deionized water, 0.05g polyvinylpyrrolidone is added, uses 1kw
Above cell disruptor ultrasound 120min, obtains graphene oxide aqueous liquid dispersion.
Step 3 prepares the composite particles that graphene oxide coats aminated nano silica
By 100ml nano silica aqueous solution made from step 1 and 100ml graphene oxide aqueous liquid dispersion, receive
The quality of rice silica and graphene oxide is 5:1, sufficiently after ultrasonic agitation that mixed liquor is spray-dried, is provided with spray
The inlet temperature of mist drying machine is 160 DEG C, and outlet temperature is 120 DEG C, and drying time is set as 1.5s.Fig. 2 is nanometer titanium dioxide
The electromicroscopic photograph of the clad structure of silicon and graphene oxide, it can be observed that the clad structure is in the spherical shape of uniform particle sizes.
Step 4 preparation has the graphene oxide spherical housing of hollow structure
The hydrofluoric acid solution that 100ml concentration is 10wt% is poured into graphene oxide made from step 3 and coats aminated receive
In the composite particles of rice silica, after magnetic agitation 24 hours, then centrifugal filtration uses deionized water with ethanol washing 2 times
Washing is until filtrate pH is 7 repeatedly.Fig. 3 is the electromicroscopic photograph of hollow ball structure.
Step 5 prepares hollow sphere graphene-titanium dioxide composite photocatalyst
Ethyl alcohol, each 100ml of isopropanol are poured into 500ml beaker, stirring and each 60min of ultrasonic disperse weigh metatitanic acid four
Butyl ester quality 0.5g stirs each 60min of ultrasonic disperse, and graphene oxide hollow sphere 0.5g is added, and stirring and ultrasonic disperse are each
60min is subsequently filled into high-temperature high-pressure reaction kettle, and 360min is reacted at 200 DEG C, and (graphene oxide is completed at high temperature under high pressure
Deoxidation, while butyl titanate hydrolyzes at high temperature under high pressure, and is precipitated on the surface of graphene), after the reaction was completed, to filtration product
It is adequately washed, and 60 DEG C drying 12 hours in an oven, completes preparation, wherein titanium dioxide and graphene mass ratio
For 1:4.
Photocatalysis performance test:
It degrades under visible light, using 50mg/L ammonia nitrogen and the organic phosphorus aqueous solution of 5mg/L, measures titanium dioxide, graphene
Photocatalysis performance of the photochemical catalyst in 10 hours, test result made from composite titanium dioxide and above-described embodiment 1 are shown in figure
4。
As shown in Figure 4: being imitated using the photocatalysis of hollow sphere graphene-titanium dioxide composite photocatalyst provided by the invention
Rate is higher than the 33% of lamellar structure graphene composite titanium dioxide, and showing can be significant using the hollow ball structure carrier of the application
Improve the catalytic efficiency of photochemical catalyst.
Embodiment 2
Step 1 prepares aminated nanometer silicon dioxide particle dispersion liquid
Taking 0.5g average grain diameter is the nanometer silicon dioxide particle of 200nm, is dispersed in 500ml N, N- dimethyl methyl
In amide (DMF), 0.05g ethylenediamine is added after ultrasonic disperse, continues ultrasonic machine and disperses 1 hour, 2mg HATU is added, will react
Container is transferred to 60 DEG C of water-baths and after the continuous reaction of reflux environment relaying 6 hour, is centrifugated product, and with after ethanol washing 6 times
Vacuum drying 12 hours at 50 DEG C, obtain aminated nanometer silicon dioxide particle.
By aminated nanometer silicon dioxide particle 0.4g ultrasonic disperse in 100ml water, forms the aminated of 0.4wt% and receive
Rice silica aqueous dispersion.
Step 2 prepares graphene oxide aqueous liquid dispersion
Graphene oxide is prepared using Hummers method is improved
Reaction vessel is placed in ice-water bath after taking 4g nano graphite powder and 3g sodium nitrate to mix, under magnetic stirring plus
Enter the 200ml concentrated sulfuric acid, be sufficiently mixed uniformly, then point 5 addition 25g potassium hyperchlorates and 15g potassium permanganate, control temperature does not surpass
20 DEG C are crossed, after stirring a period of time, reaction vessel is placed under room temperature (25 DEG C), continues stirring and continues for 24 hours.Under agitation
It is slowly added to 300ml deionized water, temperature is controlled at 98 DEG C, and after stirring 120min, the hydrogen peroxide of 100ml 30%, reaction is added
After sixty minutes, it is washed with 5wt%HCl solution and deionized water until separating liquid is in neutrality, then by filtration product at 90 DEG C
Vacuum drying.
Above-mentioned filtration product 0.5g is dispersed in 500ml deionized water, 0.05g polyvinylpyrrolidone is added, uses 1kw
Above cell disruptor ultrasound 120min, obtains graphene oxide aqueous liquid dispersion.
Step 3 prepares the composite particles that graphene oxide coats aminated nano silica
By 100ml nano silica aqueous solution made from step 1 and 100ml graphene oxide aqueous liquid dispersion, receive
The quality of rice silica and graphene oxide is 4:1, sufficiently after ultrasonic agitation that mixed liquor is spray-dried, is provided with spray
The inlet temperature of mist drying machine is 160 DEG C, and outlet temperature is 120 DEG C, and drying time is set as 1.5s.Confirmation oxygen is observed through Electronic Speculum
Graphite alkene is uniformly coated on silica surface.
Step 4 preparation has the graphene oxide spherical housing of hollow structure
The hydrofluoric acid solution that 100ml concentration is 10wt% is poured into graphene oxide made from step 3 and coats aminated receive
In the composite particles of rice silica, after magnetic agitation 24 hours, then centrifugal filtration uses deionized water with ethanol washing 2 times
Washing is until filtrate pH is 7 repeatedly.Confirm it with hollow ball structure by Electronic Speculum.
Step 5 prepares hollow sphere graphene-titanium dioxide composite photocatalyst
Ethyl alcohol, each 100ml of isopropanol are poured into 500ml beaker, stirring and each 60min of ultrasonic disperse weigh metatitanic acid four
Butyl ester quality 2g stirs each 60min of ultrasonic disperse, and graphene oxide hollow sphere 0.5g is added, and stirring and ultrasonic disperse are each
60min is subsequently filled into high-temperature high-pressure reaction kettle, and 360min is reacted at 200 DEG C, and (graphene oxide is completed at high temperature under high pressure
Deoxidation, while butyl titanate hydrolyzes at high temperature under high pressure, and is precipitated on the surface of graphene), after the reaction was completed, to filtration product
It is adequately washed, and 60 DEG C drying 12 hours in an oven, completes preparation, wherein titanium dioxide and graphene mass ratio
For 1:1.
Photocatalysis performance test:
It is tested using condition same as Example 1, as a result: use hollow sphere graphene provided by the invention
The photocatalysis efficiency of composite titanium dioxide photocatalyst is higher than the 15% of lamellar structure graphene composite titanium dioxide.
Embodiment 3
Step 1 prepares aminated nanometer silicon dioxide particle dispersion liquid
Taking 0.5g average grain diameter is the nanometer silicon dioxide particle of 200nm, is dispersed in 500ml N, N- dimethyl methyl
In amide (DMF), 0.05g ethylenediamine is added after ultrasonic disperse, continues ultrasonic machine and disperses 1 hour, 2mgHATU is added, will react
Container is transferred to 60 DEG C of water-baths and after the continuous reaction of reflux environment relaying 6 hour, is centrifugated product, and with after ethanol washing 6 times
Vacuum drying 12 hours at 50 DEG C, obtain aminated nanometer silicon dioxide particle.
By aminated nanometer silicon dioxide particle 1g ultrasonic disperse in 100ml water, the aminated nanometer two of 1wt% is formed
Silica aqueous dispersions.
Step 2 prepares graphene oxide aqueous liquid dispersion
Graphene oxide is prepared using Hummers method is improved
Reaction vessel is placed in ice-water bath after taking 4g nano graphite powder and 3g sodium nitrate to mix, under magnetic stirring plus
Enter the 200ml concentrated sulfuric acid, be sufficiently mixed uniformly, then point 5 addition 25g potassium hyperchlorates and 15g potassium permanganate, control temperature does not surpass
20 DEG C are crossed, after stirring a period of time, reaction vessel is placed under room temperature (25 DEG C), continues stirring and continues for 24 hours.Under agitation
It is slowly added to 300ml deionized water, temperature is controlled at 98 DEG C, and after stirring 120min, the hydrogen peroxide of 100ml 30%, reaction is added
After sixty minutes, it is washed with 5wt%HCl solution and deionized water until separating liquid is in neutrality, then by filtration product at 90 DEG C
Vacuum drying.
Above-mentioned filtration product 0.8g is dispersed in 500ml deionized water, 0.05g polyvinylpyrrolidone is added, uses 1kw
Above cell disruptor ultrasound 120min, obtains graphene oxide aqueous liquid dispersion.
Step 3 prepares the composite particles that graphene oxide coats aminated nano silica
By 100ml nano silica aqueous solution made from step 1 and 100ml graphene oxide aqueous liquid dispersion, receive
The quality of rice silica and graphene oxide is 6.25:1, sufficiently after ultrasonic agitation that mixed liquor is spray-dried, wherein setting
The inlet temperature for setting spray dryer is 160 DEG C, and outlet temperature is 120 DEG C, and drying time is set as 1.5s.It is true through Electronic Speculum observation
Recognize graphene oxide and is uniformly coated on silica surface.
Step 4 preparation has the graphene oxide spherical housing of hollow structure
The hydrofluoric acid solution that 100ml concentration is 10wt% is poured into graphene oxide made from step 3 and coats aminated receive
In the composite particles of rice silica, after magnetic agitation 24 hours, then centrifugal filtration uses deionized water with ethanol washing 2 times
Washing is until filtrate pH is 7 repeatedly.Confirm it with hollow ball structure by Electronic Speculum.
Step 5 prepares hollow sphere graphene-titanium dioxide composite photocatalyst
Ethyl alcohol, each 100ml of isopropanol are poured into 500ml beaker, stirring and each 60min of ultrasonic disperse weigh metatitanic acid four
Butyl ester quality 0.5g stirs each 60min of ultrasonic disperse, and graphene oxide hollow sphere 1.1g is added, and stirring and ultrasonic disperse are each
60min is subsequently filled into high-temperature high-pressure reaction kettle, and 360min is reacted at 200 DEG C, and (graphene oxide is completed at high temperature under high pressure
Deoxidation, while butyl titanate hydrolyzes at high temperature under high pressure, and is precipitated on the surface of graphene), after the reaction was completed, to filtration product
It is adequately washed, and 60 DEG C drying 12 hours in an oven, completes preparation, wherein titanium dioxide and graphene mass ratio
For 1:9.
Photocatalysis performance test:
It is tested using condition same as Example 1, as a result: use hollow sphere graphene provided by the invention
The photocatalysis efficiency of composite titanium dioxide photocatalyst is higher than the 20% of lamellar structure graphene composite titanium dioxide.
Embodiment 4
Step 1 prepares aminated nanometer silicon dioxide particle dispersion liquid
Taking 0.5g average grain diameter is the nanometer silicon dioxide particle of 200nm, is dispersed in 500ml N, N- dimethyl methyl
In amide (DMF), 0.05g ethylenediamine is added after ultrasonic disperse, continues ultrasonic machine and disperses 1 hour, 2mgHATU is added, will react
Container is transferred to 60 DEG C of water-baths and after the continuous reaction of reflux environment relaying 6 hour, is centrifugated product, and with after ethanol washing 6 times
Vacuum drying 12 hours at 50 DEG C, obtain aminated nanometer silicon dioxide particle.
By aminated nanometer silicon dioxide particle 0.4g ultrasonic disperse in 100ml water, forms the aminated of 0.4wt% and receive
Rice silica aqueous dispersion.
Step 2 prepares graphene oxide aqueous liquid dispersion
Graphene oxide is prepared using Hummers method is improved
Reaction vessel is placed in ice-water bath after taking 4g nano graphite powder and 3g sodium nitrate to mix, under magnetic stirring plus
Enter the 200ml concentrated sulfuric acid, be sufficiently mixed uniformly, then point 5 addition 25g potassium hyperchlorates and 15g potassium permanganate, control temperature does not surpass
20 DEG C are crossed, after stirring a period of time, reaction vessel is placed under room temperature (25 DEG C), continues stirring and continues for 24 hours.Under agitation
It is slowly added to 300ml deionized water, temperature is controlled at 98 DEG C, and after stirring 120min, the hydrogen peroxide of 100ml 30%, reaction is added
After sixty minutes, it is washed with 5wt%HCl solution and deionized water until separating liquid is in neutrality, then by filtration product at 90 DEG C
Vacuum drying.
Above-mentioned filtration product 0.4g is dispersed in 500ml deionized water, 0.05g polyvinylpyrrolidone is added, uses 1kw
Above cell disruptor ultrasound 120min, obtains graphene oxide aqueous liquid dispersion.
Step 3 prepares the composite particles that graphene oxide coats aminated nano silica
By 100ml nano silica aqueous solution made from step 1 and 100ml graphene oxide aqueous liquid dispersion, receive
The quality of rice silica and graphene oxide is 5:1, sufficiently after ultrasonic agitation that mixed liquor is spray-dried, is provided with spray
The inlet temperature of mist drying machine is 160 DEG C, and outlet temperature is 120 DEG C, and drying time is set as 1.5s.Confirmation oxygen is observed through Electronic Speculum
Graphite alkene is uniformly coated on silica surface.
Step 4 preparation has the graphene oxide spherical housing of hollow structure
The hydrofluoric acid solution that 100ml concentration is 15wt% is poured into graphene oxide made from step 3 and coats aminated receive
In the composite particles of rice silica, after magnetic agitation 24 hours, then centrifugal filtration uses deionized water with ethanol washing 2 times
Washing is until filtrate pH is 7 repeatedly.Confirm it with hollow ball structure by Electronic Speculum.
Step 5 prepares hollow sphere graphene-titanium dioxide composite photocatalyst
Ethyl alcohol, each 100ml of isopropanol are poured into 500ml beaker, stirring and each 60min of ultrasonic disperse weigh metatitanic acid four
Butyl ester quality 0.5g stirs each 60min of ultrasonic disperse, and graphene oxide hollow sphere 0.5g is added, and stirring and ultrasonic disperse are each
60min is subsequently filled into high-temperature high-pressure reaction kettle, and 360min is reacted at 200 DEG C, and (graphene oxide is completed at high temperature under high pressure
Deoxidation, while butyl titanate hydrolyzes at high temperature under high pressure, and is precipitated on the surface of graphene), after the reaction was completed, to filtration product
It is adequately washed, and 60 DEG C drying 12 hours in an oven, completes preparation, wherein titanium dioxide and graphene mass ratio
For 1:4.
Photocatalysis performance test:
It is tested using condition same as Example 1, as a result: use hollow sphere graphene provided by the invention
The photocatalysis efficiency of composite titanium dioxide photocatalyst is higher than the 25% of lamellar structure graphene composite titanium dioxide.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (16)
1. a kind of preparation method of hollow sphere graphene oxide carrier, which is characterized in that this method comprises:
1) it is aoxidized the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide is spray-dried
The composite particles of the aminated nanometer silicon dioxide particle of graphene coated；
2) it is carried out using the composite particles that acid coats aminated nanometer silicon dioxide particle to the graphene oxide that step 1) obtains
Etching removes the aminated nanometer silicon dioxide particle in composite particles, obtains hollow sphere graphene oxide carrier.
2. the preparation method of hollow sphere graphene oxide carrier according to claim 1, which is characterized in that described to contain amine
The content of aminated nanometer silicon dioxide particle in the aqueous liquid dispersion of base nanometer silicon dioxide particle and graphene oxide
For 0.5-10wt%；
Preferably, the graphite oxide in the aqueous liquid dispersion containing aminated nanometer silicon dioxide particle and graphene oxide
The content of alkene is 0.05-5wt%.
3. the preparation method of hollow sphere graphene oxide carrier according to claim 1 or 2, which is characterized in that step 1)
In, by aminated nanometer silicon dioxide particle aqueous liquid dispersion and graphene oxide aqueous liquid dispersion be mixed to get described in contain
There is the aqueous liquid dispersion of aminated nanometer silicon dioxide particle and graphene oxide；
Preferably, the aminated nanometer silicon dioxide particle is by connecing nanometer silicon dioxide particle and amine compound
Touching reaction obtains；
Preferably, the amine compound is selected from N- methanediamine, ethylenediamine, N, N- dimethyl cyclohexyl amine, methylamine, aniline, ring
One of hexylamine, hexamethylene diamine, ethylamine hydrochloride and acetate triethylamine are a variety of；
Preferably, the partial size of the nanometer silicon dioxide particle is 0.01-1 μm.
4. the preparation method of hollow sphere graphene oxide carrier according to claim 3, which is characterized in that the nanometer two
In the haptoreaction of silicon oxide particle and amine compound, the mass ratio of amine compound and nanometer silicon dioxide particle is 1:
(5-20)。
5. the preparation method of hollow sphere graphene oxide carrier according to claim 3, which is characterized in that described aminated
Solvent in nanometer silicon dioxide particle aqueous liquid dispersion be selected from methanol, ethyl alcohol, isopropanol, ethylene glycol, n-butanol, glycerine,
N,N-dimethylformamide, tetrahydrofuran or N-Methyl pyrrolidone.
6. the preparation method of hollow sphere graphene oxide carrier according to claim 1, which is characterized in that the acid is hydrogen
Fluoric acid.
7. hollow sphere graphene oxide carrier made from the method as described in any one of claim 1-6.
8. a kind of hollow sphere graphene carrier, which is characterized in that by carrying hollow sphere graphene oxide as claimed in claim 7
Body obtains the hollow sphere graphene carrier through hydrothermal reduction.
9. hollow sphere graphene carrier according to claim 8, which is characterized in that the condition of the hydrothermal reduction includes:
Reaction temperature is 100-300 DEG C, reaction time 120-720min.
10. a kind of photochemical catalyst, which is characterized in that the photochemical catalyst includes hollow sphere graphene described in claim 8 or 9
Carrier and the photocatalyst activity component being supported on hollow sphere graphene carrier；
Preferably, the mass ratio of the photocatalyst activity component and graphene is 1:(0.05-9.9).
11. photochemical catalyst according to claim 10, which is characterized in that the photocatalyst activity group is divided into titanium dioxide
One of titanium, zinc oxide, cobaltosic oxide, di-iron trioxide, platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide are a variety of；
Preferably, the photocatalyst activity group is divided into titanium dioxide.
12. a kind of preparation method of photochemical catalyst, which is characterized in that carry hollow sphere graphene oxide as claimed in claim 7
Body and catalyst activity component are made through hydrothermal reduction.
13. preparation method according to claim 12, which is characterized in that the condition of the hydrothermal reduction includes: reaction temperature
Degree is 100-300 DEG C, reaction time 120-720min.
14. preparation method according to claim 12, which is characterized in that the photocatalyst activity group is divided into titanium dioxide
One of titanium, zinc oxide, cobaltosic oxide, di-iron trioxide, platinum, ruthenium, palladium, zinc sulphide or cadmium sulfide are a variety of；
Preferably, the photocatalyst activity group be divided into titanium dioxide, zinc oxide, cobaltosic oxide, di-iron trioxide, platinum, ruthenium,
The presoma of palladium, zinc sulphide or cadmium sulfide.
15. preparation method according to claim 14, which is characterized in that the photocatalyst activity group is divided into titanium dioxide
Titanium；
Preferably, the presoma of the titanium dioxide is butyl titanate, titanium sulfate, titanium trichloride, titanium tetrachloride, titanium oxyoxalate
Ammonium, titanium tetrafluoride or Titanium Nitrate.
16. hollow sphere graphene carrier described in claim 8 or 9 is preparing the application in photochemical catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910562676.2A CN110354835A (en) | 2019-06-26 | 2019-06-26 | Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910562676.2A CN110354835A (en) | 2019-06-26 | 2019-06-26 | Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110354835A true CN110354835A (en) | 2019-10-22 |
Family
ID=68217054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910562676.2A Pending CN110354835A (en) | 2019-06-26 | 2019-06-26 | Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110354835A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056550A (en) * | 2019-11-20 | 2020-04-24 | 武汉理工大学 | Preparation method of graphene oxide/organic hollow silicon dioxide nanocomposite |
| CN111905807A (en) * | 2020-07-06 | 2020-11-10 | 安徽理工大学 | High instantaneous photocurrent nanometer TiO2Polyaniline/graphene composite material and preparation method thereof |
| CN113894282A (en) * | 2021-10-21 | 2022-01-07 | 上海交通大学 | Nano fluid stably dispersed at medium and high temperature and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437494A (en) * | 2014-12-08 | 2015-03-25 | 华东理工大学 | Fenton-like catalyst of graphene coated ferriferrous oxide (Fe3O4) micro-spheres as well as preparation method and application thereof |
| CN109833862A (en) * | 2019-01-22 | 2019-06-04 | 太原理工大学 | A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material |
-
2019
- 2019-06-26 CN CN201910562676.2A patent/CN110354835A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437494A (en) * | 2014-12-08 | 2015-03-25 | 华东理工大学 | Fenton-like catalyst of graphene coated ferriferrous oxide (Fe3O4) micro-spheres as well as preparation method and application thereof |
| CN109833862A (en) * | 2019-01-22 | 2019-06-04 | 太原理工大学 | A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material |
Non-Patent Citations (1)
| Title |
|---|
| 张福学等: "《无驱动结构微机械陀螺及其应用》", 31 December 2013, 国防工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056550A (en) * | 2019-11-20 | 2020-04-24 | 武汉理工大学 | Preparation method of graphene oxide/organic hollow silicon dioxide nanocomposite |
| CN111056550B (en) * | 2019-11-20 | 2023-02-28 | 武汉理工大学 | Preparation method of graphene oxide/organic hollow silicon dioxide nanocomposite |
| CN111905807A (en) * | 2020-07-06 | 2020-11-10 | 安徽理工大学 | High instantaneous photocurrent nanometer TiO2Polyaniline/graphene composite material and preparation method thereof |
| CN113894282A (en) * | 2021-10-21 | 2022-01-07 | 上海交通大学 | Nano fluid stably dispersed at medium and high temperature and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105498821B (en) | It is a kind of for composite material of catalytic degradation nitrogen oxides and its preparation method and application | |
| CN110354835A (en) | Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application | |
| CN105056929B (en) | A kind of graphene/titania composite material with tiny balloon shape and preparation method thereof | |
| CN103803643A (en) | Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof | |
| CN107754785B (en) | Graphene-manganese oxide composite catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method thereof | |
| CN104003368A (en) | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof | |
| CN101284227B (en) | Alumina group/nano titanium dioxide-nucleus/shell structure composite microballoons and preparation method thereof | |
| CN106000474B (en) | A kind of porphyrin/titanium dioxide uniformly organizes the preparation method and applications of nanosphere altogether | |
| CN105289433A (en) | Method for large-scale preparation of transition metal oxide porous microsphere | |
| CN103894218A (en) | Titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine and preparation method of material | |
| CN103041872B (en) | The preparation method of the porous silica microballoon of supported noble metals | |
| CN105312051A (en) | Nano gold-mesoporous silica composite nanotube, preparation and applications thereof | |
| CN105237586A (en) | Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn) | |
| CN107572509B (en) | Nitrogen-doped hollow carbon/graphite nodule nano material and preparation method thereof | |
| CN102020283A (en) | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter | |
| CN108837827A (en) | A kind of bilayer core-shell structure platinum catalyst and its preparation method and application | |
| CN103143359A (en) | Magnetic recyclable hollow TiO2-SiO2-CoFe2O4 nano photocatalytic material and preparation method thereof | |
| CN102718255B (en) | Preparation method of titanium dioxide hollow nano structure | |
| CN109603760B (en) | Magnetic nano material NiFe for adsorbing tetracycline hydrochloride2O4Preparation method of @ N-C | |
| CN109574069B (en) | Carbon quantum dot induced titanium dioxide hierarchical nanostructure and preparation method thereof | |
| CN107792888A (en) | A kind of high-specific surface area ZnCo2O4Preparation method | |
| CN107116228A (en) | A kind of method that solid phase reduction prepares extra-fine nickel powder | |
| CN110950421A (en) | MgO micro-sphere with high specific surface area and preparation method and application thereof | |
| CN108855056A (en) | A kind of bilayer core-shell structure palladium catalyst and its preparation method and application | |
| CN110947396B (en) | Spherical manganese oxide coated iron oxide core shell structural composite, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191022 |