CN108114754A - Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide - Google Patents
Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide Download PDFInfo
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- CN108114754A CN108114754A CN201711259276.1A CN201711259276A CN108114754A CN 108114754 A CN108114754 A CN 108114754A CN 201711259276 A CN201711259276 A CN 201711259276A CN 108114754 A CN108114754 A CN 108114754A
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- metal fullerene
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 114
- 239000002184 metal Substances 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- -1 fullerene modified titanic oxide Chemical class 0.000 title claims abstract description 25
- 229910003472 fullerene Inorganic materials 0.000 title abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 123
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 103
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 38
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 230000001699 photocatalysis Effects 0.000 claims description 21
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 12
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 241001597008 Nomeidae Species 0.000 abstract 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002114 nanocomposite Substances 0.000 description 13
- 239000002086 nanomaterial Substances 0.000 description 13
- 239000010439 graphite Substances 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000010891 electric arc Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001362 electron spin resonance spectrum Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000005298 paramagnetic effect Effects 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000001698 laser desorption ionisation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003032 molecular docking Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 240000001439 Opuntia Species 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003986 organophosphate insecticide Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002023 wood Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/80—Preparation of compounds containing amino groups bound to a carbon skeleton by photochemical reactions; by using free radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
Abstract
The present embodiments relate to a kind of composite material, preparation method and the applications of carboxylated metal fullerene modified titanic oxide.The composite material carries the TiO of hydroxyl by including carboxylated metal fullerene derivative and surface2Raw material be prepared, the carboxylated metal fullerene derivative and the surface carry the TiO of hydroxyl2It is connected by ester bond, the ester bond is the surface OH formation of the COOH and titanium dioxide in carboxylated metal fullerene derivative.Carboxylated metal fullerene derivant structure is stablized, and has characteristic absorption in visible region, photoresponse scope is wide, level structure and TiO2Matching degree is high, by modifying carboxylated metal fullerene derivative in titanium dioxide surface, can easy, efficiently realize the separation of photo-generate electron-hole pair, strong operability.
Description
Technical field
The present invention relates to the compound of photocatalysis field more particularly to carboxylated metal fullerene Derivatives Modified titanium dioxide
Material and its preparation method and application.
Background technology
Titanium dioxide (TiO2) because its strong oxidizing property, nontoxicity, light and chemical stability and it is cheap the advantages that due to become
Optimal environmental improvement catalysis material.TiO2Can by pollutant quickly complete oxidation be CO2And H2The innocuous substances such as O,
It can realize safe efficient, the selective capture and degradation of micropollutants in water.Just because of these excellent performances, make
Obtain TiO2Hydro carbons, halides, hydroxy acid, surfactant, dyestuff, itrogenous organic substance, organophosphorus insecticide in degradation water etc.
Aspect is widely used.
But the application of titanium dioxide is there are two crucial technical barriers, these technical barriers restrict photocatalytic degradation this
The large-scale practical application of one technology.It is relatively low to the utilization rate of solar energy first, common titanium dioxide energy gap is
3.2eV, spectrum respective range is relatively narrow, and light absorption wavelength is concentrated mainly on ultra-violet (UV) band (λ<387nm), it is radiated the ultraviolet of ground
Light part only accounts for 3% or so of sunlight, and titanium dioxide can not utilize the visible light part of solar energy, so having to sunlight
It is very low to imitate utilization rate；Secondly because the recombination rate of photo-generated carrier is very high, cause quantum efficiency relatively low, common titanium dioxide
The quantum efficiency of catalyst only has 4% or so, it is difficult to handle the industrial wastewater and exhaust gas that quantity is big, concentration is high.Therefore, construct steady
Fixed efficient and with visible light activity novel photocatalysis material just becomes the most important thing of current photocatalytic degradation area research.
Metal fullerene physicochemical properties are extremely abundant, have good optical characteristics and Quantum Properties, and its kind
Class is various, and the point group symmetry of carbon cage is also numerous and disorderly changeable, and the big pi-conjugated system of height delocalization can accelerate electron-transport, tool
There is excellent electron transfer characteristic.However, the modification for selecting suitable metal fullerene controllable forms catalysis in nano material
Performance is high, can large-scale application composite material research ability first meeting clue.
The information for being disclosed in the background section is merely intended to increase the understanding of the general background to the present invention, without answering
When being considered as recognizing or imply that the information structure has been the prior art well known to persons skilled in the art in any form.
The content of the invention
Technical problem
To solve existing TiO2The extinction efficiency of catalysis material is low, luminous energy utilization rate is low, electron-hole is compound fast
The problem of, it is an object of the invention to provide a kind of carboxylated metal fullerene Derivatives Modified TiO of structure novel2It is compound
Material and its preparation method and application.The composite material is as photochemical catalyst in use, spectral absorption scope is wide, electron-hole
Recombination probability is low.
Solution
Purpose to realize the present invention, the embodiment of the present invention provide a kind of carboxylated metal fullerene Derivatives Modified TiO2's
Composite material carries the TiO of hydroxyl by including carboxylated metal fullerene derivative and surface2Raw material be prepared,
The carboxylated metal fullerene derivative and the surface carry the TiO of hydroxyl2It is connected by ester bond, the ester bond is carboxyl
Change the surface-OH formation of the-COOH and titanium dioxide in metal fullerene derivative.
Surface-the OH that-COOH in carboxylated metal fullerene derivative loses-OH, titanium dioxide is formed in water loses
It goes after-H to react and to form ester bond and be connected, obtain composite material.
The embodiment of the present invention additionally provides a kind of carboxylated metal fullerene Derivatives Modified TiO2Composite material system
Preparation Method comprises the following steps：
Carboxylated metal fullerene derivative and surface are carried to the TiO of hydroxyl2Heating reaction obtains carboxylated metal richness
Strangle ene derivative modification TiO2Composite material.
Above-mentioned composite material or above-mentioned preparation method are in a kind of possible realization method, the carboxylated metal fullerene
The general structure of derivative is B3N@C2m(C(COOH)2)n, wherein B=Sc, La, Y, Ho, Lu, Dy, Er, m=39~44, n=1
~4；Optionally, carboxylated metal fullerene derivative is Sc3N@C78(C(COOH)2)2。
In a kind of possible realization method, surface carries the TiO of hydroxyl for above-mentioned composite material or above-mentioned preparation method2It is
It is generated using butyl titanate as raw material by hydro-thermal reaction；Butyl titanate is first hydrolyzed to titanium dioxide in the solvent containing water
Titanium continues to be reacted with carboxylated metal fullerene derivative afterwards.
Above-mentioned composite material or above-mentioned preparation method are in a kind of possible realization method, the TiO2For sheet TiO2。
Above-mentioned composite material or above-mentioned preparation method are in a kind of possible realization method, the sheet TiO2It is a length of
40nm ± 10nm, width are 40nm ± 10nm, and thickness is 4nm ± 2nm.Sheet TiO of the present invention2For ultra-thin TiO2Nanometer sheet.
Above-mentioned composite material or above-mentioned preparation method are in a kind of possible realization method, by the item for controlling hydro-thermal reaction
Part makes the TiO of generation2For sheet.The following conditions in control hydro-thermal reaction make the TiO of generation2For sheet：By adding in hydrofluoric acid
Adjustment pH value is 1-3, and the optional pH value that adjusts is 2, and 18h~for 24 hours is reacted under conditions of 180 DEG C~200 DEG C.Under this condition
It can obtain the preferable sheet Anatase TiO of crystallinity2.When using different types of acid adjustment pH instead, it may appear that Rutile Type
TiO2Or the situation of Anatase/rutile two-phase coexistent；Sheet TiO can not be generated under the conditions of other pH2；Reaction temperature
Less than 180 DEG C, the crystallinity of product is poor, while pattern is more chaotic.
Above-mentioned composite material is in a kind of possible realization method, TiO2The load of upper carboxylated metal fullerene derivative
It measures as 0.5%~4%, is optionally 0.5-1.5%, further alternative is 1%.Carboxylated metal fullerene derivative is born
Carrying capacity is the mass percent that carboxylated metal fullerene derivative accounts for composite material, and computational methods are：In preparation process
In, the quality of quality/gained composite material of the carboxylated metal fullerene derivative of reduction in reaction system.
For above-mentioned preparation method in a kind of possible realization method, surface carries the TiO of hydroxyl2With carboxylated metal fowler
The molar ratio of ene derivative is 200~3500:1, it is optionally 350-3200, further alternative is 1000-3200:1, then into
One step is optionally 1450-1700:1, further optional is 1590:1.
In a kind of possible realization method, carboxylated metal fullerene derives for above-mentioned composite material or above-mentioned preparation method
Object and surface carry the TiO of-OH2The condition of heating reaction is reacts 12h~for 24 hours at 80 DEG C~200 DEG C.
Above-mentioned composite material or above-mentioned preparation method are in a kind of possible realization method, the carboxylated metal fullerene
The preparation of derivative is according to document " Cai, T.；Xu,L.；Shu,C.；Champion,H.
A.；Reid,J.E.；Anklin,C.；Anderson,M.R.；Gibson,H.W.；Dorn,H.C.,Selective
Formation of a Symmetric Sc3N@C78Bisadduct:Adduct Docking Controlled by an
Internal Trimetallic Nitride Cluster.Journal of the American Chemical
Society2008,130, (7), 2136-2137.) " it carries out.
A kind of composite material p-nitrophenyl obtained using above-mentioned composite material or above-mentioned preparation method and/or nitrobenzene are spread out
The method that biology carries out photo catalytic reduction, comprises the following steps：
In a solvent, nitrobenzene and/or nitrobenzene derivative and above-mentioned composite material are mixed, obtains mixed liquor, it is black
The air in mixed liquor is discharged under dark condition, mixed liquor is irradiated using the light source containing visible ray.
In a kind of possible realization method, the general formula of the nitrobenzene derivative is the method for above-mentioned photo catalytic reduction
C6H5NO2The position of R, wherein R group can be selected in-NO2Ortho position, meta position and contraposition, R group for-CN ,-COOH ,-NH3、-
CX3,-CHO ,-NH2,-OH ,-Cl ,-Br ,-CO ,-alkyl or-Ph.
The method of above-mentioned photo catalytic reduction often reduces 0.05mol nitrobenzenes and/or nitre in a kind of possible realization method
Base benzene derivative needs the composite material 10-20mg, is optionally 15mg.
The method of above-mentioned photo catalytic reduction further includes formic acid in a kind of possible realization method in the mixed liquor, can
Choosing, the nitrobenzene and/or the molar ratio of nitrobenzene derivative and formic acid are 1:4~1:360, it is further alternative, it is described
The molar ratio of nitrobenzene and/or nitrobenzene derivative and formic acid is 1:4~10, further optionally, the nitrobenzene and/or
The molar ratio of nitrobenzene derivative and formic acid is 1:8.
In a kind of possible realization method, the solvent is included in water or isopropanol the method for above-mentioned photo catalytic reduction
At least one, optionally, it is 1 that the solvent, which includes volume ratio,：The water and isopropanol of 85-90.
In a kind of possible realization method, the selectable wave band of ultraviolet light is the method for above-mentioned photo catalytic reduction
260nm~420nm；The selectable wave band of visible ray is 420nm~800nm.
The method of above-mentioned photo catalytic reduction in a kind of possible realization method, illumination be mapped to sample energy can be 5~
25mw；The time of light irradiation can be 1min~for 24 hours, be optionally 1-5h, further alternative is 4h.
Advantageous effect
(1) metal fullerene stable structure has characteristic absorption in visible region, and photoresponse scope is wide, level structure with
TiO2Matching degree is high, by modifying carboxylated metal fullerene derivative in titanium dioxide surface, can it is easy, efficiently realize light
The separation of raw electron-hole pair, strong operability.
(2) titanium dioxide laminated structure constructs the distance for shortening electron transfer, is conducive to photo-generate electron-hole pair
Separation and the diffusion of photo-generated carrier, and its quantum effect enhances the redox ability of photo-generate electron-hole pair, further
Promote the stability and photocatalytic activity of composite material.
(3) preparation of the carboxylated metal fullerene derivative used in the present invention, Isolation and purification method are convieniently synthesized,
It is of low cost；The composite structure of carboxylated metal fullerene Derivatives Modified titanium dioxide produced by the present invention is novel, raw
Production. art is simple, mild condition, and required equipment investment is few, of low cost, and yield is high, easily operated, is conducive to industrialize big rule
Mould is produced and promoted.
(4) inventor makes photoproduction electric by the selection to carboxylated metal fullerene derivative load capacity on titanium dioxide
Son-hole is to efficiently separating, light abstraction width increase, while has expanded its application in optical physics, photochemistry.
(5) composite material produced by the present invention can efficiently photo catalytic reduction nitrobenzene, and its is easy to operate, reaction condition
Mildly, can at room temperature nitrobenzene compounds it is highly selective (>99.9%) and high conversion (>99%) be converted into benzene
Amine, method is simply controllable, highly practical.
According to below with reference to the accompanying drawings becoming to detailed description of illustrative embodiments, other feature of the invention and aspect
It is clear.
Description of the drawings
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not formed to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Any embodiment here as illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Figure 1A is sheet TiO prepared by the embodiment of the present invention 12Scanning electron microscope (SEM) figure, Figure 1B be sheet TiO2It is saturating
Electron microscope is penetrated, Fig. 1 C are answering for carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide prepared by the embodiment of the present invention 1
Transmission electron microscope (TEM) figure of condensation material.
Fig. 2 is the sheet TiO prepared in the embodiment of the present invention 12With carboxylated metal fullerene Derivatives Modified sheet two
The XRD diagram of the composite material of titanium oxide.
Fig. 3 A and Fig. 3 B are respectively the carboxylated metal fullerene Derivatives Modified sheet two prepared in the embodiment of the present invention 1
The XPS of the composite material of titanium oxide tests full spectrogram and the fine spectrograms of C1s.
Fig. 4 is the sheet TiO prepared in the embodiment of the present invention 12With carboxylated metal fullerene Derivatives Modified sheet two
The UV-Vis DRS light figure of the composite material of titanium oxide.
Fig. 5 is the photoelectric current spectrogram of composite material in the embodiment of the present invention 4.
Fig. 6 A and Fig. 6 B are the electron paramagnetic resonance spectrum (EPR) figure that hole and electron amount are represented in the embodiment of the present invention 4.
Specific embodiment
Below in conjunction with the accompanying drawings, the specific embodiment of the present invention is described in detail, it is to be understood that the guarantor of the present invention
Shield scope is not restricted by specific implementation.
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
Part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
All other embodiments obtained without creative efforts belong to the scope of protection of the invention.Unless
Separately have it is other explicitly indicate that, otherwise in entire disclosure and claims, term " comprising " or its conversion such as "comprising" or
" including " etc. will be understood to comprise stated element or component, and not exclude other elements or other compositions
Part.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without some details, the present invention can equally be implemented.In some instances, for
Method well known to those skilled in the art, means, element are not described in detail, in order to highlight the purport of the present invention.
Metal fullerene has the similar property of electron deficient olefins, and C=C double bonds are easily by addition, in metal fullerene
Some functional moleculars are modified on carbon cage, can obtain having both the novel substance of metal fullerene and functional molecular characteristic, so as to regulate and control
Solvability, level structure, photoelectric properties and biochemical function of the molecule in different solvents.Metal fullerene stable structure, from
Ultraviolet to have light absorption near infrared region, photochemical properties are excellent, the excellent properties that have in itself due to metal fullerene and solely
Special current-carrying subcharacter, when being coupled with other substances, can influence the electronic transmission performance between molecule, and electronics occurs at interface
Transfer process changes the band structure of composite material, at ambient temperature, electronics and hole it is dense, and its is excellent
Visible light absorption can widen the spectral absorption scope of material, can also be by changing the embedded cluster of metal fullerene
Species, carbon cage symmetry and derivatization mode regulate and control excitation state kinetic property.Therefore, metal fullerene is a kind of preferable
Carrier of photocatalyst.The composite material of metal fullerene modification can effectively widen spectral absorption scope, increase light-use
Efficiency reduces electron-hole recombination probability, improves photocatalytic activity.
The controllable preparation of the nanocomposite of 1 carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide of embodiment
(1) sheet TiO2The preparation of nano material：
5ml (40wt%) hydrofluoric acid of 0.07mol butyl titanates and control pH is mixed, obtains mixed liquor, mixed liquor
200 DEG C of heat preservation 20h in 100ml reaction kettles are put into, cools down after reaction and obtains the solution containing plate-like titanium dioxide, solution centrifuged
Filter, is first washed with deionized 3 times, then is washed 3 times with absolute ethyl alcohol, and sheet dioxy is obtained after being dried overnight in 80 DEG C of baking ovens
Change titanium solid powder 0.068mol.
(2) preparation of carboxylated metal fullerene derivative is according to document " Cai, T.；Xu,L.；Shu,C.；Champion,
H.A.；Reid,J.E.；Anklin,C.；Anderson,M.R.；Gibson,H.W.；Dorn,H.C.,Selective
Formation of a Symmetric Sc3N@C78Bisadduct:Adduct Docking Controlled by an
Internal Trimetallic Nitride Cluster.Journal of the American Chemical
Society2008,130, (7), and 2136-2137.) " it carries out, detailed process includes：
The ScNi that following embodiments use2Alloy is purchased from Beijing Non-Fervoous Metal Inst..
Metal fullerene Sc3N@C78Preparation method, Sc3N@C78Molecule is to be put in DC arc discharge stove by electric arc
Electrical method (- Huffman methods) synthesis, operating process includes：First the solid graphite stick that outer diameter is 8mm is drilled to
Internal diameter for 6mm or so hollow plumbago pipe, then by ScNi2Alloy and graphite powder are 3 according to mass ratio:1 ratio is uniformly mixed,
It is subsequently filled in graphite-pipe, tamps；Filled metal/graphite stick is mounted on to anode and the fixation of electric arc furnaces, closes stove
Lid opens vacuum pump；The valve between furnace chamber and vacuum pump is opened, to electric arc stove evacuation, when being evacuated to air pressure less than 10Pa, is beaten
Cooling circulating water is opened, opens electric welding machine, adjusts electric current to 100A, unlatching stepper motor movement metal/graphite stick is allowed to and cathode
Graphite plate contacts, and metal/graphite stick is preheated, and excludes the air and moisture that wherein adsorb, preheats 30 minutes or so,
Electric welding machine is closed, the valve between furnace chamber and vacuum pump is closed, stops vacuum pump；Breather valve is slowly opened, is filled with to electric arc furnaces
The N of 6Torr2With the He gas of 194Torr, electric welding machine is opened, electric current is adjusted to 130A, opens stepper motor movement metal/graphite
Stick is allowed to disengage with cathode graphite plate, forms highfield between cathode and anode at this time and discharges, and continues to adjust stepping electricity
Machine makes two pole tensions keep 40V or so, discharges stablize the most at this time；Dazzling yellow-green light is sent during electric discharge, between the two poles of the earth, this
When the two poles of the earth between temperature can be up to more than 4000K, while the metal/graphite stick of anode is by the electronic impact Cheng Fei of cathode emission
Scattered particle, in the arc discharge area atomization of high temperature, the atom of gasification cools down particle during arc zone is flown away from
And then cluster is reassembled into, in this way, various fullerenes and metal fullerene just generate；With the consumption of anode metal/graphite rod,
Stepper motor must be adjusted at any time makes the two poles of the earth stable discharging；After metal/graphite stick is exhausted, electric arc furnaces cooling is waited, opens electricity
Arc stove collect gained grey soot, be put into paper bag, in Soxhlet extractor with toluene extraction 12 it is small when or so to get containing various
The extracting solution of empty fullerene and metal fullerene；It will be fixed containing the toluene of various fullerenes and metal fullerene extraction solution warp
Property filter paper multiple times of filtration after use high performance liquid chromatography separation and purification：First using Buckyprep columns (20 × 250mm,
Cosmosil first step separation) is carried out, is separated essentially according to the size of Fullerene Carbon cage；Then the crude product obtained carries out
Second step separates, and with Buckyprep-M columns (20 × 250mm, Cosmosil), mainly the fullerene of hollow carbon cage and has gold
The metal fullerene for belonging to embedded cluster separates；Finally purified again with Buckyprep columns (20 × 250mm, Cosmosil),
The metal fullerene of various configuration is separated, wherein, using toluene as mobile phase in experiment, the flow velocity of toluene is 12ml/min,
Sample introduction concentration is 1mg/ml, every time fixed sample introduction 12ml, monitors wavelength using the UV of 310nm, while base is combined in separation process
Matter Assisted Laser Desorption ionization time of flight mass spectrometry analyzes each chromatographic peak, and chromatographic peak goes out the peak position corresponding time
For 44-50 minutes, the Sc of more than 99% purity is obtained3N@C78。
(3) preparation of metal fullerene carboxylated derivative：
By 1mg Sc3N@C78It is dissolved into 8 μ l bromo diethyl malonates in the o-dichlorohenzene of 3ml, forms solution A, it will
5ulDBU (1,8- diazabicylo, 11 carbon -7- alkene) is added in solution A, mixed liquid B is formed, by mixed liquid B room temperature in Ar
Under stir reaction 5h, then in N2Protection is lower to remove solvent, is filtered after obtained solid product is dissolved in toluene, obtains solution C, will
Solution C is passed into HPLC and is analyzed, wherein, using toluene as mobile phase in experiment, the flow velocity of toluene is 2ml/min, sample introduction
Concentration is 1mg/ml, every time fixed sample introduction 12ml, monitors wavelength using the UV of 310nm, while binding matrix is auxiliary in separation process
Laser desorption ionization time of flight mass spectrometry is helped to analyze each chromatographic peak, chromatographic peak goes out the peak position corresponding time and is
40-45 minutes, isolated product dried 20h after rotating immediately in 60 DEG C of vacuum drying chambers, obtains solid D, Ran Houqu
In 5mg solid D and 18mgNaH solution 30ml toluene, 80 DEG C of mixed liquor stirs 10h under Ar, is then added drop-wise to 1ml methanol mixed
It closes in liquid, adds 20mlHCl, the precipitation of acquisition is filtered, and successively with toluene, 2MHCl, H2O, benzene are washed, finally
Obtained solid is dissolved into methanol, then solution revolving and 50 DEG C are dried in vacuo for 24 hours, obtain gold by centrifugation removal solid
Belong to fullerene carboxylated derivative Sc3N@C78(C(COOH)2)2, i.e.,
(3) preparation of the nanocomposite of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide：
Under conditions of ultrasound, by 1mg (0.78 μm of ol) carboxylated metal fullerene derivatives Sc3N@C78(C(COOH)2
)2, 99mg (1.24mmol) plate-like titanium dioxides and the mixing of 50ml ethyl alcohol, obtain mixed liquor, mixed liquor is put into 100ml reactions
100 DEG C of heat preservation 12h, obtain the composite wood containing carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide in kettle after cooling
The solution of material, solution centrifugal filtration are first washed with deionized 3 times, then are washed 3 times with absolute ethyl alcohol, in 40 DEG C of vacuum drying
The sheet-like titanium dioxide nanomaterial of carboxylated metal fullerene Derivatives Modified is obtained after being dried overnight in case.
Sheet TiO prepared by 1 step of the embodiment of the present invention (1)2Scanning electron microscope (SEM) and transmission electron microscope
(TEM) figure as shown in FIG. 1A and 1B, controls TiO2A length of 40nm ± 10nm, width be 40nm ± 10nm, thickness for 4nm ±
2nm is evenly distributed.Its pattern is observed under 10kV high pressures using Japanese HITACHI S-4800 scanning electron microscope
Analysis.
The nanometer of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide is answered in 1 step of the embodiment of the present invention (3)
Transmission electron microscope (TEM) figure of condensation material as shown in Figure 1 C, is surveyed using Flied emission transmission electron microscope JEOL JEM-2100F
The microstructure of test agent, operating voltage 160kV can clearly see sheet TiO2Nano material and carboxylated metal fullerene
The original structure of material is maintained after derivative is compound, while size is uninfluenced.
SEM, TEM can intuitively the sheet TiO that significantly observes2With the sheet-like morphology of nanocomposite and size
Size.
The sheet TiO prepared in the embodiment of the present invention 12Nano material and carboxylated metal fullerene Derivatives Modified sheet
The XRD diagram of the nanocomposite of titanium dioxide as shown in Fig. 2, carry out the test of Sample crystals structure using X-ray diffractometer,
The wavelength of X-ray be λ=0.154nm, operation voltage be 40kV, operation electric current 20mA, sweep speed be 10 °/min, step width
For 0.02 °, 2 θ scanning ranges are 10-80 °.Figure it is seen that sheet TiO prepared in embodiment 12Nano material is
Do not contain Rutile Type and the pure anatase crystal of plate titanium phase, 2 θ be 25.3 °, 36.9 °, 37.8 °, 38.6 °, 48.0 °,
Diffraction maximum and standard card Detitanium-ore-type TiO at 53.9 °, 55.1 °, 62.7 °, 70.3 °, 75.1 °2(JCPDS 71-1166)
The middle indices of crystallographic plane be (101), (103), (004), (112), (200), (105), (211), (204), (116), (220), (215)
Diffraction maximum it is corresponding.According to Fig. 2, the composite material diffraction peak after carboxylated metal fullerene derivative has been modified
It puts and does not change, show that the introducing of metal fullerene does not destroy original crystal structure, but due to metal fullerene load capacity
It is smaller, therefore apparent metal fullerene characteristic diffraction peak is not shown in the composite.
The carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide prepared in the embodiment of the present invention 1 it is nano combined
The fine spectrogram difference of the full spectrograms of XPS and C1S of material is as shown in Figure 3A and Figure 3B.By Fig. 3 A can be seen that composite material be by
Ti, O, C element are formed.The C1s that Fig. 3 B are obtained using the signal that deconvolutes after Gauss curve fitting is finely composed, the results showed that,
Sc3N@C78(C(COOH)2)2The TiO of modification2XPS figures in the combination of C1S can be located at 284.8,286.2 and 288.8eV respectively.
Wherein the major peaks of C1s are located at 284.8eV, corresponding to Sc3N@C78Sp2 hydridization carbon on (C (COOH) 2) 2, is located at
The spike of 286.2eV corresponds to C-O keys, and a relatively weak peak occurs in 288.8eV under the action of carbonyl carbon, this
Kind surface functional group can provide the active site being directly connected to anatase nanometer crystal.Therefore it can be proved that in Sc3N@C78(C
(COOH)2)2The TiO of modification2In, TiO2- OH groups in nanometer sheet pass through esterification and Sc3N@C78(C(COOH)2)2Surface
On-COOH group formation Ti-O-C=O keys.
The sheet TiO prepared in the embodiment of the present invention 12Nano material and carboxylated metal fullerene Derivatives Modified sheet
The UV-Vis DRS spectrogram of the composite material of titanium dioxide is as shown in figure 4, using Shimadzu UV-2550 ultraviolet spectrometry light
Degree meter tests the light absorpting ability of sample, and measurement carries out at room temperature, with BaSO4For reference, measurement wave-length coverage is
300-1000nm.From fig. 4, it can be seen that sheet TiO prepared in embodiment 12Nano material is in the ultra-violet (UV) band of 300-400nm
In domain there is very high absorption value, do not absorbed in the range of the 400-1000nm of visible light region, this is by TiO2Itself property
What matter determined.Metal fullerene Sc3N@C78There is visible light region to have characteristic absorption, there are two more bright at 450nm and 625nm
Aobvious absworption peak.We utilize absorption of the metal fullerene in visible region characteristic of field, carry out carboxylation reaction and then modify to arrive
Sheet TiO2In nano material, be conducive to increase absorption of the material in visible light region, improve the utilization rate of light.As a result such as Fig. 4
Shown, red shift occurs for the light absorption spectrogram of the composite material of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide, and
Composite material is provided with certain absorption in the range of the 400-1000nm of visible light region, so as to show carboxylated metal fullerene
The introducing of derivative not only contributes to the separation of photo-generate electron-hole pair, and can widen the light abstraction width of composite material, from
And improve the utilization rate of light.
Embodiment 2
Below in conjunction with the accompanying drawings, the specific embodiment of the present invention is retouched in detail by taking photocatalysis nitrobenzene reduction as an example
It states, it is to be understood that protection scope of the present invention is not restricted by specific implementation, prepared material removes p-nitrophenyl
Reduction have excellent photocatalysis performance, inventor is equally to following a variety of nitro compounds according to identical photocatalysis method
It is tested, can reach more than 65% conversion ratio and more than 99% selectivity.
The nanocomposite photocatalysis nitrobenzene reduction of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide
The research of application, step are as follows：
Using 0.05mmol nitrobenzenes, 15mg composite catalysts and the 2.225ml isopropanols and 0.025ml as solvent
Water mixes, and adds the formic acid of 0.4mmol and stirs 30min in dark to reach adsorption equilibrium, Ran Houyong under Ar gas shieldeds
(300W,λ>420nm) xenon-mercury lamp irradiates 4h as visible light source, and reaction result is tested by gas-chromatography (GC).Formic acid is at this
Effect in a catalyst system and catalyzing has two aspects：First, hole trapping agents, two are to provide H sources, and provide nitrobenzene reduction needs into aniline
The H wanted.
The present invention uses the content and structure of of chromatographic reduzate each component, and main substance to be detected is
Nitrobenzene, formic acid and aniline etc., using SGE SE-54 capillary chromatographs (0.25mm × 30m × 0.5um), fid detector,
80 DEG C of injector temperature, 300 DEG C of column temperature, 30 DEG C/min of heating rate, 300 DEG C of detector temperature, nitrogen are as carrier gas, flow velocity
0.04mL/min, is inside designated as tridecane, and the aniline peak position corresponding time is 4-5 minutes, and nitrobenzene peak position corresponds to the time and is
5-6 minutes, content was determined by areas of peak normalization method.The carboxylated gold prepared in embodiment 1 is calculated according to chromatograph result
Belong to the conversion ratio and selectivity of the nanocomposite photocatalysis nitrobenzene reduction of fullerene derivate modification plate-like titanium dioxide,
The results are shown in Table 1 for it,
Table 1
| Catalyst | Solvent | Time | Conversion ratio | Selectivity | |
| 1 | -- | Isopropanol/water | 4h | -- | -- |
| 2 | TiO2 | Isopropanol/water | 4h | 9.8 | >99.9 |
| 3 | Sc3N@C78(C(COOH)2)2 | Isopropanol/water | 4h | 48.7 | >99.9 |
| 4 | Composite material | Isopropanol/water | 4h | 99.9 | >99.9 |
Reaction condition：Nitrobenzene (0.05mmol), catalyst (15mg), formic acid (0.4mmol), isopropanol (2.225), water
(0.025ml), 4h, it is seen that illumination, argon gas atmosphere, tridecane are measured as internal standard gas chromatography (GC).
As shown in table 1, under visible light illumination, the nanometer of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide
Composite material makes more than 99% nitrobenzene reduction into aniline in 4h, and simple carboxylated metal fullerene derivative and piece
Conversion ratio of the shape titanium dioxide in 4h is respectively 48.7% and 9.8%.Under reaction condition same as Example 2, to table 2
In a variety of nitrobenzene derivatives reduced, conversion ratio and selectivity as shown in table 2.
Table 2
Therefore, the compound photocatalytic for being greatly improved material of carboxylated metal fullerene derivative and titanium dioxide
Can, expand application of the photocatalysis technology in terms of organic synthesis
Embodiment 3
The nanocomposite photoelectric current property research of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide, step
It is rapid as follows：
(1) preparation of the plate-like titanium dioxide of carboxylated metal fullerene Derivatives Modified/FTO electrode slices：
By the sheet TiO of 3mg carboxylated metal fullerene Derivatives Modifieds2Composite material and the mixing of 0.5ml ethyl alcohol, ultrasound
After 30min, continue to stir evenly, the mixing drop-coated of 10 μ l is taken then to be put into sheet glass to the FTO glass surfaces cleaned
In baking oven, 110 DEG C of heat preservation 12h.
(2) the plate-like titanium dioxide nanocomposite photoelectricity current test of metal fullerene modification：
Photoelectric current is tested using three-electrode system, and using Pt pieces as to electrode, calomel is as reference electrode, the sample of preparation
For product electrode as working electrode, electrolyte is the Na of 0.5mol/L2SO4Liquid is molten, (300W, λ>420nm) xenon-mercury lamp is as visible ray
Light source, the bias of additional 0.1V.
Sheet TiO prepared by the embodiment of the present invention 12Nano material and carboxylated metal fullerene Derivatives Modified sheet
The photoelectricity flow graph of the nanocomposite of titanium dioxide is as shown in figure 5, use (300W, λ>420nm) xenon-mercury lamp irradiates, material valency
Electron absorption energy is excited to conduction band in band, generates photo-generate electron-hole pair, under the bias effect of additional 0.1V, photoproduction
Electronics is transferred to Pt plate electrodes from working electrode, generates current signal, and the current signal of the more voluminous life of light induced electron is stronger；When
Light source is closed, electron-hole is compound, and current signal disappears.It can be clearly seen that by Fig. 5, under excited by visible light, carboxylated
The photo-signal that the nanocomposite of metal fullerene Derivatives Modified plate-like titanium dioxide generates can when electric current is stablized
Up to 10 μ A/cm2, with pure sheet TiO2(1.5μA/cm2) compare, there is stronger photo-signal, show carboxylated metal fowler
The introducing of ene derivative promotes the separation of electron-hole in composite material, so as to generate more light induced electrons, meanwhile,
By Fig. 5 it is observed that under the excitation of light repeatedly, the nanometer of carboxylated metal fullerene Derivatives Modified plate-like titanium dioxide is answered
The photoresponse current signal of condensation material may remain in 8 μ A/cm2More than, show that composite material has good photochemical stable
Property.
Embodiment 4
The electronic transfer process of the plate-like titanium dioxide nanocomposite of carboxylated metal fullerene Derivatives Modified is ground
Study carefully (ESR), step is as follows：
Sheet TiO prepared by the embodiment of the present invention 12Nano material and carboxylated metal fullerene Derivatives Modified sheet
The electron paramagnetic resonance spectrum (EPR) (ESR) of the nanocomposite of titanium dioxide is as shown in Figure 6 A and 6 B.Fig. 6 A are two kinds of samples
Sheet TiO2The production of the hydroxyl radical free radical of nano material and composite material, sample test sample making course are to take 5mg respectively
TiO20.5mlH is dissolved in respectively with 5mg composite samples2In O, form mixed liquor A and B, then take again the DMPO of 10 μ l with
0.5mlH2O is miscible, forms solution C, tests TiO2When hydroxyl radical free radical generates, 50 μ lA and 50 μ lC is taken to mix, mixed liquor is put
It in capillary, is tested, when test compound material hydroxyl radical free radical generates, 50 μ lB and 50 μ lC is taken to mix, it then will be mixed
It closes liquid to be placed in capillary, be tested.It tests as in visible ray (λ>Under 420nm) irradiating, the electron paramagnetic of test sample is total to
Vibration wave composes (ESR) property.
Fig. 6 B are two kinds of sample TiO2With the production of composite material superoxide radical, sample test sample making course is point
5mg TiO are not taken2It is dissolved in respectively in 0.5ml methanol with 5mg composite samples, forms mixed liquor D and E, then take 10 μ l again
DMPO and 0.5ml methanol it is miscible, formed solution F, test TiO2When superoxide radical generates, 50 μ lD and 50 μ lF is taken to mix,
Mixed liquor is placed in capillary, is tested, when test compound material superoxide radical generates, 50 μ E and 50 μ lF is taken to mix,
Then mixed liquor is placed in capillary, is tested.It tests as in visible ray (λ>Under 420nm) irradiating, the electricity of test sample
Sub- paramagnetic resonance spectrum (ESR) property.
DMPO is a kind of spin catching agent very high to oxygen radical arresting efficiency, generates stable spin adduct.
(λ>420nm) under radiation of visible light, specimen material generates photo-generate electron-hole pair, and hole can interact with water intermediate ion and give birth to
Into hydroxyl radical free radical, electronics and the oxygen interaction generation superoxide radical in methanol.Oxygen freedom can be captured using DMPO
The characteristic of base, DMPO can capture OH and OOH and form DMPO-OH and DMPO-OOH respectively, can detect that electron paramagnetic is total to
It shakes, so as to obtain electron paramagnetic resonance spectrum (EPR) and sample Electron transfer process is studied, as a result respectively such as Fig. 6 A and Fig. 6 B
It is shown.From Fig. 6 A, with sheet TiO2Nano material is compared, the sheet titanium dioxide of carboxylated metal fullerene Derivatives Modified
Titanium electron paramagnetic resonance is stronger, therefore with more OH, show with carboxylated metal fullerene derivative it is compound after, material
Material can generate more holes, meanwhile, it is also observed that by Fig. 6 B, the sheet dioxy of carboxylated metal fullerene Derivatives Modified
More electronics will be generated under visible light illumination by changing titanium composite material, hence, it can be determined that carboxylated metal fullerene derives
The introducing of object affects the electronic transmission performance between molecule, makes electronics that electronic transfer process occur at interface, changes compound
The band structure of material promotes the separation of photo-generate electron-hole, has positive effect for promoting photocatalysis performance.
Embodiment 5
To sheet TiO2The load capacity of upper carboxylated metal fullerene derivative is optimized, and carboxyl is had chosen in experiment
The composite material that the load capacity for changing metal fullerene derivative is 0.5%, 1%, 1.5%, 2% and 4% (answer by different loads amounts
Condensation material is prepared according to the method in embodiment 1, only sheet TiO in change method2With carboxylated metal fullerene derivative
Molar ratio, the composite material that the load capacity of carboxylated metal fullerene derivative is 0.5%, 1%, 1.5%, 2% and 4% exists
Surface carries the TiO of hydroxyl during preparation2Molar ratio with carboxylated metal fullerene derivative is respectively 3114:1、1590:1、
1028:1、767:1、376:1) it is tested, according to the detection method in Fig. 4, by can in UV-vis DRS spectrum
To find out that load capacity is higher, the absorption in visible light region is bigger.But according to the detection method of Fig. 5 by photoelectricity current test,
It was found that being best for the separated effect of nanocomposite electron-hole of load 1%, the promotion of photoelectric current is most apparent,
When loading fewer or more, photocurrent variations all unobvious carry out ESR according to the detection method of Fig. 6 A and Fig. 6 B
The test of spectrum finds, what corresponding OH free radicals and superoxide radical rose when 1% load capacity be most it will be evident that so
We constrain load capacity, and it is optimal exactly to load 1%.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
To modify to the technical solution recorded in foregoing embodiments or carry out equivalent substitution to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical solution spirit and
Scope.
Claims (10)
1. a kind of carboxylated metal fullerene Derivatives Modified TiO2Composite material, by including carboxylated metal fullerene
Derivative and surface carry the TiO of hydroxyl2Raw material be prepared, the carboxylated metal fullerene derivative and the surface
TiO with hydroxyl2It is connected by ester bond, the ester bond is-COOH and titanium dioxide in carboxylated metal fullerene derivative
What the surface-OH of titanium was formed.
2. a kind of carboxylated metal fullerene Derivatives Modified TiO2Composite material preparation method, comprise the following steps：It will
Carboxylated metal fullerene derivative and surface carry the TiO of hydroxyl2Heating reaction, obtains carboxylated metal fullerene derivative
Modify TiO2Composite material.
3. the preparation method described in composite material according to claim 1 or claim 2, which is characterized in that the carboxylic
The general structure of base metal fullerene derivative is B3N@C2m(C(COOH)2)n, wherein B=Sc, La, Y, Ho, Lu, Dy or Er,
M=39~44, n=1~4；Optionally, carboxylated metal fullerene derivative is Sc3N@C78(C(COOH)2)2。
4. the preparation method described in composite material according to claim 1 or claim 2, which is characterized in that the table
Face carries the TiO of hydroxyl2For sheet；Optionally, surface carries the sheet TiO of hydroxyl2Size for long 40nm ± 10nm, width
40nm ± 10nm and thickness 4nm ± 2nm.
5. the preparation method described in composite material according to claim 4 or claim 4, which is characterized in that sheet
Surface carries the TiO of hydroxyl2It is prepared in the following manner：It is carried out using butyl titanate as raw material by hydro-thermal reaction
Hydrolysis, by adding in hydrofluoric acid adjustment pH value as 1-3 and being reacted under conditions of 180 DEG C~200 DEG C in hydro-thermal reaction system
To control the condition of hydro-thermal reaction.
6. the preparation method described in composite material according to claim 5 or claim 5, which is characterized in that in hydro-thermal
It is 2 by adding in hydrofluoric acid to adjust pH value in reaction system；Optionally, in hydro-thermal reaction system, at 180 DEG C~200 DEG C
Under the conditions of react 18h~for 24 hours to control the condition of hydro-thermal reaction.
7. composite material according to claim 1, which is characterized in that TiO2Upper carboxylated metal fullerene derivative is born
Carrying capacity is 0.5%~4%, is optionally 0.5-1.5%, further alternative is 1%.
8. preparation method according to claim 2, which is characterized in that surface carries the TiO of hydroxyl2It is rich with carboxylated metal
The molar ratio for strangling ene derivative is 200~3500:1, it is optionally 350-3200, further alternative is 1000-3200:1, then
Further alternative is 1450-1700:1, further optional is 1590:1.
9. composite material or claim 2-6 described in one of a kind of usage right requirement 1,3-7, the preparation side described in one of 8
The method that the composite material p-nitrophenyl and/or nitrobenzene derivative that method obtains carry out photo catalytic reduction, comprises the following steps：
In solvent, nitrobenzene and/or nitrobenzene derivative and composite material are mixed, mixed liquor is obtained, is discharged under dark condition mixed
The air in liquid is closed, mixed liquor is irradiated using the light source containing visible ray.
10. according to the method described in claim 9, it is characterized in that, the general formula of the nitrobenzene derivative is C6H5NO2R,
The position of middle R group is selected in-NO2Ortho position, meta or para position, R group for-CN ,-COOH ,-NH3、-CX3,-CHO ,-NH2、-
OH ,-Cl ,-Br ,-CO ,-alkyl or-Ph.
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| CN108889291A (en) * | 2018-06-13 | 2018-11-27 | 中国科学院化学研究所 | SnO2Micro nano structure fulvene compounding material of modification and its preparation method and application |
| CN111040857A (en) * | 2019-12-27 | 2020-04-21 | 中山大学 | Electrorheological fluid and preparation method thereof |
| CN111111428A (en) * | 2019-10-21 | 2020-05-08 | 中国科学院化学研究所 | Application of fullerene and semiconductor composite material loaded by fullerene derivative in photocatalytic degradation of indoor VOCs (volatile organic compounds) |
| CN112126217A (en) * | 2020-10-12 | 2020-12-25 | 广东工业大学 | Fullerene/carbon nanotube/thermoplastic resin composite film, and preparation method and application thereof |
| CN113164867A (en) * | 2019-03-26 | 2021-07-23 | 北京福纳康生物技术有限公司 | Application of fullerene and fullerene derivative composite material in degradation of formaldehyde and indoor VOCs or bacteriostasis |
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| CN108889291A (en) * | 2018-06-13 | 2018-11-27 | 中国科学院化学研究所 | SnO2Micro nano structure fulvene compounding material of modification and its preparation method and application |
| CN108889291B (en) * | 2018-06-13 | 2020-10-23 | 中国科学院化学研究所 | SnO2Modified fullerene composite material with micro-nano structure and preparation method and application thereof |
| CN113164867A (en) * | 2019-03-26 | 2021-07-23 | 北京福纳康生物技术有限公司 | Application of fullerene and fullerene derivative composite material in degradation of formaldehyde and indoor VOCs or bacteriostasis |
| CN113164867B (en) * | 2019-03-26 | 2022-08-05 | 北京福纳康生物技术有限公司 | Application of fullerene and fullerene derivative composite material in degrading formaldehyde and indoor VOCs or inhibiting bacteria |
| CN111111428A (en) * | 2019-10-21 | 2020-05-08 | 中国科学院化学研究所 | Application of fullerene and semiconductor composite material loaded by fullerene derivative in photocatalytic degradation of indoor VOCs (volatile organic compounds) |
| CN111040857A (en) * | 2019-12-27 | 2020-04-21 | 中山大学 | Electrorheological fluid and preparation method thereof |
| CN111040857B (en) * | 2019-12-27 | 2022-09-06 | 中山大学 | Electrorheological fluid and preparation method thereof |
| CN112126217A (en) * | 2020-10-12 | 2020-12-25 | 广东工业大学 | Fullerene/carbon nanotube/thermoplastic resin composite film, and preparation method and application thereof |
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