CN106984312B - A kind of composite photocatalyst and preparation method thereof - Google Patents
A kind of composite photocatalyst and preparation method thereof Download PDFInfo
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- CN106984312B CN106984312B CN201710271195.7A CN201710271195A CN106984312B CN 106984312 B CN106984312 B CN 106984312B CN 201710271195 A CN201710271195 A CN 201710271195A CN 106984312 B CN106984312 B CN 106984312B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- -1 substituted-nitrobenzene Chemical class 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract 4
- 239000010931 gold Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical class [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention belongs to the preparation fields of photochemical catalyst, and in particular to the Au-TiO that one kind simply synthesizes2‑Bi2WO6Photochemical catalyst and preparation method thereof.With TiO2Nanometer sheet is as material core, by the method for simple electrostatic self-assembled by itself and Bi2WO6Nanometer sheet and Au Nanocomposites obtain the TiO of Au nanometer particle load2‑Bi2WO6The two-dimentional composite photocatalyst of two dimension-.The present invention is for the first time by Au-TiO2‑Bi2WO6Composite photo-catalyst restores substituted-nitrobenzene for water phase photocatalysis to selectively.The Au-TiO of synthesis2‑Bi2WO6Photochemical catalyst has high catalytic efficiency and highly selective.The method for preparing catalyst is simple, conveniently recycles and reuses, which has widely practical value and application prospect in technical field of material and selective organic synthesis field.
Description
Technical field
The invention belongs to catalyst preparation and the sustainable development fields of environment and the energy, and in particular to a kind of compound
Photochemical catalyst and preparation method thereof.
Background technique
Chemical energy is directly converted solar energy by artificial photosynthesis provides one to solve the energy and environmental crisis
The environmentally protective approach of kind.The key problem of this advanced technology is to design efficient catalyst to absorb to the maximum extent too
Sunlight generates a large amount of photo-generated carrier to driving redox reaction.However, most of traditional semiconductor catalysts
Ideal solar energy utilization ratio is extremely difficult to since the recombination rate of electron hole pair is high.Semiconductor and semiconductor compound and
Metal Supported on semiconductor provides good approach to improve the separative efficiency of electron hole.But single carrier separation
Approach can not maximumlly improve its separative efficiency, and it is then point that the transfer of the carrier in a variety of channels, which is effectively combined,
New possibility is provided from efficiency maximization.
Heterojunction semiconductor is one of the common strategy for improving electron hole separative efficiency, wherein two dimension-two-dimensional hetero-junction
Composite photo-catalyst is believed to realize better carrier separation efficiency due to its good interfacial contact.On the other hand,
Metallic can promote the separation of carrier in the load of semiconductor surface by the electronics on transfer semiconductor conduction band；And
And the metallic for there is surface plasma resonance effect (SPR), such as Au and Ag, they can pass through SPR enhancement effect
To further increase photocatalytic activity.Then, we have synthesized one Au nanometers with the method design of two step electrostatic self-assembleds
The TiO of particle loading2-Bi2WO6The two-dimentional composite photo-catalyst of two dimension-, and investigated it and restored aromatic nitro in photocatalysis to selectively
Application in terms of compound.
Summary of the invention
The purpose of the present invention is to provide a kind of Au-TiO2-Bi2WO6Composite photocatalyst and preparation method thereof, this is urged
Agent is easily prepared, environmentally friendly；The Au-TiO2-Bi2WO6Catalyst is by effectively combining a variety of electron transfers to realize
Activity of the high electron hole separative efficiency and photo catalytic reduction substituted-nitrobenzene to corresponding amine.
The substituted-nitrobenzene and corresponding amine have the following structure:
、、、、、、、、、
To achieve the above object, the present invention adopts the following technical scheme:
A kind of Au-TiO2-Bi2WO6The preparation method of photochemical catalyst, comprising the following steps:
(1) TiO2The preparation of nanometer sheet: by positive four butyl ester of 5 ml metatitanic acids (Ti (OBu)4) and 1 ml hydrofluoric acid (HF) mixing stir
It is transferred in 50 ml reaction kettles after mixing uniformly, 24 h of hydro-thermal at 180 DEG C is then centrifuged for, washs, is dried to obtain TiO2Nanometer
Piece；
(2) TiO2The modification of nanometer sheet: by TiO made from step (1)2Nanometer sheet 3- aminopropyl triethoxysilane
(APTES) it modifies, obtains the positively charged TiO in surface2Nanometer sheet；
(3) Bi2WO6The preparation of nanometer sheet: by 1 mmol sodium tungstate (Na2WO4·2H2O), 2 mmol bismuth nitrate Bi
(NO3)3·5H2O and 0.05 g cetyl trimethylammonium bromide (CTAB) are added in 80 ml distilled water, after being mixed evenly
It is transferred in 100 mL reaction kettles, 24 h of hydro-thermal at 120 DEG C is then centrifuged for, washs, is dried to obtain Bi2WO6Nanometer sheet；
(4) preparation of Au nanoparticle: by 26 ml, 2.8 mM sodium citrate (Na3C6H5O7·2H2O) solution is added to 50
0.4 mM gold chloride (H of ml2AuCl4) in solution, be mixed evenly, then 5 ml, 12 mM sodium borohydride (NaBH4) is dripped
It adds, obtains Au nanometer particle colloid solution (Au NPs) after stirring 2 h at room temperature；
(5) Au-TiO2-Bi2WO6The preparation of compound: by the TiO after modification2Nanometer sheet and Bi2WO6Nanometer sheet and Au
Nanoparticle is proportionally mixed evenly, and is then centrifuged for, washs, is dried to obtain Au-TiO2-Bi2WO6Composite photo-catalyst.
In above-mentioned step (4): the concentration of prepared gold nanoparticle colloid solution is 0.05 mg/ml.
Compound the preparation method comprises the following steps: first by TiO in above-mentioned step (5)2Nanometer sheet and Bi2WO6Nanometer sheet is compound, then
By TiO2-Bi2WO6Compound and Au Nanocomposites.
Above-mentioned Au-TiO2-Bi2WO6In photochemical catalyst, Bi2WO6Nanometer sheet and TiO2The mass ratio of nanometer sheet is 1:10,
Au nanoparticle and TiO2-Bi2WO6The mass ratio of composite photo-catalyst is 1:1000, the Au-TiO2-Bi2WO6Photocatalysis
Agent shows excellent photo catalytic reduction and replaces the active and higher of p-nitrophenyl under the irradiation of ultraviolet-visible all band light
Selectivity；By taking selective reduction 4- nitroaniline as an example, 16 min, the conversion of paranitroanilinum are irradiated under ultraviolet-visible light
Rate is 99%, selectively reaches 97%.
Specific step is as follows for photocatalysis to selectively reduction:
(1) 10 mg Au-TiO are taken2-Bi2WO6Photochemical catalyst, 60 mg hole trapping agents ammonium formates and 40 ml 10
The substituted-nitrobenzene solution of mg/l stirs evenly in reaction flask, and is passed through nitrogen (80 ml/min), inhales in the dark state
Attached 1.5 h, makes substituted-nitrobenzene reach adsorption equilibrium in photocatalyst surface；
(2) under nitrogen protection, illumination is carried out to above-mentioned system, takes 2 ml reaction liquids every 4 min, reaction terminates
Afterwards, it is centrifuged, recycles catalyst, solution is analyzed by ultraviolet-visible spectrophotometer and liquid chromatogram.
Remarkable advantage of the invention is:
(1) of the invention by Au-TiO2-Bi2WO6Composite photocatalyst restores substituted-nitrobenzene for photocatalysis to selectively,
With high catalytic efficiency, have to a kind of accordingly product highly selective.
(2) Au-TiO2-Bi2WO6The preparation method of photochemical catalyst is simple, low in cost, convenient for amplification production and to environment
It is friendly.
Detailed description of the invention
Fig. 1 is blank TiO respectively2(the A figure in Fig. 1), blank Bi2WO6(the B figure in Fig. 1), TiO2-Bi2WO6(in Fig. 1
C figure) and Au-TiO2-Bi2WO6Transmission electron microscope (TEM) figure of (the D figure in Fig. 1) composite material.
Fig. 2 is blank TiO2, TiO2-Bi2WO6And Au-TiO2-Bi2WO6Composite material selectivity under ultraviolet-visible light
Restore paranitroanilinum activity figure.
Fig. 3 is blank TiO2, TiO2-Bi2WO6And Au-TiO2-Bi2WO6Photoelectric current test chart.
Specific embodiment
Below in conjunction with the specific embodiment content that the present invention is furture elucidated, but these embodiments are not intended to limit the present invention
Protection scope.
Embodiment 1
Blank TiO2Preparation:
By positive four butyl ester of 5 ml metatitanic acids (Ti (OBu)4) and 1 ml hydrofluoric acid (HF) be mixed evenly after be transferred to 50 ml
In reaction kettle, 24 h of hydro-thermal at 180 DEG C is then centrifuged for, washs, is dried to obtain TiO2Nanometer sheet.
By 10 mg TiO2The paranitroanilinum of 40 ml, 10 mg/l is added in nanosheet photocatalyst and 60 mg ammonium formates
In solution, 1 h is stirred under dark condition, while being passed through nitrogen (80 ml/min) and exhausting the air in solution, reaches absorption
It places it under ultraviolet-visible light and irradiates after balance.2 ml solution are taken out from reaction solution every 4 min, pass through ultraviolet-visible
Spectrophotometer and liquid chromatogram are analyzed.
Embodiment 2
TiO2-Bi2WO6Preparation:
By positive four butyl ester of 5 ml metatitanic acids (Ti (OBu)4) and 1 ml hydrofluoric acid (HF) be mixed evenly after be transferred to 50 ml
In reaction kettle, 24 h of hydro-thermal at 180 DEG C is then centrifuged for, washs, is dried to obtain TiO2Nanometer sheet.By obtained TiO2It receives
Rice piece (40 mg) and 2 ml 3- aminopropyl triethoxysilanes (APTES) are distributed in 200 ml ethyl alcohol, are flowed back at 60 DEG C
4 h are then centrifuged for, wash, being dried to obtain the positively charged TiO in surface2Nanometer sheet.By 1 mmol sodium tungstate (Na2WO4·2H2O),
2 mmol bismuth nitrate Bi (NO3)3·5H2O and 0.05 g cetyl trimethylammonium bromide (CTAB) are added in 80 ml distilled water,
It is transferred to after being mixed evenly in 100 mL reaction kettles, 24 h of hydro-thermal at 120 DEG C is then centrifuged for, washs, is dried to obtain
Bi2WO6Nanometer sheet.By the uniform Bi of ultrasonic disperse2WO6The aqueous solution (4 ml, 0.5 mg/ml) of nanometer sheet is slowly dropped to super
TiO after the finely dispersed positive electricity modification of sound2The aqueous solution (20 ml 1mg/ml) of nanometer sheet stirs 30 min, is centrifuged, washing
Be dried to obtain TiO2-10%Bi2WO6Sample (10% is mass fraction).
By 10 mg TiO2-10%Bi2WO6Composite photo-catalyst and 60 mg ammonium formates be added 40 ml, 10 mg/l to nitre
In base aniline solution, 1 h is stirred under dark condition, while being passed through nitrogen (80 ml/min) and exhausting the air in solution, is reached
It places it under ultraviolet-visible light and irradiates after to adsorption equilibrium.2 ml solution are taken out from reaction solution every 4 min, pass through purple
Outside-visible spectrophotometer and liquid chromatogram are analyzed.
Embodiment 3
Au-TiO2-Bi2WO6Preparation:
By positive four butyl ester of 5 ml metatitanic acids (Ti (OBu)4) and 1 ml hydrofluoric acid (HF) be mixed evenly after be transferred to 50 ml
In reaction kettle, 24 h of hydro-thermal at 180 DEG C is then centrifuged for, washs, is dried to obtain TiO2Nanometer sheet.By obtained TiO2It receives
Rice piece (40 mg) and 2 ml 3- aminopropyl triethoxysilanes (APTES) are distributed in 200 ml ethyl alcohol, are flowed back at 60 DEG C
4 h are then centrifuged for, wash, being dried to obtain the positively charged TiO in surface2Nanometer sheet.By 1 mmol sodium tungstate (Na2WO4·2H2O),
2 mmol bismuth nitrate Bi (NO3)3·5H2O and 0.05 g cetyl trimethylammonium bromide (CTAB) are added in 80 ml distilled water,
It is transferred to after being mixed evenly in 100 mL reaction kettles, 24 h of hydro-thermal at 120 DEG C is then centrifuged for, washs, is dried to obtain
Bi2WO6Nanometer sheet.By 26 ml, 2.8 mM sodium citrate (Na3C6H5O7·2H2O) solution is added to 50 ml, 0.4 mM chlorine gold
Acid (H2AuCl4) in solution, be mixed evenly, then the dropwise addition of 5 ml, 12 mM sodium borohydride (NaBH4) is entered, in room temperature
Under the conditions of stir 2 h after obtain Au nanometer particle colloid solution (Au NPs).By the uniform Bi of ultrasonic disperse2WO6The water of nanometer sheet
Solution (4 ml, 0.5 mg/ml) is slowly dropped to the TiO after the uniform positive electricity modification of ultrasonic disperse2The aqueous solution (20 of nanometer sheet
1 mg/ml of ml), 30 min are stirred, TiO is washed and is dried to obtain in centrifugation2-10%Bi2WO6Sample.By Au nanometer particle colloid
Solution (0.05 mg/ml of 1ml) is slowly dropped to the uniform TiO of ultrasonic disperse2-10%Bi2WO6Aqueous solution (50 ml, 1 mg/
Ml), 30 min are stirred, 0.1%Au-TiO is washed and is dried to obtain in centrifugation2-10%Bi2WO6(0.1% and 10% is quality point to sample
Number).
By 10 mg 0.1%Au-TiO2-10%Bi2WO640 ml, 10 mg/ is added in composite photo-catalyst and 60 mg ammonium formates
In the p-nitrophenyl amine aqueous solution of l, 1 h is stirred under dark condition, while being passed through nitrogen (80 ml/min) for the air in solution
It exhausts, reaches to place it under ultraviolet-visible light after adsorption equilibrium and irradiate.2 ml solution are taken out from reaction solution every 4 min,
It is analyzed by ultraviolet-visible spectrophotometer and liquid chromatogram.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (3)
1. a kind of preparation method of composite photocatalyst, it is characterised in that: the photochemical catalyst is Au-TiO2-Bi2WO6It is compound
Type photochemical catalyst is to pass through TiO2Nanometer sheet and Bi2WO6The compound two dimension of nanometer sheet-two dimensional heterostructures material simultaneously loads Au
What nanoparticle obtained；In the catalyst, Bi2WO6Nanometer sheet and TiO2The mass ratio of nanometer sheet is 1:10, Au nanoparticle
Son and TiO2-Bi2WO6Compound two dimension-two dimensional heterostructures material mass ratio is 1:1000；The following steps are included:
(1) TiO2The preparation of nanometer sheet: 50 are transferred to after positive four butyl ester of 5 ml metatitanic acids and 1 ml hydrofluoric acid are mixed evenly
In ml reaction kettle, 24 h of hydro-thermal at 180 DEG C is then centrifuged for, washs, is dried to obtain TiO2Nanometer sheet；
(2) TiO2The modification of nanometer sheet: by TiO made from step (1)2Nanometer sheet is modified with 3- aminopropyl triethoxysilane, is obtained
The TiO positively charged to surface2Nanometer sheet；
(3) Bi2WO6The preparation of nanometer sheet: by 1 mmol sodium tungstate, 2 mmol bismuth nitrates and 0.05 g cetyl trimethyl bromine
Change ammonium to be added in 80 ml distilled water, be transferred to after being mixed evenly in 100 mL reaction kettles, 24 h of hydro-thermal at 120 DEG C,
It is then centrifuged for, washs, is dried to obtain Bi2WO6Nanometer sheet；
(4) it is molten that 26 ml, 2.8 mM sodium citrate solution the preparation of Au nanoparticle: is added to 50 ml, 0.4 mM gold chloride
It in liquid, is mixed evenly, then the dropwise addition of 5 ml, 12 mM sodium borohydride is entered, is obtained after stirring 2 h at room temperature
Au nanometer particle colloid solution；
(5) Au-TiO2-Bi2WO6The preparation of compound: by the TiO after modification2Nanometer sheet and Bi2WO6Nanometer sheet mixing, then again
It is mixed evenly with Au nanoparticle, is then centrifuged for, washs, is dried to obtain Au-TiO2-Bi2WO6Composite photo-catalyst.
2. the preparation method of composite photocatalyst according to claim 1, it is characterised in that: in the step (4)
The concentration for the Au nanometer particle colloid solution prepared is 0.05 mg/ml.
3. a kind of application of the composite photocatalyst of method preparation as described in claim 1, it is characterised in that: prepared light
Catalyst restores substituted-nitrobenzene to corresponding amine for photocatalysis to selectively.
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| CN108043400B (en) * | 2017-12-08 | 2019-10-18 | 浙江工业大学 | A kind of Au-Bi2MoO6/ diatomite composite material and the preparation method and application thereof |
| CN109894149B (en) * | 2017-12-11 | 2021-11-16 | 中国科学院大连化学物理研究所 | Composite nano-structure catalyst and preparation and application thereof |
| CN112091232A (en) * | 2020-09-11 | 2020-12-18 | 合肥工业大学 | Rapid preparation of Au-TiO under acidic condition2Method of composite construction |
| CN113289610A (en) * | 2021-03-18 | 2021-08-24 | 合肥工业大学 | Bi2WO6/Si composite photoelectrocatalysis anode material and preparation method thereof |
| CN114405526A (en) * | 2021-12-29 | 2022-04-29 | 天津工业大学 | Preparation and application of two-dimensional MXene nanosheet modified porous Au @ Ag @ Pd core-shell structure photocatalyst |
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