CN107349966A - A kind of Pt@MOFs/TiO2Photochemical catalyst and preparation method and application - Google Patents
A kind of Pt@MOFs/TiO2Photochemical catalyst and preparation method and application Download PDFInfo
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- CN107349966A CN107349966A CN201710591951.4A CN201710591951A CN107349966A CN 107349966 A CN107349966 A CN 107349966A CN 201710591951 A CN201710591951 A CN 201710591951A CN 107349966 A CN107349966 A CN 107349966A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 claims description 2
- QFSKIUZTIHBWFR-UHFFFAOYSA-N chromium;hydrate Chemical compound O.[Cr] QFSKIUZTIHBWFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 239000002082 metal nanoparticle Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000013177 MIL-101 Substances 0.000 description 14
- 239000011651 chromium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 210000001367 artery Anatomy 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
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- 230000005611 electricity Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of Pt@MOFs/TiO2The preparation method of photochemical catalyst and application.The present invention uses Double solvent method, first passes through the self assembly of the organic solvent by noble metal nano particles and the MOF prepared, Pt@MOFs is then made under reducing agent existence condition, finally by TiO2It is dispersed in the Pt@MOFs aqueous solution, it is final that the MOFs photochemical catalysts with three-decker are made.Prepared photochemical catalyst can be widely applied for the fields such as waste water treatment, atmospheric cleaning.Catalyst prepared by the present invention improves the separation rate of photo-generate electron-hole, not only enables combined pollutant to separate simultaneously synchronization process, finally improves its photocatalysis efficiency；And because its photo-generate electron-hole divides the raising of interest rate also so that its photocatalysis efficiency to Single Pollution thing is also improved.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of Pt@MOFs/TiO2Photochemical catalyst and its preparation side
Method and application.
Background technology
In recent years, by the three-dimensional porous shape MOFs materials that central metallic ions and organic ligand form because it has big ratio
Surface area, the diversity of species and structure, chemically functionalization, high porosity and the adjustable characteristic of structure and as research heat
Point, it is in absorption/storage CO2, hydrogen storage, Chemical Decomposition, drug delivery and heterogeneous catalysis etc. all show it is huge should
Use prospect；Simultaneously with TiO2For representative Photocatalitic Technique of Semiconductor because with energy consumption is low, reaction condition is gentle, non-secondary pollution
The advantages that, before photocatalysis, electrochemical capacitor, solar cell and environment pollution control etc. have application well
Scape.However, work as TiO2During as photooxidation catalyst, the problem of serious photo-generated carrier is compound be present, cause its catalysis effect
Rate is not high.In recent years, the methods of building hetero-junctions and load cocatalyst is used as promoting the hand of electron hole separation
Section.
Currently for the processing method mainly first absorption reprocessing, but again of heavy metal-hardly degraded organic substance combined pollution
The defects of metal and dyestuff can have competitive Adsorption in catalyst surface, and photo-generate electron-hole recombination rate is high.The present invention adopts
With Double solvent method, by by organic ligand, source metal, noble metal source and TiO2Hydrolytic polymerization, washing in specific solvent
And three layers of MOFs photochemical catalysts are prepared in vacuum drying method.This MOFs photochemical catalysts are due to its multistage pore canal knot
Structure, heavy metal and dyestuff macromolecular can be separated, be beneficial to the absorption of reactant, also cause incident light inside it
Multiple reflection is carried out so as to be advantageous to improve the utilization to light；Simultaneously by Pd nano-particles and TiO2It is supported on respectively in material
Outer surface, the separation in this space cause the electronics on surface and hole to move in the opposite direction, and this will greatly reduce electronics-sky
Cave is compound.Material designed by the present invention provides new thinking for the processing of combined pollution.
The content of the invention
It is an object of the invention to overcome to have competitive Adsorption, and photoproduction electricity in catalyst surface in multiple pollutant
A kind of the defects of son-hole-recombination rate is high, there is provided Pt MOFs/TiO2Photochemical catalyst and preparation method and application.Obtained
The more single MOFs of photochemical catalyst shows more significant photocatalytic activity lifting.
The object of the invention is achieved through the following technical solutions：
A kind of Pt@MOFs/TiO2The preparation method of photochemical catalyst, by organic ligand, source metal, noble metal source and
TiO2Three layers of MOFs photochemical catalysts are prepared in hydrolytic polymerization, washing and vacuum drying method in specific solvent.Institute
It is the MOFs for having specific pore passage structure to state photochemical catalyst, and on the one hand this unique multi-stage artery structure is advantageous to mass transfer and carried
The high absorption to light；On the other hand, its multi-stage artery structure can separate heavy metal and dyestuff macromolecular, be beneficial to
The absorption of reactant.
A kind of Pt@MOFs/TiO2The preparation method of photochemical catalyst, by by organic ligand, source metal, noble metal source and
TiO2Three layers of MOFs photocatalysis materials are prepared in hydrolytic polymerization, washing and vacuum drying method in the aqueous solution containing acid
Material.
A kind of Pt@MOFs/TiO2The preparation method of photochemical catalyst, comprises the following steps：
(1) MOFs preparation：The organic ligand of 3~5g source metals and 1~3g is added to 50~70ml deionized water
In, mixed solution A is obtained, stirs 0.5~1h at room temperature, then acid solution is added into mixed solution A, mixing 0.5~
1h, mixed solution B is obtained, mixed solution B is transferred in ptfe autoclave inner bag, then by ptfe autoclave
Inner bag is put into autoclave, 9~13h of hydro-thermal reaction, then solution is filtered through 200~300 mesh stainless steel filter screens, be clear
Wash, be dried in vacuo, finally give MOFs；The source metal includes nine water chromic nitrates, chromium chloride hexahydrate or six water chromium sulfates；Institute
Stating organic ligand includes terephthalic acid (TPA), amino terephthalic acid (TPA) or trimesic acid；
(2) Pt@MOFs preparation：0.1~0.3g MOFs is added into 10~30mL petroleum ether organic solutions, ultrasound
Mix, stir 0~30min at room temperature, obtain solution C, then the H by 0.7~0.8ml2PtCl6It is added dropwise to molten in stirring
In liquid C, continue 2~4h of stirring at room temperature, add 0.06~0.07g sodium borohydrides, stir 5~7h at room temperature, then by solution
Through the filtering of 200~300 mesh stainless steel filter screens, cleaning, vacuum drying, Pt@MOFs photochemical catalysts are finally produced；
(3)Pt@MOFs/TiO2Preparation：0.1~0.3g Pt@MOFs are added into 10~30mL deionized water,
Ultrasound mixes, and stirs 0~30min at room temperature, obtains solution D, then the TiO by 0.001~0.003g2It is added to molten in stirring
In liquid D, continue 5~7h of stirring at room temperature, then solution filtered through 200~300 mesh stainless steel filter screens, cleans, be dried in vacuo,
Finally produce Pt@MOFs/TiO2Photochemical catalyst.
In the above method, in step (1), the temperature stirred at room temperature be 25~35 DEG C, stir speed (S.S.) be 15~
25r/min；The mass percent concentration of the acid solution is 30%~100%.
In the above method, in step (1), the hydrothermal temperature is 180~200 DEG C；The hydro-thermal reaction pressure is
0.1~0.3MPa；The vacuum drying temperature is 140~160 DEG C, and drying time is 10~12h.
In the above method, step (2) temperature stirred at room temperature is 25~35 DEG C, and stir speed (S.S.) is 15~25r/
min。
In the above method, step (2) vacuum drying temperature is 140~160 DEG C, and drying time is 10~12h.
In the above method, step (3) temperature stirred at room temperature is 25~35 DEG C, and stir speed (S.S.) is 15~25r/
min。
In the above method, step (3) vacuum drying temperature is 140~160 DEG C, and drying time is 10~12h.
A kind of Pt@MOFs/TiO2Photocatalyst applications are administered in heavy metal-organic matter combined pollution and atmospheric cleaning is led
Domain.
Material prepared by the present invention is prepared with existing material in the presence of difference substantially, the present invention using Double solvent method
Obtain with three-decker (surfaces externally and internally difference supported precious metal nano-particle and TiO2) Pt@MIL-101/TiO2Photocatalysis
Agent.This obtained morphology controllable, specific surface area is big, has three layers of MOFs photochemical catalysts of multi-stage artery structure, its inner surface
For precious metals pt, outer surface TiO2.The TiO of its outer surface2Hole and electronics can be produced under light illumination, and inner surface is expensive
Metal nanoparticle Pt can be enriched with electronics, so that photo-generate electron-hole efficiently separates, so as to improve photocatalysis efficiency.
Compared with prior art, the present invention has following advantage：
Three layers of MOFs photochemical catalysts prepared by the present invention, its inner surface are noble metal nano particles Pt, outer surface TiO2,
Intermediate carrier is MOFs.It is primarily due to the adjustable aperture structures of MOFs itself and allows it by the size for regulating and controlling aperture, will
Target contaminant heavy metal-hardly degraded organic substance is separated, and heavy metal can be entered because its particle diameter is smaller by MOFs materials
The inside of photochemical catalyst, and hardly degraded organic substance can not enter photocatalysis due to its particle diameter larger compared to heavy metal ion
The inside of agent, so as to have the function that separated from contaminants, while the TiO of its outer surface load2Sky can be produced under light illumination
Cave and electronics, caused electronics can be enriched on the noble metal nano particles Pt of inner surface via MOFs material transmission, so as to
So that reduction reaction occurs into the heavy metal inside photochemical catalyst；The TiO of outer surface load2The hole of enrichment can make absorption
Oxidation reaction occurs for the hardly degraded organic substance in photochemical catalyst outer surface.Catalyst prepared by present invention invention improves photoproduction electricity
The separation rate in son-hole, not only enable combined pollutant to separate simultaneously synchronization process, finally improve its photocatalysis effect
Rate；And because its photo-generate electron-hole divides the raising of interest rate also so that its photocatalysis efficiency to Single Pollution thing also obtains
Improve.
Brief description of the drawings
Fig. 1 is MIL-101 of the present invention, Pt@MIL-101 and Pt@MIL-101/TiO2The XRD of photochemical catalyst；
Fig. 2A is MIL-101 of the present invention field emission scanning electron microscope figure FE-SEM；
Fig. 2 B are Pt@MIL-101 field emission scanning electron microscope figure FE-SEM；
Fig. 2 C are Pt@MIL-101/TiO2The field emission scanning electron microscope figure FE-SEM of photochemical catalyst；
Fig. 3 A be MIL-101 of the present invention Flied emission transmission electron microscope picture HR-TEM,
Fig. 3 B are Pt@MIL-101 Flied emission transmission electron microscope picture HR-TEM；
Fig. 3 C are Pt@MIL-101/TiO2The Flied emission transmission electron microscope picture HR-TEM of photochemical catalyst；
Fig. 4 A~Fig. 4 D are MIL-101 and Pt@MIL-101/TiO of the present invention2Photochemical catalyst is to Cr (VI)-rhodamine B
Photocatalytic degradation effect figure, wherein Fig. 4 A are the reduction photocatalytic degradation effect figure to single Cr, and Fig. 4 B are the drop to single RhB
The reduction photocatalytic degradation effect figure of solution, Fig. 4 C are the reduction photocatalytic degradation effect figure to compound Cr, and Fig. 4 D are to compound RhB
Degraded reduction photocatalytic degradation effect figure.
Embodiment
Make further specific detailed description, but embodiments of the present invention are not to the present invention with reference to specific embodiment
It is limited to this, for especially not dated technological parameter, can refer to routine techniques progress.
Embodiment 1
MIL-101 preparation：The terephthalic acid (TPA) of the water chromic nitrates of 4.002g nine and 1.661g is added to the water-soluble of 70ml
In liquid A, 0.5h is stirred at room temperature, then 0.5ml hydrofluoric acid solutions B is added into mixed solution A, mixes 0.5h, will be mixed
Close solution C to be transferred in ptfe autoclave inner bag, then ptfe autoclave inner bag be put into autoclave,
10h is reacted under 220 DEG C of HTHPs, then solution is filtered through 250 mesh stainless steel filter screens, be clear with DMF, deionized water respectively
Wash 3 times, be dried in vacuo under the conditions of 150 DEG C, finally give MIL-101.
Pt@MIL-101 preparation：0.1g MIL-101 is added into 20mL petroleum ether organic solutions, ultrasound mixes,
30min is stirred at room temperature, obtains solution A, then the H by 0.73ml2PtCl6It is added dropwise in the solution A in stirring, at room temperature
Continue to stir 3h, add 0.068g sodium borohydrides, stir 6h at room temperature, then solution is filtered through 250 mesh stainless steel filter screens,
3 times cleaned with DMF, deionized water respectively, be dried in vacuo under the conditions of 150 DEG C, finally produce Pt@MIL-101 photochemical catalysts.
Embodiment 2
MIL-101 preparation：The terephthalic acid (TPA) of the water chromic nitrates of 4.000g nine and 1.660g is added to the water-soluble of 60ml
In liquid A, 0.5h is stirred at room temperature, then 2ml hydrofluoric acid solutions B is added into mixed solution A, is mixed 0.5h, will be mixed
Solution C is transferred in ptfe autoclave inner bag, then ptfe autoclave inner bag is put into autoclave,
12h is reacted under 220 DEG C of HTHPs, then solution is filtered through 250 mesh stainless steel filter screens, cleaned respectively with DMF, deionized water
3 times, be dried in vacuo under the conditions of 150 DEG C, finally give MIL-101.
Pt@MIL-101 preparation：0.1g MIL-101 is added into 20mL petroleum ether organic solutions, ultrasound mixes,
30min is stirred at room temperature, obtains solution A, then the H by 0.73ml2PdCl4It is added dropwise in the solution A in stirring, at room temperature
Continue to stir 3h, add 0.068g sodium borohydrides, stir 6h at room temperature, then solution is filtered through 250 mesh stainless steel filter screens,
3 times cleaned with DMF, deionized water respectively, be dried in vacuo under the conditions of 150 DEG C, finally produce Pt@MIL-101 photochemical catalysts.
Embodiment 3
Pt@MIL-101/TiO2Preparation：0.1g Pd@MIL-101 are added into 20mL deionized water, ultrasound is mixed
It is even, 30min is stirred at room temperature, obtains solution A, then the TiO by 0.003g2It is slowly added into the solution A in stirring, at room temperature
Continue to stir 6h, then solution is filtered through 250 mesh stainless steel filter screens, cleans 3 times, at 150 DEG C with DMF, deionized water respectively
Under the conditions of be dried in vacuo, finally produce Pt@MIL-101/TiO2Photochemical catalyst.The XRD (Fig. 1) of different photochemical catalysts shows expensive
Pt metal and TiO2It is loaded modified not destroy MIL-101 structure.From ESEM (Fig. 2A~Fig. 2 C) and transmission electron microscope
It can be seen that the presence of obvious three-decker in (Fig. 3 A~Fig. 3 C).
Embodiment 4
Photocatalytic activity is analyzed：Cr (VI)-rhodamine B is used as model composition pollutant, more different photochemical catalysts
Photocatalytic activity.Photocatalytic degradation reaction is carried out in homemade photocatalytic reaction device, catalyst amountses 100mg, light
Source light intensity is ultraviolet 1.6mW/cm3；Cr (VI) and the initial concentration of rhodamine B are 10mg/L, liquor capacity 100mL；Open
1h dark adsorption reaction is first carried out before opening light source；By determining absorbance of the solution at 540nm wavelength and combined standard
Curve calculates Cr (VI) clearance, and the absorbance and combined standard curve at 554nm wavelength calculate the removal of rhodamine B
Rate：D=(C0-C)/C0* 100%, C0For Cr (VI), rhodamine B initial concentration, C is t Cr (VI), the concentration of rhodamine B.
Test result indicates that：Pt@MIL-101/TiO2Photochemical catalyst shows the photocatalytic activity higher than MIL-101 (Fig. 4 A~figure
4D), compared to MIL-101, Pt@MIL-101/TiO2No matter for single Cr (VI) pollutions or RhB pollutions or for
Cr (VI)-RhB combined pollutions, its catalytic activity are all significantly improved；On the other hand, Pt@MIL-101/TiO2Due to its material
The characteristic of material itself can come separated from contaminants, redox reaction be carried out simultaneously respectively in its surfaces externally and internally, so as to carry
The separative efficiency of high photo-generate electron-hole, finally cause its catalytic activity to combined pollution have again relative to Single Pollution into
The raising of one step.Generally speaking, Pt@MIL-101/TiO2Compared to MIL-101, there is higher catalytic activity.
Above example be only to illustrate technical scheme and non-critical condition limitation, this area it is general
Or else logical personnel, which should be appreciated that, can deviate in the spirit and scope of the present invention that claims are limited to its details or shape
Formula makes a variety of changes to it.
Claims (9)
- A kind of 1. Pt@MOFs/TiO2The preparation method of photochemical catalyst, it is characterised in that by by organic ligand, source metal, your gold Category source and TiO2Three layers of MOFs is prepared in hydrolytic polymerization, washing and vacuum drying method in the aqueous solution containing acid Catalysis material；Comprise the following steps：(1) MOFs preparation：3~5g source metals and 1~3g organic ligand are added in 50~70ml deionized water, obtained To mixed solution A, 0.5~1h is stirred at room temperature, then acid solution is added into mixed solution A, is mixed 0.5~1h, is obtained To mixed solution B, mixed solution B is transferred in ptfe autoclave inner bag, then by ptfe autoclave inner bag It is put into autoclave, 9~13h of hydro-thermal reaction, then solution is filtered through 200~300 mesh stainless steel filter screens, cleaned, be true Sky is dried, and finally gives MOFs；The source metal includes nine water chromic nitrates, chromium chloride hexahydrate or six water chromium sulfates；It is described to have Machine part includes terephthalic acid (TPA), amino terephthalic acid (TPA) or trimesic acid；(2) Pt@MOFs preparation：0.1~0.3g MOFs is added into 10~30mL petroleum ether organic solutions, ultrasound is mixed It is even, 0~30min is stirred at room temperature, obtains solution C, then the H by 0.7~0.8ml2PtCl6The solution C being added dropwise in stirring In, continue 2~4h of stirring at room temperature, add 0.06~0.07g sodium borohydrides, stir 5~7h at room temperature, then solution is passed through The filtering of 200~300 mesh stainless steel filter screens, cleaning, vacuum drying, finally produce Pt@MOFs photochemical catalysts；(3)Pt@MOFs/TiO2Preparation：0.1~0.3g Pt@MOFs are added into 10~30mL deionized water, ultrasound Mix, stir 0~30min at room temperature, obtain solution D, then the TiO by 0.001~0.003g2The solution D being added in stirring In, continue 5~7h of stirring at room temperature, then solution is filtered through 200~300 mesh stainless steel filter screens, cleans, be dried in vacuo, most After produce Pt@MOFs/TiO2Photochemical catalyst.
- 2. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, it is characterised in that in step (1), institute It is 25~35 DEG C to state the temperature stirred at room temperature, and stir speed (S.S.) is 15~25r/min；The mass percent concentration of the acid solution For 30%~100%.
- 3. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, it is characterised in that in step (1), institute Hydrothermal temperature is stated as 180~200 DEG C；The hydro-thermal reaction pressure is 0.1~0.3MPa；The vacuum drying temperature is 140~160 DEG C, drying time is 10~12h.
- 4. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, it is characterised in that step (2) described room The temperature of the lower stirring of temperature is 25~35 DEG C, and stir speed (S.S.) is 15~25r/min.
- 5. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, it is characterised in that step (2) vacuum is done Dry temperature is 140~160 DEG C, and drying time is 10~12h.
- 6. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, it is characterised in that step (3) described room The temperature of the lower stirring of temperature is 25~35 DEG C, and stir speed (S.S.) is 15~25r/min.
- 7. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, it is characterised in that step (3) vacuum is done Dry temperature is 140~160 DEG C, and drying time is 10~12h.
- 8. a kind of Pt@MOFs/TiO are prepared by any one of claim 1~7 preparation method2Photochemical catalyst.
- A kind of 9. Pt@MOFs/TiO described in claim 82Photocatalyst applications in heavy metal-organic matter combined pollution administer with And atmospheric cleaning field.
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