CN106732797A - A kind of phosphotungstic acid loading type Pd metal organic framework catalyst - Google Patents
A kind of phosphotungstic acid loading type Pd metal organic framework catalyst Download PDFInfo
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- CN106732797A CN106732797A CN201611124310.XA CN201611124310A CN106732797A CN 106732797 A CN106732797 A CN 106732797A CN 201611124310 A CN201611124310 A CN 201611124310A CN 106732797 A CN106732797 A CN 106732797A
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- metal organic
- phosphotungstic acid
- organic framework
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 28
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000011068 loading method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000003814 drug Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000013291 MIL-100 Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000013144 Fe-MIL-100 Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- RGCHNYAILFZUPL-UHFFFAOYSA-N trimethyl benzene-1,3,5-tricarboxylate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(C(=O)OC)=C1 RGCHNYAILFZUPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229960000278 theophylline Drugs 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- -1 Iron(III) chloride hexahydrates Chemical class 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron(III) chloride Substances Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of phosphotungstic acid loading type Pd metal organic framework catalyst and its preparation method and application, carrier PTA MIL 100 (Fe) are dispersed in ethanol water, in N2Under atmosphere, can quickly by (PW using ultraviolet light12O40)3−It is reduced to (PW12O40)4−, add H2PdCl4, Pd2+Can be by (PW12O40)4−Moment reduces, and obtains Pd PTA MIL 100 (Fe) composite.The present invention utilizes (PW12O40)4−The method of assistance, grows the precious metals pd nano particle of high dispersive, in this process, it is not necessary to any additional reducing agent, surfactant and organic stabilizer and heat treatment process on MOF.The Pd nano particle good dispersions of preparation, utilization rate is high, and urges the medicine and personal-care supplies in drop neutralizing water environment with very efficient light at room temperature.
Description
Technical field
The invention belongs to the photocatalysis technology field in environmental improvement, and in particular to a kind of phosphotungstic acid loading type Pd-metal
Organic framework catalyst.
Background technology
Metal organic framework（Metal-Organic Frameworks, MOFs）Be a class with metal cation as node,
Organic ligand is the novel porous materials with periodic network structure that connector is constituted.In recent years, with MOFs materials as base
The photocatalysis technology of plinth gets more and more people's extensive concerning.However, with reference to the actual conditions of photocatalytic applications, it has been found that grind at present
The photocatalysis technology based on MOFs materials studied carefully remains that photo-generated carrier low separation efficiency is high and Solar use
The relatively low many problems of rate.Be the performance of further optimization MOFs photochemical catalysts, Au, Pd and Pt etc. with excellent electricity, urge
The expensive metals of performance such as change are introduced in MOFs.
The method for being used for preparing noble metal-MOFs composites at present has a lot, for example：Chemical reduction method, chemical gaseous phase
Deposition and electrochemical reduction.But the above method is generally than relatively time-consuming, severe reaction conditions.Generally need to add by force in course of reaction
Reducing agent such as sodium borohydride etc. may destroy MOFs underlying structures, and noble metal granule is easily caused in reduction process
A large amount of reunions of grain, average particle size is excessive.Thus it is common to use high polymer（Such as PVP）Precious metal surface is wrapped up, but this
The interracial contact between metal and carrier will be caused insufficient, it is impossible to effective transfer and separation photo-generated carrier.Therefore having must
The surface that noble metal is deposited on a kind of simple and effective method nanometer sheet is developed, without regard to organic ligand
Even reducing agent.
Phosphotungstic acid not only serves as the homogeneous photochemical catalysis agent of function admirable and preferable electron carrier, its intrinsic light-induced variable
Valence effect can also in-situ reducing noble metal.Therefore, phosphotungstic acid is encapsulated into MIL-100 (Fe) and carrier PTA-MIL- is obtained
100 (Fe), and make noble metal nano particles be dispersed in carrier surface to be made trielement composite material, MOF, phosphorus can not only be had concurrently
The dual-use function property of wolframic acid and noble metal nano particles, and there may be some novel cooperative effects.
The content of the invention
It is an object of the invention to be directed to deficiency of the prior art, there is provided a kind of phosphotungstic acid loading type Pd-metal is organic
Skeleton catalyst and its preparation method and application, is reduced the palladium ion of positive divalence by the metal with variable valence in carrier
Be deposited on the surface of carrier into Metal Palladium, solution prepare in the prior art noble metal/metal organic framework composite catalyst it is time-consuming,
The problems such as needing reducing agent and stabilizer, obtained Pd-PTA-MIL-100 (Fe) composite can be applied to photocatalysis field.
The preparation method is simple and easy to apply, do not need complex and expensive equipment, synthesis condition are gentle, and go for other metals
Load application is upper.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of phosphotungstic acid loading type Pd-metal organic framework catalyst, Pd nano particles are scattered in carrier surface, and particle diameter is 4-
8 nm；The carrier is a kind of metal organic framework compound PTA-MIL-100 (Fe) for being packaged with phosphotungstic acid.
Phosphotungstic acid loading type Pd-metal organic framework method for preparing catalyst as described above：By Iron(III) chloride hexahydrate,
Trimethyl trimesate, phosphotungstic acid and water are added in autoclave, after stirring 30 minutes, are placed in 130 DEG C of constant temperature ovens
Insulation 72 hours, natural cooling, the orange powder sample that reaction is obtained is carrier PTA-MIL-100 (Fe)；By ethanol, water and
PTA-MIL-100 (Fe) mixes, 100W ultrasound 30-60 min, after being passed through the oxygen in nitrogen removal solution, uses ultraviolet light（254
nm）Irradiation 10-30 min, add H2PdCl4, Pd- metal organic framework catalyst is obtained（Pd-PTA-MIL-100(Fe)）.
Described Pd-PTA-MIL-100 (Fe) catalyst can apply to the medicine during light at room temperature urges drop neutralizing water environment
With personal-care supplies.
Remarkable advantage of the invention is：
1）It is of the invention different from conventional noble metal method for preparing composite catalyst：Conventional method is mainly in carrier surface by leaching
Stain reducing process, deposition-precipitation method, but preparation method of the invention is (PW12O40)4−- assist to prepare, in this process, it is not required to
Want any additional reducing agent, surfactant and organic stabilizer and heat treatment process；
2）Palladium particle is smaller, uniform in catalyst obtained in preparation method of the invention, the particle diameter of prepared palladium nano-particles
It is 4-8 nm, in carrier surface good dispersion, does not have that there is stronger phase interaction between agglomeration, and noble metal and carrier
With so that the catalyst for preparing has good photocatalytic activity；
3）The preparation method that the present invention is used is simple and easy to apply, is conducive to large-scale popularization, with very big universality.It is many expensive
Metal（Such as gold, silver, platinum, copper, nickel）Successfully can be loaded on carrier using the technology.Therefore, it can by adding
Two or more precious metal salt, so as to prepare precious metal alloys loaded catalyst, and can be expensive by changing
The addition of slaine largely changes the load capacity of noble metal；
4）The catalyst prepared using the present invention, is applied to light at room temperature and urges drop to dissolve medicine and personal nursing in water environment
Articles for use；The catalyst can easily carry out separating treatment, reuse efficiency high, preceding with practical value very high and application
Scape.
Brief description of the drawings
Fig. 1 is the saturating X-ray powder diffraction spectrum of Pd-PTA-MIL-100 (Fe) catalyst synthesized by the embodiment of the present invention 1
Figure；
Fig. 2 is the transmission electron microscope picture of Pd-PTA-MIL-100 (Fe) catalyst synthesized by the embodiment of the present invention 1；
Fig. 3 (a) is the activity of the embodiment of the present invention 1 gained Pd-PTA-MIL-100 (Fe) catalyst room temperature photocatalytic degradation theophylline
Figure；Fig. 3 (b) is the work of the embodiment of the present invention 1 gained Pd-PTA-MIL-100 (Fe) catalyst room temperature photocatalytic degradation brufen
Property figure.
Specific embodiment
The present invention propose a kind of general, quick phosphotungstic acid loading type Pd-metal organic framework method for preparing catalyst and
Its application.There is variable valence using part metals, its lower valency form often has the property of certain reducing power, first makes
The metal of standby lower valency, is then reacted using its reducing power with the precious metal cation with oxidability.In this process
In, it is not necessary to any additional reducing agent, surfactant and organic stabilizer and heat treatment process.
The carrier of photochemical catalyst of the invention is MIL-100 (Fe).With (PW12O40)4−- method reduction Pd the ions assisted,
The particle diameter of Pd nano particles is 4-8 nm.
It is of the invention to concretely comprise the following steps：
（1）The preparation process of MIL-100 (Fe) carrier is as follows：By 0.378 g Iron(III) chloride hexahydrates（1.4 mmol）、0.272
G trimethyl trimesates（1.0 mmol）, 0.0525 g phosphotungstic acids and 10 mL H2O is added in 30 mL autoclaves,
After stirring 30 minutes, it is placed in 130 DEG C of constant temperature ovens and is incubated 72 hours.Hydrothermal reaction kettle is stood and is cooled to by reaction after terminating
Room temperature, by sample filtering, after the excess ions being attached in precipitation are washed away with distilled water, freeze-day with constant temperature number is small in being put into drying box
When, obtain orange powder as PTA-MIL-100 (Fe).Dried sample needs to be further purified with ethanol.First by second
Alcohol adds appropriate PTA-MIL-100 (Fe), and the constant temperature stirring 3h under the conditions of 60 DEG C, filtering, 60 DEG C of vacuum drying are obtained and carry
Body PTA-MIL-100 (Fe).
（2）By the ethanol of 8 mL, the carrier of the water of 8 mL, and 0.05g is added in Pyrex vials, ultrasonic 30-60
Min, ultrasonic power is 100W, is allowed to be uniformly dispersed.After oxygen in removing solution full of nitrogen in vial, ultraviolet light is used
（254 nm）Above-mentioned dispersion liquid 10-30 min are irradiated, suspension color is slightly deepened, this is due to there is blueness (PW12O40)4−
Generation.(the PW of generation12O40)4−In ethanol water, in N2Can be with stable existence under atmosphere.294 μ are added in toward system
The H of the mg/mL of L 102PdCl4, Pd2+Can be by (PW12O40)4−Quick reduction generation Pd0, while (PW12O40)4−Can be oxidized
Return to (PW12O40)3−, finally give Pd-PTA-MIL-100 (Fe) composite.
Embodiment 1
The preparation of Pd-PTA-MIL-100 (Fe) catalyst
By the ethanol of 8 mL, the carrier of the water of 8 mL, and 0.05g is added in Pyrex vials, ultrasonic 45 min, ultrasonic work(
Rate is 100W, is allowed to be uniformly dispersed.After oxygen in removing solution full of nitrogen in vial, ultraviolet light is used（254 nm）Irradiation
The min of above-mentioned dispersion liquid 20, suspension color is slightly deepened, and this is due to there is blueness (PW12O40)4−Generation.Generation
(PW12O40)4−In ethanol water, in N2Can be with stable existence under atmosphere.The mg/mL of 294 μ L 10 are added in toward system
H2PdCl4, Pd2+Can be by (PW12O40)4−Quick reduction generation Pd0, while (PW12O40)4−Return can be oxidized
(PW12O40)3−, finally give Pd-PTA-MIL-100 (Fe) composite.It is with 1%Pd-3%PTA-MIL-100 (Fe) sample
Example, Fig. 1 is illustrated and composed with the X-ray powder diffraction of 1%Pd-3%PTA-MIL-100 (Fe) catalyst synthesized by this preparation method
Figure, Fig. 2 illustrates the transmission electron microscope picture with 1%Pd-3%PTA-MIL-100 (Fe) catalyst synthesized by this preparation method.
Application examples
Pd-PTA-MIL-100 (Fe) composite light at room temperature urges the medicine and personal-care supplies in drop neutralizing water environment
Experiment has selected two kinds of typical medicines with personal-care supplies as simulating pollution thing：Theophylline and brufen, reaction temperature
It is room temperature to spend, and reaction atmosphere is air atmosphere.Specific experiment step is as follows：5 mg catalyst samples, 40 μ L hydrogen peroxide
（H2O2, 30%）With the medicine in 40 mL water environments and personal-care supplies solution（20 ppm）It is added to Pyrex reactors
In, solution ph（pH=4）Using 2 M H2SO4Solution is adjusted.Above-mentioned suspension need to be sufficiently stirred for 2 hours in the dark, protect
Card sample and medicine reach adsorption-desorption balance with personal-care supplies solution.Then, xenon lamp of the system in 300 W（North
Jing Bofei Lays company）Continue visible ray down（λ≥ 420 nm）Irradiation carries out light-catalyzed reaction.4 mL are sampled at regular intervals,
Centrifugation（12000 rpm, 3 min）, take supernatant liquor.Using the high performance liquid chromatograph of Agilent companies（HPLC-6890）
Analysis PPCPs change in concentration.We are selected at room temperature, using XtimateTMC18 posts（4.6 mm × 150 mm, particle diameter chi
Very little is 5.0 μm）Product is analyzed.Selection water-methanol（35:65, v/v）Mixed solution is used for the stream that theophylline is separate
Dynamic phase, in 0.8 mL/min, detector wavelength is arranged on 272 nm to flow control.And brufen then selects water-acetonitrile（70:
30, v/v）Used as mobile phase, in 1.3 mL/min, detector wavelength is arranged on 222 nm to flow control.
Shown in response situation such as Fig. 3 (a) and Fig. 3 (b), Pd-PTA-MIL-100 (Fe) catalyst shows preferable light
Catalysis activity.By the reaction of about 180 minutes, most of theophylline can be degraded with brufen.These results show Pd-
The activity of medicine and personal-care supplies of PTA-MIL-100 (Fe) catalyst with photocatalytic degradation under water phase normal temperature higher.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (5)
1. a kind of phosphotungstic acid loading type Pd-metal organic framework compound catalyst, it is characterised in that：Pd nano particles are scattered in
Carrier surface, and particle diameter is 4-8 nm；The carrier is a kind of metal organic framework compound PTA- for being packaged with phosphotungstic acid
MIL-100(Fe)。
2. phosphotungstic acid loading type Pd-metal organic framework compound catalyst according to claim 1, it is characterised in that：
The preparation method of the carrier is：Iron(III) chloride hexahydrate, trimethyl trimesate, phosphotungstic acid and water are added into reaction under high pressure
In kettle, after stirring 30 minutes, it is placed in 130 DEG C of constant temperature ovens and is incubated 72 hours, natural cooling, the orange powder that reaction is obtained
Sample is PTA-MIL-100 (Fe).
3. a kind of method for preparing phosphotungstic acid loading type Pd-metal organic framework catalyst as claimed in claim 1 or 2, its
It is characterised by：Ethanol, water and carrier are mixed, 100 W ultrasound 30-60 min, after being passed through the oxygen in nitrogen removal solution, with purple
Outer light irradiation 10-30 min, add H2PdCl4, Pd- metal organic framework catalyst is obtained.
4. the preparation method of phosphotungstic acid loading type Pd-metal organic framework catalyst according to claim 3, its feature exists
In：A length of 254 nm of ultraviolet light wave.
5. a kind of application of phosphotungstic acid loading type Pd-metal organic framework catalyst as claimed in claim 1, its feature exists
In：Medicine and personal-care supplies that described Pd- metal organic frameworks catalyst is used in room temperature photocatalytic degradation water environment.
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