CN107349966B - A kind of Pt@MOFs/TiO2Photochemical catalyst and the preparation method and application thereof - Google Patents
A kind of Pt@MOFs/TiO2Photochemical catalyst and the preparation method and application thereof Download PDFInfo
- Publication number
- CN107349966B CN107349966B CN201710591951.4A CN201710591951A CN107349966B CN 107349966 B CN107349966 B CN 107349966B CN 201710591951 A CN201710591951 A CN 201710591951A CN 107349966 B CN107349966 B CN 107349966B
- Authority
- CN
- China
- Prior art keywords
- mofs
- preparation
- tio
- photochemical catalyst
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 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
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 28
- 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 12
- 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
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 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
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 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
- 238000006555 catalytic reaction Methods 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
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 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
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 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
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 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
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001875 compounds Chemical class 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
- 230000005611 electricity Effects 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
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing 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
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption 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
- 238000005259 measurement Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 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
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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 and application of photochemical catalyst.The present invention uses Double solvent method, first passes through the self assembly of the organic solvent of the MOF by noble metal nano particles and preparation, Pt@MOFs is then made under reducing agent existence condition, finally by TiO2It is dispersed in the aqueous solution of Pt@MOFs, it is final that the MOFs photochemical catalyst with three-decker is made.Prepared photochemical catalyst can be widely applied for the fields such as waste water treatment, atmospheric cleaning.The catalyst that the present invention invents preparation 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 since its photo-generate electron-hole divides the raising of interest rate but also it is also improved to the photocatalysis efficiency of Single Pollution object.
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 technique
In recent years, the three-dimensional porous shape MOFs material being made of central metallic ions and organic ligand has big ratio due to it
Surface area, type and structure diversity, can chemistry functional, high porosity and the adjustable characteristic of structure and become research heat
Point is adsorbing and storing CO2, hydrogen storage, Chemical Decomposition, drug delivery and heterogeneous catalysis etc. all show huge answer
Use prospect；Simultaneously with TiO2For representative Photocatalitic Technique of Semiconductor because have low energy consumption, reaction condition is mild, without secondary pollution
The advantages that, photocatalysis, electrochemical capacitor, solar battery and in terms of have well application before
Scape.However, working as TiO2When as photooxidation catalyst, there is a problem of that serious photo-generated carrier is compound, leads to its catalysis effect
Rate is not high.In recent years, building the methods of hetero-junctions and load cocatalyst is used as promoting the hand of electron hole separation
Section.
For heavy metal-hardly degraded organic substance combined pollution processing method, mainly first absorption is reprocessed at present, but again
Metal and dyestuff are the defects of catalyst surface can have competitive Adsorption 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 catalyst is prepared in vacuum drying method.This MOFs photochemical catalyst is due to its multistage pore canal knot
Heavy metal and dyestuff macromolecular can be separated, be beneficial to the absorption of reactant by structure, but also incident light is inside it
Multiple reflection is carried out to be conducive to improve the utilization to light；Simultaneously by Pd nanoparticle and TiO2It is supported in material respectively
Outer surface, so that the electrons and holes on surface move in the opposite direction, this will greatly reduce electronics-sky for the separation in this space
Cave is compound.Material designed by the present invention provides new thinking for the processing of combined pollution.
Summary 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
The defects of son-hole-recombination rate is high provides a kind of Pt MOFs/TiO2Photochemical catalyst and the preparation method and application thereof.Obtained
The more single MOFs of photochemical catalyst shows more significant photocatalytic activity and is promoted.
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 catalyst is prepared in hydrolytic polymerization, washing and vacuum drying method in specific solvent.Institute
Stating photochemical catalyst is the MOFs with specific cellular structure, and on the one hand this unique multi-stage artery structure is conducive to mass transfer and mentions
Absorption of the height to light；On the other hand, 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 material is 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, comprising the following steps:
(1) organic ligand of 3~5g source metal and 1~3g the preparation of MOFs: is added to the deionized water of 50~70ml
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 obtains mixed solution B, and mixed solution B is transferred in ptfe autoclave liner, then by ptfe autoclave
Liner is put into autoclave, 9~13 h of hydro-thermal reaction, then solution is filtered through 200~300 mesh stainless steel filter screens, is clear
It washes, be dried in vacuo, finally obtain 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) preparation of Pt@MOFs: the MOFs of 0.1~0.3g is added into 10~30mL petroleum ether organic solution, ultrasound
It mixes, stirs 0~30min at room temperature, obtain solution C, then by the H of 0.7~0.8ml2PtCl6It is added dropwise to molten in stirring
In liquid C, continue 2~4h of stirring at room temperature, add 0.06~0.07 g sodium borohydride, stirs 5~7h at room temperature, then by solution
It is last up to Pt@MOFs photochemical catalyst through the filtering of 200~300 mesh stainless steel filter screens, cleaning, vacuum drying；
(3)Pt@MOFs/TiO2Preparation: the Pt@MOFs of 0.1~0.3g is added into the deionized water of 10~30mL,
Ultrasound mixes, and stirs 0~30min at room temperature, obtains solution D, then by the TiO of 0.001~0.003g2It is added in stirring
In solution D, continue 5~7h of stirring at room temperature, then solution is filtered through 200~300 mesh stainless steel filter screens, is cleaned, vacuum is done
It is dry, it is last up to Pt@MOFs/TiO2Photochemical catalyst.
In the above method, in step (1), the temperature stirred at room temperature be 25~35 DEG C, stirring rate 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 stirring rate is 15~25 r/
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 stirring rate is 15~25 r/
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.
There is difference substantially in material prepared by the present invention and existing material, the present invention is prepared using Double solvent method
It obtains with three-decker (surfaces externally and internally difference supported precious metal nano-particle and TiO2) Pt@MIL-101/TiO2Photocatalysis
Agent.This morphology controllable obtained, large specific surface area, three layers of MOFs photochemical catalyst with multi-stage artery structure, inner surface
For precious metals pt, outer surface TiO2.The TiO of its outer surface2Hole and electronics can be generated under light illumination, and inner surface is expensive
Metal nanoparticle Pt can be enriched with electronics, so that photo-generate electron-hole efficiently separates, to improve photocatalysis efficiency.
Compared with prior art, the present invention has the advantage that
Three layers of MOFs photochemical catalyst prepared by the present invention, inner surface are noble metal nano particles Pt, outer surface TiO2,
Intermediate vector is MOFs.Be primarily due to the adjustable aperture structure of MOFs itself make it possible to by regulate and control aperture size, will
Target contaminant heavy metal-hardly degraded organic substance separates, and heavy metal can be entered since its partial size is smaller by MOFs material
The inside of photochemical catalyst, and hardly degraded organic substance due to its compared to the biggish partial size of heavy metal ion without can enter photocatalysis
The inside of agent, to have the function that separated from contaminants, while the TiO of its outer surface load2Sky can be generated under light illumination
Cave and electronics, the electronics of generation can be transmitted via MOFs material to be enriched on the noble metal nano particles Pt of inner surface, thus
So that reduction reaction occurs into the heavy metal inside photochemical catalyst；The TiO of outer surface load2The hole of enrichment can make to adsorb
Oxidation reaction occurs for the hardly degraded organic substance in photochemical catalyst outer surface.The catalyst that the present invention invents preparation improves photoproduction electricity
Son-hole separation rate not only enables combined pollutant to separate simultaneously synchronization process, finally improves its photocatalysis effect
Rate；And since its photo-generate electron-hole divides the raising of interest rate but also it also obtains the photocatalysis efficiency of Single Pollution object
It improves.
Detailed description of the invention
Fig. 1 is MIL-101 of the present invention, Pt@MIL-101 and Pt@MIL-101/TiO2The XRD of photochemical catalyst schemes；
Fig. 2A is the field emission scanning electron microscope figure FE-SEM of MIL-101 of the present invention；
Fig. 2 B is the field emission scanning electron microscope figure FE-SEM of Pt@MIL-101；
Fig. 2 C is 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 is the Flied emission transmission electron microscope picture HR-TEM of Pt@MIL-101；
Fig. 3 C is Pt@MIL-101/TiO2The Flied emission transmission electron microscope picture HR-TEM of photochemical catalyst；
Fig. 4 A~Fig. 4 D is 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 is the reduction photocatalytic degradation effect figure to single Cr, and Fig. 4 B is 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 is to compound RhB
Degradation reduction photocatalytic degradation effect figure.
Specific embodiment
The present invention will be further specifically described in detail with reference to specific embodiments, but embodiments of the present invention are not
It is limited to this, for not specifically specified technological parameter, can refer to routine techniques progress.
Embodiment 1
The preparation of MIL-101: the terephthalic acid (TPA) of nine water chromic nitrate of 4.002g 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 solution B is added into mixed solution A, 0.5h is mixed, will mix
It closes solution C to be transferred in ptfe autoclave liner, then ptfe autoclave liner is put into autoclave,
10h is reacted under 220 DEG C of high temperature and pressure, then solution is filtered through 250 mesh stainless steel filter screens, is clear with DMF, deionized water respectively
It washes 3 times, be dried in vacuo under the conditions of 150 DEG C, finally obtain MIL-101.
The preparation of Pt@MIL-101: the MIL-101 of 0.1g is added into 20mL petroleum ether organic solution, and ultrasound mixes,
30min is stirred at room temperature, obtains solution A, then by the H of 0.73ml2PtCl6It is added dropwise in the solution A in stirring, at room temperature
Continue to stir 3h, adds 0.068g sodium borohydride, stir 6h at room temperature, then solution is filtered through 250 mesh stainless steel filter screens,
3 times are cleaned with DMF, deionized water respectively, are dried in vacuo under the conditions of 150 DEG C, it is last up to Pt@MIL-101 photochemical catalyst.
Embodiment 2
The preparation of MIL-101: the terephthalic acid (TPA) of nine water chromic nitrate of 4.000g 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 solution B is added into mixed solution A, 0.5h is mixed, will mix
Solution C is transferred in ptfe autoclave liner, then ptfe autoclave liner is put into autoclave,
12h is reacted under 220 DEG C of high temperature and pressure, then solution is filtered through 250 mesh stainless steel filter screens, is cleaned respectively with DMF, deionized water
3 times, be dried in vacuo under the conditions of 150 DEG C, finally obtain MIL-101.
The preparation of Pt@MIL-101: the MIL-101 of 0.1g is added into 20mL petroleum ether organic solution, and ultrasound mixes,
30min is stirred at room temperature, obtains solution A, then by the H of 0.73ml2PdCl4It is added dropwise in the solution A in stirring, at room temperature
Continue to stir 3h, adds 0.068g sodium borohydride, stir 6h at room temperature, then solution is filtered through 250 mesh stainless steel filter screens,
3 times are cleaned with DMF, deionized water respectively, are dried in vacuo under the conditions of 150 DEG C, it is last up to Pt@MIL-101 photochemical catalyst.
Embodiment 3
Pt@MIL-101/TiO2Preparation: the Pd@MIL-101 of 0.1g is added into the deionized water of 20mL, ultrasound is mixed
It is even, 30min is stirred at room temperature, obtains solution A, then by the TiO of 0.003g2It is slowly added into the solution A in stirring, at room temperature
Continue to stir 6h, then solution filtered through 250 mesh stainless steel filter screens, with DMF, deionized water cleans 3 times, at 150 DEG C respectively
Under the conditions of be dried in vacuo, it is last up to Pt@MIL-101/TiO2Photochemical catalyst.The XRD diagram (Fig. 1) of different photochemical catalysts shows
Precious metals pt and TiO2It is loaded modified not destroy MIL-101 structure.From scanning electron microscope (Fig. 2A~Fig. 2 C) and transmission electricity
It can be seen that the presence of apparent three-decker in mirror (Fig. 3 A~Fig. 3 C).
Embodiment 4
Photocatalytic activity analysis: using Cr (VI)-rhodamine B for model composition pollutant, more different photochemical catalysts
Photocatalytic activity.Photocatalytic degradation reaction carries out in homemade photocatalytic reaction device, catalyst amounts 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；It opens
The dark adsorption reaction of 1h is first carried out before opening light source；Pass through absorbance value and combined standard of the measurement solution at 540nm wavelength
Curve calculates the removal rate of Cr (VI), and the absorbance value and combined standard curve at 554 nm wavelength calculate the removal of rhodamine B
Rate: D=(C0-C)/C0* 100%, C0For Cr (VI), rhodamine B initial concentration, C is t moment Cr (VI), rhodamine B it is dense
Degree.The results showed that Pt@MIL-101/TiO2Photochemical catalyst show photocatalytic activity more higher than MIL-101 (Fig. 4 A~
Fig. 4 D), compared to MIL-101, Pt@MIL-101/TiO2No matter single Cr (VI) pollution or RhB are polluted or right
In Cr (VI)-RhB combined pollution, catalytic activity is all significantly improved；On the other hand, Pt@MIL-101/TiO2Due to it
The characteristic of material itself can come separated from contaminants, carry out redox reaction simultaneously respectively in its surfaces externally and internally, thus
The separative efficiency for improving photo-generate electron-hole, there is it again relative to Single Pollution to the catalytic activity of combined pollution
It is further to improve.Generally speaking, Pt@MIL-101/TiO2Compared to MIL-101, there is higher catalytic activity.
Above embodiments be only to illustrate technical solution of the present invention and non-critical condition limitation, this field it is general
Or else logical personnel, which should be appreciated that, can deviate in the spirit and scope of the present invention defined by claims to its details or shape
Formula makes a variety of changes it.
Claims (9)
1. a kind of Pt@MOFs/TiO2The preparation method of photochemical catalyst, which comprises the following steps:
(1) preparation of MOFs: the organic ligand of 3~5g source metal and 1~3g are added in the deionized water of 50~70ml, obtained
To mixed solution A, 0.5~1h is stirred at room temperature, then acid solution is added into mixed solution A, 0.5~1h is mixed, obtains
To mixed solution B, mixed solution B is transferred in ptfe autoclave liner, then by ptfe autoclave liner
It is put into autoclave, 9~13h of hydro-thermal reaction, then solution is filtered through 200~300 mesh stainless steel filter screens, is cleaned, is true
Sky is dry, finally obtains MOFs；The source metal includes nine water chromic nitrates, chromium chloride hexahydrate or six water chromium sulfates；It is described to have
Machine ligand includes terephthalic acid (TPA), amino terephthalic acid (TPA) or trimesic acid；
(2) preparation of Pt@MOFs: the MOFs of 0.1~0.3g is added into 10~30mL petroleum ether organic solution, and ultrasound is mixed
It is even, 0~30min is stirred at room temperature, obtains solution C, then by the H of 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 borohydride, stirs 5~7h at room temperature, then solution is passed through
The filtering of 200~300 mesh stainless steel filter screens, cleaning, vacuum drying, it is last up to Pt@MOFs photochemical catalyst；
(3)Pt@MOFs/TiO2Preparation: the Pt@MOFs of 0.1~0.3g is added into the deionized water of 10~30mL, ultrasound
It mixes, stirs 0~30min at room temperature, obtain solution D, then by the TiO of 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
Afterwards up to Pt@MOFs/TiO2Photochemical catalyst；The Pt@MOFs/TiO2The MOFs catalysis material that photochemical catalyst is three layers.
2. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that in step (1), institute
Stating the temperature stirred at room temperature is 25~35 DEG C, and stirring rate is 15~25r/min；The mass percent concentration of the acid solution
It is 30%~100%.
3. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that in step (1), institute
Stating 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, drying time is 10~12h.
4. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that step (2) described room
The lower temperature stirred of temperature is 25~35 DEG C, and stirring rate is 15~25r/min.
5. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that step (2) vacuum is dry
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, which is characterized in that step (3) described room
The lower temperature stirred of temperature is 25~35 DEG C, and stirring rate is 15~25r/min.
7. Pt@MOFs/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that step (3) vacuum is dry
Dry temperature is 140~160 DEG C, and drying time is 10~12h.
8. a kind of Pt@MOFs/TiO being prepared by any one of claim 1~7 preparation method2Photochemical catalyst.
9. a kind of Pt@MOFs/TiO according to any one of claims 82Photocatalyst applications in heavy metal-organic matter combined pollution administer with
And atmospheric cleaning field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710591951.4A CN107349966B (en) | 2017-07-19 | 2017-07-19 | A kind of Pt@MOFs/TiO2Photochemical catalyst and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710591951.4A CN107349966B (en) | 2017-07-19 | 2017-07-19 | A kind of Pt@MOFs/TiO2Photochemical catalyst and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107349966A CN107349966A (en) | 2017-11-17 |
| CN107349966B true CN107349966B (en) | 2019-10-18 |
Family
ID=60284557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710591951.4A Active CN107349966B (en) | 2017-07-19 | 2017-07-19 | A kind of Pt@MOFs/TiO2Photochemical catalyst and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107349966B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620132A (en) * | 2018-05-03 | 2018-10-09 | 华南理工大学 | A kind of Pt NPs@MOFs photochemical catalysts and the preparation method and application thereof |
| CN110773154A (en) * | 2019-10-09 | 2020-02-11 | 华南理工大学 | Precious metal composite catalyst for purifying coal-fired organic waste gas and preparation method and application thereof |
| CN113559941A (en) * | 2021-08-24 | 2021-10-29 | 大连工业大学 | MOFs material-based metal nanoparticle-loaded catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103008012A (en) * | 2012-12-12 | 2013-04-03 | 华东师范大学 | Metal organic skeleton structure material load platinum catalyst, as well as preparation method and application thereof |
| CN105233872A (en) * | 2015-10-22 | 2016-01-13 | 辽宁大学 | Pd @MIL-101 composite and preparation method and application thereof |
| CN105289509A (en) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | Preparation method of mesoporous composite material with core-shell structure |
| CN106807446A (en) * | 2017-02-06 | 2017-06-09 | 辽宁大学 | A kind of composites of Ag@MIL 101 and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2556183A1 (en) * | 2010-04-08 | 2013-02-13 | Katholieke Universiteit Leuven | Photo-electrochemical cell |
-
2017
- 2017-07-19 CN CN201710591951.4A patent/CN107349966B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103008012A (en) * | 2012-12-12 | 2013-04-03 | 华东师范大学 | Metal organic skeleton structure material load platinum catalyst, as well as preparation method and application thereof |
| CN105233872A (en) * | 2015-10-22 | 2016-01-13 | 辽宁大学 | Pd @MIL-101 composite and preparation method and application thereof |
| CN105289509A (en) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | Preparation method of mesoporous composite material with core-shell structure |
| CN106807446A (en) * | 2017-02-06 | 2017-06-09 | 辽宁大学 | A kind of composites of Ag@MIL 101 and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| "Catalytic chromium reduction using formic acid and metal nanoparticles immobilized in a metal–organic framework";Mahendra Yadav et al;《Chemcomm communication》;20130304;第49卷;第3327-3329页 * |
| "Metal-organic framework templated synthesis of TiO2@MIL-101 coreshell architectures for high-efficiency adsorption and photocatalysis";Na Chang et al;《Materials Letters》;20170421;第200卷;第55–58页 * |
| "Titanium Dioxide Reinforced Metal–Organic Framework Pd Catalysts: Activity and Reusability Enhancement in Alcohol Dehydrogenation Reactions and Improved Photocatalytic Performance";Dominic Tilgner et al;《ChemCatChem》;20151007;第7卷;第3916-3922页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107349966A (en) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qiu et al. | The photocatalytic reduction of U (VI) into U (IV) by ZIF-8/g-C3N4 composites at visible light | |
| Wang et al. | Design, modification and application of semiconductor photocatalysts | |
| CN107617447A (en) | A kind of Ag@MOFs/TiO2The preparation method of photochemical catalyst and application | |
| Chen et al. | NH2-UiO-66 (Zr) with fast electron transfer routes for breaking down nitric oxide via photocatalysis | |
| Abdelhameed et al. | Engineering highly effective and stable nanocomposite photocatalyst based on NH2-MIL-125 encirclement with Ag3PO4 nanoparticles | |
| Jiang et al. | Assembling polyoxo-titanium clusters and CdS nanoparticles to a porous matrix for efficient and tunable H2-evolution activities with visible light | |
| Liu et al. | A facile approach for the synthesis of Z-scheme photocatalyst ZIF-8/gC 3 N 4 with highly enhanced photocatalytic activity under simulated sunlight | |
| Jiang et al. | Constructing graphite-like carbon nitride modified hierarchical yolk–shell TiO 2 spheres for water pollution treatment and hydrogen production | |
| Mohamed et al. | A novel design of porous Cr2O3@ ZnO nanocomposites as highly efficient photocatalyst toward degradation of antibiotics: a case study of ciprofloxacin | |
| Mohamed et al. | Enhanced CO2 photocatalytic conversion into CH3OH over visible‐light‐driven Pt nanoparticle-decorated mesoporous ZnO–ZnS S-scheme heterostructures | |
| Wang et al. | Ag NPs decorated C–TiO2/Cd0. 5Zn0. 5S Z-scheme heterojunction for simultaneous RhB degradation and Cr (VI) reduction | |
| Xie et al. | Hierarchical Bi2MoO6 microsphere photocatalysts modified with polypyrrole conjugated polymer for efficient decontamination of organic pollutants | |
| He et al. | NH2-MIL-125 (Ti) encapsulated with in situ-formed carbon nanodots with up-conversion effect for improving photocatalytic NO removal and H2 evolution | |
| Chang et al. | A promising Z-scheme heterojunction via loading Ag/AgCl into porous Co3O4 derived from ZIF-67 for visible light driven photocatalysis | |
| Shao et al. | Facile construction of a ZIF-67/AgCl/Ag heterojunction via chemical etching and surface ion exchange strategy for enhanced visible light driven photocatalysis | |
| He et al. | Construction of Schottky-type Ag-loaded fiber-like carbon nitride photocatalysts for tetracycline elimination and hydrogen evolution | |
| Liu et al. | Fabrication of highly efficient heterostructured Ag-CeO2/g-C3N4 hybrid photocatalyst with enhanced visible-light photocatalytic activity | |
| CN107349966B (en) | A kind of Pt@MOFs/TiO2Photochemical catalyst and the preparation method and application thereof | |
| Zhong et al. | Liquid phase deposition of flower-like TiO2 microspheres decorated by ZIF-8 nanoparticles with enhanced photocatalytic activity | |
| Alshaikh et al. | Templated synthesis of CuCo2O4-modified g-C3N4 heterojunctions for enhanced photoreduction of Hg2+ under visible light | |
| CN109675607A (en) | Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material | |
| Mei et al. | Efficient SO2 removal and highly synergistic H2O2 production based on a novel dual-function photoelectrocatalytic system | |
| Mohamed et al. | Construction of hierarchical ZnS@ ZnO secured from metal–organic framework-ZnS@ ZIF-8 for enhanced photoreduction of CO2 | |
| CN103846096A (en) | Silver/silver bromide/silver metavanadate plasma compound photocatalyst and preparation method thereof | |
| CN107224982A (en) | Cu/Pd alloys for reduction dechlorination material modify TiO2The preparation method of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |