CN109331881A - A kind of metal organic framework modification cadmium sulfide composite photo-catalyst and its preparation method and application - Google Patents
A kind of metal organic framework modification cadmium sulfide composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN109331881A CN109331881A CN201811110705.3A CN201811110705A CN109331881A CN 109331881 A CN109331881 A CN 109331881A CN 201811110705 A CN201811110705 A CN 201811110705A CN 109331881 A CN109331881 A CN 109331881A
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 80
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 50
- 230000004048 modification Effects 0.000 title claims abstract description 47
- 238000012986 modification Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 81
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 12
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 10
- 229960004217 benzyl alcohol Drugs 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical compound [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
Abstract
The invention discloses a kind of metal organic framework modification cadmium sulfide composite photo-catalysts and its preparation method and application, metal organic framework modification cadmium sulfide composite photo-catalyst is with three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti) for carrier, and cadmium sulfide is supported on MIL-125 (Ti) carrier and obtains.The metal organic framework modification cadmium sulfide composite photo-catalyst that the present invention is prepared has the advantages that environmentally protective, large specific surface area, reaction site are more, photo-generate electron-hole utilization rate is high, photocatalytic activity is high, stability is good and corrosion resistant, cadmium sulfide nano-particles are deposited on MIL-125 (Ti) by sedimentation and obtain metal organic framework modification cadmium sulfide composite photo-catalyst, have the advantages that simple process, cost of material are low, energy consumption is less and time-consuming short；Metal organic framework modification cadmium sulfide composite photo-catalyst of the present invention has the advantages that selectivity is high, application method is simple in the application of benzyl alcohol selective preparing benzaldehyde by oxidizing.
Description
Technical field
The present invention relates to composite photo-catalyst field, specifically a kind of metal organic framework modifies cadmium sulfide composite photocatalyst
Agent and its preparation method and application.
Background technique
It is one of the key areas studied at present that aromatic alcohol selective oxidation, which produces corresponding aromatic aldehyde,.In actual industry
In production, the method for usually used production aromatic aldehyde is benzyl chloride Hydrolyze method, and the product of the method production is relatively difficult to separate, especially
It is the chloride ion in reaction solution containing higher concentration so that in every field, the application especially in medicine receives aromatic aldehyde
Limitation, photocatalysis technology study it had made great progress in recent years as a kind of green synthesis techniques.Photocatalysis technology
It as a kind of green syt new technology, is compared with other methods, with energy-efficient, secondary pollution is small, cleaning is nontoxic and technique
The advantages that simplifying, this makes photocatalysis technology all have wide answer in terms of organic synthesis, wastewater purification and air cleaning
Use prospect.
Cadmium sulfide (CdS) is a kind of direct semiconductor with visible light absorption capacity, its forbidden bandwidth value is about 2.4
eV.Research shows that in terms of CdS has the function of very strong absorption light ability, electrochemistry, and can also under the excitation of visible light
Generate fluorescence.Moreover, the relatively narrow forbidden bandwidth of CdS makes it have very high utilization efficiency, thus often quilt to visible light
As photochemical catalyst can be studied.At present, CdS is in many fields by unprecedented application and research.Such as: solar battery, light
Quick resistance etc..
Although CdS has many good qualities, production application excessively in can also find that there are many problems.It is urged in light
Change in reaction, if by illumination self photoetch phenomenon can be occurred for CdS for a long time, photohole can be by the S in cadmium sulfide2-Oxygen
It is melted into sulphur simple substance.To largely reduce carrier yield, the rate of light-catalyzed reaction is influenced.And CdS nanometers
Material substance is easy that more serious agglomeration occurs in a solvent, can not sufficiently be used to occur so as to cause the surface CdS
Light-catalyzed reaction.The lower specific surface area of CdS is also to hinder an important factor for CdS is as excellent photochemical catalyst.So we
It can be seen that CdS has very big prospect of the application in photocatalysis technology field, but there is also some obstructions, how to improve CdS's
Photocatalytic activity becomes the important research topic of researchers.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of metal organic framework modification cadmium sulfide composite photo-catalyst and
Preparation method and application, the metal organic framework modification cadmium sulfide composite photo-catalyst being prepared have environmentally protective, ratio
Surface area is big, reaction site is more, photo-generate electron-hole utilization rate is high, photocatalytic activity is high, stability is good and corrosion resistant excellent
Point.
The technical solution of the present invention is as follows:
A kind of metal organic framework modification cadmium sulfide composite photo-catalyst, is with three-dimensional porous titanium-based metal organic backbone MIL-
125 (Ti) are carrier, and cadmium sulfide is supported on MIL-125 (Ti) carrier and obtains.
The mass percent of MIL-125 (Ti) is in the metal organic framework modification cadmium sulfide composite photo-catalyst
11.32%~20.55%.
The specific surface area of the metal organic framework modification cadmium sulfide composite photo-catalyst is 300~400m2/g；It is described
MIL-125 (Ti) be laminated structure.
A kind of preparation method of metal organic framework modification cadmium sulfide composite photo-catalyst, first by three-dimensional porous titanium fund
Belong to organic backbone MIL-125 (Ti), sulphur simple substance and caddy to be added in solvent under dark surrounds, is stirred for uniformly being mixed
Liquid is closed, after then uniform mixed liquor carries out photochemical precipitation reaction under ultraviolet lamp, is finally centrifuged, washs, is dry, obtaining gold
Belong to organic backbone and modifies cadmium sulfide composite photo-catalyst.
The mass ratio of the sulphur simple substance and caddy is 3:20；The solution selects ethanol solution.
The three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti) is prepared using following steps: being weighed
A certain amount of terephthalic acid (TPA) is added in the mixed solution containing N,N-dimethylformamide and anhydrous methanol, is stirred evenly
Afterwards, tetrabutyl titanate is added, after being sufficiently stirred, mixed liquor is poured into high temperature and pressure crystallizing kettle, by high temperature and pressure crystallization
It after kettle is sealed, is placed on crystallization 20h, crystallization in 150 DEG C of baking oven and finishes, take out high temperature and pressure crystallizing kettle, pour out reaction solution,
Then after washing, being centrifuged again, after obtained solid is placed on 200 DEG C of baking oven drying, three-dimensional porous titanium-based metal organic backbone is obtained
MIL-125(Ti)；Wherein, the content ratio of the terephthalic acid (TPA), mixed solution and tetrabutyl titanate is 0.5g:10mL:
0.25~0.27mL, in the mixed solution, the volume ratio of n,N-Dimethylformamide and anhydrous methanol is 9:1.
Three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti), sulphur simple substance and the caddy is under dark surrounds
It is added in solution and carries out ultrasonic vibration and obtain uniform mixed liquor, then uniform mixed liquor irradiates 6h progress light under ultraviolet lamp
It after chemical deposition reaction, is finally centrifuged, washs, dried in 100 DEG C of vacuum drying ovens, obtain metal organic framework modification cadmium sulfide
Composite photo-catalyst CdS-MIL-125 (Ti).
A kind of application of metal organic framework modification cadmium sulfide composite photo-catalyst, i.e., described metal organic framework modification
Application of the cadmium sulfide composite photo-catalyst in benzyl alcohol selective preparing benzaldehyde by oxidizing has specifically included following steps: will
Metal organic framework modification cadmium sulfide composite photo-catalyst is mixed with benzotrifluoride, benzyl alcohol is then added, under dark condition
Oscillation absorption, after reaching adsorption equilibrium, carries out light-catalyzed reaction under light illumination, to complete benzyl alcohol selective oxidation preparation
Benzaldehyde.
The content ratio of the described metal organic framework modification cadmium sulfide composite photo-catalyst, benzotrifluoride and benzyl alcohol is
25mg:9~11mL:0.8-1.2mL.
The carry out light-catalyzed reaction under light illumination, wherein illumination wavelength be greater than 420nm, light-catalyzed reaction when
Between be 60min.
Advantages of the present invention:
(1), metal organic framework modification cadmium sulfide composite photo-catalyst of the present invention is with three-dimensional porous titanium-based metal organic backbone
MIL-125 (Ti) is carrier, and cadmium sulfide is supported on MIL-125 (Ti) carrier and obtains；In the present invention, MIL-125 (Ti) is one
The three-dimensional porous titanium-based metal organic framework material of kind has unique physicochemical properties, such as open crystal structure, Gao Bibiao
Area, high porosity and adjustable aperture, nontoxicity and more catalytic reaction activity site；Meanwhile MIL-125 (Ti) is generated
Photohole be higher than the valence band of cadmium sulfide, there is good facilitation to the promotion of photocatalysis performance；The present invention is with MIL-
125 (Ti) modification cadmium sulfide can significantly improve the separative efficiency of electron-hole in CdS semiconduct and increase composite wood
The specific surface area of material efficiently solves low specific surface area existing for cadmium sulfide monomer itself, electron-hole recombination rate height, light and urges
The problems such as changing poor activity；In conclusion the metal organic framework modification cadmium sulfide composite photo-catalyst tool that the present invention is prepared
There are more environmentally protective, large specific surface area, reaction site, photo-generate electron-hole utilization rate height, photocatalytic activity height, stability good
And the advantages that corrosion-resistant, it is a kind of hypotoxicity, material economic and environment-friendly, practical application value is high.
(2), the preparation method of metal organic framework modification cadmium sulfide composite photo-catalyst of the present invention, being will by sedimentation
Cadmium sulfide nano-particles, which are deposited on MIL-125 (Ti), obtains metal organic framework modification cadmium sulfide composite photo-catalyst, has
Simple process, cost of material be low, energy consumption less and time-consuming short advantage.
(3), metal organic framework modification cadmium sulfide composite photo-catalyst of the present invention is in benzyl alcohol selective preparing benzaldehyde by oxidizing
Application in, have the advantages that selectivity height, application method it is simple.
Detailed description of the invention
Fig. 1 is the SEM figure of the three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti) of the present invention;
Fig. 2 is the SEM figure of metal organic framework modification cadmium sulfide composite photo-catalyst CdS-MIL-125 (Ti) of the present invention;
Fig. 3 is the photoluminescence spectra figure of MIL-125 (Ti) and CdS-MIL-125 (Ti) that the present invention is prepared;
Fig. 4 is nitrogen adsorption-desorption isotherm figure of MIL-125 (Ti) and CdS-MIL-125 (Ti) that the present invention is prepared;
Fig. 5 is the HRTEM figure for the CdS-MIL-125 (Ti) that the present invention is prepared;
Fig. 6 is the photocatalysis performance histogram of CdS-MIL-125 (Ti) circular response of the invention being prepared three times.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of metal organic framework modification cadmium sulfide composite photo-catalyst, is with three-dimensional porous titanium-based metal organic backbone
MIL-125 (Ti) is carrier, and cadmium sulfide is supported on MIL-125 (Ti) carrier and obtains；It is multiple that metal organic framework modifies cadmium sulfide
The specific surface area of light combination catalyst is 300~400m2/ g, MIL-125 (Ti) are laminated structure, metal organic framework modification vulcanization
The mass percent of MIL-125 (Ti) is 11.32%~20.55% in cadmium composite photo-catalyst.
A kind of preparation method of metal organic framework modification cadmium sulfide composite photo-catalyst, has specifically included following steps:
(1), solvent structure MIL-125 (Ti):
It weighs 0.5g terephthalic acid (TPA) and is added to the mixed solution containing 9mL N,N-dimethylformamide and 1mL anhydrous methanol
In, after mixing evenly, 0.26mL tetrabutyl titanate is added, after being sufficiently stirred, mixed liquor is poured into high temperature and pressure crystallizing kettle
In, it after high temperature and pressure crystallizing kettle is sealed, is placed on crystallization 20h, crystallization in 150 DEG C of baking oven and finishes, take out high temperature and pressure
Crystallizing kettle pours out reaction solution, after then being washed, be centrifuged with anhydrous methanol again, after obtained solid is placed on 200 DEG C of baking oven drying, obtains
To the three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti) of laminated structure；
(2), photochemical precipitation method synthesis CdS-MIL-125 (Ti):
First by the three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti) of 50mg, sulphur simple substance and caddy under dark surrounds
Be added in ethanol solution and carry out ultrasonic vibration and obtain uniform mixed liquor, then uniform mixed liquor irradiated under ultraviolet lamp 6h into
It after the reaction of row photochemical precipitation, is finally centrifuged, washs, dried in 100 DEG C of vacuum drying ovens, obtain metal organic framework modification sulphur
Cadmium composite photo-catalyst CdS-MIL-125 (Ti)；Wherein, the mass ratio of sulphur simple substance and caddy is 3:20.
Metal organic framework modifies cadmium sulfide composite photo-catalyst answering in benzyl alcohol selective preparing benzaldehyde by oxidizing
With, it is to mix with 10mL benzotrifluoride 25mg metal organic framework modification cadmium sulfide composite photo-catalyst, then addition 1mL benzene
Methanol vibrates absorption under dark condition, after reaching adsorption equilibrium, carries out under light irradiation of the illumination wavelength greater than 420nm
The light-catalyzed reaction of 60min, to complete benzyl alcohol selective preparing benzaldehyde by oxidizing.
By the MIL-125 (Ti) that step (1) is prepared and the CdS-MIL-125 (Ti) that step (2) is prepared into
Row electron microscope scanning obtains SEM figure and (schemes see the SEM that Fig. 1 and Fig. 2, Fig. 1 are MIL-125 (Ti), Fig. 2 CdS-MIL-
The SEM of 125 (Ti) schemes), and carry out photoluminescence spectra and analyze to obtain photoluminescence spectra figure (see figure 3), carry out nitrogen adsorption-
Desorption isotherm tests to obtain nitrogen adsorption-desorption isotherm figure (see figure 4)；The CdS-MIL-125 that step (2) is prepared
(Ti) transmission electron microscopy is carried out to obtain HRTEM figure (see figure 5) and carry out the photocatalysis performance of circular response three times testing to obtain
Photocatalysis performance histogram (see figure 6).
In Fig. 1, it can be seen that the disk shape of rule is presented in the MIL-125 (Ti) being prepared, and can be cadmium sulfide
Load provides enough sites.From Fig. 2, it is round thin that discovery cadmium sulfide nanoparticles are evenly distributed in MIL-125 (Ti)
Around piece, two kinds of compounds, which closely glue, forms CdS-MIL-125 (Ti) compound.
Fig. 3 is the photoluminescence spectra of MIL-125 (Ti) Yu CdS-MIL-125 (Ti) two kinds of materials, comparison discovery, CdS-
The photoluminescence intensity of MIL-125 (Ti) is significantly lower than MIL-125 (Ti), illustrates in CdS-MIL-125 (Ti) composite material
Photohole-electronics is lower than the photohole-electronics recombination rate of MIL-125 (Ti) to recombination rate, and then confirms that cadmium sulfide increases
The catalytic activity of strong MIL-125 (Ti).
Fig. 4 is that MIL-125 (Ti) and CdS-MIL-125 (Ti) two kinds of material nitrogen physisorption curves are said by comparison
After bright cadmium sulfide is supported on MIL-125 (Ti), the 3 D pore canal of MIL-125 (Ti) makes its adsorbed gas by Partial Blocking
Ability reduces.
Can be seen that by Fig. 5 high-resolution-ration transmission electric-lens formd between two kinds of materials of cadmium sulfide and MIL-125 (Ti) it is different
Matter knot facilitates the smooth migration of electronics therebetween.
In Fig. 6, using phenmethylol conversion ratio as ordinate, using cycle-index as abscissa, from fig. 6 it can be seen that by
After recycling three times, metal organic framework modification cadmium sulfide composite photo-catalyst (CdS-MIL-125 (Ti)) of the present invention still shows
Efficient photocatalysis performance out, degradation efficiency is still up to 19.7% after recycling three times, this illustrates the metal that the present invention is prepared
Organic backbone modification cadmium sulfide composite photo-catalyst has the advantages that photocatalysis performance is stable, before having good practical application
Scape.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of metal organic framework modifies cadmium sulfide composite photo-catalyst, it is characterised in that: be with three-dimensional porous titanium-based metal
Organic backbone MIL-125 (Ti) is carrier, and cadmium sulfide is supported on MIL-125 (Ti) carrier and obtains.
2. a kind of metal organic framework according to claim 1 modifies cadmium sulfide composite photo-catalyst, it is characterised in that: institute
State metal organic framework modification cadmium sulfide composite photo-catalyst in MIL-125 (Ti) mass percent be 11.32%~
20.55%。
3. a kind of metal organic framework according to claim 1 modifies cadmium sulfide composite photo-catalyst, it is characterised in that: institute
The specific surface area for the metal organic framework modification cadmium sulfide composite photo-catalyst stated is 300~400m2/g；The MIL-125
It (Ti) is laminated structure.
4. a kind of preparation method of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 1,
It is characterized in that: first by three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti), sulphur simple substance and caddy under dark surrounds
It is added in solvent, is stirred for the liquid that is uniformly mixed, then it is anti-to carry out photochemical precipitation under ultraviolet lamp for uniform mixed liquor
Ying Hou is finally centrifuged, washs, is dry, obtains metal organic framework modification cadmium sulfide composite photo-catalyst.
5. a kind of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 4 is prepared,
Be characterized in that: the mass ratio of the sulphur simple substance and caddy is 3:20；The solution selects ethanol solution.
6. a kind of preparation method of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 4,
Be characterized in that: the three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti) is prepared using following steps: being weighed
A certain amount of terephthalic acid (TPA) is added in the mixed solution containing N,N-dimethylformamide and anhydrous methanol, is stirred evenly
Afterwards, tetrabutyl titanate is added, after being sufficiently stirred, mixed liquor is poured into high temperature and pressure crystallizing kettle, by high temperature and pressure crystallization
It after kettle is sealed, is placed on crystallization 20h, crystallization in 150 DEG C of baking oven and finishes, take out high temperature and pressure crystallizing kettle, pour out reaction solution,
Then after washing, being centrifuged again, after obtained solid is placed on 200 DEG C of baking oven drying, three-dimensional porous titanium-based metal organic backbone is obtained
MIL-125(Ti)；Wherein, the content ratio of the terephthalic acid (TPA), mixed solution and tetrabutyl titanate is 0.5g:10mL:
0.25~0.27mL, in the mixed solution, the volume ratio of n,N-Dimethylformamide and anhydrous methanol is 9:1.
7. a kind of preparation method of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 4,
Be characterized in that: three-dimensional porous titanium-based metal organic backbone MIL-125 (Ti), sulphur simple substance and the caddy is under dark surrounds
It is added in solution and carries out ultrasonic vibration and obtain uniform mixed liquor, then uniform mixed liquor irradiates 6h progress light under ultraviolet lamp
It after chemical deposition reaction, is finally centrifuged, washs, dried in 100 DEG C of vacuum drying ovens, obtain metal organic framework modification cadmium sulfide
Composite photo-catalyst CdS-MIL-125 (Ti).
8. a kind of application of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 1, feature
Be: the metal organic framework modification cadmium sulfide composite photo-catalyst is in benzyl alcohol selective preparing benzaldehyde by oxidizing
Using having specifically included following steps: metal organic framework modification cadmium sulfide composite photo-catalyst being mixed with benzotrifluoride, so
After benzyl alcohol is added, under dark condition vibrate absorption, after reaching adsorption equilibrium, carry out light-catalyzed reaction under light illumination, from
And complete benzyl alcohol selective preparing benzaldehyde by oxidizing.
9. a kind of application of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 8, feature
Be: the content ratio that the metal organic framework modifies cadmium sulfide composite photo-catalyst, benzotrifluoride and benzyl alcohol is 25mg:
9~11mL:0.8-1.2mL.
10. a kind of application of metal organic framework modification cadmium sulfide composite photo-catalyst according to claim 8, feature
It is: the carry out light-catalyzed reaction under light illumination, wherein illumination wavelength is greater than 420nm, and the time of light-catalyzed reaction is
60min。
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| CN111450898A (en) * | 2020-05-18 | 2020-07-28 | 安徽工业大学 | Amorphous CoS for photocatalytic degradation of organic dyesx/MOF composite catalyst and preparation method thereof |
| WO2022052067A1 (en) * | 2020-09-11 | 2022-03-17 | 中国科学院大连化学物理研究所 | Metal organic framework material mil-125, preparation method therefor, and use thereof |
| CN115041235A (en) * | 2022-06-22 | 2022-09-13 | 湖南师范大学 | Titanium metal organic framework loaded copper sulfide composite photocatalyst and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109755540A (en) * | 2019-03-07 | 2019-05-14 | 肇庆市华师大光电产业研究院 | A kind of lithium sulfur battery anode material and preparation method thereof |
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| CN111450898A (en) * | 2020-05-18 | 2020-07-28 | 安徽工业大学 | Amorphous CoS for photocatalytic degradation of organic dyesx/MOF composite catalyst and preparation method thereof |
| CN111450898B (en) * | 2020-05-18 | 2021-12-21 | 安徽工业大学 | Amorphous CoS for photocatalytic degradation of organic dyesx/MOF composite catalyst and preparation method thereof |
| WO2022052067A1 (en) * | 2020-09-11 | 2022-03-17 | 中国科学院大连化学物理研究所 | Metal organic framework material mil-125, preparation method therefor, and use thereof |
| CN115041235A (en) * | 2022-06-22 | 2022-09-13 | 湖南师范大学 | Titanium metal organic framework loaded copper sulfide composite photocatalyst and preparation method and application thereof |
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Application publication date: 20190215 |