CN108855216A - Metal organic frame MIL-101 (Cr) optic catalytic composite material and the preparation method and application thereof of cadmium sulfide package - Google Patents
Metal organic frame MIL-101 (Cr) optic catalytic composite material and the preparation method and application thereof of cadmium sulfide package Download PDFInfo
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- CN108855216A CN108855216A CN201810591721.2A CN201810591721A CN108855216A CN 108855216 A CN108855216 A CN 108855216A CN 201810591721 A CN201810591721 A CN 201810591721A CN 108855216 A CN108855216 A CN 108855216A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 92
- 239000013178 MIL-101(Cr) Substances 0.000 title claims abstract description 90
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 58
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 9
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate 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
- 238000003756 stirring Methods 0.000 claims description 7
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 6
- 239000011636 chromium(III) chloride Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 238000005457 optimization Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 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
- B01J31/16—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
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/80—Preparation of compounds containing amino groups bound to a carbon skeleton by photochemical reactions; by using free radicals
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
Abstract
The invention discloses metal organic frame MIL-101 (Cr) optic catalytic composite materials and the preparation method and application thereof of cadmium sulfide package, metal organic frame MIL-101 (Cr) is prepared first, then it is cleaned and is activated, metal organic frame MIL-101 (Cr) again with mercaptoethylmaine, Cd (Ac)2·2H2O, thioacetamide reacts to obtain metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package, which has good conversion ratio and selectivity in photocatalysis to selectively nitro compound reducing.Preparation process of the present invention is simple, and reaction condition is mild, and the microstructure to optimization composite material simultaneously expands its application in the organic conversion reaction of selectivity and has important reference role and practical application value.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of metal organic frame MIL-101 of cadmium sulfide package
(Cr) optic catalytic composite material and the preparation method and application thereof.
Background technique
On the one hand photocatalysis technology can be used for the controls of environmental pollution such as water, air and soil as a green technology；
On the other hand, photolysis water hydrogen, carbon dioxide reduction and organic transformation reaction etc. be can be used for.With the continuous hair of the technology
Exhibition, the research that photocatalysis technology is used for field of environment-friendly organic synthesis is concerned.In recent years, metal-organic framework material due to
Tailorability is had both with biggish specific surface area, topological structure abundant, adjustable band structure and structure, can be designed
The features such as property, easy modulation, become the out-phase photocatalyst material for having much potentiality.Cadmium sulfide has suitable band structure, is
Excellent visible light conductor photocatalysis material.Therefore, by metal organic frame MIL-101 (Cr) in conjunction with cadmium sulfide, sufficiently
The advantage for playing the two all has important scientific research meaning in materials synthesis and photocatalysis field.However, due to metal
The synthesis condition of organic framework materials and the synthesis condition of cadmium sulfide mismatch, and there are cadmium sulfide particles to exist for traditional combination
The problems such as load is uneven on metal organic frame, and particle size and load capacity are unable to control.Based on this, new preparation side is developed
Method constructs the metal organic frame-cadmium sulfide composite material with good interface effect, and the advantage for giving full play to the two is used in combination
It has broad application prospects in photocatalysis to selectively organic synthesis.
Summary of the invention
The purpose of the present invention is to provide a kind of metal organic frame MIL-101 (Cr) photocatalysis of cadmium sulfide package is compound
The application of material and preparation method thereof and the optic catalytic composite material in the reaction of selective organic transformation.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package, including it is following
Step：
（1）Prepare metal organic frame MIL-101 (Cr)：CrCl is added in the polytetrafluoroethyllining lining of 25 mL3·6H2O、
Terephthalic acid (TPA) and deionized water, ultrasonic 15-25 min；Then polytetrafluoroethyllining lining is placed in 200-220 DEG C of baking oven
24-28 h is reacted, centrifugation takes precipitating to dry, obtains metal organic frame MIL-101 (Cr)；
（2）The removal of impurities and activation of metal organic frame MIL-101 (Cr)：Metal organic frame MIL-101 (Cr) is dispersed in nothing
In water-ethanol, metal organic frame MIL-101 (Cr) is then washed and is dried with dehydrated alcohol by 75-85 DEG C of reflux 20-24 h
It is dry；
（3）Prepare metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：Metal after drying is had
Machine frame MIL-101 (Cr) is dispersed in dehydrated alcohol, and mercaptoethylmaine is added and stirs 5-10min, then mixture exists
2-2.5 h is reacted at 80-85 DEG C；Add Cd (Ac)2·2H2O the reaction was continued 2-2.5 h；Add thioacetamide continuation
React 12-14 h；Then by product centrifugation, washing, drying, the metal organic frame MIL-101 (Cr) of cadmium sulfide package is obtained
Optic catalytic composite material.
Step（1）In, the CrCl3·6H2The mass ratio of O and terephthalic acid (TPA) is 266.6：160-170, preferably
266.6∶166.6。
Step（1）In, the centrifugally operated is specific as follows：Product is first centrifuged 3-4 under the revolving speed of 3000-3500 r/min
Min takes filtrate to be centrifuged 2 times under the revolving speed of 3000-3500 r/min again, then by filtrate 8000-8500 r/min's
5-6 min is centrifuged under revolving speed, merging is centrifuged obtained precipitating every time.
Step（2）In, the drying is the dry 10-14 h in the baking oven that temperature is 110-130 DEG C.
Step（3）In, the metal organic frame MIL-101 (Cr), mercaptoethylmaine, Cd (Ac)2·2H2O thioacetamide
Mass ratio be 40：35-45 ：40-50 ：10-15, preferably 40: 40: 44.2: 12.4.
Step（3）In, the amount ratio of the metal organic frame MIL-101 (Cr) and ethyl alcohol is 40 mg: 20-30mL.
Step（3）In, the washing is successively to be washed using dehydrated alcohol and deionized water, and the drying temperature is 60-
65℃。
In metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package prepared by the present invention, vulcanization
Cadmium can equably be wrapped in the surface metal organic frame MIL-101 (Cr), and it is organic which can be applied to photocatalysis to selectively
In conversion reaction, it is used for photocatalysis to selectively nitro compound reducing, specific step is as follows：
（1）Metal organic frame MIL-101 (Cr) light of a certain amount of p-nitrophenyl amine aqueous solution, ammonium formate, cadmium sulfide package is taken to urge
Change composite material to be placed in a reaction flask, and is passed through nitrogen（60 mL/min）, certain time is adsorbed in the dark state, is made to nitre
Base aniline solution reaches adsorption equilibrium in photocatalyst surface；
（2）Under nitrogen protection, visible light is carried out to above-mentioned system（λ>420 nm）Illumination takes appropriate anti-afterwards at regular intervals
Answer liquid, after reaction, be centrifuged to extracting reaction solution（10000 rpm/min）, using ultraviolet-uisible spectrophotometer pair
Supernatant liquor is analyzed.
Remarkable advantage of the invention is：
（1）Metal organic frame MIL-101 (Cr) optic catalytic composite material for the cadmium sulfide package that the present invention obtains is uniform in size,
Cadmium sulfide is preferably wrapped in the surface metal organic frame MIL-101 (Cr).
（2）The photocatalytic activity of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package is high, makes
Make at low cost, simple production process.
Detailed description of the invention
Fig. 1 is the XRD diagram of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package.
Fig. 2 is the DRS figure of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package.
Fig. 3 is the SEM figure of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package.
Fig. 4 is the catalysis of metal organic frame MIL-101 (Cr) optic catalytic composite material and cadmium sulfide of cadmium sulfide package
Activity figure.
Specific embodiment
A kind of preparation method of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package, including
Following steps：
（1）Prepare metal organic frame MIL-101 (Cr)：CrCl is added in the polytetrafluoroethyllining lining of 25 mL3·6H2O、
Terephthalic acid (TPA) and deionized water, ultrasonic 15-25 min；Then polytetrafluoroethyllining lining is placed in 200-220 DEG C of baking oven
24-28 h is reacted, product is first centrifuged 3-4 min under the revolving speed of 3000-3500 r/min, takes filtrate again in 3000-3500
It is centrifuged 2 times under the revolving speed of r/min, then filtrate is centrifuged to 5-6 min under the revolving speed of 8000-8500 r/min, merged each
It is centrifuged obtained precipitating, drying obtains metal organic frame MIL-101 (Cr)；
Wherein, CrCl3·6H2The mass ratio of O and terephthalic acid (TPA) is 266.6：160-170, preferably 266.6: 166.6；
（2）The removal of impurities and activation of metal organic frame MIL-101 (Cr)：Metal organic frame MIL-101 (Cr) is dispersed in nothing
In water-ethanol, metal organic frame MIL-101 (Cr) is then washed and is dried with dehydrated alcohol by 75-85 DEG C of reflux 20-24 h
It is dry；
（3）Prepare metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：Metal after drying is had
Machine frame MIL-101 (Cr) is dispersed in dehydrated alcohol, and mercaptoethylmaine is added and stirs 5-10min, then mixture exists
2-2.5 h is reacted at 80-85 DEG C；Add Cd (Ac)2·2H2O the reaction was continued 2-2.5 h；Add thioacetamide continuation
React 12-14 h；Then product is centrifuged, precipitating is successively washed using dehydrated alcohol and deionized water, and 60-65 DEG C of drying obtains
Metal organic frame MIL-101 (Cr) optic catalytic composite material wrapped up to cadmium sulfide；
Wherein, the metal organic frame MIL-101 (Cr), mercaptoethylmaine, Cd (Ac)2·2H2The mass ratio of O thioacetamide
It is 40：35-45 ：40-50 ：10-15, preferably 40: 40: 44.2: 12.4；
The amount ratio of the metal organic frame MIL-101 (Cr) and ethyl alcohol is 40 mg: 20-30mL.
Embodiment 1
One, the preparation of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package
（1）Prepare metal organic frame MIL-101 (Cr)：266.6 mg CrCl3·6H2O is added to the polytetrafluoroethyl-ne of 25 mL
In alkene liner；166.6 mg terephthalic acid (TPA)s are added, 15 min of ultrasound after 7.2 mL deionized waters are added；In 210 DEG C of baking oven
24 h of middle reaction；It is centrifuged 3 min under the revolving speed of 3000 rpm/min, takes filtrate to be centrifuged again 2 times, then in 8000 rpm/
It is centrifuged 5 min under the revolving speed of min, precipitating is taken to dry.
（2）The removal of impurities and activation of metal organic frame MIL-101 (Cr)：A certain amount of MIL-101 (Cr) is dispersed in 200
In the dehydrated alcohol of mL, 80 DEG C of 24 h of reflux；Product is washed with dehydrated alcohol, is dried in vacuo in 120 DEG C of vacuum drying oven
12 h；
（3）Prepare metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：40 mg were dried in vacuo
MIL-101 (Cr) be dispersed in the dehydrated alcohol of 20 mL, 40 mg mercaptoethylmaines are added, stir anti-at 80 DEG C after 5 min
Answer 2 h；44.2 mg Cd (Ac) are added2·2H2O the reaction was continued 2 h；It is added 12.4 mg thioacetamides the reaction was continued 12 h；
Product centrifugation, precipitating dehydrated alcohol and deionized water are washed respectively, are dried at 60 DEG C, and the metal of cadmium sulfide package is obtained
Organic frame MIL-101 (Cr) optic catalytic composite material.
Fig. 1-3 be respectively cadmium sulfide package metal organic frame MIL-101 (Cr) optic catalytic composite material XRD diagram,
DRS figure and SEM figure.
Two, photocatalysis to selectively nitro compound reducing
Disperse metal organic frame MIL-101 (Cr) optic catalytic composite material that cadmium sulfide wraps up in pair of 20 mL, 10 ppm
It is dark to adsorb 0.5 h in nitroaniline soiution, in logical nitrogen（60 mL/min）Under the conditions of, it is placed in visible light（λ>420 nm）Lower light
According to metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package can be by 98% to nitro in 8 min
Aniline is converted into p-phenylenediamine.
Comparative example 1
One, the preparation of cadmium sulfide
In the dehydrated alcohol of 20 mL, 40 mg mercaptoethylmaines are added, stir 5 min；44.2 mg Cd (Ac) are added2·
2H2O reacts 2 h at 80 DEG C；It is added 12.4 mg thioacetamides the reaction was continued 12 h；Product centrifugation, precipitates anhydrous second
Pure and mild deionized water is washed respectively；It is dried at 60 DEG C, obtains bright sulfur cadmium.
Two, photocatalysis to selectively nitro compound reducing
It disperses cadmium sulfide powder in the p-nitrophenyl amine aqueous solution of 20 mL, 10 ppm, it is dark to adsorb 0.5 h, in logical nitrogen（60
mL/min）Under the conditions of, it is placed in visible light（λ>420 nm）Lower illumination, Cadmium Sulfide powder powder material can only be by 46% pairs in 8 min
Nitroaniline is converted into p-phenylenediamine.
Fig. 4 is the catalysis of metal organic frame MIL-101 (Cr) optic catalytic composite material and cadmium sulfide of cadmium sulfide package
Activity figure.By embodiment 1 and comparative example 1 it is found that metal organic frame MIL-101 (Cr) photocatalysis composite wood of cadmium sulfide package
Material has photocatalysis performance more higher than blank cadmium sulfide, illustrates metal organic frame MIL-101 (Cr) light of cadmium sulfide package
Catalytic composite materials can preferably play its excellent properties and then show better photocatalytic activity.
Embodiment 2
A kind of preparation method of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：
（1）Prepare metal organic frame MIL-101 (Cr)：266.6 mg CrCl3·6H2O is added to the polytetrafluoroethyl-ne of 25 mL
In alkene liner；160 mg terephthalic acid (TPA)s are added, 15 min of ultrasound after 7 mL deionized waters are added；It then will be in polytetrafluoroethylene (PTFE)
Lining, which is placed in 200 DEG C of baking oven, reacts 28 h, and product is first centrifuged 4 min under the revolving speed of 3000 r/min, and filtrate is taken to exist again
Be centrifuged 2 times under the revolving speed of 3000 r/min, filtrate be then centrifuged 6 min under the revolving speed of 8000 r/min, merge every time from
The precipitating that gains in depth of comprehension arrive, drying, obtains metal organic frame MIL-101 (Cr)；
（2）The removal of impurities and activation of metal organic frame MIL-101 (Cr)：Metal organic frame MIL-101 (Cr) is dispersed in nothing
In water-ethanol, metal organic frame MIL-101 (Cr) is then washed and is dried with dehydrated alcohol by 75 DEG C of 24 h of reflux；
（3）Prepare metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：After 40 mg drying
Metal organic frame MIL-101 (Cr) is dispersed in 20 mL dehydrated alcohols, and 35 mg mercaptoethylmaines are added and stir 5 min, so
Mixture is reacted into 2.5 h at 80 DEG C afterwards；Add 40 mg Cd (Ac)2·2H2O the reaction was continued 2.5 h；Add 10 mg
Thioacetamide the reaction was continued 14 h；Then product being centrifuged, precipitating is successively washed using dehydrated alcohol and deionized water, and 60 DEG C
Drying obtains metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package.
Embodiment 3
A kind of preparation method of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：
（1）Prepare metal organic frame MIL-101 (Cr)：266.6 mg CrCl3·6H2O is added to the polytetrafluoroethyl-ne of 25 mL
In alkene liner；170 mg terephthalic acid (TPA)s are added, ultrasound 25min after 7.5 mL deionized waters is added；Then by polytetrafluoroethylene (PTFE)
Liner, which is placed in 220 DEG C of baking oven, reacts 24 h, and product is first centrifuged 3min under the revolving speed of 3500 r/min, and filtrate is taken to exist again
Be centrifuged 2 times under the revolving speed of 3500 r/min, filtrate be then centrifuged 5 min under the revolving speed of 8500 r/min, merge every time from
The precipitating that gains in depth of comprehension arrive, drying, obtains metal organic frame MIL-101 (Cr)；
（2）The removal of impurities and activation of metal organic frame MIL-101 (Cr)：Metal organic frame MIL-101 (Cr) is dispersed in nothing
In water-ethanol, metal organic frame MIL-101 (Cr) is then washed and is dried with dehydrated alcohol by 85 DEG C of 20 h of reflux；
（3）Prepare metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：After 40 mg drying
Metal organic frame MIL-101 (Cr) is dispersed in 30 mL dehydrated alcohols, and 45 mg mercaptoethylmaines are added and stir 10min, so
Mixture is reacted into 2 h at 85 DEG C afterwards；Add 50 mg Cd (Ac)2·2H2O the reaction was continued 2 h；Add 15 mg sulphur
For acetamide the reaction was continued 12 h；Then product is centrifuged, precipitating is successively washed using dehydrated alcohol and deionized water, 65 DEG C of bakings
It is dry, obtain metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (9)
1. a kind of preparation method of metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package, feature
It is：It includes the following steps：
（1）Prepare metal organic frame MIL-101 (Cr)：CrCl is added in polytetrafluoroethyllining lining3·6H2O, terephthaldehyde
Acid and deionized water, ultrasonic 15-25 min；Then polytetrafluoroethyllining lining is placed in 200-220 DEG C of baking oven and reacts 24-28
H, product centrifugation, takes precipitating to dry, obtains metal organic frame MIL-101 (Cr)；
（2）The removal of impurities and activation of metal organic frame MIL-101 (Cr)：Metal organic frame MIL-101 (Cr) is dispersed in nothing
In water-ethanol, metal organic frame MIL-101 (Cr) is then washed and is dried with dehydrated alcohol by 75-85 DEG C of reflux 20-24 h
It is dry；
（3）Prepare metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package：Metal after drying is had
Machine frame MIL-101 (Cr) is dispersed in dehydrated alcohol, and mercaptoethylmaine is added and stirs 5-10min, then mixture exists
2-2.5 h is reacted at 80-85 DEG C；Add Cd (Ac)2·2H2O the reaction was continued 2-2.5 h；Add thioacetamide continuation
React 12-14 h；Then by product centrifugation, washing, drying, the metal organic frame MIL-101 (Cr) of cadmium sulfide package is obtained
Optic catalytic composite material.
2. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package according to claim 1
Preparation method, it is characterised in that：Step（1）In, the CrCl3·6H2The mass ratio of O and terephthalic acid (TPA) is 266.6：160-
170。
3. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package according to claim 1
Preparation method, it is characterised in that：Step（1）In, the centrifugally operated is specific as follows：Product is first 3000-3500 r/min's
It is centrifuged 3-4 min under revolving speed, takes filtrate to be centrifuged 2 times under the revolving speed of 3000-3500 r/min again, then filtrate exists
5-6 min is centrifuged under the revolving speed of 8000-8500 r/min, merging is centrifuged obtained precipitating every time.
4. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package according to claim 1
Preparation method, it is characterised in that：Step（2）In, the drying is the dry 10-14 h in the baking oven that temperature is 110-130 DEG C.
5. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package according to claim 1
Preparation method, it is characterised in that：Step（3）In, the metal organic frame MIL-101 (Cr), mercaptoethylmaine, Cd (Ac)2·
2H2The mass ratio of O thioacetamide is 40：35-45 ：40-50 ：10-15.
6. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package according to claim 1
Preparation method, it is characterised in that：Step（3）In, the amount ratio of the metal organic frame MIL-101 (Cr) and ethyl alcohol is 40
mg∶20-30mL。
7. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package according to claim 1
Preparation method, it is characterised in that：Step（3）In, the washing is successively to be washed using dehydrated alcohol and deionized water, the baking
Dry temperature is 60-65 DEG C.
8. metal organic frame MIL-101 (Cr) light that -7 any preparation methods obtain cadmium sulfide package according to claim 1 is urged
Change composite material.
9. metal organic frame MIL-101 (Cr) optic catalytic composite material of cadmium sulfide package as claimed in claim 8 is answered
With, it is characterised in that：The optic catalytic composite material is used for photocatalysis to selectively nitro compound reducing.
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