CN109569726A - A kind of MOFs/CNT photochemical catalyst and preparation method - Google Patents
A kind of MOFs/CNT photochemical catalyst and preparation method Download PDFInfo
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- CN109569726A CN109569726A CN201811455719.9A CN201811455719A CN109569726A CN 109569726 A CN109569726 A CN 109569726A CN 201811455719 A CN201811455719 A CN 201811455719A CN 109569726 A CN109569726 A CN 109569726A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013206 MIL-53 Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000013207 UiO-66 Substances 0.000 claims abstract description 18
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 239000002041 carbon nanotube Substances 0.000 claims description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002835 absorbance Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 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
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- 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
- B01J2531/48—Zirconium
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- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of MOFs/CNT photochemical catalyst and preparation methods, MOFs is respectively MIL-53 (Al) and UIO-66 (Zr), preparation method is multi-walled carbon nanotube to be added in the metal salt solution of MOFs, it is made using hydro-thermal method in 180-190 DEG C of reaction, the MOFs/CNT of synthesis uses heat-treating methods to be purified and activated again.Obtained MOFs/CNT has the characteristics that stablize, reuses high, has good degradation effect to phenolic comp ' ds pollution.
Description
Technical field
The present invention relates to photocatalyst technology fields, more particularly to a kind of MOFs/CNT photochemical catalyst and preparation method.
Background technique
Metal organic framework (metal-organic frameworks, MOFs) be also Porous coordination polymer, is by gold
Belonging to ion or metal cluster unit and organic ligand has periodical multidimensional network knot by one kind that coordination is self-assembly of
The porous crystalline material of structure.MOFs has potential application prospect in many fields, mainly include gas storage with separate,
Catalysis, sensor, drug delivery and proton conductor etc..Metal cluster in MOFs structure is believed to play the part of semiconductor quantum
The role of point, while its organic ligand is based on " antenna effect ", is used to activate these metal clusters under photo-excitation conditions, from
And make it possible the photochemical catalyst of MOFs, and be used for light-catalyzed reaction.Some researches show that MIL-53 (Fe) can be in purple
Still light degradation rate is not too high to degradation of methylene blue (MB) under conditions of outside-visible or visible light.
Carbon nanotube (CNT) possesses bigger serface, high chemical stability, preferable adsorption capacity, also because its is unique
Immanent structure (one-dimensional official jargon, draw ratio) and show unique metal or semiconducting electrical conductivity.Research shows that carbon nanotube with
TiO2, ZnO is compound to can be improved TiO2, ZnO photocatalytic activity.Composite carbon nanometer tube can promote point of photo-generate electron-hole
From raising hydroxyl radical free radical content enhances photosensitization.How MOFs is carried on carbon nanotube and synthesizes stable, recycling
The high composite photo-catalyst of rate, is the technical problem to be solved in the present invention.
Summary of the invention
It is respectively MIL-53 (Al) and UIO-66 that the present invention, which provides a kind of MOFs/CNT photochemical catalyst and preparation method, MOFs,
(Zr), preparation method is multi-walled carbon nanotube to be added in the metal salt solution of MOFs, is reacted using hydro-thermal method in 180-190 DEG C
It is made, the MOFs/CNT of synthesis uses heat-treating methods to be purified and activated again.Obtained MOFs/CNT, which has, to be stablized, again
High feature is utilized again, has good degradation effect to phenolic comp ' ds pollution.
A kind of MOFs/CNT photochemical catalyst of the invention and preparation method technical solution are a kind of MOFs/CNT photocatalysis
MOFs is carried on the photochemical catalyst of carbon nanotube synthesis by agent.
MOFs is respectively MIL-53 (Al) and UIO-66 (Zr).
The metal salt solution of MOFs is added in multi-walled carbon nanotube by the preparation method of the MOFs/CNT photochemical catalyst
In, it is made using hydro-thermal method in 180-190 DEG C of reaction, the MOFs/CNT of synthesis uses heat-treating methods to be purified and lived again
Change.
MIL-53 (Al)/CNT composite material preparation step:
(1) aluminum nitrate is taken, ultrasonic dissolution in the n,N-Dimethylformamide that terephthalic acid (TPA) is dissolved in respectively adds a certain amount of
Multi-wall carbon nano-tube be in control mixture；
(2) 180-190 DEG C of reaction 48-72h of mixture；
(3) natural cooling at room temperature after reaction, obtains light brown solidliquid mixture, N, N- dimethyl is used after filtering
Formamide washs 1-3 times, adds supersound washing in ethyl alcohol, moves in 120 DEG C of baking ovens and dry；
(4) product after drying is placed in 350-650 DEG C of baking 5-8h, the MIL activated (Al) -53/CNT composite material.
In step (1), the solid-to-liquid ratio of multi-walled carbon nanotube and MIL-53 (Al) are 1-50g/L, nitric acid in MIL-53 (Al)
The concentration of aluminium is 0.024-0.115mol/L, and the concentration of terephthalic acid (TPA) is 0.016-0.069 mol/L.
In step (2), mixture is transferred to polytetrafluoroethyllining lining tank, then be placed in stainless steel hydrothermal reaction kettle,
Reaction kettle sealing is placed in 180-190 DEG C of baking oven and reacts 48-72h.
UIO-66 (Zr)/CNT composite material preparation step:
1. weighing zirconium chloride, terephthalic acid (TPA) distinguishes ultrasonic dissolution in n,N-Dimethylformamide, and multi-wall carbon nano-tube is added
Pipe, ultrasonic mixing uniformly obtain mixture；
2. by mixture in 180-200 DEG C of reaction 48-72h；
3. reaction kettle is taken out natural cooling at room temperature after reaction, black-and-blue solidliquid mixture is obtained, is filtered, then
It is washed 1-3 times with N,N-dimethylformamide, is then placed in 120 DEG C and dries；
4. 5-8h is dried under the conditions of the product after drying is put into 350-650 DEG C, the UI0-66(Zr activated)/CNT composite wood
Material.
Step 1. in, the solid-to-liquid ratio of multi-walled carbon nanotube and UIO-66 (Zr) are 1-50g/L；Four chlorinations in UIO-66 (Zr)
The concentration of zirconium is 9.56 × 10-3- 0.207 mol/L, the concentration of terephthalic acid (TPA), 0.0123-0.187 mol/L.
Step 2. in, mixture is moved into polytetrafluoroethyllining lining tank, then is placed in stainless steel hydrothermal reaction kettle, will be anti-
It answers kettle sealing to be placed in 180-200 DEG C of baking oven and reacts 48-72h.
The multi-walled carbon nanotube is commercial carbon nanotube.
The evaluation method of photocatalysis performance:
Entire light-catalyzed reaction carries out in photo catalysis reactor, using mercury lamp as light source, respectively by 50mL 20mg/L to nitro
Phenol is added in photocatalysis test tube, and 0.01gMOFs/CNT photochemical catalyst is added, is adsorbed under preceding 30min dark condition, then
It opens and carries out photocatalytic degradation.Measurement of ultraviolet-visible spectrophotometer absorbance is utilized every sampling in 5 minutes.Record concentration at any time
Between variation relation.
The invention has the benefit that it is an advantage of the invention that preparing MOFs and multi-walled carbon nanotube are compound novel light and urging
Agent enhances the absorption to pollutant and accelerates the migration and separative efficiency of photo-generated carrier, overcomes the defect of MOFs, increase
The specific surface area of MOFs increases the suction-operated to pollutant.The MOFs/CNT that the present invention obtains, which has, to be stablized, reuses height
The characteristics of, there is good degradation effect to phenolic comp ' ds pollution.
Fig. 1 is the SEM electromicroscopic photograph of MIL-53 (Al)/CNT, it can be seen that the subtle CNT of MIL-53 (Al) surface doping；Figure
2 be the SEM electromicroscopic photograph of UIO-66 (Zr)/CNT, the subtle CNT of UIO-66 (Zr) surface doping fine crushing；Fig. 3 is MIL-53
(Al)/CNT XRD diagram piece, peak shape and MIL-53 (Al) are consistent；Fig. 4 be UIO-66 (Zr)/CNT XRD diagram piece, peak shape with
UIO-66 (Zr) is consistent.
Detailed description of the invention:
Fig. 1 show MIL-53 (Al)/CNT SEM electromicroscopic photograph；
Fig. 2 show UIO-66 (Zr)/CNT SEM electromicroscopic photograph；
Fig. 3 show MIL-53 (Al)/CNT XRD diagram piece；
Fig. 4 show UIO-66 (Zr)/CNT XRD diagram piece；
Fig. 5 show MIL-53 (Al)/CNT to the circulation light degradation curve of p-nitrophenol；
Fig. 6 show UIO-66 (Zr)/CNT to the circulation light degradation curve of p-nitrophenol.
Specific embodiment:
For a better understanding of the present invention, below with specific example come the technical solution that the present invention will be described in detail, but it is of the invention
It is not limited thereto.
Embodiment 1
1.3g aluminum nitrate is weighed, 0.288g terephthalic acid (TPA) distinguishes ultrasonic dissolution in the n,N-Dimethylformamide of 25mL,
The carbon nanotube for adding 1g pours the mixture into polytetrafluoroethyllining lining tank, then is placed in stainless steel cauldron, will react
Kettle sealing, which is placed in 180 DEG C of baking ovens, reacts 72h.Reaction kettle is taken out after reaction, at room temperature natural cooling, is obtained
It to light brown solidliquid mixture, is washed three times after filtering with n,N-Dimethylformamide, adds supersound washing in ethyl alcohol, move to
It is dried in 120 DEG C of baking ovens, transfers in 350 DEG C of Muffle furnaces and dry 5h, MIL-53 (the Al)/CNT composite material activated.
50mL 20mg/L p-nitrophenyl phenol solution is added in photocatalysis test tube, 0.01g MIL-53 (Al)/CNT is added
Composite material is adsorbed under preceding 30min dark condition, is then opened light source and is carried out photocatalytic degradation.It was sampled every 5 minutes
Utilize measurement of ultraviolet-visible spectrophotometer absorbance.Record absorbance changes with time relationship.By used 0.01g
It is reentered into after MIL-53 (Al)/CNT composite material low temperature drying in the p-nitrophenol of new 50mL 20mg/L and repeats light drop
Solution preocess.Circulate operation 5 times, absorbance is recorded respectively and is changed with time relationship, draws light degradation curve graph, as shown in Figure 5.
It can be seen that the performance of MIL-53 (Al)/CNT sample is highly stable, significant change does not occur for its activity after circulate operation 5 times.
Embodiment 2
1.449g zirconium chloride is weighed, 0.932g terephthalic acid (TPA) distinguishes ultrasonic dissolution in 30mLN, dinethylformamide,
0.5g carbon nanotube is added, ultrasonic mixing is uniform, mixture is moved into polytetrafluoroethyllining lining tank, then be placed in stainless steel reaction
In kettle, reaction kettle sealing is placed in 180 DEG C of baking ovens and reacts 72h.Reaction kettle is taken out at room temperature after reaction
Natural cooling, obtained black-and-blue solidliquid mixture, filtering, then washed three times with n,N-Dimethylformamide, it is then placed within
It is dried in 120 DEG C of baking ovens, then sample is put into 350 DEG C of Muffle furnaces and dries 5h, the UI0-66(Zr activated)/CNT composite wood
Material.
50mL 20mg/L p-nitrophenyl phenol solution is added in photocatalysis test tube, it is multiple that 0.01gUIO-66 (Zr)/CNT is added
Condensation material is adsorbed under preceding 30min dark condition, is then opened light source and is carried out photocatalytic degradation.Every the benefit of sampling in 5 minutes
With measurement of ultraviolet-visible spectrophotometer absorbance.Record absorbance changes with time relationship.It will be used
Weight in the p-nitrophenol of new 50mL 20mg/L is reentered into after 0.01gUIO-66 (Zr)/CNT composite material low temperature drying
Compound light degradation process.Circulate operation 5 times, absorbance is recorded respectively and is changed with time relationship, light degradation curve graph is drawn, such as schemes
Shown in 6.It can be seen that the performance of UIO-66 (Zr)/CNT sample is highly stable, its activity does not occur bright after circulate operation 5 times
Aobvious variation.
Claims (9)
1. a kind of MOFs/CNT photochemical catalyst, which is characterized in that MOFs is carried on to the photochemical catalyst of carbon nanotube synthesis.
2. a kind of MOFs/CNT photochemical catalyst according to claim 1, which is characterized in that MOFs is respectively MIL-53 (Al)
With UIO-66 (Zr).
3. the preparation method of MOFs/CNT photochemical catalyst as described in claim 1, which is characterized in that by multi-walled carbon nanotube plus
Enter in the metal salt solution of MOFs, is made using hydro-thermal method in 180-190 DEG C of reaction, the MOFs/CNT of synthesis is again using heat treatment
Method purified and activated.
4. the preparation method of MOFs/CNT photochemical catalyst according to claim 3, which is characterized in that MIL-53 (Al)/CNT
The preparation step of composite material:
(1) aluminum nitrate is taken, ultrasonic dissolution in the n,N-Dimethylformamide that terephthalic acid (TPA) is dissolved in respectively adds a certain amount of
Multi-wall carbon nano-tube be in control mixture；
(2) 180-190 DEG C of reaction 48-72h of mixture；
(3) natural cooling at room temperature after reaction, obtains light brown solidliquid mixture, N, N- dimethyl is used after filtering
Formamide washs 1-3 times, adds supersound washing in ethyl alcohol, moves in 120 DEG C of baking ovens and dry；
(4) product after drying is placed in 350-650 DEG C of baking 5-8h, the MIL activated (Al) -53/CNT composite material.
5. the preparation method of MOFs/CNT photochemical catalyst according to claim 4, which is characterized in that more in step (1)
The solid-to-liquid ratio of wall carbon nano tube and MIL-53 (Al) are 1-50g/L, and the concentration of aluminum nitrate is 0.024- in MIL-53 (Al)
0.115mol/L, the concentration of terephthalic acid (TPA) are 0.016-0.069 mol/L.
6. the preparation method of MOFs/CNT photochemical catalyst according to claim 4, which is characterized in that in step (2), will mix
It closes object and is transferred to polytetrafluoroethyllining lining tank, then be placed in stainless steel hydrothermal reaction kettle, reaction kettle sealing is placed on 180-
48-72h is reacted in 190 DEG C of baking ovens.
7. the preparation method of MOFs/CNT photochemical catalyst according to claim 3, which is characterized in that UIO-66 (Zr)/CNT
The preparation step of composite material:
1. weighing zirconium chloride, terephthalic acid (TPA) distinguishes ultrasonic dissolution in n,N-Dimethylformamide, and multi-wall carbon nano-tube is added
Pipe, ultrasonic mixing uniformly obtain mixture；
2. by mixture in 180-190 DEG C of reaction 48-72h；
3. reaction kettle is taken out natural cooling at room temperature after reaction, black-and-blue solidliquid mixture is obtained, is filtered, then
It is washed 1-3 times with N,N-dimethylformamide, is then placed in 120 DEG C and dries；
4. 5-8h is dried under the conditions of the product after drying is put into 350-650 DEG C, the UI0-66(Zr activated)/CNT composite wood
Material.
8. the preparation method of MOFs/CNT photochemical catalyst according to claim 7, which is characterized in that step 1. in, multi wall
Carbon nanotube and the solid-to-liquid ratio of UIO-66 (Zr) are 1-50g/L；The concentration of zirconium chloride is 9.56 × 10 in UIO-66 (Zr)-3-
0.207 mol/L, the concentration of terephthalic acid (TPA), 0.0123-0.187 mol/L.
9. the preparation method of MOFs/CNT photochemical catalyst according to claim 7, which is characterized in that step 2. in, will mix
It closes object and moves into polytetrafluoroethyllining lining tank, then be placed in stainless steel hydrothermal reaction kettle, reaction kettle sealing is placed on 180-200
48-72h is reacted in DEG C baking oven.
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