CN109482241A - TiO2/ MOF-5 photochemical catalyst and preparation method thereof - Google Patents
TiO2/ MOF-5 photochemical catalyst and preparation method thereof Download PDFInfo
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- CN109482241A CN109482241A CN201811494393.0A CN201811494393A CN109482241A CN 109482241 A CN109482241 A CN 109482241A CN 201811494393 A CN201811494393 A CN 201811494393A CN 109482241 A CN109482241 A CN 109482241A
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- 239000013132 MOF-5 Substances 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 66
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011261 inert gas Chemical group 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 239000011701 zinc Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010457 zeolite 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
Abstract
The present invention relates to a kind of TiO2/ MOF-5 photochemical catalyst and preparation method thereof, the TiO2The preparation method of/MOF-5 photochemical catalyst is the following steps are included: provide MOF-5 material；The mixed solution of second alcohol and water is prepared, and adjusts pH value to pH value 2-4, obtains the first solution；By the mixing of butyl titanate, glacial acetic acid and ethyl alcohol, the second solution is formed；MOF-5 material is added in the second solution, third solution is obtained；First solution is added in third solution and is stirred evenly；Filtering, gained filtrate is aged, and is dried, and is calcined up to TiO2/ MOF-5 photochemical catalyst.The TiO that this method is prepared2/ MOF-5 photochemical catalyst photocatalysis efficiency with higher.
Description
Technical field
The present invention relates to photocatalysis technology fields, in particular to TiO2/ MOF-5 photochemical catalyst and preparation method thereof.
Background technique
Photocatalysis technology, that is, semiconductor light-catalyst technology can be used to degradation of organic waste water, reducing heavy metal ion, net
Change air, sterilization, antifog etc..Nano-titanium dioxide (TiO2) it is used as a kind of photochemical catalyst, it is that a kind of N-shaped of function admirable is partly led
Body material can make full use of solar energy, not only energy-efficient but also environmentally friendly, and show preferable light when reacting and stablize
Property and higher reactivity, nontoxic, inexpensive are without secondary pollution, are a kind of current application prospect nanometers the most wide
Functional material.
MOF-5 is a most typical representative in metal-organic framework complex family, is developed in metal organic complex
With the meaning of milestone in history.MOF-5 is by 4 Zn2+With 1 O2-[the Zn formed4O]6+Inorganic group and organic group
[O2C-C-C6H4-CO2]2-The 3 D stereo rigid-skeleton formed with octahedral form connection, chemical basic unit are
Zn4O(BDC)3, structure are as follows:
Each Zn4O cluster is connect with 6 organic ligand units respectively, and each organic ligand and 2 Zn4O unit is connected,
With three-dimensional orthogonal cellular structure.The research of Langmuir specific surface area about MOF-5 material, the data that each researcher delivers
And it is different, Yaghi seminar Hailian Li et al. report specific surface area is up to 2900m2The ratio table of the reports such as/g, Rowsell
Area is bigger, can achieve 3362m2/g.In short, MOF-5 is that a kind of specific surface area and hole capacity rate are more living than common solid carrier
The contour a kind of very potential frame compound of property charcoal, zeolite, molecular sieve, silica.Due to MOF-5 have it is very huge
Specific surface area and cellular structure abundant, can be by TiO2Combine with MOF-5 and composite material is made, is i.e. TiO2/MOF-5
Photochemical catalyst.
Currently used TiO2The synthetic method of/MOF-5 is that butyl titanate is directly added in MOF-5, close after stirring
Envelope ageing, is then dried, and is ground.Even if this method MOF-5 has biggish specific surface area, the titania oxide supported amount on MOF-5
Still lower, cause the catalytic efficiency of obtained catalyst lower, limits its application.
Summary of the invention
Based on this, it is necessary to provide a kind of TiO with greater catalytic efficiency2/ MOF-5 photochemical catalyst and its preparation side
Method.
A kind of TiO2The preparation method of/MOF-5 photochemical catalyst, comprising the following steps:
MOF-5 material is provided；
The mixed solution of second alcohol and water is prepared, and adjusts pH value to pH value 2-4, obtains the first solution；
Butyl titanate, glacial acetic acid and ethyl alcohol are mixed, the second solution is formed；
The MOF-5 material is mixed with second solution, obtains third solution；
First solution is added in the third solution and is stirred evenly；
Filtering, gained filtrate is aged, and is dried, and is calcined up to the TiO2/ MOF-5 photochemical catalyst.
Above-mentioned TiO2The preparation method of/MOF-5 photochemical catalyst first mixes butyl titanate and glacial acetic acid, forms second
It is mixed to form third solution with MOF-5 material again after solution, the alcohol water mixed solution that pH is 2-4 is then instilled into third solution
In, the local concentration of hydrolysis can be effectively improved in this way, so that butyl titanate is fast in the moment that alcohol water mixed solution instills
Speed hydrolysis, and be supported on MOF-5 material, load capacity of the titanium oxide on MOF-5 can be effectively improved, while obtained
TiO2/ MOF-5 photochemical catalyst has merit, can effectively improve unit mass TiO2The catalysis of/MOF-5 photochemical catalyst
Efficiency.
In one embodiment, using the nitric acid tune pH to 2-4 of 4mol/L-6mol/L.
In one embodiment, in first solution, the volume ratio of the ethyl alcohol and the water is (1.5-3):
1。
In one embodiment, in second solution, the volume ratio of the glacial acetic acid and the ethyl alcohol is 1:
(1.5-8)。
In one embodiment, in second solution, the volume ratio of the glacial acetic acid and the ethyl alcohol is 1:
(1.5-4)。
In one embodiment, in second solution, the total volume of both the glacial acetic acid and ethyl alcohol with it is described
The ratio of the volume of butyl titanate is (2.5-4): 1.
In one embodiment, first solution was added in the third solution in the step of stirring evenly, it will
First solution is added drop-wise in the third solution with the speed of 1-3 drop per second.
In one embodiment, the temperature of the calcining is 200 DEG C -700 DEG C, calcination time 1-4h.
In one embodiment, the temperature of the calcining is 450 DEG C -700 DEG C.
In one embodiment, the atmosphere of the calcining is the mixed gas that oxygen and inert gas form, and
The volume ratio of the oxygen and the inert gas is 1:(2-5).
In one embodiment, further include the steps that preparing MOF-5 material:
Zinc nitrate, terephthalic acid (TPA) and n,N-Dimethylformamide are mixed, triethylamine is added, is reacted, consolidate
Body, collects the solid, and washing is drying to obtain the MOF-5.
In one embodiment, the molar ratio of the terephthalic acid (TPA) and the zinc nitrate is in 1:(0.8-1.5).
The TiO that the above method is prepared2/ MOF-5 photochemical catalyst.
The TiO that the above method is prepared2/ MOF-5 photochemical catalyst load capacity with higher, can effectively improve and urge
The catalytic efficiency of agent.
Detailed description of the invention
Fig. 1 is the TiO of embodiment 12The XRD diagram of/MOF-5 photochemical catalyst；
Fig. 2 is the TiO of embodiment 12The electron microscope of/MOF-5 photochemical catalyst.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
Specific embodiment is set forth below, and the present invention will be described.
Embodiment 1
Step 1: the synthetic agent of MOF-5 is Zn (NO3)2·6H2O, 1,4- phthalic acid (H2BDC), N, N- dimethyl
Formamide (DMF) and triethylamine (TEAC).
First by the Zn (NO of 1.21g3)2·6H2O and 40ml n,N-Dimethylformamide (DMF) is contained in beaker, in room
By 0.34g terephthalic acid (TPA) (H under temperature2BDC) be added in beaker, be stirred continuously, wait solid be completely dissolved after after, then general
1.3mL triethylamine TEAC is added in mixed solution, is stirred continuously, and stirring makes it react about 3h, obtains white solid, takes out pressure
Filtering is washed 3-4 times during taking out press filtration with DMF, and unreacted inorganic salts and organic acid in product are removed.Finally sample is put
Enter in baking oven and dries.Dress sample is ground after drying.
Step 2: taking 4.5ml distilled water, the mixing of 8.9ml dehydrated alcohol is 3 with the 5mol/L nitric acid solution tune pH prepared,
The first solution is made；4.5ml glacial acetic acid is added in 26.7ml dehydrated alcohol, with vigorous stirring, by four fourth of 8.9ml metatitanic acid
Ester is slowly added into above-mentioned solution, forms shallow yellow transparent solution, forms the second solution；MOFs-5 material 0.6546g is weighed,
MOF-5 material is slowly poured into the second solution, is allowed to be uniformly mixed, obtains third solution；With vigorous stirring, will
First solution is slowly added into third solution with the speed of 1 drop per second, drips stopping stirring.React the collosol and gel generated
It is filtered under diminished pressure, is aged under room temperature, then product is put into baking oven and is dried for 100 DEG C.It (is in by dried product
It is granular) ground, then product is put into high temperature furnace and is calcined, be allowed in 500 DEG C of calcining 2h, calcination process lead to oxygen with
Nitrogen ratios are the mixed gas of 1:3, obtain the TiO of embodiment 12/ MOF-5 photochemical catalyst, XRD diagram is as shown in Figure 1, Electronic Speculum
Figure is as shown in Figure 2.
Embodiment 2
Step 1: the synthetic agent of MOF-5 is Zn (NO3)2·6H2O, 1,4- phthalic acid (H2BDC), N, N- dimethyl
Formamide (DMF) and triethylamine (TEAC).
First by the Zn (NO of 1.21g3)2·6H2O and 40ml n,N-Dimethylformamide (DMF) is contained in beaker, in room
By 0.34g terephthalic acid (TPA) (H under temperature2BDC) be added in beaker, be stirred continuously, wait solid be completely dissolved after after, then general
1.3mL triethylamine TEAC is added in mixed solution, is stirred continuously, and stirring makes it react about 3h, obtains white solid, takes out pressure
Filtering is washed 3-4 times during taking out press filtration with DMF, and unreacted inorganic salts and organic acid in product are removed.Finally sample is put
Enter in baking oven and dries.Dress sample is ground after drying.
Step 2: taking 8.9ml distilled water, the mixing of 8.9ml dehydrated alcohol is 3 with the 5mol/L nitric acid solution tune pH prepared,
The first solution is made；4.5ml glacial acetic acid is added in 26.7ml dehydrated alcohol, with vigorous stirring, by four fourth of 8.9ml metatitanic acid
Ester is slowly added into above-mentioned solution, forms shallow yellow transparent solution, forms the second solution；MOFs-5 material 0.6546g is weighed,
MOF-5 material is slowly poured into the second solution, is allowed to be uniformly mixed, obtains third solution；With vigorous stirring, will
First solution is slowly added into third solution with the speed of 1 drop per second, drips stopping stirring.React the collosol and gel generated
It is filtered under diminished pressure, is aged under room temperature, then product is put into baking oven and is dried for 100 DEG C.It (is in by dried product
It is granular) ground, then product is put into high temperature furnace and is calcined, be allowed in 500 DEG C of calcining 2h, calcination process lead to oxygen with
Nitrogen ratios are the mixed gas of 1:3, obtain the TiO of embodiment 12/ MOF-5 photochemical catalyst.
Embodiment 3
Step 1: the synthetic agent of MOF-5 is Zn (NO3)2·6H2O, 1,4- phthalic acid (H2BDC), N, N- dimethyl
Formamide (DMF) and triethylamine (TEAC).
First by the Zn (NO of 1.21g3)2·6H2O and 40ml n,N-Dimethylformamide (DMF) is contained in beaker, in room
By 0.34g terephthalic acid (TPA) (H under temperature2BDC) be added in beaker, be stirred continuously, wait solid be completely dissolved after after, then general
1.3mL triethylamine TEAC is added in mixed solution, is stirred continuously, and stirring makes it react about 3h, obtains white solid, takes out pressure
Filtering is washed 3-4 times during taking out press filtration with DMF, and unreacted inorganic salts and organic acid in product are removed.Finally sample is put
Enter in baking oven and dry, dress sample is ground after drying.
Step 2: taking 4.5ml distilled water, the mixing of 8.9ml dehydrated alcohol is 3 with the 5mol/L nitric acid solution tune pH prepared,
The first solution is made；4.5ml glacial acetic acid is added in 26.7ml dehydrated alcohol, with vigorous stirring, by four fourth of 8.9ml metatitanic acid
Ester is slowly added into above-mentioned solution, forms shallow yellow transparent solution, forms the second solution；MOFs-5 material 0.6546g is weighed,
MOF-5 material is slowly poured into the second solution, is allowed to be uniformly mixed, obtains third solution；With vigorous stirring, will
First solution is slowly added into third solution with the speed of 1 drop per second, drips stopping stirring.React the collosol and gel generated
It is filtered under diminished pressure, is aged under room temperature, then product is put into baking oven and is dried for 100 DEG C.It (is in by dried product
It is granular) ground, then product is put into high temperature furnace and is calcined, be allowed in 300 DEG C of calcining 2h, calcination process lead to oxygen with
Nitrogen ratios are the mixed gas of 1:3, obtain the TiO of embodiment 22/ MOF-5 photochemical catalyst.
Comparative example 1
Step 1: the synthetic agent of MOF-5 is Zn (NO3)2·6H2O, 1,4- phthalic acid (H2BDC), N, N- dimethyl
Formamide (DMF) and triethylamine (TEAC).
First by the Zn (NO of 1.21g3)2·6H2O and 40ml n,N-Dimethylformamide (DMF) is contained in beaker, in room
By 0.34g terephthalic acid (TPA) (H under temperature2BDC) be added in beaker, be stirred continuously, wait solid be completely dissolved after after, then general
1.3mL triethylamine TEAC is added in mixed solution, is stirred continuously, and stirring makes it react about 3h, obtains white solid, takes out pressure
Filtering is washed 3-4 times during taking out press filtration with DMF, and unreacted inorganic salts and organic acid in product are removed.Finally sample is put
Enter in baking oven and dry, dress sample is ground after drying.
Step 2: it is molten to be added to the mixing that 35.6ml dehydrated alcohol and 4.5ml distilled water mix for 4.5ml glacial acetic acid
In liquid, with vigorous stirring, 8.9ml butyl titanate is slowly added into above-mentioned solution, forms shallow yellow transparent solution, and
With 5mol/L nitric acid solution tune pH value of solution to 3, the first solution is formed；MOFs-5 material 0.6546g is weighed, MOF-5 material is slow
Slowly it is poured into above-mentioned first solution, is allowed to be uniformly mixed.The collosol and gel that reaction generates is filtered under diminished pressure, old under room temperature
Change, then product is put into baking oven and is dried for 100 DEG C.Dried product (being in granular form) is ground, then will
Product is put into high temperature furnace and calcines, and is allowed to the mixing for leading to oxygen in 300 DEG C of calcining 2h, calcination process and nitrogen ratios are 1:3
Gas obtains the TiO of comparative example 12/ MOF-5 photochemical catalyst.
Photocatalytic Degradation of Formaldehyde test
By the TiO of embodiment 1- embodiment 3 and comparative example 12/ MOF-5 photochemical catalyst carries out Photocatalytic Degradation of Formaldehyde test；
Test principle: TiO is carried out in homemade photocatalysis experimental box2Formaldehyde degradation by photocatalytic oxidation process experiment, passes through ultraviolet light
Catalyst is irradiated to realize the formaldehyde in degradation aqueous solution in source, and the reactivity of photochemical catalyst is by measuring illumination after a certain period of time
The degradation rate of formaldehyde is evaluated.
Test method: 2mL formaldehyde stock solution and 100mL water are accurately pipetted in reaction tank, is shaken up.Accurately pipette 2.5mL
Solution absorbance to be measured in test tube.Catalyst 0.25g is weighed in reaction tank, after shaking up, is put into reactor, is opened ultraviolet
Lamp carries out illumination degrading 5h, wherein takes a sample per hour, first jog reaction tank is answered before taking, be uniformly mixed solution, then again
A moment is stood, then pipettes about 5mL solution in absorbance to be measured in test tube with pipette.Meanwhile doing a blank that catalyst is not added
Comparative experiments.
Deionized water will be added to 25mL equipped with the test tube of sampling liquid, while do a blank test, sample is replaced with 25mL water,
Again plus 2.5mL acetylacetone,2,4-pentanedione solution, it shakes up, the heating water bath 10min in 909100 DEG C, takes out cooling.At wavelength 414nm,
Using water as reference measurement absorbance.The light absorption value substitution resulting formula of standard curve can be calculated into concentration of formaldehyde, recycled
Formula 1.3 calculates degradation rate D%:
A in formula0, AtAbsorbance respectively before reaction with solution when reacting t moment；Finally production degradation rate and time are bent
Line compares the degradation property of catalyst, and compares with blank test, test result is as follows table 1.
Table 1
From embodiment 1- embodiment 3 it can be seen that the Ni that the above method is prepared adulterates TiO2/ MOF-5 photochemical catalyst tool
There is stronger photocatalysis.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of TiO2The preparation method of/MOF-5 photochemical catalyst, which comprises the following steps:
MOF-5 material is provided；
The mixed solution of second alcohol and water is prepared, and adjusts pH value to pH value 2-4, obtains the first solution；
Butyl titanate, glacial acetic acid and ethyl alcohol are mixed, the second solution is formed；
The MOF-5 material is mixed with second solution, obtains third solution；
First solution is added in the third solution and is stirred evenly；
Filtering, gained filtrate is aged, and is dried, and is calcined up to the TiO2/ MOF-5 photochemical catalyst.
2. TiO according to claim 12The preparation method of/MOF-5 photochemical catalyst, which is characterized in that the temperature of the calcining
Degree is 200 DEG C -700 DEG C, calcination time 1-4h.
3. TiO according to claim 22The preparation method of/MOF-5 photochemical catalyst, which is characterized in that the gas of the calcining
Body atmosphere is the mixed gas that oxygen and inert gas form, and the volume ratio of the oxygen and the inert gas is 1:(2-
5)。
4. TiO according to claim 12The preparation method of/MOF-5 photochemical catalyst, which is characterized in that molten described first
In liquid, the volume ratio of the ethyl alcohol and the water is (1.5-3): 1.
5. TiO according to claim 12The preparation method of/MOF-5 photochemical catalyst, which is characterized in that molten described second
In liquid, the volume ratio of the glacial acetic acid and the ethyl alcohol is 1:(1.5-8).
6. TiO according to claim 12The preparation method of/MOF-5 photochemical catalyst, which is characterized in that molten described second
In liquid, the ratio of the volume of the total volume and butyl titanate of both the glacial acetic acid and ethyl alcohol is (2.5-4): 1.
7. TiO according to claim 12The preparation method of/MOF-5 photochemical catalyst, which is characterized in that molten by described first
Liquid was added in the third solution in the step of stirring evenly, and first solution is added drop-wise to institute with the speed of 1-3 drop per second
It states in third solution.
8. TiO according to claim 1-72The preparation method of/MOF-5 photochemical catalyst, which is characterized in that also wrap
The step of including preparation MOF-5 material:
Zinc nitrate, terephthalic acid (TPA) and n,N-Dimethylformamide are mixed, triethylamine is added, reacts, obtains solid, is received
Collect the solid, washing is drying to obtain the MOF-5.
9. TiO according to claim 82The preparation method of/MOF-5 photochemical catalyst, which is characterized in that the terephthaldehyde
Sour and the zinc nitrate molar ratio is in 1:(0.8-1.5).
10. the TiO that the described in any item methods of claim 1-9 are prepared2/ MOF-5 photochemical catalyst.
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