CN109482242A - Ni adulterates TiO2/ MOF-5 photochemical catalyst and preparation method thereof - Google Patents
Ni adulterates TiO2/ MOF-5 photochemical catalyst and preparation method thereof Download PDFInfo
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- 239000013132 MOF-5 Substances 0.000 title claims abstract description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 79
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229960000583 acetic acid Drugs 0.000 claims abstract description 17
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000011261 inert gas Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 239000011701 zinc Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 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
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide 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
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 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
- 230000035699 permeability Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of Ni to adulterate TiO2/ MOF-5 photochemical catalyst and preparation method thereof, the preparation method is the following steps are included: step 1: zinc nitrate, nickel nitrate, terephthalic acid (TPA), n,N-Dimethylformamide and triethylamine being mixed, after reacting 1-10h, solid is collected, washing is drying to obtain Ni doping MOF-5；Step 2: butyl titanate, glacial acetic acid, Ni doping MOF-5 and alcohol water mixed solvent being mixed, are stirred to react, to which after the reaction was completed, filtering collects gained filtrate and is aged, dries, calcining and adulterate TiO2/MOF-5 photochemical catalyst up to Ni.The Ni doping TiO2/MOF-5 photochemical catalyst that the above method is prepared has stronger water resistance, can effectively improve the application range of catalyst.
Description
Technical field
The present invention relates to catalysis material technical field, in particular to Ni adulterates TiO2/ MOF-5 photochemical catalyst and its preparation
Method.
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.MOF-5 is a kind of very potential frame compound, and specific surface area and hole capacity rate are carried than common solid
Body active carbon, zeolite, molecular sieve, silica are contour.But MOF-5 water resistance is bad, it is easy to hydrolyze, seriously should such urge
The application of agent.
Summary of the invention
Based on this, it is necessary to provide a kind of potent Ni doping TiO with certain water resistance2/ MOF-5 photochemical catalyst and
Preparation method.
A kind of Ni doping TiO2The preparation method of/MOF-5 photochemical catalyst, comprising the following steps:
Zinc nitrate, nickel nitrate, terephthalic acid (TPA), n,N-Dimethylformamide and triethylamine are mixed, after reacting 1-10h,
Solid is collected, washing is drying to obtain Ni doping MOF-5；
Butyl titanate, glacial acetic acid, Ni doping MOF-5, glacial acetic acid and alcohol water mixed solvent are mixed, stirring is anti-
It answers, to which after the reaction was completed, filtering collects gained filtrate and is aged, dries, calcining and adulterate TiO up to the Ni2/ MOF-5 light is urged
Agent.
Above-mentioned Ni adulterates TiO2The preparation method of/MOF-5 photochemical catalyst is by addition nickel nitrate, so that obtained MOF-
Doped with nickel in 5, the water resistance of MOF-5 is effectively improved, and then improves obtained Ni doping TiO2/ MOF-5 light is urged
The application range of agent.And by using butyl titanate and MOF-5 (Ni) material as raw material in the above method, and it is aided with glacial acetic acid
Accelerate tetrabutyl titanate hydrolysis, so that is generated is titania oxide supported on Ni doping MOF-5, being formed has preferable physical behavior
Ni adulterates TiO2/MOF-5。
In one embodiment, in the step 1, the molar ratio of the zinc nitrate and the nickel nitrate is 1:
(0.5-3)；And/or；The molar ratio of the terephthalic acid (TPA) and the zinc nitrate is 1:(0.8-1.5).
By the control of zinc nitrate, nickel nitrate and terephthalic acid (TPA) in above-mentioned molar ratio range, can further it be promoted made
The water resistance of the Ni doping MOF-5 obtained, and the specific surface area of obtained Ni doping MOF-5 can be improved, improve titanium oxide
Load capacity.
In one embodiment, in the step 1, the n,N-Dimethylformamide (DMF) and the zinc nitrate
It is (30-50) with the ratio between the quality sum of the nickel nitrate: 1.
In one embodiment, in the step 1, the zinc nitrate is zinc nitrate hexahydrate (Zn (NO3)2·
6H2O), the nickel nitrate is Nickelous nitrate hexahydrate (Ni (NO3)2·6H2O)。
In implementing wherein one, in the step 2, the temperature of the calcining is 200 DEG C -700 DEG C, calcination time 1-
4h。
By controlling temperature at 200 DEG C -700 DEG C, the photocatalysis efficiency of photochemical catalyst can be effectively improved.
By that within the above range, carbon dioxide conversion can be made at the rutile titania with more high catalytic activity temperature control
Mine crystal form, and be conducive to such as C, H organic atoms in MOF-5 with substance (such as CO of volatile2、H2) etc. O forms are overflowed,
Further enhance the catalytic activity of catalyst.
In implementing wherein one, in the step 2, the temperature of the calcining is 450 DEG C -700 DEG C.
In implementing wherein one, the mixed gas that the atmosphere of the calcining forms for oxygen and inert gas, and institute
The volume ratio for stating oxygen and the inert gas is 1:(2-5).
By the way that such as C, H organic atoms can be conducive in the mixed gas for using oxygen and inert gas to form can wave
Substance (such as CO of hair property2、H2) etc. O forms are overflowed, and MOF-5 material is made to retain MOF-5 in the form of metal oxide (such as ZnO)
Skeleton structure, keep high permeability and high-specific surface area, and then enhance the load capacity of titanium dioxide.
In one embodiment, the inert gas includes nitrogen, helium and argon gas.
In one embodiment, in the step 2, by zinc nitrate, nickel nitrate, terephthalic acid (TPA), N, N- dimethyl
The step of formamide and triethylamine mix the following steps are included:
Zinc nitrate, nickel nitrate and DMF are mixed, the terephthalic acid (TPA) (H is then added2BDC), it is completely dissolved to solid
Afterwards, the triethylamine (TEAC) is added.
In one embodiment, butyl titanate, glacial acetic acid, Ni doping MOF-5 material and alcohol water are mixed molten
Agent mixing, the step of being stirred to react the following steps are included:
The alcohol water mixed solution 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 Ni is adulterated into MOF-5 and second solution mixes, obtains third solution；
First solution is added in the third solution and is uniformly mixed.
First butyl titanate and glacial acetic acid are mixed, is formed after the second solution and to be mixed to form the with Ni doping MOF-5 material
Three solution, then the alcohol water mixed solution that pH is 2-4 is instilled in third solution, the localized rich of hydrolysis can be effectively improved in this way
Degree, so that butyl titanate hydrolyzes rapidly in the moment that alcohol water mixed solution instills, and is supported on Ni doping MOF-5 material,
Load capacity of the titanium oxide on Ni doping MOF-5 can be effectively improved, while obtained Ni adulterates TiO2/ MOF-5 light is urged
Agent has excellent physical behavior, can effectively improve unit mass Ni doping TiO2The catalysis of/MOF-5 photochemical catalyst is imitated
Rate.
In one embodiment, using the nitric acid tune pH to 2-4 of 4mol/L-6mol/L.
In implementing wherein one, in first solution, the volume ratio of the ethyl alcohol and the water is (1.5-3): 1.
In implementing wherein one, in second solution, the volume ratio of the glacial acetic acid and the ethyl alcohol is 1:(1.5-
8)。
In implementing wherein one, in second solution, the volume ratio of the glacial acetic acid and the ethyl alcohol is 1:(1.9-
4)。
In implementing wherein one, in second solution, the total volume and the titanium of both the glacial acetic acid and ethyl alcohol
The ratio of the volume of sour four butyl esters is (2.5-4): 1.
In implementing wherein one, first solution was added in the third solution in the step of stirring evenly, by institute
The first solution is stated to be added drop-wise in the third solution with the speed of 1-3 drop per second.
The Ni that above-mentioned preparation method is prepared adulterates TiO2/ MOF-5 photochemical catalyst.
The Ni that above-mentioned preparation method is prepared adulterates TiO2The MOF-5 that/MOF-5 photochemical catalyst is adulterated by using Ni,
The water resistance of MOF-5 can be effectively improved, and then improves obtained Ni and adulterates TiO2The applicable model of/MOF-5 photochemical catalyst
It encloses.
Detailed description of the invention
Fig. 1 is the TiO of embodiment 12The XRD of/MOF-5 (Ni) (Zn: Ni=1: 1) catalyst is tested；
Fig. 2 is the TiO of embodiment 22The XRD of/MOF-5 (Ni) (Zn: Ni=1: 2) catalyst is tested；
Fig. 3 is the TiO of embodiment 12The electron microscope of/MOF-5 (Ni) (Zn: Ni=1: 1) catalyst；
Fig. 4 is the TiO of embodiment 22The electron microscope of/MOF-5 (Ni) (Zn: Ni=1: 2) catalyst；
Fig. 5 is the XRD comparison diagram of the 2 hours front and backs of water process MOF-5 in comparative example 1；
Fig. 6 is the Ni doping MOF-5 (Zn in embodiment 12+: Ni2+=1:1) it is compared with the XRD of 2 hours front and backs of water process
Figure；
Fig. 7 is the Ni doping MOF-5 (Zn in embodiment 22+: Ni2+=1:2) it is compared with the XRD of 2 hours front and backs of water process
Figure.
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 synthesis of Ni doping MOF-5, first by the Zn (NO of 0.61g3)2·6H2O、0.6gNi(NO3)2·6H2O
It is contained in beaker with 40ml n,N-Dimethylformamide (DMF), at room temperature by 0.34g terephthalic acid (TPA) (H2BDC it) is added to
In beaker, be stirred continuously, after waiting solid to be completely dissolved after, then 1.4mL triethylamine TEAC is added in mixed solution, no
Disconnected stirring, stirring make it react about 3h, obtain white solid, take out press filtration, are washed 3-4 times, are removed with DMF during taking out press filtration
Remove unreacted inorganic salts and organic acid in product.Finally sample is put into baking oven and is dried.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；
Ni doping MOF-5 material 0.6546g is weighed, Ni doping MOF-5 material is slowly poured into the second solution, is allowed to
It is uniformly mixed, forms third solution；With vigorous stirring, the first solution is slowly added into the with the speed of 1 drop per second
In three solution, stopping stirring being dripped.The collosol and gel that reaction generates is filtered under diminished pressure, and is aged under room temperature, then by product
It is put into baking oven and is dried for 100 DEG C.Dried product (being in granular form) is ground, product is then put into high temperature furnace
Middle calcining is allowed to lead to oxygen in 500 DEG C of calcining 2h, calcination process and nitrogen ratios is the mixed gas of 1:2 to get embodiment
1 Ni adulterates TiO2/ MOF-5 photochemical catalyst.The XRD test chart of embodiment 1 is referring to Fig. 1, and electron microscope is referring to Fig. 3.
Embodiment 2
Step 1: the synthesis of Ni doping MOF-5, first by the Zn (NO of 0.41g3)2·6H2O、0.8gNi(NO3)2·6H2O
It is contained in beaker with 40ml n,N-Dimethylformamide (DMF), at room temperature by 0.34g terephthalic acid (TPA) (H2BDC it) is added to
In beaker, be stirred continuously, after waiting solid to be completely dissolved after, then 1.4mL triethylamine TEAC is added in mixed solution, no
Disconnected stirring, stirring make it react about 3h, obtain white solid, take out press filtration, are washed 3-4 times, are removed with DMF during taking out press filtration
Remove unreacted inorganic salts and organic acid in product.Finally sample is put into baking oven and is dried.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；
Ni doping MOF-5 material 0.6546g is weighed, Ni doping MOF-5 material is slowly poured into the second solution, is allowed to
It is uniformly mixed, forms third solution；With vigorous stirring, the first solution is slowly added into the with the speed of 1 drop per second
In three solution, stopping stirring being dripped.The collosol and gel that reaction generates is filtered under diminished pressure, and is aged under room temperature, then by product
It is put into baking oven and is dried for 100 DEG C.Dried product (being in granular form) is ground, product is then put into high temperature furnace
Middle calcining is allowed to lead to oxygen in 500 DEG C of calcining 2h, calcination process and nitrogen ratios is the mixed gas of 1:2 to get embodiment
2 Ni adulterates TiO2/ MOF-5 photochemical catalyst, referring to fig. 2, electron microscope is referring to fig. 4 for the XRD test chart of embodiment 2.
Embodiment 3
It is substantially the same manner as Example 1, the difference is that, the calcination temperature in second step becomes 300 DEG C.Obtain embodiment
3 Ni adulterates TiO2/ MOF-5 photochemical catalyst.
Comparative example 1
It is substantially the same manner as Example 1, the difference is that, it is added without Ni (NO3)2·6H2O.Obtain the TiO of comparative example 12/
MOF-5 photochemical catalyst.
Photocatalytic Degradation of Formaldehyde test
The Ni of embodiment 1- embodiment 3 and comparative example 1 is adulterated into TiO2/ MOF-5 photochemical catalyst carries out formaldehyde photocatalysis drop
Solution 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.
Water resistance experiment
It respectively takes the MOF-5 (Ni) of 0.5gMOF-5 or each doping ratio to be placed in 80 DEG C of stirred in water bath to handle 2 hours, mistake
It is dried in vacuo 2 hours at 80 DEG C after filter, with XRD analysis, as a result as illustrated in figs. 5-7.Wherein, Fig. 5 is the MOF-5 in comparative example 1
With the XRD comparison diagram of 2 hours front and backs of water process, Fig. 6 is the Ni doping MOF-5 (Zn in embodiment 12+: Ni2+=1:1) at water
The XRD comparison diagram of 2 hours front and backs is managed, Fig. 7 is the Ni doping MOF-5 (Zn in embodiment 22+: Ni2+=1:2) it is small with water process 2
The XRD comparison diagram of Shi Qianhou.
As shown in Figure 5, at 80 DEG C after water process 2 hours, peak position and peak intensity change greatly MOF-5, and 7 degree, 13 degree 14
Characteristic peak near degree disappears, the slightly left avertence shifting of the characteristic peaks near 10 degree, illustrate to hydrolyze it is obvious, changes in crystal structure compared with
Greatly.Work as Zn as shown in Figure 62+: Ni2+When for 1:1, MOF-5 (Ni) is at 80 DEG C after water process 2 hours, map peak position and peak intensity
Also there is large change, but characteristic peak is all retained near 9 degree, 16 degree, 18 degree, crystal form retains relatively complete, explanation
MOF-5 (Ni) (1:1) water resistance will be got well with respect to MOF-5.As shown in Figure 7, work as Zn2+:Ni2+When for 1:2, MOF-5 (Ni) map peak
Less, most of characteristic peak all retains, and illustrates that MOF-5 (Ni) (1:2) water resistance is more preferable at this time for position and peak intensity variation.Thus
As it can be seen that water resistance is enhanced as MOF-5 as doping nickel content improves.
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 Ni adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which comprises the following steps:
Step 1: zinc nitrate, nickel nitrate, terephthalic acid (TPA), n,N-Dimethylformamide and triethylamine being mixed, 1-10h is reacted
Afterwards, solid is collected, washing is drying to obtain Ni doping MOF-5；
Step 2: butyl titanate, glacial acetic acid, Ni doping MOF-5 and alcohol water mixed solvent being mixed, are stirred to react, to anti-
After the completion of answering, filtering collects gained filtrate and is aged, dries, calcining and adulterate TiO up to the Ni2/ MOF-5 photochemical catalyst.
2. Ni according to claim 1 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that described
In step 1, the molar ratio of the zinc nitrate and the nickel nitrate is 1:(0.5-3)；And/or
The molar ratio of the terephthalic acid (TPA) and the zinc nitrate is 1:(0.8-1.5).
3. Ni according to claim 1 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that described
In step 2, the temperature of the calcining is 200 DEG C -700 DEG C, calcination time 1-4h.
4. Ni according to claim 3 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that described to forge
The atmosphere of burning 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)。
5. Ni according to claim 1-4 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, feature exist
In in the step 2, by the specific of butyl titanate, glacial acetic acid, Ni doping MOF-5 and the mixing of alcohol water mixed solvent
Operation are as follows:
The alcohol water mixed solution 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 Ni is adulterated into MOF-5 and second solution mixes, obtains third solution；
First solution is added in the third solution and is uniformly mixed.
6. Ni according to claim 5 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that described
In first solution, the volume ratio of the ethyl alcohol and the water is (1.5-3): 1.
7. Ni according to claim 5 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that described
In second solution, the volume ratio of the glacial acetic acid and the ethyl alcohol is 1:(1.5-8).
8. Ni according to claim 5 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that described
In second solution, 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。
9. Ni according to claim 5 adulterates TiO2The preparation method of/MOF-5 photochemical catalyst, which is characterized in that will be described
First solution was added in the third solution in the step of stirring evenly, and first solution is dripped with the speed of 1-3 drop per second
It is added in the third solution.
10. the Ni that the described in any item preparation methods of claim 1-9 are prepared adulterates TiO2/ MOF-5 photochemical catalyst.
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| CN113913898A (en) * | 2021-09-16 | 2022-01-11 | 浙江大学 | TiO 22Reflection type electrochromic film and preparation method thereof |
| CN113967482A (en) * | 2021-10-14 | 2022-01-25 | 大连理工大学 | Method for preparing bimetallic hexahedral nanosheet Ti-Ni-MOF catalyst through mesoscale regulation and control and application |
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