CN109289927A - The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ - Google Patents
The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ Download PDFInfo
- Publication number
- CN109289927A CN109289927A CN201811392251.3A CN201811392251A CN109289927A CN 109289927 A CN109289927 A CN 109289927A CN 201811392251 A CN201811392251 A CN 201811392251A CN 109289927 A CN109289927 A CN 109289927A
- Authority
- CN
- China
- Prior art keywords
- iron
- nano
- titanium dioxide
- visible light
- composite catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 150000002505 iron Chemical class 0.000 claims abstract description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 230000001699 photocatalysis Effects 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000013215 MIL-88B Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000013206 MIL-53 Substances 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 59
- 239000000243 solution Substances 0.000 description 31
- 238000007146 photocatalysis Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010561 standard procedure Methods 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000013291 MIL-100 Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- IRPVABHDSJVBNZ-RTHVDDQRSA-N 5-[1-(cyclopropylmethyl)-5-[(1R,5S)-3-(oxetan-3-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyrazol-3-yl]-3-(trifluoromethyl)pyridin-2-amine Chemical compound C1=C(C(F)(F)F)C(N)=NC=C1C1=NN(CC2CC2)C(C2[C@@H]3CN(C[C@@H]32)C2COC2)=C1 IRPVABHDSJVBNZ-RTHVDDQRSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 238000013313 FeNO test Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/40—Regeneration or reactivation
-
- 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
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to field of environment pollution control, and in particular to a kind of preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@；The present invention is by by trivalent iron salt, 2- amino terephthalic acid (TPA) and nano-TiO2It is added in n,N-Dimethylformamide, ultrasonic disperse uniformly obtains precursor solution；Precursor solution is subjected to hydro-thermal reaction again, the iron-based MOF visible light composite catalyst of nano-titanium dioxide@is made；Under sun light action, the catalyst can efficiently restore Cr (VI) under mild neutrallty condition, have the characteristics that high-efficient, low energy consumption, be widely portable to a variety of chromate waste water processing.
Description
Technical field
The invention belongs to field of environment pollution control, and in particular to a kind of visible photoreactivation of the iron-based MOF of nano-titanium dioxide
The preparation method and applications of catalyst.
Background technique
Traditional fossil energy has non-renewable, and a series of environmental problems can be generated during utilization.Therefore, it seeks
It looks for alternative energy and will not cause damages again to environment, to developing national economy, realize that sustainable development is of great significance.
Solar energy is a kind of clean reproducible energy, is effective method using solar energy degradation, conversion environment pollutant.Light is urged
Change technology converts solar energy into chemical energy, has the characteristics that at low cost, environmentally protective, without secondary pollution, is people in recent years
Focus of attention technology, and the core of photocatalysis technology is exactly to select the photochemical catalyst of economical and efficient, improves catalytic efficiency.
Cr (VI) wastewater source is extensive, and the industrial circles such as plating, printing and dyeing, intermetallic composite coating all can largely discharge chromate waste water,
Cr (VI) has the characteristics that carcinogenicity, not biodegradable simultaneously, has become the global environment being concerned in recent years and asks
Topic.Photocatalysis treatment hexavalent chromium wastewater generally requires to be acid condition at present, but especially weaves for some industrial wastewaters
Industrial wastewater is mostly the spy for containing dyestuff, Cr (VI) and a variety of small molecule organic pollutants in neutral meta-alkalescence and waste water simultaneously
Point, therefore realize that the efficient reduction of Cr (VI) and effective degradation of organic pollutant are with real under mild neutrallty condition
The exploration of border application value, and solve the effective way that photo-reduction medicine consumption is high, time-consuming.
TiO2As apply a kind of wider photochemical catalyst, photocatalytic oxidation degradation organic pollutant, decompose aquatic products hydrogen,
The fields such as disinfection there has been extensive use.However, its forbidden bandwidth is larger (3.2eV), it is only capable of the luminous energy using ultraviolet light wave band
Amount, is applied to produce certain limitation.MOFs is that a kind of passed through by organic ligand and metallic atom (metal cluster) is coordinated work
With or electrostatic interaction building porous functional material, have the function of that large specific surface area, structure and Modulatory character be strong, unsaturated coordination
The advantages such as quantity is more, theoretically catalytic activity with higher.Currently, MOFs has been received significant attention in photocatalysis field,
There is the iron-based MOFs of document report that there is preferable visible light catalytic performance, (the Journal of Hazardous such as Liang
Materials, 2015,287,364-372) handled simultaneously under visible light conditions using MIL-53 (Fe) Cr in water phase (VI) with
Dyestuff, but its reaction condition is harsh and rate is slower, while simple MOFs material is asked in the presence of " electron-hole " recombination rate is excessively high
Topic, weakens its photocatalysis performance to a certain extent.In order to further increase photochemical catalyst to the utilization efficiency of solar energy, drop
Low " electron-hole " recombination rate, researcher attempt by constructing composite photo-catalyst by matrix of MOFs.For example,
CN106238100A (number of patent application 201610607408.4) proposes that a kind of titanium dioxide nanoplate load MIL-100 (Fe) is multiple
The titanium dioxide nanoplate of hydrothermal synthesis is dispersed in MIL-100 (Fe) precursor solution by the preparation method of light combination catalyst
Repeatedly water-bath-suction filtration process, program is cumbersome, energy consumption is more, and pollutant removal advantage is unobvious.
CN107913675A (number of patent application 201711156483.4) discloses a kind of MOF modification stannous sulfide composite photo-catalyst
Preparation loads stannous sulfide, and be applied to the reduction of Cr (VI), the composite material first with MIL-53 (Fe) for carrier
Stage synthesizes MIL-53 (Fe) by hydro-thermal reaction, and second stage mixes stannous bromide in the homogeneous solution of MIL-53 (Fe),
It is eventually adding containing S2-Solution carries out precipitation reaction and completes preparation.Secondary pollution, and deposition effect can be generated in material synthesis processes
It is not easy to control.
Currently, there is no Cr in the iron-based MOF visible light composite catalyst efficient process neutrality water environment of nano-titanium dioxide
(VI) report.
Summary of the invention
The present invention is low to solar energy utilization ratio for photochemical catalyst in the prior art, electron-hole recombination rate is high, preparation
The problems such as cumbersome, provides a kind of iron-based MOF visible light composite catalyst { TiO of nano-titanium dioxide@2@NH2- MIL (Fe) }
Preparation method, and it is applied to the Cr (VI) under mild neutrallty condition in sunlight irradiation Efficient Conversion removal water phase.
To solve the above problems, technical scheme is as follows:
A kind of iron-based MOF visible light composite catalyst of nano-titanium dioxide@, mole of the titanium dioxide and iron-based MOF
Than being 5%~20%.
Preferably, the iron-based MOF is NH2-MIL-88B(Fe)、NH2-MIL-53(Fe)、NH2In-MIL-101 (Fe)
It is a kind of.
The preparation method of the above-mentioned iron-based MOF visible light composite catalyst of nano-titanium dioxide@, comprising the following steps:
Step 1, by trivalent iron salt, 2- amino terephthalic acid (TPA) and nano-TiO2It is added in n,N-Dimethylformamide,
Ultrasonic disperse uniformly obtains precursor solution；
Step 2, by precursor solution obtained in step 1,12~48h of hydro-thermal reaction at 100~150 DEG C is made and receives
The rice iron-based MOF visible light composite catalyst of titanium dioxide@.
Preferably, the trivalent iron salt is the mixing of iron chloride, ferric nitrate, any one or a few in ferric sulfate.
Preferably, the molar ratio of the trivalent iron salt, 2- amino terephthalic acid (TPA) and n,N-Dimethylformamide is 1:
(0.5~2): (140~280), nano-TiO2Mass ratio with N,N-dimethylformamide is 1:(500~2500).
Preferably, the hydrothermal temperature be 110~150 DEG C, the reaction time be 12~for 24 hours.
Preferably, in step 2, after the completion of the hydro-thermal reaction, product is carried out from, washing, dry；It is highly preferred that washing
The solvent used is washed as methanol or ethyl alcohol, vacuum drying temperature is 50~70 DEG C.
The above-mentioned iron-based MOF visible light composite catalyst of nano-titanium dioxide@can be used for removing the Cr (VI) in water phase.
Concrete application method are as follows:
The iron-based MOF visible light composite catalyst of the nano-titanium dioxide@is added in the solution containing Cr (VI), is adjusted
PH is 5~9, magnetic agitation dark reaction, and after reaching adsorption equilibrium, photo catalytic reduction reaction is carried out under illumination.
Preferably, the dosage of the photochemical catalyst is 0.25~0.75g/L.
It preferably, also include small organic molecule in the solution containing Cr (VI), the small organic molecule is lemon
Lemon acid, ammonium oxalate, ethyl alcohol, EDTA-2Na, any one or a few the mixing in methyl orange (MO).Efficiency raising 40%~
500%.
Compared with the existing technology, advantages of the present invention is as follows,
(1) source of iron and nano-TiO used in the present invention2From a wealth of sources, cheap, environmental-friendly, synthetic operation is simple, work
The skill period is short, low energy consumption.
(2) the iron-based MOF visible light composite catalyst of nano-titanium dioxide@proposed by the present invention, makes full use of NH2-MIL
(Fe) ultraviolet light response of visible light-responded property and titanium dioxide；And quantum efficiency is improved, TiO2With NH2-MIL(Fe)
Between can be effectively carried out electronics transfer reduce " electron-hole " recombination rate, promote photocatalysis performance raising.
(3) the iron-based MOF visible light composite catalyst pattern of nano-titanium dioxide@prepared by the present invention is controllable, passes through tune
Section load TiO2Content, the proportion of trivalent iron salt and 2- amino terephthalic acid (TPA) can the different hetero-junctions materials of synthetic surface coverage
Material, preparation parameter is easily controllable, reproducible.
(4) the iron-based MOF visible light composite catalyst of nano-titanium dioxide@prepared by the present invention can repeatedly regenerate and repeat benefit
With, materialization and stable mechanical performance, the Cr (VI) being applied in photo catalytic reduction neutrality water environment under sunlight conditions, reaction
Speed is fast, and Cr (VI) removal rate reaches 95% or more in 30min, and environment and economic significance are significant, have a extensive future.
Detailed description of the invention
Fig. 1 is TiO obtained in the embodiment of the present invention 12@NH2The SEM of-MIL-88B (Fe) catalyst schemes；
Fig. 2 is the TiO of different mol ratios2@NH2- MIL-88B (Fe) catalyst to pH 7 water phase Cr (VI) photocatalysis also
Former efficiency curve；
Fig. 3 is TiO derived from different iron-based MOFs2@NH2- MIL (Fe) catalyst is to water phase Cr (VI) light under the conditions of pH 7
Catalytic reduction efficiency curve；
Fig. 4 is gained TiO in embodiment 1 under condition of different pH2@NH2- MIL-88B (Fe) to water phase Cr (VI) photocatalysis also
Former efficiency curve；
Fig. 5 is that different small organic molecules act on gained TiO in lower embodiment 12@NH2- MIL-88B (Fe) is to 7 condition of pH
Lower water phase Cr (VI) photo catalytic reduction efficiency curve
Fig. 6 is TiO in present example 142@NH2- MIL-88B (Fe) catalyst photo catalytic reduction water phase Cr (VI) reuse
Experiment effect figure；
Fig. 7 is TiO in present example 152@NH2Practical sunlight catalytic reduction water phase Cr (VI) of-MIL-88B (Fe) is real
Test effect picture；
Fig. 8 is TiO in present example 162@NH2- MIL-88B (Fe) photo catalytic reduction water phase Cr (VI), methyl orange are compound
Pollutant experiment effect figure.
Specific embodiment
Embodiment 1:
(1) 0.017g TiO is taken2(P25), 0.27g Iron trichloride hexahydrate (FeCl3.6H2O) and 0.18g 2- amino is to benzene two
Formic acid is dissolved in 20mL N,N-dimethylformamide, ultrasonic disperse；It is transferred in the autoclave of polytetrafluoroethyllining lining,
110 DEG C of reaction 12h, centrifuge separation, filter washing, are dried in vacuo 8h at 70 DEG C, obtain TiO2@NH2-MIL-88B(Fe)(TM-
B) photochemical catalyst.In the catalyst, the molar ratio of titanium dioxide and iron-based MOF are 10%.
(2) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the light reaction pipe of 50mL, is added
Gained photochemical catalyst, 3mg small organic molecule in 20mg (1).
(3) adjusting pH value of solution is 7, and 40min, 500W xenon lamp irradiation, at interval of a period of time are sufficiently stirred under dark condition
Sampling, National Standard Method measure remnants Cr (VI) concentration.
TiO is obtained in this example2@NH2The SEM figure of-MIL-88B (Fe) photochemical catalyst is shown in Fig. 1, according to SEM as can be seen that
NH2- MIL-88B (Fe) still maintains its club-like structure, and surface is distributed TiO2Nanoparticle illustrates prepared by composite photo-catalyst
Success.Experimental result is shown in Fig. 2, describes the ratio between (VI) concentration of Cr in reaction process and initial Cr (VI) concentration and change with time
Trend.
Comparative example 1:
A kind of NH2The preparation method of-MIL-88B (Fe) material, includes the following steps:
(1) 0.27g Iron trichloride hexahydrate (FeCl is weighed3.6H2O) and 20mL N is added in the 2- amino terephthalic acid (TPA) of 0.18g,
In dinethylformamide, magnetic agitation 0.5h under normal temperature condition obtains homogeneous solution.Above-mentioned mixed solution is transferred to poly- four
In the autoclave of vinyl fluoride liner, 110 DEG C of reaction 12h；Be cooled to room temperature, be centrifugated, methanol and water washing respectively three times,
It filters, 8h is dried in vacuo at 70 DEG C to get NH is arrived2-MIL-88B(Fe)。
(2) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the light reaction pipe of 50mL, is added
Gained photochemical catalyst, 3mg small organic molecule in 20mg (1).
(3) adjusting pH value of solution is 7, and 40min, 500W xenon lamp irradiation, at interval of a period of time are sufficiently stirred under dark condition
Sampling, National Standard Method measure remnants Cr (VI) concentration.Experimental result is shown in Fig. 2, (VI) concentration of Cr in reaction process and initial is described
The ratio between Cr (VI) concentration trend that changes with time.
Embodiment 2:
Present embodiment and embodiment 1 are except that TiO described in step (1)2(P25) additive amount is
0.0085g, other are same as Example 1, obtain photochemical catalyst (TM-a).Experimental result is shown in Fig. 2, Cr in reaction process is described
(VI) the ratio between concentration and initial Cr (VI) concentration trend that changes with time.
In the photochemical catalyst (TM-a), the molar ratio of titanium dioxide and iron-based MOF are 5%.
Embodiment 3:
Present embodiment and embodiment 1 are except that be TiO in step (1)2(P25) additive amount is 0.0255g,
He is same as Example 1, obtains photochemical catalyst (TM-c).Experimental result is shown in Fig. 2, describe (VI) concentration of Cr in reaction process with
The ratio between initial Cr (VI) concentration trend that changes with time.In the photochemical catalyst (TM-c), mole of titanium dioxide and iron-based MOF
Than being 15%.
Embodiment 4:
Present embodiment and embodiment 1 are except that be TiO in step (1)2(P25) additive amount is 0.034g,
He is same as Example 1, obtains photochemical catalyst (TM-d).Experimental result is shown in Fig. 2, describe (VI) concentration of Cr in reaction process with
The ratio between initial Cr (VI) concentration trend that changes with time.
In the photochemical catalyst (TM-d), the molar ratio of titanium dioxide and iron-based MOF are 20%.
Embodiment 5:
Present embodiment and embodiment 1 are except that be 100 DEG C of temperature of hydro-thermal reaction in step (1), other and reality
It is identical to apply example 1, there is same structure and photocatalysis performance in gained photochemical catalyst and embodiment 1.
Embodiment 6:
Present embodiment and embodiment 1 are except that be Iron trichloride hexahydrate (FeCl in step (1)3.6H2O), 2- amino
The additive amount of terephthalic acid (TPA) is respectively 0.27g and 0.36g.Other are same as Example 1, gained photochemical catalyst and embodiment 1
In have same structure and photocatalysis performance.
Embodiment 7:
Present embodiment and embodiment 1 except that be that n,N-Dimethylformamide dosage is 10mL in step (1),
He is same as Example 1, has same structure and photocatalysis performance in gained photochemical catalyst and embodiment 1.
Embodiment 8:
Present embodiment and embodiment 1 are except that be to add nine water ferric nitrate of 0.404g in step (1)
(FeNO3.9H2) or 0.526g Fe O2(SO4)3·7H2O, other are same as Example 1, in gained photochemical catalyst and embodiment 1
With similar structure and photocatalysis performance.
Embodiment 9:
(1) 0.017g TiO is taken2(P25), 0.27g Iron trichloride hexahydrate (FeCl3.6H2O) and 0.09g 2- amino is to benzene two
Formic acid is dissolved in 20mL N,N-dimethylformamide；It is transferred in the autoclave of polytetrafluoroethyllining lining, 120 DEG C of reactions
12h, centrifuge separation, filter washing, are dried in vacuo 8h at 70 DEG C, obtain TiO2@NH2- MIL-101 (Fe) photochemical catalyst.
(2) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the light reaction pipe of 50mL, is added
Gained photochemical catalyst, 3mg small organic molecule in 20mg (1).
(3) adjusting pH value of solution is 7, and 40min, 500W xenon lamp irradiation, at interval of a period of time are sufficiently stirred under dark condition
Sampling, National Standard Method measure remnants Cr (VI) concentration.Experimental result is shown in Fig. 3, (VI) concentration of Cr in reaction process and initial is described
The ratio between Cr (VI) concentration trend that changes with time.
Embodiment 10:
Except that hydrothermal temperature is 150 DEG C in step (1), the reaction time is for present embodiment and embodiment 7
For 24 hours, it is cooled to room temperature, is centrifugated, methanol and water washing respectively three times, filter, and vacuum drying 8h is at 50 DEG C to get arriving TiO2@
NH2- MIL-53 (Fe) composite material.Other are same as Example 7.Experimental result is shown in Fig. 3, Cr in reaction process (VI) is described
The ratio between concentration and initial Cr (VI) concentration trend that changes with time.
Embodiment 11:
Present embodiment and embodiment 8 except that in step (1) the hydro-thermal reaction reaction time be 48h, other and reality
It is identical to apply example 8, gained has similar structure and photocatalysis performance in gained catalyst and embodiment 8.
Embodiment 12:
(1) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the light reaction pipe of 50mL, is added
Gained photochemical catalyst, 3mg small organic molecule in 20mg embodiment 1.
(2) adjusting pH value of solution is 5,6,7,8,9, and 40min is sufficiently stirred under dark condition, and 500W xenon lamp irradiates, at interval of
A period of time samples, and National Standard Method measures remnants Cr (VI) concentration.Experimental result is shown in Fig. 4, it is dense to describe Cr in reaction process (VI)
The ratio between degree and initial Cr (VI) concentration trend that changes with time.
Embodiment 13:
(1) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the light reaction pipe of 50mL, is added
Gained photochemical catalyst in 20mg embodiment 1,3mg small organic molecule is respectively ammonium oxalate, ethyl alcohol, citric acid.
(2) adjusting pH value of solution is 7, and 40min, 500W xenon lamp irradiation, at interval of a period of time are sufficiently stirred under dark condition
Sampling, National Standard Method measure remnants Cr (VI) concentration.Experimental result is shown in Fig. 5, (VI) concentration of Cr in reaction process and initial is described
The ratio between Cr (VI) concentration trend that changes with time.
Embodiment 14:
(1) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the light reaction pipe of 50mL, is added
Gained photochemical catalyst, 3mg small organic molecule in 20mg embodiment 1.
(2) adjusting pH value of solution is 7, and 40min, 500W xenon lamp irradiation, at interval of a period of time are sufficiently stirred under dark condition
Sampling, National Standard Method measure remnants Cr (VI) concentration.
(3) catalyst after reaction is recovered by centrifugation, is washed using the nitric acid solution of 1mol/L, is dried for standby, makes
With the catalyst after above-mentioned regeneration, step (1), the degradation experiment in (2) are repeated.Experimental result is shown in Fig. 6, describe circulation experiment
The removal efficiency of Cr (VI) in the process.
Embodiment 15:
(1) Cr (VI) solution for preparing 0.2mmol/L at room temperature, takes 40mL solution in the beaker of 50mL, and 20mg is added
Gained photochemical catalyst, 3mg small organic molecule in embodiment 1.
(2) adjusting pH value of solution is 7, and 40min is sufficiently stirred under dark condition, and sunlight irradiates 1h, and National Standard Method measurement is remaining
Cr (VI) concentration.Experimental result is shown in Fig. 7, the removal efficiency that Cr (VI) during circulation experiment is changed over time is described.
Embodiment 16:
(1) four groups of solution for containing Cr (VI) and methyl orange (MO) are configured at room temperature, and concentration proportioning is respectively 10/0mg/L, 0/
20mg/L, 10/10mg/L, 10/20mg/L, 10/30mg/L take 40mL solution in the light reaction pipe of 50mL, and it is real that 20mg is added
Apply gained photochemical catalyst in example 1.
(2) adjusting pH value of solution is 7, and 40min is sufficiently stirred under dark condition, and 500W xenon lamp irradiates 2.5h, National Standard Method measurement
Remaining Cr (VI), MO concentration.Experimental result is shown in Fig. 8, describe the removal efficiency of Cr (VI) and MO under different initial concentrations.
Comparative example 2:
Present embodiment and embodiment 1 are except that TiO in step (1)2(P25) additive amount is 0.043g, other
Same as Example 1, experimental result is shown in Table 1.
Comparative example 3:
Present embodiment and embodiment 1 are except that hydrothermal synthesis temperature is 180 DEG C in step (1), other and implementation
Example 1 is identical, and experimental result is shown in Table 1.
Comparative example 4:
Present embodiment and embodiment 1 except that the dosage of synthesis photochemical catalyst is 30mg in step (2), other
Same as Example 1, experimental result is shown in Table 1.
Comparative example 5:
Present embodiment and embodiment 1 except that the dosage of synthesis photochemical catalyst is 10mg in step (2), other
Same as Example 1, experimental result is shown in Table 1.
Cr (VI) photo catalytic reduction efficiency in 1 comparative example 2~5 of table
| Serial number | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Cr (VI) removal efficiency (%) | 70.4% | 21.6% | 91.5% | 62.7% |
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of iron-based MOF visible light composite catalyst of nano-titanium dioxide@, which is characterized in that the titanium dioxide with it is iron-based
The molar ratio of MOF is 5%~20%.
2. the iron-based MOF visible light composite catalyst of nano-titanium dioxide@as described in claim 1, which is characterized in that the iron
Base MOF is NH2-MIL-88B(Fe)、NH2-MIL-53(Fe)、NH2One of-MIL-101 (Fe).
3. the preparation method of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@as described in claim 1, feature
It is, comprising the following steps:
Step 1, by trivalent iron salt, 2- amino terephthalic acid (TPA) and nano-TiO2It is added in n,N-Dimethylformamide, ultrasound point
It dissipates and uniformly obtains precursor solution；
Step 2, by precursor solution obtained in step 1, nanometer two is made in 12~48h of hydro-thermal reaction at 100~150 DEG C
The iron-based MOF visible light composite catalyst of titanium oxide@.
4. the preparation method of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@as claimed in claim 3, feature
It is, the trivalent iron salt is the mixing of iron chloride, ferric nitrate, any one or a few in ferric sulfate.
5. the preparation method of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@as claimed in claim 3, feature
It is, the molar ratio of the trivalent iron salt, 2- amino terephthalic acid (TPA) and n,N-Dimethylformamide is 1:(0.5~2): (140
~280), nano-TiO2Mass ratio with N,N-dimethylformamide is 1:(500~2500).
6. the preparation method of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@as claimed in claim 3, feature
It is, in step 2, after the completion of the hydro-thermal reaction, product is carried out from, washing, dry；It is highly preferred that washing use is molten
Agent is methanol or ethyl alcohol, and vacuum drying temperature is 50~70 DEG C.
7. the iron-based MOF visible light composite catalyst of nano-titanium dioxide@as claimed in any one of claims 1 to 6 is in removal water phase
In Cr (VI) in application.
8. the use as claimed in claim 7, which is characterized in that method particularly includes:
The iron-based MOF visible light composite catalyst of the nano-titanium dioxide@is added in the solution containing Cr (VI), adjusting pH is
5~9, magnetic agitation dark reaction after reaching adsorption equilibrium, carries out photo catalytic reduction reaction under illumination.
9. application as claimed in claim 8, which is characterized in that the dosage of the photochemical catalyst is 0.25~0.75g/L.
10. application as claimed in claim 8, which is characterized in that also have comprising small molecule in the solution containing Cr (VI)
Machine object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811392251.3A CN109289927A (en) | 2018-11-21 | 2018-11-21 | The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811392251.3A CN109289927A (en) | 2018-11-21 | 2018-11-21 | The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109289927A true CN109289927A (en) | 2019-02-01 |
Family
ID=65144784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811392251.3A Pending CN109289927A (en) | 2018-11-21 | 2018-11-21 | The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109289927A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110331001A (en) * | 2019-07-11 | 2019-10-15 | 福建师范大学福清分校 | The preparation method and applications of the immobilized ionic liquid of ferrous metals organic backbone |
| CN110424022A (en) * | 2019-06-26 | 2019-11-08 | 武汉科技大学 | Compound MIL-101 hetero-junctions light anode of nanometer rods alpha-ferric oxide and preparation method thereof |
| CN110523438A (en) * | 2019-09-02 | 2019-12-03 | 中国科学技术大学 | A kind of ferrous metals organic framework material, preparation method and the application of modification |
| CN110698685A (en) * | 2019-10-21 | 2020-01-17 | 安徽中烟工业有限责任公司 | MOFs material for cigarette filter tip and preparation method and application thereof |
| CN110882725A (en) * | 2019-12-06 | 2020-03-17 | 北京科技大学 | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof |
| CN111036303A (en) * | 2019-12-09 | 2020-04-21 | 燕山大学 | Photocatalytic oxidation desulfurization catalyst, preparation method, application and regeneration method thereof |
| CN111408413A (en) * | 2020-03-30 | 2020-07-14 | 浙江工商大学 | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof |
| CN111617804A (en) * | 2020-05-19 | 2020-09-04 | 南京大学 | Preparation method and application of layered visible light composite catalyst |
| CN112076792A (en) * | 2020-08-28 | 2020-12-15 | 盐城工学院 | Method for constructing TiO by utilizing hydrogen bond2Method for preparing nanotube-MOF composite photocatalyst and application thereof |
| CN111135869B (en) * | 2019-12-29 | 2021-05-07 | 苏州阿德旺斯新材料有限公司 | Preparation method of titanium dioxide nanobelt @ MOF composite material |
| CN111135870B (en) * | 2019-12-29 | 2021-05-07 | 苏州阿德旺斯新材料有限公司 | Titanium dioxide nanobelt @ MOF composite material and application thereof |
| CN113000071A (en) * | 2021-03-05 | 2021-06-22 | 成都理工大学 | Porous visible light photocatalysis ZnFe2O4-TiO2Preparation method and regeneration method of/PVDF composite membrane |
| WO2021135253A1 (en) * | 2019-12-29 | 2021-07-08 | 苏州阿德旺斯新材料有限公司 | Titanium dioxide nanobelt@mof composite material, preparation method therefor, and use thereof |
| CN113457745A (en) * | 2021-07-07 | 2021-10-01 | 中国海洋大学 | Selective reduction of nitrate to N2Preparation method and application of photocatalyst |
| CN114225965A (en) * | 2021-12-31 | 2022-03-25 | 中原工学院 | D-A covalent organic framework catalyst with diazosulfide structure and preparation method and application thereof |
| CN114436337A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Chemical ring hydrogen production oxygen carrier and preparation method thereof |
| CN114588946A (en) * | 2022-01-13 | 2022-06-07 | 河海大学 | Preparation method and application of ferrous iron-doped Fe-MOF-based composite material |
| CN114632549A (en) * | 2022-03-07 | 2022-06-17 | 河南师范大学 | alpha-TiO2@NH2Preparation method of-MIL-125 composite photocatalytic material |
| CN114632548A (en) * | 2022-03-07 | 2022-06-17 | 河南师范大学 | One-step synthesis of alpha-TiO2@NH2Method for preparing-MIL-125 composite photocatalytic material |
| CN114939439A (en) * | 2022-06-23 | 2022-08-26 | 西北师范大学 | Preparation and application of titanium dioxide/MOF (Fe)/polyacrylonitrile nanofiber membrane |
| CN115646551A (en) * | 2022-11-08 | 2023-01-31 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816900A (en) * | 2014-03-19 | 2014-05-28 | 福州大学 | Metal oxide/TiO2 nanocatalyst and preparation method thereof |
| CN106238100A (en) * | 2016-07-28 | 2016-12-21 | 北京科技大学 | The preparation of titanium dioxide nanoplate load MIL 100 (Fe) composite photocatalyst material and application process |
| CN106596656A (en) * | 2016-12-15 | 2017-04-26 | 福州大学 | Titanium dioxide-supported ferric oxide nanoheterostructure gas-sensitive element synthesized on basis of MOF template method |
| CN107159313A (en) * | 2017-06-14 | 2017-09-15 | 上海应用技术大学 | A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst |
-
2018
- 2018-11-21 CN CN201811392251.3A patent/CN109289927A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816900A (en) * | 2014-03-19 | 2014-05-28 | 福州大学 | Metal oxide/TiO2 nanocatalyst and preparation method thereof |
| CN106238100A (en) * | 2016-07-28 | 2016-12-21 | 北京科技大学 | The preparation of titanium dioxide nanoplate load MIL 100 (Fe) composite photocatalyst material and application process |
| CN106596656A (en) * | 2016-12-15 | 2017-04-26 | 福州大学 | Titanium dioxide-supported ferric oxide nanoheterostructure gas-sensitive element synthesized on basis of MOF template method |
| CN107159313A (en) * | 2017-06-14 | 2017-09-15 | 上海应用技术大学 | A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst |
Non-Patent Citations (2)
| Title |
|---|
| LEI HE等: "A novel magnetic MIL-101(Fe)/TiO2 composite for photo degradation of tetracycline under solar light", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| LI SHI等: "An Amine-Functionalized Iron(III) Metal–Organic Framework as Effi cient Visible-Light Photocatalyst for Cr(VI) Reduction", 《ADV. SCI.》 * |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110424022A (en) * | 2019-06-26 | 2019-11-08 | 武汉科技大学 | Compound MIL-101 hetero-junctions light anode of nanometer rods alpha-ferric oxide and preparation method thereof |
| CN110331001A (en) * | 2019-07-11 | 2019-10-15 | 福建师范大学福清分校 | The preparation method and applications of the immobilized ionic liquid of ferrous metals organic backbone |
| CN110523438A (en) * | 2019-09-02 | 2019-12-03 | 中国科学技术大学 | A kind of ferrous metals organic framework material, preparation method and the application of modification |
| CN110698685A (en) * | 2019-10-21 | 2020-01-17 | 安徽中烟工业有限责任公司 | MOFs material for cigarette filter tip and preparation method and application thereof |
| CN110882725A (en) * | 2019-12-06 | 2020-03-17 | 北京科技大学 | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof |
| CN111036303B (en) * | 2019-12-09 | 2021-03-23 | 燕山大学 | Photocatalytic oxidation desulfurization catalyst, preparation method, application and regeneration method thereof |
| CN111036303A (en) * | 2019-12-09 | 2020-04-21 | 燕山大学 | Photocatalytic oxidation desulfurization catalyst, preparation method, application and regeneration method thereof |
| CN111135869B (en) * | 2019-12-29 | 2021-05-07 | 苏州阿德旺斯新材料有限公司 | Preparation method of titanium dioxide nanobelt @ MOF composite material |
| CN111135870B (en) * | 2019-12-29 | 2021-05-07 | 苏州阿德旺斯新材料有限公司 | Titanium dioxide nanobelt @ MOF composite material and application thereof |
| WO2021135253A1 (en) * | 2019-12-29 | 2021-07-08 | 苏州阿德旺斯新材料有限公司 | Titanium dioxide nanobelt@mof composite material, preparation method therefor, and use thereof |
| CN111408413A (en) * | 2020-03-30 | 2020-07-14 | 浙江工商大学 | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof |
| CN111408413B (en) * | 2020-03-30 | 2022-09-20 | 浙江工商大学 | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof |
| CN111617804A (en) * | 2020-05-19 | 2020-09-04 | 南京大学 | Preparation method and application of layered visible light composite catalyst |
| CN111617804B (en) * | 2020-05-19 | 2022-11-08 | 南京大学 | Preparation method and application of layered visible light composite catalyst |
| CN112076792B (en) * | 2020-08-28 | 2022-06-24 | 盐城工学院 | Method for constructing TiO by utilizing hydrogen bond2Method for preparing nanotube-MOF composite photocatalyst and application thereof |
| CN112076792A (en) * | 2020-08-28 | 2020-12-15 | 盐城工学院 | Method for constructing TiO by utilizing hydrogen bond2Method for preparing nanotube-MOF composite photocatalyst and application thereof |
| CN114436337B (en) * | 2020-10-19 | 2024-01-09 | 中国石油化工股份有限公司 | Oxygen carrier for chemical looping hydrogen production and preparation method thereof |
| CN114436337A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Chemical ring hydrogen production oxygen carrier and preparation method thereof |
| CN113000071B (en) * | 2021-03-05 | 2022-07-29 | 成都理工大学 | Porous visible light photocatalysis ZnFe 2 O 4 -TiO 2 Preparation method and regeneration method of/PVDF composite membrane |
| CN113000071A (en) * | 2021-03-05 | 2021-06-22 | 成都理工大学 | Porous visible light photocatalysis ZnFe2O4-TiO2Preparation method and regeneration method of/PVDF composite membrane |
| CN113457745A (en) * | 2021-07-07 | 2021-10-01 | 中国海洋大学 | Selective reduction of nitrate to N2Preparation method and application of photocatalyst |
| CN113457745B (en) * | 2021-07-07 | 2022-03-29 | 中国海洋大学 | Selective reduction of nitrate to N2Preparation method and application of photocatalyst |
| CN114225965A (en) * | 2021-12-31 | 2022-03-25 | 中原工学院 | D-A covalent organic framework catalyst with diazosulfide structure and preparation method and application thereof |
| CN114588946A (en) * | 2022-01-13 | 2022-06-07 | 河海大学 | Preparation method and application of ferrous iron-doped Fe-MOF-based composite material |
| CN114632548A (en) * | 2022-03-07 | 2022-06-17 | 河南师范大学 | One-step synthesis of alpha-TiO2@NH2Method for preparing-MIL-125 composite photocatalytic material |
| CN114632549A (en) * | 2022-03-07 | 2022-06-17 | 河南师范大学 | alpha-TiO2@NH2Preparation method of-MIL-125 composite photocatalytic material |
| CN114939439A (en) * | 2022-06-23 | 2022-08-26 | 西北师范大学 | Preparation and application of titanium dioxide/MOF (Fe)/polyacrylonitrile nanofiber membrane |
| CN114939439B (en) * | 2022-06-23 | 2023-12-12 | 西北师范大学 | Preparation and application of titanium dioxide/MOF (Fe)/polyacrylonitrile nanofiber membrane |
| CN115646551A (en) * | 2022-11-08 | 2023-01-31 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
| CN115646551B (en) * | 2022-11-08 | 2023-12-08 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109289927A (en) | The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ | |
| CN106076421B (en) | A kind of MIL-53 (Fe)/g-C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| Pan et al. | Recent progress in 2D metal-organic framework photocatalysts: synthesis, photocatalytic mechanism and applications | |
| CN110437458B (en) | Reusable Fenton-like catalyst [ NH ]2-MIL-101(Fe)]Preparation and application methods of | |
| CN108745418B (en) | Heterojunction MOF catalyst and preparation method and application thereof | |
| CN100398201C (en) | Composite bismuth vanadium photocatalyst supported by cobalt oxide and preparation method thereof | |
| CN111617805B (en) | Light Fenton catalyst, preparation method, application and water treatment agent thereof | |
| CN106881111B (en) | The composite bismuth vanadium photocatalyst and its preparation method and application of cuprous oxide and silver-colored mutual load | |
| CN105170190A (en) | Preparation method of phosphotungstic acid @MIL(Fe) photocatalyst | |
| CN107159313A (en) | A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst | |
| CN110918126A (en) | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst | |
| CN104959141A (en) | Reducing-oxidized graphene/amorphous carbon composite material loading Cu/Cu2O photocatalyst as well as preparation method and application of composite material | |
| CN106345505A (en) | Porous-heterostructure composite photocatalyst and preparation method thereof | |
| CN111408413B (en) | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof | |
| CN106807361A (en) | A kind of unformed bismuth tungstate bismuth oxide ternary organic composite photochemical catalyst of bismuth and preparation method | |
| Liu et al. | Synergistic effect of single-atom Cu and hierarchical polyhedron-like Ta3N5/CdIn2S4 S-scheme heterojunction for boosting photocatalytic NH3 synthesis | |
| CN113000067A (en) | Bimetallic mixed ligand metal organic framework photocatalyst and preparation method thereof | |
| Wang et al. | Green synthesis of MIL-100 (Fe) derivatives and revealing their structure-activity relationship for 2, 4-dichlorophenol photodegradation | |
| CN100460067C (en) | Composite bismuth vanadium photocatalyst supported by nickel oxide and preparation method thereof | |
| CN107913675B (en) | Metal organic framework modifies stannous sulfide composite photo-catalyst and its preparation method and application | |
| Wang et al. | Noble‐metal‐free MOF derived ZnS/CeO2 decorated with CuS cocatalyst photocatalyst with efficient photocatalytic hydrogen production character | |
| CN112517081A (en) | Composite photocatalyst of metal stannum porphyrin axial functionalized titanium dioxide and preparation method thereof | |
| He et al. | Facile fabrication of Fe-BDC/Fe-2MI heterojunction with boosted photocatalytic activity for Cr (VI) reduction | |
| Su et al. | Heterostructured Bi2O2CO3/rGO/PDA photocatalysts with superior activity for organic pollutant degradation: Structural characterization, reaction mechanism and economic assessment | |
| Wang et al. | One-step synthesis of novel Ni-doped Cu2 (OH) 3F Fenton-like catalyst driven by visible light: Single activity and synergistic effect enhanced by bimetallic cooperation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190201 |
|
| RJ01 | Rejection of invention patent application after publication |