CN109046425A - Composite photo-catalyst TiO derived from a kind of MOF base2/g-C3N4Preparation method - Google Patents
Composite photo-catalyst TiO derived from a kind of MOF base2/g-C3N4Preparation method Download PDFInfo
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- CN109046425A CN109046425A CN201810916965.3A CN201810916965A CN109046425A CN 109046425 A CN109046425 A CN 109046425A CN 201810916965 A CN201810916965 A CN 201810916965A CN 109046425 A CN109046425 A CN 109046425A
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 239000012621 metal-organic framework Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001045 blue dye Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to field of material technology, and in particular to composite photo-catalyst TiO derived from a kind of MOF base2/g‑C3N4Preparation method, which is prepared by hydro-thermal method and calcination method, is specifically prepared porous titanium-based metal organic frame MIL-125 using hydro-thermal method, is obtained porous TiO through calcine technology2Nano particle；Melamine growth in situ is obtained into composite photo-catalyst TiO on porous titanium-based metal organic frame MIL-125 by calcine technology2/g‑C3N4.The preparation method is simple, can effectively solve TiO2Low and low to the visible light utilization efficiency problem of particle agglomeration, specific surface area, improves TiO by the porous structure of titanium-based metal organic frame MIL-1252Specific surface area, g-C3N4TiO can be effectively improved2Optical response range, composite photo-catalyst TiO2/g‑C3N4The space length of photo-generate electron-hole can be effectively widened, inhibits the two compound, so that photocatalysis efficiency is greatly improved, and low in cost, it is environmental-friendly, be conducive to practical application and industrialized production.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of catalysis material and preparation method thereof.
Background technique
In recent years, energy crisis and environmental pollution have become global acute problem.Semiconductor catalyst can be effectively
Clean energy resource and degradable organic pollutant are converted solar energy into, thus alleviating energy crisis and reduce environmental pollution, it is wide
General attention.TiO2It is common one of semiconductor material, has preferable photoelectric properties, photocatalysis performance and good chemistry steady
It is qualitative, the advantages such as nontoxicity, but its nano particle specific surface area is small, forbidden band is wider, and it can only be by the minor proportion in sunlight
Ultraviolet excitation is not responding to the visible light in sunlight and photo-generate electron-hole is easily compound.g-C3N4It is nonmetallic photocatalysis
Agent, it is seen that light absorption is very strong, but specific surface area is also relatively small, and photo-generate electron-hole is easily compound, therefore, photocatalysis performance compared with
Difference.The two is combined and constructs direct TiO2/g-C3N4Composite photo-catalyst improves sun light utilization efficiency.Meanwhile
TiO2Conduction band electron and g-C3N4Between valence band hole under internal electrostatic field action, TiO2Conduction band electron is easy to migrate and g-C3N4
Valence band hole is compound, to widen TiO2Valence band hole and g-C3N4Space length between conduction band electron, effectively inhibits
Electron hole it is compound, to substantially increase photocatalysis performance.
About TiO2/g-C3N4Composite photo-catalyst has many patent documents to report, such as: Chinese patent document
CN106914263A discloses a kind of preparation method of composite visible light catalyst, first disperses titanium source and nitrogen source in ethanol
It is even, water is then added dropwise into ethyl alcohol and obtains mixed material；Mixed material is evaporated to obtain presoma under stirring；Then will
The presoma of preparation is transferred in Muffle furnace, is calcined 0.5~12h at 300 DEG C~800 DEG C in Muffle furnace, is obtained TiO2/g-
C3N4Composite visible light catalyst.But poor by photochemical catalyst photocatalysis effect prepared by the method, degradation of methylene blue efficiency is still
It is so to be improved.
Again for example: Chinese patent document CN107837817A discloses a kind of carbon dots/carbonitride/titanium dioxide composite wood
Material, the material are combined by three-phase carbon dots, class graphene carbonitride and titanium dioxide；Wherein, carbonitride possesses biggish table
Area can just provide the space that can be deposited for titanium dioxide nanoplate, titanium dioxide is made not reunite, meanwhile, nitridation
The relatively narrow forbidden bandwidth of carbon can increase optical response range again, and also using the unique electron transfer capacity of carbon dots come further
Inhibit the compound of Pair production, to increase photocatalysis performance.Although the patent document is increased by the compound mode of carbon dots
The specific surface of photochemical catalyst, but compared to the photochemical catalyst prepared by MOF metal organic framework, specific surface area is still
Smaller, photocatalysis effect is not so good as the photochemical catalyst prepared by MOF metal organic framework.
Metal-organic framework (MOF) is the substance that metal ion and organic ligand are combined by coordinate bond, is a kind of
New crystalline, porous coordination polymer, aperture-controllable size, the shape in hole.Preparing, there is the MOF template light of high surface area to urge
Agent can not only increase the exposed amount in photocatalytic activity site, can also promote mass transfer and the transmission of photo-generated charge carriers.
The institute that branch one of of the titanium-based metal organic frame MIL-125 as MOFs has MOFs is advantageous, has wide application
Prospect.
Currently, preparing TiO by template of MIL-1252/g-C3N4Composite photocatalyst material has not been reported.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of high catalytic activity, high stability, can industrial applications
Composite photo-catalyst TiO derived from MOF base2/g-C3N4Preparation method.The present invention mainly utilizes hydro-thermal method to prepare porous titanium
Base Metal organic frame MIL-125 obtains porous TiO through calcine technology2Nano particle；By calcine technology by melamine
Growth in situ obtains composite photo-catalyst TiO on porous titanium-based metal organic frame MIL-1252/g-C3N4, can have
Effect utilizes solar energy, improves photocatalysis efficiency.
Technical scheme is as follows:
Composite photo-catalyst TiO derived from a kind of MOF base2/g-C3N4Preparation method, comprise the following steps that
(1) butyl titanate, terephthalic acid (TPA), dimethylformamide and ethyl alcohol are uniformly mixed, obtain mixed liquor；It will mix
After closing liquid hydro-thermal reaction, cooling, washing, drying obtain titanium-based metal organic frame MIL-125；
(2) MIL-125 and melamine are uniformly mixed, in 400-700 DEG C of heat treatment 1-3h, natural cooling to get
TiO2/g-C3N4Composite photo-catalyst.
, according to the invention it is preferred to, butyl titanate in step (1), terephthalic acid (TPA), dimethylformamide and ethyl alcohol
Molar ratio is 1:(1-20): (1-50): (1-30)；Further preferred 1:(5-15): (10-25): (20-30)；
, according to the invention it is preferred to, 100-300 DEG C of temperature of hydro-thermal reaction, the hydro-thermal reaction time 5- in step (1)
40h；
Further preferably, 150-200 DEG C, the hydro-thermal reaction time 20-30h.
, according to the invention it is preferred to, washing detergent used is dimethylformamide and dehydrated alcohol in step (1).
, according to the invention it is preferred to, the molar ratio of MIL-125 and melamine is 1:(0.05-0.5 in step (2)), into
The preferred 1:(0.1-0.4 of one step).
, according to the invention it is preferred to, the temperature being heat-treated in step (2) is 300-700 DEG C；
It is further preferred that being warming up to heat treatment temperature with the heating rate of 2-30 DEG C/min.Entire heat treatment process is equal
It carries out in air atmosphere.
, according to the invention it is preferred to, product is ground to micron order little particle after step (2) natural cooling, obtains TiO2/
g-C3N4Composite photo catalyst powder.
The positive effect of the present invention is embodied in:
1, the TiO that the present invention is prepared using MIL-125 as template2/g-C3N4Composite photo-catalyst, because it is with high-ratio surface
Long-pending and abundant pore structure is that constructing for photochemical catalyst provides advantage, and as photochemical catalyst, it is capable of providing more negative
Site is carried, photocatalytic activity is improved.
2, TiO prepared by the present invention2/g-C3N4Composite photo-catalyst both remains TiO2Physicochemical properties are stable, nontoxic
The advantages that, and inherit g-C3N4To the high-selenium corn performance advantage of visible light.
3, photochemical catalyst produced by the present invention can be applied to photolysis water hydrogen and environmental contaminants degradation, especially methylene
Blue dyestuff has good degradation effect, improves inorganic composite nano material in the application of Photocatalyzed Hydrogen Production and degradation field.
4, preparation method of the present invention is simple, can effectively solve TiO2Particle agglomeration, specific surface area are low and to visible light benefit
With the low problem of rate, TiO is improved by the porous structure of titanium-based metal organic frame MIL-1252Specific surface area, g-C3N4
TiO can be effectively improved2Optical response range, composite photo-catalyst TiO2/g-C3N4Photo-generate electron-hole can effectively be widened
Space length, both inhibit compound, to greatly improve photocatalysis efficiency, and the photochemical catalyst is low in cost, physical chemistry
Property is stablized, nontoxic, environmental-friendly to be conducive to practical application and industrialized production.
Detailed description of the invention
Fig. 1 is TiO made from embodiment 12/g-C3N4The SEM picture of composite photo-catalyst.
Fig. 2 is the TiO that comparative example 1 obtains2SEM picture.
Fig. 3 is the g-C that comparative example 2 obtains3N4SEM picture.
Fig. 4 is TiO made from embodiment 12/g-C3N4The UV-vis DRS figure of composite photo-catalyst.
Case is embodied
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right With reference to embodiment
The present invention is described in further detail, but the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following implementations
Example.
Embodiment 1:
0.39ml butyl titanate, 13.5ml dimethylformamide, 1.5ml ethyl alcohol are measured, 1.5g terephthalic acid (TPA) is weighed,
By above-mentioned raw materials ultrasound 10min, 1h is then mixed at room temperature, forms uniform mixed liquor；Above-mentioned mixed liquor is packed into
Hydrothermal reaction kettle, 160 DEG C of hydro-thermal reactions for 24 hours, after natural cooling, remove supernatant, with terephthalic acid (TPA) and dehydrated alcohol
It is each to wash three times, and the dry 5h in 60 DEG C of baking ovens, products obtained therefrom is MIL-125.
It weighs 500mg MIL-125 and 100mg melamine and is placed in agate mortar and be fully ground, mix 10min；It will mix
It closes uniform MIL-125 and melamine mixture is fitted into crucible, be then put into Muffle furnace and be heat-treated, heat up journey
Sequence are as follows: from room temperature with the heating rate of 5 DEG C/min, 500 DEG C are raised to, and keeps the temperature 2h, subsequent furnace cooling, entire heat treatment process
Carry out in air atmosphere；Obtained photocatalysis composite is poured into agate mortar, is fully ground into micron small
TiO2/g-C3N4 composite photo-catalyst is made in grain.
TiO made from the present embodiment2/g-C3N4Composite photo-catalyst produces hydrogen and degradation property test under visible light, produces hydrogen
Performance test conditions are as follows: 300W xenon lamp is 10ml methanol and 40ml deionization as light source, catalyst amount 20mg, sacrifice agent
Water, the H after 3 hours2Yield is 1.4mmol/h/g.Degradation property test condition are as follows: 300W xenon lamp is used as light source, catalyst
Amount is 30mg, and dyestuff is 50ml methylene blue dye, concentration are as follows: its drop to methylene blue dye after 10mg/L, 150min
Solution rate reaches 93%.
Embodiment 2:
0.39ml butyl titanate, 13.5ml dimethylformamide, 1.5ml ethyl alcohol are measured, 1.5g terephthalic acid (TPA) is weighed,
By above-mentioned raw materials ultrasound 10min, 1h is then mixed at room temperature, forms uniform mixed liquor；Above-mentioned mixed liquor is packed into
Hydrothermal reaction kettle, 160 DEG C of hydro-thermal reactions for 24 hours, after natural cooling, remove supernatant, with terephthalic acid (TPA) and dehydrated alcohol
It is each to wash three times, and the dry 5h in 60 DEG C of baking ovens, products obtained therefrom is MIL-125；
It weighs 500mg MIL-125 and 200mg melamine and is placed in agate mortar and be fully ground, mix 10min；It will mix
It closes uniform MIL-125 and melamine mixture is fitted into crucible, be then put into Muffle furnace and be heat-treated, heat up journey
Sequence are as follows: from room temperature with the heating rate of 5 DEG C/min, 500 DEG C are raised to, and keeps the temperature 2h, subsequent furnace cooling, entire heat treatment process
Carry out in air atmosphere；Obtained photocatalysis composite is poured into agate mortar, is fully ground into micron small
TiO is made in grain2/g-C3N4Composite photo-catalyst.
TiO made from the present embodiment2/g-C3N4Composite photo-catalyst produces hydrogen and degradation property test under visible light, produces hydrogen
Performance test conditions are as follows: 300W xenon lamp is 10ml methanol and 40ml deionization as light source, catalyst amount 20mg, sacrifice agent
Water, the H after 3 hours2Yield is 2.3mmol/h/g.Degradation property test condition are as follows: 300W xenon lamp is used as light source, catalyst
Amount is 30mg, and dyestuff is 50ml methylene blue dye, concentration are as follows: its drop to methylene blue dye after 10mg/L, 150min
Solution rate reaches 98%.
Embodiment 3:
0.39ml butyl titanate, 13.5ml dimethylformamide, 1.5ml ethyl alcohol are measured, 1.5g terephthalic acid (TPA) is weighed,
By above-mentioned raw materials ultrasound 10min, 1h is then mixed at room temperature, forms uniform mixed liquor；Above-mentioned mixed liquor is packed into
Hydrothermal reaction kettle, 160 DEG C of hydro-thermal reactions for 24 hours, after natural cooling, remove supernatant, with terephthalic acid (TPA) and dehydrated alcohol
It is each to wash three times, and the dry 5h in 60 DEG C of baking ovens, products obtained therefrom is MIL-125.
It weighs 500mg MIL-125 and 375mg melamine and is placed in agate mortar and be fully ground, mix 10min；It will mix
It closes uniform MIL-125 and melamine mixture is fitted into crucible, be then put into Muffle furnace and be heat-treated, heat up journey
Sequence are as follows: from room temperature with the heating rate of 5 DEG C/min, 500 DEG C are raised to, and keeps the temperature 2h, subsequent furnace cooling, entire heat treatment process
Carry out in air atmosphere；Obtained photocatalysis composite is poured into agate mortar, is fully ground into micron small
TiO is made in grain2/ g-C3N4 composite photo-catalyst.
TiO made from the present embodiment2/g-C3N4Composite photo-catalyst produces hydrogen and degradation property test under visible light, produces hydrogen
Performance test conditions are as follows: 300W xenon lamp is 10ml methanol and 40ml deionization as light source, catalyst amount 20mg, sacrifice agent
Water, the H after 3 hours2Yield is 0.9mmol/h/g.Degradation property test condition are as follows: 300W xenon lamp is used as light source, catalyst
Amount is 30mg, and dyestuff is 50ml methylene blue dye, concentration are as follows: its drop to methylene blue dye after 10mg/L, 150min
Solution rate reaches 85%.
Comparative example 1
This comparative example presses prior art preparation TiO2.It is 21% to the degradation rate of methylene blue dye after 150min.H2It produces
Rate is 0.1mmol/h/g
Comparative example 2
The preparation of this comparative example is g-C3N4, melamine is placed in crucible, being put into Muffle furnace in temperature is 520 DEG C
Lower calcining 2h, i.e. acquisition g-C3N4.It is 60% to the degradation rate of methylene blue dye after 150min.H2Yield is 0.3mmol/
h/g
Test example 1
TiO made from testing example 12/g-C3N4The SEM picture of composite photo-catalyst, as shown in Figure 1.It can by Fig. 1
To find out, TiO2Surface is wrapped in g-C3N4, substantially increased by the porous structure of titanium-based metal organic frame MIL-125
TiO2Specific surface area.
The TiO that test comparison example 1 obtains2SEM picture, as shown in Figure 2.The g-C that test comparison example 2 obtains3N4SEM
Picture, as shown in Figure 3.
TiO made from testing example 12/g-C3N4The UV-vis DRS figure of composite photo-catalyst, as shown in Figure 4.
As seen from Figure 4, TiO2/g-C3N4All there is stronger absorbability in ultraviolet light and visible light region.
Test example 2
The obtained different photochemical catalysts of embodiment 1-3 and comparative example 1-2 are subjected to degradation test to methylene blue, as a result such as
Shown in table 1.
Degradation efficiency of the different photochemical catalysts of table 1 to methylene blue
As shown in Table 1, TiO prepared by the present invention2/g-C3N4Composite photo-catalyst has excellent degradation to methylene blue
Performance.Test example 3
The different photochemical catalysts catalysis H2-producing capacity test that embodiment 1-3 and comparative example 1-2 are obtained, as a result such as 2 institute of table
Show.
The different photochemical catalysts of table 2 are catalyzed H2-producing capacity
| Number | H2Yield (mmol/h/g) |
| Embodiment 1 | 1.4 |
| Embodiment 2 | 2.3 |
| Embodiment 3 | 0.9 |
| Comparative example 1 | 0.1 |
| Comparative example 2 | 0.3 |
As shown in Table 2, TiO prepared by the present invention2/g-C3N4Composite photo-catalyst has excellent H2-producing capacity.
Claims (10)
1. composite photo-catalyst TiO derived from a kind of MOF base2/g-C3N4Preparation method, comprise the following steps that
(1) butyl titanate, terephthalic acid (TPA), dimethylformamide and ethyl alcohol are uniformly mixed, obtain mixed liquor；By mixed liquor
After hydro-thermal reaction, cooling, washing, drying obtain titanium-based metal organic frame MIL-125；
(2) MIL-125 and melamine are uniformly mixed, in 400-700 DEG C of heat treatment 1-3h, natural cooling is to get TiO2/g-
C3N4Composite photo-catalyst.
2. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature exists
In the molar ratio of, butyl titanate in step (1), terephthalic acid (TPA), dimethylformamide and ethyl alcohol be 1:(1-20): (1-
50): (1-30).
3. composite photo-catalyst TiO derived from MOF base according to claim 22/g-C3N4Preparation method, feature exists
In the molar ratio of, butyl titanate in step (1), terephthalic acid (TPA), dimethylformamide and ethyl alcohol be 1:(5-15): (10-
25): (20-30).
4. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature exists
In 100-300 DEG C of temperature of hydro-thermal reaction, the hydro-thermal reaction time 5-40h in step (1).
5. composite photo-catalyst TiO derived from MOF base according to claim 42/g-C3N4Preparation method, feature exists
In 150-200 DEG C of temperature of hydro-thermal reaction, the hydro-thermal reaction time 20-30h in step (1).
6. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature exists
In washing detergent used is dimethylformamide and dehydrated alcohol in step (1).
7. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature exists
In the molar ratio of MIL-125 and melamine is 1:(0.05-0.5 in step (2)).
8. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature exists
In the temperature being heat-treated in step (2) is 300-700 DEG C.
9. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature exists
In being warming up to heat treatment temperature in step (2) with the heating rate of 2-30 DEG C/min.
10. composite photo-catalyst TiO derived from MOF base according to claim 12/g-C3N4Preparation method, feature
It is, product is ground to micron order little particle after step (2) natural cooling, obtains TiO2/g-C3N4Composite photo-catalyst powder
End.
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