CN104148042B - A kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material - Google Patents
A kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material Download PDFInfo
- Publication number
- CN104148042B CN104148042B CN201410394338.XA CN201410394338A CN104148042B CN 104148042 B CN104148042 B CN 104148042B CN 201410394338 A CN201410394338 A CN 201410394338A CN 104148042 B CN104148042 B CN 104148042B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- carbon containing
- containing titanium
- preparation
- porous carbon
- 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.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004005 microsphere Substances 0.000 claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 229920005553 polystyrene-acrylate Polymers 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001400 block copolymer Polymers 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000802 evaporation-induced self-assembly Methods 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 30
- 230000001699 photocatalysis Effects 0.000 description 14
- 238000007146 photocatalysis Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 is incubated 2h Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to the preparation method of a kind of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material.The method is with polystyrene acrylate microsphere emulsion, block copolymer, ethanol and titanium source as raw material; with filter paper as matrix; at room temperature evaporation induced self-assembly, then heat treatment obtains described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material under hot polymerization and inert atmosphere protection.Products therefrom has macropore, mesoporous hierarchical porous structure, duct queueing discipline, macropore size uniformity, and size is adjustable 200～400nm, and mesopore size is 3～5nm；Phosphorus content is 16～21wt%, and the effective uptake region to sunlight is 200～800nm.The present invention has abandoned the dependence to the conventional matrix material such as steel disc, silicon chip, and technique is simple, low for equipment requirements, workable, and the carbon containing titanium dioxide membrane material of preparation has been widened the response range to solar spectrum, had excellent visible light catalytic performance.
Description
Technical field
The present invention relates to the preparation of titanium oxide photochemical catalyst material, a kind of have macropore, the carbon containing of mesoporous graded porous structure
The preparation method of titanium dioxide self-supported membrane catalysis material.
Background technology
TiO2A kind of important N-type semiconductor photocatalyst, have good photocatalytic activity and chemical stability etc. many its
His physicochemical characteristic, the most active in the research of photocatalysis and energy field.TiO2First crucial mistake of light-catalyzed reaction mechanism
Journey is TiO2Semiconductor absorber photon is to produce electron-hole pair, and the band gap of quasiconductor is depended in the realization of this step.Anatase
With Rutile Type TiO2Band gap be respectively 3.2 and 3.0eV, i.e. can only be by wavelength <ultraviolet excitation of 387nm, and this portion
Light splitting ratio in solar spectrum only accounts for about 5%.At present, TiO2The problems such as spectral response range is narrow, quantum yield is low
It is still and limits its key factor carrying out photocatalytic applications.Therefore, research and development light absorpting ability photocatalysis in limit of visible spectrum
Agent, widens TiO2Response range to solar spectrum, improves the utilization rate to solar energy, is TiO2The development of catalysis material
Direction.
In nano-scale, owing to there is quantum confined effect, the performance that transports in electronics and hole is changed, electronic band structure
Also can be moved, therefore nanorize can reduce energy gap.Additionally, have the nano material of loose structure, have bigger
Specific surface area, can increase the catalysis activity of surface reaction site and regulation surface atom；Abundant pore structure also helps light
Transmission, can effectively intensified response thing and the diffusion of product molecule, minimizing resistance to mass tranfer.In recent years, hierarchical porous structure TiO2's
Construct research and become nanorize focus.He Tao etc. based on LPD principle, use biological template agent (staphylococcus aureus) with
TiO2Particle solution is prepared for the TiO with hierarchical porous structure2(J.Phys.Chem.C 2014,118,4607), has random
The 500nm macropore of distribution and 1.93～3.92nm mesoporous, preparation technology is the harshest, and the degree of order of product mesopore is the best, and
Simple nanorize is to TiO2The adjustment of energy gap is limited.
For improving TiO further2Photocatalyst is to the utilization rate of sunlight and improves photocatalytic activity, researchers use metal from
Son doping, semiconductors coupling, noble metal loading or nonmetal doping are to TiO2Photocatalyst is modified research.Calendar year 2001 Asahi
Et al. first proposed the anion doped modified TiO such as N, P, C at Science2Photocatalyst.As third generation photocatalyst
Nonmetal doping modification TiO2Photocatalyst, nonmetal doping can optimize electron cloud structure, cause TiO2Band gap reduces.
But relative to metal ion mixing, nonmetallic ion-doped study on the modification also compares less, mainly has carbon, nitrogen, sulfur etc..Its
In, TiO2With the composite of C have uniqueness advantage: the introducing of carbon can not only optimize band structure, introduce impurity energy level,
Reduce energy gap, TiO under suppression high temperature2The transformation of crystal formation, light induced electron can also be transmitted by its excellent electric conductivity in time,
Hinder the compound of light induced electron and hole, and then be effectively improved its photocatalysis performance.Yuan Zhongyong etc. (CN200710056968.6)
Mix with titanate esters, carbon source (DDA, vitamin B6) and ethanol (or ethanol and the mixed liquor of water), aging obtain white powder
End, obtains the porous oxidation titanium powder of carbon doping after nitrogen atmosphere heat treatment.There is random hole, big hole dimension in this powder body
300～1000nm, mesopore size 2.0～24nm, its UV-vis absorption spectrum Einstein shift to 440nm, energy gap regulating effect is excellent
Good.But, with duct ordered arrangement, the hierarchical porous structure TiO of structured size2Compare, the porous powder of this random arrangement,
It is unfavorable for being effectively improved duct inner transmission matter and product quickly spreads, be unfavorable for effectively promoting the specific surface area utilization rate of material and light is urged
Change avtive spot.Additionally, there is the shortcoming being not easily recycled and recycling in powder body material.
Therefore, collaborative nonmetal doping and the advantage of ordered porous nanorize structure, it is many that further research and development have orderly classification
The preparation method of the carbon containing titanic oxide material of pore structure, the technique that described method relates to is simple, and products therefrom can effectively promote it
Photocatalysis performance, has important propelling meaning to titania meterial in the application of photocatalysis field.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material,
The technique that the method relates to is simple, and the carbon containing titanic oxide material prepared can widen the response range to sunlight, is effectively improved it
Visible light catalytic performance.
For achieving the above object, the technical scheme is that a kind of orderly classifying porous carbon containing titanium dioxide self-supported membrane photocatalysis
The preparation method of material, it is characterised in that be with polystyrene acrylate microsphere emulsion, block copolymer, ethanol and titanium source
Raw material, with filter paper as matrix, uses self assembly principle, in the orderly classifying porous carbon containing titanium dioxide described in the preparation of filter paper previous step
Titanium self-supported membrane catalysis material, comprises the following steps:
(1) block copolymer and ethanol are mixed, under agitation, add titanium source, be subsequently added polystyrene acrylate
Microsphere emulsion, stirring, obtain mixed liquor；
(2) gained mixed liquor infiltrated filter paper and transfer in flat bottom evaporating dishes,double, at room temperature evaporation induced self-assembly, then through heat
Gather and carry out heat treatment under an inert atmosphere, obtaining described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material.
According to such scheme, described polystyrene acrylate microsphere emulsion be microspheres quality mark be the ethanol emulsion of 20%, by
H2O, styrene, acrylic acid, Ammonium persulfate., mix and blend 7～10h prepares under an argon atmosphere, in thus obtained microsphere emulsion,
Microsphere Size is homogeneous, and size is adjustable 200～400nm.
According to such scheme, described block copolymer is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
P123(PEO20PPO70PEO20) or F127 (PEO100PPO70PEO100), wherein EO is oxirane, and PO is epoxy
Propane.
According to such scheme, described titanium source is titanium tetrachloride or butyl titanate, or the two mixes with arbitrary proportion.
According to such scheme, described block copolymer, ethanol, polystyrene acrylate (PSA) microsphere emulsion and titanium source
Mass ratio be: (0.3～0.5): (20～30): (2～3): 1.
It is 2h according to the mixing time after addition polystyrene acrylate microsphere emulsion in such scheme, above-mentioned steps (1).
According to such scheme, described heat polymerization temperature is 80 DEG C, and hot polymerization temperature retention time is 24～48h.
According to such scheme, the heat treatment temperature step of above-mentioned steps (2) is: under inert atmosphere protection, with 1～3 DEG C/min
Ramp to 400～600 DEG C, be incubated 2～4h.
According to such scheme, described inert atmosphere is argon or nitrogen.
According to such scheme, prepared orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material has classifying porous knot
, there is macropore and mesoporous, macropore size uniformity in structure, size is adjustable 200～400nm, mesoporous is distributed on macropore hole wall, is situated between
Hole dimension is 3～5nm；The specific surface area of products therefrom is 76～106m2/ g, phosphorus content is 16～21wt%, has sunlight
Effect absorbing wavelength scope is 200～800nm.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the carbon containing titanium dioxide self-supported membrane catalysis material that prepared by the present invention, have ordered arrangement graded porous structure,
Higher specific surface area and big pore volume, can promote heterogeneous mass transfer and the realization enrichment to light in catalytic process, and beneficially electronics is fast
Speed, effectively transmit, beneficially effective diffusion of product；Introducing carbon is modified, and is widening it to visible light-responded model
While enclosing, may additionally facilitate the separation of photo-generated carrier, make the photocatalysis performance of carbon containing titanic oxide material prepared by the present invention obtain
To being effectively improved.The photocatalysis test result of crystal violet is shown by products therefrom, assimilation effect in 200～800nm wave-length coverages
Good, compared with P25, the assimilation effect of visible ray is significantly improved, good stability.
(2) carbon of the present invention the carbon being introduced through in polystyrene acrylate microsphere emulsion and block copolymer and
Filter paper carbonization realizes, it is not necessary to add other specific carbon sources.Polystyrene acrylate microsphere and block copolymer are respectively as system
The macropore template of standby described orderly classifying porous material and mesoporous mould material, also serve as reacting required carbon source, simplify reaction
The kind of needed raw material.
(3) present invention is with filter paper as matrix material, has abandoned the dependence to the conventional matrix material such as silicon chip, steel disc；At indifferent gas
Under atmosphere after filter paper carbonization, it is not necessary to remove filter paper, directly as the part in products therefrom film, eliminate and remove matrix material
Step, simplifies preparation technology；With filter paper as matrix, make products therefrom film have certain intensity, and utilize filter paper after infiltration
Flexibility, the shape of products therefrom film can be regulated, obtain shape or the Product Films of structure such as lamellar, tubular or lamination, adapt to
Concrete application demand.
(4) present invention uses one-step method to prepare orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, the work related to
Skill is simple, and low for equipment requirements, operability is good, and the preparation for high efficiency photocatalyst provides feasible thinking and means, has
It is beneficial to promote the photocatalysis technology application in Environmental capacity field.
Accompanying drawing explanation
The invention will be further described below in conjunction with the accompanying drawings, in accompanying drawing:
Fig. 1 is the XRD figure spectrum of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of embodiment 1 preparation.
Fig. 2 is the SEM image of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of embodiment 1 preparation.
Fig. 3 is the nitrogen adsorption isothermal of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of embodiment 1 preparation
Line chart.
Fig. 4 is the graph of pore diameter distribution of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of embodiment 1 preparation.
Fig. 5 be embodiment 1 preparation orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material and P25 ultraviolet-
The visible spectrogram that diffuses.
Fig. 6 is the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of embodiment 1 preparation, prepared by embodiment 5
Titanic oxide material and the photocatalytic degradation crystal violet efficiency chart of P25.
Detailed description of the invention
For making the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with the accompanying drawings and embodiment, to the present invention
It is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to limit
Determine the present invention.
In example 1 below-5, the block copolymer of selection is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
Thing P123 (PEO20PPO70PEO20), EO is oxirane, and PO is expoxy propane.
Select polystyrene acrylate microsphere emulsion be microsphere solid content be the polystyrene acrylate microsphere ethanol of 20wt%
Emulsion, Microsphere Size is about 200nm and 400nm, and preparation method includes: under room temperature condition, adds 120g in there-necked flask
H2O, and it is passed through argon, it is sequentially added into 10g styrene, 0.5g acrylic acid, is stirred mixing with the speed of 850～1000r/min
Close；It is warming up to 75 DEG C and keeps constant temperature after stirring 0.5h, add 0.2g Ammonium persulfate., under the speed of 1000～1500r/min
Constant temperature stirring 7h, obtains white polystyrene acrylate microspheres emulsion；Thus obtained microsphere emulsion is centrifuged, after ethanol purge,
It is made into the ethanol emulsion (i.e. polystyrene acrylate microsphere emulsion) that microsphere solid content is 20wt%, Microsphere Size in gained emulsion
Homogeneous, for about 200nm.In above-mentioned preparation technology, the consumption of regulation Ammonium persulfate. is 0.02g, extends between constant temperature stirring guarantor
To 10h, i.e. obtain the polystyrene acrylate microsphere emulsion that particle diameter is about 400nm.
The span of described Ammonium persulfate. is 0.02g～0.2g, can realize in gained polystyrene acrylate microsphere ethanol emulsion
Microsphere Size is adjustable 200～400nm.
Embodiment 1
A preferred embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, bag
Include following steps:
0.16g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer P123 and 10g ethanol are mixed, in play
Under strong stirring condition, adding 0.29g titanium tetrachloride and 0.11g butyl titanate, the 20wt% being subsequently added the above-mentioned preparation of 1g gathers
Styrene-acrylate microsphere ethanol emulsion (microspherulite diameter is about 200nm, the ethanol emulsion for microspheres quality mark is 20%),
It is stirred at room temperature 2h, obtains mixed liquor.Mixed liquor is infiltrated ashless filter paper and transfers to, in flat bottom evaporating dishes,double, at room temperature make
Ethanol volatilizees, and is then placed in 80 DEG C of baking ovens and is incubated 48h, then be warming up to the heating rate of 3 DEG C/min under an argon atmosphere
400 DEG C, naturally cooling to room temperature after insulation 2h, the black product of gained is described orderly classifying porous carbon containing titanium dioxide certainly
Support membrane catalysis material, carbon content is about 17wt%.
The XRD figure spectrum of products therefrom is shown in Fig. 1, and as seen from the figure, prepared product principal phase is anatase phase titanium dioxide.SEM
Image is shown in Fig. 2, there is spherical pore in illustrative material, and aperture is homogeneous and regular densely arranged, and size is about 200nm, on hole wall
There is less hole.Nitrogen adsorption isotherm figure is shown in that Fig. 3, graph of pore diameter distribution are shown in Fig. 4, illustrates to exist in product meso-hole structure, knot
Conjunction Fig. 2 understands, and mesoporous is distributed on macropore hole wall, and mesopore size concentrates on 3～5nm, and the specific surface area of product is 91m2/g。
From Fig. 2, Fig. 3 and Fig. 4 analysis, products therefrom has ordered big hole, mesoporous graded porous structure.The purple of products therefrom
Outward-visible diffuse-reflectance absorption spectrum is shown in that Fig. 5, result show, compared with commodity titanium dioxide P25, products therefrom is at wavelength 380～800
Showing notable assimilation effect between nm, in ultraviolet light range, the assimilation effect of (200～380nm) still keeps good, and
Significantly reducing does not occurs in long wavelength range internal absorbance, and is absorbance >=1.20 at 800nm at wavelength, shows that products therefrom is to can
See that photoresponse is notable.
Take the present embodiment sample 50mg, join in 50mL crystal violet solution (concentration 10mg/L), be placed in stirring in camera bellows
60min, using high voltage mercury lamp (125W, dominant wavelength 365nm) subsequently is that experimental light sources carries out photocatalytic degradation.Fig. 6 shows
After 120min, the present embodiment product reaches 93.64% to the clearance of crystal violet, and after 160min, products therefrom is to crystal violet
Clearance is 99.65%, and the clearance of contrast P25 is only 60.13%.
Embodiment 2:
An embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, including as follows
Step:
0.16g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer P123 and 10g ethanol are mixed, in play
Under strong stirring condition, add 0.4g titanium tetrachloride, be subsequently added the 20wt% polystyrene acrylate microsphere of the above-mentioned preparation of 1g
Ethanol emulsion (microspherulite diameter is about 200nm), is stirred at room temperature 2h, obtains mixed liquor.Mixed liquor is infiltrated ashless filter paper
And transfer in flat bottom evaporating dishes,double, at room temperature make ethanol volatilize, be then placed in 80 DEG C of baking ovens and be incubated 48h, then at argon
Being warming up to 400 DEG C with the heating rate of 3 DEG C/min under atmosphere, naturally cool to room temperature after insulation 2h, the black product of gained is i.e.
For described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, carbon content is about 16wt%.
The present embodiment products therefrom is tested through SEM and pore-size distribution and is shown, product has macropore, mesoporous graded porous structure, greatly
Hole dimension is about 200nm, and mesopore size is 3～5nm.After photocatalytic degradation 160min, 50mL is crystallized by 50mg sample
The clearance of purple solution (concentration 10mg/L) is 79.72%.
Embodiment 3:
An embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, including as follows
Step:
0.16g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer P123 and 10g ethanol are mixed, in play
Under strong stirring condition, adding 0.4g butyl titanate, the 20wt% polystyrene acrylate being subsequently added the above-mentioned preparation of 1g is micro-
Ball ethanol emulsion (microspherulite diameter is about 200nm), is stirred at room temperature 2h.Mixed liquor is infiltrated ashless filter paper and transfers to put down
In end evaporating dish, at room temperature make ethanol volatilize, be then placed in 80 DEG C of baking ovens and be incubated 48h, more under an argon atmosphere with 3 DEG C
The heating rate of/min is warming up to 400 DEG C, naturally cools to room temperature after insulation 2h, and it is many that the black product of gained is described classification
Hole carbon containing titanium dioxide self-supported membrane catalysis material, carbon content is about 21wt%.
The present embodiment products therefrom is tested through SEM and pore-size distribution and is shown, product has macropore, mesoporous graded porous structure, greatly
Hole dimension is about 200nm, and mesopore size is 3～5nm.After photocatalytic degradation 160min, 50mL is crystallized by 50mg sample
The clearance of purple solution (concentration 10mg/L) is 84.89%.
Embodiment 4
An embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, including as follows
Step:
0.16g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer P123 and 10g ethanol are mixed, in play
Under strong stirring condition, adding 0.29g titanium tetrachloride and 0.11g butyl titanate, the 20wt% being subsequently added the above-mentioned preparation of 1g gathers
Styrene-acrylate microsphere ethanol emulsion (microspherulite diameter is about 400nm), is stirred at room temperature 2h, obtains mixed liquor.Will
Mixed liquor infiltration ashless filter paper is also transferred in flat bottom evaporating dishes,double, at room temperature makes ethanol volatilize, is then placed in 80 DEG C of baking ovens also
Insulation 48h, then it is warming up to 400 DEG C with the heating rate of 3 DEG C/min under an argon atmosphere, naturally cool to room temperature after insulation 2h,
The black product of gained is described classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, and carbon content is about 20wt%.
The present embodiment gained is tested through SEM and pore-size distribution and is shown have macropore, mesoporous graded porous structure, and big hole dimension is about
For 400nm, mesopore size is 3～5nm.After photocatalytic degradation 160min, 50mg sample is (dense to 50mL crystal violet solution
Degree 10mg/L) clearance be 72.12%.
Comparative example
One contrast embodiment of orderly classifying porous titanium dioxide self-supported membrane catalysis material preparation method, preparation process is same
Embodiment 1, difference is that heat treatment condition is: be warming up to 400 DEG C in air atmosphere, is incubated 2h, and products therefrom is
The titanic oxide material of carbon-free graded porous structure.SEM and pore-size distribution test show, product has macropore, mesoporous knot
Structure, big hole dimension is about 200nm, and mesopore size is 3～5nm, and specific surface area is 106m2/g.Photocatalytic degradation 160min
After, 50mg sample is 76.04% to the clearance of 50mL crystal violet solution (concentration 10mg/L), sees Fig. 6.Result shows,
Carbon-free graded porous structure titanium dioxide, although there is excellent pore passage structure similarly to Example 1, but it is at visible ray
In the range of photocatalysis effect significantly reduce, further illustrate orderly classifying porous carbon containing titanium dioxide self-supported membrane in embodiment 1
Material has excellent photocatalysis performance.
The bound value of each raw material that relates to of invention, interval value can realize the present invention, the technological parameter of the present invention (as temperature,
Time etc.) lower limit value and interval value can realize the present invention, embodiment numerous to list herein.
Claims (8)
1. the preparation method of an orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, it is characterised in that with poly-
Styrene-acrylate microsphere emulsion, block copolymer, ethanol and titanium source are raw material, with filter paper as matrix, use self assembly former
Reason, the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material described in a step preparation, comprise the following steps:
(1) block copolymer and ethanol are mixed, under agitation, add titanium source, be subsequently added polystyrene acrylate
Microsphere emulsion, stirring, obtain mixed liquor；
(2) gained mixed liquor infiltrated filter paper and transfer in flat bottom evaporating dishes,double, at room temperature evaporation induced self-assembly, then through heat
Gather and carry out heat treatment under an inert atmosphere, obtaining described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material；
Described titanium source is titanium tetrachloride or butyl titanate, or the two mixes with arbitrary proportion.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, described polystyrene acrylate microsphere emulsion be microspheres quality mark be the ethanol emulsion of 20%, by H2O、
Styrene, acrylic acid, Ammonium persulfate., mix and blend 7～10h prepares under an argon atmosphere, in thus obtained microsphere emulsion, microsphere chi
Very little homogeneous, size is adjustable 200～400nm.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, described block copolymer is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
PEO20PPO70PEO20Or PEO100PPO70PEO100, wherein EO is oxirane, and PO is expoxy propane.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, the mass ratio in described block copolymer, ethanol, polystyrene acrylate microsphere emulsion and titanium source is:
(0.3～0.5): (20～30): (2～3): 1.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, adding the mixing time after polystyrene acrylate microsphere emulsion in above-mentioned steps (1) is 2h.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, described heat polymerization temperature is 80 DEG C, and hot polymerization temperature retention time is 24～48h.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, the heat treatment temperature step of above-mentioned steps (2) is: with the ramp of 1～3 DEG C/min to 400～600 DEG C,
Insulation 2～4h.
The preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material the most according to claim 1,
It is characterized in that, the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared has graded porous structure, deposits
At macropore and mesoporous, macropore size uniformity, size is adjustable 200～400nm, mesoporous is distributed on macropore hole wall, mesopore size
It is 3～5nm；The specific surface area of products therefrom is 76～106m2/ g, phosphorus content is 16～21wt%, the effective absorption to sunlight
Scope is 200～800nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410394338.XA CN104148042B (en) | 2014-08-12 | 2014-08-12 | A kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410394338.XA CN104148042B (en) | 2014-08-12 | 2014-08-12 | A kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104148042A CN104148042A (en) | 2014-11-19 |
| CN104148042B true CN104148042B (en) | 2016-08-24 |
Family
ID=51873781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410394338.XA Active CN104148042B (en) | 2014-08-12 | 2014-08-12 | A kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104148042B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549204B (en) * | 2014-12-23 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN105060295A (en) * | 2015-08-06 | 2015-11-18 | 南京大学 | Preparation method of TiC material with meso structure |
| US11724232B2 (en) * | 2015-11-30 | 2023-08-15 | Cornell University | Porous resin structures |
| CN109999800A (en) * | 2019-05-09 | 2019-07-12 | 金陵科技学院 | A kind of ordered structure Ag/TiO2Nanocomposite and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002306963A (en) * | 2001-04-13 | 2002-10-22 | Toshiba Corp | Photocatalyst substance absorbing visible light, method for decomposing water and method for fixing carbon |
| CN100584448C (en) * | 2007-03-22 | 2010-01-27 | 天津神能科技有限公司 | Carbon doped titanium-oxide graded hole photocatalytic material and preparing method |
-
2014
- 2014-08-12 CN CN201410394338.XA patent/CN104148042B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104148042A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gu et al. | Carbon vacancies and hydroxyls in graphitic carbon nitride: Promoted photocatalytic NO removal activity and mechanism | |
| Hou et al. | Variable dimensional structure and interface design of g-C3N4/BiOI composites with oxygen vacancy for improving visible-light photocatalytic properties | |
| Dong et al. | The pn-type Bi5O7I-modified porous C3N4 nano-heterojunction for enhanced visible light photocatalysis | |
| Wang et al. | Facile synthesis of C3N4/NiIn2S4 heterostructure with novel solar steam evaporation efficiency and photocatalytic H2O2 production performance | |
| Ye et al. | Constructing a system for effective utilization of photogenerated electrons and holes: photocatalytic selective transformation of aromatic alcohols to aromatic aldehydes and hydrogen evolution over Zn3In2S6 photocatalysts | |
| US20220355284A1 (en) | Perylene imide and composite photocatalytic material thereof, preparation method therefor and application thereof in removing organic pollutants from water | |
| CN106914264B (en) | Preparation method of composite visible light catalyst | |
| Lu et al. | Fabrication of a monoclinic/hexagonal junction in WO3 and its enhanced photocatalytic degradation of rhodamine B | |
| Xu et al. | Ferroelectric oxide nanocomposites with trimodal pore structure for high photocatalytic performance | |
| Liu et al. | A direct Z-scheme Bi 2 WO 6/NH 2-UiO-66 nanocomposite as an efficient visible-light-driven photocatalyst for NO removal | |
| Wang et al. | Understanding the charge separation and transfer in mesoporous carbonate-doped phase-junction TiO2 nanotubes for photocatalytic hydrogen production | |
| Qin et al. | Construction of multi-shelled Bi2WO6 hollow microspheres with enhanced visible light photo-catalytic performance | |
| CN104148042B (en) | A kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material | |
| Li et al. | Multi-layer three-dimensionally ordered bismuth trioxide/titanium dioxide nanocomposite: synthesis and enhanced photocatalytic activity | |
| Ding et al. | In-situ formation of nanosized 1T-phase MoS2 in B-doped carbon nitride for high efficient visible-light-driven H2 production | |
| Zhang et al. | Uncovering Original Z Scheme Heterojunctions of COF/MOx (M= Ti, Zn, Zr, Sn, Ce, and Nb) with Ascendant Photocatalytic Selectivity for Virtually 99.9% NO‐to‐NO3− Oxidation | |
| Bi et al. | Conductive black titania nanomaterials for efficient photocatalytic degradation of organic pollutants | |
| Yao et al. | One-dimensional hierarchical CeVO 4/TiO 2 heterostructures with enhanced photocatalytic performance | |
| Wan et al. | Facile fabrication of oxygen and carbon co-doped carbon nitride nanosheets for efficient visible light photocatalytic H 2 evolution and CO 2 reduction | |
| Hu et al. | Ultrathin graphitic carbon nitride modified PbBiO2Cl microspheres with accelerating interfacial charge transfer for the photodegradation of organic contaminants | |
| Liu et al. | AP/N type compounded Cu 2 O/TiO 2 photo-catalytic membrane for organic pollutant degradation | |
| Wang et al. | All-in-one photocatalysis device for one-step high concentration H2O2 photoproduction | |
| Zheng et al. | Photocatalytic H2 evolution of selective phase CZTS synthesized by ultrasonic spray pyrolysis method | |
| Liu et al. | Template-free synthesis of tetragonal graphitic carbon nitride microtubes doped by sodium chloride for enhanced photocatalytic H2 performance under visible light irradiation | |
| Azami et al. | Influence of the nitrogen pots from graphitic carbon nitride with the presence of wrinkled silica-titania for photodegradation enhancement of 2-chlorophenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |