CN101850246B - SnO2 photonic crystal/ TiO2 composite membrane photocatalyst and preparation method thereof - Google Patents

SnO2 photonic crystal/ TiO2 composite membrane photocatalyst and preparation method thereof Download PDF

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CN101850246B
CN101850246B CN2009101311261A CN200910131126A CN101850246B CN 101850246 B CN101850246 B CN 101850246B CN 2009101311261 A CN2009101311261 A CN 2009101311261A CN 200910131126 A CN200910131126 A CN 200910131126A CN 101850246 B CN101850246 B CN 101850246B
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photonic crystal
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陈胜利
王爱军
董鹏
胡春田
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China University of Petroleum Beijing
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Abstract

The invention relates to a novel composite membrane photocatalyst and a preparation method thereof. The novel composite membrane photocatalyst comprises a nanocrystal TiO2 membrane and a photonic crystal membrane, wherein a photonic crystal material is transparent near a TiO2 absorption edge, and the frequency band of a photonic band gap is designed to be same as that of the TiO2 absorption edge. A polymer organic-microballoon sequential assembly (Opal structure) is used as a template in the preparation process, and the preparation method of the novel composite membrane photocatalyst comprises the following steps of: filling SnO2 into a gap of the template to obtain an SnO2/polymer organic-microballoon composite structure; then burning to remove the template, then coating the nanocrystal TiO2 membrane on a surface, and then burning to obtain a photonic crystal/TiO2 composite membrane photocatalyst in a reverse Opal structure. The novel composite membrane photocatalyst can effectively enhance the utility ratio of light, thereby having higher photocatalytic activity; in addition, the invention is suitable for multiple aspects, such as various light-catalyzed reaction, atmospheric purification, sewage treatment, and the like.

Description

SnO 2Photonic crystal/TiO 2Composite membrane photocatalyst and preparation method thereof
Technical field
The present invention relates to a kind of novel SnO 2Photonic crystal/TiO 2Composite membrane photocatalyst and preparation side thereof.This catalyst is applicable to the many aspects such as photocatalytic process, atmospheric cleaning, sewage disposal.
Background technology
TiO 2, chemically stable high due to its photocatalytic activity, safety non-toxic and the advantage such as with low cost, the environment-friendly type catalysis material that is considered to have most the exploitation future has broad application prospects in fields such as the degraded of atmosphere and water pollutant, solar cells.But TiO so far 2Not yet obtain large-scale application as catalysis material, major reason is TiO 2Quantum yield low and light utilization ratio that energy gap causes greatly is low (for example the utilization ratio of sunshine only have～1%).Anatase crystal TiO 2The forbidden band wide be 3.2eV (electron-volt), only absorb the energy less than the 387nm wavelength light, this part light energy only accounts for about 4% of solar energy.How improving the light utilization ratio is TiO 2A key of photochemical catalyst large-scale application, it to the developing novel environment friendly energy, control and the tool of curbing environmental pollution is of great significance.
The below is the main raising TiO that has reported 2The method of light utilization efficiency:
CN 200410016323 has reported a kind of nitrogen adulterated TiOx mesoporous photocatalytic material, it is characterized in that take titanium oxide as matrix, and crystalline phase is Anatase, and is nitrogenous 1.6～7.6%, and mesopore orbit is of a size of 1～8nm.The UV-vis spectrum of this nitrogen adulterated TiOx mesoporous photocatalytic material just begins to absorb at 735nm, through 4 hours, can make 90% methylene blue degraded with photocatalyst.
CN 200810196528 has reported a kind of preparation method of noble metal modified titanium dioxide photocatalyst, at first uses TiO 2, noble metal water soluble salt and organic matter preparation suspension, transfer the rear ultrasonic concussion in pH to 1～12, drop in photo catalysis reactor under power 8～125W ultraviolet source in 0～90 ℃ of reaction 0.5～8 hour, obtain the TiO that is modified by precious metals ag or Au or Pt or Pd after separation, washing, drying 2Photochemical catalyst, wherein, TiO 2Content be 90～99.99%, bullion content is 0.01～10%.This catalyst Photocatalytic activity is high, and surface hydrophobic is strong, and the catabolite that adheres to easily cleans.
CN02103829 has reported a kind of nano titanium dioxide photocatalyst and preparation method thereof, and described catalyst comprises the nano titanium oxide of semi-conducting material doping as matrix and coated conjugated system organic matter on described matrix.Wherein nano titanium dioxide photocatalyst reaches the nanoscale degree of scatter, and particle size is in 100nm.Result of the test shows that this kind photochemical catalyst has obvious degradation to the organic pollution in water as fat, benzene etc.
In addition, Hore etc. is at TiO 2Introducing macropore in photochemical catalyst makes light at TiO 2Scattering in Catalytic Layer, thus increase light path, finally improve the Optical Absorption rate (Sakatani Y., Grosso D., Nicole L.et al., J.Mater.Chem.2006,16,77-82).
But above method is to TiO 2The improvement degree of photocatalytic activity is all limited.For example can make TiO by other species that adulterate 2The absorption band red shift improves absorptivity, and energy gap diminishes, the oxidation/reduction current potential (Redox potential) of photo-generated carrier (being electronics and hole) descends but this may cause again, thereby reduces TiO 2Photo-catalysis capability.Wavelength almost can be fully by conventional TiO less than the light of ABSORPTION EDGE 2Film catalyst absorbs, and wavelength can not excite TiO greater than the light of ABSORPTION EDGE 2The valence state electronics is to conduction band.Obviously, do not changing TiO 2The prerequisite of chemical constitution under, improve TiO 2Near ABSORPTION EDGE absorptivity should be a fine approach that improves photocatalysis performance.This project proposes a kind of SnO 2Anti-Opal photonic crystal/TiO 2The two-layer compound film photocatalyst is at conventional TiO 2Compound one deck SnO on film 2Anti-Opal photonic crystal, and with SnO 2The design of photon band gap frequency band and the TiO of anti-Opal 2The ABSORPTION EDGE frequency band identical.When light from TiO 2When layer was injected composite catalyst, wavelength was less than TiO 2The light of ABSORPTION EDGE is substantially fully by TiO 2Absorb and correspondingly catalytic reaction contributed.Near ABSORPTION EDGE light is partly by TiO 2Absorb, another part light passes TiO 2Layer enters SnO 2Anti-Opal layer of photonic crystals.At SnO 2Anti-Opal layer of photonic crystals and TiO 2The layer at the interface, SnO 2The periodic structure of anti-Opal photonic crystal is destroyed.At the defect layer place of this photonic crystal, light localization can cause wavelength light display work in photon band gap to strengthen, and makes TiO 2Near the absorptivity of layer ABSORPTION EDGE is significantly improved, thereby improved TiO 2The photocatalysis efficiency of layer.
Summary of the invention
The invention provides a kind of NEW TYPE OF COMPOSITE film photocatalyst and preparation method thereof.This catalyst is by nanocrystalline TiO 2Film and crystal film with photon form.The photonic crystal material is at TiO 2ABSORPTION EDGE attachment transparent and the design of photon band gap frequency band and TiO 2The ABSORPTION EDGE frequency band identical.The preparation method of composite membrane first assembles the organic microballoon of monodisperse polymer on quartz substrate, form the Opal structure, then fills photon crystal material in polymer organic microballoon Opal structure, then is coated with the nanocrystalline TiO of one deck on its surface 2Film.Last roasting is removed organic microsphere template and is obtained photonic crystal/TiO 2The nanocomposite film photocatalyst.This composite membrane photocatalyst can effectively improve the utilization ratio of light, thereby has higher photocatalytic activity.Composite membrane photocatalyst preparation method provided by the invention comprises the following steps:
1, preparation polymer mono-dispersion microballoon.
2, assembling polymer mono-dispersion microballoon obtains polymer Opal stay in place form.
3, with SnO2 filled polymer Opal stay in place form and be coated with the TiO2 film on the surface.
The template particles of 4, removing wherein with roasting obtains composite membrane photocatalyst.
Preparation method's key provided by the invention is the ingenious peculiar property that utilizes photonic crystal.Photonic crystal is that a kind of refractive index presents periodically variable material, and its cycle and visible wavelength magnitude are comparable.Photonic crystal has two key properties: first photonic crystal can stop the light of some specific wavelength to be propagated, and namely band gap occurred on photonic band gap, is called photon band gap and also is forbidden photon band (Photonic band gap); It two is photon locals.When introducing suitable impurity or defective in photonic crystal, its intrinsic periodic structure can be destroyed, thereby a defect state that frequency is extremely narrow can appear in forbidden photon band, with the photon that the defect state frequency is coincide can be by local in the position that defective occurs, in case depart from defective locations, light just will be decayed rapidly, this means fault location have than around higher distribution of light intensity.Utilize these two characteristics of photonic crystal, can not change TiO 2The prerequisite of chemical constitution under (do not reduce energy gap, do not reduce TiO 2Photo-catalysis capability), improve TiO 2Near ABSORPTION EDGE absorptivity, thus TiO improved 2Photocatalysis efficiency.
Why the present invention adopts SnO 2As the material of layer of photonic crystals, be because it is to TiO 2Near ABSORPTION EDGE light does not absorb.Again due to single SnO that disperses 2Microballoon is not easy to synthesize, so adopt the inverse Opal structure photonic crystal.With SnO 2The design of photon band gap frequency band and the TiO of anti-Opal photonic crystal 2The ABSORPTION EDGE frequency band identical.When light from TiO 2When layer was injected composite catalyst, near the light ABSORPTION EDGE was partly by TiO 2Absorb, another part light passes TiO 2Layer enters SnO 2Anti-Opal layer of photonic crystals.At SnO 2Anti-Opal layer of photonic crystals and TiO 2The layer at the interface, SnO 2The periodic structure of anti-Opal photonic crystal is destroyed.At the defect layer place of this photonic crystal, light localization can cause wavelength light display work in photon band gap to strengthen, and makes TiO 2Near the absorptivity of layer ABSORPTION EDGE is significantly improved and (is equivalent to TiO 2The ABSORPTION EDGE red shift), thus improved TiO 2The photocatalysis efficiency of layer.
The present invention adopts the synthetic SnO of the ligand exchange Hydrolyze method (ligand-exchange hydrolysis ofmetal-fluoro complexs) of metal/fluoro complex 2, the consumption of F-1 is by completing with acid reaction.Reaction equation is as follows:
Figure G2009101311261D00031
Figure G2009101311261D00032
H 3BO 3Add and consumed the HF in solution, the reaction of (1) formula is carried out to the right, thereby is separated out gradually SnO 2
The SnO that separates out 2Slowly fill the space of PS Opal, calcination obtains SnO after removing template 2Anti-Opal.
The nanocrystalline TiO that the present invention adopts 2By obtaining after phthalandione four isopropyl ester hydrolytic precipitations, peptization, hydro-thermal reaction.
Description of drawings
The SEM photo of the colloidal crystal template of 260nm PS microballoon vertical deposition method assembling in Fig. 1 embodiment 2.
The transmission spectrum of the PS micelle crystal for preparing under the different suspension concentrations of 260nm PS in Fig. 2 embodiment 2.
TiO in Fig. 3 embodiment 3 after hydro-thermal reaction 2The TEM figure of sol particle.
Nanocrystalline TiO in Fig. 4 embodiment 4 2The SEM figure of perforated membrane.
TiO in Fig. 5 embodiment 4 2The BJH graph of pore diameter distribution of perforated membrane.
260nmPS template and filling SnO in Fig. 6 embodiment 7 2After the transmission spectrum of template.
In Fig. 7 embodiment 7 by the standby 3-D ordered multiporous SnO of LPD legal system 2The SEM photo of film.
SnO in Fig. 8 embodiment 8 2Photonic crystal/TiO 2The SEM figure at nanocomposite film photocatalyst interface.
The change in concentration figure of xenon lamp irradiation Methyl Orange in Fig. 9 embodiment 9.
The specific embodiment
Below introduce in detail realization of the present invention and the beneficial effect that has by specific embodiment, understand better novelty essence of the present invention place to help the reader, but but do not consist of restriction to the present invention's practical range.
Synthesizing of embodiment 1, nano/submicron polystyrene microsphere
Adopt the synthetic PS microballoon of emulsion polymerization.Add 450mL deionized water, 0.25g SSS (NaSS) and 0.28g NaHCO in the there-necked flask of 1000mL 3, heating water bath to 75 ℃, rotating speed transfers to 330r/min.Then the styrene monomer that adds 60mL to wash.With a certain amount of initator potassium persulfate (K 2S 2O 8) be dissolved in the 50mL deionized water, be added drop-wise in reaction system.Stop reaction after 12h, obtain the PS microballoon of 260nm left and right.Can control by the addition of controlling emulsifying agent the size of particle diameter.
The preparation of embodiment 2, polystyrene latex crystal template
Above-mentioned synthetic PS microballoon is made into 0.1% suspension and joins in measuring cup, with vertical insertion of quartz substrate (or glass substrate) of cleaning, obtain PS micelle crystal template after 55 ℃ of lower evaporating off water after ultrasonic dispersion.Fig. 1 is SEM (SEM) photo of PS (260nm) the Opal photonic crystal of assembling.Use the same method, assembling obtains PS Opal photonic crystal in different solids content PS microsphere suspension liquids.Fig. 2 is ultraviolet-visible (UV-Vis) transmission spectrum of the PS micelle crystal for preparing under the different suspension concentrations of 260nm PS.
Embodiment 3, TiO 2Nanocrystalline preparation
The dilute nitric acid solution of 0.1mol/L is joined in jacketed reactor magnetic agitation and water-bath circulating-heating.After temperature transfers to 35 ℃, the mixed solution of 15mL isopropyl alcohol and 25mL tetraisopropyl titanate is dropwise joined in reactor, generate white cotton-shaped TiO 2Precipitation.After drip finishing, temperature is transferred to 80 ℃ of peptization 8h, filter to remove the precipitation that there is no peptization with sand core funnel, then colloidal sol is poured in autoclave, 210-230 ℃ of crystallization 12 hours, obtain TiO 2Nanocrystalline suspension.TiO after Fig. 3 hydro-thermal reaction 2The TEM figure of sol particle.As seen from Figure 3, TiO after hydro-thermal reaction 2Sol particle presents the octahedra shape of approximate regulation, illustrates after hydrothermal treatment consists that in the TEM photo, particle is monocrystalline.Except the only a few particle was large, the grain diameter major part was in the 8-10nm left and right.
Embodiment 4, nanocrystalline TiO 2The preparation of porous membrane
At above-mentioned TiO 2Add with respect to TiO in nanocrystalline suspension 2The polyethylene glycol of 40w% (PEG) after ultrasonic dispersing and dissolving, obtains white pasty state mixed slurry.Utilize sol evenning machine with TiO 2Nanocrystalline mixed slurry in the upper spin-coating film of quartz substrate (or glass substrate).After film at room temperature dried, 450 ℃ and roasting 30min can obtain nanocrystalline TiO like this to remove PEG 2Perforated membrane.Fig. 4 is nanocrystalline TiO 2The SEM figure of perforated membrane.As can be seen from Figure 4 most of grain diameter in the 10nm left and right, is rich in hole between particle.Utilize Micromerities ASAP type automatic absorbing instrument to carry out specific area and pore structure analysis to perforated membrane, the results are shown in Figure 5.By finding out in Fig. 5, the aperture mainly is distributed between 5～20nm, and the most probable aperture is 7.8nm.This and the aperture (Fig. 4) of observing with SEM coincide.The average pore size of film is at 10.8nm, and the BET specific area is 116m 2/ g, pore volume are 0.31cm 3/ g.
Embodiment 5, SnO 2The preparation of liquid deposition (LPD) solution
With SnF 2Be dissolved in deionized water, then drip excessive H in solution 2O 2With its oxidation and generate SnO 2NH 2The O light-yellow precipitate.To precipitate centrifugal after, repeatedly rinse and at room temperature dry with deionized water, get 0.1mol SnO 2NH 2The O solid is dissolved in the HF solution of 66mL 40% and obtains SnF 4-HF solution.H 3BO 3Be dissolved in the H that obtains 0.5mol/L in deionized water 3BO 3Solution.H with the 0.5mol/L of 50mL 3BO 3Solution is added in the 1.5mL mentioned solution, then adds 30mL water, obtains LPD solution after mixing.
Embodiment 6, Ti0 2/ SnO 2The preparation of composite membrane
The quartz substrate (or glass substrate) of cleaning is dipped vertically in the LPD solution described in the embodiment 5 of 30 ℃ the SnO that slowly separates out 2Can be attached to gradually on substrate, take out from LPD solution after 12 hours, use deionized water rinsing, then at room temperature dry, obtain SnO 2Film.According to the step of embodiment 4 at SnO 2Spin coating one deck TiO on film 2Nano-crystal film obtains TiO 2/ SnO 2Laminated film.
Embodiment 7, PS/SnO 2Composite construction and SnO 2The preparation of 3-D ordered multiporous film
The PS Opal photonic crystal template that embodiment 5 is obtained is dipped vertically in the LPD solution of 30 ℃, and solution infiltrates microballoon hole, the SnO that slowly separates out under the effect of capillary force 2Can be full of gradually hole.Take out PS micelle crystal template after 12h from LPD solution, under room temperature, dry 3h, obtain PS/SnO 2Composite construction.Fig. 6 is the 260nmPS template and fills SnO 2After the transmission spectrum of template.The band gap position of PS template is 611nm, fills SnO 2Rear band gap position is at 643nm.With this PS/SnO 2Composite construction roasting in 450 ℃ of Muffle furnaces obtained 3-D ordered multiporous SnO in 2 hours 2Film (as shown in Figure 7).
Embodiment 8, SnO 2Photonic crystal/TiO 2The nanocomposite film photocatalyst
Utilize sol evenning machine with the TiO described in embodiment 4 2Nanocrystalline mixed slurry at 3-D ordered multiporous SnO 2Spin coating thin film on film.After film at room temperature dries, to remove PEG, can obtain SnO at 450 ℃ of roasting 30min like this 2Photonic crystal/TiO 2Nanocomposite film photocatalyst (seeing Fig. 8).
The performance test of embodiment 9, photochemical catalyst
Light-catalyzed reaction is carried out in homemade reaction unit, uses the methyl orange solution of 10mg/L as reactant, and light source is the 150W xenon lamp.Add the 3.0301g methyl orange solution in 45mm * 12mm * 12mm quartz colorimetric utensil, add to contain TiO 221 * 10 -4The SnO of g 2Photonic crystal/TiO 2Film photocatalyst film (photocatalyst film evenly is attached on the substrate of 25mm * 10mm * 1mm), illumination degrading.When carrying out 2h, 6h, 9h and 12h, reaction measures the concentration of methyl orange solution, the degradation efficiency of mensuration film at 465nm place with UV-2100PC type ultraviolet-uisible spectrophotometer.
In order to investigate SnO 2Photonic crystal/TiO 2Whether film photocatalyst is than conventional TiO 2Film photocatalyst has higher photocatalytic activity, we with above-mentioned step measurements catalyst-free film (blank sample), TiO 2Film, SnO 2/ TiO 2The performance of the photochemical catalyst price reduction methyl orange of film.TiO in photochemical catalyst 2Weight, the weight of methyl orange solution see Table 1 (TiO in catalyst 2Amount identical with the weight ratio of methyl orange).The concentration of methyl orange solution is seen Fig. 9 over time.
Do not add as seen from Figure 9 TiO 2During catalyst, methyl orange is not degraded substantially.The length of time is little on the degradation effect impact.And add pure TiO 2Photocatalysis membrana and SnO 2/ TiO 2Composite photocatalysis membrane and SnO 2Photonic crystal/TiO 2In the system of composite photocatalysis membrane, methyl orange degradation is obvious.And SnO 2Photonic crystal/TiO 2The composite photocatalysis membrane degradation effect is best, SnO 2/ TiO 2Film takes second place, pure TiO 2The membrane degradation effect is the poorest.
Each sample TiO in table 1 light degradation experiment 2The quality of quality and corresponding methyl orange solution
Figure G2009101311261D00071

Claims (8)

1. the preparation method of a composite membrane photocatalyst, the step of the method comprises:
Utilization singly is dispersed with the organic polymer microballoon and is prepared into certain thickness polymer Opal photonic crystal template on quartz substrate or glass substrate;
With SnO 2Be filled in this polymer Opal photonic crystal template hole;
Calcination is removed polymer Opal photonic crystal template and is obtained SnO at 300～800 ℃ of temperature 2Crystal film with photon;
At this SnO 2Light gives the nanocrystalline TiO of crystal film surface coating one deck 2Film;
Calcination obtains SnO 2Photonic crystal/TiO 2Composite membrane photocatalyst.
2. in preparation method claimed in claim 1, the material that singly is dispersed with the organic polymer microballoon comprises copolymer or the blend of polystyrene, polymethacrylates, polyethylene, polypropylene, fluorinated polymer, polyamide, polydiene, PEO, PPOX, Merlon and above-mentioned substance.
3. in the preparation method described in claim 1, polymer Opal photonic crystal method for preparing template comprises vertical deposition method, spin-coating method, drop-coating, vertical czochralski method; The thickness of polymer Opal photonic crystal template is used concentration or assembling temperature or spin speed or the pull rate control of suspension by assembling.
4. in the preparation method described in claim 1, nanocrystalline TiO 2Painting method comprise spin coating, blade coating, dipping method of pulling up.
5. SnO 2Photonic crystal/TiO 2Composite membrane photocatalyst, this composite membrane photocatalyst are to adopt the described method preparation of claim 1.
6. composite membrane photocatalyst claimed in claim 5, SnO 2Crystal film with photon is generally inverse Opal structure, and its thickness is equivalent to the thickness of 10～50 layers of tiny balloon, and the cavity diameter of anti-Opal photonic crystal hollow core microballoon is 100 nanometers～300 nanometers.
7. in composite membrane photocatalyst claimed in claim 5, SnO 2The photon band gap of layer of photonic crystals is positioned at TiO 2Layer ABSORPTION EDGE place.
Composite membrane photocatalyst claimed in claim 5 be used for that photocatalysis is synthetic, atmospheric cleaning, sewage disposal.
CN2009101311261A 2009-04-03 2009-04-03 SnO2 photonic crystal/ TiO2 composite membrane photocatalyst and preparation method thereof Expired - Fee Related CN101850246B (en)

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CN107442114A (en) * 2017-07-26 2017-12-08 齐齐哈尔大学 A kind of Pt loads 3DOMSn4+Adulterate TiO2The preparation of material
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CN1404919A (en) * 2002-11-08 2003-03-26 清华大学 Preparation for inferface composite semi-conductor nano thinfilm optical catalyst

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