CN101890370B - Nano-titanium dioxide and polyphosphazene based composite optical catalyst and preparation method thereof - Google Patents
Nano-titanium dioxide and polyphosphazene based composite optical catalyst and preparation method thereof Download PDFInfo
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- CN101890370B CN101890370B CN2010102450442A CN201010245044A CN101890370B CN 101890370 B CN101890370 B CN 101890370B CN 2010102450442 A CN2010102450442 A CN 2010102450442A CN 201010245044 A CN201010245044 A CN 201010245044A CN 101890370 B CN101890370 B CN 101890370B
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- titanium oxide
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- poly phosphazene
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Abstract
The invention discloses a nano-titanium dioxide and polyphosphazene based composite optical catalyst and a preparation method thereof in the technical field of catalyst preparation. The preparation method comprises the steps of: putting 1 part by weigh of hexachlorocyclotriphosphazenes, 2.16 parts by weigh of bisphenol and 1-5 parts by weigh of nano-titanium dioxide into 2500 parts by weigh of organic solvent, and obtaining a dispersing solution after ultrasonic dispersion; further adding 73 parts by weigh of acid binding agent, obtaining the dispersion solution of a target product through warming water bath, and filtering, washing and drying to obtain the nano-titanium dioxide and polyphosphazene based composite optical catalyst. In the invention, the nano-titanium dioxide and polyphosphazene based composite optical catalyst with a nuclear shell structure is obtained by cladding and modifying Degussa P25 nano-titanium dioxide with polyphosphazene. Compared with the P25, the optical catalyst has an excellent absorption property on a target organic pollutant and shows higher optical catalytic activity in the presence of the irradiation of ultraviolet light.
Description
Technical field
What the present invention relates to is a kind of method of catalyst technical field, specifically is a kind of composite photo-catalyst based on nano titanium oxide and poly phosphazene and preparation method thereof.
Background technology
Along with the quickening of process of industrialization, the trade waste row who comprises all kinds of organic compounds has in a large number caused severe contamination to nature to ecology.In order to solve this extremely urgent problem, the photocatalytic degradation technology extensive concern that caused people in 20 years in the past, because compare with traditional biodegradationpathway, photocatalytic degradation has higher efficient.Anatase-type nanometer titanium dioxide has high catalytic activity, nontoxic and good characteristics such as chemical stability, is a kind of the most frequently used photochemical catalyst.But titanium dioxide is relatively poor to target organic pollutant adsorption property, and catalytic activity is not high under the lower environment of pollutant levels, and uses the back to reclaim difficulty, big limitations its practical application.Therefore, strengthening nano titanium oxide through surface modification is the effective way of a kind of its photocatalytic activity of further raising and efficient to organic adsorption capacity.
Literature search through to prior art is found; Holland's " applied catalysis; B collects: environment " periodical in 2008 the 79th the volume the 2nd phase the 171st～178 page of (T.Guo, Z.P.Bai, C.Wu; T.Zhu, Influence of relative humidity on thephotocatalytic oxidation (PCO) of toluene by TiO
2Loaded on activated carbon fibers:PCO rateand intermediates accumulation; Applied Catalysis B:Environmental; 2008; 79 (2): reported a kind of titanium dioxide nanoparticle has been carried on the formed area load type of porous active carbon fiber surface composite photo-catalyst 171～178) that this photochemical catalyst has excellent adsorption capacity and photocatalytic activity to toluene, but the fastness of this method load relatively a little less than; Titanium dioxide nanoparticle comes off from the porous active carbon fiber surface easily, has limited recycling of catalyst." materials chemistry journal periodical is in 2002 the 12nd the 5th phases of volume the 1391st～1396 page of (T.Tsumura, N.Kojitani, I.Izumi, N.Iwashita, M.Toyoda, M.Inagaki, Carbon coating of anatase-type TiO in Britain
2And photoactivity; Journal of Material Chemistry; 2002,12 (5): 1391-1396) reported and a kind ofly obtain the method for hud typed composite photo-catalyst, though this method can strengthen the adsorption capacity of titanium dioxide effectively with porous carbon materials clad nano titanium dioxide granule; Handle but need carry out high temperature cabonization to presoma usually, the complex steps condition is harsh.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of composite photo-catalyst based on nano titanium oxide and poly phosphazene and preparation method thereof is provided, with resulting the composite photo-catalyst of poly phosphazene coating modification Degussa P25 nano titanium oxide based on nano titanium oxide and poly phosphazene with nucleocapsid structure.This photochemical catalyst is compared with P25, the target organic pollution is had excellent absorption property, and under UV-irradiation, demonstrate higher photocatalytic activity.
The present invention realizes that through following technical scheme the present invention specifically may further comprise the steps:
Said nano titanium oxide is a Degussa P25 nano titanium oxide.
Said organic solvent is the mixed solvent of oxolane and absolute ethyl alcohol, and volume ratio is 1: 1.
Said acid binding agent is a triethylamine.
Describedly add tepidarium and be meant: reaction is 5 hours in 40 ℃ of ultrasound baths,
Said hyperacoustic power is 100 watts.
The present invention relates to the catalyst that method for preparing obtains and have nucleocapsid structure, is nuclear with Degussa P25 nano titanium oxide, and poly phosphazene is a shell, and wherein: the structural formula of poly phosphazene is following:
Compared with prior art, the present invention has following beneficial effect: (1) preparation method of the present invention is simply effective, and mild condition; (2) poly phosphazene of the present invention has unique pore structure and absorption property; For the composite photo-catalyst based on nano titanium oxide and poly phosphazene provides higher specific surface and adsorption capacity; Make the target organic pollution can be enriched in the titanium dioxide granule surface effectively; Form local higher reactant concentration in photocatalyst sites, the poly phosphazene clad has good permeability to ultraviolet light simultaneously, thereby has promoted photocatalytic activity and efficient greatly; (3) poly phosphazene of the present invention is a kind of organic-inorganic hybrid polymer with highly cross-linked structure; Have good chemistry and heat endurance; And reaction monomers can be at an easy rate in the polymerization of target substrate surface in situ be cross-linked to form the poly phosphazene clad of thickness homogeneous and controllable, so poly phosphazene is a kind of desirable encapsulating material.With its clad nano titanium dioxide, can form firm " protective layer " of one deck on the titanium dioxide nanoparticle surface, prevent inactivation and the loss in use of photochemical catalyst center effectively.In addition, highly cross-linked organic-inorganic hybrid structure also can make poly phosphazene clad self keep out light-catalyzed reaction effectively, and the composite photo-catalyst based on nano titanium oxide and poly phosphazene can efficiently and stably be recycled.
Description of drawings
Fig. 1 is the synthetic route and the chemical constitution sketch map of preparation poly phosphazene clad;
Fig. 2 is the mechanism of preparation based on the composite photo-catalyst of nano titanium oxide and poly phosphazene;
Fig. 3 is the FFIR figure based on the composite photo-catalyst of nano titanium oxide and poly phosphazene that embodiment 1 makes;
Fig. 4 is the X-ray diffraction spectrogram based on the composite photo-catalyst of nano titanium oxide and poly phosphazene that embodiment 1 makes;
Fig. 5 is stereoscan photograph and the transmission electron microscope photo based on the composite photo-catalyst of nano titanium oxide and poly phosphazene that embodiment 1 makes;
Fig. 6 is stereoscan photograph and the transmission electron microscope photo based on the composite photo-catalyst of nano titanium oxide and poly phosphazene that embodiment 2 makes;
Fig. 7 is stereoscan photograph and the transmission electron microscope photo based on the composite photo-catalyst of nano titanium oxide and poly phosphazene that embodiment 3 makes.
The specific embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
As shown in Figure 1; The synthetic route and the chemical constitution of the poly phosphazene clad for preparing for following examples; Among the figure: hexachlorocyclotriphosphazene and bisphenol S are done under the condition of acid binding agent at triethylamine; In titanium dioxide nanoparticle surface in situ generation polycondensation reaction, the hydrogen chloride of generation is absorbed by triethylamine and forms triethylamine hydrochloride.
As shown in Figure 2, be the mechanism explanation that following examples prepare based on the composite photo-catalyst of nano titanium oxide and poly phosphazene, wherein: the initial period of polycondensation reaction, poly phosphazene exists with the form of elementary nano particle under the ultrasonic wave effect.Because elementary nano particle has high surface ability, they stick to the surface of titanium dioxide nanoparticle at an easy rate.Along with the carrying out of polycondensation reaction, the poly phosphazene generation that sticks to the titanium dioxide nanoparticle surface is crosslinked, thereby forms the clad with highly cross-linked structure then.In other words, in the process that forms nano titanium oxide/poly phosphazene nucleocapsid structure, nano titanium oxide has played the effect of " original position template ".
In the 100mL round-bottomed flask; 0.02g hexachlorocyclotriphosphazene, 0.0432g bisphenol S and 0.05g Degussa P25 nano titanium oxide are dispersed in the mixed solvent of 60mL oxolane and absolute ethyl alcohol (volume ratio is 1: 1), sonicated was uniformly dispersed it in 30 minutes.In above-mentioned dispersion liquid, add the 2mL triethylamine then, reaction is 5 hours in 40 ℃, the ultrasound bath of 100W.Reaction centrifugalizes target product after finishing, and 3500 rev/mins of centrifuge speeds separate and remove solvent after 15 minutes.Use acetone and deionized water washed product 3 times respectively, in 80 ℃ baking oven, obtain the composite photo-catalyst based on nano titanium oxide and poly phosphazene of white powder then after dry 10 hours.
The implementation result of present embodiment: Fig. 3 is the FFIR figure based on the composite photo-catalyst of nano titanium oxide and poly phosphazene of preparation.Can know by figure, be positioned at 3200～3600cm
-1(a) and 1630cm
-1(b) absworption peak belongs to the stretching vibration and the flexural vibrations of nano titanium oxide surface hydroxyl respectively.400～800cm
-1(c) broad peak belongs to the flexural vibrations of Ti-O key.Obviously, the spectrogram of prepared composite photo-catalyst based on nano titanium oxide and poly phosphazene not only comprises all characteristic peaks (C=C (Ph): 1591cm of poly phosphazene
-1(e) and 1490cm
-1(f); O=S=O:1294cm
-1(g) and 1154cm
-1(i); P=N:1187cm
-1(h); P-N:880cm
-1(k); P-O-(Ph): 941cm
-1But also comprise the characteristic peak (Ti-O:400～800cm of nano titanium oxide (j)),
-1(l)), explain that product is the compound of nano titanium oxide and poly phosphazene.
As shown in Figure 4, be the X-ray diffraction spectrogram based on the composite photo-catalyst of nano titanium oxide and poly phosphazene of preparation, wherein: the P25 nano titanium oxide comprises two kinds of crystalline forms: anatase and rutile.The spectrogram of prepared composite photo-catalyst based on nano titanium oxide and poly phosphazene not only comprises all diffraction maximums of nano titanium oxide; (14.5 ° of characteristic peaks that equally also comprise poly phosphazene; Wide amorphous peak; Indicated like asterisk), explain that product is the compound of nano titanium oxide and poly phosphazene, and the crystalline form of compound back nano titanium oxide has no variation.
As shown in Figure 5, be the stereoscan photograph and the transmission electron microscope photo based on the composite photo-catalyst of nano titanium oxide and poly phosphazene of preparation, product has nucleocapsid structure; With the nano titanium oxide is nuclear; Poly phosphazene is a shell, and poly phosphazene coating thickness homogeneous, is about 3～5nm.Show that present embodiment has successfully prepared the composite photo-catalyst based on nano titanium oxide and poly phosphazene.
The prepared BET specific area based on the composite photo-catalyst of nano titanium oxide and poly phosphazene of present embodiment reaches 65.6m
2g
-1, be higher than the preceding P25 nano titanium oxide (46.5m of coating modification
2g
-1), explain that it has loose structure.With the methylene blue is the template organic pollution; Under ultraviolet light conditions, carry out the photocatalytic degradation experiment; The result shows: the prepared composite photo-catalyst based on nano titanium oxide and poly phosphazene has excellent adsorption capacity to the target organic matter; Adsorbance is 19 times of unmodified P25 nano titanium oxide, and photocatalytic activity is compared unmodified P25 nano titanium oxide and improved 20.1%.Simultaneously, the prepared composite photo-catalyst based on nano titanium oxide and poly phosphazene also has good stable property, can recycle.
In the 100mL round-bottomed flask; 0.02g hexachlorocyclotriphosphazene, 0.0432g bisphenol S and 0.03g Degussa P25 nano titanium oxide are dispersed in the mixed solvent of 60mL oxolane and absolute ethyl alcohol (volume ratio is 1: 1), sonicated was uniformly dispersed it in 30 minutes.In above-mentioned dispersion liquid, add the 2mL triethylamine then, reaction is 5 hours in 40 ℃, the ultrasound bath of 100W.Reaction centrifugalizes target product after finishing, and 3500 rev/mins of centrifuge speeds separate and remove solvent after 15 minutes.Use acetone and deionized water washed product 3 times respectively, in 80 ℃ baking oven, obtain the composite photo-catalyst based on nano titanium oxide and poly phosphazene of white powder then after dry 10 hours.
As shown in Figure 6, be the stereoscan photograph and the transmission electron microscope photo based on the composite photo-catalyst of nano titanium oxide and poly phosphazene of preparation.
Embodiment 3
In the 100mL round-bottomed flask; 0.02g hexachlorocyclotriphosphazene, 0.0432g bisphenol S and 0.09g Degussa P25 nano titanium oxide are dispersed in the mixed solvent of 60mL oxolane and absolute ethyl alcohol (volume ratio is 1: 1), sonicated was uniformly dispersed it in 30 minutes.In above-mentioned dispersion liquid, add the 2mL triethylamine then, reaction is 5 hours in 40 ℃, the ultrasound bath of 100W.Reaction centrifugalizes target product after finishing, and 3500 rev/mins of centrifuge speeds separate and remove solvent after 15 minutes.Use acetone and deionized water washed product 3 times respectively, in 80 ℃ baking oven, obtain the composite photo-catalyst based on nano titanium oxide and poly phosphazene of white powder then after dry 10 hours.
As shown in Figure 7, be the stereoscan photograph and the transmission electron microscope photo based on the composite photo-catalyst of nano titanium oxide and poly phosphazene of preparation.
Claims (7)
1. the preparation method based on the composite photo-catalyst of nano titanium oxide and poly phosphazene is characterized in that, may further comprise the steps:
Step 1 places 2500 weight portion organic solvents with 1 weight portion hexachlorocyclotriphosphazene, 2.16 weight portion bisphenol Ss and 1～5 weight portion nano titanium oxide, obtains dispersion liquid through ultrasonic dispersion;
Step 2 further adds 73 weight portion acid binding agents, through adding the dispersion liquid that tepidarium obtains target product, and must be after the filtration washing drying based on the composite photo-catalyst of nano titanium oxide and poly phosphazene.
2. the preparation method of the composite photo-catalyst based on nano titanium oxide and poly phosphazene according to claim 1 is characterized in that said nano titanium oxide is a Degussa P25 nano titanium oxide.
3. the preparation method of the composite photo-catalyst based on nano titanium oxide and poly phosphazene according to claim 1 it is characterized in that said organic solvent is the mixed solvent of oxolane and absolute ethyl alcohol, and volume ratio is 1: 1.
4. the preparation method of the composite photo-catalyst based on nano titanium oxide and poly phosphazene according to claim 1 is characterized in that said acid binding agent is a triethylamine.
5. the preparation method of the composite photo-catalyst based on nano titanium oxide and poly phosphazene according to claim 1 is characterized in that, describedly adds tepidarium and is meant: reaction is 5 hours in 40 ℃ of ultrasound baths.
6. the preparation method of the composite photo-catalyst based on nano titanium oxide and poly phosphazene according to claim 5 is characterized in that said hyperacoustic power is 100 watts.
7. a composite photo-catalyst for preparing according to arbitrary described method among the claim 1-6 is characterized in that having nucleocapsid structure, is nuclear with Degussa P25 nano titanium oxide, and poly phosphazene is a shell, and wherein: the structural formula of poly phosphazene is following:
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| CN1075810C (en) * | 1995-05-18 | 2001-12-05 | 巴斯福股份公司 | Titanium dioxide-catalysed cyclisation in the liquid phase of 6 -amino caproic acid nitrile to caprolactam |
| CN1401696A (en) * | 2002-09-24 | 2003-03-12 | 吉林大学 | Flexible, flame-retardant, waterproof and corrosion-resistant polymer shape memory material |
| CN1646602A (en) * | 2002-04-18 | 2005-07-27 | 巴斯福股份公司 | Method for producing polyamides |
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| WO2008147359A1 (en) * | 2007-05-31 | 2008-12-04 | Carrier Corporation | Deactivation resistant photocatalyst and method of preparation |
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| CN1075810C (en) * | 1995-05-18 | 2001-12-05 | 巴斯福股份公司 | Titanium dioxide-catalysed cyclisation in the liquid phase of 6 -amino caproic acid nitrile to caprolactam |
| CN1646602A (en) * | 2002-04-18 | 2005-07-27 | 巴斯福股份公司 | Method for producing polyamides |
| CN1401696A (en) * | 2002-09-24 | 2003-03-12 | 吉林大学 | Flexible, flame-retardant, waterproof and corrosion-resistant polymer shape memory material |
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