CN104138764A - Preparation method of efficient visible light excited carbon and fluorine codoped titanium dioxide photocatalyst - Google Patents
Preparation method of efficient visible light excited carbon and fluorine codoped titanium dioxide photocatalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of semiconductor photocatalysis, and concretely relates to a preparation method of an efficient visible light excited carbon and fluorine codoped titanium dioxide photocatalyst. A pretreated titanium dioxide catalyst is doped with carbon tetrafluoride as a discharge gas by adopting a dielectric barrier discharge plasma generator in order to dope carbon and fluorine elements into titanium dioxide crystal lattices in activated forms. The method has the advantages of one step synthesis, simple operation, short time, low energy consumption, controllable doped amount, high catalyst activity and the like. Codoping reduces the forbidden band width of the photocatalyst, makes the catalyst have enhanced visible light absorption capability, and also makes the catalyst have catalytic degradation effect on organic pollutants under the irradiation of visible lights. The above obtained catalyst can be used in the photocatalytic degradation process of a common pollutant 2,4,6-trichlorophenol (TCP). An evaluation result obtained by adopting a same evaluation device shows that the catalyst obtained in the invention has a higher catalysis activity than other codoped titanium dioxide photocatalysts prepared through traditional methods.
Description
Technical field
The invention belongs to Photocatalitic Technique of Semiconductor field, be specifically related to a kind of efficient visible light and excite the preparation method of carbon and fluorin-doped titanium dioxide optical catalyst.
Background technology
1972, Fujishima and Honda found the TiO of illumination
2monocrystalline energy decomposition water, thus the interest of people to photosensitized oxidation reduction reaction caused, advance the research of the photoredox reaction of organic matter and inorganic matter.Canadian scientist Carey in 1976 etc. for catalysis photodissociation pollutant, open conductor photocatalysis and are applied to the prelude of Study on Environmental Protection by semi-conducting material.At the beginning of the eighties, photochemical application study emphasis starts to turn to field of environment protection, and wherein the photochemical degradating of pollutant especially comes into one's own.In time subsequently, photocatalysis is being widely studied aspect the processing of organic and inorganic pollution.Quantity research shows greatly, and most photochemical catalysts at room temperature can be realized the degree of depth mineralising to pollutant, requires also very low to consersion unit.Current received photocatalysis principle is thought: in the time that semiconductor is subject to energy and is more than or equal to the irradiation of its band gap, the electronics in valence band is stimulated and transits to conduction band, produces light induced electron-hole pair.Photohole in excitation state and electronics have two kinds of possible paths, and one is to participate in light-catalyzed reaction, and the electronics of surperficial adsorbed material or solvent is captured in hole, make the not light absorbing material of script oxidized.Electronics, by surface electronic receptor capture, makes electron acceptor generation reduction reaction.Another kind is that photohole and electronics generation are compound, and the energy of generation distributes with the form of heat or light.
TiO
2mainly run into two outstanding problems as the application of catalysis material.The one, TiO
2band-gap energy is larger, can only be by ultraviolet excitation, and can not directly be excited by visible ray.The 2nd, the electron-hole pair recombination rate producing is high, and quantum efficiency is reduced greatly.So how effectively to improve TiO by modification
2to the utilization of visible ray, and reducing electron-hole pair recombination rate, improve its quantum efficiency, make catalyst under visible ray, show superior catalytic performance, is current TiO
2the research emphasis of photocatalysis technology.
Carbon doping is the more a kind of adulterant of research at present, and theoretical research shows, after doping, C2p track can with O2p track generation hybridism, the energy level of the hybridized orbit of generation, higher than original valence-band level, has therefore reduced the band-gap energy of titanium dioxide.And after fluorine doping because electric charge alimentation can form oxygen vacancies and Ti at titanium dioxide surface
3+, improve the effect of catching to light induced electron-hole, can also improve the acidity of catalyst, make catalyst surface adsorb more organic pollutant molecule, therefore photocatalytic activity is had to remarkable impact.
Summary of the invention
The object of the invention is to provide a kind of efficient visible light to excite the preparation method of carbon and fluorin-doped titanium dioxide optical catalyst.
The technical solution used in the present invention is for achieving the above object:
A kind of efficient visible light excites the preparation method of carbon and fluorin-doped titanium dioxide optical catalyst, it is characterized in that: adopt dielectric barrier discharge plasma generator, taking carbon tetrafluoride as discharge gas, pretreated titanium deoxide catalyst is carried out to doping treatment, carbon and fluorine element are mixed to titanium dioxide lattice with activated form.
When described doping treatment electric discharge, discharge frequency is 8～12kHz, and pressure regulator input voltage is 60～80V, and carbon tetrafluoride flow velocity is 60～80ml/min, and be 5～30min discharge time.
The pretreatment of described titanium dioxide is by titanium deoxide catalyst roasting 1～4h, to remove the material of adsorption at 350～450 DEG C.
Described carbon and fluorin-doped titanium dioxide optical catalyst are applied in TCP degradation reaction.
In described degradation reaction, TCP concentration is 60 × 10
-6gml
-1, catalyst amount is every liter of TCP solution of 1g, and light source is 110W high-pressure mercury lamp, and with the ultraviolet light below optical filter elimination wavelength 400nm, reaction condition is 30 DEG C, standard atmospheric pressure, the reaction time is 4h; The mensuration of TCP concentration adopts high performance liquid chromatograph (Jasco LC2000), and splitter is ODS-C
18reverse-phase chromatographic column (250mm × 4.6mm, m), flow velocity is 1mL/min to 5 μ, and it is 210nm that ultraviolet detects wavelength, and mobile phase is methanol/water=90:10, and column temperature is room temperature, sampling volume is 20 μ L.
The present invention has advantages of: the present invention adopts one-step synthesis, easy and simple to handle, and consuming time short, energy consumption is low, and doping is controlled, and gained catalyst activity is high.Because codope effect has reduced the energy gap of photochemical catalyst, catalyst is strengthened the absorbability of visible ray, under the irradiation of visible ray, there is the catalytic degradation ability to organic pollution.By gained catalyst, for common pollutant 2,4, the Photocatalytic Degradation Process of 6-trichlorophenol, 2,4,6,-T (TCP), adopts identical evaluating apparatus, compared with other co-doping titanium dioxide photocatalysts of preparing, shows higher catalytic activity with conventional method.
Brief description of the drawings
The structure chart of the dielectric barrier discharge reactor that Fig. 1 provides for the embodiment of the present invention, wherein 1 is high-field electrode; 2 is earthing pole; 3 is ground; 4 is quartz ampoule; 5 is heat insulation layer; 6 is catalyst precarsor bed; 7 is gas access; 8 is gas vent.
Photochemical catalyst and the comparison diagram of raw material P25 to light absorbability that Fig. 2 provides for the embodiment of the present invention, wherein a is raw material P25, b is carbon and fluorin-doped photochemical catalyst prepared by embodiment 1.
The photochemical catalyst process Ar that Fig. 3 provides for the embodiment of the present invention
+the x-ray photoelectron energy spectrogram of the fluorine element after surface sputtering, wherein a is photochemical catalyst prepared by embodiment 4, and b is photochemical catalyst prepared by embodiment 1, and c is photochemical catalyst prepared by embodiment 3, and d is photochemical catalyst prepared by embodiment 2.
The x-ray photoelectron energy spectrogram of titanium elements in the photochemical catalyst that Fig. 4 provides for the embodiment of the present invention and raw material P25, wherein a is raw material P25, b is carbon and fluorin-doped photochemical catalyst prepared by embodiment 1.
The x-ray photoelectron energy spectrogram of carbon in the photochemical catalyst that Fig. 5 provides for the embodiment of the present invention, wherein a is photochemical catalyst prepared by embodiment 1, and b is photochemical catalyst prepared by embodiment 6, and c is photochemical catalyst prepared by embodiment 5.
The photochemical catalyst Ar that Fig. 6 provides for the embodiment of the present invention 1
+the x-ray photoelectron energy spectrogram of the carbon before and after surface sputtering, wherein a is the spectrogram before sputter, b is the spectrogram after sputter.
The fluorescence emission spectrogram of the photochemical catalyst that Fig. 7 provides for the embodiment of the present invention, wherein a is raw material P25, and b is photochemical catalyst prepared by embodiment 2, and c is photochemical catalyst prepared by embodiment 3, d is photochemical catalyst prepared by embodiment 4, and e is photochemical catalyst prepared by embodiment 1.
Photochemical catalyst and comparative example 3 that Fig. 8 provides for the embodiment of the present invention, the comparison diagram of the adsorption capacity of the photochemical catalyst of 4 preparations to organic pollution TCP, wherein a is photochemical catalyst prepared by embodiment 1, and b is photochemical catalyst prepared by comparative example 3, and c is photochemical catalyst prepared by comparative example 4.
The photochemical catalyst that Fig. 9 embodiment of the present invention provides and raw material P25 are to organic pollution TCP photocatalytic degradation effect contrast figure, wherein a is raw material P25, b is photochemical catalyst prepared by embodiment 1, c is photochemical catalyst prepared by embodiment 2, d is photochemical catalyst prepared by embodiment 3, e is photochemical catalyst prepared by embodiment 4, and f is photochemical catalyst prepared by embodiment 5, and g is photochemical catalyst prepared by embodiment 6.
The photochemical catalyst of the photochemical catalyst that Figure 10 provides for the embodiment of the present invention and comparative example 1～4 preparation is to organic pollution TCP photocatalytic degradation effect contrast figure, wherein a is photochemical catalyst prepared by embodiment 1, b is photochemical catalyst prepared by comparative example 1, c is photochemical catalyst prepared by comparative example 2, d is photochemical catalyst prepared by comparative example 3, and e is photochemical catalyst prepared by comparative example 4.
Detailed description of the invention
Embodiment 1:
A) raw material finished product titanium dioxide P25 is carried out to pretreatment, roasting 1h under 400 ° of C, to remove the material of adsorption.
B), taking carbon tetrafluoride as discharge gas, adopt dielectric barrier discharge plasma generator after carbon and fluorine element activation, to mix titanium dioxide lattice.Reactor is made up of a quartz ampoule and two electrodes.Using the stainless steel wire that diameter is 2.5mm is high-field electrode, and is installed on quartz ampoule shaft core position, and one end is connected with AC power.Taking the aluminium foil that is closely wrapped in quartz ampoule outside as earthing pole, and it is connected with the earth.Plasma producing apparatus structure chart as shown in Figure 1 or adopt existing commercially available plasma producing apparatus.The above-mentioned pretreated raw material finished product titanium dioxide P25 of 1g is put into quartz ampoule, and discharge frequency is adjusted to 10kHz, and pressure regulator input voltage is 80V, and carbon tetrafluoride flow velocity is 80ml/min, and be 20min discharge time.After reaction finishes, input voltage is slowly closed to generator after zeroing.After catalyst is cooling, take out, obtain carbon and fluorin-doped titanium dioxide catalyst.
Photochemical catalyst and the comparison diagram of raw material P25 to light absorbability that Fig. 2 provides for the embodiment of the present invention, wherein a is raw material P25, b is carbon and fluorin-doped photochemical catalyst prepared by embodiment 1.Can find out that raw material P25 absorbs visible ray hardly, and carbon prepared by embodiment 1 and fluorin-doped photochemical catalyst significantly strengthen to the absorption of visible ray.By can the be absorbed wavelength value on border of the tangent line of absorption curve slope maximum and the intersection point of axis of abscissas, be respectively as shown in the figure 404nm and 436nm.By formula E
g=1240/ λ, can calculate the band-gap energy of two samples, is respectively 3.07eV and 2.84eV.Therefore carbon and fluorin-doped effect reduce titanium dioxide band-gap energy, and the absorption of visible ray is significantly strengthened.
Embodiment 2～4:
The discharge time that changes B step in embodiment 1, other steps and condition are constant, obtain carbon and fluorine element content data in table 1: table 1
| Embodiment | Discharge time (min) | Fluorine element doping (at.%) | Carbon doping (at.%) |
| 2 | 5 | 0.6 | 0.4 |
| 3 | 10 | 1.1 | 0.7 |
| 1 | 20 | 1.9 | 1.1 |
| 4 | 30 | 2.7 | 1.3 |
Embodiment 5,6:
The input voltage that changes B step in embodiment 1, other steps and condition are constant, obtain carbon and fluorine element content data in table 2: table 2
| Embodiment | Input voltage (V) | Fluorine element doping (at.%) | Carbon doping (at.%) |
| 5 | 60 | 0 | 0.3 |
| 6 | 70 | 0.7 | 0.5 |
| 1 | 80 | 1.9 | 1.1 |
The effect of above-mentioned each embodiment photochemical catalyst is referring to Fig. 3-7;
As seen from Figure 3, when catalyst is through Ar
+surface sputtering is removed after the material of adsorption, and F element still occurs at 689.7eV place in conjunction with energy peak.According to bibliographical information, this replaces in conjunction with belonging to F element the Ti-F key [Applied Catalysis B:Environmental96 (2010) 458-465] forming after Lattice Oxygen.Can calculate the peak area in spectrogram according to professional XPSPEAK41 software, can calculate thus the doping of F element, list table 1 in.
Be that in the x-ray photoelectron energy spectrogram of titanium elements in visible light catalyst and raw material P25, P25 occurs that at 458.4eV and 464.1eV place two in conjunction with can peaks, should belong to Ti by Fig. 4
4+2p
3/2and Ti
4+2p
1/2.Photochemical catalyst prepared by embodiment 1 is except above-mentioned two combination energy peaks, and the combination at 457.7eV and 463.3eV two places can should belong to Ti according to bibliographical information
3+2p
3/2and Ti
3+2p
1/2[Applied Surface Science252 (2006) 7532-7538].Ti in catalyst prepared by embodiment 1
3+generation be to cause the imbalance of electric charge caused [Applied Catalysis B:Environmental132-133 (2013) 460-468] because F-ion replaces after Lattice Oxygen.Further confirm that thus F element has mixed the lattice of titanium dioxide.
In spectrogram all there is strong combination energy peak in three samples at 284.6eV place as seen from Figure 5, should belong to C-C key.In addition two weak combination energy peaks that are positioned at 288.6eV and 291.6eV place, according to bibliographical information, belong to respectively C element and mix the Ti-O-C key and the discharge gas CF that after lattice, form
4in C-F key [Environmental Science Tcehnology45 (2011) 6970-6977; Chemistry:an Asian Journal5 (2010) 1171-1177].It can be confirmed that C element has also mixed titanium dioxide lattice.In addition, a, b, the combination energy peak intensity that c tri-samples are positioned at 288.6eV place reduces gradually, illustrates that the content of doping C element reduces gradually.Can calculate the peak area in spectrogram according to professional XPSPEAK41 software, can calculate thus the doping of C element, list table 2 in.In addition, in table 1, in the C element doping amount of each sample and table 2, the F element doping amount of each sample is also to calculate according to professional XPSPEAK41 software.As can be seen from the above two tables, the doping of C and F increases along with the increase of discharge time.And under lower discharge voltage as 60V, C and F element doping amount are wanted the significantly doping lower than electrion, as 80V.
In spectrogram, be only left to be positioned at as seen from Figure 6 the combination energy peak at 288.6eV place, this belongs to C element in conjunction with energy peak and mixes the Ti-O-C key forming after lattice, has further confirmed that C element has mixed the lattice of titanium dioxide.
Because the peak in fluorescence spectrum is that the energy discharging because electron-hole pair is compound produces, therefore more the bright electron hole pair recombination rate of novel is lower for peak intensity as seen from Figure 7, and quantum efficiency is higher.In spectrogram, can find out, the peak intensity maximum of raw material P25, and after doping, the peak intensity of sample has reduction in various degree, illustrates that chanza has reduced the recombination rate of electron hole pair to some extent.In addition, the peak intensity of doped samples first reduces along with the increase of discharge time, and in the time that doping time is 20min, peak intensity is minimum, then continues to increase discharge time, and peak intensity increases.This illustrates that the doping while being 20min discharge time is optimum doping amount, and the F element of doping can form oxygen vacancies and Ti at catalyst surface
3+, improve the effect of catching to light induced electron-hole, improve separation of charge efficiency.But long when discharge time, when doping is excessive, the F element of doping becomes the complex centre of electron hole pair on the contrary, and therefore recombination rate increases on the contrary.
Comparative example 1
Adopt Sol-gel method synthetic nitrogen and fluorin-doped titanium dioxide catalyst [Applied Catalysis B:Environmental132-133 (2013) 460-468].
3.4ml butyl titanate is added drop-wise under strong agitation to 50ml NH
4in F solution, mol ratio Ti/F=1:2 in the suspension that makes to obtain.By after the suspension room temperature ageing 24h obtaining, 100 DEG C of dry 48h.The xerogel obtaining is at 5 DEG C/min of 500 DEG C of roasting 2h(heating rates), obtain carbon and fluorin-doped titanium dioxide catalyst.
Comparative example 2
Adopt the synthetic sulphur of hydro-thermal method and fluorin-doped titanium dioxide catalyst [Applied Catalysis B:Environmental96 (2010) 458-465].
0.015mol NH
4f and 0.015mol thiocarbamide join in 30ml ethanol, strong agitation 30min.0.01mol butyl titanate adds after above-mentioned mixed liquor, continues to stir 30min.Under strong agitation, 1.5ml acetic acid and 1ml deionized water are added in above-mentioned mixed liquor.Pack the product obtaining into autoclave, at 120 DEG C, keep 20h.Naturally after cooling, product is taken out, with after deionized water and alcohol flushing 3 times, after 80 DEG C of dry 10h, packs Muffle furnace into, 5 DEG C/min of 450 DEG C of roasting 3h(heating rates), obtain sulphur and fluorin-doped titanium dioxide catalyst.
Comparative example 3
Adopt the synthetic sulphur of Hydrolyze method and carbon co-doped titanium deoxide catalyst [Journal of Colloid and Interface Science311 (2007) 514-522].
Under strong agitation, 0.031mol isopropyl titanate and 0.124mol thiocarbamide are dispersed in 200ml ethanol, obtain solution A.1ml ammoniacal liquor is added in 0.125mol deionized water and obtains solution B.Under strong agitation, solution B is slowly added drop-wise in solution A, continue to stir 20min and make it complete hydrolysis.At 60 DEG C, after solvent evaporated, solid is put into 80 DEG C of dry 10h of baking oven.By product 5 DEG C/min of roasting 2h(heating rate at 500 DEG C), obtain sulphur and carbon co-doped titanium deoxide catalyst.
Comparative example 4
Adopt ionic-implantation synthetic nitrogen and carbon co-doped titanium deoxide catalyst [Journal of Solid State Chemistry192 (2012) 305-311].
Under strong agitation, 1g business titanium dioxide P25 is joined in 80ml ethylenediamine and obtains suspension.The suspension obtaining is proceeded to there-necked flask, 120 DEG C of backflow 24h.This suspension is kept to 72h at 80 DEG C, the remaining ethylenediamine of evaporate to dryness.By the solid obtaining 5 DEG C/min of roasting 5h(heating rate at 500 DEG C), obtain nitrogen and carbon co-doped titanium deoxide catalyst.
Above-described embodiment is prepared to gained catalyst and each application of comparative example catalyst in TCP degradation reaction:
Be 60 × 10 by 100ml concentration
-6gml
-1dyestuff TCP add quartz reactor (commercial product), catalyst amount is 0.1g, light source is 110W high-pressure mercury lamp, with the ultraviolet light below optical filter elimination wavelength 400nm, under the condition stirring, in dye solution, pass into air, reaction condition is 30 DEG C, standard atmospheric pressure, and the reaction time is 4h.Take out after catalyst is removed in the centrifugation of 5ml dye solution supernatant is proceeded to high performance liquid chromatograph (Jasco LC2000) analysis conversion ratio at interval of 30min, splitter is ODS-C
18reverse-phase chromatographic column (250mm × 4.6mm, m), flow velocity is 1mL/min to 5 μ, and it is 210nm that ultraviolet detects wavelength, and mobile phase is methanol/water=90:10, and column temperature is room temperature, sampling volume is that 20 μ L(are referring to Fig. 8,9 and 10).
The catalyst that as seen from Figure 8 prepared by embodiment 1 is obviously greater than the catalyst of comparative example 3,4 preparations to the adsorption capacity of TCP.This is the acidity that the doping of F element in the catalyst of preparing due to embodiment 1 can improve catalyst, makes catalyst surface adsorb more organic pollutant molecule [Applied Catalysis B:Environmental132-133 (2013) 460-468].
Raw material P25 is very low to the light degradation activity of TCP as seen from Figure 9, and the C of embodiment 1～6 preparation and the titanium dioxide optical catalyst of F codope have raising in various degree to the light degradation activity of TCP.In addition, can find out in the photochemical catalyst of preparing under identical discharge voltage, catalytic activity first increases the trend reducing afterwards, photocatalyst activity the best of wherein preparing with embodiment 1 along with the increase of discharge time presents.Although but photochemical catalyst longer active but decline to some extent discharge time prepared by embodiment 4, this is because excessive F doping has aggravated the compound of electron hole pair, has reduced quantum efficiency.For the photochemical catalyst of preparing under different discharge voltages, can find out that catalytic activity increases gradually with the increase of discharge voltage, this is the lattice that more easily mixes titanium dioxide due to C under high voltage and F element.
Figure 10 can find out, photochemical catalyst prepared by embodiment 1 shows better to TCP Photocatalytic activity than other dual element codoping titanium oxide catalysts of comparative example 1～4 preparation.This is that energy level due to the hybridized orbit producing after one side C doping is higher than original valence-band level, reduce the band-gap energy of titanium dioxide, titanium dioxide is significantly strengthened the absorption of visible ray, on the other hand after fluorine doping because charge unbalance can form oxygen vacancies and Ti at titanium dioxide surface
3+, improve the effect of catching to light induced electron-hole, reduce the recombination rate of electron-hole pair, can also improve the acidity of catalyst, make catalyst surface adsorb more organic pollutant molecule, therefore C and F codope show good synergy, and photocatalytic activity is significantly improved.
Claims (5)
1. an efficient visible light excites the preparation method of carbon and fluorin-doped titanium dioxide optical catalyst, it is characterized in that: adopt dielectric barrier discharge plasma generator, taking carbon tetrafluoride as discharge gas, pretreated titanium deoxide catalyst is carried out to doping treatment, carbon and fluorine element are mixed to titanium dioxide lattice with activated form.
2. excite the preparation method of carbon and fluorin-doped titanium dioxide optical catalyst by efficient visible light claimed in claim 1, it is characterized in that: when described doping treatment electric discharge, discharge frequency is 8～12kHz, pressure regulator input voltage is 60～80V, carbon tetrafluoride flow velocity is 60～80ml/min, and be 5～30min discharge time.
3. excite the preparation method of carbon and fluorin-doped titanium dioxide optical catalyst by efficient visible light claimed in claim 1, it is characterized in that: the pretreatment of described titanium dioxide is by titanium deoxide catalyst roasting 1～4h, to remove the material of adsorption at 350～450 DEG C.
4. the preparation method who excites carbon and fluorin-doped titanium dioxide optical catalyst by efficient visible light claimed in claim 1, is characterized in that: described carbon and fluorin-doped titanium dioxide optical catalyst are applied in TCP degradation reaction.
5. the preparation method who excites carbon and fluorin-doped titanium dioxide optical catalyst by efficient visible light claimed in claim 4, is characterized in that: in described degradation reaction, TCP concentration is 60 × 10
-6gml
-1, catalyst amount is every liter of TCP solution of 1g, and light source is 110W high-pressure mercury lamp, and with the ultraviolet light below optical filter elimination wavelength 400nm, reaction condition is 30 DEG C, standard atmospheric pressure, the reaction time is 4h; The mensuration of TCP concentration adopts high performance liquid chromatograph (Jasco LC2000), and splitter is ODS-C
18reverse-phase chromatographic column (250mm × 4.6mm, m), flow velocity is 1mL/min to 5 μ, and it is 210nm that ultraviolet detects wavelength, and mobile phase is methanol/water=90:10, and column temperature is room temperature, sampling volume is 20 μ L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110653004A (en) * | 2019-09-05 | 2020-01-07 | 上海化工研究院有限公司 | Catalyst for trapping and catalyzing VOCs degradation and preparation method and application thereof |
| CN112387264A (en) * | 2020-11-16 | 2021-02-23 | 西南石油大学 | TiO based on plasma treatment2Method of modifying TiO2Photocatalyst and application |
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|---|---|---|---|---|
| US4574177A (en) * | 1982-02-01 | 1986-03-04 | Texas Instruments Incorporated | Plasma etch method for TiO2 |
| CN101528976A (en) * | 2006-11-02 | 2009-09-09 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer molded product and method for producing the same |
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2013
- 2013-05-10 CN CN201310172540.3A patent/CN104138764B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4574177A (en) * | 1982-02-01 | 1986-03-04 | Texas Instruments Incorporated | Plasma etch method for TiO2 |
| CN101528976A (en) * | 2006-11-02 | 2009-09-09 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer molded product and method for producing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110653004A (en) * | 2019-09-05 | 2020-01-07 | 上海化工研究院有限公司 | Catalyst for trapping and catalyzing VOCs degradation and preparation method and application thereof |
| CN110653004B (en) * | 2019-09-05 | 2022-09-09 | 上海化工研究院有限公司 | Catalyst for trapping and catalyzing VOCs degradation and preparation method and application thereof |
| CN112387264A (en) * | 2020-11-16 | 2021-02-23 | 西南石油大学 | TiO based on plasma treatment2Method of modifying TiO2Photocatalyst and application |
| CN112387264B (en) * | 2020-11-16 | 2022-02-08 | 西南石油大学 | TiO based on plasma treatment2Method of modifying TiO2Photocatalyst and application |
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