CN104028292B - N-TiO2/ C and N-TiO2And preparation method thereof - Google Patents
N-TiO2/ C and N-TiO2And preparation method thereof Download PDFInfo
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- CN104028292B CN104028292B CN201410266520.7A CN201410266520A CN104028292B CN 104028292 B CN104028292 B CN 104028292B CN 201410266520 A CN201410266520 A CN 201410266520A CN 104028292 B CN104028292 B CN 104028292B
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Abstract
The present invention relates to a kind of N-TiO2/ C and N-TiO2And preparation method thereof, specifically disclose heat treatment in a kind of air and prepare nitrogen adulterated TiOx and the method with the nano-complex of carbon thereof. Its preparation method comprises the following steps: mix the 10wt% tetramethyl oxyammonia aqueous solution (1) with ethylene glycol, add isopropyl titanate, stirs, and gained solution is in 200 DEG C of hydro-thermal 8h; (2) by centrifugal in ethanol and deionized water the hydrothermal product of step (1) acquisition, cleaning, and dry in 70 DEG C of air; (3) by the desciccate in step (2) at 250 ~ 550 DEG C, heat treatment 2h in air, obtains nano-complex or the nitrogen adulterated TiOx of nitrogen adulterated TiOx/carbon. It is high that the nano-complex of nitrogen adulterated TiOx/carbon that the present invention obtains and nitrogen adulterated TiOx have nitrogen content, and absorption spectra is extended to and can, by light region, has the advantages such as visible light photocatalysis active. The preparation method who adopts has simple and easy to do, and safety coefficient is high, low cost and other advantages.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide nano material, especially a kind of nano-complex (N-TiO of nitrogen adulterated TiOx/carbon2/ C) or nitrogen adulterated TiOx (N-TiO2) preparation method, belong to the preparation field of chemical material, aspect photocatalytic degradation pollutant, having very important purposes.
Background technology
Low owing to having cost, nontoxic, chemical synthesis is convenient, the characteristics such as Heat stability is good, and titanium oxide is a kind of very common photochemical catalyst. Titanium oxide has three kinds of crystal formations, rutile, anatase and brockites. Wherein, anatase is the most frequently used photochemical catalyst. The principle of photocatalysis to degrade organic matter is, under illumination condition, in incident photon, energy is higher than the photon of energy gap by valence band Electron absorption, and then electron transition is to conduction band. Light induced electron is transferred to dyestuff from the conduction band of titanium oxide, dyestuff generation oxidation reaction, so that oxidized. The energy gap of anatase is 3.2eV, the oxidized titanium of ultraviolet luminous energy that only has wavelength to be less than 380nm absorbs, and the energy of ultraviolet light only accounts for 7% of sun nature spectrum, therefore, the anatase that common synthetic method obtains is very low to the utilization ratio of light, is necessary to improve the response of anatase to visible light wave range.
For improving the response of anatase titanium oxide to whole natural daylight wave band, can improve from following two aspects, the one, pattern regulation and control, the 2nd, chemical regulation. Pattern regulation and control are mainly the specific areas by increasing titanium oxide, increase porosity and increase absorption or the exposure particular crystal plane of titanium oxide to dyestuff, enliven face as [100] or [101] etc. and carry out for example, the photodissociation to organic dyestuff (: methylene blue, methylene orange, magenta etc.) of accelerating oxidation titanium. Pattern regulation and control do not relate to the energy gap that changes titanium oxide, therefore little on the enhancing impact of light absorption. And another kind of method, chemical regulation, thus be mainly that the energy gap that changes titanium oxide by doping reaches the absorption to visible ray. Doping is conventional method, comprises doping metals and nonmetal. From the angle of application, metal cost compare is high, thus to nonmetalloid C, H, S, the doping research of N is many. But, titanium oxide is being carried out to C, H, when N doping, the most frequently used method is to heat-treat under special atmosphere. Such as, nitrogen adulterated TiOx is generally that titanium oxide is carried out to high-temperature heat treatment under nitrogen atmosphere, and hydrogen doping titanium oxide is heat treatment titanium oxide under hydrogen shield. Except experiment working condition is required height, also there is safety problem in the heat treatment of carrying out under special atmosphere, whole process production cost also increases greatly. Therefore, at relative low temperature, and do not need special atmosphere, become a study hotspot such as adulterating under air conditions.
Meanwhile, research discovery, simple nitrogen adulterated TiOx, although titanium oxide energy gap is narrowed, has widened its spectral response range, and the hole that doping is introduced, unintentionally for carrier provides complex centre, causes photo-generated carrier utilization ratio to reduce. For addressing this problem, can carry out modification to the titanium oxide of nitrogen doping. Such as, nitrogen adulterated TiOx and carbon are carried out compound. Material with carbon element is because the characteristic of its powerful Electronic saving ability and metal conduction band can be accepted light induced electron. Research is found, after the coated titanium oxide of carbon nanomaterial, because the fermi level between carbon and titanium oxide is poor, causes electronics to carbon nanomaterial direction generation enrichment, has therefore promoted the separation of photohole-electronics, and the photocatalysis efficiency of titanium oxide is improved. But, at present relative less with the compound research of carbon for nitrogen adulterated TiOx, and existing preparation method's reaction condition is not gentle, and higher to requirement for experiment condition.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of N-TiO is provided2/ C and N-TiO2And preparation method thereof. Utilize incomplete hydro-thermal reaction to prepare predecessor, follow-up heat treatment process control TiO2Doping vario-property, different temperatures obtains the TiO of different chemical composition2Product, i.e. N-TiO2/ C or N-TiO2。
The preparation method of the nano-complex of nitrogen adulterated TiOx or itself and carbon comprises the steps:
1) tetramethyl ammonium hydroxide solution is joined in ethylene glycol, the volume ratio of tetramethyl ammonium hydroxide solution and ethylene glycol is 1:3, the two adds isopropyl titanate after stirring, the volume that titanium isopropoxide solution adds is 1/10 of tetramethyl oxyammonia solution, continues to be stirred to acquisition homogeneous solution under room temperature;
2) homogeneous solution obtaining in step 1) is moved in polytetrafluoroethylene (PTFE) water heating kettle liner, with stainless steel outer sleeve sealing, then hydro-thermal reaction 8h at 200 DEG C, naturally cools to room temperature;
3) utilize acetone, alcohol and deionized water eccentric cleaning step 2 respectively) product that obtains, and dry in air ambient;
4) desciccate step 3) being obtained is heat-treated, and heat treatment temperature is 250 ~ 550 DEG C, and heat treatment time is 2h, and heat treatment atmosphere is air atmosphere, obtains the nano-complex of nitrogen adulterated TiOx or nitrogen adulterated TiOx/carbon.
Described tetramethyl ammonium hydroxide solution is 10wt% tetramethylammonium hydroxide aqueous solution.
When described heat treatment temperature is 250 ~ 400 DEG C, obtain the nano-complex of nitrogen adulterated TiOx/carbon; When heat treatment temperature is 400 ~ 550 DEG C, obtain nitrogen adulterated TiOx.
The nano-complex nitrogen content of nitrogen adulterated TiOx/carbon prepared by described preparation method is 2.23 ~ 3.32%, and carbon content is 19 ~ 23%, and specific area is 55 ~ 80m2/ g, in the nano-complex of described nitrogen adulterated TiOx/carbon, titanium oxide is anatase crystal.
Nitrogen adulterated TiOx nitrogen content prepared by described preparation method is 1.94 ~ 2.56%, and specific area is 45 ~ 58m2/ g, in described nitrogen adulterated TiOx, titanium oxide is anatase crystal.
It is high that the nano-complex of nitrogen adulterated TiOx/carbon that the present invention obtains and nitrogen adulterated TiOx have nitrogen content, and absorption spectra is extended to and can, by light region, has the advantages such as visible light photocatalysis active. The preparation method who adopts heat-treats under air atmosphere, has avoided the inconvenience that heat treatment is brought under special atmosphere (as hydrogen, nitrogen, indifferent gas), and whole preparation process is simple and easy to do, and safety coefficient is high, and cost is low. And by controlling heat treatment temperature, can obtain very easily N-TiO2/ C or N-TiO2And the control of realization to its nitrogen content, carbon content.
Brief description of the drawings
The XRD collection of illustrative plates of nitrogen adulterated TiOx/carbon nano-complex prepared by Fig. 1 the inventive method example 1;
The high-resolution photo of nitrogen adulterated TiOx/carbon nano-complex prepared by Fig. 2 the inventive method example 1;
The XPS score of nitrogen adulterated TiOx/carbon nano-complex prepared by Fig. 3 the inventive method example 1 and N1s open score;
The ultraviolet-ray visible absorbing spectrum of nitrogen adulterated TiOx/carbon nano-complex prepared by Fig. 4 the inventive method example 1;
The XRD collection of illustrative plates of nitrogen adulterated TiOx prepared by Fig. 5 the inventive method example 3;
The XPS score of nitrogen adulterated TiOx prepared by Fig. 6 the inventive method example 3 and N1s open score;
The Raman collection of illustrative plates of nitrogen adulterated TiOx prepared by Fig. 7 the inventive method example 3;
The ultraviolet-ray visible absorbing spectrum of nitrogen adulterated TiOx prepared by Fig. 8 the inventive method example 3.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, but therefore do not limit the scope of the invention. After having read the content of the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modification falls into the scope of the claims in the present invention equally.
Embodiment 1
Nitrogen adulterated TiOx/carbon nano-complex is as shown in Figures 1 to 4 to adopt following methods prepare and obtain:
1) 10mL tetramethyl ammonium hydroxide solution is joined in 30mL ethylene glycol and stirs 10min, then add 1mL isopropyl titanate, under room temperature, stir 0.5h, obtain homogeneous solution.
2) homogeneous solution obtaining in step 1) is moved into the polytetrafluoroethylene (PTFE) that volume is 80mL
In water heating kettle liner, after stainless steel outer sleeve sealing, hydro-thermal reaction 8h at 200 DEG C, from
So be cooled to room temperature.
3) utilize acetone, alcohol and deionized water 1 step 2 of eccentric cleaning respectively) obtain
Product, and dry 10h in 70 DEG C of air ambients.
4) desciccate step 3) being obtained is heat-treated. Heat treatment temperature is 250 DEG C, heat
Processing time is 2h, and heat treatment atmosphere is air atmosphere, obtains receiving of nitrogen adulterated TiOx/carbon
Rice compound.
Fig. 1 is the XRD collection of illustrative plates of nitrogen adulterated TiOx/carbon nano-complex of preparing of example 1, as can be seen from Figure, the product obtaining is anatase crystal, although crystallinity is poor, but in 2 θ=25.3,37.9,48.15, the diffraction maximum at 54.05,55.28 ° of places such as grade can be corresponding one by one with anatase JCPDS card No.84-1285.
Fig. 2 is the high resolution electron microscopy photo of nitrogen adulterated TiOx/carbon nano-complex of preparing of example 1, can observe carbon and the crystal grain of crystallite dimension between 3 ~ 8nm of disordering in figure. The analysis of lattice diffraction fringe can obtain, and the crystal grain in white circle is anatase crystal grain.
Fig. 3 is the XPS collection of illustrative plates of nitrogen adulterated TiOx/carbon nano-complex of preparing of example 1, have nitrogen, and nitrogen content is higher in the product that wherein in embedded N1s spectrogram, strong electronics shows to obtain in conjunction with peak. And analyze and learn, the doped forms of nitrogen is gapped nitrogen both, has again replacement nitrogen.
Fig. 4 is the ultraviolet-ray visible absorbing spectrum of nitrogen adulterated TiOx/carbon nano-complex of preparing of example 1, by learning in figure, prepared nitrogen adulterated TiOx/carbon nano-complex all has obvious absorption in whole ultraviolet-visible region, corresponding to the appearance of black of product. Can predict the visible light photocatalysis active of product.
Embodiment 2
A kind of nitrogen adulterated TiOx/carbon nano-complex is to adopt following methods prepare and obtain:
1) 10mL tetramethyl ammonium hydroxide solution is joined in 30mL ethylene glycol and stirs 10min, then add 1mL isopropyl titanate, under room temperature, stir 0.5h, obtain homogeneous solution.
2) homogeneous solution obtaining in step 1) is moved into the polytetrafluoroethylene (PTFE) that volume is 80mL
In water heating kettle liner, after stainless steel outer sleeve sealing, hydro-thermal reaction 8h at 200 DEG C, from
So be cooled to room temperature.
3) utilize acetone, alcohol and deionized water 1 step 2 of eccentric cleaning respectively) obtain
Product, and dry 10h in 70 DEG C of air ambients.
4) desciccate step 3) being obtained is heat-treated. Heat treatment temperature is 350 DEG C, heat
Processing time is 2h, and heat treatment atmosphere is air atmosphere, obtains receiving of nitrogen adulterated TiOx/carbon
Rice compound.
Embodiment 3
A nitrogen adulterated TiOx as shown in Fig. 5 to Fig. 8 is to adopt following methods prepare and obtain:
1) 10mL tetramethyl ammonium hydroxide solution is joined in 30mL ethylene glycol and stirs 10min, then add 1mL isopropyl titanate, under room temperature, stir 0.5h, obtain homogeneous solution.
2) homogeneous solution obtaining in step 1) is moved into the polytetrafluoroethylene (PTFE) that volume is 80mL
In water heating kettle liner, after stainless steel outer sleeve sealing, hydro-thermal reaction 8h at 200 DEG C, from
So be cooled to room temperature.
3) utilize acetone, alcohol and deionized water 1 step 2 of eccentric cleaning respectively) obtain
Product, and dry 10h in 70 DEG C of air ambients.
4) desciccate step 3) being obtained is heat-treated. Heat treatment temperature is 450 DEG C, heat
Processing time is 2h, and heat treatment atmosphere is air atmosphere, obtains nitrogen adulterated TiOx.
Fig. 5 is the XRD collection of illustrative plates of the nitrogen adulterated TiOx prepared of example 3, and as can be seen from Figure, the product of acquisition is Anatase titanium oxide, and crystallinity is good, in 2 θ=25.3,37.9, the diffraction maximum at 48.15,54.05,55.28 ° of places such as grade can be corresponding one by one with anatase JCPDS card No.84-1285.
Fig. 6 is the XPS collection of illustrative plates of the nitrogen adulterated TiOx prepared of example 3, wherein in embedded N1s spectrogram, can observe electronics in conjunction with peak, have nitrogen, and nitrogen content is higher in the product that shows to obtain. And analyze and learn, the doped forms of nitrogen is gapped nitrogen both, has again replacement nitrogen.
Fig. 7 is the Raman collection of illustrative plates of the nitrogen adulterated TiOx prepared of example 3,100 ~ 700cm-1Between anatase structured corresponding to product of the peak that produces, wherein wave number is 580cm-1The peak at place has characterized the existence of nitrogen. Meanwhile, 1000 ~ 2000cm-1Between show in product not carbon containing without Raman peaks, be nitrogen adulterated TiOx.
Fig. 8 is the ultraviolet-ray visible absorbing spectrum of the nitrogen adulterated TiOx prepared of example 3, and by learning in figure, prepared its absorption region of nitrogen adulterated TiOx, than pure zirconia titanium, is extended to visibility region by ultraviolet region, echoes mutually with the yellow appearance of product. And, " absorption tail " (450 ~ 550nm) that absorption spectra produces with typical nitrogen doped products. Can predict the visible light photocatalysis active of product.
Embodiment 4
A kind of nitrogen adulterated TiOx of the present invention is to adopt following methods prepare and obtain:
1) 10mL tetramethyl ammonium hydroxide solution is joined in 30mL ethylene glycol and stirs 10min, then add 1mL isopropyl titanate, under room temperature, stir 0.5h, obtain homogeneous solution.
2) homogeneous solution obtaining in step 1) is moved into the polytetrafluoroethylene (PTFE) that volume is 80mL
In water heating kettle liner, after stainless steel outer sleeve sealing, hydro-thermal reaction 8h at 200 DEG C, from
So be cooled to room temperature.
3) utilize acetone, alcohol and deionized water 1 step 2 of eccentric cleaning respectively) obtain
Product, and dry 10h in 70 DEG C of air ambients.
4) desciccate step 3) being obtained is heat-treated. Heat treatment temperature is 550 DEG C, heat
Processing time is 2h, and heat treatment atmosphere is air atmosphere, obtains nitrogen adulterated TiOx.
Claims (3)
1. a preparation method for the nano-complex of nitrogen adulterated TiOx or itself and carbon, is characterized in that, comprises the steps:
1) tetramethyl ammonium hydroxide solution is joined in ethylene glycol, the volume ratio of tetramethyl ammonium hydroxide solution and ethylene glycol is 1:3, the two adds isopropyl titanate after stirring, the volume that titanium isopropoxide solution adds is 1/10 of tetramethyl ammonium hydroxide solution, continues to be stirred to acquisition homogeneous solution under room temperature;
2) homogeneous solution obtaining in step 1) is moved in polytetrafluoroethylene (PTFE) water heating kettle liner, with stainless steel outer sleeve sealing, then hydro-thermal reaction 8h at 200 DEG C, naturally cools to room temperature;
3) utilize acetone, alcohol and deionized water eccentric cleaning step 2 respectively) product that obtains, and dry in air ambient;
4) desciccate step 3) being obtained is heat-treated, and heat treatment temperature is 250 ~ 550 DEG C, and heat treatment time is 2h, and heat treatment atmosphere is air atmosphere, obtains the nano-complex of nitrogen adulterated TiOx or nitrogen adulterated TiOx/carbon;
Described tetramethyl ammonium hydroxide solution is 10wt% tetramethylammonium hydroxide aqueous solution;
When described heat treatment temperature is 250 ~ 400 DEG C, obtain the nano-complex of nitrogen adulterated TiOx/carbon; When heat treatment temperature is 400 ~ 550 DEG C, obtain nitrogen adulterated TiOx.
2. a nano-complex for nitrogen adulterated TiOx/carbon that as claimed in claim 1 prepared by preparation method, is characterized in that: the nano-complex nitrogen content of described nitrogen adulterated TiOx/carbon is 2.23 ~ 3.32%, carbon content is 19 ~ 23%, and specific area is 55 ~ 80m2/ g, in the nano-complex of described nitrogen adulterated TiOx/carbon, titanium oxide is anatase crystal.
3. the nitrogen adulterated TiOx that as claimed in claim 1 prepared by preparation method, is characterized in that: described nitrogen adulterated TiOx nitrogen content is 1.94 ~ 2.56%, and specific area is 45 ~ 58m2/ g, in described nitrogen adulterated TiOx, titanium oxide is anatase crystal.
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| CN105680019A (en) * | 2016-03-16 | 2016-06-15 | 江苏乐能电池股份有限公司 | Preparation method of high-rate ternary material |
| CN107983384B (en) * | 2016-10-26 | 2019-11-26 | 中国科学院福建物质结构研究所 | A kind of N doping TiO2C-material, preparation method and application |
| CN107670681B (en) * | 2017-10-11 | 2020-01-14 | 辽宁工程技术大学 | Nitrogen-doped TiO2Method for preparing powder |
| CN108246335B (en) * | 2018-01-31 | 2020-03-31 | 辽宁工程技术大学 | Nitrogen-silver doped nano TiO2Method for preparing powder |
| CN109718823B (en) * | 2018-12-10 | 2021-10-26 | 齐鲁工业大学 | N-doped TiO2/C composite material and preparation method and application thereof |
| CN112850784B (en) * | 2021-02-26 | 2022-09-23 | 中国检验检疫科学研究院 | Synthetic method and application of sheet TiO nano material |
| CN113181950B (en) * | 2021-04-29 | 2022-08-23 | 浙江大学 | Photocatalyst for degrading antibiotics in water by activating persulfate under assistance of visible light |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600881A (en) * | 2012-04-01 | 2012-07-25 | 河南理工大学 | Preparation method for nitrogen and carbon co-doped nanometer titanium dioxide visible-light photocatalyst |
| CN103801353A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon-nitrogen codoped titanium dioxide visible-light photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102600881A (en) * | 2012-04-01 | 2012-07-25 | 河南理工大学 | Preparation method for nitrogen and carbon co-doped nanometer titanium dioxide visible-light photocatalyst |
| CN103801353A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon-nitrogen codoped titanium dioxide visible-light photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| "One-step hydrothermal synthesis of N-doped TiO2/C nanocomposites with high visible light photocatalytic activity";Dong-Hong Wang et al;《Nanoscale》;20111205;第4卷;第576~584页 * |
| "氮掺杂纳米二氧化钛的制备及其光催化性能";刘广军等;《山东化工》;20091231;第38卷;第16页第2栏第2段、1.1节和2.1节 * |
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