CN104148042A - Preparation method of ordered hierarchically porous carbon-containing titania self-supporting film photocatalytic material - Google Patents
Preparation method of ordered hierarchically porous carbon-containing titania self-supporting film photocatalytic material Download PDFInfo
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Abstract
The invention relates to a preparation method of an ordered hierarchically porous carbon-containing titania self-supporting film photocatlytic material. According to the invention, polystyrene acrylate microsphere emulsion, a block copolymer, ethanol, and a titanium source are adopted as raw materials, and a filter paper is adopted as a substrate; evaporation is allowed under room temperature, such that self-assembly is induced; and thermal polymerization and heat treatment under inert atmosphere protection are carried out, such that the ordered hierarchically porous carbon-containing titania self-supporting film photocatlytic material is obtained. The obtained product has a macropore and mesopore hierarchical porous structure. Pore channels are regularly arranged. The macropores have uniform sizes which are adjustable within a range of 200-400nm. The sizes of the mesopores are 3-5nm. A carbon content is 16-21wt%. An effective sunlight absorption range is 200-800nm. According to the invention, dependence on traditional substrates such as steel sheet and silicon sheet is avoided. The method has the advantages of simple process, low requirement on equipment, and high operability. The prepared carbon-containing titania film material has expanded solar spectrum response range and good visible light catalytic performance.
Description
Technical field
The present invention relates to the preparation of titanium oxide photochemical catalyst material, particularly a kind of preparation method of the carbon containing titanium dioxide self-supported membrane catalysis material with macropore, mesoporous graded porous structure.
Background technology
TiO
2be a kind of important N-type semiconductor photochemical catalyst, there are many other physicochemical characteristics such as good photocatalytic activity and chemical stability etc., always very active in the research of photocatalysis and energy field.TiO
2first critical process of light-catalyzed reaction mechanism is TiO
2semiconductor absorbs photon to produce electron-hole pair, and semi-conductive band gap is depended in the realization of this step.Anatase and Rutile Type TiO
2band gap be respectively 3.2 and 3.0eV, can only be by the ultraviolet excitation of wavelength <387nm, and the ratio of this part light in solar spectrum only accounts for 5% left and right.At present, TiO
2the problems such as spectral response range is narrow, quantum yield is low are still the key factor that limits it and carry out photocatalytic applications.Therefore, the photochemical catalyst of research and development light absorpting ability in limit of visible spectrum, widens TiO
2to the response range of solar spectrum, improve the utilization rate to solar energy, be TiO
2the developing direction of catalysis material.
In nano-scale, owing to there being quantum confined effect, the performance that transports in electronics and hole is changed, and electronic band structure also can be moved, therefore nanometer can reduce energy gap.In addition, there is the nano material of loose structure, there is larger specific area, can increase the catalytic activity of surface reaction site and adjusting surface atom; Abundant pore structure also helps the transmission of light, and the effectively diffusion of intensified response thing and product molecule reduces resistance to mass tranfer.In recent years, hierarchical porous structure TiO
2the research of constructing become nanometer focus.He Tao etc., based on LPD principle, adopt biological template agent (staphylococcus aureus) and TiO
2particle solution has been prepared the TiO with hierarchical porous structure
2(J.Phys.Chem.C 2014,118,4607), 500nm macropore and the 1.93～3.92nm with random distribution are mesoporous, and preparation technology is comparatively harsh, and the degree of order of product mesopore is not good, and simple nanometer is to TiO
2the adjustment of energy gap is limited.
For further improving TiO
2photochemical catalyst is to the utilization rate of sunshine and improve photocatalytic activity, and researchers adopt that metal ion mixing, semiconductor are compound, noble metal loading or nonmetal doping be to TiO
2photochemical catalyst carries out study on the modification.First the people such as calendar year 2001 Asahi have proposed the anion doped modification TiO such as N, P, C at Science
2photochemical catalyst.As the nonmetal doping modification TiO of third generation photochemical catalyst
2photochemical catalyst, nonmetal doping can be optimized electron cloud structure, causes TiO
2band gap reduces.But with respect to metal ion mixing, nonmetallic ion-doped study on the modification also compares less, mainly contains carbon, nitrogen, sulphur etc.Wherein, TiO
2there is unique advantage with the composite of C: the introducing of carbon not only can be optimized band structure, introduces impurity energy level, reduce energy gap, suppresses TiO under high temperature
2the transformation of crystal formation, its good electric conductivity can also, in time by light induced electron transmission, hinder the compound of light induced electron and hole, and then effectively improve its photocatalysis performance.Titanate esters for Yuan Zhongyong etc. (CN200710056968.6), carbon source (DDA, pyridoxamine) and ethanol (or mixed liquor of ethanol and water) mix, the aging white powder that obtains, and obtain the porous oxidation titanium powder of carbon doping after nitrogen atmosphere heat treatment.There is random hole in this powder, large hole dimension 300～1000nm, and mesoporous size 2.0～24nm, its UV-vis absorption spectrum Einstein shift is to 440nm, and energy gap regulating effect is good.But, with the hierarchical porous structure TiO of duct ordered arrangement, structured size
2compare, this random porous powder of arranging, is unfavorable for effectively improving duct inner transmission matter and product rapid diffusion, is unfavorable for effectively promoting specific area utilization rate and the photocatalytic activity site of material.In addition there is the shortcoming that is difficult for recovery and reuse in powder body material.
Therefore, the advantage of collaborative nonmetal doping and ordered porous nanometer structure, further research and development have the preparation method of the carbon containing titanic oxide material of orderly graded porous structure, the technique that described method relates to is simple, products therefrom can effectively promote its photocatalysis performance, and titania meterial is had to important propelling meaning in the application of photocatalysis field.
Summary of the invention
The object of this invention is to provide a kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, the technique that the method relates to is simple, the carbon containing titanic oxide material making can be widened the response range to sunshine, effectively improves its visible light catalytic performance.
For achieving the above object, technical scheme of the present invention is: a kind of preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, it is characterized in that, taking polystyrene acrylate microballoon emulsion, block copolymer, ethanol and titanium source as raw material, taking filter paper as matrix, adopt self assembly principle, at the described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of filter paper previous step preparation, comprise the following steps:
(1) block copolymer and ethanol are mixed, under stirring condition, add titanium source, add subsequently polystyrene acrylate microballoon emulsion, stir, obtain mixed liquor;
(2) gained mixed liquor is infiltrated to filter paper and transfers in flat bottom evaporating dishes,double, at room temperature evaporation induced self-assembly, then heat-treat through hot polymerization with under inert atmosphere, obtain described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material.
According to such scheme, described polystyrene acrylate microballoon emulsion is that microspheres quality mark is 20% ethanol emulsion, by H
2o, styrene, acrylic acid, ammonium persulfate, under argon gas atmosphere, mix and blend 7～10h makes, in thus obtained microsphere emulsion, microballoon size homogeneous, size is adjustable at 200～400nm.
According to such scheme, described block copolymer is PEO-PPOX-PEO triblock copolymer P123 (PEO
20pPO
70pEO
20) or F127 (PEO
100pPO
70pEO
100), wherein EO is oxirane, PO is expoxy propane.
According to such scheme, described titanium source is titanium tetrachloride or butyl titanate, or the two mixes with arbitrary proportion.
According to such scheme, the mass ratio in described block copolymer, ethanol, polystyrene acrylate (PSA) microballoon emulsion and titanium source is: (0.3～0.5): (20～30): (2～3): 1.
According to such scheme, in above-mentioned steps (1), adding the mixing time after polystyrene acrylate microballoon emulsion is 2h.
According to such scheme, described heat polymerization temperature is 80 DEG C, and hot polymerization temperature retention time is 24～48h.
According to such scheme, the heat treatment temperature step of above-mentioned steps (2) is: under inert atmosphere protection, be warming up to 400～600 DEG C with the speed of 1～3 DEG C/min, insulation 2～4h.
According to such scheme, described inert atmosphere is argon gas or nitrogen.
According to such scheme, the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material making has graded porous structure, has macropore and mesoporous, large hole dimension homogeneous, size is adjustable at 200～400nm, mesoporous being distributed on macropore hole wall, the mesoporous 3～5nm that is of a size of; The specific area of products therefrom is 76～106m
2/ g, phosphorus content is 16～21wt%, is 200～800nm to effective absorbing wavelength scope of sunshine.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the carbon containing titanium dioxide self-supported membrane catalysis material that prepared by the present invention, there is the graded porous structure of ordered arrangement, higher specific area and large pore volume, can promote heterogeneous mass transfer and the enrichment of realization to light in catalytic process, be conducive to electronics and transmit quickly and efficiently, be conducive to effective diffusion of product; Introduce carbon and carry out modification, widen its to visible light-responded scope in, also can promote the separation of photo-generated carrier, the photocatalysis performance of carbon containing titanic oxide material prepared by the present invention is effectively improved.Products therefrom shows the photocatalysis test result of crystal violet, and good absorbing effect in 200～800nm wave-length coverage, compared with P25, significantly improves good stability to the assimilation effect of visible ray.
(2) introducing of carbon of the present invention realizes by the carbon in polystyrene acrylate microballoon emulsion and block copolymer and filter paper carbonization, without adding other specific carbon sources.Polystyrene acrylate microballoon and block copolymer as macropore template and the mesoporous mould material of the described orderly classifying porous material of preparation, also as the required carbon source of reaction, have been simplified the kind of reaction needed raw material respectively.
(3) the present invention, taking filter paper as matrix material, has abandoned the dependence to the conventional matrix material such as silicon chip, steel disc; Under inert atmosphere, after filter paper carbonization, without removing filter paper, directly as the part in products therefrom film, remove the step of removing matrix material from, simplified preparation technology; Taking filter paper as matrix, make products therefrom film there is certain intensity, and utilize the flexibility that infiltrates rear filter paper, can regulate the shape of products therefrom film, obtain the Product Films of the shapes such as sheet, tubular or lamination or structure, adapt to concrete application demand.
(4) the present invention adopts one-step method to prepare orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, the technique relating to is simple, low for equipment requirements, operability is good, for the preparation of high efficiency photocatalyst provides feasible thinking and means, be conducive to promote photocatalysis technology in the application of polluting control field.
Brief description of the drawings
Below in conjunction with accompanying drawing, the invention will be further described, in accompanying drawing:
Fig. 1 is the XRD collection of illustrative plates of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared of embodiment 1.
Fig. 2 is the SEM image of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared of embodiment 1.
Fig. 3 is the nitrogen adsorption isotherm figure of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared of embodiment 1.
Fig. 4 is the graph of pore diameter distribution of the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared of embodiment 1.
Fig. 5 is the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared of embodiment 1 and the UV-Vis DRS spectrogram of P25.
The titanic oxide material that Fig. 6 is the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material prepared of embodiment 1, prepared by embodiment 5 and the photocatalytic degradation crystal violet efficiency chart of P25.
Detailed description of the invention
For making object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
In following examples 1-5, the block copolymer of selecting is PEO-PPOX-PEO triblock copolymer P123 (PEO
20pPO
70pEO
20), EO is oxirane, PO is expoxy propane.
The polystyrene acrylate microballoon emulsion of selecting is that microballoon solid content is the polystyrene acrylate microballoon ethanol emulsion of 20wt%, and microballoon size is about 200nm and 400nm, and preparation method comprises: under room temperature condition, add 120gH in there-necked flask
2o, and pass into argon gas, add successively 10g styrene, 0.5g acrylic acid, be uniformly mixed with the speed of 850～1000r/min; Stir and be warming up to 75 DEG C and keep constant temperature after 0.5h, add 0.2g ammonium persulfate, under the speed of 1000～1500r/min, constant temperature stirs 7h, obtains white polystyrene acrylate microballoon emulsion; Thus obtained microsphere emulsion is carried out after centrifugal, ethanol cleans, and being made into microballoon solid content is the ethanol emulsion (being polystyrene acrylate microballoon emulsion) of 20wt%, and microballoon size homogeneous in gained emulsion is 200nm left and right.In above-mentioned preparation technology, regulating the consumption of ammonium persulfate is 0.02g, and between prolongation constant temperature stirs and protects, to 10h, obtaining particle diameter is the polystyrene acrylate microballoon emulsion of 400nm left and right.
The span of described ammonium persulfate is 0.02g～0.2g, can realize in gained polystyrene acrylate microballoon ethanol emulsion microballoon size adjustable at 200～400nm.
Embodiment 1
A preferred embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, comprises the steps:
0.16g PEO-PPOX-PEO triblock copolymer P123 and 10g ethanol are mixed, under intense agitation, add 0.29g titanium tetrachloride and 0.11g butyl titanate, (microspherulite diameter is about 200nm to add subsequently the 20wt% polystyrene acrylate microballoon ethanol emulsion of the above-mentioned preparation of 1g, for the microspheres quality mark ethanol emulsion that is 20%), at room temperature stir 2h, obtain mixed liquor.Mixed liquor is infiltrated to ashless filter paper and transfer in flat bottom evaporating dishes,double, at room temperature make ethanol volatilization, then put into 80 DEG C of baking ovens and be incubated 48h, under argon gas atmosphere, be warming up to 400 DEG C with the heating rate of 3 DEG C/min again, after insulation 2h, naturally cool to room temperature, the black product of gained is described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, and carbon content is about 17wt%.
Fig. 1 is shown in by the XRD collection of illustrative plates of products therefrom, and as seen from the figure, prepared product principal phase is anatase phase titanium dioxide.SEM image is shown in Fig. 2, has spherical pore in illustrative material, and aperture homogeneous and rule are densely arranged, and size is about 200nm, has less hole on hole wall.Nitrogen adsorption isotherm figure is shown in Fig. 3, and graph of pore diameter distribution is shown in Fig. 4, illustrates in product and has meso-hole structure, known in conjunction with Fig. 2, mesoporous being distributed on macropore hole wall, and mesoporous size concentrates on 3～5nm, and the specific area of product is 91m
2/ g.Analyzed from Fig. 2, Fig. 3 and Fig. 4, products therefrom has ordered big hole, mesoporous graded porous structure.The UV-Vis DRS absorption spectrum of products therefrom is shown in Fig. 5, result shows, compared with commodity titanium dioxide P25, products therefrom shows remarkable assimilation effect between wavelength 380～800nm, in ultraviolet light range, the assimilation effect of (200～380nm) still keeps good, and not occurring remarkable reduction at long wavelength's scope internal absorbance, is absorbance >=1.20,800nm place at wavelength, show that products therefrom is to visible light-responded remarkable.
Get the present embodiment sample 50mg, join in 50mL crystal violet solution (concentration 10mg/L), be placed in camera bellows and stir 60min, adopt subsequently high-pressure sodium lamp (125W, dominant wavelength 365nm) to carry out photocatalytic degradation for experimental light sources.Fig. 6 is presented at after 120min, and the present embodiment product reaches after 93.64%, 160min the clearance of crystal violet, and products therefrom is 99.65% to the clearance of crystal violet, and the clearance of contrast P25 is only 60.13%.
Embodiment 2:
An embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, comprises the steps:
0.16g PEO-PPOX-PEO triblock copolymer P123 and 10g ethanol are mixed, under intense agitation, add 0.4g titanium tetrachloride, add subsequently the 20wt% polystyrene acrylate microballoon ethanol emulsion (microspherulite diameter is about 200nm) of the above-mentioned preparation of 1g, at room temperature stir 2h, obtain mixed liquor.Mixed liquor is infiltrated to ashless filter paper and transfer in flat bottom evaporating dishes,double, at room temperature make ethanol volatilization, then put into 80 DEG C of baking ovens and be incubated 48h, under argon gas atmosphere, be warming up to 400 DEG C with the heating rate of 3 DEG C/min again, after insulation 2h, naturally cool to room temperature, the black product of gained is described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, and carbon content is about 16wt%.
The present embodiment products therefrom shows through the test of SEM and pore-size distribution, and product has macropore, mesoporous graded porous structure, and large hole dimension is about 200nm, the mesoporous 3～5nm that is of a size of.After photocatalytic degradation 160min, 50mg sample is 79.72% to the clearance of 50mL crystal violet solution (concentration 10mg/L).
Embodiment 3:
An embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, comprises the steps:
0.16g PEO-PPOX-PEO triblock copolymer P123 and 10g ethanol are mixed, under intense agitation, add 0.4g butyl titanate, the 20wt% polystyrene acrylate microballoon ethanol emulsion (microspherulite diameter is about 200nm) that adds subsequently the above-mentioned preparation of 1g, at room temperature stirs 2h.Mixed liquor is infiltrated to ashless filter paper and transfer in flat bottom evaporating dishes,double, at room temperature make ethanol volatilization, then put into 80 DEG C of baking ovens and be incubated 48h, under argon gas atmosphere, be warming up to 400 DEG C with the heating rate of 3 DEG C/min again, after insulation 2h, naturally cool to room temperature, the black product of gained is described classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, and carbon content is about 21wt%.
The present embodiment products therefrom shows through the test of SEM and pore-size distribution, and product has macropore, mesoporous graded porous structure, and large hole dimension is about 200nm, the mesoporous 3～5nm that is of a size of.After photocatalytic degradation 160min, 50mg sample is 84.89% to the clearance of 50mL crystal violet solution (concentration 10mg/L).
Embodiment 4
An embodiment in orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material preparation method, comprises the steps:
0.16g PEO-PPOX-PEO triblock copolymer P123 and 10g ethanol are mixed, under intense agitation, add 0.29g titanium tetrachloride and 0.11g butyl titanate, add subsequently the 20wt% polystyrene acrylate microballoon ethanol emulsion (microspherulite diameter is about 400nm) of the above-mentioned preparation of 1g, at room temperature stir 2h, obtain mixed liquor.Mixed liquor is infiltrated to ashless filter paper and transfer in flat bottom evaporating dishes,double, at room temperature make ethanol volatilization, then put into 80 DEG C of baking ovens and be incubated 48h, under argon gas atmosphere, be warming up to 400 DEG C with the heating rate of 3 DEG C/min again, after insulation 2h, naturally cool to room temperature, the black product of gained is described classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, and carbon content is about 20wt%.
The present embodiment gained shows to have macropore, mesoporous graded porous structure through SEM and pore-size distribution test, and large hole dimension is about 400nm, the mesoporous 3～5nm that is of a size of.After photocatalytic degradation 160min, 50mg sample is 72.12% to the clearance of 50mL crystal violet solution (concentration 10mg/L).
Comparative example
Orderly classifying porous titanium dioxide self-supported membrane catalysis material preparation method's a contrast embodiment, preparation process is with embodiment 1, difference is that heat-treat condition is: under air atmosphere, be warming up to 400 DEG C, insulation 2h, the titanic oxide material that products therefrom is carbon-free graded porous structure.SEM and pore-size distribution are tested and are shown, product has macropore, meso-hole structure, and large hole dimension is about 200nm, the mesoporous 3～5nm that is of a size of, and specific area is 106m
2/ g.After photocatalytic degradation 160min, 50mg sample is 76.04% to the clearance of 50mL crystal violet solution (concentration 10mg/L), sees Fig. 6.Result shows, carbon-free graded porous structure titanium dioxide, although there is good pore passage structure similarly to Example 1, but its photocatalysis effect in visible-range significantly reduces, further illustrate orderly classifying porous carbon containing titanium dioxide self-supported membrane material in embodiment 1 and there is good photocatalysis performance.
Bound value, the interval value of each raw material that invention relates to can be realized the present invention, and lower limit value and the interval value of technological parameter of the present invention (as temperature, time etc.) can be realized the present invention, do not enumerate embodiment at this.
Claims (9)
1. the preparation method of an orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material, it is characterized in that, taking polystyrene acrylate microballoon emulsion, block copolymer, ethanol and titanium source as raw material, taking filter paper as matrix, adopt self assembly principle, the described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material of one step preparation, comprises the following steps:
(1) block copolymer and ethanol are mixed, under stirring condition, add titanium source, add subsequently polystyrene acrylate microballoon emulsion, stir, obtain mixed liquor;
(2) gained mixed liquor is infiltrated to filter paper and transfers in flat bottom evaporating dishes,double, at room temperature evaporation induced self-assembly, then heat-treat through hot polymerization with under inert atmosphere, obtain described orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material.
2. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, is characterized in that, described polystyrene acrylate microballoon emulsion is that microspheres quality mark is 20% ethanol emulsion, by H
2o, styrene, acrylic acid, ammonium persulfate, under argon gas atmosphere, mix and blend 7～10h makes, in thus obtained microsphere emulsion, microballoon size homogeneous, size is adjustable at 200～400nm.
3. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, is characterized in that, described block copolymer is PEO-PPOX-PEO triblock copolymer PEO
20pPO
70pEO
20or PEO
100pPO
70pEO
100, wherein EO is oxirane, PO is expoxy propane.
4. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, is characterized in that, described titanium source is titanium tetrachloride or butyl titanate, or the two mixes with arbitrary proportion.
5. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, it is characterized in that, the mass ratio in described block copolymer, ethanol, polystyrene acrylate microballoon emulsion and titanium source is: (0.3～0.5): (20～30): (2～3): 1.
6. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, is characterized in that, in above-mentioned steps (1), adding the mixing time after polystyrene acrylate microballoon emulsion is 2h.
7. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, is characterized in that, described heat polymerization temperature is 80 DEG C, and hot polymerization temperature retention time is 24～48h.
8. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, it is characterized in that, the heat treatment temperature step of above-mentioned steps (2) is: be warming up to 400～600 DEG C with the speed of 1～3 DEG C/min, insulation 2～4h.
9. the preparation method of orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material according to claim 1, it is characterized in that, the orderly classifying porous carbon containing titanium dioxide self-supported membrane catalysis material making has graded porous structure, there is macropore and mesoporous, large hole dimension homogeneous, size is adjustable at 200～400nm, mesoporous being distributed on macropore hole wall, the mesoporous 3～5nm that is of a size of; The specific area of products therefrom is 76～106m
2/ g, phosphorus content is 16～21wt%, is 200～800nm to the effective uptake region of sunshine.
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| CN104549204A (en) * | 2014-12-23 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN105060295A (en) * | 2015-08-06 | 2015-11-18 | 南京大学 | Preparation method of TiC material with meso structure |
| CN109999800A (en) * | 2019-05-09 | 2019-07-12 | 金陵科技学院 | A kind of ordered structure Ag/TiO2Nanocomposite and preparation method thereof |
| US11724232B2 (en) * | 2015-11-30 | 2023-08-15 | Cornell University | Porous resin structures |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549204A (en) * | 2014-12-23 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN105060295A (en) * | 2015-08-06 | 2015-11-18 | 南京大学 | Preparation method of TiC material with meso structure |
| US11724232B2 (en) * | 2015-11-30 | 2023-08-15 | Cornell University | Porous resin structures |
| CN109999800A (en) * | 2019-05-09 | 2019-07-12 | 金陵科技学院 | A kind of ordered structure Ag/TiO2Nanocomposite and preparation method thereof |
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