CN101371981A - Nano titanic oxide photocatalyst of high activity with phosphoric acid surface modification as well as synthetic method - Google Patents
Nano titanic oxide photocatalyst of high activity with phosphoric acid surface modification as well as synthetic method Download PDFInfo
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- CN101371981A CN101371981A CNA2007100726865A CN200710072686A CN101371981A CN 101371981 A CN101371981 A CN 101371981A CN A2007100726865 A CNA2007100726865 A CN A2007100726865A CN 200710072686 A CN200710072686 A CN 200710072686A CN 101371981 A CN101371981 A CN 101371981A
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Abstract
The invention relates to a phosphate surface modified nanometer titanium dioxide high active photocatalyst and a synthetic method. Nanometer titanium dioxide is an important inorganic semiconductor functional material. Surface modification is a modification method which is adopted frequently. However, a surface modification report of the mesoporous silica on the nanometer titanium dioxide is not seen. Under intensely mixing condition, uniform solution of tetra-n-butyl and absolute ethanol is slowly splashed into a mixed system which comprises absolute ethanol, secondary distilled water and concentrated nitric acid and then is stirred to obtain light yellow titanium dioxide sol. Then, the sol is moved to a high pressure reaction vessel to be sealed, cooled hydrothermally to room temperature. Supernatant is thrown away to obtain light yellow paste-pattern nanometer titanium dioxide which is then moved into a beaker. A certain amount of phosphoric acid solution is added in the beaker to be stirred and heated to certain temperature until the solution is viscous. Then drying, grinding and roasting are implemented. Phosphate surface modified nanometer anatase titanium dioxide shows good photo catalytic activity which is even higher than P-25 titanium dioxide of international commodity. The invention relates to a nanometer material.
Description
Technical field:
The present invention relates to the nano titanium oxide high-activity photocatalyst and the synthetic method of phosphoric acid surface modification,
Background technology:
Nano titanium oxide is a kind of important inorganic semiconductor functional material, and the performance that has unique aspects such as catalysis, electricity, optics and photochemistry owing to it causes that people pay close attention to widely.Nano titanium oxide is considered to one of more satisfactory photochemical catalyst with its stable chemical property, strong oxidation-reduction quality, anti-photoetch, nontoxic, low cost and other advantages.The optically catalytic TiO 2 oxidation technology is expected to become the pollutant Prevention Technique of efficient, the energy-saving and environmental protection of a new generation.But cause the utilization rate of sunshine lowlyer because of its band-gap energy (3.2eV) is higher, simultaneously also have the lower problem of self quantum efficiency, thereby limited the practicability of optically catalytic TiO 2 oxidation technology.In order further to improve the photocatalysis performance of titanium dioxide, finishing often is adopted a kind of method.But do not see the report that adopts phosphoric acid nano titanium oxide to be carried out finishing as yet.According to newest research results as can be known, the titanium dioxide anatase is to be begun by the anatase particle internal interface of reuniting to the transformation mutually of rutile, along with heat treatment temperature raises, gradually internally to the outside expansion, until the surface.Can infer in generation to change the initial stage mutually that reunion of anatase crystallite or sintering are not remarkable, begin to take shape particle inside simultaneously and contained a small amount of rutile and the outside shell structurre that is mainly the anatase phase.The optical absorption that a small amount of rutile can not influence titanium dioxide is mutually contained in particle inside, separate but help surperficial anatase generation photogenerated charge because energy level mates by the formed homogeneity out-phase knot of two kinds of crystalline phases of anatase and rutile, this is favourable to photocatalysis.Therefore, by improving the nano titanium oxide crystal phase transition temperature and being the mixed crystal phase that contains a small amount of rutile, the design of nano titanium oxide that may realize having design features such as particle size is tiny, specific area is big, degree of crystallinity height is synthetic, and then obtains nano titanium oxide with high light catalytic activity.The finishing of phosphoric acid has not only changed the surface nature of nanometer anatase titania, and improved it largely by the transition temperature of anatase to the rutile phase, and then improved the photocatalytic activity of nanometer anatase titania significantly, even surpass international commodity P-25 type titanium dioxide.Therefore, adopt proper method to realize the finishing of phosphoric acid, can further improve its degree of crystallinity, finally reach the purpose of improving the material photoelectric properties nanometer anatase titania.In the present invention, utilize phosphoric acid surface modification to realize effective improvement first to the nano titanium dioxide photocatalyst performance.
Goal of the invention:
The nano titanium oxide high-activity photocatalyst and the synthetic method that the purpose of this invention is to provide a kind of synthetic phosphoric acid surface modification, attempt to change the surface nature of nanometer anatase titania by phosphoric acid surface modification, and improve it largely by the transition temperature of anatase to the rutile phase, and then improve the photocatalytic activity of nanometer anatase titania significantly, even surpass the photocatalytic activity of international commodity P-25 type titanium dioxide.Constructed novel semi-conductor nano material is used to improve the performance of material at aspects such as photocatalysis.
Above-mentioned purpose realizes by following technical scheme:
The synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification, even mixed liquor speed with 30 of per minutes under intense agitation of butyl titanate and absolute ethyl alcohol is splashed into lentamente by absolute ethyl alcohol, in the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed, continue to stir 2 hours, obtain flaxen TiO 2 sol, be that a unit transfers in the teflon-lined autoclave with 30mL then with TiO 2 sol, sealing, hydro-thermal is 6 hours under 160 ℃ condition, be cooled to room temperature, outwell supernatant, obtain flaxen paste nano titanium oxide, transfer to the paste nano titanium oxide in the beaker then and pour phosphate aqueous solution into, stir, heating is stirred until thickness, dry, grind, roasting finally obtains the nano titanium dioxide powder that phosphoric acid is modified.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, the even mixed liquor of described butyl titanate and absolute ethyl alcohol is under the room temperature continuous stirring condition, the 20mL butyl titanate is joined in the 20mL absolute ethyl alcohol lentamente, continue to stir 30 minutes, obtain even mixed liquor, described absolute ethyl alcohol, the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed is under the room temperature continuous stirring condition, the 80mL absolute ethyl alcohol is joined in the 20mL redistilled water, the red fuming nitric acid (RFNA) that adds 4mL70% again, continue to stir 30 minutes, obtain mixed system.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, it is described that to transfer to slurry in the beaker and pour phosphate aqueous solution into be that the paste nano titanium oxide in each autoclave is transferred in the beaker of 100mL, then add the redistilled water of 1mL or the serial phosphate aqueous solution that concentration is 0.05-1.2mol/L, stirred 1 hour, described heating is to be raised to 80 ℃ with 10 ℃/min from room temperature, continuous stirring under constant temperature, evaporating solvent is until thickness.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, described drying are in drying box under 100 ℃ of temperature dry 6 hours.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, described roasting is to heat up under heating rate is the condition of 10 ℃/min, roasting in Muffle furnace, sintering temperature are respectively 700 ℃, 800 ℃ and 900 ℃, and roasting time is 2 hours.Finally obtain through the nano titanium oxide of heat treatments at different or the nano titanium dioxide powder of different amount phosphoric acid modification.
The nano titanium oxide high-activity photocatalyst product of the phosphoric acid surface modification that said method is made.
This technical scheme has following beneficial effect:
1. the present invention has realized the synthetic of high-activity nano titanium dioxide photochemical catalyst by phosphoric acid surface modification.Phosphoric acid surface modification has not only changed the surface texture of nanometer anatase titania, and has improved its dispersiveness, has especially suppressed the reunion of nano-anatase crystallite effectively in heat treatment process, and then has improved phase transition temperature and degree of crystallinity.Finally realized having design feature and nano titanium dioxide photocatalysts that show the high light catalytic activity such as small particle size, bigger serface, high-crystallinity, even surpassed P-25 type titanium dioxide.
The present invention by colloidal sol-water-heat process obtained that granularity is uniformly dispersed, size is about 6nm, ball-type, dispersiveness titanium dioxide nano-particle preferably, it has shown photocatalytic activity preferably, and for further modification and preparation titanium dioxide nanocrystalline light anode material etc. provide advantage.
3, the technology of the nano titanium oxide of synthesis of nano titanium dioxide of the present invention and phosphoric acid surface modification is simple, cost is low, reaction condition is gentle, easy to operate, be easy to realize industrialization.
4, the present invention has confirmed to utilize the method for phosphoric acid surface modification can improve the performance of nano titanium dioxide photocatalyst effectively, this will for design synthetic other efficiently nanometer semiconductor structure functional material etc. new thinking and method is provided.
5, the property representation of the nano titanium oxide of nano titanium oxide that is synthesized among the present invention and phosphoric acid surface modification mainly contains: X-ray diffraction analysis (being used for analyzing phase structure and phase composition and assessment nano microcrystalline size), transmission electron microscope and photocatalysis performance test (assessment photocatalytic activity)
Description of drawings:
Accompanying drawing 2 is the TEM photos without heat treated nano titanium oxide.From scheming as seen, the TiO 2 particles that is obtained is a ball-type, and granularity is uniformly dispersed, and is better dispersed.Particle size is about 6nm, and this is consistent with the crystallite dimension that the Scherrer formula is calculated, and has illustrated that also TiO 2 particles is easy to disperse.
Accompanying drawing 3 is the XRD diffraction patterns through the nano titanium dioxide powder of 700 ℃ of heat treated different amount phosphoric acid surface modifications.As seen from the figure, the titanium dioxide of modifying without phosphoric acid under 700 ℃ of heat-treat conditions is based on rutile mutually, and under the lower situation of finishing phosphoric acid amount (＜1%), but has only a small amount of rutile to occur, and increases phosphoric acid amount again, almost all is anatase.Illustrated that the finishing of phosphoric acid can improve the phase transition temperature of nanometer anatase titania significantly.
Accompanying drawing 4 is the XRD diffraction patterns through the nano titanium dioxide powder of 800 ℃ of heat treated different amount phosphoric acid surface modifications.As seen from the figure, the titanium dioxide of modifying without phosphoric acid under 800 ℃ of heat-treat conditions is the rutile phase all almost, and under the lower situation of finishing phosphoric acid amount (＜1%), but has only a small amount of rutile to occur, increasing phosphoric acid amount again, almost all is anatase.Illustrated that the finishing of phosphoric acid can improve the phase transition temperature of nanometer anatase titania significantly.
Accompanying drawing 5 is the XRD diffraction patterns through the nano titanium dioxide powder of 900 ℃ of heat treated different amount phosphoric acid surface modifications.As seen from the figure, under 900 ℃ of heat-treat conditions, even the phosphoric acid amount of finishing (12%) is bigger, a large amount of rutile phases has but appearred in resulting titanium dioxide, and with a spot of anatase.The analysis of comprehensive front as can be known, the finishing of an amount of phosphoric acid can improve the phase transition temperature of nanometer anatase titania significantly.For example the phosphoric acid amount of finishing is 1% o'clock, and under 800 ℃ of heat-treat conditions, titanium dioxide sample is based on anatase, and contains a small amount of rutile phase.It is compared with the titanium dioxide sample with mixed crystal phase composition of 550 ℃ of heat treated unmodifieds, and degree of crystallinity has improved significantly.
Table one has reflected the nanometer two of heat treatments at different in photocatalytic degradation rhodamine B aqueous solution process The photocatalytic activity of titanium oxide. In the light-catalyzed reaction process, be take the 150W xenon lamp as light source, use 0.1g Prepared titanium dioxide optical catalyst and 40mL concentration are the rhodamine B water solution system of 20mg/L, Illumination 45 minutes utilizes the concentration that detects rhodamine B about the visible features absorption value of 553nm. From Subordinate list one as seen, when heat treatment temperature was 550 ℃, the nano titanium dioxide photocatalysis activity was the highest, this Be to contain a small amount of Rutile Type and relevant take anatase as main mixed crystal phase composition with it. Contain a small amount of rutile Mixed crystal be conducive to mutually photogenerated charge and separate, to such an extent as to photocatalytic activity is higher.
The photocatalytic activity of the table one rhodamine B aqueous solution on the nano titanium oxide of heat treatments at different
| Sample | T-untreated | T-450 | T-550 | T-650 |
| Degradation rate (%) | 18.5 | 24.6 | 33.2 | 21.3 |
T-X:T represents titanium dioxide; X represents heat treatment temperature.
Table two is nano titanium oxides that the rhodamine B aqueous solution is modified at 700 ℃ of heat treated different amount phosphoric acid Photocatalytic activity on the particle.
The photocatalytic activity of the table two rhodamine B aqueous solution on the nano titanium oxide that 700 ℃ of heat treated different amount phosphoric acid are modified
| Sample | T-550 | PT-0.5-700 | PT-1-700 | PT-3-700 | P-25 |
| Degradation rate (%) | 33.2 | 68.7 | 77.8 | 71.7 | 76.0 |
PT-X-Y:T represents titanium dioxide; PT represents the titanium dioxide that phosphoric acid is modified; X represents the percentage composition that phosphoric acid is modified; Y represents Heat treatment temperature; P-25 represents international commodity P-25 type titanium dioxide.
Table three is nano-titania particles that the rhodamine B aqueous solution is modified at 800 ℃ of heat treated different amount phosphoric acid On photocatalytic activity. From table two and table three as can be known, modify through the heat treated an amount of phosphoric acid of higher temperature The photocatalytic activity of nano titanium oxide will be higher than through 550 ℃ of heat treated nano titanium oxides, even super Cross the photocatalytic activity of P-25 type titanium dioxide.
The photocatalytic activity of the table three rhodamine B aqueous solution on the nano titanium oxide that 800 ℃ of heat treated different amount phosphoric acid are modified
| Sample | PT-0.5-800 | PT-1-800 | PT-3-800 |
| Degradation rate (%) | 54.4 | 77.0 | 73.3 |
PT-X-Y:PT represents the titanium dioxide that phosphoric acid is modified; X represents the percentage composition that phosphoric acid is modified; Y represents heat treatment temperature.
In sum, through the titanium dioxide of 700 ℃ or 800 ℃ heat treated an amount of phosphoric acid surface modifications Photocatalytic activity is higher than the photocatalytic activity through 550 ℃ of heat treated titanium dioxide of unmodified significantly, even Surpassed P-25 type titanium dioxide. XRD characterization result according to bibliographical information and front can infer, Through the raising of the photocatalytic activity of the titanium dioxide of an amount of phosphoric acid surface modification and phosphoric acid modify suppress mutually transformation and It is relevant further to improve anatase phase titanium dioxide degree of crystallinity. Guaranteeing than small particle size and bigger serface Condition under, degree of crystallinity improves and to be conducive to again photogenerated charge and to separate, to such an extent as to photocatalysis performance is obviously changed Kind. Therefore, the present invention has realized synthesis of nano titanium dioxide high activity light preferably by phosphoric acid surface modification The purpose of catalyst.
The specific embodiment of the present invention:
Embodiment 1:
The synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification, even mixed liquor speed with 30 of per minutes under intense agitation of butyl titanate and absolute ethyl alcohol is splashed into lentamente by absolute ethyl alcohol, in the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed, continue to stir 2 hours, obtain flaxen TiO 2 sol, be that a unit transfers in the teflon-lined autoclave with 30mL then with TiO 2 sol, sealing, hydro-thermal is 6 hours under 160 ℃ condition, be cooled to room temperature, outwell supernatant, obtain flaxen paste nano titanium oxide, transfer to the paste nano titanium oxide in the beaker then and pour phosphate aqueous solution into, stir, heating is stirred until thickness, dry, grind, roasting finally obtains the nano titanium dioxide powder that phosphoric acid is modified.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, the even mixed liquor of described butyl titanate and absolute ethyl alcohol is under the room temperature continuous stirring condition, the 20mL butyl titanate is joined in the 20mL absolute ethyl alcohol lentamente, continue to stir 30 minutes, obtain even mixed liquor, described absolute ethyl alcohol, the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed is under the room temperature continuous stirring condition, the 80mL absolute ethyl alcohol is joined in the 20mL redistilled water, the red fuming nitric acid (RFNA) that adds 4mL70% again, continue to stir 30 minutes, obtain mixed system.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, it is described that to transfer to slurry in the beaker and pour phosphate aqueous solution into be that the paste nano titanium oxide in each autoclave is transferred in the beaker of 100mL, then add the redistilled water of 1mL or the serial phosphate aqueous solution that concentration is 0.05-1.2mol/L, stirred 1 hour, described heating is to be raised to 80 ℃ with 10 ℃/min from room temperature, continuous stirring under constant temperature, evaporating solvent is until thickness.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, described drying are in drying box under 100 ℃ of temperature dry 6 hours.
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, described roasting is to heat up under heating rate is the condition of 10 ℃/min, roasting in Muffle furnace, sintering temperature are respectively 700 ℃, 800 ℃ and 900 ℃, and roasting time is 2 hours.Finally obtain through the nano titanium oxide of heat treatments at different or the nano titanium dioxide powder of different amount phosphoric acid modification.
The product that obtains in order to last method is protected by the present invention.
Embodiment 2:
The synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification, even mixed liquor speed with 30 of per minutes under intense agitation of butyl titanate and absolute ethyl alcohol is splashed into lentamente by absolute ethyl alcohol, in the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed, continue to stir 2 hours, obtain flaxen TiO 2 sol, be that a unit transfers in the teflon-lined autoclave with 30mL then with TiO 2 sol, sealing, hydro-thermal is 6 hours under 160 ℃ condition, be cooled to room temperature, outwell supernatant, obtain flaxen paste nano titanium oxide, transfer to the paste nano titanium oxide in the beaker then and pour phosphate aqueous solution into, stir, heating is stirred until thickness, dry, grind, roasting finally obtains the nano titanium dioxide powder that phosphoric acid is modified.
Embodiment 3:
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, the even mixed liquor of described butyl titanate and absolute ethyl alcohol is under the room temperature continuous stirring condition, the 20mL butyl titanate is joined in the 20mL absolute ethyl alcohol lentamente, continue to stir 30 minutes, obtain even mixed liquor, described absolute ethyl alcohol, the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed is under the room temperature continuous stirring condition, the 80mL absolute ethyl alcohol is joined in the 20mL redistilled water, the red fuming nitric acid (RFNA) that adds 4mL 70% again, continue to stir 30 minutes, obtain mixed system.
Embodiment 4:
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, it is described that to transfer to slurry in the beaker and pour phosphate aqueous solution into be that the paste nano titanium oxide in each autoclave is transferred in the beaker of 100mL, then add the redistilled water of 1mL or the serial phosphate aqueous solution that concentration is 0.05-1.2mol/L, stirred 1 hour, described heating is to be raised to 80 ℃ with 10 ℃/min from room temperature, continuous stirring under constant temperature, evaporating solvent is until thickness.
Embodiment 5:
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, described drying are in drying box under 100 ℃ of temperature dry 6 hours.
Embodiment 6:
The synthetic method of the nano titanium oxide high-activity photocatalyst of described phosphoric acid surface modification, described roasting is to heat up under heating rate is the condition of 10 ℃/min, roasting in Muffle furnace, sintering temperature are respectively 700 ℃, 800 ℃ and 900 ℃, and roasting time is 2 hours.Finally obtain through the nano titanium oxide of heat treatments at different or the nano titanium dioxide powder of different amount phosphoric acid modification.
Embodiment 7:
The product that obtains in order to last method is protected by the present invention.
Claims (9)
1. the synthetic method of the nano titanium oxide high-activity photocatalyst of a phosphoric acid surface modification, it is characterized in that: even mixed liquor speed with 30 of per minutes under intense agitation of butyl titanate and absolute ethyl alcohol is splashed into lentamente by absolute ethyl alcohol, in the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed, continue to stir 2 hours, obtain flaxen TiO 2 sol, be that a unit transfers in the teflon-lined autoclave with 30mL then with TiO 2 sol, sealing, hydro-thermal is 6 hours under 160 ℃ condition, be cooled to room temperature, outwell supernatant, obtain flaxen paste nano titanium oxide, transfer to the paste nano titanium oxide in the beaker then and pour phosphate aqueous solution into, stir, heating is stirred until thickness, dry, grind, roasting finally obtains the nano titanium dioxide powder of phosphoric acid surface modification.
2. the synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification according to claim 1, it is characterized in that: the even mixed liquor of described butyl titanate and absolute ethyl alcohol is under the room temperature continuous stirring condition, the 20mL butyl titanate is joined in the 20mL absolute ethyl alcohol lentamente, continue to stir 30 minutes, obtain even mixed liquor, described absolute ethyl alcohol, the mixed system that redistilled water and red fuming nitric acid (RFNA) are formed is under the room temperature continuous stirring condition, the 80mL absolute ethyl alcohol is joined in the 20mL redistilled water, again at the red fuming nitric acid (RFNA) that adds 4mL 70%, continue to stir 30 minutes, obtain mixed system.
3. the synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification according to claim 1 and 2, it is characterized in that: described to transfer to slurry in the beaker and pour phosphate aqueous solution into be that the paste nano titanium oxide in each autoclave is transferred in the beaker of 100mL, then add the redistilled water of 1mL or the serial phosphate aqueous solution that concentration is 0.05-1.2mol/L, stirred 1 hour, described heating is to be raised to 80 ℃ with 10 ℃/min from room temperature, continuous stirring under constant temperature, evaporating solvent is until thickness.
4. the synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification according to claim 1 and 2 is characterized in that: described drying is in drying box under 100 ℃ of temperature dry 6 hours.
5. the synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification according to claim 3 is characterized in that: described drying is in drying box under 100 ℃ of temperature dry 6 hours.
6. according to the synthetic method of the nano titanium oxide high-activity photocatalyst of claim 1 or 2 or 5 described phosphoric acid surface modifications, it is characterized in that: described roasting is to heat up under heating rate is the condition of 10 ℃/min, roasting in Muffle furnace, sintering temperature is respectively 700 ℃, 800 ℃ and 900 ℃, and roasting time is 2 hours.Finally obtain through the nano titanium oxide of heat treatments at different or the nano titanium dioxide powder of different amount phosphoric acid modification.
7. the synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification according to claim 3, it is characterized in that: described roasting, be under heating rate is the condition of 10 ℃/min, to heat up, roasting in Muffle furnace, sintering temperature is respectively 700 ℃, 800 ℃ and 900 ℃, and roasting time is 2 hours.Finally obtain through the nano titanium oxide of heat treatments at different or the nano titanium dioxide powder of different amount phosphoric acid modification.
8. the synthetic method of the nano titanium oxide high-activity photocatalyst of phosphoric acid surface modification according to claim 4, it is characterized in that: described roasting, be under heating rate is the condition of 10 ℃/min, to heat up, roasting in Muffle furnace, sintering temperature is respectively 700 ℃, 800 ℃ and 900 ℃, and roasting time is 2 hours.Finally obtain through the nano titanium oxide of heat treatments at different or the nano titanium dioxide powder of different amount phosphoric acid modification.
9. the nano titanium oxide high-activity photocatalyst product of the phosphoric acid surface modification made of a said method.
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| CN109360979B (en) * | 2018-10-17 | 2021-07-27 | 福建师范大学 | Phosphate radical modified porous titanium dioxide and application thereof in sodium ion battery |
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| CN113078266A (en) * | 2021-03-18 | 2021-07-06 | 中北大学 | Polyacid-modified titanium dioxide nano material and preparation method and application thereof |
| CN113078266B (en) * | 2021-03-18 | 2022-12-27 | 中北大学 | Polyacid-modified titanium dioxide nano material and preparation method and application thereof |
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