CN102380366B - Bismuth and silicon doped nano titanium dioxide photocatalyst, preparation and application thereof - Google Patents
Bismuth and silicon doped nano titanium dioxide photocatalyst, preparation and application thereof Download PDFInfo
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- CN102380366B CN102380366B CN201110274965.6A CN201110274965A CN102380366B CN 102380366 B CN102380366 B CN 102380366B CN 201110274965 A CN201110274965 A CN 201110274965A CN 102380366 B CN102380366 B CN 102380366B
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Abstract
The invention belongs to the nano titanium dioxide catalyst technical field, concretely relates to a bismuth and silicon doped nano titanium dioxide photocatalyst, its preparation and its application. The doping amount of bismuth in the catalyst by mole fraction is 0.2-1.1%, the doping amount of silicon is 4.8-15.6%. The bismuth and silicon doped nano titanium dioxide photocatalyst has the advantages of pure crystalline phase, high specific surface, multiple surface acidity points, visible light response and organic pollutant adsorption. The catalyst of the invention can be rapidly degraded by using visible light and sunshine, so that the catalyst keeps high visible photodegradation efficiency and high photocatalytic activity.
Description
Technical field
The invention belongs to the nano titanic oxide catalyst technical field, be specifically related to a kind of bismuth, silicon coblended nano titanium dioxide photocatalyst and preparation thereof, application.
Background technology
Chlorophenols compound is widely used in timber preservative, antirust agent, bactericide and herbicide etc., carry out a biological disposal upon in addition in the tail water of municipal sewage and industrial wastewater and also contain chlorophenols compound, be the very big and widely distributed environmental contaminants of a class toxicity, and chlorophenol can produce at the metabolic response of occurring in nature many chloros dioxin that toxicity is larger.The country such as the U.S., China has listed it in the priority pollutant list.
What in the method for current processing chlorophenol pollutant, use was more is photocatalytic method.Titanium dioxide has stable chemical nature, the advantage such as cheap and easy to get, nontoxic as photochemical catalyst, can produce the hydroxyl radical free radical with strong oxidability under the illumination effect, finally can make organic pollution be completely oxidized to CO
2, H
2o and other inorganic ions, can carry out advanced treating to the organic pollution in waste water.But due to the band-gap energy of titanium dioxide large (3.2 eV), can only under UV-irradiation, could cause light-catalyzed reaction, and the ultraviolet light energy only accounts for the 3%-5% of solar energy, the recombination rate of photo-generated carrier is high in addition, and photocatalysis efficiency is lower.These shortcomings have seriously restricted the application in practice of optically catalytic TiO 2 technology.In order to take full advantage of visible ray or sunshine, titanium dioxide optical catalyst is carried out to modification, make it absorb visible ray and improve the major subjects that its photocatalytic activity is still this field face.It is compound etc. that at present the method for modifying of titanium dioxide mainly contains noble metal loading, metal ion mixing, nonmetal doping, surface sensitizing, semiconductor.
Common transition metal or rare earth ion in metallic ion-doping modification.It is generally acknowledged, transition metal ions is introduced to TiO
2in lattice, can introduce impurity energy level and defect level in its forbidden band band gap, make the photon that energy is less can excite electronics and the hole of catching on doped energy-band, the TiO after doping
2being excited institute's energy requirement diminishes, and its spectral response range can be expanded to visible region to a certain extent.The rare earth ion doping generally can cause TiO
2the expansion of lattice, the lattice dilatation meeting of appropriateness causes more oxygen defect, and becomes the trap of catching light induced electron, greatly strengthens effective separation in light induced electron-hole, thereby improves its photocatalysis performance.
Because the atomic radius of bismuth is 103pm, the atomic radius of titanium is 61pm, and in preparing the titania-doped process of bismuth ion, the trivalent bismuth ion can not enter TiO
2lattice in, but with bismuth oxide (Bi
2o
3) form be scattered in equably TiO
2the surface of nano particle.Bi
2o
3energy gap be 2.85eV, can be greater than by wavelength the excited by visible light of 400 nm, itself be also a kind of visible light catalyst of very potential degradation of contaminant.Yet, use separately Bi
2o
3there are two large defects as photochemical catalyst: the one, light induced electron and hole are easily compound, and photo-quantum efficiency is low; The 2nd, Bi
2o
3unstable in course of reaction, may be by Bi
2o
3be transformed into bismuthyl carbonate (Bi
2o
2) CO
3.
For the titania nanoparticles of bismuth ion doping, the trivalent bismuth is mainly with Bi
2o
3form be scattered in equably TiO
2the surface of nano particle.Under the irradiation of visible ray, Bi
2o
3absorb the visible ray generation light induced electron-hole pair that is excited, due to Bi
2o
3the valence band band edge compare TiO
2low, photohole can be from Bi
2o
3valence band bottom transfer to TiO
2valence band, and then the more hole generation hydroxyl radical free radical that is hunted down, this process is feasible on thermodynamics, at modified catalyst surface Bi
2o
3with TiO
2form the hetero-junctions of surperficial decentralized between nano particle.The formation of this surface micro-structure, both made photochemical catalyst have visible light activity, significantly strengthened again the right separation in light induced electron-hole, improved TiO
2the quantum efficiency of photochemical catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of bismuth, silicon coblended nano titanium dioxide photocatalyst and preparation thereof, application, this bismuth, silicon coblended nano titanium dioxide photocatalyst can be realized photocatalysis under the visible ray condition.
The present invention is by the following technical solutions:
Bismuth, silicon coblended nano titanium dioxide photocatalyst, it is characterized in that: in molar fraction, the doping of bismuth is 0.2 ~ 1.1 %, and the doping of silicon is 4.8 ~ 15.6 %.
The preparation method of bismuth, silicon coblended nano titanium dioxide photocatalyst comprises the following steps:
The adulterate ethanol solution of presoma and the ethanol solution of silicon doping presoma of bismuth added in reactor, and adjusting pH with nitric acid is 1-3, stirs evenly; Then stir the lower ethanol solution that drips the titanium alkoxide, stirring at room is hydrolyzed in 8 ~ 10 hours, obtains monodispersed TiO 2 sol; The TiO 2 sol obtained is dried and within 6 ~ 9 hours, obtained xerogel at 80 ~ 100 ℃; Calcine under 400 ~ 800 ℃ 1 ~ 3 hour after will the gained xerogel grinding, obtain bismuth, silicon coblended nano titanium dioxide photocatalyst.
The mol ratio of bismuth and titanium is 0.005:1 ~ 0.1:1, and the mol ratio of silicon and titanium is 0.05:1 ~ 1:1.
The concentration of the ethanol solution of bismuth doping presoma is 0.01 ~ 0.05 mol/L, and the concentration of the ethanol solution of silicon doping presoma is 0.1 ~ 0.5 mol/L, and the concentration of the ethanol solution of titanium alkoxide is 0.5 ~ 2 mol/L.
Described titanium alkoxide is butyl titanate or isopropyl titanate; Described bismuth doping presoma is bismuth nitrate, bismuth chloride or bismuth acetate; Described silicon doping presoma is ethyl orthosilicate or sodium metasilicate.
Bismuth, the silicon coblended application of nano titanium dioxide photocatalyst aspect the degrading chlorophenol pollutant.
Bismuth of the present invention, silicon coblended nano titanium dioxide photocatalyst have the performance that crystalline phase is pure, specific surface is high, surface acidity point is many, visible light-responded, average grain diameter is between 10.6 ~ 24.1 nm, adopt bismuth, silicon doped nano titanium dioxide simultaneously, make bismuth, silicon coblended nano titanium dioxide photocatalyst under the irradiation of visible ray, catalytic oxidation to occur, generate harmless CO
2, H
2o, Cl
-deng product, and, after mixing silicon, the specific area of titanium dioxide and chemical composition all can change, and silicon can enter TiO
2the body phase, Si
4+can replace Ti
4+position, stop TiO
2grain growth, particle agglomeration and crystal transition, enlarge markedly the specific area of catalyst, improve its adsorption capacity to organic pollution, make more pollutant constantly be adsorbed on catalyst surface, utilize again visible ray, sunshine to decompose very soon simultaneously, thereby make catalyst remain efficient Visible Light Induced Photocatalytic efficiency, in addition silicon mix the surface acidity that also can significantly strengthen catalyst, and then improve TiO
2photocatalytic activity.
It is initiation material that titanium alkoxide, bismuth salt and silicon precursor are take in the present invention, first bismuth salt and silicon precursor are dissolved in ethanol, and add a certain amount of salpeter solution to form mixed solution, then by the ethanol solution of titanium alkoxide, under agitation slowly be added drop-wise in above-mentioned mixed solution, stir certain hour under room temperature and be hydrolyzed, obtain monodisperse titanium dioxide colloidal sol; Colloidal sol is dried and obtained flaxen gel.Can obtain nano titanium dioxide photocatalyst at different temperature lower calcinations.
Preparation method of the present invention adopts the sol-gel process Kaolinite Preparation of Catalyst under normal temperature and pressure, and the reaction condition gentleness is easy to control, and each component is fully contact in the colloid change procedure, modification when being easy to bismuth, silicon, building-up process and equipment are simple, and raw material is easy to get, and are easy to suitability for industrialized production.
the accompanying drawing explanation
Fig. 1. the transmission electron microscope photo of embodiment 1 bismuth, silicon coblended nano titanium dioxide photocatalyst;
Fig. 2. the X-ray diffractogram of embodiment 1 bismuth, silicon coblended nano titanium dioxide photocatalyst;
Fig. 3. the XPS spectrum figure of embodiment 1 bismuth, silicon coblended nano titanium dioxide photocatalyst;
Fig. 4. the 4f track XPS spectrum figure of the bismuth of embodiment 1 bismuth, silicon coblended nano TiO 2;
Fig. 5. the 2p track XPS spectrum figure of the silicon of embodiment 1 bismuth, silicon coblended nano TiO 2;
Fig. 6. embodiment 1 bismuth, silicon coblended nano titanium dioxide photocatalyst and the uv-visible absorption spectra of P25;
Fig. 7. bismuth in embodiment 1, silicon coblended nano titanium dioxide photocatalyst and single bismuth doped Ti O
2, single silicon doping TiO
2, P25 visible light catalysis activity relatively.
The specific embodiment
Measuring the ethanol solution of 50ml 0.02 mol/L bismuth nitrate, 50ml 0.1 mol/L ethyl orthosilicate in reactor, is 2 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the butyl titanate of 100ml 2mol/L slowly is added drop-wise in above-mentioned mixed solution, there will be white precipitate during beginning, after dropwising, continue to stir 10 hours, make butyl titanate further be hydrolyzed and obtain monodisperse sol; Then colloidal sol is dried 8 hours at 90 ℃, remove ethanol and moisture, obtain xerogel, 450 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 1.5 hours, in molar fraction, the doping of bismuth is 0.4 %, and the doping of silicon is 4.8 %.
Fig. 1 is the transmission electron microscope photo of this sample, can find out that the synthetic sample particle diameter of the present embodiment is 10.6 nm; The X-ray diffractogram that Fig. 2 is the synthetic bismuth of the present embodiment, silicon coblended nano titanium dioxide photocatalyst, the crystal formation that shows this sample is anatase; The full spectrogram of the XPS that Fig. 3 is sample, Fig. 4 illustrate bismuth in sample with Bi
2o
3form is attached to TiO
2on surface, Fig. 5 illustrates that silicon has mixed TiO
2in lattice, SiO
2with TiO
2between form crystal boundary, thereby stoped TiO
2growing up and reunion of crystal grain; The uv-visible absorption spectra that Fig. 6 is the synthetic bismuth of the present embodiment, silicon coblended nano titanium dioxide photocatalyst and P25 relatively, can find out, red shift has occurred in bismuth, silicon coblended nano titanium dioxide photocatalyst absorption spectrum, since 650 nm, absorption is arranged; Fig. 7 is the synthetic bismuth of the present embodiment, silicon coblended nano titanium dioxide photocatalyst and single bismuth doped Ti O
2, single silicon doping TiO
2, P25 degraded 2,4-Dichlorophenol the visible light catalyst specific activity, result shows that this catalyst reaches 89.2 % to the degradation rate of 2,4-Dichlorophenol, is respectively single bismuth doped Ti O
2, single silicon doping TiO
2with 2.2 times, 8.9 times of P25 with 5.0 times.
Measuring the ethanol solution of 50ml 0.04 mol/L bismuth nitrate, 50ml 0.2 mol/L ethyl orthosilicate in reactor, is 1.5 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the butyl titanate of 200ml 1mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 8 hours, obtain monodisperse sol; Gained colloidal sol is dried 9 hours to obtain to xerogel at 90 ℃, and 500 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 2 hours, and in molar fraction, the doping of bismuth is 0.9 %, and the doping of silicon is 7.6 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is Anatase, and certain red shift has occurred uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 12.8 nm.
Degradation rate to the 4-chlorophenol under the present embodiment sample radiation of visible light is 81.5%, and its activity is single silicon doping TiO
28.3 times.
Measuring the ethanol solution of 50ml 0.01 mol/L bismuth acetate, 50ml 0.3 mol/L sodium metasilicate in reactor, is 2.5 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the isopropyl titanate of 100ml 2mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 10 hours, obtain monodisperse sol; Gained colloidal sol is dried 8 hours to obtain to xerogel at 100 ℃, and 500 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 2 hours, and in molar fraction, the doping of bismuth is 0.2 %, and the doping of silicon is 12.1 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is Anatase, and red shift to a certain degree occurs uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 11.9 nm.
Degradation rate to 2,4-chlorophenol under the present embodiment sample radiation of visible light is 74.6%, and its activity is 5.1 times of P25.
Measuring the ethanol solution of 50ml 0.01 mol/L bismuth acetate, 50ml 0.3 mol/L sodium metasilicate in reactor, is 1 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the butyl titanate of 400ml 0.5mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 9 hours, obtain monodisperse sol; Gained colloidal sol is dried 9 hours to obtain to xerogel at 80 ℃, and 600 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 2.5 hours, and in molar fraction, the doping of bismuth is 0.2 %, and the doping of silicon is 11.3 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is Anatase, and red shift has to a certain degree occurred uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 16.4 nm.
Degradation rate to the 4-chlorophenol under the present embodiment sample radiation of visible light is 67.8%, and its activity is single silicon doping TiO
27.5 times.
embodiment 5
Measuring the ethanol solution of 50ml 0.05 mol/L bismuth acetate, 50ml 0.1 mol/L sodium metasilicate in reactor, is 2 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the isopropyl titanate of 100ml 2mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 10 hours, obtain monodisperse sol; Gained colloidal sol is dried 8 hours to obtain to xerogel at 90 ℃, and 650 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 2 hours, and in molar fraction, the doping of bismuth is 1.1 %, and the doping of silicon is 5.5 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is Anatase, and red shift has occurred uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 20.5 nm.
Degradation rate to 2,4-chlorophenol under the present embodiment sample radiation of visible light is 74.6%, and its activity is 5.3 times of commercial P25.
embodiment 6
Measuring the ethanol solution of 50ml 0.01 mol/L bismuth chloride, 50ml 0.5 mol/L sodium metasilicate in reactor, is 3 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the isopropyl titanate of 200ml 1mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 10 hours, obtain monodisperse sol; Gained colloidal sol is dried 7 hours to obtain to xerogel at 100 ℃, and 700 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 2 hours, and in molar fraction, the doping of bismuth is 0.3 %, and the doping of silicon is 15.6 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is Anatase, and red shift has occurred uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 17.2 nm.
Degradation rate to the 4-chlorophenol under the present embodiment sample radiation of visible light is 72.3%, and its activity is 4.5 times of P25.
embodiment 7
Measuring the ethanol solution of 50ml 0.02 mol/L bismuth chloride, 50ml 0.2 mol/L sodium metasilicate in reactor, is 2.5 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the butyl titanate of 100ml 2mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 10 hours, obtain monodisperse sol; Gained colloidal sol is dried 8 hours to obtain to xerogel at 90 ℃, and 800 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 2 hours, and in molar fraction, the doping of bismuth is 0.4 %, and the doping of silicon is 8.0 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is mainly Anatase, approximately contain 10.6% Rutile Type, red shift to a certain degree occurs in uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 24.1 nm.
Degradation rate to 2,4,5-trichlorophenol under the present embodiment sample radiation of visible light is 65.7%, and its activity is single silicon doping TiO
26.8 times.
embodiment 8
Measuring the ethanol solution of 50ml 0.02 mol/L bismuth nitrate, 50ml 0.2 mol/L ethyl orthosilicate in reactor, is 1.5 toward wherein adding salpeter solution to adjust pH, after stirring evenly, obtains mixed solution; Under stirring at room, the ethanol solution of the butyl titanate of 100ml 2mol/L is added drop-wise in above-mentioned mixed solution, dropwises rear continuation and stir 8 hours, obtain monodisperse sol; Gained colloidal sol is dried 8 hours to obtain to xerogel at 90 ℃, and 800 ℃ of calcinings obtain faint yellow bismuth, silicon coblended nano titanium dioxide photocatalyst in 1.5 hours, and in molar fraction, the doping of bismuth is 0.5 %, and the doping of silicon is 7.1 %.
Synthetic bismuth, the silicon coblended nano titanium dioxide photocatalyst X-ray diffractogram of the present embodiment shows that its crystalline phase is mainly Anatase, approximately contain 5.0% Rutile Type, red shift has occurred in uv-visible absorption spectra, and transmission electron microscope shows that this sample particle diameter is 22.5 nm.
Degradation rate to 2,4,5-trichlorophenol under the present embodiment sample radiation of visible light is 69.6%, and its activity is 4.8 times of P25.
Embodiment P25 used refers to the titanium dioxide optical catalyst of the code name P25 that German Degussa company produces.
In above embodiment, adopt the embodiment sample to the experiment condition of typical chlorophenol pollutant in light degradation sewage (as 4-chlorophenol, 2,4-Dichlorophenol, 2,4,5-trichlorophenol) to be: the initial concentration 1 * 10 of chlorophenol pollutant
-4mol/L, catalyst amount 1.0 g/L, light source adopts the xenon lamp of 300W or halogen tungsten lamp (light that is less than 420 nm with optical filter elimination wavelength take guarantee that irradiation light is visible ray entirely), take the evaluation index that the removal efficiency of chlorophenol pollutant is photocatalytic activity in Photocatalytic Degradation Process, visible light activity is with bismuth or the single doped Ti O of silicon
2and P25 is benchmark.
Above data show, using the degradation rate of chlorophenol pollutant as the evaluation foundation of catalyst efficiency, under other condition same cases, the catalytic efficiency of this catalyst parachlorphenol pollutant is apparently higher than P25 (titanium dioxide optical catalyst of the code name P25 that German Degussa company produces), catalyst of the present invention photocatalysis effect in the use procedure of continuous 3 ~ 36h remains stable simultaneously, deactivation phenomenom do not occur.
Claims (5)
1. bismuth, silicon coblended nano titanium dioxide photocatalyst, it is characterized in that: in molar fraction, the doping of bismuth is 0.2 ~ 1.1 %, and the doping of silicon is 4.8 ~ 15.6 %, and wherein, bismuth is with Bi
2o
3form is attached to TiO
2on surface, the silicon mixed enters TiO
2lattice, SiO
2with TiO
2between form crystal boundary.
2. the preparation method of bismuth claimed in claim 1, silicon coblended nano titanium dioxide photocatalyst is characterized in that comprising the following steps:
The adulterate ethanol solution of presoma and the ethanol solution of silicon doping presoma of bismuth added in reactor, and adjusting pH with nitric acid is 1-3, stirs evenly; Then stir the lower ethanol solution that drips the titanium alkoxide, stirring at room is hydrolyzed in 8 ~ 10 hours, obtains monodispersed TiO 2 sol; The TiO 2 sol obtained is dried and within 6 ~ 9 hours, obtained xerogel at 80 ~ 100 ℃; Calcine under 400 ~ 800 ℃ 1 ~ 3 hour after will the gained xerogel grinding, obtain bismuth, silicon coblended nano titanium dioxide photocatalyst.
3. the preparation method of bismuth as claimed in claim 2, silicon coblended nano titanium dioxide photocatalyst, it is characterized in that: the mol ratio of bismuth and titanium is 0.005:1 ~ 0.1:1, the mol ratio of silicon and titanium is 0.05:1 ~ 1:1.
4. the preparation method of bismuth, silicon coblended nano titanium dioxide photocatalyst as claimed in claim 2 or claim 3, it is characterized in that: the concentration of the ethanol solution of bismuth doping presoma is 0.01 ~ 0.05 mol/L, the concentration of the ethanol solution of silicon doping presoma is 0.1 ~ 0.5 mol/L, and the concentration of the ethanol solution of titanium alkoxide is 0.5 ~ 2 mol/L.
5. the preparation method of bismuth as claimed in claim 4, silicon coblended nano titanium dioxide photocatalyst, it is characterized in that: described titanium alkoxide is butyl titanate or isopropyl titanate; Described bismuth doping presoma is bismuth nitrate, bismuth chloride or bismuth acetate; Described silicon doping presoma is ethyl orthosilicate or sodium metasilicate.
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| CN103806270B (en) * | 2014-02-18 | 2016-01-20 | 南通纺织职业技术学院 | A kind of modifying titanium dioxide hydrosol and preparation method thereof |
| CN105664995B (en) * | 2016-03-08 | 2018-06-01 | 济宁学院 | A kind of multielement codoped nanaotitania catalysis material |
| JP6179839B1 (en) | 2017-02-14 | 2017-08-23 | エム・テクニック株式会社 | Silicon-doped metal oxide particles, and ultraviolet absorbing composition comprising silicon-doped metal oxide particles |
| CN107572579B (en) * | 2017-10-19 | 2019-08-06 | 重庆工商大学 | A kind of spherical zinc oxide gas sensing material and preparation method thereof of bismuth doping |
| CN109201036B (en) * | 2018-09-20 | 2021-07-16 | 中国城市建设研究院有限公司 | Preparation method of visible light photocatalyst for water treatment process |
| CN109972149B (en) * | 2019-05-06 | 2020-12-22 | 中国科学院海洋研究所 | Bi2Te3/Bi2O3/TiO2Preparation method of ternary heterojunction film |
| CN110882688A (en) * | 2019-12-10 | 2020-03-17 | 佛山科学技术学院 | Preparation method of photodegradation catalyst for oilfield sewage |
| CN113800590B (en) * | 2021-09-30 | 2023-03-21 | 江苏大学 | Method for synthesizing IO-BTO (input/output-to-BTO) nano-reactor by pollutant intervention photoinduction strategy and application of method |
| CN114570348B (en) * | 2022-03-02 | 2024-03-12 | 济南大学 | Titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by irradiation of visible light and application thereof |
| CN114921170A (en) * | 2022-05-20 | 2022-08-19 | 上海立邦长润发涂料有限公司 | Anti-fogging UV (ultraviolet) finishing oil for automobile rearview mirror and preparation method thereof |
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