CN101157027A - Modified non-metal impure nanometer TIO* photocatalyst and its preparing method - Google Patents
Modified non-metal impure nanometer TIO* photocatalyst and its preparing method Download PDFInfo
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- CN101157027A CN101157027A CNA2007101565926A CN200710156592A CN101157027A CN 101157027 A CN101157027 A CN 101157027A CN A2007101565926 A CNA2007101565926 A CN A2007101565926A CN 200710156592 A CN200710156592 A CN 200710156592A CN 101157027 A CN101157027 A CN 101157027A
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Abstract
The invention relates to nonmetallic doped nanometer TiO2 photocatalyst through being modified and the preparation method thereof. The chemical formula of the photocatalyst of the invention is TiO2-XYX/WO3, TiO2-XYX/ZnO, or TiO2-XYX/Cu2O, the crystal grain size is 10 to 200 nm, crystal grains comprises anatase, or simultaneously comprises two crystal forms of anatase and rutile, the range of ultraviolet-visible absorption spectrum is of 230 to 600 nm, and Y is N, C, or S. The invention has the preparation method that the precursors TiN, TiC, or TiS2 of a non-metallic compound containing Ti are dipped in the solution of a compound of W, Zn, or Cu containing certain concentration, and are dried with the normal pressure or the reduced pressure, the obtained powder is calcined under the aerobic or non-oxidative condition, the calcination temperature is at 200 to 900 DEG C, and the reaction time needs 0.1 to 10 hours.
Description
Technical field
The invention belongs to technical field of chemistry, relate to nonmetal doping nano titanium dioxide photocatalyst of a kind of process modification and preparation method thereof, this catalyst is mainly used in room air pollution control technology field.
Background technology
The room air pollution degree exceeds outdoor 5～10 times, and people had 80～90% times to spend indoor, and to a certain extent, effect of air pollution on human health is mainly indoor.The investigation that China Association for Standardization provides shows: 60% disease is caused by room air pollution.In the latter stage nineties, along with the high speed development of the raising, particularly building materials industry of domestic housing reform and national life level, the rise of fitting-up craze is become the main mode of indoor pollution by the pollution that ornament materials caused.
Under the present living conditions of China, the rate of curing the disease and the death rate that are caused by room air are very high, major pollutants in the room air have nitrogen oxide, sulfide, formaldehyde and benzene series thing, wherein the pollution of the formaldehyde that is caused by finishing material, benzene series thing VOCs (VOCs) such as (benzene,toluene,xylenes) has become the main pollution factor of present room air.Western developed country has been issued decree, control is carried out in discharging to VOCs, China also defines the emission limit of 33 kinds of pollutants in " discharge standard of air pollutants " that enacted and enforced in 1997, wherein major part is formaldehyde, benzene series thing VOCs such as (benzene,toluene,xylenes).Therefore volatile organic matter has become the main object and the target of present room air pollution research.
Remove airborne VOCs, usually adopting ventilates directly is discharged to outdoorly, or with charcoal absorption and catalytic oxidation decomposition method, these measures all can cause secondary pollution.In recent years and since photocatalysis technology have nontoxic, reaction condition is gentle, selectivity is little, the mineralization rate advantages of higher, at degradation of contaminant, especially the organic matter aspect more and more is subject to people's attention.Gas-solid phase conductor photocatalysis oxidation reaction especially aspect the degraded of VOCs, owing to itself distinctive outstanding feature, has become hot research in recent years gradually, and has more and more shown its broad application prospect.
Yet as catalysis material, TiO
2Forbidden band broad (3.2eV), not response only can absorb the ultraviolet light less than 387nm, to solar energy utilization ratio low (about 3～5%) in visible-range; The recombination rate height of carrier, quantum yield is low, causes photocatalysis efficiency lower, these two defective effects its effective utilization to sunshine, restricted its application aspect room air improvement, how on visible light-responded basis, to improve TiO
2Photocatalytic activity, the preparation effective catalyst become present problem demanding prompt solution.In order to address this problem, the method that all adopts is basically at present mixed exactly, a kind of doping techniques that the most of research workers of metal ion mixing take, and its principle is that metal ion is incorporated into TiO
2Intracell, thus in its lattice, introduce new electric charge, form defective or change lattice types, influence light induced electron and hole moving situation, adjust its distribution or change TiO
2Band structure, finally cause its photocatalytic activity to change.Though yet the doping of metal ion can improve TiO
2Activity under visible light, but also exist certain defective, thus because the doping of metal ion makes metal ion become the complex centre, make TiO
2Descend at the photocatalytic activity of ultra-violet (UV) band, in addition because the doping of metal ion also can make TiO
2The bad stability of itself.
Along with calendar year 2001 Asahi (R.Asahi, T.Morikawa, T.Ohwahi, K.Aoki, Y.Taga.Visible-Light Photocatalysis in Nitrogen-doped Titanium Oxides, Science, 2001,293:269～271) on Science, replace the TiO that the nitrogen of Lattice Oxygen mixes about nitrogen
2-XN
XMake delivering of its paper not reducing under the photoactive prerequisite of ultraviolet, opened TiO with visible light activity
2The prelude of nonmetal doping.But, all also exist certain defective with regard to the present most of research workers' that provide nonmetal doping technology.
Publication number is: CN1454710, patent is by name: nitrogenous optically catalytic TiO 2 film and preparation method thereof, provide a kind of method that adopts magnetically controlled sputter method to prepare a kind of nitrogenous optically catalytic TiO 2 film, its complex process but also need expensive equipment; Patent publication No. is: CN1712128A, patent is by name: the preparation method of the anatase-type nanometer titanium dioxide that a kind of nitrogen mixes, announced that a kind of need provide titanium source, precipitating reagent, nitrogenous source and water, and according to certain ratio mixing, pass through hydro-thermal reaction then, drying obtains the nano-TiO that a kind of nitrogen mixes after the oven dry
2Method, but the prescription of this technology is comparatively complicated, the factor of influence is too many, condition is wayward; Patent publication No. is: CN150616A, and patent is by name: the preparation method of nitrogen-doped titanium dioxide powder provides in a kind of compound that ammoniacal liquor is added drop-wise to gradually titanium, then through filtering, drying after the oven dry, obtains the nano-TiO that a kind of nitrogen mixes behind high temperature sintering
2Method, but this method preparation technology is miscellaneous, has been difficult to the industrial applications prospect, and activity of such catalysts also needs further raising.
Nonmetal doping can be realized TiO by being with regulation and control
2Photochemical catalyst as seen photochemical makes up the semiconductor that can be with coupling on this basis, can further reduce the recombination rate of photo-generated carrier, increases quantum yield, improves its photocatalysis efficiency, and process is retrieved, and does not have the patent disclosure of this respect.
Summary of the invention
The nano-TiO that the purpose of this invention is to provide the nonmetal doping of a kind of process modification
2Photochemical catalyst with and preparation method thereof.
The present invention is through the nano-TiO of the nonmetal doping of modification
2Its chemical formula of photochemical catalyst is:
TiO
2-XY
X/ WO
3, TiO
2-XY
X/ ZnO or TiO
2-XY
X/ Cu
2The O one, described nano-TiO
2The crystallite dimension of photocatalyst granular is 10～200nm, contains anatase or contains anatase simultaneously and two kinds of crystal formations of rutile, and the scope of uv-visible absorption spectra is from 230～600nm, and Y is chemical element N, C or S one.
The nano-TiO of the nonmetal doping of above-mentioned process modification
2The preparation method of photochemical catalyst is:
Nonmetallic compound with Ti is a presoma, to contain W, the compound of Zn or Cu one is as modifier, containing the Ti presoma is immersed in and contains certain density W, in the solution of the compound of Zn or Cu one, normal pressure or drying under reduced pressure, the gained powder is calcined under aerobic or oxygen free condition, calcining heat is 200～900 ℃, and the reaction time is 0.1～10h.
The nonmetallic compound presoma of above-mentioned Ti is TiN, TiC or TiS
2One; The modifier of the described W of containing compound is wolframic acid (H
2WO
4), wolframic acid ammonia ((NH
4)
2WO
4) or metatungstic acid ammonia ((NH
4)
6W
7O
246H
2O) one; The modifier of the described Zn of containing compound is zinc nitrate (Zn (NO
3)
2), zinc sulfate (ZnSO
4), zinc acetate (Zn (CHCOO)
2) or zinc chloride (ZnCl
2) one; The described Cu that contains is copper nitrate (Cu (NO for compound modified dose
3)
2), copper sulphate (CuSO
4), Schweinfurt green (Cu (CHCOO)
2) or copper chloride (CuCl
2) one.
The above-mentioned W that contains, compound modified dose molar content of Zn or Cu one is TiN or TiC or TiS
20.01%～10% of consumption.
Generally speaking, N, C, S atom and Ti need provide extra nitrogen, carbon, sulphur source when forming Ti-N key, Ti-C key and Ti-S key, the preparation process complexity, and cost is higher.
The present invention is itself just to have TiN, TiC and the TiS of Ti-N key, Ti-C key and Ti-S key
2Be presoma, provide under the prerequisite in other nitrogen, carbon, sulphur source and titanium source not needing, directly calcine the nano-TiO of synthetic nitrogen, carbon, sulfur doping
2-XN
X, TiO
2-XC
XAnd TiO
2-XS
X, to overcome some defectives of bringing in the prior art.Yet, TiO
2-XN
X, TiO
2-XC
XAnd TiO
2-XS
XUltra-violet (UV) band and visible region activity remain further to be improved.Before calcining with TiN, TiC and TiS
2Be immersed in the solution that contains W, Zn, Cu, by calcination processing, at TiO
2-XN
X, TiO
2-XC
XAnd TiO
2-XS
XThe a certain amount of conductor oxidate of surface deposition further improves its light-catalysed effect.
Nonmetallic compound with Ti is a presoma, with the compound that contains W, Zn, Cu etc. as modifier, contain in the solution that the Ti presoma is immersed in compounds such as containing certain density W, Zn, Cu, normal pressure or drying under reduced pressure, the gained powder is calcined under aerobic or oxygen free condition, calcining heat is 200～900 ℃, and the reaction time is 0.1h～10h.
During reaction with a certain amount of TiN, TiC or TiS
2Be transferred in the ceramic crucible, calcine under aerobic or oxygen free condition, reaction temperature is 200～900 ℃, and the reaction time is 0.1h～10h, obtains the TiO that contains different crystal forms of nitrogen, carbon and sulfur doping
2-XN
X, TiO
2-XC
XAnd TiO
2-XS
X, directly use the cooling back, and the value of X is controlled by calcination condition.
Utilize the nano-TiO of the nonmetal doping that the inventive method prepares
2The crystallite dimension of particle is 5～20nm, contains anatase or contains anatase simultaneously and two kinds of crystal formations of rutile, and the scope of uv-visible absorption spectra is from 230～600nm.
From the angle of photocatalysis effect, described nitrogen doped Ti O
2-XN
X, TiO
2-XC
XAnd TiO
2-XS
XIn the process of degraded benzene, the non-secondary pollution thing generates, and has all generated water and carbon dioxide, in humidity, under the identical condition of conditions such as oxygen concentration, its ultraviolet catalytic degradation effect is 1.1～4.5 times of commercial P25, and the visible light catalytic effect is 5～20 times of commercial P25.TiO through semiconductor modification raising
2-XY
X/ WO
3, TiO
2-XY
X/ ZnO and TiO
2-XY
X/ Cu
2O, its ultraviolet catalytic degradation effect is TiO
2-XY
X1.1～5.0 times, the visible light catalytic effect is TiO
2-XY
X1.05～5.0 times.Above-mentioned catalyst of while photocatalysis effect in the use of continuous 8～48h remains stable, does not find deactivation phenomenom.
Description of drawings
The XRD figure of Fig. 1 embodiment 4 catalyst shows prepared nano-TiO
2Powder mixes with rutile with anatase and exists mutually.
The UV-vis absorption spectrum of Fig. 2 embodiment 2 catalyst and P25, the former begins just to have absorption from 560nm.(1-P25; The catalyst of 2-embodiment 2 preparations).
The XPS collection of illustrative plates of the powder of Fig. 3 embodiment 3 shows the existence of nitrogen.
The XPS collection of illustrative plates of the powder of Fig. 4 embodiment 7 shows the existence of sulphur.
The specific embodiment
Embodiment 1
Preparation condition: employing TiC is a presoma, takes by weighing 3.0gTiC and places crucible, and calcining heat is 450 ℃ under aerobic conditions, calcination time 2h, and cooling obtains the nano-TiO that C mixes
2Catalyst.Chemical formula: TiO
2-XC
X
Preparation condition: employing TiN is a presoma, takes by weighing 3.0gTiN and places crucible, and calcining heat is 550 ℃ under oxygen free condition, calcination time 4h, and cooling obtains the nano-TiO that N mixes
2Catalyst.Chemical formula: TiO
2-XN
X
Preparation condition: employing TiS is a presoma, takes by weighing 3.0gTiS and places crucible, and calcining heat is 700 ℃ under oxygen free condition, calcination time 3h, and cooling obtains the nano-TiO that S mixes
2Catalyst.Chemical formula: TiO
2-XS
X
Further improve above method as follows:
Preparation condition: employing TiN is a presoma, takes by weighing 3.0gTiN and places beaker, and the configuration molar concentration is 1% wolframic acid ammonia ((NH
4)
2WO
4) solution 100ml, said two devices is mixed stirring, dry under reduced pressure, the gained powder places crucible, under aerobic conditions, calcine, 550 ℃ of temperature, calcination time 2h, cooling obtains TiO
2-XN
X/ WO
3
Embodiment 5
Preparation condition: employing TiC is a presoma, takes by weighing 3.0gTiC and places beaker, and the configuration molar concentration is 5% zinc nitrate (Zn (NO
3)
2) solution 100ml, said two devices is mixed stirring, dry under reduced pressure, the gained powder places crucible, under aerobic conditions, calcine, 450 ℃ of temperature, calcination time 5h, cooling obtains TiO
2-XC
X/ ZnO.
Embodiment 6
Preparation condition: employing TiS is a presoma, takes by weighing 3.0gTiS and places beaker, and the configuration molar concentration is 10% copper nitrate (Cu (NO
3)
2) solution 100ml, said two devices is mixed stirring, dry under condition of normal pressure, the gained powder places crucible, under aerobic conditions, calcine, 650 ℃ of temperature, calcination time 2h, cooling obtains TiO
2-XS
X/ Cu
2O.
Embodiment 7
Preparation condition: employing TiN is a presoma, takes by weighing 3.0gTiN and places beaker, and the configuration molar concentration is 0.01% zinc acetate (Zn (CHCOO)
2) solution 100ml, said two devices is mixed stirring, dry under condition of normal pressure, the gained powder places crucible, under oxygen free condition, calcine, 800 ℃ of temperature, calcination time 5h, cooling obtains TiO
2-XN
X/ ZnO.
Embodiment 8
Preparation condition: employing TiC is a presoma, takes by weighing 3.0gTiC and places beaker, and the configuration molar concentration is 2% copper chloride (CuCl
2) solution 100ml, said two devices is mixed stirring, dry under reduced pressure, the gained powder places crucible, and calcining heat is 400 ℃ under aerobic conditions, calcination time 10h, cooling obtains TiO
2-XC
X/ Cu
2O.
Embodiment 9
Preparation condition: employing TiS is a presoma, takes by weighing 3.0gTiS and places beaker, and the configuration molar concentration is 8% metatungstic acid ammonia ((NH
4)
6W
7O
246H
2O) solution 100ml mixes stirring with said two devices, and dry under condition of normal pressure, the gained powder places crucible, and calcining heat is 600 ℃ under aerobic conditions, calcination time 3h, and cooling obtains TiO
2-XS
X/ WO
3
Embodiment 10
Preparation condition: employing TiC is a presoma, takes by weighing 3.0gTiC and places beaker, and the configuration molar concentration is 3% copper sulphate (CuSO
4) solution 100ml, said two devices is mixed stirring, dry under condition of normal pressure, the gained powder places crucible, and calcining heat is 500 ℃ under oxygen free condition, calcination time 2h, cooling obtains TiO
2-XC
X/ Cu
2O.
Embodiment 11
Preparation condition: employing TiN is a presoma, takes by weighing 3.0gTiS and places beaker, and the configuration molar concentration is 0.5% metatungstic acid ammonia ((NH
4)
6W
7O
246H
2O) solution 100ml mixes stirring with said two devices, and dry under reduced pressure, the gained powder places crucible, and calcining heat is 900 ℃ under aerobic conditions, calcination time 0.1h, and cooling obtains TiO
2-XN
X/ WO
3
Embodiment 12
Preparation condition: employing TiS is a presoma, takes by weighing 3.0gTiS and places beaker, and the configuration molar concentration is 6% zinc sulfate (ZnSO
4) solution 100ml, said two devices is mixed stirring, dry under condition of normal pressure, the gained powder places crucible, and calcining heat is 650 ℃ under oxygen free condition, calcination time 6h, cooling obtains TiO
2-XS
X/ ZnO.
Sample to example 1～12 carries out the photocatalytic activity test
Continuous Flow is adopted in test, and experiment condition is: the initial concentration 1mg/m of toluene
3 Relative humidity 60%, oxygen content 21%, catalyst consumption 0.2g, it is the xenon lamp of 150W that light source adopts power, ratio with the first order reaction apparent speed constant in the photochemical catalytic oxidation process is the evaluation index of photocatalytic activity, and the ultraviolet light activity is benchmark with P25, and visible light activity is thought the TiO of modification
2-XY
XBe benchmark, concrete outcome sees Table 1.
Table 1
| The embodiment sequence number | Presoma | Calcination condition | Doped chemical | Maximum absorption wavelength (nm) | Modifier | Photocatalytic activity | |
| Ultraviolet light (less than 400nm) | Visible light (greater than 400nm) | ||||||
| Embodiment 1 | TiC | 450℃，2h | C | 550 | - | 1.1 | 1 |
| |
TiN | 550℃，4h | N | 450 | - | 1.5 | 1 |
| |
|
700℃，3h | S | 425 | - | 1.4 | 1 |
| |
TiN | 450℃，2h | N | 465 | Wolframic acid ammonia | 2.8 | 2.6 |
| Embodiment 5 | TiC | 550℃，4h | C | 505 | Zinc nitrate | 4.5 | 2.4 |
| Embodiment 6 | TiS 2 | 700℃，2h | S | 435 | Copper nitrate | 3.8 | 3.8 |
| Embodiment 7 | TiN | 800℃，5h | N | 415 | Zinc acetate | 3.6 | 2.3 |
| Embodiment 8 | TiC | 400℃，10h | C | 520 | Copper chloride | 3.6 | 4.5 |
| Embodiment 9 | TiS 2 | 600℃，3h | S | 450 | Metatungstic acid ammonia | 2.9 | 3.6 |
| Embodiment 10 | TiC | 500℃，2h | C | 485 | Copper sulphate | 2.3 | 3.2 |
| Embodiment 11 | TiN | 900℃，0.1h | N | 436 | Metatungstic acid ammonia | 2.0 | 2.6 |
| Embodiment 12 | TiS 2 | 650℃，6h | S | 420 | Zinc sulfate | 1.8 | 2.1 |
As can be seen from Table 1, respectively with TiN, TiC and TiS
2Nano-TiO for the nonmetal doping of precursor preparation
2All obtained very significantly absorbing wavelength red shift and very high ultraviolet and visible light catalysis activity, carried out semiconductor deposition modification, TiO at catalyst surface by infusion process
2-XY
XUltraviolet and visible light catalysis activity can further improve.The present invention can be to utilize solar energy (visible light) efficiently to purify the air of a room to pollute provides technical foundation.
Claims (4)
1. pass through the nano-TiO of the nonmetal doping of modification
2Photochemical catalyst is characterized in that: its chemical formula is: TiO
2-XY
X/ WO
3, TiO
2-XY
X/ ZnO or TiO
2-XY
X/ Cu
2The O one, described nano-TiO
2The crystallite dimension of photocatalyst granular is 10～200nm, contains anatase or contains anatase simultaneously and two kinds of crystal formations of rutile, and the scope of ultraviolet one visible absorption spectra is from 230～600nm, and Y is chemical element N, C or S one.
2. pass through the nano-TiO of the nonmetal doping of modification according to claim 1
2The preparation method of photochemical catalyst, it is characterized in that: the nonmetallic compound with Ti is a presoma, to contain W, the compound of Zn or Cu one is as modifier, contains the Ti presoma and is immersed in and contains certain density W, in the solution of the compound of Zn or Cu one, normal pressure or drying under reduced pressure, the gained powder is calcined under aerobic or oxygen free condition, and calcining heat is 200～900 ℃, and the reaction time is 0.1～10h.
As described in the claim 2 through the nano-TiO of the nonmetal doping of modification
2The preparation method of photochemical catalyst is characterized in that: the nonmetallic compound presoma of described Ti is TiN, TiC or TiS
2One; The modifier of the described W of containing compound is wolframic acid (H
2WO
4), wolframic acid ammonia ((NH
4)
2WO
4) or metatungstic acid ammonia ((NH
4)
6W
7O
246H
2O) one; The modifier of the described Zn of containing compound is zinc nitrate (Zn (NO
3)
2), zinc sulfate (ZnSO
4), zinc acetate (Zn (CHCOO)
2) or zinc chloride (ZnCl
2) one; The described Cu that contains is copper nitrate (Cu (NO for compound modified dose
3)
2), copper sulphate (CuSO
4), Schweinfurt green (Cu (CHCOO)
2) or copper chloride (CuCl
2) one.
As described in the claim 2 through the nano-TiO of the nonmetal doping of modification
2The preparation method of photochemical catalyst is characterized in that: the described W of containing, compound modified dose molar content of Zn or Cu one is TiN or TiC or TiS
20.01%～10% of consumption.
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|---|---|---|---|
| CNA2007101565926A CN101157027A (en) | 2007-11-09 | 2007-11-09 | Modified non-metal impure nanometer TIO* photocatalyst and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101565926A CN101157027A (en) | 2007-11-09 | 2007-11-09 | Modified non-metal impure nanometer TIO* photocatalyst and its preparing method |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=39305333
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| CN101898139A (en) * | 2010-06-25 | 2010-12-01 | 张麒 | Formula of titanium dioxide photochemical catalyst doped with tungstic oxide and preparation method |
| CN102008949A (en) * | 2010-11-01 | 2011-04-13 | 浙江大学 | Preparation method of demercuration catalyst for non-metal-modified one-dimensionally structured titanium dioxide |
| CN102274739A (en) * | 2011-05-31 | 2011-12-14 | 中国科学院新疆理化技术研究所 | Copper-nitrogen double-doped titanium dioxide photocatalytic material |
| CN102343260A (en) * | 2011-06-28 | 2012-02-08 | 中国科学院金属研究所 | Method for preparing boron-doped titanium dioxide crystal containing specific crystal plane |
| CN102658186A (en) * | 2012-05-02 | 2012-09-12 | 厦门大学 | Tungsten carbide-titanium dioxide composite photocatalysis material and preparation method thereof |
| CN104803435A (en) * | 2014-01-23 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Sewage treatment purification agent, preparation method and applications thereof |
| CN106492801A (en) * | 2016-08-31 | 2017-03-15 | 嘉兴性天环保科技有限公司 | A kind of preparation method of Ti-base catalyst and the formaldehyde minimizing technology using Ti-base catalyst |
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| CN101898139A (en) * | 2010-06-25 | 2010-12-01 | 张麒 | Formula of titanium dioxide photochemical catalyst doped with tungstic oxide and preparation method |
| CN102008949A (en) * | 2010-11-01 | 2011-04-13 | 浙江大学 | Preparation method of demercuration catalyst for non-metal-modified one-dimensionally structured titanium dioxide |
| CN102008949B (en) * | 2010-11-01 | 2012-05-23 | 浙江大学 | Preparation method of demercuration catalyst for non-metal-modified one-dimensionally structured titanium dioxide |
| CN102274739A (en) * | 2011-05-31 | 2011-12-14 | 中国科学院新疆理化技术研究所 | Copper-nitrogen double-doped titanium dioxide photocatalytic material |
| CN102343260A (en) * | 2011-06-28 | 2012-02-08 | 中国科学院金属研究所 | Method for preparing boron-doped titanium dioxide crystal containing specific crystal plane |
| CN102658186A (en) * | 2012-05-02 | 2012-09-12 | 厦门大学 | Tungsten carbide-titanium dioxide composite photocatalysis material and preparation method thereof |
| CN104803435A (en) * | 2014-01-23 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Sewage treatment purification agent, preparation method and applications thereof |
| CN106492801A (en) * | 2016-08-31 | 2017-03-15 | 嘉兴性天环保科技有限公司 | A kind of preparation method of Ti-base catalyst and the formaldehyde minimizing technology using Ti-base catalyst |
| CN109225247A (en) * | 2018-10-18 | 2019-01-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Tungsten oxide-cuprous oxide heterojunction photovoltaic pole material preparation method and products thereof and application |
| CN111921521A (en) * | 2020-08-13 | 2020-11-13 | 上海聚治新材料科技有限公司 | Preparation method of tungsten/zinc lattice inter-doped efficient nano weak photocatalyst |
| CN111921521B (en) * | 2020-08-13 | 2023-04-07 | 上海聚治新材料科技有限公司 | Preparation method of tungsten/zinc lattice inter-doped efficient nano weak photocatalyst |
| CN111874988A (en) * | 2020-09-01 | 2020-11-03 | 中认英泰检测技术有限公司 | Based on multi-element co-doped TiO2Organic wastewater treatment method of nano photocatalytic material |
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