CN107824181A - A kind of preparation method of visible-light photocatalyst - Google Patents
A kind of preparation method of visible-light photocatalyst Download PDFInfo
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- CN107824181A CN107824181A CN201711018202.9A CN201711018202A CN107824181A CN 107824181 A CN107824181 A CN 107824181A CN 201711018202 A CN201711018202 A CN 201711018202A CN 107824181 A CN107824181 A CN 107824181A
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- butyl titanate
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 6
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003081 TiO2−x Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a kind of visible-light photocatalyst preparation method, butyl titanate, ethanol, hydrazine hydrate, AgNO are weighed3, after butyl titanate is dispersed in into ethanol, add N2H4·H2O, 0.5 ~ 1.5h of ultrasound in ice-water bath, form TiO2Precursor sol, it is transferred in water heating kettle, AgNO is added into water heating kettle under ultrasonic state3, at 160 200 DEG C, after reacting 6 ~ 10h, obtain anatase TiO2/ Ag visible light catalysts.The present invention passes through N2H4·H2The TiO produced after O reduction2The Lacking oxygen being internally formed acts synergistically with Ag, widens the absorption spectrum ranges of sample, the conduction velocity and separative efficiency of photo-generated carrier is improved, so as to improve visible light catalytic efficiency.The present invention is reacted in TiO by in-situ reducing2Internal and surface forms Lacking oxygen and the load corresponding Nano Silver of visible ray respectively, and preparation method is simple, easily controllable.
Description
Technical field
The invention belongs to inorganic functional material field, is related to a kind of catalyst, specifically a kind of anatase TiO2/Ag
The preparation method of visible-light photocatalyst.
Background technology
As process of industrialization is aggravated, the industrial pollutants that some industries are discharged just increasingly are threatening the health of the mankind.Its
In, a serious environmental problem is become as the water pollution caused by the organic dyestuff that textile printing and dyeing industry is discharged.For solution
Certainly this problem, scientist constantly look for new method and made a return journey except the organic pollution in water body.Wherein, with TiO2For representative
Photocatalysis technology turns into one of Environmental Studies focus in the late two decades, and it has, and energy consumption is low, cheap, nontoxic and nothing two
The features such as secondary pollutant produces, is with a wide range of applications in terms of industrial wastewater treatment.
But TiO2Broad-band gap (anatase is about 3.2eV, and rutile is about 3.0eV) cause it to absorb only to account for
3%~5% ultraviolet light of sunshine, significantly limit TiO2The photo-quantum efficiency of photochemical catalyst.Therefore, researcher is not
It is disconnected to be directed to widening TiO2Photochemical catalyst spectral response range, its photo-quantum efficiency is improved, wherein, to TiO2Carry out reduction treatment
It is a kind of effective method.By reduction treatment, TiO2Part oxygen atom lacks in crystal, forms Lacking oxygen, and Lacking oxygen has
Beneficial to TiO2Light absorbs, charge transport, Charge transfer on interface and adsorption in photocatalytic process etc., lived so as to improve catalysis
Property.Zhu et al. is at 450 DEG C to TiH2And TiO2Mixture calcined to obtain blue TiO2-x:H photochemical catalysts.In the reality
In testing, hydrogen atom is from TiH under high temperature2Middle effusion, a portion hydrogen atom and TiO2In oxygen atom combine generation water, make
TiO2Occurs Lacking oxygen in crystal, another part hydrogen atom occupies part Lacking oxygen position and interstitial site.Adulterate hydrogen atom
Cooperative effect between Lacking oxygen can effectively widen TiO2Photoresponse scope, improve catalytic efficiency.But the experiment is simply logical
Cross and take oxygen by force to form Lacking oxygen, temperature needed for experiment is higher, and power consumption is larger, is unfavorable for energy-conserving and environment-protective.Patent CN 105664902
A kind of trivalent titanium ion auto-dope titanium dioxide nanoplate catalyst is disclosed in A, the patent first uses hydro-thermal reaction method, utilizes
Hydrofluoric acid prepares titanium dioxide nanoplate as solvent, then using sodium borohydride by part Ti4+It is reduced into Ti3+, obtain three
Valency titanium ion auto-dope titanium dioxide nanoplate catalyst, on the one hand, Ti3+TiO can be improved in the localized modes that conduction band bottom is formed2It is right
The absorption of visible ray, on the other hand, for Ti3+The TiO of doping2For, in order to keep the electroneutral of crystal, often there are two Ti3+
During generation, then an O can be lost2-, so as to produce Lacking oxygen in crystal, make catalyst be easier to capture free electron, enhancing
Redox ability.But hydrofluoric acid has extremely strong corrosivity, and easily personnel and equipment are damaged, and single dioxy
The catalytic effect for changing titanium semiconductor is limited, it is impossible to meets actual requirement.Perhaps using ethanol as solvent, butyl titanate is for Pingchang et al.
Presoma, the loaded nano titanium dioxide photocatalysis agent of Ag surface modifications is prepared for solvent-thermal method.Research finds, surface A g
Modification improves TiO2Specific surface area, make its absorb band edge extend to visible-range, in addition, the presence of Ag particles can be effective
Ground suppresses the again compound of electronics and hole, makes TiO2Photocatalysis performance obtain certain raising.But the patent does not add also
Former agent, TiO2Lacking oxygen is not formed, in Visible Light Induced Photocatalytic 10-4In the experiment of mol/L methylene blue (MB) solution the used time compared with
It is long, just MB has been degraded after 3h.
The content of the invention
For the above-mentioned technical problem in prior art problem, the invention provides a kind of preparation of visible-light photocatalyst
Method, the visible-light photocatalyst that the preparation method of described this visible-light photocatalyst will solve to prepare in the prior art are urged
Change ineffective technical problem.
The invention provides a kind of preparation method of visible-light photocatalyst, comprise the following steps:
1) butyl titanate, ethanol, N are weighed2H4·H2O and AgNO3, described butyl titanate, ethanol, N2H4·H2O
And AgNO3Mol ratio be 1:(25~35):(5~10):(0.1~0.2);
2) after butyl titanate being dispersed in into ethanol, N is added2H4·H2O, 0.5~1.5h of ultrasound in ice-water bath, formed
TiO2Precursor sol, it is transferred in water heating kettle;
3) AgNO is added into water heating kettle under ultrasonic state3, at 160-200 DEG C, after reacting 6~10h, obtain rutile titania
Ore deposit TiO2/ Ag visible-light photocatalysts.
Innovative proposition of the invention is using hydrazine hydrate coordination and reduction, by simple hydro-thermal process, it is not necessary to after
The high-temperature process of phase, the support type Lacking oxygen titanium dioxide optical catalyst TiO of Ag surface modifications can be prepared using one kettle way2-X/
Ag, in this process, hydrazine hydrate is by part Ti4+It is reduced into Ti3+, trivalent titanium ion auto-dope titanium dioxide is obtained, so as to be formed
Lacking oxygen;Reducing agent is used as simultaneously by AgNO3In Ag+It is reduced to simple substance Ag.Pass through N2H4·H2The TiO produced after O reduction2It is interior
Lacking oxygen and the Ag that portion is formed act synergistically, and widen the absorption spectrum ranges of sample, can absorb visible ray, at the same carry Ag with
TiO2Between the heterojunction structure that is formed can extend the conducting path of photo-generated carrier, reduce answering for photohole and light induced electron
Efficiency is closed, the conduction velocity and separative efficiency of photo-generated carrier are improved, so as to improve visible light catalytic efficiency.Course of reaction is gentle
It is controllable, it is simple to operate, it is adapted to large-scale industrial production.
The present invention compares with prior art, and its technological progress is significant.The present invention is reacted in TiO by in-situ reducing2
Internal and surface forms Lacking oxygen and the load corresponding Nano Silver of visible ray respectively, and preparation method is simple, easily controllable.By this hair
Anatase TiO prepared by bright method2/ Ag visible-light photocatalyst powders outward appearance is in blueness, epigranular, soilless sticking, it is seen that
There is good photocatalysis effect under light irradiation.Such anatase TiO2/ Ag powders, under visible light illumination, it can be incited somebody to action in 1h
20mg/L methylene blue solution is degradable.
Brief description of the drawings:
Fig. 1 is TiO prepared by embodiment 12/ Ag visible-light photocatalysts SEM schemes;
Fig. 2 is TiO prepared by embodiment 22/ Ag visible-light photocatalysts SEM schemes;
Fig. 3 is TiO prepared by embodiment 32/ Ag visible-light photocatalysts SEM schemes;
Fig. 4 is TiO prepared by embodiment 1,2,32The XRD spectra of/Ag visible-light photocatalysts.
Embodiment
With reference to embodiment and relevant chart, the present invention will be described in detail, but real the invention is not restricted to give
Example:
Embodiment 1
1) according to butyl titanate (Ti (OC4H9)4):Ethanol:N2H4·H2O:AgNO3Mol ratio be 1:25:5:0.1 point
Also known as take sample;
2) by Ti (OC4H9)4After being dispersed in ethanol, N is added2H4·H2O, the ultrasonic 0.5h in ice-water bath, form TiO2Before
Body colloidal sol is driven, is transferred in water heating kettle;
3) AgNO is added into water heating kettle under ultrasonic state3, at 160 DEG C, after reacting 6h, obtain anatase TiO2/Ag
Visible-light photocatalyst.
SEM tests are carried out to gained sample using Japanese Hitachi S-4800II, as a result as shown in figure 1, gained sample
Epigranular, soilless sticking.
XRD spectra test is carried out to gained sample using German Brooker D8Advance, as a result as shown in figure 4, gained sample
There is TiO simultaneously in the XRD spectra of product2With the characteristic peak of Ag simple substance, illustrate the TiO for having Lacking oxygen2With the compound success of Ag simple substance.
By the anatase TiO prepared by the present embodiment2/ Ag visible-light photocatalysts, added with 0.05g/100mL ratio
Into 20mg/L methylene blue solution, under irradiating under visible light, methylene blue solution is degradable finish in 65min.
Embodiment 2
1) according to butyl titanate (Ti (OC4H9)4):Ethanol:N2H4·H2O:AgNO3Mol ratio be 1:30:7.5:
0.15 weighs sample respectively;
2) by Ti (OC4H9)4After being dispersed in ethanol, N is added2H4·H2O, the ultrasonic 1h in ice-water bath, form TiO2Forerunner
Body colloidal sol, is transferred in water heating kettle;
3) AgNO is added into water heating kettle under ultrasonic state3, at 180 DEG C, after reacting 8h, obtain anatase TiO2/Ag
Visible-light photocatalyst.
SEM tests are carried out to gained sample using Japanese Hitachi S-4800II, as a result as shown in Fig. 2 gained sample
Epigranular, soilless sticking.
XRD spectra test is carried out to gained sample using German Brooker D8Advance, as a result as shown in figure 4, gained sample
There is TiO simultaneously in the XRD spectra of product2With the characteristic peak of Ag simple substance, illustrate the TiO for having Lacking oxygen2With the compound success of Ag simple substance.
By the anatase TiO prepared by the present embodiment2/ Ag visible-light photocatalysts, added with 0.05g/100mL ratio
Into 20mg/L methylene blue solution, under irradiating under visible light, methylene blue solution is degradable finish in 60min.
Embodiment 3
1) according to butyl titanate (Ti (OC4H9)4):Ethanol:N2H4·H2O:AgNO3Mol ratio be 1:35:10:0.2
Sample is weighed respectively;
2) by Ti (OC4H9)4After being dispersed in ethanol, N is added2H4·H2O, the ultrasonic 1.5h in ice-water bath, form TiO2Before
Body colloidal sol is driven, is transferred in water heating kettle;
3) AgNO is added into water heating kettle under ultrasonic state3, at 200 DEG C, after anti-10h, obtain anatase TiO2/Ag
Visible-light photocatalyst.
SEM tests are carried out to gained sample using Japanese Hitachi S-4800II, as a result as shown in figure 3, gained sample
Epigranular, soilless sticking.
XRD spectra test is carried out to gained sample using German Brooker D8Advance, as a result as shown in figure 4, gained sample
There is TiO simultaneously in the XRD spectra of product2With the characteristic peak of Ag simple substance, illustrate the TiO for having Lacking oxygen2With the compound success of Ag simple substance.
By the anatase TiO prepared by the present embodiment2/ Ag visible-light photocatalysts, added with 0.05g/100mL ratio
Into 20mg/L methylene blue solution, under irradiating under visible light, methylene blue solution is degradable finish in 62min.
Claims (1)
1. a kind of preparation method of visible-light photocatalyst, it is characterised in that comprise the following steps:
1)Weigh butyl titanate, ethanol, N2H4·H2O and AgNO3, described butyl titanate, ethanol, N2H4· H2O and
AgNO3Mol ratio be 1:(25~35):(5~10):(0.1~0.2);
2)After butyl titanate is dispersed in into ethanol, N is added2H4· H2O, 0.5 ~ 1.5h of ultrasound in ice-water bath, form TiO2Before
Body colloidal sol is driven, is transferred in water heating kettle;
3)AgNO is added into water heating kettle under ultrasonic state3, at 160-200 DEG C, after reacting 6 ~ 10h, obtain anatase
TiO2/ Ag visible-light photocatalysts.
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Cited By (4)
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CN108579775A (en) * | 2018-05-15 | 2018-09-28 | 浙江大学城市学院 | A kind of silver orthophosphate/silver/titanium dioxide nano flower composite material and the preparation method and application thereof |
CN109663584A (en) * | 2018-12-19 | 2019-04-23 | 中南大学 | The preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst |
CN109967074A (en) * | 2019-03-20 | 2019-07-05 | 金华职业技术学院 | A kind of preparation method and application of the titanium dioxide optical catalyst of silver load |
CN115849449A (en) * | 2022-11-24 | 2023-03-28 | 中国人民解放军军事科学院军事医学研究院 | N-type semiconductor photo-anode and preparation method and application thereof |
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CN108579775B (en) * | 2018-05-15 | 2020-09-11 | 浙江大学城市学院 | Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application thereof |
CN109663584A (en) * | 2018-12-19 | 2019-04-23 | 中南大学 | The preparation method of Lacking oxygen type metal oxide semiconductor photochemical catalyst |
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CN109967074A (en) * | 2019-03-20 | 2019-07-05 | 金华职业技术学院 | A kind of preparation method and application of the titanium dioxide optical catalyst of silver load |
CN115849449A (en) * | 2022-11-24 | 2023-03-28 | 中国人民解放军军事科学院军事医学研究院 | N-type semiconductor photo-anode and preparation method and application thereof |
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