CN107824181A - A kind of preparation method of visible-light photocatalyst - Google Patents

A kind of preparation method of visible-light photocatalyst Download PDF

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Publication number
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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China
Prior art keywords
tio
visible
agno
ethanol
butyl titanate
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CN201711018202.9A
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Chinese (zh)
Inventor
张娜
张小磊
甘传先
万通
陈琪
房永征
刘玉峰
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/50Silver
    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16Reducing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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

A kind of preparation method of visible-light photocatalyst
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.
CN201711018202.9A 2017-10-26 2017-10-26 A kind of preparation method of visible-light photocatalyst Pending CN107824181A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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CN102909009A (en) * 2012-11-16 2013-02-06 厦门大学 Preparing method of crystalline silver loaded TiO2 nanometer particle
CN103240068A (en) * 2013-05-22 2013-08-14 湛江师范学院 Preparation method of self-doped titanium dioxide nanorod
CN106423153A (en) * 2016-09-21 2017-02-22 武汉大学 Preparation method and oxygen indicator of silver-doped titanium dioxide nanotubes
CN106582595A (en) * 2016-12-28 2017-04-26 上海应用技术大学 Preparation method for blue TiO2 catalyst
CN107088405A (en) * 2017-04-24 2017-08-25 太原理工大学 A kind of preparation method of modified nano-titanium dioxide photochemical catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102909009A (en) * 2012-11-16 2013-02-06 厦门大学 Preparing method of crystalline silver loaded TiO2 nanometer particle
CN103240068A (en) * 2013-05-22 2013-08-14 湛江师范学院 Preparation method of self-doped titanium dioxide nanorod
CN106423153A (en) * 2016-09-21 2017-02-22 武汉大学 Preparation method and oxygen indicator of silver-doped titanium dioxide nanotubes
CN106582595A (en) * 2016-12-28 2017-04-26 上海应用技术大学 Preparation method for blue TiO2 catalyst
CN107088405A (en) * 2017-04-24 2017-08-25 太原理工大学 A kind of preparation method of modified nano-titanium dioxide photochemical catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN109663584B (en) * 2018-12-19 2021-07-06 中南大学 Preparation method of oxygen vacancy type metal oxide semiconductor photocatalyst
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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