CN104741134B

CN104741134B - A kind of TiO2The preparation method of/ZnS two-layer compound nano-tube arrays

Info

Publication number: CN104741134B
Application number: CN201410521312.7A
Authority: CN
Inventors: 曲晓飞; 杜芳林; 候雨尘
Original assignee: Qingdao University of Science and Technology
Current assignee: Qingdao University of Science and Technology
Priority date: 2014-10-04
Filing date: 2014-10-04
Publication date: 2017-03-29
Anticipated expiration: 2034-10-04
Also published as: CN104741134A

Abstract

The present invention relates to a kind of TiO₂The preparation method of/ZnS two-layer compound nano-tube arrays, TiO₂It is a kind of broad-band gap (3.2eV) semi-conducting material, has the advantages that oxidability is strong due to which, do not occur that photoetch, catalysis activity are high, wide, the nontoxic own Jing that originates becomes a kind of more deep catalysis material of multiple association area researchs after illumination.But TiO₂Quantum efficiency is still suffered from use low, powder particle is easily reunited inactivation, it is difficult to the defect such as recycle.In order to solve the above problems, photocatalysis efficiency is improved, generally to TiO₂It is modified process.The present invention is template with porous anodic aluminium oxide, using the method for liquid phase layer assembly, ZnS is nested into TiO₂In nanotube.The two-layer compound nanotube that the present invention is obtained, considerably increases TiO₂With the contact area of ZnS；Simultaneously because the two special valence band structure, improves separation of charge rate, improves photocatalysis efficiency.Nanotube is present in the form of an array, it is easy to reclaim from processing in sewage, it is to avoid cause secondary pollution, this has highly important application value in terms of sewage disposal.

Description

A kind of TiO2The preparation method of/ZnS two-layer compound nano-tube arrays

Technical field：

The present invention relates to a kind of preparation method of inorganic composite nano pipe array, more particularly to a kind of TiO₂/ ZnS is double-deck The preparation method of composite nano tube array, in particular, adopts liquid phase deposition for template using porous anodic alumina films AAO/TiO is prepared first₂Nano-tube array, then in AAO/TiO₂ZnS is prepared using hydro-thermal method on the basis of array and is nested in TiO₂ Two-layer compound TiO inside nanotube₂/ ZnS nano-tube arrays.This technology belongs to the preparation field of nano material.

Background technology：

In recent years, volatile organic matter VOCS (Volatile of the industrial wastewater especially from generations such as petrochemical industries Organic Compounds) impact to environment is increasing, and the sustainable development of ecological environment is had a strong impact on, has been caused The extensive concern of society.With attention of the country to sewage drainage standard, sewage drainage standard more and more higher, promote enterprise demand Low cost, high efficiency, the easy sewage water treatment method of operating procedure.But existing conventional sewage processing method is to biodegradable tired The disposal ability of difficult volatile organic content is not enough, and is accompanied by greater energy consumption cost more, makes enterprise hang back, even Interests are made a desperate move and abandon sewage disposal operation.Therefore seek a kind of easy to be economical, efficient sewage water treatment method has become society Can focal issue.

Photocatalysis technology is a kind of new sewage disposal technology, using Strong oxdiative ability or the generation indirectly of photohole Hydroxyl radical free radical degradation of contaminant, because which has process is simple, energy consumption is low, gets most of the attention the features such as low cost, especially Which is to organic wastewater, high-strength acidic and alkaline waste water etc. with stronger catalytic degradation ability.TiO₂It is a kind of wide bandgap semiconductor materials, Energy gap is about 3.2eV, has that oxidability is strong due to which, photoetch does not occur after illumination, and catalysis activity is high, chemically stable Property good, the wide low cost of originating, it is nontoxic the advantages of own Jing become the photocatalysis fields such as wastewater treatment, purification of air and sterilization A kind of more deep catalysis material of research.But TiO₂Problems with has been still suffered from use：(1)TiO₂Taboo Band is wider, can only absorbing wavelength below 385nm short-wave band light, energy probably only accounts for the 4% of solar energy, how to utilize The visible ray or even infrared energy of total luminous energy more than 45% are accounted for, is to determine that can catalysis material be answered extensive reality is able to Prerequisite.(2)TiO₂Also higher to recombination rate as the photo-generate electron-hole of single semi-conducting material, its quantum is imitated The low defect of rate also limits its use to a certain extent.(3) Conventional nano TiO₂Powder particle easy in inactivation, thus not Utilize beneficial to long-time, cycle characteristics is poor, easily reunite and reduce active reaction surface area, adsorption capacity is poor, and particle is tiny to be difficult to The critical defects such as recycling, its application is by a definite limitation.

In order to solve the above problems, photocatalysis efficiency is improved, generally to TiO₂It is modified process, such as metal or nonmetallic Ion doping, photosensitizer and other semiconductors couplings etc..Semiconductors coupling is the effective means of one of which, and which is in photocell Still there is larger research space in field in terms of photocatalytic degradation sewage using more.

The activity of photochemical catalyst has very big contact with pattern, size and structure.For TiO₂/ ZnS composites, it is most with Graininess pattern is present, or with random scattered nanotube-shaped existence form, and majority is to be attached to TiO with ZnS particles₂Pipe Outer wall, in sewage is processed is difficult to reclaim, easily causes secondary pollution.

The content of the invention：

It is an object of the invention to provide a kind of TiO₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is existing to overcome Technical deficiency.It is template with porous anodic aluminium oxide, using the method for layer assembly, semiconductor ZnS is nested into TiO₂In nanotube.The technique belongs to a kind of environmentally friendly preparation method, while this preparation method process is simple, equipment Require relatively low, with low cost, the potentiality with large-scale production and application.

A kind of TiO₂The preparation method of/ZnS two-layer compound nano-tube arrays, which concretely comprises the following steps:

(1) from porous anodic alumina films be template, to analyze pure Zn (CH₃COO)₂, Na₂S₂O₃And TiF₄As original Material；

(2) TiF of 0.01～1mol/L of configuration concentration₄The aqueous solution, anodic oxidation aluminium formwork is immersed in matched somebody with somebody solution, is protected 40～100 DEG C of system temperature is held, the time, 3～15min made TiO₂Hole of the precursor sol uniform deposition to anodic oxidation aluminium formwork In road；

(3) step (2) products obtained therefrom is taken out to be placed in the baking oven that temperature is 50～100 DEG C and is dried 0.5～2h, obtained TiO containing anodic oxidation aluminium formwork₂Presoma nano-tube array；

(4) TiO will be loaded with₂The anodic oxidation aluminium formwork of presoma is immersed in the Zn that concentration is 0.01～2mol/L (CH₃COO)₂And Na₂S₂O₃In solution, 100～200 DEG C of hydrothermal temperature is kept in the water heating kettle with polytetrafluoroethylene (PTFE) as liner, 2～24h of hydrothermal conditions, product deionized water is cleaned, drying, is finally given ZnS and is nested in TiO₂In nanotube Double-deck TiO₂/ ZnS composite nano tube arrays.

ZnS is about 3.6eV as a kind of important metal sulfide semiconductor, band gap width.By TiO₂It is compound with ZnS, On the one hand due to TiO₂Conduction band about 0.75eV lower than ZnS so that light induced electron is transferred to TiO from ZnS₂On, and photoproduction Hole is then from TiO₂It is transferred in valence band in the valence band of ZnS, so as to improve separation of charge, reduces electron-hole recombinations, carry Photocatalysis efficiency is risen.Detached electronics and hole freely can be reacted with the active material of adsorption.The opposing party Face, two-layer pipe also cause ZnS and TiO₂Contact area has and largely improves, and is conducive to the raising of catalytic efficiency.Relatively In TiO prepared by the catalyst material that dispersity is present, the present invention₂/ ZnS composite nano tubes are present in the form of an array, it is easy to Recycle from processing in sewage, it is to avoid secondary pollution also reduces the production cost of catalyst simultaneously.

The invention has the beneficial effects as follows：

Nanotube is prepared using AAO templates, caliber suitably can be adjusted, and course of reaction is easily controllable.TiO is modified with ZnS₂ Nanotube, due to the band structure cross effect of the two, improves separation of charge efficiency, reduces electron-hole recombinations, is lifted Photocatalysis efficiency.Double-layer nanometer tubular construction is conducive to increasing TiO₂With the contact area of ZnS, dividing beneficial to photo-generate electron-hole From.Additionally, catalyst is present with nano-tube array form, it is easy to reclaim from processing in sewage, it is to avoid cause secondary pollution.It is excellent Photocatalysis performance and simple possible continuity preparation technology so that TiO₂/ ZnS two-layer compounds nano-tube array is at sewage Reason field has a wide range of applications.

Description of the drawings：

Fig. 1, TiO₂The upper surface SEM pictures of/ZnS two-layer compound nano-tube arrays

Fig. 2, TiO₂The side SEM pictures of/ZnS two-layer compound nano-tube arrays

Fig. 3, TiO₂The side magnification at high multiple SEM pictures of/ZnS two-layer compound nano-tube arrays

Fig. 4, TiO₂The EDS collection of illustrative plates of/ZnS two-layer compound nano-tube arrays

Fig. 5, TiO₂The TEM pictures of/ZnS two-layer compound nanotubes

Specific embodiment：

Embodiment 1

The TiF of 0.04M is prepared in beaker₄Solution, heats TiF₄Anodic oxidation aluminium formwork is soaked completely by solution to 60 DEG C Enter to keep the immersion time to be 9min.Then sample is taken out to be placed in the baking oven that temperature is 80 DEG C and is dried 1h.Subsequently will load There is TiO₂The anodic oxidation aluminium formwork of presoma is immersed in the Zn (CH of 0.04M₃COO)₂With the Na of 0.04M₂S₂O₃In mixed solution, The hydro-thermal reaction in the water heating kettle with polytetrafluoroethylene (PTFE) as liner, 180 DEG C of hydrothermal temperature, reaction time 6h.Use after taking out sample Deionized water is cleaned, and drying is nested in TiO by ZnS₂TiO in nanotube₂/ ZnS two-layer compound nano-tube arrays.By Fig. 1 TiO can more clearly be found out₂The inside and outside wall of/ZnS two-layer compound nanotubes, wall thickness 60nm or so, aperture 200nm or so.By Fig. 2 can be seen that the TiO of preparation₂/ ZnS two-layer compound nano-tube arrays length is 25 μm or so.More clearly can be seen by Fig. 3 Go out TiO₂The nano tube structure of parcel ZnS.Include Ti, O, Zn, S, Al, C, Pt, Si in multiple tube array as seen from Figure 4 Deng element, wherein Pt from SEM test when spray Pt operations.From anodic oxidation aluminium formwork, Si comes from when SEM is tested Al Silicon chip.Ti in addition, O, Zn, S content are significantly higher, can primarily determine that with anodised aluminium as template, using group layer by layer Dress technology has successfully prepared TiO₂/ ZnS two-layer compound nano-tube array structures.By Fig. 5 it can clearly be seen that ZnS is nested in TiO₂ Double-layer nanometer tubular construction in nanotube.

Claims

1. a kind of TiO₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that:

(1) from porous anodic alumina films be template, to analyze pure Zn (CH₃COO)₂, Na₂S₂O₃And TiF₄As raw material；

(2) configure certain density TiF₄The aqueous solution, anodic oxidation aluminium formwork is immersed in matched somebody with somebody solution, system temperature one is kept Determine scope, appropriate time makes TiO₂Precursor sol uniform deposition is in the duct of anodic oxidation aluminium formwork；

(3) step (2) products obtained therefrom is taken out and be dried in an oven a period of time, obtain the TiO containing anodic oxidation aluminium formwork₂ Presoma nano-tube array；

(4) TiO will be loaded with₂The anodic oxidation aluminium formwork of presoma is immersed in certain density Zn (CH₃COO)₂And Na₂S₂O₃It is molten In liquid, in the water heating kettle with polytetrafluoroethylene (PTFE) as liner keep hydrothermal temperature proper range, hydro-thermal process for a period of time, subsequently By product deionized water wash clean, dry, finally give the TiO containing anodic oxidation aluminium formwork₂The two-layer compound of cladding ZnS Nano-tube array.

2. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that described mould Plate is porous anodic alumina films, and film thickness is 20～60 μm, and channel diameter is 100～250nm, lower through-hole on fenestra road.

3. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that described TiO₂/ ZnS composite Nanos length of tube is 20～60 μm, and wall thickness is 20～80nm.

4. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that described TiF₄Solution concentration is 0.01～1mol/L.

5. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that step (2) In, keep 40～100 DEG C of system temperature, 3～15min of time.

6. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that step (3) In temperature dry in an oven be 50～100 DEG C, drying time is 0.5～2h.

7. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that described Na₂S₂O₃With Zn (CH₃COO)₂The concentration of the aqueous solution is 0.01～2mol/L.

8. TiO as claimed in claim 1₂The preparation method of/ZnS two-layer compound nano-tube arrays, it is characterised in that step (4) Middle employing hydro-thermal reaction, hydrothermal temperature are 100～200 DEG C, 2～24h of hydrothermal conditions.