CN101531396B

CN101531396B - TiO2 nanotube with molecular imprinting functionalization

Info

Publication number: CN101531396B
Application number: CN200910043182XA
Authority: CN
Inventors: 罗胜联; 刘承斌; 唐艳红; 杨丽霞; 刘荣华; 何晔娟
Original assignee: Hunan University
Current assignee: Hunan University
Priority date: 2009-04-22
Filing date: 2009-04-22
Publication date: 2010-12-29
Anticipated expiration: 2029-04-22
Also published as: CN101531396A

Abstract

The invention discloses a TiO2 nanotube with molecular imprinting functionalization and relates to a TiO2 nanotube with inorganic semiconductor film modification of organic pollutant imprinting; wherein, the imprinting matrix material is an inorganic semiconductor; and the imprinting molecule is an organic pollutant. The molecular imprinting polymer synthesized by molecular imprinting technology which adopts inorganic nano material as imprinting matrix has high mechanical strength and the identification point is not easy to be damaged. As an absorptive carrier, the TiO2 nanotube greatly reduces nonspecific absorption and reduces embedding phenomenon, thus having very optimistic development prospect in the aspects of photocatalysis, mimic enzymes, sensors and biometric identification, etc.

Description

A kind of molecular imprinting functionalization TiO 2Nanotube

Technical field

The present invention relates to the imprinting functionalization TiO of a class novel texture ₂Nano-tube material.

Background technology

Because the functional not strong and hydrophobicity characteristics of the chemical reaction of most organic pollutant molecules are at possess hydrophilic property TiO ₂Surface adsorption is very low, and this also is to utilize TiO ₂Eliminate one of bottleneck of hydrophobic organic pollutant, therefore strengthen organic pollutant at TiO ₂The absorption research on photocatalyst material surface is extremely important to the efficient reduction of organic pollutant.A kind of analog antibody-antigen-specific identification and bonded artificial bio-membrane mould plate technique-molecular imprinting have caused everybody interest.In this technology, template molecule (microsphere) forms stabilized complex with one or more function monomers by covalent linkage or noncovalent interaction such as hydrogen bond, Van der Waals force, ionization, hydrophobic interaction and π-π effect etc., add linking agent and cause the function monomer polymerization, remove again template molecule obtain molecularly imprinted polymer (Molecularly imprinted polymers, MIP).MIP has the cavity that shape, size and template molecule are complementary, and the functional group of particular arrangement is arranged, and can produce the specific recognition effect with template molecule.Molecular imprinting is showing tempting application prospect aspect the selective enrichment organic pollutant.But, organic polymer trace matrix is being modified TiO ₂Have some problems when being used for photochemical catalysis: imprinted polymer covers TiO ₂The surface influences TiO ₂Photoabsorption and charge transfer; Imprinted polymer can be degraded in photocatalytic process; Organic polymer trace matrix mechanicalness and thermostability are bad, cause the shape memory instability.And inorganic polymer trace film is expected to address the above problem, and it has the big and advantages such as favorable mechanical stability and thermostability of specific surface area, can overcome the rigidity of organic polymer and the shortcoming of inertia difference, becomes the molecular imprinting development trend.

Summary of the invention

The object of the present invention is to provide the film modified TiO of organic pollutant trace inorganic semiconductor ₂Nanotube.

The present invention seeks to realize by following manner:

A kind of molecular imprinting functionalization TiO ₂Nanotube is at TiO ₂Be combined with on the nanotube walls surface by organic pollutant trace inorganic semiconductor film, wherein the trace substrate material is an inorganic semiconductor, and microsphere is an organic pollutant.

Described organic pollutant comprises persistence organic pollutant.

Inorganic semiconductor trace substrate material is TiO ₂, CdS, CdSe, SiC, WO ₃, ZnS, ZnO, SnO ₂, Nb ₂O ₅, ZrO ₂, V ₂O ₅, Ta ₂O ₅Or SrTiO ₃

TiO ₂Nanotube is pure TiO ₂Nanotube, or compound TiO ₂Nanotube.

Described compound TiO ₂Nanotube comprises that precious metal doping is compound, semi-conductor is compound, ion doping is compound or nonmetal doping compound TiO ₂Nanotube, or comprise compound TiO altogether more than 2 kinds or 2 kinds in precious metal doping, semi-conductor, ion doping and the nonmetal doping ₂Nanotube.

Described compound TiO ₂The precious metal doping of nanotube is compound to comprise that the metal doping more than a kind or a kind among Pt, Pd, Au and the Ag is compound.

Described compound TiO ₂The compound nonmetallic doped and compounded more than a kind or a kind that comprises among C, N, S and the B of the nonmetal doping of nanotube.

Described compound TiO ₂Compound CdS, CdSe, SiC, the WO of comprising of the semi-conductor of nanotube ₃, ZnS, ZnO, SnO ₂, Nb ₂O ₅, ZrO ₂, V ₂O ₅, Ta ₂O ₅And SrTiO ₃In semi-conductive compound more than a kind or a kind.

Described compound TiO ₂The compound Fe that comprises of the ion doping of nanotube ³⁺, Co ²⁺, Cr ³⁺, Zn ²⁺, Zr ⁴⁺, Nb ⁵⁺, Ga ³⁺, W ⁶⁺, Fe (CN) ₆ ^4-, MoS ₄ ^2-, Li ⁺, Na ⁺, K ⁺, Ba ²⁺, Ca ²⁺And SO ₄ ^2-In ionic doped and compounded more than a kind or a kind.

The present invention can adopt template, electrochemistry anodic oxidation or Hydrothermal Preparation TiO ₂Nanotube; Adopt anode co-oxidation deposition, gas/liquid is permeated mutually or method such as in-situ oxidation reduction prepares compound TiO ₂Nanotube; Adopt methods such as sol-gel, galvanic deposit, chemical vapour deposition, physical vapor deposition, self-assembly or spraying thermolysis at TiO ₂The nanotube walls surface preparation contains the TiO of organic pollutant ₂, CdS, CdSe, SiC, WO ₃, ZnS, ZnO, SnO ₂, Nb ₂O ₅, ZrO ₂, Ta ₂O ₅Or SrTiO ₃Deng the inorganic semiconductor film; Methods such as employing solvent elution, hydrolysis, thermal treatment or catalyzed degradation are removed the organic pollutant microsphere in the trace thin film layer.

The present invention is the molecular imprinting synthetic molecularly imprinted polymer physical strength height of trace matrix with the inorganic nano material, and identification point is survivable.As absorption carrier, reduced non-specific adsorption widely, reduce the embedding phenomenon, make it that very optimistic development prospect be arranged at aspects such as photochemical catalysis, analogue enztme, transmitter and bio-identification.

Description of drawings

Fig. 1 is for adopting surperficial sol-gel technique imprinting functionalization TiO ₂Nanotube principle diagrammatic sketch.

Embodiment

Following examples are intended to illustrate the present invention rather than limitation of the invention further.

Embodiment 1

(1) TiO ₂The preparation of nanotube

Under the 35-60V volts DS, be anode with pure titanium or titanium alloy, platinized platinum is a negative electrode, is to prepare TiO in the hydrofluoric acid of 0.5-3% and the dimethyl sulfoxide (DMSO) blended ionogen at hydrofluoric acid quality percentage composition ₂Nanotube is calcined nanotube 4-6 hour under 400-500 ℃ of aerobic conditions, makes its crystallization forming.

(2) imprinting functionalization TiO ₂The nanotube preparation

Adopt surperficial sol-gel technique preparation: preparation process as shown in Figure 1.Among Fig. 1, M=Zn, R are sec.-propyl or normal-butyl, ● represent organic pollutant molecule,

The room that stays in the organic pollutant molecule rear film is removed in representative.

With TiO ₂Nanotube is immersed in for some time in the alcoholic solution of the tetra isopropyl oxygen base zinc that contains octabromodiphenyl ether microsphere, and hydrolysis then places air drying again, according to film thickness needs, TiO ₂Nanotube can soak-hydrolysis-drying treatment repeatedly, and the TiO that the microsphere after drying can obtain the modification of octabromodiphenyl ether trace ZnO film is removed in heat drying typing then at last ₂Nanotube.

Embodiment 2

Use M among the embodiment 1 instead Ti, all the other conditions can be prepared octabromodiphenyl ether trace TiO with embodiment 1 ₂The TiO of film modification ₂Nanotube.

Embodiment 3

Use M among the embodiment 1 instead Zr, all the other conditions can be prepared octabromodiphenyl ether trace ZrO with embodiment 1 ₂The TiO of film modification ₂Nanotube.

Embodiment 4

(1) TiO ₂The preparation of nanotube

With embodiment 1.

(2) imprinting functionalization TiO ₂The nanotube preparation

With TiO ₂Nanotube is immersed in for some time in the CdS colloidal sol that contains the pentachlorobenzene microsphere, places air drying again, according to film thickness needs, TiO ₂Nanotube can soak-drying treatment repeatedly, heat drying typing then, and last flush away template molecule after drying can obtain the TiO of pentachlorobenzene trace CdS film modification ₂Nanotube.

Embodiment 5

Use CdS among the embodiment 4 instead ZnS, all the other conditions can be prepared the TiO of pentachlorobenzene trace ZnS film modification with embodiment 4 ₂Nanotube.

Embodiment 6

Use CdS among the embodiment 4 instead CdSe, all the other conditions can be prepared the TiO of pentachlorobenzene trace CdSe film modification with embodiment 4 ₂Nanotube.

Embodiment 7

(1) TiO ₂The preparation of nanotube

With embodiment 1.

(2) C-TiO ₂The composite nano tube preparation

TiO with (one) preparation ₂Nanotube places the anaerobic vacuum system, is carbon source with the polyoxyethylene glycol, in 500-600 ℃ of calcining 2-12 hour, makes polyoxyethylene glycol dehydration carbonization obtain C-TiO ₂Composite nano tube.

(3) imprinting functionalization C-TiO ₂The composite nano tube preparation

TiO with (two) step among the embodiment 1 ₂Nanotube changes C-TiO into ₂Composite nano tube, octabromodiphenyl ether changes perfluoro octyl sulfonic acid into, and all the other prepare the C-TiO of perfluoro octyl sulfonic acid trace ZnO film modification with (two) step among the embodiment 1 ₂Composite nano tube.

Embodiment 8

(1) Fe-C-TiO ₂The composite nano tube preparation

C-TiO with embodiment 7 preparations ₂Nanotube places the FeSO4 electroplate liquid to electroplate, and electroplating current density is 0.002-0.005A/s, obtains Fe-C-TiO ₂Composite nano tube.

(2) imprinting functionalization Fe-C-TiO ₂The composite nano tube preparation

C-TiO with (three) step among the embodiment 7 ₂Composite nano tube changes Fe-C-TiO into ₂Composite nano tube, all the other prepare the Fe-C-TiO of perfluoro octyl sulfonic acid trace ZnO film modification with (three) step among the embodiment 7 ₂Composite nano tube.

Claims

1. molecular imprinting functionalization TiO ₂Nanotube is characterized in that, at TiO ₂Be combined with on the nanotube walls surface by organic pollutant trace inorganic semiconductor film, wherein the trace substrate material is an inorganic semiconductor, and microsphere is an organic pollutant; Described inorganic semiconductor trace substrate material is TiO ₂, CdS, CdSe, SiC, WO ₃, ZnS, ZnO, SnO ₂, Nb ₂O ₅, ZrO ₂, V ₂O ₅, Ta ₂O ₅Or SrTiO ₃

2. a kind of molecular imprinting functionalization TiO according to claim 1 ₂Nanotube is characterized in that, described organic pollutant comprises persistence organic pollutant.

3. a kind of molecular imprinting functionalization TiO according to claim 1 and 2 ₂Nanotube is characterized in that, TiO ₂Nanotube is pure TiO ₂Nanotube, or compound TiO ₂Nanotube.

4. a kind of molecular imprinting functionalization TiO according to claim 3 ₂Nanotube is characterized in that, described compound TiO ₂Nanotube comprises that precious metal doping is compound, semi-conductor is compound, ion doping is compound or nonmetal doping compound TiO ₂Nanotube, or comprise compound TiO altogether more than 2 kinds in precious metal doping, semi-conductor, ion doping and the nonmetal doping ₂Nanotube.

5. a kind of molecular imprinting functionalization TiO according to claim 4 ₂Nanotube is characterized in that, described compound TiO ₂The precious metal doping of nanotube is compound to comprise among Pt, Pd, Au and the Ag that metal doping is compound more than a kind.

6. a kind of molecular imprinting functionalization TiO according to claim 4 ₂Nanotube is characterized in that, described compound TiO ₂The nonmetal doping of nanotube is compound to comprise among C, N, S and the B nonmetallic doped and compounded more than a kind.

7. a kind of molecular imprinting functionalization TiO according to claim 4 ₂Nanotube is characterized in that, described compound TiO ₂Compound CdS, CdSe, SiC, the WO of comprising of the semi-conductor of nanotube ₃, ZnS, ZnO, SnO ₂, Nb ₂O ₅, ZrO ₂, V ₂O ₅, Ta ₂O ₅And SrTiO ₃In semi-conductive compound more than a kind.

8. a kind of molecular imprinting functionalization TiO according to claim 4 ₂Nanotube is characterized in that, described compound TiO ₂The compound Fe that comprises of the ion doping of nanotube ³⁺, Co ²⁺, Cr ³⁺, Zn ²⁺, Zr ⁴⁺, Nb ⁵⁺, Ga ³⁺, W ⁶⁺, Fe (CN) ₆ ^4-, MoS ₄ ^2-, Li ⁺, Na ⁺, K ⁺, Ba ²⁺, Ca ²⁺And SO ₄ ^2-In ionic doped and compounded more than a kind.