CN103041798A

CN103041798A - Preparation method for metal oxide modified nano-TiO2 film material

Info

Publication number: CN103041798A
Application number: CN201210545972XA
Authority: CN
Inventors: 宋仁国; 李鑫伟; 项博; 王超
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2012-12-17
Filing date: 2012-12-17
Publication date: 2013-04-17

Abstract

The invention discloses a preparation method for a metal oxide modified nano-TiO2 film material. The method comprises the following steps: (1) a pure titanium sheet is prepared to a rectangular sheet with dimensions of 25 mm*15 mm*2 mm; (2) the titanium sheet is pretreated through sanding, oil removing, hydrochloric acid liquid rinsing, ultrasonic de-ionized water cleaning and vacuum drying; (3) the pretreated titanium sheet is placed on micro-arc oxidization equipment; the experiment parameters are as follows: the voltage is 420 V; the preparation time is 30 min; the concentration of Na3PO4 in a phosphate electrolyte system is 10 g/L; the concentration of NaF is 1 g/L; the electrolytic temperature is controlled below 35 DEG C; then 2-20 mmol metal oxide is added in the electrolyte, and is reacted under the magnetic stirring so as to synchronously implement the doping and the micro-arc oxidization, wherein the titanium sheet as anode is dipped in treating agent; and a stainless steel vessel provided with a cooling system is used as cathode; and (4) the prepared nano-TiO2 film is rinsed by de-ionized water and is dried. The nano-TiO2 film prepared by the method has high photocatalytic degradation rate, and brings convenience to industrial production.

Description

A kind of modified metal oxide nano-TiO 2The preparation method of thin-film material

Technical field

The present invention relates to a kind of nano-TiO ₂Thin-film material, especially a kind of composite Nano TiO ₂The preparation method of thin-film material.

Background technology

In numerous semiconductor light-catalysts, TiO ₂Strong because of its oxidability, chemical stability good, catalytic activity is high, the advantage such as nontoxic is in the core status in the photocatalysis research, is widely used in the fields such as automatically cleaning, environmental pollution improvement as the nano titanium oxide of semi-conducting material by people because of himself nontoxic, inexpensive, high activity and the speciality such as high stability.But present stage prepares nano-TiO ₂Method ubiquity cost high, process is wayward, products obtained therefrom is still take unfavorable recovery, the granulated powders that easily runs off as the defective such as main.Can't satisfy people for high-quality TiO ₂The actual demand of photochemical catalyst.At present, the nano-TiO that exists with form of film ₂Photochemical catalyst has replaced the graininess nano-TiO gradually ₂Form the emphasis for the stage research of people elder generation,, there are not the problems such as loss in the film attitude, but are inferior to the particulate form nano-TiO in catalytic activity in conjunction with firmly than particulate form ₂(reduced specific area when film adheres to and also just reduced response area).Zhai Yuchun etc. mention prepared TiO in " lanthanum nitrate is processed the impact on differential arc oxidation titanium dioxide film photocatalysis performance " (" China rare earth journal ", the 4th phase of 23 volumes in 2005,434-437 page or leaf) ₂The photocatalytic activity of film is up to 34.8%.

Summary of the invention

For solving above shortcomings in the differential arc oxidization technique, the invention provides a kind of nano-TiO ₂The preparation method of thin-film material is by the prepared TiO of ion infusion process ₂The photocatalytic activity of film has significantly improved TiO near 60% ₂The efficient of film light catalytic degradation.

The technical solution used in the present invention is as follows:

A kind of modified metal oxide nano-TiO ₂The preparation method of thin-film material, comprise the steps: that (1) is prepared into pure titanium sheet the rectangle thin slice of 25mm * 15mm * 2mm, (2) the titanium sheet is carried out preliminary treatment, comprise: sand papering, oil removing, hydrochloric acid solution rinsing, ultrasonic wave washed with de-ionized water and vacuum drying, (3) pretreated titanium sheet is placed in microarc oxidation equipment provided on, experiment parameter is: voltage 420V, preparation time 30min, Na in the phosphate electrolyte system ₃PO ₄Concentration is 10g/L, NaF concentration is 1g/L, electrolysis temperature is controlled at below 35 ℃, then the metal oxide with 2-20mmol joins in the electrolyte, react under magnetic agitation, carry out simultaneously with differential arc oxidation so that mix, wherein the titanium sheet is immersed in the treatment fluid as anode, as negative electrode, (4) are with the nano-TiO for preparing with the rustless steel container of cooling system ₂Film carries out rinsed with deionized water and drying.

Described metal oxide is: one or more in zinc oxide, vanadic anhydride, silver oxide, cerium oxide, lanthana, dysprosia or the lead oxide.

Beneficial effect of the present invention is mainly reflected in: the nano-TiO of (1) preparation ₂The photocatalytic activity of film is high; (2) course of reaction is easily controlled; (3) raw material is cheap, common, and technique is simple, cost is low, is beneficial to suitability for industrialized production.

Description of drawings

Fig. 1 is the nano-TiO that cerium oxide is modified ₂The XRD diffracting spectrum of film.

Fig. 2 is nano-TiO behind the cerium oxide electrolysis modifying ₂The SEM photo of film.

Fig. 3 is nano-TiO behind the cerium oxide electrolysis modifying ₂The EDS of film can spectrogram.

Fig. 4 is nano-TiO behind the metal oxide electrolysis modifying ₂Film is on the figure that affects of methylene blue Photocatalytic Decoloration.

The specific embodiment

The present invention is described further below in conjunction with concrete mode:

Embodiment 1:

The pure titanium sheet of the rectangle of raw material: 25mm * 15mm * 2mm, the Na of 10g/L ₃PO ₄Solution, the NaF solution of 1g/L, 10mmol cerium oxide.

Step: pretreated titanium sheet is placed in microarc oxidation equipment provided upper (experiment parameter is: voltage 420V, preparation time 30min, Na in the phosphate electrolyte system ₃PO ₄Concentration is 10g/L, and NaF concentration is 1g/L, and electrolysis temperature is controlled at below 35 ℃), the cerium oxide of 10mmol is joined in the electrolyte, under magnetic agitation, react, carry out simultaneously with differential arc oxidation so that mix, at last with the nano-TiO for preparing ₂Film carries out rinsed with deionized water, drying.

Embodiment 2:

The pure titanium sheet of the rectangle of raw material: 25mm * 15mm * 2mm, the Na of 10g/L ₃PO ₄Solution, the NaF solution of 1g/L, 20mmol silver oxide.

Step: pretreated titanium sheet is placed in microarc oxidation equipment provided upper (experiment parameter is: voltage 420V, preparation time 30min, Na in the phosphate electrolyte system ₃PO ₄Concentration is 10g/L, and NaF concentration is 1g/L, and electrolysis temperature is controlled at below 35 ℃), the silver oxide of 20mmol is joined in the electrolyte, under magnetic agitation, react, carry out simultaneously with differential arc oxidation so that mix, at last with the nano-TiO for preparing ₂Film carries out rinsed with deionized water, drying.

Embodiment 3:

The pure titanium sheet of the rectangle of raw material: 25mm * 15mm * 2mm, the Na of 10g/L ₃PO ₄Solution, the NaF solution of 1g/L, 5mmol vanadic anhydride.

Step: pretreated titanium sheet is placed in microarc oxidation equipment provided upper (experiment parameter is: voltage 420V, preparation time 30min, Na in the phosphate electrolyte system ₃PO ₄Concentration is 10g/L, and NaF concentration is 1g/L, and electrolysis temperature is controlled at below 35 ℃), the vanadic anhydride of 5mmol is joined in the electrolyte, under magnetic agitation, react, carry out simultaneously with differential arc oxidation so that mix, at last with the nano-TiO for preparing ₂Film carries out rinsed with deionized water, drying.

Embodiment 4:

Raw material preparation: the pure titanium sheet of the rectangle of 25mm * 15mm * 2mm, the Na of 10g/L ₃PO ₄Solution, the NaF solution of 1g/L, 10mmol lead oxide.

Step: pretreated titanium sheet is placed in microarc oxidation equipment provided upper (experiment parameter is: voltage 420V, preparation time 30min, Na in the phosphate electrolyte system ₃PO ₄Concentration is 10g/L, and NaF concentration is 1g/L, and electrolysis temperature is controlled at below 35 ℃), the lead oxide of 10mmol is joined in the electrolyte, under magnetic agitation, react, carry out simultaneously with differential arc oxidation so that mix, at last with the nano-TiO for preparing ₂Film carries out rinsed with deionized water, drying.

Adopt Thermo ARL X ' TRA type X-ray diffractometer (XRD) to measure nano-TiO ₂The phase structure of film; Measure the surface microscopic topographic of sample with Hitachi S-4700 type ESEM (SEM), and carry out power spectrum (EDS) analysis (scan mode of power spectrum is face scanning).

(1) XRD analysis: Fig. 1 is the nano-TiO that cerium oxide is modified ₂The XRD diffracting spectrum of film.As can be seen from the figure, CeO ₂Entered lattice, and content is considerable.Illustrate and by the reaction energy, can help well Ce by directly reaction ⁴⁺And oxide enters into intracell.Under a certain amount of prerequisite, mixing of they can be at TiO ₂Introduce more defective locations in the lattice, form more trap center, suppress well the compound of Pair production, improve catalytic activity.

(2) SEM and EDS analyze: Fig. 2 and 3 is respectively nano-TiO behind the cerium oxide electrolysis modifying ₂The SEM photo of film and EDS can spectrograms.From the SEM photo, can find out CeO ₂Nano-TiO behind the electrolysis modifying ₂There is dense said minuscule hole in film surface, the relevant Ce in surface ⁴⁺Deposit do not have the bulk aggregate to form, this has well brought into play as alloy at nano-TiO for preventing that hole from stopping up and the minimizing of effective surface area all plays a positive role ₂Promote light-catalysed effect in the film.The considerable content of Cu ion shows that this element has entered nano-TiO on the energy spectrogram ₂Film.

(3) photocatalysis performance: Fig. 4 is nano-TiO behind several metal oxide electrolysis modifyings ₂Film is on the impact of methylene blue Photocatalytic Decoloration.As can be seen from the figure, through the nano-TiO behind several metal oxide electrolysis modifyings ₂The film light catalytic performance all increases.

Claims

1. modified metal oxide nano-TiO ₂The preparation method of thin-film material, it is characterized in that, comprise the steps: that (1) is prepared into pure titanium sheet the rectangle thin slice of 25mm * 15mm * 2mm, (2) the titanium sheet is carried out preliminary treatment, comprise: sand papering, oil removing, hydrochloric acid solution rinsing, ultrasonic wave washed with de-ionized water and vacuum drying, (3) with pretreated titanium sheet be placed in microarc oxidation equipment provided on, experiment parameter is: voltage 420V, preparation time 30min, Na in the phosphate electrolyte system ₃PO ₄Concentration is 10g/L, NaF concentration is 1g/L, electrolysis temperature is controlled at below 35 ℃, then the metal oxide with 2-20mmol joins in the electrolyte, react under magnetic agitation, carry out simultaneously with differential arc oxidation so that mix, wherein the titanium sheet is immersed in the treatment fluid as anode, as negative electrode, (4) are with the nano-TiO for preparing with the rustless steel container of cooling system ₂Film carries out rinsed with deionized water and drying.

2. a kind of modified metal oxide nano-TiO according to claim 1 ₂The preparation method of thin-film material is characterized in that, described metal oxide is: one or more in zinc oxide, vanadic anhydride, silver oxide, cerium oxide, lanthana, dysprosia or the lead oxide.