CN101041585A

CN101041585A - Oriented porous spinelle film and preparation method thereof

Info

Publication number: CN101041585A
Application number: CN 200710064206
Authority: CN
Inventors: 王连英; 刘淼; 李仓
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2007-03-06
Filing date: 2007-03-06
Publication date: 2007-09-26
Anticipated expiration: 2027-03-06
Also published as: CN100528803C

Abstract

The invention discloses an oriented porous spinel film and making method in the ceramic film technical domain, which comprises the following steps: adopting solvent evaporating method to prepare oriented composite metal hydroxide LDHs film; solving oxide M2+O selectively under certain temperature after sintering; obtaining the product with continuous centimeter grade and aperture at 40-400nm evenly.

Description

Oriented porous spinelle film and preparation method thereof

Affiliated field

The invention belongs to the ceramic membrane technical field, be specifically related to a kind of oriented porous spinelle film and preparation method thereof.

Background technology

Ceramic membrane is compared with organic film, has a clear superiority at aspects such as thermostability, chemical stability, mechanical property, work-ing life, cleaning and regenerations, might progressively be substituted in widely used organic film of industrial circle and metallic films such as medicine, food.Yet most business-like ceramic membranes are difficult to satisfy the needs of high-temperature operation, as γ-Al ₂O ₃, TiO ₂, ZrO ₂Film undergoes phase transition in certain temperature range easily, causes its aperture to raise and become big with temperature; γ-Al ₂O ₃Film at high temperature meets acidity or alkaline medium easily ruptures; SiO ₂Film is met water vapour and is then become fragile.Therefore explore the new material system that is fit to high-temperature operation and seem particularly important and urgent.

(be called for short spinel, structural formula is M to spinel type composite metal oxide ²⁺M ³⁺ ₂O ₄) have high melt point (as MgAl ₂O ₄Fusing point be 2135 ℃) and before its melting temperature, do not undergo phase transition, thereby porous spinelle film is one of ideal system of preparation refractory ceramics separatory membrane.Spinelle film with orientation is a class important in the ordered nano film, its particle long-range order is arranged and specific orientation is arranged, thereby show the characteristic that differs from unordered nano thin-film and nano-powder material, for the high efficiency of nano-structure array material, intellectuality, miniaturization etc. provide opportunity; And be research model with the nano-structure array of long-range order, specific orientation, can help studying its transformation mechanism in atomic scale direct viewing metal oxide crystalline phase conversion process.

The report of at present relevant porous spinelle film is actually rare, the main sol-gel method that adopts of its preparation.Document [Zhang G.C. (Zhang Guochang), Chen Y.F. (Chen Yunfa), Wu Z.J. (Wu Zhenjiang), Xie Y.S. (Xie Yusheng), Engineering Chemistry and Metallurgy (chemical industry metallurgical), 2000,21 (3), 225-230] adopt sol-gel method, with metal powder magnalium and the two alkoxide of isopropanol reaction synthetic Al-Mg metal, at porous a-Al ₂O ₃Prepare the MgAl of the about 12nm in aperture on the carrier ₂O ₄Composite ceramic film.

Document [Chu Wei, Larbot A., Cot L., Xie Zaiku, Chen Qingling, catalysis journal, 2000,21 (5), 479-480] adopts sol-gel method, by to AlOOH and HNO ₃Add CoCl in the reaction synthetic aluminium colloidal sol ₂Solution and the PVA solution that contains linking agent make the compound colloidal sol of building, and the coating roasting prepares the CoAl that mean pore size is 4.3-5.6nm on ceramic alumina ₂O ₄Film.

The spinelle film that has flourishing pore structure and orientation has simultaneously been gathered the advantage of porous Ceramic Separation Membrane and orientation spinelle film, for it has opened up more wide Application Areas.Do not see at present the preparation method that the bibliographical information oriented porous spinelle film is arranged.

With complex metal hydroxide (Layered Double Hydroxides is abbreviated as LDHs) is precursor, carries out solid state reaction and can obtain bivalent metal oxide (M when being higher than 700 ℃ ²⁺O) and spinel (M ²⁺M ³⁺ ₂O ₄) mixture, M wherein ²⁺O just obtains that crystalline phase is single, the regulatable spinel of composition and aperture after by the selectivity corrosion.The LDHs precursor is to pile up the lamellar compound that forms by interlayer anion and positively charged laminate, and its similar is in brucite Mg (OH) ₂, by MO ₆Octahedra shared seamed edge and form the main body laminate, the divalent-metal ion on the laminate can be in certain limit by the trivalent metal ion isomorphous substitution of similar radius, and metal ion can reach the homodisperse of atomic level.The LDHs synthetic method is simple, and desired raw material is cheap and easy to get, and production cost is lower.M by regulation and control LDHs precursor ²⁺/ M ³⁺Element ratio, maturing temperature, roasting time can be prepared the spinel in different apertures.

Summary of the invention

The objective of the invention is to: a kind of oriented porous spinelle film and preparation method thereof is provided.Can regulate and control the laminate metallic element kind and the composition of LDHs precursor as required, obtain the spinelle film of different compositions, different pore sizes.

Oriented porous spinelle film of the present invention have centimetre-sized continuously, crystal grain presents (111) orientation, the aperture is 40～400nm, the uniform characteristics of particle distribution.

The method that the present invention prepares oriented porous spinelle porcelain film is: at first prepare the uniform sheet LDHs nanoparticle of size distribution, it is mixed with certain density suspension, adopt solvent evaporated method to prepare orientation LDHs film precursor; After the roasting, product is converted into orientation M under specified temp ²⁺O/M ²⁺M ³⁺ ₂O ₄Laminated film; Then this laminated film is put into the acidity (HNO of finite concentration, temperature ₃Or HCl) or alkalescence (NaOH) solution in, make M wherein ²⁺O can obtain oriented porous spinelle film optionally by corrosion.The concrete operations step is as follows:

A. adopt the required orientation LDHs film precursor of solvent evaporated method (seeing Chinese patent application 200510130781.7) preparation.

B. adopt the required orientation M of orderly complex metal hydroxide precursor methods (seeing Chinese patent application 200610114340.2) preparation ²⁺O/M ²⁺M ³⁺ ₂O ₄Laminated film.

C. with orientation M ²⁺O/M ²⁺M ³⁺ ₂O ₄Laminated film is put into the HNO that concentration is 0.1～10mol/L ₃Or HCl (M ²⁺=Mg ²⁺, Ni ²⁺, Zn ²⁺, Co ²⁺, Cu ²⁺Or Ca ²⁺) or NaOH (M ²⁺=Zn ²⁺) in the solution, under 20～180 ℃ temperature, left standstill 10 minutes～15 days, separate and wash 5～10 times after just can obtain oriented porous spinelle film.

The divalent metal M of porous spinelle film of the present invention ²⁺Can be Mg ²⁺, Ni ²⁺, Zn ²⁺, Co ²⁺, Cu ²⁺Or Ca ²⁺In a kind of, trivalent metal cation M ³⁺Be Al ³⁺, Fe ³⁺, Cr ³⁺, Mn ³⁺Or Ga ³⁺In a kind of.

Above-mentioned materials is carried out these methods of sign proof such as XRD, SEM and successfully prepare oriented porous spinelle film.The strongest diffraction peak is the characteristic diffraction peak of spinel (111) crystal face in its XRD spectra, and peak intensity shows that much larger than the intensity of other diffraction peak the crystal grain of oriented porous spinelle film has good (111) orientation.The SEM photo of film surface and tangent plane shows that particles dispersed is more even, and the aperture is 40～400nm.

The invention has the advantages that: can regulate and control the laminate metallic element kind and the composition of LDHs precursor as required, obtain the spinelle film of different compositions, different pore sizes; Need not the monocrystal chip induced growth, need not template, equipment requirements is simple, processing ease, and production cost is low, and environmental friendliness is expected to realize continuous large-scale production.

Description of drawings

Fig. 1 is the embodiment of the invention 1 resulting oriented porous NiAl ₂O ₄Film and be ground into X-ray diffraction (XRD) spectrogram of powder after product.

Fig. 2 is the embodiment of the invention 1 resulting oriented porous NiAl ₂O ₄Film surface amplifies 20,000 times field emission scanning electron microscope (FESEM) photo.

Fig. 3 is the embodiment of the invention 1 resulting oriented porous NiAl ₂O ₄Film surface amplifies 100,000 times field emission scanning electron microscope (FESEM) photo.

Fig. 4 is the embodiment of the invention 1 resulting oriented porous NiAl ₂O ₄The film tangent plane amplifies 2,000 times field emission scanning electron microscope (FESEM) photo.

Fig. 5 is the embodiment of the invention 1 resulting oriented porous NiAl ₂O ₄The film tangent plane amplifies 50,000 times field emission scanning electron microscope (FESEM) photo.

Embodiment

Embodiment 1

Steps A: take by weighing 38.68g Ni (NO ₃) ₂6H ₂O and 24.99g Al (NO ₃) ₃9H ₂O is dissolved in 250mL and removes CO ₂Water in, be mixed with mixing salt solution, other gets 15.20g NaOH and is dissolved in 250mL and removes CO ₂Water in, rapidly alkaline solution and mixing salt solution were poured in the full back-mixing rotation liquid film reactor into reaction under the room temperature 1 minute, the gained slurries are at 100 ℃, N ₂Protection is crystallization 8 hours down, and centrifugation is washed and taken by weighing a certain amount of product to the neutrality and be mixed with the aqueous solution that 10mL concentration is 4.3wt%, stirs under the room temperature, pour in the culture dish that diameter is 90mm, 40 ℃ dry 6 hours down, can obtain NiAl-NO ₃The LDHs precursor, its Ni ²⁺/ Al ³⁺=2.

Step B: the NiAl-NO that steps A is obtained ₃The LDHs precursor is put into retort furnace, 1000 ℃ of following roastings 4 hours, promptly obtains NiAl-MMO ₁₀₀₀Nano thin-film.

Step C: take by weighing the NiAl-MMO that 0.40g step B obtains ₁₀₀₀Nano thin-film is put into the single port flask of 100mL, adds 40mL 6mol/L HNO ₃Left standstill under 80 ℃ 8 hours behind the solution, separating, washing 7 times just obtains the blue transparent NiAl of orientation ₂O ₄Film.The acid vapour of evaporation refluxes through the condensing tube condensation that the flask bottleneck connects.Take out a small amount of orientation NiAl ₂O ₄Behind the thin-film grinding, obtain NiAl ₂O ₄Powder, so as with orientation NiAl ₂O ₄Film contrasts its orientation.

Resulting NiAl ₂O ₄The XRD spectra of film and powder as shown in Figure 1, as can be seen, NiAl ₂O ₄(Fig. 1 three obvious diffraction peaks only occur in a) to the XRD spectra of film, and wherein the strongest diffraction peak is NiAl ₂O ₄(111) characteristic diffraction peak of crystal face, peak shape is sharp-pointed and the peak is stronger, the strong more weak then corresponding NiAl of diffraction peak relatively in peak ₂O ₄(311) and (511) crystal face; And with the NiAl that obtains behind this thin-film grinding ₂O ₄NiAl has appearred in the XRD spectra of powder (Fig. 1 b) ₂O ₄The characteristic diffraction peak of a plurality of crystal faces is with NiAl in the standard card ₂O ₄The XRD spectra basically identical.Above-mentioned analysis revealed NiAl ₂O ₄The particle of film has good (111) orientation, and orientation film orientation of particle after grinding is destroyed.Fig. 2 and Fig. 3 are NiAl ₂O ₄Film surface amplifies the FESEM photo of 20,000 times and 100,000 times, and Fig. 4 and Fig. 5 are NiAl ₂O ₄The film tangent plane amplifies the FESEM photo of 2,000 times and 50,000 times.By Fig. 2-Fig. 5 as seen, particles dispersed is more even in the film, and the aperture is 50～100nm.

Embodiment 2

Steps A: take by weighing 41.03g Mg (NO ₃) ₂6H ₂O and 30.01g Al (NO ₃) ₃9H ₂O is dissolved in 300mL and removes CO ₂In the water, be mixed with mixing salt solution, other gets 19.2g NaOH and is dissolved in 300mL and removes CO ₂In the water, rapidly alkaline solution and mixing salt solution were poured in the full back-mixing rotation liquid film reactor into reaction under the room temperature 1 minute, the gained slurries are at 100 ℃, N ₂Protection is crystallization 8h down, and centrifugation is washed the sample that obtains and taken by weighing a certain amount of product to the neutrality and be mixed with the aqueous solution that 10mL concentration is 2.0wt%; stir under the room temperature; pour in the culture dish that diameter is 90mm, at room temperature dry 4 days, can obtain MgAl-NO ₃The LDHs precursor, its Mg ²⁺/ Al ³⁺=2.

Step B: the MgAl-NO that steps A is obtained ₃The LDHs precursor is put into retort furnace, 900 ℃ of following roastings 6 hours, promptly obtains MgAl-MMO ₉₀₀Nano thin-film.

Step C: take by weighing the MgAl-MMO that 0.50g step B obtains ₉₀₀Nano thin-film is put into the single port flask of 100mL, leaves standstill under 50 ℃ 10 hours after adding 60mL 3mol/L HCl solution, and separating, washing 10 times just obtains the white translucent MgAl of orientation ₂O ₄Film.The acid vapour of evaporation refluxes through the condensing tube condensation that the flask bottleneck connects.Take out a small amount of orientation MgAl ₂O ₄Behind the thin-film grinding, obtain MgAl ₂O ₄Powder, so as with orientation MgAl ₂O ₄Film contrasts its orientation.

Resulting MgAl ₂O ₄The strongest diffraction peak is MgAl in the XRD spectra of film ₂O ₄(111) characteristic diffraction peak of crystal face, and peak intensity shows that much larger than the intensity of other diffraction peak it has good (111) orientation.MgAl ₂O ₄The SEM photo of film surface and tangent plane shows that particles dispersed is more even, and the aperture is 40～80nm.

Embodiment 3

Steps A: take by weighing 28.56g Zn (NO ₃) ₂6H ₂O and 18.01g Al (NO ₃) ₃9H ₂O is dissolved in 150mL and removes CO ₂Water in, be mixed with mixing salt solution, other gets 9.12g NaOH and is dissolved in 150mL and removes CO ₂Water in, rapidly alkaline solution and mixing salt solution were poured in the full back-mixing rotation liquid film reactor into reaction under the room temperature 1 minute, the gained slurries are at 100 ℃, N ₂Protection is crystallization 8 hours down, and centrifugation is washed and taken by weighing a certain amount of product to the neutrality and be mixed with the aqueous solution that 10mL concentration is 3.6wt%, stirs under the room temperature, pour in the culture dish that diameter is 90mm, 60 ℃ dry 4 hours down, can obtain ZnAl-NO ₃The LDHs precursor, its Zn ²⁺/ Al ³⁺=2.

Step B: the ZnAl-NO that steps A is obtained ₃The LDHs precursor is put into retort furnace, 1100 ℃ of following roastings 2 hours, promptly obtains ZnAl-MMO ₁₁₀₀Nano thin-film.

Step C: take by weighing the ZnAl-MMO that 0.25g step B obtains ₁₁₀₀Nano thin-film is put into the hydrothermal reaction kettle of 20mL, leaves standstill under 150 ℃ 1 hour after adding 16mL 10mol/LNaOH solution, and separating, washing 6 times just obtains the white translucent ZnAl of orientation ₂O ₄Film.Take out a small amount of orientation ZnAl ₂O ₄Behind the thin-film grinding, obtain ZnAl ₂O ₄Powder, so as with orientation ZnAl ₂O ₄Film contrasts its orientation.

Resulting ZnAl ₂O ₄The strongest diffraction peak is ZnAl in the XRD spectra of film ₂O ₄(111) characteristic diffraction peak of crystal face, and peak intensity shows that much larger than the intensity of other diffraction peak it has good (111) orientation.ZnAl ₂O ₄The SEM photo of film surface and tangent plane shows that particles dispersed is more even, and the aperture is 100～300nm.

Claims

1, a kind of oriented porous spinelle film is characterized in that: centimetre-sized is continuous, crystal grain presents (111) orientation, the aperture is that 40～400nm, particle distribution are even.

2, a kind of method for preparing the described oriented porous spinelle film of claim 1, concrete preparation process is:

A. adopt solvent evaporated method to prepare required orientation complex metal hydroxide LDHs film precursor;

B. adopt orderly complex metal hydroxide precursor methods to prepare required orientation metal oxide (M ²⁺O)/spinel (M ²⁺M ³⁺ ₂O ₄) laminated film;

C. with orientation M ²⁺O/M ²⁺M ³⁺ ₂O ₄Laminated film is put into the HNO that concentration is 0.1～10mol/L ₃Or in the HCl solution, under 20～180 ℃ temperature, left standstill 10 minutes～15 days, separate and wash 5～10 times after obtain oriented porous spinelle film.

3, in accordance with the method for claim 2, it is characterized in that: the divalent metal M of the described porous spinelle film of c step ²⁺Can be Mg ²⁺, Ni ²⁺, Zn ²⁺, Co ²⁺, Cu ²⁺Or Ca ²⁺In a kind of, trivalent metal cation M ³⁺Be Al ³⁺, Fe ³⁺, Cr ³⁺, Mn ³⁺Or Ga ³⁺In a kind of.