CN101255556A - Method for preparing porous zinc oxide particle studded composite film - Google Patents

Method for preparing porous zinc oxide particle studded composite film Download PDF

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CN101255556A
CN101255556A CNA2008101030102A CN200810103010A CN101255556A CN 101255556 A CN101255556 A CN 101255556A CN A2008101030102 A CNA2008101030102 A CN A2008101030102A CN 200810103010 A CN200810103010 A CN 200810103010A CN 101255556 A CN101255556 A CN 101255556A
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ldhs
znalco
zinc oxide
zno
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CN101255556B (en
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杨兰
王彩霞
周伟
段雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention relates to a method for preparing porous zinc oxide partial mosaic composite film, belonging to the field of composite metal oxide film technology. M<II>ZnAlCO<3>LDHs anion lamellar compound serum is prepared by nucleation/crystallization isolation method, the general formula of M<II>ZnAlCO<3>LDHs is MxZn6-xAl2(OH)16CO3.4H2O; then M<II>ZnAlCO3LDHs coating precursor is prepared on a substrate by serum coating technology, ZnO-TMOs/ZnAL3O4 zinc oxide composite film is got by pyrolysis, the general formula of xZnO-yMOa/ZnAL3O4 is ZnO-TMOs/ZnAL3O4. The invention has the advantages that: by controlling the kinds and relative proportions thereof of divalent metal cations, series zinc oxide partial mosaic composite film, which has uniformly disperse partials, micrometer thickness and good adhesive attraction and is loose and porous, is got, laying a foundation for applying zinc oxide micrometer/nanometer composite film material to catalysis, adsorption and gas sensor.

Description

A kind of method for preparing porous zinc oxide particle studded composite film
Technical field
The invention belongs to the technical field of composite metal oxide film, a kind of method for preparing porous zinc oxide particle studded composite film particularly is provided.
Background technology
Zinc oxide (ZnO) is widely used in fields such as piezoelectricity, photoelectricity, catalysis, transmitter as direct wide band gap semiconducter.In recent years studies show that zinc oxide composite demonstrates than single wide band gap semiconducter at aspect of performances such as photoabsorption, photochemical catalysis, opto-electronic conversion has higher activity, thereby causes the extensive attention of researcher.Up to the present, multiple film preparing technology has been applied in the preparation research of ZnO binary laminated film as technology such as dc magnetron sputtering, collosol and gel-spin coating, collosol and gel-vacuum-evaporation and pulse laser ablations.For example: at Sensors andActuators B, 1999, among the 55:47-54, people such as Hong Y.Bae have reported that employing collosol and gel-spin-coating method prepares the ZnO/CuO film; At Solid State Ionics, 2003, among the 160:197-207, people such as Y.-N.NuLi adopt the preparation of pulse laser ablation technology to have the Ta of electroluminescent properties 2O 5/ ZnO film; At Sensors and ActuatorsB, 2003, among the 96:477-481, people such as W.-P.Tai adopt Prepared by Sol Gel Method Al doping ZnO/TiO 2Film is also studied its psychometric performance; At Talanta 2007,73 (3): among the 523-528, people such as Z.Zhang adopt collosol and gel-vacuum vapor deposition method preparation to have the ZnO/TiO of photocatalytic activity 2Film.Although above-mentioned technology of preparing helps obtaining fine and close zinc oxide composite film,, its inter-granular porosity is little also to have limited their application in fields such as catalysis, absorption, gas sensors.
Characteristics such as the Modulatory character that negatively charged ion stratiform compound (layered double hydroxies is called for short LDHs) is formed because of laminate, laminate metal ion high dispersion are so be suitable for as preparation ZnO/ZnFe 2O 4Laminated film (seeing Chinese patent application 200610011513.8) and ZnO/ZnAl 2O 4The presoma of self-supporting film (seeing Chinese patent application 200610114340.2).Although with binary LDHs is that forerunner's physical efficiency prepares even particle size distribution, the finely dispersed binary composite metal oxide film of each component, but above-mentioned binary laminated film densification, inter-granular porosity is less, and catalytic efficiency, air-sensitive performance, adsorptivity etc. can be affected in actual applications.
Transition metal oxide (Transition metal oxides, be called for short TMOs)) adulterated zinc oxide composite powder material is because the synergistic effect of each component is good, and has some key properties that single oxide do not possess and be subjected to extensive concern.For example, CuO-ZnO/Al 2O 3Compound system is to carbon monoxide selective oxidizing reaction, the low temperature water gas transformationreation, and reactions such as dimethyl ether by methanol dehydration have advantages of high catalytic activity and selectivity; NiO/ZnO/ZrO 2Compound system has excellent catalytic activity and selectivity to the alcohol vapour reforming reaction; Zinc oxide and gahnite (ZnAl 2O 4) compound system is as sorbent material, be used for removing sulphur impurity from fuel gas; With ternary M IIZnAnAlLDHs is that the ZnO compound system that presoma obtains goes out advantages of high catalytic activity and selectivity to the methanol steam reforming reaction and display.The polynary composite powder material of zinc oxide is carried out filming, not only can realize recycling, and, because thin-film material has features such as high-specific surface area and lattice surface defective, can improve its catalytic activity and absorption property.Therefore, seek novel method and prepare that high-specific surface area, inter-granular porosity are big, the ZnO composite film material of each component good dispersity has theory and application value.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing porous zinc oxide particle studded composite film.This method adopts low price, synthesis technique is simple, the structure component is adjustable, the ternary negatively charged ion stratiform compound M of metal ion high dispersing IIZnAlCO 3LDHs is a presoma, kind and relative proportion thereof by divalent metal in the control LDHs presoma laminate, prepare porous series zinc oxide particle studded composite film material, solve traditional method and prepare in the zinc oxide composite film process, drawback such as zinc oxide multicomponent mixture bad dispersibility, inter-granular porosity are little.
The present invention at first adopts nucleation/crystallization isolation method to prepare M IIZnAlCO 3The LDHs slurry liquid, M IIZnAlCO 3The LDHs general formula is M xZn 6-xAl 2(OH) 16CO 34H 2O, wherein x is 0～6; M is Co, Ni, and Cu Mn), adopts the slurry coating technology to prepare M on substrate then IIZnAlCO 3The LDHs coating precursor obtains ZnO-TMOs/ZnAl through thermolysis 2O 4Laminated film, ZnO-TMOs/ZnAl 2O 4General formula is xZnO-yMO a/ ZnAl 2O 4(M is Co, Ni, Cu, Mn; X is 0～5, and y is 5-x, and a is 4/3 or 1) its processing step is as follows:
(1) M IIZnAlCO 3The preparation of LDHs slurries
With deionized water preparation mixing salt solution and mixed ammonium/alkali solutions, the mixing salt solution of measuring the mixed ammonium/alkali solutions of 75～85ml and 100ml dropwise adds in the full back-mixing rotation liquid film reactor react simultaneously, adopt nucleation/crystallization isolation method, crystallization 6-15h in 40～90 ℃ of water-baths, centrifuge washing separates, add water ultra-sonic dispersion 20～60min, obtain size, stable M at 70-120nm IIZnAlCO 3The LDHs slurries.
(2) preparation M IIZnAlCO 3The LDHs coating
The slurries of step (1) preparation are coated on the substrate, and 10～30 ℃ of dry solidifications obtain M IIZnAlCO 3The LDHs dry coating.
(3) elevated temperature heat is decomposed
M with step (2) preparation IIZnAlCO 3The LDHs coating, sintering under 700-1100 ℃ sintering temperature heats up with 1～10 ℃/min temperature rise rate, and constant temperature 2～4 hours is reduced to room temperature with the rate of cooling of 1～10 ℃/min afterwards, obtains ZnO-TMOs/ZnAl 2O 4Laminated film.
M IIZnAlCO 3M in the LDHs general formula IIRepresent divalent-metal ion Co 2+, Ni 2+, Cu 2+, Mn 2+In any; 0＜x＜6; (M 2++ Zn 2+)/Al 3+Mol ratio be 2～4: 1.
M in the slurries IIZnAlCO 3LDHs content is 5～20% mass percents.
Substrate of the present invention is alumina substrate, quartz plate, monocrystalline silicon piece.Substrate is the substrate after the employing clean-out system ultrasonic cleaning, and the clean-out system of employing is 1～3 kind in acetone, ethanol, the deionized water.
Mixed ammonium/alkali solutions of the present invention is the mixing solutions of sodium hydroxide and anhydrous sodium carbonate; Described mixing salt solution is divalent-metal ion M 2+And Zn 2+With trivalent metal ion Al 3+Mixing solutions.
The invention has the advantages that: by regulation and control M IIZnAlCO 3The kind and the relative proportion thereof of divalent metal in the LDHs presoma laminate, obtain Zinc oxide particles homodisperse, thickness at micron order, serial zinc oxide particle studded composite film material that sticking power is good, loose porous, lay a good foundation for realizing the application of zinc oxide micrometer/nano composite film in catalysis, absorption, gas sensor etc.
Description of drawings
Fig. 1 is ZnCoAlCO in the embodiment of the invention 1 3The XRD spectra of LDHs powder.
Fig. 2 is from ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4Scrape the XRD spectra of powder on the film.
Fig. 3 is ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4Film XPS spectrum figure.
Fig. 4 is ZnO-Co on the alumina substrate in the embodiment of the invention 1 3O 4/ ZnAl 2O 4The SEM photograph of film.
Fig. 5 is from ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4Scrape the TEM photograph of powder on the film.
Fig. 6 is from ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4Film TEM goes up the EDS spectrogram in zone (a).
Fig. 7 is from ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4Film TEM goes up the EDS spectrogram in zone (b).
Fig. 8 is ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4The EDS face of Zn is swept spectrogram in the film.
Fig. 9 is ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4The EDS face of Al is swept spectrogram in the film.
Figure 10 is ZnO-Co in the embodiment of the invention 1 3O 4/ ZnAl 2O 4The EDS face of Co is swept spectrogram in the film.
Figure 11 is ZnO-Co in the embodiment of the invention 2 3O 4/ ZnAl 2O 4The SEM photograph of film.
Figure 12 is from ZnO-NiO/ZnAl in the embodiment of the invention 3 2O 4Scrape the powder XRD spectra on the film.
Figure 13 is ZnO-NiO/ZnAl on the quartz substrate in the embodiment of the invention 3 2O 4Film SEM photograph.
Embodiment
Embodiment 1
Co (NO with deionized water preparation 0.05mol/L 3) 26H 2O, the Zn (NO of 0.25mol/L 3) 26H 2Al (the NO of O and 0.1mol/L 3) 39H 2O mixing salt solution 100ml is with the sodium hydroxide of deionized water preparation 1.7mol/L and the yellow soda ash mixed ammonium/alkali solutions 80ml of 0.54mol/L.To mix saline solution and mixed alkali liquor more dropwise is added dropwise to fast simultaneously in the full back-mixing rotation liquid film reactor and reacts crystallization 6h under 90 ℃ of water-baths.With the reaction solution centrifugation, use deionized water wash afterwards three times at 3500r/min, get centrifugal resulting precipitation 3g then and be scattered in the 50ml deionized water, ultrasonic 1h prepares stable CoZnAlCO 3The LDHs suspension slurry.Adopt coating technology on alumina substrate, to prepare CoZnAlCO 3The LDHs coating, dry 72h under the room temperature.For the slurry preparation process is carried out quality monitoring, take out a small amount of slurry dried after, carry out the X-ray diffraction analysis, the result observes CoZnAlCO as shown in Figure 1 3-LDHs typical (003), (006), (012), (015), (018), (010), (110) and (113) crystal face characteristic diffraction peak.
With the temperature rise rate of 1 ℃/min to CoZnAlCO 3-LDHs dry coating slowly heats up, and 900 ℃ of following insulation 2h control rate of temperature fall afterwards, is cooled to cooling below 500 ℃ with the rate of cooling of 1 ℃/min, cools to room temperature afterwards with the furnace.By from the X-ray diffraction (Fig. 2) that scrapes film except (100), (002) of observing ZnO, (101), (102), (110), (103), (220), (112), (201), (004) and (202) crystal face characteristic diffraction peak, also observe Co 3O 4(111), (220), (311), (222), (400), (422), (511), (440), (531) and (620) crystal face characteristic diffraction peak and ZnAl 2O 4(220), (311), (400), (331), (422), (511), (440), (620) and (533) crystal face characteristic diffraction peak, illustrate that this laminated film is made up of three kinds of components.(Fig. 3) observes Co from XPS spectrum 3O 4Co 2p3/2And Co 2p1/2The peak, and can know the satellite peak that shaken of seeing them, therefore proved that further cobalt is with Co 3O 4Be present in mutually in this composite oxide film.SEM (Fig. 4) analytical results shows, has prepared the porous particle studded composite film on alumina substrate.TEM (Fig. 5) and constituency EDS (Fig. 6,7) analytical results shows that macrobead is a ZnO crystal grain among Fig. 4, (Co 2++ Zn 2+)/Al 3+Mol ratio is near 3, and is identical with feed ratio, ZnO, Co 3O 4And ZnAl 2O 4The molar fraction of phase is respectively 74.5%, 7.0% and 18.5%.Sweep from the SEM face that (Fig. 8, Fig. 9 can see film ZnO, Co everywhere in Figure 10) 3O 4, ZnAl 2O 4Each component uniform distribution.
Embodiment 2
Co (NO with deionized water preparation 0.006mol/L 3) 26H 2O, the Zn (NO of 0.3mol/L 3) 26H 2Al (the NO of O and 0.1mol/L 3) 39H 2O mixing salt solution 100ml is with the sodium hydroxide of deionized water preparation 1.7mol/L and the yellow soda ash mixed ammonium/alkali solutions 80ml of 0.54mol/L.Adopt with embodiment 1 the same terms and prepared thickness at micron order, even, porous ZnO-Co 3O 4/ ZnAl 2O 4Composite granular film, as shown in figure 11.
Embodiment 3
Ni (NO with deionized water preparation 0.05mol/L 3) 26H 2O, the Zn (NO of 0.25mol/L 3) 26H 2Al (the NO of O and 0.lmol/L 3) 39H 2O mixing salt solution 100ml is with the sodium hydroxide of deionized water preparation 1.7mol/L and the yellow soda ash mixed ammonium/alkali solutions 80ml of 0.54mol/L.To mix saline solution and mixed alkali liquor more dropwise is added dropwise to fast simultaneously in the full back-mixing rotation liquid film reactor and reacts crystallization 6h under 90 ℃ of water-baths.Centrifugation is used deionized water wash three times afterwards, gets centrifugal resulting precipitation 3g then and is scattered in the 50ml deionized water, and ultrasonic 1h prepares stable NiZnAlCO 3The LDHs suspension slurry.Adopt coating technology on alumina substrate, to prepare NiZnAlCO 3The LDHs coating, dry 72h under the room temperature.
Adopt with embodiment 1 the same terms and carry out roasting, can prepare thickness equally at micron order, even, porous ZnO-NiO/ZnAl 2O 4Film.See (012), (021), (202), (220), (223), (205) and (042) characteristic diffraction peak of NiO from X-ray diffraction spectrum (as Figure 12), the analytical results from scanning electron microscope (Figure 13) has proved that successfully having prepared submicron ZnO crystal grain on alumina substrate is embedded in nano NiO/ZnAl simultaneously 2O 4Porous composite particle film in the matrix.
Embodiment 4
Cu (NO with deionized water preparation 0.05mol/L 3) 26H 2O, the Zn (NO of 0.25mol/L 3) 26H 2Al (the NO of O and 0.1mol/L 3) 39H 2O mixing salt solution 100ml is with the sodium hydroxide of deionized water preparation 1.7mol/L and the yellow soda ash mixed ammonium/alkali solutions 80ml of 0.54mol/L.To mix saline solution and mixed alkali liquor more dropwise is added dropwise to fast simultaneously in the full back-mixing rotation liquid film reactor and reacts crystallization 6h under 90 ℃ of water-baths.Centrifugation is used deionized water wash three times afterwards, gets centrifugal resulting precipitation 3g then and is scattered in the 50ml deionized water, and ultrasonic 1h prepares stable CuZnAlCO 3The LDHs suspension slurry.Adopt coating technology on alumina substrate, to prepare CuZnAlCO 3The LDHs coating, dry 72h under the room temperature.Adopt with embodiment 1 the same terms and carry out sintering, can prepare thickness equally at micron order, even, porous ZnO-CuO/ZnAl 2O 4Film.
Embodiment 5
Prepare stable CoZnAlCO with embodiment 1 the same terms 3The LDHs slurries.Adopt the slurry coating technology on cleaned quartz substrate, prepared thickness at micron order, even, porous ZnO-Co 3O 4/ ZnAl 2O 4Composite granular film.

Claims (6)

1, a kind of method for preparing zinc oxide particle studded composite film at first adopts nucleation/crystallization isolation method to prepare M IIZnAlCO 3LDHs negatively charged ion stratiform compound slurries, M IIZnAlCO 3The LDHs general formula is M xZn 6-xAl 2(OH) 16CO 34H 2O; Adopt the slurry coating technology on substrate, to prepare M then IIZnAlCO 3The LDHs coating precursor obtains ZnO-TMOs/ZnAl through thermolysis 2O 4Zinc oxide composite film, ZnO-TMOs/ZnAl 2O 4General formula is xZnO-yMO a/ ZnAl 2O 4, wherein M is Co, Ni, Cu, a kind of among the Mn; X is 0～5, and y is 5-x, and a is 4/3 or 1; Its processing step is as follows:
(1) M IIZnAlCO 3The preparation of LDHs slurries
With deionized water preparation mixing salt solution and mixed ammonium/alkali solutions, the mixing salt solution of measuring the mixed ammonium/alkali solutions of 75～85ml and 100ml dropwise adds in the full back-mixing rotation liquid film reactor react simultaneously, adopt nucleation/crystallization isolation method, crystallization 6-15h in 40～90 ℃ of water-baths, centrifuge washing separates, add water ultra-sonic dispersion 20～60min, obtain size, stable M at 70-120nm IIZnAlCO 3The LDHs slurries;
(2) preparation M IIZnAlCO 3The LDHs coating
The slurries of step (1) preparation are coated on the substrate, and 10～30 ℃ of dry solidifications obtain M IIZnAlCO 3The LDHs dry coating;
(3) elevated temperature heat is decomposed
M with step (2) preparation IIZnAlCO 3The LDHs coating, under 700-1100 ℃, with 1～10 ℃/min temperature rise rate intensification sintering, constant temperature 2～4 hours is reduced to room temperature with 1～10 ℃/min speed afterwards, obtains ZnO-TMOs/ZnAl 2O 4Film.
2, according to claim 1 described method, it is characterized in that: M IIZnAlCO 3M in the LDHs general formula IIRepresent divalent-metal ion Co 2+, Ni 2+, Cu 2+, Mn 2+In any; 0＜x＜6; (M 2++ Zn 2+)/Al 3+Mol ratio be 2～4: 1.
3, method according to claim 1 is characterized in that: M in the slurries IIZnAlCO 3LDHs content is 5～20% mass percents.
4, method according to claim 1 is characterized in that: described substrate is alumina substrate, quartz plate, monocrystalline silicon piece.
5, method according to claim 1 is characterized in that: described substrate is the substrate after the employing clean-out system ultrasonic cleaning, and the clean-out system of employing is 1～3 kind in acetone, ethanol, the deionized water.
6, method according to claim 1 is characterized in that: described mixed ammonium/alkali solutions is the mixing solutions of sodium hydroxide and anhydrous sodium carbonate; Described mixing salt solution is divalent-metal ion M 2+And Zn 2+With trivalent metal ion Al 3+Mixing solutions.
CN2008101030102A 2008-03-28 2008-03-28 Method for preparing porous zinc oxide particle studded composite film Expired - Fee Related CN101255556B (en)

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CN101856616A (en) * 2010-05-18 2010-10-13 北京化工大学 Method for preparing zinc oxide composite film visible light catalyst
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Publication number Priority date Publication date Assignee Title
CN101856616A (en) * 2010-05-18 2010-10-13 北京化工大学 Method for preparing zinc oxide composite film visible light catalyst
CN102583467A (en) * 2012-02-24 2012-07-18 山东大学 Method using hydrotalcite-like substance with low zinc-aluminum molar ratio as precursor to manufacture zinc-aluminum spinel
CN103191746A (en) * 2013-03-20 2013-07-10 北京化工大学 Carbon supported core-shell structure nano metal catalyst as well as preparation method and application thereof
CN112569803A (en) * 2019-09-30 2021-03-30 成都易态科技有限公司 Preparation method of composite porous film
CN113750950A (en) * 2020-06-05 2021-12-07 中国石油化工股份有限公司 Purifying agent for removing carbonyl metal compound and preparation method and application thereof
CN113750950B (en) * 2020-06-05 2024-03-26 中国石油化工股份有限公司 Purifying agent for removing carbonyl metal compound and preparation method and application thereof
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