CN1908244A - Method of preparing composite metal oxide thin film using hydrotalcite analog as precursor - Google Patents
Method of preparing composite metal oxide thin film using hydrotalcite analog as precursor Download PDFInfo
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- CN1908244A CN1908244A CN 200610089768 CN200610089768A CN1908244A CN 1908244 A CN1908244 A CN 1908244A CN 200610089768 CN200610089768 CN 200610089768 CN 200610089768 A CN200610089768 A CN 200610089768A CN 1908244 A CN1908244 A CN 1908244A
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Abstract
the invention discloses a composite metal oxide film preparing method based on similar hydrotalcite as former, which is characterized by the following: adopting original synthetic technology to obtain the former of similar hydrotalcite on the AAO/Al; realizing the conversion from hydrotalcite film to composite metal oxide film with structural general formula as M12+zM22+1-x-zAl3+xO1+x/2.
Description
Technical field
The invention belongs to the preparing technical field of composite metal oxide film, particularly providing a kind of is the method that presoma prepares composite metal oxide film with the houghite.
Background technology
Houghite (hydrotalcite-like compounds is called for short HTLcs) is a kind of complex metal hydroxide (layered double hydroxies is called for short LDHs) with laminate structure.Houghite can be directly as catalyzer and support of the catalyst because of its special property that shows on chemistry and structure.Yet the houghite more applications is as catalyst precursor, is about to use after its roasting at a certain temperature makes complex metal oxides again.Houghite deutero-complex metal oxides, with its special structure, as, high-ratio surface, divalence and trivalent metal height homodisperse, surface have more alkali center, and the variation of kind and excellent catalytic performance, become the new catalytic material that DEVELOPMENT PROSPECT and using value are quite arranged.It causes the concern of increasing researcher as support of the catalyst, solid base catalyst and redox catalyst.Houghite deutero-O composite metallic oxide catalyst is Powdered in the practical application, is difficult to recycling after the use.Make its filming on the corresponding matrix if catalyzer is fixed on, can solve its loss, be convenient to recycling, thereby reduce cost.In addition, thin-film material has features such as high-specific surface area and lattice surface defective, and catalyst filmization can be improved its catalytic activity.In recent years, although reported the research of some O composite metallic oxide catalyst filmings,, be only limited to some TiO
2The research of composite metal oxide film catalyzer and carried catalyst aspect, therefore, it is imperative to carry out the derive research of composite metal oxide filmization of houghite.
Have multiple film preparing technology at present, as, methods such as the vapour deposition of sputter, ion beam induced and Organometallic Chemistry, collosol and gel, coating pyrolytic decomposition, electrochemistry have been applied to the preparation research of composite metal oxide film material.Wherein the coating sintering method is a kind of method that often adopts in recent years, and for example, at J.Phys.Chem.B 2001,105, among the 4816-4823, people such as Sergey K.Poznyak adopt sol-gel method to prepare TiO on silicon substrate
2-In
2O
3Composite metal oxide film; At Langmuir 2005,21, among the 8035-8041, people such as Song-Zhu Chu are at Sn/In
2O
3Adopt continuous anodic oxidation and sol-gel method on/the glass basis, prepared TiO
2/ Al
2O
3Composite metal oxide film.In the preparation report of numerous composite metal oxide films, all adopt spin coating technique that precursor sol liquid is deposited on the matrix.Exist so inevitably the film surface inhomogeneous, with matrix bond not closely, the not high defective of practicality.Therefore, explore new film deposition techniques and have practical significance, i.e. preparation has the composite metal oxide film of high adhesive force, difficult drop-off, to realize that complex metal oxides is in industrial widespread use.
Summary of the invention
The object of the present invention is to provide a kind of is the method that presoma prepares composite metal oxide film with the houghite, remedies the deficiency of present houghite deutero-complex metal oxides on using, and widens its Application Areas simultaneously.A kind of new film deposition techniques is provided,, has adopted the original position synthetic technology to prepare the hydrotalcite film presoma to improve the defective that exists in the coating sintering method.
The present invention adopts the original position synthetic technology, by the direct aluminium source of surface on the aluminum substrate (AAO/Al) of anodic oxidation that utilize, prepared polynary hydrotalcite film presoma, obtain the serial composite metal oxide film material of even structure, growth densification, successive, difficult drop-off then by high-temperature roasting, its chemical general formula is: M
1 2+ zM
2 2+ 1-x-zAl
3+ xO
1+x/2, wherein, M
1 2+And M
2 2+Represent divalent-metal ion Mg respectively
2+, Co
2+, Cu
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any two kinds of elements, [M
1 2++ M
2 2+]/[Al
3+] molar ratio be 2～6, [M
1 2+]/[M
2 2+] mol ratio is 0.2～6; The span of x, z is respectively 0.2≤x≤0.3,0.03≤z≤0.7.
Its concrete processing step is as follows:
The preparation of a:AAO/Al matrix
Is raw material with purity greater than 90% aluminium flake, according to the size of electrolyzer it is cut into rectangle.Earlier aluminium flake is dipped in that ultrasonic 3～5min removes surface and oil contaminant in acetone or the ethanol, again aluminium flake is changed in 1%～5% the sodium hydroxide solution and soak 1～3min to remove its surperficial zone of oxidation, rinse well with deionized water at last, put into electrolyzer and make negative electrode, adopt stereotype to make anode, electrolytic solution is the sulphuric acid soln of 0.1～2mol/l, and oxidation voltage is 0.1～20V/cm
2The aluminium flake electrolysis time is 0.5～2.5 hour, after treating that the aluminium flake surface forms anodic aluminum oxide layer, take out aluminium flake, rinse out the acid solution of aluminium flake remained on surface with deionized water after, be placed in 60 ℃～90 ℃ in the baking oven dry 6～15 hours, and took out the AAO/Al matrix of handling well at last, it is placed in moisture eliminator and preserve.
B: the preparation of hydrotalcite film presoma
1. in glass reactor, with M
1 2+And M
2 2+Soluble inorganic salt be dissolved in the deionized water, be mixed with the solution that concentration is 0.003～0.1mol/l, the feed ratio of precipitation agent is [precipitation agent]/[M
1 2++ M
2 2+]=4～40.
2. the AAO/Al substrate for preparing among the step a is cut into rectangular-shaped pieces, two angle perforation with AAO/Al substrate homonymy, with fine rule with its vertical hanging in glass reactor central authorities, the AAO/Al substrate needs all to immerse in the reaction solns, places baking oven to react glass reactor; If when needing to contain in the composite metal oxide film of preparation cobalt etc. and in air, the metallic element of oxidizing reaction taking place easily; then glass reactor should be placed water-bath heating, carry out protection of inert gas simultaneously, oxidized and can not get target product to avoid metallic element.Temperature of reaction is under 70 ℃～90 ℃, and through 6～80 hours reaction, original position was synthesized the hydrotalcite film presoma on the AAO/Al matrix.
3. the hydrotalcite film presoma that 2. step made takes out, and with deionized water rinsing 1～5 time, places 50 ℃～90 ℃ dry 6～12 hours of baking oven, is put in the moisture eliminator after the taking-up and preserves.
C: the preparation of composite metal oxide film
The hydrotalcite film for preparing among the step b is placed retort furnace, and the control heat-up rate is 1～10 ℃/min, and controlled temperature is in 450 ℃～600 ℃ scope, be incubated 4～8 hours, furnace cooling naturally cools to room temperature afterwards, has prepared composite metal oxide film.
The present invention utilizes precipitation agent evenly to decompose in reaction process, the reaction conditions gentleness, everywhere pH value homogeneous in the solution, help the co-precipitation of multiple metal in the solution, can also control simultaneously the decomposition rate of precipitation agent by control reaction temperature and reaction times, thereby realize controlled preparation, and then can realize houghite derive composite metal oxide film growth compactness, continuity, the controlled preparation of the kind of metallic element and structure thereof to this precursor thin-film.The precipitation agent that adopts can be urea or volatile salt, the better effects if of urea wherein, and wafer is more complete on the film of acquisition, and crystalline phase is single.
Anodic aluminum oxide layer on the aluminium flake in electrolytic process at the aluminium flake surface enrichment Al
3+, therefore when reaction soln reaches certain pH value, with divalent cation in the reaction solution at this matrix surface generation coprecipitation reaction, thereby formed hydrotalcite film at matrix surface.In addition because this stronger chemical action between film and the matrix, make combine closely continuous and difficult drop-off between the synthetic composite metal oxide film that obtains and the matrix.
In addition, the hydrotalcite film that forms is owing to be subjected to the influence of minimum effect of its lattice energy and lattice orientation effect, in its each structural unit, its chemical constitution is constant, still can keep the structural unit of sheet structure after making its roasting, thereby obtain the composite metal oxide film of composition and even structure.
The invention has the advantages that: directly utilize the surface through the aluminium source on the aluminium flake matrix of anodic oxidation treatment with in-situ synthesis, the hydrotalcite film for preparing is a presoma, realizes the conversion of hydrotalcite film to composite metal oxide film by roasting.Can obtain by this method uniform particles disperse, fine and close, continuously, thickness is at micron order, serial composite metal oxide film material that sticking power is good, for realizing that complex metal oxides lays the foundation in industrial widespread use.
Description of drawings
Fig. 1 is the XRD spectra of the AAO/Al matrix that adopts among the present invention.
Fig. 2 amplifies the SEM photo of 10,000 times and 100,000 times respectively for the AAO/Al matrix that adopts among the present invention.
Fig. 3 is the EDS spectrogram of the AAO/Al matrix that adopts among the present invention.
Fig. 4 scrapes off the XRD spectra of powder for the Zn/Mg/Al hydrotalcite film presoma that obtains in the embodiment of the invention 1.
Fig. 5 is the SEM spectrogram of the Zn/Mg/Al hydrotalcite film presoma that obtains in the embodiment of the invention 1.
Fig. 6 can spectrogram for the EDS of the Zn/Mg/Al hydrotalcite film presoma that obtains in the embodiment of the invention 1.
Fig. 7 is the XRD spectra of the Zn/Mg/Al composite metal oxide film that obtains in the embodiment of the invention 1.
Fig. 8 is the SEM figure of the Zn/Mg/Al composite metal oxide film in the embodiment of the invention 1.
The EDS figure that Fig. 9 obtains for the Zn/Mg/Al composite metal oxide film in the embodiment of the invention 1 scans when magnification is 300 times.
The EDS figure that Figure 10 obtains for the Zn/Mg/Al composite metal oxide film in the embodiment of the invention 1 scans when magnification is 3000 times.
The EDS figure that Figure 11 obtains for the Zn/Mg/Al composite metal oxide film in the embodiment of the invention 1 scans when magnification is 5000 times.
The XRD spectra of the Ni/Co/Al composite metal oxide film that Figure 12 obtains for the embodiment of the invention 2.
The SEM spectrogram of the Ni/Co/Al composite metal oxide film that Figure 13 obtains for the embodiment of the invention 2.
Figure 14 is the EDS figure of the Ni/Co/Al composite metal oxide film that obtains in the embodiment of the invention 2.
Embodiment
Steps A: place dehydrated alcohol and deionized water for ultrasonic to clean 3min high-purity aluminium flake, put it into then in the NaOH solution of 0.1M and dissolve 2min, use deionized water rinsing 1min then, aluminium flake after the flushing is put into electrolyzer, aluminium flake is as negative electrode, and lead flake is as anode, and concentration is made electrolytic solution for the 1mol/l sulphuric acid soln, carry out the constant voltage oxidation, operating voltage is 16V, and electric current is 1A, and electrolysis time is 1h, electrolysis temperature is a room temperature, and aluminium flake oxidation area is 10 * 7 * 2=126cm
2Well-oxygenated aluminium flake is taken out, wash away the remaining acid solution in surface with deionized water, at 70 ℃ of dry 12h down, it is cut specification into 17mm * 25mm, bind fine rule on two jiaos of its homonymy, it is stand-by to put into moisture eliminator.Can spectrogram (Fig. 3) prove by X-ray diffraction spectrogram (Fig. 1) and SEM electromicroscopic photograph (Fig. 2) and EDS and on aluminium flake, to have formed the porous aluminum oxide film.
Step B: take by weighing Mg (NO
3)
26H
2O 1.2307g, Zn (NO
3)
26H
2O 0.3570g, urea 2.8829g is dissolved in the 200ml deionized water [Mg
2+]/[Zn
2+]=1/2, [urea]/[M
1 2++ M
2 2+]=4, the ionic concn of total divalent metal is 0.03mol/l, the AAO/Al matrix is hung vertically in the glass reactor, matrix all immerses in the reaction solution, in 90 ℃ of baking ovens, react 72h, take out substrate afterwards, with deionized water rinse out remain in the surface reaction solution after, dry 12h under 70 ℃, prepare Zn/Mg/Al hydrotalcite film presoma, can see (003), (006), (012), (015), (018), (110) and (113) characteristic diffraction peak of houghite from accompanying drawing 4.The Zn/Mg/Al hydrotalcite film presoma that obtains as seen from Figure 5 has continuously, fine and close characteristics uniformly, Zn/Mg/Al houghite sheet structure on the film is high-visible, as seen from Figure 6, this film that obtains is that interlayer anion is the Zn/Mg/Al hydrotalcite film of carbonate.
Step C: the hydrotalcite film that drying is good places retort furnace, is warming up to 500 ℃ with the speed of 5 °/min, and 500 ℃ of insulations 6 hours, cools to room temperature naturally by furnace cooling then.The film that can spectrogram (Fig. 9) be obtained as can be seen by the SEM electromicroscopic photograph (Fig. 8) of X-ray diffraction spectrogram (Fig. 7), film and EDS is the Zn/Mg/Al houghite composite metal oxide film of deriving.Tangible matrix Al wherein appears in this XRD spectra
2O
3Strong diffraction peak and ZnO are weak and MgAl does not appear in wide diffraction peak
2O
4, ZnAl
2O
4With the diffraction peak of MgO, the peak shape broad of collection of illustrative plates, burr are more obvious, illustrate to have the MgO that much should belong to high dispersing or the crystallite and the amorphous phase of Zn/Mg composite oxides.Because the maturing temperature of presoma is not high, should not have MgAl yet
2O
4, ZnAl
2O
4The crystalline phase of spinel generates.In addition, can visually see by Fig. 8 electromicroscopic photograph that to have formed thickness be micron-sized continuous individual layer Zn/Mg/Al composite metal oxide film.In addition, (Figure 11) proof has formed and has formed equally distributed Zn/Mg/Al composite metal oxide film on the AAO/Al matrix EDS of the Zn/Mg/Al composite metal oxide film that obtains under different amplification energy spectrogram for Fig. 9, Figure 10.
Steps A: anodised aluminium flake preparation method is with embodiment 1
Step B: take by weighing Co (NO
3)
26H
2O 0.04362g, Ni (NO
3)
26H
2O 0.1310g, urea 2.8829g is dissolved in the 200ml deionized water [Co
2+]/[Ni
2+]=1/3, [urea]/[M
1 2++ M
2 2+]=40.The ionic concn of total divalent metal is 0.003mol/l; the AAO/Al matrix is hung vertically in the glass reactor; matrix all immerses in the reaction solution; adopt nitrogen protection, in 90 ℃ of water-baths, react 6h, take out aluminium flake afterwards; after rinsing out the reaction solution that remains in the surface with deionized water, at 70 ℃ of following dry 12h.
Step C: the hydrotalcite film presoma that drying is good places retort furnace, is warming up to 600 ℃ with the heat-up rate of 5 ℃/min from room temperature, and 600 ℃ of insulations 8 hours, cools to room temperature naturally by furnace cooling then.XRD and SEM figure (Figure 12 and Figure 13), and EDS spectrogram (Figure 14) proves and has obtained the Ni/Co/Al houghite composite metal oxide film of deriving.Tangible Al wherein only appears in this XRD spectra
2O
3CoAl does not appear in the strong diffraction peak of matrix and NiO
2O
4, NiAl
2O
4With the diffraction peak of CoO, the peak shape broad of collection of illustrative plates, burr are more obvious, illustrate to have the CoO that much should belong to high dispersing or the crystallite and the amorphous phase of Co/Ni composite oxides.Because the maturing temperature of presoma is not high, should not have CoAl yet
2O
4, NiAl
2O
4The crystalline phase of spinel generates.
Steps A: anodised aluminium flake preparation method is with embodiment 1
Step B: take by weighing Ni (NO
3)
26H
2O 1.3086g, Mg (NO
3)
26H
2O 0.3846g, urea 2.8829g is dissolved in the 200ml deionized water [Mg
2+]/[Ni
2+]=1/3,, [urea]/[M
1 2++ M
2 2+]=4, the ionic concn of total divalent metal is 0.03mol/l, the AAO/Al matrix is hung vertically in the glass reactor, the AAO/Al matrix all immerses in the reaction soln, in 90 ℃ of baking ovens, react 48h, take out aluminium flake afterwards, rinse out the reaction solution that remains in the surface with deionized water after, at 70 ℃ of following dry 12h.
Step C: the hydrotalcite film presoma that drying is good places retort furnace, is warming up to 600 ℃ with the heat-up rate of 5 ℃/min from room temperature, and 600 ℃ of insulations 8 hours, furnace cooling cooled to room temperature naturally then.Obtained the Ni/Mg/Al composite metal oxide film.
Steps A: anodised aluminium flake preparation method is with embodiment 1
Step B: take by weighing Cu (NO
3)
26H
2O 1.8072g, Mg (NO
3)
26H
2O 0.3846g, urea 2.8829g, [Cu
2+]/[Mg
2+] /=3/1, be dissolved in the 200ml deionized water, the ionic concn of total divalent metal is 0.03mol/l, the AAO/Al matrix is hung vertically in the glass reactor, matrix all immerses in the reaction solution, reacts 18h in 90 ℃ of baking ovens, takes out aluminium flake afterwards, after rinsing out the reaction solution that remains in the surface with deionized water, at 70 ℃ of following dry 12h.
Step C: the hydrotalcite film presoma that drying is good places retort furnace, heat-up rate with 5 ℃/min is warming up to 450 ℃ from room temperature, and 450 ℃ of insulations 8 hours, furnace cooling cooled to room temperature naturally then, has obtained the Cu/Mg/Al composite metal oxide film.
Steps A: anodised aluminium flake preparation method is with embodiment 1
Step B: take by weighing Zn (NO
3)
26H
2O0.1487, Mg (NO
3)
26H
2O 0.02564g, volatile salt 0.4517g, [Mg
2+]/[Zn
2+]=1/5, be dissolved in the 200ml deionized water, the ionic concn of total divalent metal is 0.003mol/l, the AAO/Al matrix is hung vertically in the glass reactor, matrix all immerses in the reaction solution, reacts 80h in 90 ℃ of baking ovens, takes out aluminium flake afterwards, after rinsing out the reaction solution that remains in the surface with deionized water, at 70 ℃ of following dry 12h.
Step C: the hydrotalcite film presoma that drying is good places retort furnace, heat-up rate with 5 ℃/min is warming up to 600 ℃ from room temperature, and 600 ℃ of insulations 8 hours, furnace cooling cooled to room temperature naturally, has obtained the Zn/Mg/Al composite metal oxide film.
Claims (4)
1. one kind is the method that presoma prepares composite metal oxide film with the houghite, adopt the original position synthetic technology directly to utilize through the aluminium source on the surperficial anodised aluminum substrate AAO/Al, at first on matrix, obtain polynary hydrotalcite film presoma, then through roasting make uniform particles disperse, fine and close, continuously, thickness is at micron order, composite metal oxide film that sticking power is good, the general structure of rete is: M
1 2+ zM
2 2+ 1-x-zAl
3+ xO
1+x/2Processing step is:
The preparation of a:AAO/Al matrix
Employing purity is raw material greater than 90% aluminium flake, be cut into rectangle, elder generation is dipped in aluminium flake in acetone or the ethanol respectively and ultrasonic 3～5min removes surface and oil contaminant, again aluminium flake is changed over to and soak 1～3min in 1%～5% the sodium hydroxide solution and remove its surperficial zone of oxidation, rinse well with deionized water at last, put into electrolyzer and make negative electrode, adopt stereotype to make anode, electrolytic solution is the sulphuric acid soln of 0.1～2mol/l, and oxidation voltage is 0.1～20V/cm
2, the aluminium flake electrolysis time is 0.5～2.5 hour, treat that aluminium flake surface forms anodic aluminum oxide layer after, take out aluminium flake, rinse out the acid solution of aluminium flake remained on surface with deionized water after, be placed in 60 ℃～90 ℃ in the baking oven dry 6～15 hours, take out aluminium flake and it is put in the moisture eliminator preserves;
B: the preparation of hydrotalcite film
Step 1: in glass reactor, with M
1 2+And M
2 2+Soluble inorganic salt be dissolved in the deionized water, be mixed with the solution that concentration is 0.003～0.1mol/l, [M
1 2++ M
2 2+]/[Al
3+] molar ratio be 2～6, [M
1 2+]/[M
2 2+] mol ratio is 0.2～6, with precipitation agent according to [precipitation agent]/[M
1 2++ M
2 2+The ratio stirring and dissolving of]=4～40 is in this inorganic salt solution;
Step 2: the aluminium flake for preparing among the step a is cut into rectangle, two angles perforation with the homonymy of aluminium flake, after tying up fine rule, vertical hanging is in glass reactor central authorities, matrix location is fixed by the sealing cover of glass reactor, the AAO/Al matrix needs all to immerse in the reaction soln, place baking oven to react glass reactor, when containing the cobalt metal element that oxidizing reaction easily takes place in the composite metal oxide film of preparation in air, reaction is put into water-bath with glass reactor and is carried out, carry out protection of inert gas simultaneously, oxidized and the situation that chemical valence changes takes place occur to avoid metallic element; Temperature of reaction is 70 ℃～90 ℃, and the reaction times is 6～80 hours.
Step 3: will be in the step 2 the aluminium flake matrix finished of reaction take out, with deionized water rinsing 1～5 time, place 50 ℃～90 ℃ dry 6～12 hours of baking oven, be put in the moisture eliminator after the taking-up and preserve, the pH value scope of having reacted is 8.0～10.0;
C: the preparation of composite metal oxide film
The hydrotalcite film for preparing among the step b is placed retort furnace, be to heat up under the condition of 1～10 ℃/min to carry out roasting at heat-up rate, 450 ℃～600 ℃ insulation roastings 4～8 hours, cool to room temperature naturally after, take out sample, obtained composite metal oxide film.
2. method according to claim 1 is characterized in that: M
1 2+ zM
2 2+ 1-x-zAl
3+ xO
1+x/2M in the formula
1 2+And M
2 2+Represent divalent-metal ion Mg respectively
2+, Co
2+, Cu
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any two kinds of elements.
3. method according to claim 1 is characterized in that: M
1 2+ zM
2 2+ 1-x-zAl
3+ xO
1+x/2The span of x, z is respectively 0.2≤x≤0.3,0.03≤z≤0.7 in the formula.
4. according to claim 1 described method, it is characterized in that: the precipitation agent that is adopted is urea or volatile salt.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008151495A1 (en) * | 2007-06-15 | 2008-12-18 | Beijing University Of Chemical Technology | Super-hydrophobic double-layered-hydroxides thin film and the method for making the same |
| WO2013021368A1 (en) | 2011-08-11 | 2013-02-14 | Universidade De Aveiro | Conversion films based on lamellar double-hydroxides for active protection against corrosion |
| CN103952720A (en) * | 2014-04-29 | 2014-07-30 | 北京化工大学 | Metal substrate/cobalt-containing hydrotalcite nano-film electrode and preparation method thereof |
| CN105986292A (en) * | 2016-01-20 | 2016-10-05 | 安徽大学 | Preparation method for titanium dioxide nanotube array decorated with cobalt and nickel double-layer hydroxide and application of photoelectron-chemistry hydrolysis hydrogen production |
| CN108796549A (en) * | 2018-05-23 | 2018-11-13 | 深圳大学 | Metallic compound coats composite material, preparation method and the application of copper nano-wire |
| CN109012187A (en) * | 2018-08-29 | 2018-12-18 | 北京工业大学 | A kind of method of growth in situ layered bi-metal oxide nanofiltration membrane |
| CN109126481A (en) * | 2018-08-29 | 2019-01-04 | 北京工业大学 | A kind of compound membrane preparation method of LDO/ polyelectrolyte for organic solvent nanofiltration |
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2006
- 2006-07-14 CN CN 200610089768 patent/CN1908244A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008151495A1 (en) * | 2007-06-15 | 2008-12-18 | Beijing University Of Chemical Technology | Super-hydrophobic double-layered-hydroxides thin film and the method for making the same |
| WO2013021368A1 (en) | 2011-08-11 | 2013-02-14 | Universidade De Aveiro | Conversion films based on lamellar double-hydroxides for active protection against corrosion |
| CN103952720A (en) * | 2014-04-29 | 2014-07-30 | 北京化工大学 | Metal substrate/cobalt-containing hydrotalcite nano-film electrode and preparation method thereof |
| CN103952720B (en) * | 2014-04-29 | 2016-03-30 | 北京化工大学 | Metal base/containing cobalt acrylic/hydrotalcite-like nano membrane electrode and preparation method thereof |
| CN105986292A (en) * | 2016-01-20 | 2016-10-05 | 安徽大学 | Preparation method for titanium dioxide nanotube array decorated with cobalt and nickel double-layer hydroxide and application of photoelectron-chemistry hydrolysis hydrogen production |
| CN108796549A (en) * | 2018-05-23 | 2018-11-13 | 深圳大学 | Metallic compound coats composite material, preparation method and the application of copper nano-wire |
| CN109012187A (en) * | 2018-08-29 | 2018-12-18 | 北京工业大学 | A kind of method of growth in situ layered bi-metal oxide nanofiltration membrane |
| CN109126481A (en) * | 2018-08-29 | 2019-01-04 | 北京工业大学 | A kind of compound membrane preparation method of LDO/ polyelectrolyte for organic solvent nanofiltration |
| CN109126481B (en) * | 2018-08-29 | 2021-04-30 | 北京工业大学 | Preparation method of LDO/polyelectrolyte composite membrane for nanofiltration of organic solvent |
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