CN102389828B - Preparation and application of high-dispersity ZnO/GaN solid solution - Google Patents
Preparation and application of high-dispersity ZnO/GaN solid solution Download PDFInfo
- Publication number
- CN102389828B CN102389828B CN2011102930707A CN201110293070A CN102389828B CN 102389828 B CN102389828 B CN 102389828B CN 2011102930707 A CN2011102930707 A CN 2011102930707A CN 201110293070 A CN201110293070 A CN 201110293070A CN 102389828 B CN102389828 B CN 102389828B
- Authority
- CN
- China
- Prior art keywords
- zno
- polymolecularity
- solid solution
- gan solid
- gan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000006104 solid solution Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 9
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004176 ammonification Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical group [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of high-dispersity ZnO/GaN solid solution. The preparation method comprises the following step of: preparing high-dispersity layered double hydroxides (LDHs) by utilizing a co-precipitation and hydrothermal treatment method, and thus preparing a high-dispersity ZnO/GaN solid solution material in various forms such as thin film, powder and the like. The high-dispersity ZnO/GaN solid solution thin film, which is prepared by the steps of spin-coating the high-dispersity LDHs on a substrate and carrying out high-temperature ammoniation, can be used for photocatalytic water decomposing, thus the use efficiency of the catalyst is greatly improved, the use amount of the catalyst is reduced, the defect that powder is difficult to recover in powder water catalysis process is overcome, and the high-dispersity ZnO/GaN solid solution has good application prospects.
Description
Technical field
The present invention relates to a kind of solid solution, particularly a kind of preparation method of polymolecularity ZnO/GaN solid solution and the application in photocatalysis thereof.
Background technology
Solid solution is that composition can change alloy phase within the specific limits continuously, and this variation does not change the lattice type of solvent metal.According to solute atoms residing position in the solvent dot matrix, can be divided into interstitial solid solution and substitutional solid solution.Content of solute is adjustable, and then can regulate the performance of solid solution, so that solid solution shows wide application prospect in a plurality of fields such as ion-exchange, absorption, catalysis, light, electricity, magnetic.The method for preparing solid solution has multiple, comprise ion implantation, sintering process, ion-exchange, doping etc., wherein utilize layered double-hydroxide (LDHs) material be solid solution that presoma obtains after Overheating Treatment have structure height in order, have evenly multiple advantages such as distribution of porous, high-specific surface area, element.
The energy crisis environmental problem that in addition fossil fuel causes that becomes increasingly conspicuous is serious all the more in recent years, and the new forms of energy of seeking cleaning are key subjects of new century.Utilize conductor photocatalysis water H processed
2Be one of effective way of obtaining clean energy resource, wide or conduction band position is not suitable for not being suitable for photocatalysis water H processed but most of semiconductor is because of energy gap
2Japan Patent JP2005144210-A report has prepared a kind of ZnO/GaN solid solution, can regulate energy gap, and absorbing wavelength is transferred to about 420nm, is used for catalysis thereby can absorb visible light.(the Junpeng Wang such as Chinese patent CN102166527A and Wang Junpeng
Et al.J. Mater. Chem., 2011 (21): 4562) reported with (Zn
2+/ Ga
3+) layered double-hydroxide (LDHs) prepared ZnO/GaN solid solution for presoma, can with the content to 50% of GaN ~ 20%, can save the consumption of expensive GaN, thereby reduce cost.
Above-mentioned two kinds of methods all adopt nanocrystalline preparation powder method, nanocrystalline agglomeration is obvious in the preparation process, so that powder diameter is larger, cause that most of ZnO/GaN solid solution is nanocrystalline can not to contact visible light, make also simultaneously that most electronics, hole these effective catalytic centers migration distance in powder are long to cause its compound consumption and can not be used for catalysis water in inside, so that ZnO/GaN solid solution catalytic efficiency is lower.And because the catalyst that above-mentioned two kinds of methods make is Powdered, powder is difficult to reclaim in the water catalytic process, has caused the waste of catalyst.
Summary of the invention
Lower for ZnO/GaN solid solution catalytic efficiency in the prior art, in catalytic process, be difficult to the deficiency that reclaims, the invention provides a kind of preparation method who prepares polymolecularity ZnO/GaN solid solution, and the scheme that solid solution can be prepared into variform is to solve the deficiency in the above-mentioned technology.
For this reason, the invention provides a kind of preparation method of polymolecularity ZnO/GaN solid solution, comprise the steps:
(1) water-soluble Zn salt and Ga salt are dissolved in deionized water, be mixed with mixing salt solution, then in this mixing salt solution, drip precipitating reagent, accompany by simultaneously stirring, regulating the pH value is 8 ~ 9, until continue to stir 10～15 minutes after generating coprecipitate, obtains suspension again;
(2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle and carry out hydrothermal treatment consists under 100 ℃ ~ 130 ℃ temperature, obtains the polymolecularity layered double-hydroxide aqueous solution in upper solution;
(3) utilize the above-mentioned aqueous solution can make respectively polymolecularity ZnO/GaN solid solution membrane or Powdered polymolecularity ZnO/GaN solid solution, its method is respectively: the polymolecularity layered double-hydroxide aqueous solution that step (2) is obtained is spin-coated on the substrate, the substrate that spin coating is good is put into tube furnace, obtains polymolecularity ZnO/GaN solid solution membrane through ammonification under 750 ℃ ~ 850 ℃ temperature; The sediment that obtains behind the polymolecularity layered double-hydroxide aqueous solution centrifugal drying that step (2) is obtained is put into tube furnace, obtains Powdered polymolecularity ZnO/GaN solid solution through ammonification under 750 ℃ ~ 850 ℃ temperature.
Wherein, the water-soluble Zn salt described in the step (1) is ZnCl
2, ZnSO
4Or Zn (NO
3)
2, water-soluble Ga salt is GaCl
3Or Ga (NO
3)
3, the mol ratio of water-soluble Zn salt and water-soluble Ga salt is 1:1 ~ 10:1, precipitating reagent is NaOH, sodium carbonate, urea or ammoniacal liquor.
Among the preparation method of polymolecularity ZnO/GaN solid solution membrane, described substrate is Si substrate or glass substrate, and the thickness of polymolecularity ZnO/GaN solid solution membrane is less than 300nm.
In addition, the present invention also provides the polymolecularity ZnO/GaN solid solution membrane that will the make purposes as the photochemical catalyst decomposition water: the ZnO/GaN solid solution membrane is put into water, is H through radiation of visible light with water decomposition
2And O
2
It was the polymolecularity state before heat treatment that the ZnO/GaN solid solution that obtains polymolecularity must make its presoma, in heat treatment process, keep like this its original polymolecularity just can obtain the ZnO/GaN solid solution of polymolecularity, so the key of the ZnO/GaN solid solution of preparation polymolecularity is the presoma that obtains polymolecularity, namely will make polymolecularity (Zn
2+/ Ga
3+) layered double-hydroxide (LDHs).The ZnO/GaN solid solution of polymolecularity is not reunited mutually because of its nanometer sheet, so that all nanometer sheet can contact visible light, simultaneously since the polymolecularity of ZnO/GaN solid solution reduced the migration distance in electronics, hole and then reduced electronics, hole-recombination consumption, thereby can increase substantially utilization rate and the catalytic efficiency of ZnO/GaN solid solution.The ZnO/GaN solid solution catalyst is made film morphology makes it be easy to use, and is convenient to collect.And because polymolecularity (Zn
2+/ Ga
3+) layered double-hydroxide is not because contacting with each other between its nanometer sheet, so that contact fully with ammonia, reduced the ammonification time, thereby reduced the evaporation of Zn in the heat treatment process, so that Zn content loses hardly, surpass 90% ZnO/GaN solid solution so can make ZnO content.The Ga element is the resource of very rare costliness, and said method has not only reduced the consumption of Ga, has also reduced cost.
The invention has the beneficial effects as follows:
1) adopt method of the present invention can prepare the aqueous solution of polymolecularity ZnO/GaN layered double-hydroxide (LDHs), its dispersiveness is fine, places three weeks not occur precipitation, and the particle in the solution is not reunited, do not assembled, and particle diameter is little and be evenly distributed;
2) the polymolecularity ZnO/GaN layered double-hydroxide (LDHs) that adopts method of the present invention to make can be prepared into the polymolecularity ZnO/GaN solid-solution material of variform, thereby has widened the application of this material;
3) polymolecularity layered double-hydroxide (LDHs) can be preserved in the aqueous solution, has overcome traditional layered double-hydroxide (LDHs) and can only be kept at defective in the organic solvent, has reduced environmental pollution;
4) ZnO/GaN layered double-hydroxide (LDHs) is prepared into filminess, the stacking minimizing of nanometer sheet can reduce high temperature ammonification required time greatly, significantly reduces the consumption of LDHs;
5) with the ZnO/GaN solid solution membrane photocatalyst of polymolecularity, solve the difficult problem that powder is difficult to reclaim in the catalytic process, and can avoid the waste of catalyst;
6) the ZnO/GaN solid solution of polymolecularity can reduce electron-hole recombinations, can improve catalyst utilization rate and catalytic efficiency;
7) method of the present invention is simple, easy implements, and helps the industrial applications of ZnO/GaN solid solution.
Description of drawings
Fig. 1 is (Zn
2+/ Ga
3+) X-ray diffraction (XRD) collection of illustrative plates of layered double-hydroxide (LDHs);
Fig. 2 is (Zn
2+/ Ga
3+) transmission electron microscope (TEM) figure of layered double-hydroxide (LDHs);
Fig. 3 is (Zn
2+/ Ga
3+) SEM (SEM) figure of layered double-hydroxide (LDHs) precipitation;
Fig. 4 is X-ray diffraction (XRD) collection of illustrative plates of ZnO/GaN solid solution membrane;
Fig. 5 is ZnO/GaN solid solution membrane catalysis water H processed under different-waveband light
2Productive rate figure.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that these embodiment only are not used in for explanation the present invention and limit the scope of the invention.Should be understood that in addition after the content of having read instruction of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1: the preparation of polymolecularity layered double-hydroxide (LDHs)
1) with mol ratio is the Zn (NO of 4:1
3)
2And Ga (NO
3)
3Dissolve in deionized water, be mixed with mixing salt solution, then drip urea in this mixing salt solution, regulating the pH value is 9, accompanies by simultaneously stirring, until continue to stir 10 minutes after generating coprecipitate, obtains suspension again;
2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle 115 ℃ of hydrothermal treatment consists, obtains (the Zn of polymolecularity in upper solution
2+/ Ga
3+) the layered double-hydroxide aqueous solution;
Fig. 1 is (Zn
2+/ Ga
3+) X-ray diffraction (XRD) collection of illustrative plates of layered double-hydroxide (LDHs), that show among the figure is (Zn
2+/ Ga
3+) peak position of layered double-hydroxide (LDHs), as can be seen from the figure have typical layered double-hydroxide (LDHs) at the characteristic peak of 23 ° and 34 °, illustrate that product is layered double-hydroxide (LDHs).
Embodiment 2: the dispersiveness checking of the layered double-hydroxide aqueous solution
1) with mol ratio is the ZnCl of 1:1
2And GaCl
3Dissolve in deionized water, be mixed with mixing salt solution, then drip NaOH in this mixing salt solution, regulating the pH value is 8, accompanies by simultaneously stirring, until continue to stir 12 minutes after generating coprecipitate, obtains suspension again;
2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle 120 ℃ of hydrothermal treatment consists, obtains (the Zn of polymolecularity in upper solution
2+/ Ga
3+) the layered double-hydroxide aqueous solution;
3) (the Zn of polymolecularity will be obtained in the upper solution
2+/ Ga
3+) after the layered double-hydroxide aqueous solution left standstill for three weeks at ambient temperature, do not separate out precipitation in the aqueous solution, the bulky grain that also find to suspend illustrates that this aqueous solution has fabulous dispersiveness, and transmission electron microscope (TEM) collection of illustrative plates has also confirmed (the Zn that makes
2+/ Ga
3+) polymolecularity of layered double-hydroxide (LDHs).
Fig. 2 is the (Zn of upper solution
2+/ Ga
3+) transmission electron microscope (TEM) figure of layered double-hydroxide (LDHs), the LDHs in the visible upper solution does not reunite, and LDHs has polymolecularity.
Embodiment 3: the preparation of Powdered polymolecularity ZnO/GaN solid solution
1) with mol ratio is the ZnSO of 2:1
4And GaCl
3Dissolve in deionized water, be mixed with mixing salt solution, then drip ammoniacal liquor in this mixing salt solution, regulating the pH value is 8, accompanies by simultaneously stirring, until continue to stir 10 minutes after generating coprecipitate, obtains suspension again;
2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle 100 ℃ of hydrothermal treatment consists, obtains (the Zn of polymolecularity in upper solution
2+/ Ga
3+) the layered double-hydroxide aqueous solution;
3) with (Zn of the polymolecularity that obtains
2+/ Ga
3+) be precipitated thing behind the layered double-hydroxide aqueous solution centrifugal drying;
4) sediment that drying is good is put into tube furnace, carries out 750 ℃ of ammonifications and can obtain Powdered polymolecularity ZnO/GaN solid solution in 5 minutes.
Fig. 3 SEM (SEM) figure shows (Zn among the figure
2+/ Ga
3+) layered double-hydroxide (LDHs) is the nanometer sheet form and kept good hexagon pattern.
Embodiment 4: the preparation of Powdered polymolecularity ZnO/GaN solid solution
1) with mol ratio is the ZnCl of 2:1
2And GaCl
3Dissolve in deionized water, be mixed with mixing salt solution, then drip ammoniacal liquor in this mixing salt solution, regulating the pH value is 8, accompanies by simultaneously stirring, until continue to stir 15 minutes after generating coprecipitate, obtains suspension again;
2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle 130 ℃ of hydrothermal treatment consists, obtains (the Zn of polymolecularity in upper solution
2+/ Ga
3+) the layered double-hydroxide aqueous solution;
3) with (Zn of the polymolecularity that obtains
2+/ Ga
3+) be precipitated thing behind the layered double-hydroxide aqueous solution centrifugal drying;
4) sediment that drying is good is put into tube furnace, carries out 850 ℃ of ammonifications and can obtain Powdered polymolecularity ZnO/GaN solid solution in 3 minutes.
Embodiment 5: the preparation of polymolecularity ZnO/GaN solid solution membrane
1) with mol ratio is the ZnCl of 3:1
2And GaCl
3Dissolve in deionized water, be mixed with mixing salt solution, then drip sodium carbonate in this mixing salt solution, regulating the pH value is 8.5, accompanies by simultaneously stirring, until continue to stir 15 minutes after generating coprecipitate, obtains suspension again;
2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle 130 ℃ of hydrothermal treatment consists, obtains (the Zn of polymolecularity in upper solution
2+/ Ga
3+) the layered double-hydroxide aqueous solution;
3) will obtain (the Zn of polymolecularity
2+/ Ga
3+) the layered double-hydroxide aqueous solution is spin-coated on the glass substrate, thickness is 250nm;
4) substrate that spin coating is good is put into tube furnace, 850 ℃ of lower ammonifications 3 minutes, can obtain polymolecularity ZnO/GaN solid solution membrane.
Fig. 4 is the X ray diffracting spectrum (XRD) of ZnO/GaN solid solution membrane, show among the figure, peak position between the peak position of the peak position of ZnO and GaN, assorted peak, visible ZnO/GaN solid solution is single-phase existence, does not have dephasign.
Embodiment 6: the preparation of polymolecularity ZnO/GaN solid solution membrane
1) with mol ratio is the ZnSO of 10:1
4And GaCl
3Dissolve in deionized water, be mixed with mixing salt solution, then drip sodium carbonate in this mixing salt solution, regulating the pH value is 8, accompanies by simultaneously stirring, until continue to stir 10 minutes after generating coprecipitate, obtains suspension again;
2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle 100 ℃ of hydrothermal treatment consists, obtains (the Zn of polymolecularity in upper solution
2+/ Ga
3+) the layered double-hydroxide aqueous solution;
3) will obtain (the Zn of polymolecularity
2+/ Ga
3+) the layered double-hydroxide aqueous solution is spin-coated on the Si substrate, thickness is 280nm;
4) substrate that spin coating is good is put into tube furnace, 750 ℃ of lower ammonifications 5 minutes, can obtain polymolecularity ZnO/GaN solid solution membrane.
In order to detect the content of ZnO in the polymolecularity ZnO/GaN solid solution membrane, this film is carried out elementary analysis, utilize energy disperse spectroscopy (EDS) detect N, O, each element of Zn, Ga in the solid solution membrane under the standard state content of (K represents that each element is in standard state), testing result sees Table 1.
Table 1 ZnO/GaN solid solution results of elemental analyses
| Element | Weight | Atom |
| ? | Percentage | Percentage |
| N K | 1.49 | 4.33 |
| O K | 17.92 | 45.68 |
| Zn K | 73.24 | 45.69 |
| Ga K | 7.35 | 4.30 |
| Total amount | 100.00 | ? |
The result of form shows, can be calculated ZnO content and be reached 91.4% by formula Zn K/(Zn K+Ga K) (formula numerical value is the atomic percent data)=45.69/(45.69+4.30), with initial ZnSO
4And GaCl
3Mol ratio 10:1 is basic identical.Explanation in the high temperature ammonifying process, (Zn
2+/ Ga
3+) Zn in the layered double-hydroxide do not have to run off substantially.
Embodiment 7:ZnO/GaN solid solution membrane is used for photodissociation water as catalyst
1) area that embodiment 5 is made is 1cm
2The ZnO/GaN solid solution membrane put into water;
2) regulate the radiation of visible light ZnO/GaN solid solution membrane that monochromatic burner uses identical light intensity under the different-waveband;
3) measure H under the different-waveband
2And O
2Output, can obtain the efficient of ZnO/GaN solid solution membrane under different-waveband.
Fig. 5 is ZnO/GaN solid solution membrane catalysis water H processed under different-waveband light
2Productive rate figure, show among the figure that the ZnO/GaN solid solution membrane realized catalysis water H processed under the visible light condition
2
Claims (9)
1. the preparation method of a polymolecularity ZnO/GaN solid solution comprises the steps:
(1) water-soluble Zn salt and Ga salt are dissolved in deionized water, be mixed with mixing salt solution, then in this mixing salt solution, drip precipitating reagent, accompany by simultaneously stirring, regulating the pH value is 8 ~ 9, until continue to stir 10～15 minutes after generating coprecipitate, obtains suspension again;
(2) with suspension washing, the sediment that obtains after centrifugal puts into water heating kettle and carry out hydrothermal treatment consists under 100 ℃ ~ 130 ℃ temperature, obtains the polymolecularity layered double-hydroxide aqueous solution in upper solution;
(3) the polymolecularity layered double-hydroxide aqueous solution that utilizes step (2) to obtain makes polymolecularity ZnO/GaN solid solution membrane or Powdered polymolecularity ZnO/GaN solid solution.
2. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 1, it is characterized in that: the polymolecularity layered double-hydroxide aqueous solution that step (2) is obtained is spin-coated on the substrate, the substrate that spin coating is good is put into tube furnace, obtains polymolecularity ZnO/GaN solid solution membrane through ammonification under 750 ℃ ~ 850 ℃ temperature.
3. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 1, it is characterized in that: the sediment that obtains behind the polymolecularity layered double-hydroxide aqueous solution centrifugal drying that step (2) is obtained is put into tube furnace, obtains Powdered polymolecularity ZnO/GaN solid solution through ammonification under 750 ℃ ~ 850 ℃ temperature.
4. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 1, it is characterized in that: water-soluble Zn salt is ZnCl in the step (1)
2, ZnSO
4Or Zn (NO
3)
2, water-soluble Ga salt is GaCl
3Or Ga (NO
3)
3
5. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 1, it is characterized in that: the mol ratio of water-soluble Zn salt and water-soluble Ga salt is 1:1 ~ 10:1 in the step (1).
6. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 1, it is characterized in that: the precipitating reagent in the step (1) is NaOH, sodium carbonate, urea or ammoniacal liquor.
7. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 2, it is characterized in that: described substrate is Si substrate or glass substrate.
8. the preparation method of polymolecularity ZnO/GaN solid solution according to claim 2, it is characterized in that: the thickness of described polymolecularity ZnO/GaN solid solution membrane is less than 300nm.
9. the polymolecularity ZnO/GaN solid solution membrane that makes of method according to claim 2 is as the purposes of photochemical catalyst decomposition water, and it is characterized in that: the ZnO/GaN solid solution membrane is put into water, is H through radiation of visible light with water decomposition
2And O
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102930707A CN102389828B (en) | 2011-10-01 | 2011-10-01 | Preparation and application of high-dispersity ZnO/GaN solid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102930707A CN102389828B (en) | 2011-10-01 | 2011-10-01 | Preparation and application of high-dispersity ZnO/GaN solid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102389828A CN102389828A (en) | 2012-03-28 |
| CN102389828B true CN102389828B (en) | 2013-03-20 |
Family
ID=45857283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102930707A Expired - Fee Related CN102389828B (en) | 2011-10-01 | 2011-10-01 | Preparation and application of high-dispersity ZnO/GaN solid solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102389828B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103878011A (en) * | 2014-04-17 | 2014-06-25 | 哈尔滨工业大学 | Method for synthesizing GaN: ZnO solid solution photocatalyst |
| CN108117052B (en) * | 2016-11-29 | 2020-10-16 | 中国科学院金属研究所 | Two-dimensional mesoporous (GaN)1-x (ZnO) x solid solution nano material and preparation method thereof |
| CN106824242A (en) * | 2017-01-19 | 2017-06-13 | 京东方科技集团股份有限公司 | The preparation method and material for air purification of a kind of material for air purification |
| CN112675890B (en) * | 2020-12-21 | 2021-11-19 | 中国医科大学附属第一医院 | Visible light catalytic nano antibacterial material and preparation method thereof |
| CN113828343B (en) * | 2021-10-29 | 2023-05-23 | 厦门理工学院 | Surface-treated GaN-ZnO solid solution powder and surface treatment method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429028A (en) * | 2008-11-28 | 2009-05-13 | 同济大学 | Method for producing Zr0.30Ce0.45Al0.25O1.87sosoloid nano-particle |
| CN101829557A (en) * | 2010-04-20 | 2010-09-15 | 上海大学 | Magnesium modified cerium-zirconium solid solution and preparation method thereof |
| CN102166527A (en) * | 2011-01-25 | 2011-08-31 | 山东大学 | Gallium nitride/zinc oxide solid solution with high zinc content and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3834777B2 (en) * | 2003-11-11 | 2006-10-18 | 独立行政法人科学技術振興機構 | Water splitting catalyst composed of gallium nitride solid solution |
-
2011
- 2011-10-01 CN CN2011102930707A patent/CN102389828B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429028A (en) * | 2008-11-28 | 2009-05-13 | 同济大学 | Method for producing Zr0.30Ce0.45Al0.25O1.87sosoloid nano-particle |
| CN101829557A (en) * | 2010-04-20 | 2010-09-15 | 上海大学 | Magnesium modified cerium-zirconium solid solution and preparation method thereof |
| CN102166527A (en) * | 2011-01-25 | 2011-08-31 | 山东大学 | Gallium nitride/zinc oxide solid solution with high zinc content and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-144210A 2005.06.09 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102389828A (en) | 2012-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102950016B (en) | Preparation method of ZnO/g-C3N4 composite photocatalyst | |
| Jiang et al. | Novel ternary BiOI/g-C3N4/CeO2 catalysts for enhanced photocatalytic degradation of tetracycline under visible-light radiation via double charge transfer process | |
| CN113042077B (en) | Photo-thermal-photochemical synergistic conversion hydrogel material and preparation method and application thereof | |
| Liu et al. | Integrating nitrogen vacancies into crystalline graphitic carbon nitride for enhanced photocatalytic hydrogen production | |
| CN102389828B (en) | Preparation and application of high-dispersity ZnO/GaN solid solution | |
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN102080262B (en) | Visible light catalytic material, and preparation method and application thereof | |
| CN106984352A (en) | A kind of preparation method of cadmium ferrite doped graphite phase carbon nitride composite photo-catalyst | |
| CN107043222A (en) | The preparation method of phosphorus doping graphite phase carbon nitride nano thin-film | |
| CN108940332B (en) | High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst | |
| CN106111161B (en) | A kind of ZnO/ZnS/CdS composite material and preparation method of porous core-shell structure | |
| CN106362742B (en) | A kind of Ag/ZnO nano-complex and its preparation method and application | |
| CN109433185A (en) | One step hydro thermal method prepares vanadic acid indium/isomerism knot composite bismuth vanadium photocatalyst | |
| CN112604690B (en) | Method for preparing rare earth perovskite/biochar composite material by utilizing agricultural and forestry waste and application thereof | |
| CN107983353B (en) | TiO 22-Fe2O3Preparation method and application of composite powder | |
| CN108311162A (en) | A kind of preparation method and applications of ZnO/BiOI heterojunction photocatalysts | |
| CN111420664A (en) | Preparation method of flaky cuprous oxide/cobaltous oxide nanocomposite and application of flaky cuprous oxide/cobaltous oxide nanocomposite in catalyzing ammonia borane hydrolysis hydrogen production | |
| CN107051545A (en) | A kind of nano titanium oxide/copper sulfide nano nano composite material | |
| CN115418225B (en) | Preparation method of phosphorus doped modified carbon quantum dot and composite photocatalyst thereof | |
| CN108686691A (en) | A kind of preparation method of Gd2 O3 class graphite phase carbon nitride catalysis material | |
| Ma et al. | Mn0. 2Cd0. 8S modified with 3D flower‐shaped Co3 (PO4) 2 for efficient photocatalytic hydrogen production | |
| Sun et al. | Modulating charge transport behavior across the interface via g-C3N4 surface discrete modified BiOI and Bi2MoO6 for efficient photodegradation of glyphosate | |
| CN107362792B (en) | Preparation method of strontium titanate/tin niobate composite nano material | |
| CN112495399A (en) | MoS2Nano flower-Ag doped porous BiVO4Preparation method of photocatalytic degradation material | |
| CN104399493B (en) | Anthemia-shaped NiS/ZnS visible light photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Liping Inventor after: Li Yaguang Inventor after: Mei Weimin Inventor after: Yang Meijia Inventor after: Gu Jianlong Inventor after: Chen Dan Inventor after: Zhu Liyu Inventor after: Chen Qi Inventor after: Ren Yuping Inventor before: Zhu Liping Inventor before: Li Yaguang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHU LIPING LI YAGUANG TO: ZHU LIPING LI YAGUANG MEI WEIMIN YANG MEIJIA GU JIANLONG CHEN DAN ZHU CHONGYU CHEN QI REN YUPING |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130320 Termination date: 20141001 |
|
| EXPY | Termination of patent right or utility model |