CN101838011B - Preparation method of CuAlO2 microcrystal - Google Patents
Preparation method of CuAlO2 microcrystal Download PDFInfo
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- CN101838011B CN101838011B CN2010101819267A CN201010181926A CN101838011B CN 101838011 B CN101838011 B CN 101838011B CN 2010101819267 A CN2010101819267 A CN 2010101819267A CN 201010181926 A CN201010181926 A CN 201010181926A CN 101838011 B CN101838011 B CN 101838011B
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Abstract
The invention relates to a preparation method of CuAlO2 microcrystal; copper nitrate trihydrate and aluminum nitrate nonahydrate are added into ethanol to obtain solution A; triethanolamine is added into the solution A to be magnetically stirred to form uniform precursor sol; the precursor sol is dried to form dry gel, and then the dry gel is heated in a microwave oven and ground by an agate mortar for standby use; the ground dry gel is poured into an autoclave to have microwave hydrothermal reaction with glycol as the filling liquid, and is naturally cooled to room temperature after the reaction; and a product is obtained through centrifugation and separation, and is respectively washed by deionized water, absolute ethyl alcohol or isopropanol, the obtained black and gray powder is dried under a vacuum condition to obtain the CuAlO2 microcrystal. The preparation method uses a microwave hydrothermal method to prepare the CuAlO2 microcrystal, thereby not only having low manufacturing cost, being simple to operate, having short reaction cycle and low reaction temperature, but also has the advantages of high product purity, full grain growth, uniform grain size distribution, controllable shape and no need of calcination.
Description
Technical field
The present invention relates to a kind of p type transparent conductive oxide (TCO) preparation methods, be specifically related to a kind of CuAlO
2The preparation method of crystallite.
Background technology
Because transparent conductive oxide (TCO) has high transparency (broad-band gap) and specific conductivity in visible-range, have wide Application Areas, be widely used in solar cell, plane demonstration, specific function window coating and other photoelectric device field.(Hiroshi?Kawazoe，Masahiro?Yasukawa，Hiroyuki?Hyodo.P-type?electricalconduction?in?transparent?thin?films?of?CuAlO
2.Nature，1997，389(30)：939-942.)。At present the transparent conductive oxide that obtains is the n type mostly, as mix Al ZnO, mix the In of S
2O
3, mix the SnO of F
2Deng, the scarcity relatively of p type TCO has seriously restricted the exploitation and the application of transparent oxide semiconductor (TOS) related device, hindered TCO to the research and development based on the semi-conductor full impregnated Mingguang City electrical part of p-n junction, therefore, preparation is very necessary with research p type TCO material.CuAlO
2Studied by more and more scholars as a kind of natural p type TCO material.
Up to now, many investigators use diverse ways to prepare CuAlO
2Powder comprises solid reaction process (A.N.Banerjee, R.Maity, K.K.Chattopadhyay.Preparation of P-Type Transparent ConductingCuAlO
2Thin Films by Reactive DC sputtering[J] Materials Letters, 2003,58:10-13.), ion exchange method (L Dloczik, Y Tomn, R Konenkamp, et al.CuAlO
2Prepared by Ion Exchange from LiAlO
2[J] Thin Solids Films, 2004,451-452:116-119.), (Wang Qun waits .CuAlO to hydrothermal method for Gao Shanmin, Zhangjiang
2Nanocrystalline hydro-thermal-decomposition preparation and characterize [J]. functional materials, 2006,37 (1): 117-122.), sol-gel method (DENG Zan-Hong, ZHU Xue-Bin, TAO Ru-Hua, et al.Synthesis of CuAlO
2Ceramics using sol-gel[J] Materials Letters, 2007,61:686-689.) chemical Vapor deposition process (N.Koriche, A.Bouguelia, A.Aider, et al.Photocatalytic Hydrogen Evolution over Delafossite CuAlO
2[J] International Journal of HydrogenEnergy, 2005,30 (7): 693-699.) etc.
Summary of the invention
The object of the present invention is to provide that a kind of not only preparation manipulation is simple, reaction time is short, repeatability is high, and product purity height, crystal grain are grown complete, even particle size distribution, controllable shapes and do not needed the CuAlO of calcination processing
2The preparation method of crystallite.
For achieving the above object, the technical solution used in the present invention is: step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to (Cu
2+): (Al
3+The mol ratio of)=1: 1～1.2: 1 adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.4mol/L～0.7mol/L; Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 4%～12% then in solution A after; Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 5min～15min, and the cooling back is stand-by after with the agate mortar porphyrize; Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 50-70%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode or pressure control pattern to react, the temperature controlling mode hydrothermal temperature is controlled at 200～220 ℃, and pressure control pattern hydro-thermal pressure-controlling is at 1.0MPa-4.0MPa, and reaction 5h～10h naturally cools to room temperature after the reaction end; Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, dehydrated alcohol or washed with isopropyl alcohol then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
Microwave-hydrothermal method is to adopt microwave field to carry out hydro-thermal synthetic method as thermal source, and it is fast that microwave heating has speed, advantages such as no thermograde, and the present invention adopts microwave-hydrothermal method to prepare CuAlO
2Crystallite, not only preparation cost is low, simple to operate, reaction time is short, and temperature of reaction is low, and product purity height, crystal grain are grown complete, even particle size distribution, controllable shapes and do not needed calcination processing.
Description of drawings
The CuAlO that Fig. 1 prepares for the embodiment of the invention 1
2The X-ray diffraction of crystallite (XRD) collection of illustrative plates.
The CuAlO that Fig. 2 prepares for the embodiment of the invention 1
2The transmission electron microscope of crystallite (TEM) photo.
The CuAlO that Fig. 3 prepares for the embodiment of the invention 1
2The selected area electron diffraction of crystallite (SAED) photo.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1: step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to (Cu
2+): (Al
3+The mol ratio of)=1: 1 adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.5mol/L; Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 10% then in solution A after; Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 5min, and the cooling back is stand-by after with the agate mortar porphyrize; Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 50%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, the temperature controlling mode hydrothermal temperature is controlled at 200 ℃, reaction 10h, and reaction naturally cools to room temperature after finishing; Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, absolute ethanol washing then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
CuAlO with embodiment 1 gained
2Powder finds that with Japanese D/max2000PC x-ray diffractometer analytic sample of science product is the CuAlO that JCPDS is numbered 35-1401
2(Fig. 1).This sample is observed with a day JEM-3010 type transmission electron microscope (Fig. 2,3), from the prepared as can be seen CuAlO of photo
2Powder is a crystallite, and basic configuration is a hexagon.
Embodiment 2: step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to (Cu
2+): (Al
3+The mol ratio of)=1.05: 1 adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.4mol/L; Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 8% then in solution A after; Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 10min, and the cooling back is stand-by after with the agate mortar porphyrize; Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 55%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, the temperature controlling mode hydrothermal temperature is controlled at 210 ℃, reaction 8h, and reaction naturally cools to room temperature after finishing; Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, washed with isopropyl alcohol then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
Embodiment 3: step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to (Cu
2+): (Al
3+The mol ratio of)=1.1: 1 adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.6mol/L; Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 6% then in solution A after; Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 15min, and the cooling back is stand-by after with the agate mortar porphyrize; Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 60%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode to react, the temperature controlling mode hydrothermal temperature is controlled at 220 ℃, reaction 6h, and reaction naturally cools to room temperature after finishing; Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, absolute ethanol washing then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
Embodiment 4: step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to (Cu
2+): (Al
3+The mol ratio of)=1.15: 1 adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.7mol/L; Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 4% then in solution A after; Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 8min, and the cooling back is stand-by after with the agate mortar porphyrize; Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 65%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select the pressure control pattern to react, pressure control pattern hydro-thermal pressure-controlling is at 4.0MPa, and reaction 8h naturally cools to room temperature after the reaction end; Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, washed with isopropyl alcohol then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
Embodiment 5: step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to (Cu
2+): (Al
3+The mol ratio of)=1.2: 1 adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.5mol/L; Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 12% then in solution A after; Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 12min, and the cooling back is stand-by after with the agate mortar porphyrize; Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 70%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select the pressure control pattern to react, pressure control pattern hydro-thermal pressure-controlling is at 3.1MPa, and reaction 10h naturally cools to room temperature after the reaction end; Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, absolute ethanol washing then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
Claims (1)
1. CuAlO
2The preparation method of crystallite is characterized in that may further comprise the steps:
Step 1: at first with analytically pure nitrate trihydrate copper and nine water aluminum nitrates according to Cu
2+: Al
3+=1: 1～1.2: 1 mol ratio adds in the ethanol, and being mixed with concentration of metal ions is the blue clear solution A of 0.4mol/L～0.7mol/L;
Step 2: magnetic agitation forms uniform precursor sol add the trolamine of solution A volume 4%～12% then in solution A after;
Step 3: it is dry that precursor colloidal sol is put into loft drier earlier, makes it form xerogel, and the microwave oven of putting into output rating then and be 900W heats 5min～15min, and the cooling back is stand-by after with the agate mortar porphyrize;
Step 4: the xerogel after the above-mentioned grinding is poured in the hydrothermal reaction kettle, and spent glycol is as filling liquid, and compactedness is controlled at 50-70%; Seal hydrothermal reaction kettle then, put it in the two control of the MDS-8 type temperature and pressure microwave hydrothermal reaction; Select temperature controlling mode or pressure control pattern to react, the temperature controlling mode hydrothermal temperature is controlled at 200～220 ℃, and pressure control pattern hydro-thermal pressure-controlling is at 1.0MPa-4.0MPa, and reaction 5h～10h naturally cools to room temperature after the reaction end;
Step 5: open hydrothermal reaction kettle, obtain product by centrifugation, adopt deionized water, dehydrated alcohol or washed with isopropyl alcohol then respectively, the end vacuum-drying of gained grey black toner promptly gets CuAlO
2Crystallite.
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| CN102491401A (en) * | 2011-11-23 | 2012-06-13 | 陕西科技大学 | Method for preparing lanthanum cuprate nanometer crystal through combination of sol-gel and microwave hydrothermal synthesis |
| CN102502767A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Method for preparing lanthanum copper oxide (La2CuO4) powder by sol gel-hydrothermal method |
| CN113089000B (en) * | 2021-03-24 | 2022-05-17 | 福州大学 | Molybdenum-based catalyst with in-plane defects and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158049A (en) * | 2007-07-31 | 2008-04-09 | 北京工业大学 | Method for preparing P-type transparent conductive oxide CuAlO2 film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158049A (en) * | 2007-07-31 | 2008-04-09 | 北京工业大学 | Method for preparing P-type transparent conductive oxide CuAlO2 film |
Non-Patent Citations (2)
| Title |
|---|
| C. K. Ghosh et al..Preparation of nanocrystalline CuAlO2 through sol–gel route.《J Sol-Gel Sci Technol》.2009,第52卷第75-81页. * |
| Zanhong Deng et al..Synthesis of CuAlO2 ceramics using sol-gel.《Materials Letters》.2006,第61卷第686-689页. * |
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