CN1286712C - Method for preparing low dimensional nanomaterial of metal nitride - Google Patents
Method for preparing low dimensional nanomaterial of metal nitride Download PDFInfo
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- CN1286712C CN1286712C CN 200410025736 CN200410025736A CN1286712C CN 1286712 C CN1286712 C CN 1286712C CN 200410025736 CN200410025736 CN 200410025736 CN 200410025736 A CN200410025736 A CN 200410025736A CN 1286712 C CN1286712 C CN 1286712C
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Abstract
The present invention provides a very simple and convenient method for preparing low dimensional metal nitride nanometer materials(nanometer wires or nanometer rods). Low dimensional nanometer materials prepared in the prior art mainly comprise oxides or sulfide, but the effective control preparation method of low dimensional nitride nanometer materials is rarely reported. In the present invention, porous silicon oxide materials are used as hard templates, nitride precursors orderly grow in the pore canal inner wall of the porous silicon oxide materials through technology of limiting the growth of precursor crystals by using a pore canal, and low dimensional metal nitride nanometer materials with various structures and sizes can be prepared by changing the composition of the precursor species, adopting porous silicon oxide materials with different structures and pore diameters, and controlling the temperature and the time of heat treatment. The method adopts the technology of limiting the growth of crystals by using a pore canal, has the advantages of simple and convenient technology, strong controllability and high production efficiency, and is convenient for preparing metal nitride nanometer wires or nanometer rods with uniform diameters.
Description
Technical field
The invention belongs to the low-dimension nano material preparation, particularly the technology of preparing of metal (IIIA, VIB, VIIIB) nitride nanowires or nanometer rod.
Background technology
The nitrogen containing metal compound, because it has the electronic structure that is different from general oxide compound, make it have special electricity, optics, chemistry and magnetism characteristic, thereby this class material have very strong application prospect in fields such as nano electron device, magnetic recording material, chiral catalysis and photoelectric sensings.For example tantalum nitride membrane has obtained application because of its good electric property as the electricity film; Nitrided iron is as the novel magnetic pipe recording material of a class, and the performance aspect much is all to have surpassed the magnetic pipe recording material of present use; Molybdenum nitride, the class noble metal catalyst as a class has the precious metal characteristic receives much concern at catalytic fields such as catalytic dehydrogenation, selective hydrogenation, hydrogenating desulfurization, hydrodenitrifications.Low-dimension nano material is a kind of in nanometer (1/1000000000th meter) range scale, by physics or chemical action, arranges the wire that certain rule is arranged or the film like array that assemble by the base substance unit.Thereby this structure character that both had a nano particle is as quantum size effect, small-size effect, surface effects etc., has nano wire its own particularity matter again as quantum coupling effect and synergistic effect etc.Therefore the low-dimension nano material for preparing nano level metal nitride, especially metal nitride is that nano wire or nanometer rod have extremely important actual application value.
At present the technology of preparing of low-dimensional nano nitride also only limits to traditional direct nitridation method, vapour deposition process, steam and transports methods such as synthesis method.Because equipment complexity, preparation condition are harsh and need use expensive organometallics to be presoma, prepared nano nitride cost height, and be difficult to realize that the control of the single low-dimensional nano nitride of size synthesizes.In recent years, owing to be that hard template prepares low-dimension nano material and has method easy and products therefrom easy control of structure system and the more equal first-class characteristics of size with the mesoporous material, this method has caused that people pay close attention to greatly.But the research of adopting hard template method to prepare low-dimension nano material at present mainly concentrates on preparation, the sign of oxide compound, sulfide nanometer linear or nanometer rod and uses, and the preparation of nitride nano-material does not then appear in the newspapers.This is that the hard template technology of preparing of traditional on the other hand oxide nano thread is not suitable for the preparation of nitride nanowires yet because the nano level nitride particles itself is difficult to preparation on the one hand.Thereby, become a problem that urgency is to be solved how by the synthetic metal nitride nano wire of a kind of simple novel method.
Summary of the invention
The objective of the invention is to propose a kind of convenient and swift, controllability is strong, the preparation metal nitride low-dimension nano material that production efficiency is high is the novel method of nano wire or nanometer rod.
Can effectively control presoma orderly growth in the inwall of the duct of porous oxide of nitride by discovering duct restriction presoma crystal technique.Used precursor liquid is a kind of for containing the solution of organic amine, and another kind is orderly growth in the duct inwall of nitrogenous metallide.Used precursor liquid is a kind of for containing the solution of organic amine, and another kind is nitrogenous metal ion solution.With duct restriction presoma crystal technique,, make the metal nitride nano wire by two step pickling processes.Concrete technology follows these steps to carry out:
At first, choose the porous silica in required aperture as hard template;
Then, above-mentioned porous silica is immersed in the organic amine precursor liquid that concentration is 10-20wt%, the nitrogen containing metal salt precursor liquid that after 20-26 hour with concentration is 5-10wt% is again poured into wherein, through 10-12 hour, forms the presoma of metal nitride in the inwall of the duct of porous silica;
The weight ratio of above-mentioned template and precursor liquid total amount is 5.4-10.0wt%, and organic amine precursor liquid and nitrogen containing metal salt precursor liquid mol ratio are 1.34-5.04.
At last, the porous silica that will contain the metal nitride forerunner under 600-800 ℃ of oxygen free condition thermal treatment 2-4 hour, and with the nitride handled well with dilute sodium hydroxide or diluted hydrofluoric acid dissolving, filter, washing, oven dry, can obtain the nitride low-dimension nano material.
Because the surface hydroxyl of porous oxide presents slightly acidic,, help its inner preferentially adsorbed in duct at porous oxide earlier with after the weakly alkaline organic amine solution impregnation.After second kind of precursor liquid poured into, in the duct, have an effect with first kind of precursor liquid, generate the nitride presoma.This method makes precursor be easy to load, and stability is strong, avoids, and has also effectively avoided the absorption of presoma at the duct outside surface simultaneously.
Experiment is found must carry out under oxygen free condition when presoma is heat-treated, and participating in then if any oxygen, the thermal treatment product mostly is metal oxide.Thermal treatment temp should be controlled at 600-800 ℃ and be advisable, and this moment, metal nitride formed stable crystal.Last available dilute sodium hydroxide or diluted hydrofluoric acid dissolving porous silica, more after filtration, washing, oven dry can obtain the nano wire or the nanometer rod of metal nitride.
Experimental result shows that steeping fluid and porous silica ratio are less, then generates short nanometer rod, improves both ratios and can increase nanometer rod length.
Among the present invention, the porous silica hard template is SBA-15, or the MCM-41 mesoporous silicon oxide molecular sieve, or silica aerogel porous silica material.
Among the present invention, metal is the metallic element of IIIA, VIB, VIIIB family.
Among the present invention, organic amine is C
4-C
18Aliphatics organic amine or its salt.
Among the present invention, nitrogen containing metal salt is the ammonium salt or the nitrate of metal.
Among the present invention, the weight ratio of template and precursor liquid total amount is 9.7-10.0wt%, promptly gets the metal nitride nanometer rod.
Among the present invention, the weight ratio of template and precursor liquid total amount is 5.4-6.3wt%, promptly gets the metal nitride nano wire.
Metal nitride low-dimension nano material of the present invention is good as the effect of hydrogenating desulfurization or hydrodenitrification catalysts.
1, technology of the present invention is simple, can synthesize the nano wire or the nanometer rod of metal nitride apace.
2, can realize the diameter of metal nitride nano wire or nanometer rod is controlled by aperture selection to porous silica.
3, passing hole channel of the present invention restriction presoma crystal technique has been realized growing in the duct of presoma, greatly
Reduced outside the duct and adsorbed, the production rate of nano particle is reduced, improved the yield of low-dimension nano material.
Description of drawings
Fig. 1 is Mo
2The TEM figure of N nano wire.
Fig. 2 is Mo
2The XRD figure of N nano wire.
Fig. 3 is Mo
2The TEM figure of N nanometer rod.
Fig. 4 is the HRTEM figure of GaN nano wire.
Fig. 5 is the electron-diffraction diagram of GaN nano wire.
Embodiment
Embodiment 1
Mo
2The preparation of N nano wire: the SBA-15 that with the aperture is 7nm is a hard template.Earlier 8.0 gram hexadecyl brometo de amonios are dissolved in the 50ml water, under constantly stirring 6.7 gram SBA-15 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 3.5 gram ammonium molybdates is poured into wherein.To mix liquid after stirring left standstill 12 hours.To be loaded with Mo then
2The SBA-15 molecular sieve of N presoma is put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.To be loaded with Mo
2The SBA-15 molecular sieve of N is removed porous oxide with being dissolved in 15% hydrofluoric acid solution.Again through promptly obtaining the Mo of diameter 7nm after the washing and drying
2N nano wire (see figure 1).
Embodiment 2
Mo
2The preparation of N nanometer rod: the SBA-15 that chooses the aperture and be 7nm is a hard template.Earlier 8.0 gram hexadecyl brometo de amonios are dissolved in the 50ml water, under constantly stirring 10.5 gram SBA-15 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 3.5 gram ammonium molybdates is poured into wherein.To mix liquid after stirring left standstill 12 hours.To be loaded with Mo then
2The SBA-15 molecular sieve of N presoma is put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.To be loaded with Mo
2The SBA-15 molecular sieve of N is removed porous oxide with being dissolved in 15% hydrofluoric acid solution.Promptly obtain diameter 7nm, the Mo of length-to-diameter ratio between 3～4 through after the washing and drying again
2N nanometer rod (see figure 3).
Embodiment 3
Mo
2The preparation of N nanometer rod: the MCM-41 that with the aperture is 3nm is a hard template.Earlier 8.0 gram hexadecyl brometo de amonios are dissolved in the 50ml water, under constantly stirring 10.5 gram MCM-41 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 3.5 gram ammonium molybdates is poured into wherein.To mix liquid after stirring left standstill 12 hours.To be loaded with Mo then
2The MCM-41 molecular sieve of N presoma is put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.To be loaded with Mo
2The MCM-41 molecular sieve of N is removed porous oxide with being dissolved in 15% hydrofluoric acid solution.Promptly obtain diameter 3nm, the Mo of length-to-diameter ratio between 3～4 through after the washing and drying again
2The N nanometer rod.
Embodiment 4
The preparation of GaN nano wire: the SBA-15 that gets the aperture and be 7-8nm is a hard template.Earlier 6.0 gram vulkacit Hs are dissolved in the 50ml water, under constantly stirring 6.7 gram SBA-15 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 3.2 gram gallium nitrates is poured into wherein.To mix liquid after stirring left standstill 12 hours.The SBA15 molecular sieve that will be loaded with the GaN presoma is then put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.The SBA-15 molecular sieve that is loaded with GaN is removed porous oxide with being dissolved in the 2mol/L sodium hydroxide solution.Promptly obtain GaN nano wire (see figure 4) through after the washing and drying again.
Embodiment 5
The preparation of FeN nano wire, the MCM-41 that gets the aperture and be 4nm is a template.Earlier 7.3 gram lauryl amines are dissolved in the 50ml water, under constantly stirring 5.8 gram MCM-41 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 2.9 gram iron nitrates is poured into wherein.To mix liquid after stirring left standstill 12 hours.The MCM-41 molecular sieve that will be loaded with the FeN presoma is then put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.The MCM-41 molecular sieve that is loaded with FeN is removed porous oxide with being dissolved in the 2mol/L sodium hydroxide solution.Again through promptly obtaining the FeN nano wire of the about 4nm of diameter after the washing and drying.
Embodiment 6
The preparation of CoN nano wire, the MCM-41 that gets the aperture and be 3nm is a template.Earlier 7.3 gram lauryl amines are dissolved in the 50ml water, under constantly stirring 5.8 gram MCM-41 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 3.2 gram Xiao Suangus is poured into wherein.To mix liquid after stirring left standstill 12 hours.The MCM-41 molecular sieve that will be loaded with the CoN presoma is then put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.The MCM-41 molecular sieve that is loaded with CoN is removed porous oxide with being dissolved in the 2mol/L sodium hydroxide solution.Again through promptly obtaining the CoN nano wire of about 3 nanometers of diameter after the washing and drying.
Embodiment 7
The preparation of CrN nano wire, the SBA-15 that gets the aperture and be 6nm is the foraminous die plate oxide compound.Earlier 7.3 gram hexamethylenetetramines are dissolved in the 50ml water, under constantly stirring 5.8 gram SBA-15 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 3.2 gram chromium nitrates is poured into wherein.To mix liquid after stirring left standstill 12 hours.The SBA-15 molecular sieve that will be loaded with the CrN presoma is then put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.The SBA-15 molecular sieve that is loaded with CrN is removed porous oxide with being dissolved in the 2mol/L sodium hydroxide solution.Again through promptly obtaining the CrN nano wire of the about 6nm of diameter after the washing and drying.
Embodiment 8
WN
2The preparation of nanometer rod, the MCM-41 that gets the aperture and be 3nm is the foraminous die plate oxide compound.Earlier 7.3 gram lauryl amines are dissolved in the 50ml water, under constantly stirring 10.8 gram MCM-41 molecular sieves are put into wherein dipping in batches, the aqueous solution that after 24 hours 50ml is dissolved with 4.2 gram wolframic acids is poured into wherein.To mix liquid after stirring left standstill 12 hours.To be loaded with WN then
2The MCM-41 molecular sieve of presoma is put into tube furnace, and the temperature rise rate with 10 ℃/hour under nitrogen protection rises to 750 ℃, keeps reducing to room temperature after 2 hours.To be loaded with WN
2The MCM-41 molecular sieve remove porous oxide with being dissolved in the 2mol/L sodium hydroxide solution.Promptly obtain WN through after the washing and drying again
2Nanometer rod.
Claims (6)
1, a kind of preparation method of metal nitride low-dimension nano material, it is characterized in that: with duct restriction presoma crystal technique, by two step pickling processes, make metal nitride nano wire or metal nitride nanometer rod, concrete technology follows these steps to carry out:
At first, choose the porous silica in required aperture as hard template;
Then, above-mentioned porous silica is immersed in the organic amine precursor liquid that concentration is 10-20wt%, the nitrogen containing metal salt precursor liquid that after 20-26 hour with concentration is 5-10wt% is again poured into wherein, through 10-12 hour, forms the presoma of metal nitride in the inwall of the duct of porous silica;
The weight ratio of above-mentioned template and precursor liquid total amount is 5.4-10.0wt%, and organic amine precursor liquid and nitrogen containing metal salt precursor liquid mol ratio are 1.34-5.04;
Wherein the metal in the nitrogen containing metal salt is the metallic element of IIIA, VIB, VIIIB family;
Organic amine is C
4-C
18Aliphatics organic amine or C
4-C
18The salt of aliphatics organic amine;
At last, the porous silica that will contain the metal nitride forerunner under 600-800 ℃ of oxygen free condition thermal treatment 2-4 hour, and with the metal nitride handled well with dilute sodium hydroxide or diluted hydrofluoric acid dissolving, filter, washing, oven dry, can obtain the nitride low-dimension nano material.
2, the preparation method of metal nitride low-dimension nano material according to claim 1 is characterized in that the porous silica hard template is SBA-15 or MCM-41 mesoporous silicon oxide molecular sieve, or silica aerogel porous silica material.
3, the preparation method of metal nitride low-dimension nano material according to claim 1 is characterized in that nitrogen containing metal salt is the ammonium salt or the nitrate of metal.
4, the preparation method of metal nitride low-dimension nano material according to claim 1 is characterized in that the weight ratio of template and precursor liquid total amount is 9.7-10.0wt%, promptly gets the metal nitride nanometer rod.
5, the preparation method of metal nitride low-dimension nano material according to claim 1 is characterized in that the weight ratio of template and precursor liquid total amount is 5.4-6.3wt%, promptly gets the metal nitride nano wire.
6, metal nitride low-dimension nano material according to claim 1 is as the application of hydrogenating desulfurization or hydrodenitrification catalysts.
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| CN 200410025736 CN1286712C (en) | 2004-07-05 | 2004-07-05 | Method for preparing low dimensional nanomaterial of metal nitride |
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| CN102161478B (en) * | 2011-04-22 | 2013-08-07 | 南通汉瑞实业有限公司 | Preparation method of molybdenum nitride |
| CN108636443B (en) * | 2018-04-27 | 2021-03-23 | 常州大学 | Preparation method and application of efficient hydrodeoxygenation molybdenum nitride catalyst |
| CN110586151B (en) * | 2019-08-14 | 2022-12-06 | 中国科学院宁波材料技术与工程研究所 | Preparation method of ordered mesoporous transition metal nitride |
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