CN104591089B - The preparation method of a kind of Nanoparticulate hydroborate ammonate - Google Patents
The preparation method of a kind of Nanoparticulate hydroborate ammonate Download PDFInfo
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- CN104591089B CN104591089B CN201510010138.4A CN201510010138A CN104591089B CN 104591089 B CN104591089 B CN 104591089B CN 201510010138 A CN201510010138 A CN 201510010138A CN 104591089 B CN104591089 B CN 104591089B
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
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- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/23—Preparation of borohydrides of other metals, e.g. aluminium borohydride; Addition complexes thereof, e.g. Li[Al(BH4)3H]
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The present invention discloses the preparation method of a kind of Nanoparticulate hydroborate ammonate, and the method comprises the following steps: (1), under shielding gas atmosphere, hydroborate obtains complex solution after mixing with excessive organic solvent; (2) complex solution and ammonia source are uniformly mixed, and obtain Nanoparticulate hydroborate ammonate. After hydroborate is fully mixed by the inventive method with excessive organic solvent, form complex solution, again ammonia source is led in the process of complex solution and it is uniformly mixed, obtain the hydroborate ammonate of Nanoparticulate, avoid the problem of the obtained macrobead hydroborate ammonate hydrogen storage property difference of traditional method.
Description
Technical field
The present invention relates to the preparation of hydrogen storage material, it is specifically related to the preparation method of a kind of Nanoparticulate hydroborate ammonate.
Background technology
The cleanliness without any pollution green energy resource that Hydrogen Energy is abundant as a kind of resource, wide material sources, combustion heat value are high attracts widespread attention day by day, is also considered as one of the ideal fuels in future. Find the key point that a kind of efficient, safe hydrogen accumulating mode is then Hydrogen Energy application. Utilize the solid-state storage hydrogen mode of hydrogen storage material and hydrogen reaction can effectively overcome the deficiency of gas, liquid storage hydrogen mode, there is feature safe and efficient, that cost is low, and be considered as having a kind of hydrogen storage mode of development prospect.
In numerous hydrogen storage material, magnesium borohydride ammonate is considered as very potential hydrogen storage material. Wherein, six ammonia close magnesium borohydride because having high quality hydrogen-storage amount (16.78wt%), compare low hydrogen release temperature and to features such as oxygen are insensitive, and receive the extensive concern of investigator.
At present, in the world for six ammonia close magnesium borohydride synthetic method be mainly: utilize ammonia and magnesium borohydride diethyl ether solution prepare six ammonia close magnesium borohydride. First excessive dry ammonia is led to the diethyl ether solution into magnesium borohydride by its method, then filter extracting waste be deposited in heating under vacuum remove residue ether namely obtain six ammonia close magnesium borohydride. This kind of method can use magnesium borohydride diethyl ether solution that sodium borohydride and magnesium chloride react acquisition in ether as raw material, avoids the filtration in subsequent step, except processes such as solvents. But, the method also has following shortcoming: first, and it is that macrobead structure, size are relatively big that six ammonia that the method prepares close magnesium borohydride, and hydrogen storage property is had certain influence; Secondly, owing to six ammonia that the method is obtained close still containing a certain amount of solvent ether in magnesium borohydride, the purity of sample can be affected.
In sum, existing six ammonia close magnesium borohydride prepared by preparation method six ammonia close magnesium borohydride sample purities not high, its requirement as practical hydrogen storage material cannot be met. It it is one of important factor affecting material hydrogen storage property due to particle size. Therefore, six ammonia preparing different-grain diameter size close magnesium borohydride and observe grain size to the impact of its hydrogen storage property, close magnesium borohydride for six ammonia significant for hydrogen storage material. At present, existing preparation method still can not realize the preparation that grain size controlled Nanoparticulate six ammonia closes magnesium borohydride. Therefore, need development badly a kind of simple, purity height, the Nanoparticulate magnesium borohydride ammonate preparation method that grain size is controlled.
Summary of the invention
The present invention provides the preparation method of a kind of Nanoparticulate hydroborate ammonate, the method not only raw material be easy to get, simple to operate, also can prepare the hydroborate ammonate of Nanoparticulate, and purity height.
A preparation method for Nanoparticulate hydroborate ammonate, comprises the following steps:
(1) under shielding gas atmosphere, hydroborate obtains complex solution after mixing with excessive organic solvent;
(2) complex solution and ammonia source are uniformly mixed, and obtain Nanoparticulate hydroborate ammonate.
After hydroborate fully mixes with excessive organic solvent and reacts, forming complex compound, owing to the consumption of organic solvent is excessive, complex compound can dissolve in organic solvent, forms complex solution, then, fully mixes with ammonia source, reacts; Hydroborate and the bonding strength of amine groups it is weaker than due to the bonding strength of hydroborate in complex compound and organic solvent, so when ammonia source is added complex solution, replacement(metathesis)reaction can be there is, obtaining the product hydroborate ammonate that hydroborate is combined with amine groups, the particle diameter of this product is nano level. Described excessive refer to that organic solvent and hydroborate mol ratio are excessive.
Shielding gas does not participate in above-mentioned reaction, it is possible to the process of hydroborate and organic solvent reacting forming complex that ensures is not by the impact of foreign gas, it is to increase the product rate of product Nanoparticulate hydroborate ammonate. As preferably, described shielding gas is argon gas or nitrogen.
The consumption of organic solvent can affect the size of product Nanoparticulate hydroborate ammonate. The suitable proportion of organic solvent and hydroborate ammonate, can ensure the formation of nanoparticle structure, the size of control particle. As preferably, in 1g hydroborate, the consumption of described organic solvent is 0.1��20 liter.
Described hydroborate is lithium borohydride, magnesium borohydride, calcium borohydride, hydroboration yttrium, aluminum borohydride or zinc borohydride.
Described organic solvent can adopt ether organic solvent, as preferably, described organic solvent is at least one in ether, tetrahydrofuran (THF), dimethyl sulfide, methyl ethyl ether, metopryl, ethylene-propylene ether, propyl ether, isopropyl ether, diglyme, Isopropylamine, dimethyl formamide. When adopting polytype organic solvent, the usage ratio of each type organic solvent does not have strict limitation simultaneously. Described organic solvent all has easy volatile after heating, and volatilization temperature is lower than the decomposition temperature of hydroborate ammonate, thus is convenient in subsequent processes and removes organic solvent, and guarantees that hydroborate ammonate can not decompose. The minimizing technology of organic solvent is distillation, take out filter, one in centrifugal and dynamic vacuum.
As preferably, in step (1), hydroborate is mixed by the mode stirred with organic solvent. Specifically, alr mode comprises that glass stick manually stirs, ultrasonic agitation and magnetic agitation, the complex solution being dissolved in organic solvent can be obtained fast by stirring, above-mentioned alr mode can use simultaneously, accelerates the generation of complex solution in step (1) and the dissolving of complex compound.
As preferably, the rotating speed of whipping process is 100��600 revs/min, churning time is 10��60 minutes. Level of response is had material impact by churning time (i.e. reaction times), and the time is too short, easily causes reaction not exclusively, affects product rate, overlong time, and solvent easily volatilizees.
Described ammonia source is ammonia. The pressure of ammonia will affect speed of response and the time of complex compound in ammonia and organic solvent, and then affect product rate. The pressure of ammonia, can not exceed the peak pressure that reaction unit can bear. As preferably, the pressure of ammonia is 0.5��10bar.
As preferably, in step (2), the rotating speed of whipping process is 50��400 revs/min, churning time is 5 minutes��2 hours. Level of response and product shape looks are had material impact by the reaction times, and the time is too short, and reaction not exclusively, affects product rate; Time is too long, increases the reunion of nano particle, affects hydrogen discharging performance. Specifically, alr mode be that glass stick manually stirs, one in ultrasonic agitation and magnetic agitation. Wherein, ultrasonic agitation and magnetic agitation can increase the contact area of ammonia and complex compound, it is to increase speed of response, increase product rate, accelerate particles settling, reduce the size of particle.
Compared with prior art, the present invention has following useful effect:
(1) after hydroborate is fully mixed by the inventive method with excessive organic solvent, form complex solution, again ammonia source is led in the process of complex solution and it is uniformly mixed, obtain the hydroborate ammonate of Nanoparticulate, avoid the problem of the obtained macrobead hydroborate ammonate hydrogen storage property difference of traditional method;
(2) the inventive method is to the size tunable of product hydroborate ammonate, contributes to research grain size on the impact of its hydrogen storage property;
(3) the inventive method desired raw material is easily buied, simple to operate;
(4) product impurity content that the inventive method is obtained is few, and purity is greater than 95%, presents Nanoparticulate structure, and starting temperature is lower than 70 DEG C, and hydrogen desorption capacity is more than 12.0wt%.
Accompanying drawing explanation
Fig. 1 is that the fourier-transform infrared that six ammonia that the embodiment of the present invention 1 obtains close magnesium borohydride (a) and standard six ammonia closes magnesium borohydride sample (b) absorbs spectrogram;
Fig. 2 is that six ammonia that the embodiment of the present invention 2 obtains close the X-ray diffraction pattern of magnesium borohydride (a) with standard six ammonia conjunction magnesium borohydride sample (b);
Fig. 3 be obtained six ammonia of the embodiment of the present invention 2 close magnesium borohydride with the quantitative Hydrogen desorption isotherms of temperature;
Fig. 4 is the electron scanning micrograph that six ammonia that the embodiment of the present invention 3 obtains close magnesium borohydride.
Embodiment
Embodiment 1
In argon gas atmosphere, being manually uniformly mixed by glass stick by the organic solvent ether of the magnesium borohydride of 1 gram and 1 liter, churning time is 60 minutes, and rotating speed is 60 revs/min, fully after mixing, obtains the complex solution of magnesium borohydride; Leading to into pressure in complex solution is the ammonia of 0.6bar, and ultrasonic agitation mixes, and rotating speed is 400 revs/min, and churning time is 1 hour, forms the ammonia complex of magnesium borohydride; Adopting the mode of dynamic vacuum except desolventizing ether, obtained six ammonia close magnesium borohydride.
As shown in Figure 1, closing standard six ammonia conjunction magnesium borohydride sample in magnesium borohydride and Fig. 1 by six ammonia that magnesium borohydride etherate and ammonia gas react are obtained and have identical infared spectrum, the product namely prepared is that six ammonia close magnesium borohydride. The particle size of products therefrom is in 150-300 nanometer range, and its initial hydrogen discharging temperature 72 DEG C, when being heated to 500 DEG C, hydrogen desorption capacity can reach 11.9wt%. Heating is put in hydrogen process, and ammonia by product is obviously suppressed, and hydrogen purity can reach more than 70%.
Embodiment 2
In argon gas atmosphere, being mixed by ultrasonic agitation by the organic solvent dimethyl sulfide of the magnesium borohydride of 1 gram and 2 liters, churning time is 10 minutes, and rotating speed is 100 revs/min, fully after mixing, obtains the complex solution of magnesium borohydride; Leading to into pressure in complex solution is the ammonia of 1.5bar, and magnetic agitation mixes, and rotating speed is 100 revs/min, and churning time is 40 minutes, forms the ammonia complex of magnesium borohydride; Adopting the mode taking out filter except desolventizing dimethyl sulfide, obtained six ammonia close magnesium borohydride.
As shown in Figure 2, it is identical with the X-ray diffraction pattern that standard in Fig. 2 six ammonia closes magnesium borohydride sample that six obtained ammonia close magnesium borohydride, shows that preparing product is that six ammonia close magnesium borohydride. Gained six ammonia closes the particle size of magnesium borohydride, in 80-100 nanometer range, purity is greater than 95%. As shown in Figure 3, it is 66 DEG C that six obtained ammonia close the hydrogen starting temperature of putting of magnesium borohydride, and when heating temperatures is to 500 DEG C, hydrogen desorption capacity is up to 11.8wt%.
Embodiment 3
In argon gas atmosphere, being mixed by ultrasonic agitation by the organic solvent ether of the magnesium borohydride of 0.5 gram and 3 liters, churning time is 10 minutes, and rotating speed is 400 revs/min, fully after mixing, obtains the complex solution of magnesium borohydride; Leading to into pressure in complex solution is the ammonia of 0.8bar, and ultrasonic agitation mixes, and rotating speed is 300 revs/min, and churning time is 30 minutes, adopts the mode of dynamic vacuum except desolventizing ether, and obtained six ammonia close magnesium borohydride.
As shown in Figure 4, it is nanoparticle structure that six obtained ammonia close magnesium borohydride, and particle diameter is about between 20 nanometers to 100 nanometers. Its initial hydrogen discharging temperature 66 DEG C, when being heated to 500 DEG C, hydrogen desorption capacity can reach 11.8wt%.
Embodiment 4��18
Identical with the preparation method of embodiment 3, only preparation condition is made corresponding change, obtains lithium borohydride, magnesium borohydride, calcium borohydride, hydroboration yttrium, aluminum borohydride or the corresponding ammonate of zinc borohydride. Table 1 lists the product rate of the reaction conditions of different hydroborate and ammonia and product, purity, initial hydrogen discharging temperature and particle size.
R (the BH prepared under the different condition of table 14)nProduct rate, the purity of (R is lithium, magnesium, calcium, yttrium, aluminum and zinc) ammonate, put hydrogen starting temperature and particle size
As shown in table 1, obtained product purity is greater than 95%, and foreign matter content is few, presents Nanoparticulate structure, and starting temperature is lower than 70 DEG C, and hydrogen desorption capacity is more than 12.0wt%.
Claims (7)
1. the preparation method of a Nanoparticulate hydroborate ammonate, it is characterised in that, comprise the following steps:
(1) under shielding gas atmosphere, hydroborate and excessive organic solvent, be 100��600 revs/min at rotating speed, when churning time is 10��60 minutes, after being uniformly mixed, obtains complex solution;
(2) complex solution and ammonia source rotating speed are 50��400 revs/min, when churning time is 5 minutes��2 hours, are uniformly mixed, and obtain Nanoparticulate hydroborate ammonate;
In step (1) and (2), alr mode is that glass stick manually stirs, one in ultrasonic agitation and magnetic agitation.
2. preparation method as claimed in claim 1, it is characterised in that, described shielding gas is argon gas or nitrogen.
3. preparation method as claimed in claim 1, it is characterised in that, in 1g hydroborate, the consumption of described organic solvent is 0.1��20 liter.
4. preparation method as claimed in claim 1, it is characterised in that, described hydroborate is lithium borohydride, magnesium borohydride, calcium borohydride, hydroboration yttrium, aluminum borohydride or zinc borohydride.
5. preparation method as claimed in claim 1, it is characterized in that, described organic solvent is at least one in ether, tetrahydrofuran (THF), dimethyl sulfide, methyl ethyl ether, metopryl, ethylene-propylene ether, propyl ether, isopropyl ether, diglyme, Isopropylamine, dimethyl formamide.
6. preparation method as claimed in claim 1, it is characterised in that, described ammonia source is ammonia.
7. preparation method as claimed in claim 6, it is characterised in that, the pressure of ammonia is 0.5��10bar.
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