CN102180445B - Preparation method of high capacity hydrogen storage material para/m-phenylenediamine borohydride - Google Patents

Preparation method of high capacity hydrogen storage material para/m-phenylenediamine borohydride Download PDF

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CN102180445B
CN102180445B CN2011100889962A CN201110088996A CN102180445B CN 102180445 B CN102180445 B CN 102180445B CN 2011100889962 A CN2011100889962 A CN 2011100889962A CN 201110088996 A CN201110088996 A CN 201110088996A CN 102180445 B CN102180445 B CN 102180445B
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hydrogen
hydroboration
preparation
mphenylenediamine
storage material
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CN102180445A (en
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余学斌
李韶峰
龚乔龙
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Fudan University
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Abstract

The invention relates to a preparation method of efficient hydrogen storage material para/m-phenylenediamine borohydride. As an efficient hydrogen storage material, C6H10N22BH4 has good dehydriding property, can slowly release hydrogen when being heated to 60 DEG C, can release 6.5 wt percent high-purity hydrogen before being heated to 150 DEG C, and can release 8.4 wt percent hydrogen when being continuously heated to 250 DEG C. The substance can be prepared by grinding or ballmilling admixture of para/m-phenylenediamine hydrochloride and hydroboron with NH3 plus:BH4 minus mol ratio being 1:1 in inert gas. The method adopts the C6H10N22BH4 as a hydrogen source material which can release pure hydrogen at low temperature. The preparation process of the C6H10N22BH4 is simple, and easy to realize. The cost of the method is moderate.

Description

A kind of high power capacity storage hydrogen material hydroboration is right/preparation method of mphenylenediamine
Technical field
The invention belongs to the synthetic field of Hydrogen Storage technology and novel material, be specifically related to a kind of high power capacity storage hydrogen material hydroboration right/mphenylenediamine (C 6H 10N 22BH 4) the preparation method.
Background technology
The energy occupies extremely important status in human existence and development, we can say that modern society is the basis with the consumption at the huge energy.Along with increasing gradually of fossil oil consumption and petering out of storage capacity thereof; Add by its environmental pollution that causes and be on the rise; With oil, coal, Sweet natural gas is the needs that the fossil energy of representative can not satisfy rapid economic development, and seeking new forms of energy is a urgent problem to the universe [1] Hydrogen is as a kind of renewable energy source material, is expected to become the leading role in the sustainable system of the energy in future [2] Conventional in the past storage hydrogen mode has high-pressure hydrogen storing and two kinds of liquid storage hydrogen.But because the liquefying-point of hydrogen is-252.7 ℃, this has limited the development of conventional storage hydrogen mode.And utilize hydrogen-absorbing material and hydrogen reaction to generate the solid hydrogen-storing mode of sosoloid and hydrogenate, can effectively overcome the deficiency of gas, two kinds of storing modes of liquid, and storage hydrogen volume density is big, safe, the transportation facility.At present, the various countries scientist deepens continuously to the research of hydrogen storage method.According to technology trends, the emphasis that will store up hydrogen research from now on is the exploitation of the extensive hydrogen storage material of high-performance [3]
In recent years, with AlH 4 -1, BH 4 -1And NH 2 -1Light metal (Li, Na, Ca, Mg, Al etc.) hydrogenate Deng being base begins to receive various countries investigator's attention with its higher hydrogen storage capability.Result of study shows, through element substitution, means such as polynary compound and katalysis can be improved the hydrogen storage property of this type hydrogenation thing [4-5] And along with the further requirement to hydrogen storage material, the hydrogen storage material of one new individual system-B-N-H system has appearred [6-8] Its representative materials is BH 3NH 3BH 3NH 3Theoretical hydrogen be 19.5%, and have lower decomposition temperature (70 ℃ begin branch liberation hydrogen).Yet, BH 3NH 3Can association have volatile [NH in the solid phase decomposition course 2BH 2] n[NHBH] 3Cause the problems such as hydrogen purity is low of putting thus, thereby limited the practical application of B-N-H system hydrogen storage material [9-10] A lot of now researchs all center on BH 3 NH 3Launch, but all be difficult to suppress emitting of macromole gas under many circumstances.In the hydrogen storage material of B-N-H system, we have introduced organic-compound system first, utilize a type aniline material to put the impure shortcoming of hydrogen with the hydrogen storage material that lithium borohydride improves AB class B-N-H system.Our this system hydroboration is right/mphenylenediamine (C 6H 10N 22BH 4) as a kind of efficient hydrogen storage material, be heated to 60 ℃ and get final product slow release hydrogen, to 150 ℃ of high-purity hydrogens that can discharge 6.5 wt% before, continue to be heated to 250 ℃, can emit the pure hydrogen of 8.4 wt%.Effectively improved the shortcoming of the hydrogen storage material of B-N-H system.
Reference:
[1]Zütte1.A.Hydrogen?storage?methods?and?materials[J].Nature?wissens?chaften， 2004,91(4):157-172;
[2]Kleijn,?Rene,?van?der?Voet?E,?Resource?constraints?in?a?hydrogen?economy?based?on?renewable?energy?sources:?An?exploration,R&S?Energy?Rev., 2010,?9,?2784-2795;
[3]?Huang?TZ,?Wu?Z,?Feng?SL,?et?al.,?Comparison?of?hydrogen?storage?characteristics?between?as-cast?and?melt-spun?TiCr1.1V0.5Fe0.1Mn0.1?alloys,Materials?Science?and?engineering?A-Structural?Materials?Properties?Microstructure?And?Processing ,?2005 ,390 (1-2):362-365;
[4]?D.?L.?Sun,?S.?S.?Srinivasan,?G.?R.?Chen,?J.?Alloys?and?Compd.,? 2004,?372,?265;
[5]?X.?B.?Yu,?G.?S.?Walker,?D.?M.?Grant,?Chem.?Commun.? 2006,?37,?3906;
[6]?Schneider,?D.?Am.?Scient.? 2005,?93,?410-411;
[7]?Platinum?Nanoparticle?Functionalized?CNTs?as?Nanoscaffolds?and?Catalysts?To?Enhance?the?Dehydrogenation?of?Ammonia-Borane,?Li?SF,?Guo?YH,?Sun?WW,?Sun?DL,?and?X.?B.?Yu,?J.?Phys.?Chem.?C?Received:? 2010;?Revised?Manuscript?Received: 2010;
[8]?Jaska,?C.?A.;?Manners,?I.? J.?Am.?Chem.?Soc.? 2004,? 126,?1334-1335;
[9]?Jacoby,?M.?Chem.?Eng.?News? 2004,?82(January?5),?22-25;
[10]?Schneider,?D.?Am.?Scient.? 2005,?93,?410-411。
Summary of the invention
The object of the invention provide a kind of high power capacity storage hydrogen material hydroboration right/mphenylenediamine (C 6H 10N 22BH 4) the preparation method, this material can begin to put hydrogen about 60 ℃, to 250 ℃ of high-purity hydrogens that discharge 8.4wt. %.
The high power capacity storage hydrogen material hydroboration that the present invention proposes is right/preparation method of mphenylenediamine, and said hydroboration is right/and the chemical formula of mphenylenediamine is C 6H 10N 22BH 4, concrete steps are following:
With right/metaphenylene diamine hydrochloride and hydroborate with NH 3 +: BH 4 -Mol ratio 1:1 mixes, and in rare gas element, grinds or the ball milling preparation, promptly gets required product.
Among the present invention, said hydroborate is NaBH 4, LiBH 4, Ca (BH 4) 2Or Mg (BH 4) 2Deng in any.
Among the present invention, when using ball milled, two kinds of reactant mixed grinding times are 1-3 hour, and ball material weight ratio is not less than 5:1, and rotating speed is 200-500 rev/min, and the ball milling time is 1-5 hour.
The C of gained of the present invention 6H 10N 22BH 4Mainly put hydrogen methods for being heated, temperature is 60 oC-250 oBetween the C.
The present invention has the following aspects remarkable advantage:
1), uses C 6H 10N 22BH 4As hydrogen source material, this material can be emitted pure hydrogen under lower temperature.
2), C 6H 10N 22BH 4Preparation technology is simple, is easy to realize.
3), cost is moderate.
Description of drawings
Figure .1 is C 6H 10N 22BH 4Temperature programmed desorption(TPD) figure.
Fig. 2 is raw material and product X RD spectrogram, (a) para-phenylene diamine dihydrochloride, (b) LiBH 4, (c) para-phenylene diamine dihydrochloride/2LiBH 4The ball-milling reaction after product; (d) material after the milled product thermolysis.
Fig. 3 is raw material and product X RD spectrogram, (a) para-phenylene diamine dihydrochloride, (b) LiBH 4, (c) para-phenylene diamine dihydrochloride/2LiBH 4The ball-milling reaction after product; (d) material after the milled product thermolysis.
Embodiment
Further specify the present invention through embodiment below:
Embodiment 1: in the glove box that is full of argon gas atmosphere with 0.1792g para-phenylene diamine dihydrochloride and 0.0436g LiBH 4Mix, ball milling is taken out in sealing behind the ball grinder of packing into.Ball milling condition is: revolution is 200-300 rpm, joins the stainless steel ball-milling steel ball, and diameter is at 0.5-2cm, and the ball milling time is 1 hour, and operational mode is a positive and negative interval alternate run, and the positive and negative time is 6 minutes, and the midfeather time also is 6 minutes.Ball milling finishes and promptly obtains C 6H 10N 22BH 4Its synthetic route is following:
Figure 759182DEST_PATH_IMAGE002
Sample behind the ball milling is done temperature programmed desorption(TPD) figure test, and test result is as shown in Figure 1, raw material, and product and resolvent thereof are infrared, and XRD figure is composed like Fig. 2, shown in 3.

Claims (3)

1. the preparation method of high power capacity storage hydrogen material hydroboration Ursol D or hydroboration mphenylenediamine, the chemical formula that it is characterized in that said hydroboration Ursol D or hydroboration mphenylenediamine is C 6H 10N 22BH 4, concrete steps are following:
With para-phenylene diamine dihydrochloride or metaphenylene diamine hydrochloride and hydroborate with NH 3 +: BH 4 -Mol ratio 1:1 mixes, and in rare gas element, grinds or the ball milling preparation, promptly gets required product.
2. the preparation method of high power capacity storage hydrogen material hydroboration Ursol D according to claim 1 or hydroboration mphenylenediamine is characterized in that said hydroborate is NaBH 4, LiBH 4, Ca (BH 4) 2Or Mg (BH 4) 2In any.
3. the preparation method of high power capacity storage hydrogen material hydroboration Ursol D according to claim 1 or hydroboration mphenylenediamine; When it is characterized in that using ball milled; Two kinds of reactant mixed grinding times are 1-3 hour; Ball material weight ratio is not less than 5:1, and rotating speed is 200-500 rev/min, and the ball milling time is 1-5 hour.
CN2011100889962A 2011-04-11 2011-04-11 Preparation method of high capacity hydrogen storage material para/m-phenylenediamine borohydride Expired - Fee Related CN102180445B (en)

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