CN107473184B - A kind of hydroboron LiB of lithium3H8Synthetic method - Google Patents
A kind of hydroboron LiB of lithium3H8Synthetic method Download PDFInfo
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- CN107473184B CN107473184B CN201710651503.9A CN201710651503A CN107473184B CN 107473184 B CN107473184 B CN 107473184B CN 201710651503 A CN201710651503 A CN 201710651503A CN 107473184 B CN107473184 B CN 107473184B
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- hydroboron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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Abstract
The invention discloses a kind of hydroboron LiB of lithium3H8Synthetic method, belong to the synthesis technical field of hydroboron.Technical solution of the present invention main points are as follows: lithium borohydride is added in reaction vessel under conditions of anhydrous and oxygen-free, the tetrahydrofuran solution THFBH of borine is then added3, the hydroboron LiB that target product lithium is made is reacted under conditions of Yu Huiliu3H8.Operation of the present invention is simple, and low toxicity is harmless, securely and reliably, is suitble to large-scale production.
Description
Technical field
The invention belongs to the synthesis technical fields of hydroboron, and in particular to a kind of hydroboron LiB of lithium3H8's
Synthetic method.
Background technique
Anion B3H8 -Tool has been widely used, and due to its higher hydrogen content, has very big answer in hydrogen storage field
With prospect, the hydrogen storage material NH such as synthesized4[B3H8] (Inorg. Chem. 2011,50,3738-3742),
[NH3BH2NH3]B3H8(RSC Adv. 2013,3,7460-7465) contains a large amount of negative hydrogen；And it is molten common are machine
There is good dissolubility in agent, therefore can be used as reducing agent；And before can be used as the other boron-containing compounds of synthesis
Object is driven, semiconductor material MgB is such as synthesized2Predecessor Mg (B3H8)2(Inorg. Chem. 2007,46,9060-9066).
Due to the limitation of synthetic method, the B of metal cation class and other non-metal cations classes3H8Hydroboron
Do not developed well.Therefore, finding that a kind of easy to operate, safe and non-toxic and low-cost synthetic method has very much must
It wants.
M (B is just synthesized at present3H8)nThe method of class hydroboron mainly has: 1, using diborane and alkali metal, mainly
Sodium amalgam generates NaB3H8.Used very big toxicity and extremely unsafe mercury, diborane etc. in method, mercury to the harm of human body very
Greatly, and inconvenient, diborane is extremely sensitive to air, inflammable and explosive, and has severe toxicity, and operation is same abnormally dangerous.2, single
Matter iodine is in 100 DEG C of oxidation sodium borohydrides.Solvent boiling point needed at a temperature of this is higher, consuming energy, and the B synthesized3H8 -Bear from
Son is containing except the solvent not fallen.3, the tetrahydrofuran solution (THFBH of sodium amalgam and borine3) reaction.Equally exist above-mentioned side
Disadvantage in method 1 and 2.4, alkali metallic sodium is dispersed on silica gel, then to react with the tetrahydrofuran of borine at 150 DEG C.Herein
At a temperature of disperse sodium, operate it is very inconvenient, and with the presence of very high risk.5, under conditions of ball milling, alkali metallic sodium is dispersed
On inorganic salts, such as NaCl, CaCl2Deng equally existing the disadvantage in the above method 4.
The hydroboron LiB of lithium at present3H8Synthetic method mainly use lithium amalgam and THFBH3Reaction.When reaction
Between long, purification difficult, low yield.In view of the above synthesis B3H8The unfavorable factor of class hydroboron, it is necessary to design a kind of synthesis
Process can be avoided the hazardous chemical high using toxicity, and easy to operate, safe and reliable hydroboron LiB3H8Synthesis
Method.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of boron hydrogen easy to operate, safe and reliable and less toxic harmless lithium
Compound L iB3H8Synthetic method.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of hydroboron LiB of lithium3H8Conjunction
At method, it is characterised in that: lithium borohydride is added in reaction vessel under conditions of anhydrous and oxygen-free, borine is then added
Tetrahydrofuran solution THFBH3, the hydroboron LiB that target product lithium is made is reacted under conditions of Yu Huiliu3H8。
Further preferably, the hydroboron LiB of the lithium3H8Synthetic method, it is characterised in that specific steps are as follows:
In nitrogen glove box, lithium borohydride is fitted into schlenk reaction flask, schlenk reaction flask is removed into hand with after plug seal
Then the tetrahydrofuran solution THFBH for the borine that molar concentration is 0.1-1mol/L is added in casing3, wherein THFBH3With boron
The molar ratio of lithium hydride is 2:1-4:1, reacts 30-50h under counterflow condition, is filtered to remove insoluble matter, filtrate is concentrated
It removes solvent and obtains sticky transparency liquid product LiB3H8·1.5THF。
The hydroboron LiB of lithium of the present invention3H8Synthetic method in reaction equation are as follows:
LiBH4 + 2 THF·BH3 = LiB3H8 + 2 THF + H2
Compared with the prior art, the invention has the following beneficial effects: operation of the present invention is simple, low toxicity is harmless, safely may be used
It leans on, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the hydroboron LiB for the lithium that the embodiment of the present invention 1 synthesizes3H8In tetrahydrofuran11B liquid nuclear-magnetism
Figure, target product obtained is pure LiB as seen from the figure3H8。
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 500mL equipped with magneton
0.22g lithium borohydride is added in bottle, schlenk reaction flask is removed into glove box with after plug seal, is then added 200mL moles
Concentration is the tetrahydrofuran solution THFBH of the borine of 0.1mol/L3, 50h is reacted under counterflow condition, is filtered to remove insoluble
Filtrate is concentrated removing solvent and obtains sticky transparency liquid product LiB by object3H81.5THF, obtained LiB3H8·
1.5THF is weighed as 0.97 g, and calculating yield is 62%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 2
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.22g lithium borohydride is added in bottle, schlenk reaction flask is removed into glove box with after plug seal, is then added 40mL moles
Concentration is the tetrahydrofuran solution THFBH of the borine of 0.5mol/L3, 40h is reacted under counterflow condition, is filtered to remove insoluble
Filtrate is concentrated removing solvent and obtains sticky transparency liquid product LiB by object3H81.5THF, obtained LiB3H8·
1.5THF is weighed as 0.93 g, and calculating yield is 60%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 3
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.22g lithium borohydride is added in bottle, schlenk reaction flask is removed into glove box with after plug seal, is then added 40mL moles
Concentration is the tetrahydrofuran solution THFBH of the borine of 1mol/L3, 30h is reacted under counterflow condition, is filtered to remove insoluble matter,
Removing solvent is concentrated in filtrate and obtains sticky transparency liquid product LiB3H81.5THF, obtained LiB3H8·1.5THF
It is weighed as 0.97 g, calculating yield is 62%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 4
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.22g lithium borohydride is added in bottle, schlenk reaction flask is removed into glove box with after plug seal, is then added 20mL moles
Concentration is the tetrahydrofuran solution THFBH of the borine of 1mol/L3, 30h is reacted under counterflow condition, is filtered to remove insoluble matter,
Removing solvent is concentrated in filtrate and obtains sticky transparency liquid product LiB3H81.5THF, obtained LiB3H8·1.5THF
1.01 g are weighed as, calculating yield is 65%, and nuclear-magnetism detects its purity close to 100%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (1)
1. a kind of hydroboron LiB of lithium3H8Synthetic method, it is characterised in that: in nitrogen glove box, by lithium borohydride
It is fitted into schlenk reaction flask, schlenk reaction flask is removed into glove box with after plug seal, molar concentration, which is then added, is
The tetrahydrofuran solution THFBH of the borine of 0.1-1mol/L3, wherein THFBH3Molar ratio with lithium borohydride is 2:
1-4:1 reacts 30-50h under counterflow condition, is filtered to remove insoluble matter, filtrate is concentrated remove solvent obtain it is sticky transparent
Product liquid LiB3H8·1.5THF。
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| CN201710651503.9A CN107473184B (en) | 2017-08-02 | 2017-08-02 | A kind of hydroboron LiB of lithium3H8Synthetic method |
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| CN107473184B true CN107473184B (en) | 2019-09-13 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108439339B (en) * | 2018-03-10 | 2021-07-20 | 河南师范大学 | Lithium borohydride LiB3H8Preparation method of (1) |
| CN113526466B (en) * | 2021-08-31 | 2023-11-17 | 河南师范大学 | Boron hydrogen compound potassium salt KB 11 H 14 Is synthesized by the method of (2) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880221A (en) * | 2005-06-16 | 2006-12-20 | 气体产品与化学公司 | Method for producing dodecahydrododecaborates |
| CN106698346A (en) * | 2017-02-17 | 2017-05-24 | 河南师范大学 | Method for synthesizing anionic potassium hydroborate KB3H8 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880221A (en) * | 2005-06-16 | 2006-12-20 | 气体产品与化学公司 | Method for producing dodecahydrododecaborates |
| CN106698346A (en) * | 2017-02-17 | 2017-05-24 | 河南师范大学 | Method for synthesizing anionic potassium hydroborate KB3H8 |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of lithium octahydrotriborate and investigation on its thermal decomposition;He Fu et al.;《i n t e rna t i onal journal o f hydrogen energy》;20151114;第41卷;第384-391页 * |
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