CN105062033B - high-capacity organic-inorganic composite hydrogen storage material and preparation method thereof - Google Patents
high-capacity organic-inorganic composite hydrogen storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-capacity organic-inorganic composite hydrogen storage material. The organic-inorganic composite hydrogen storage material comprises an inorganic porous material and organic materials uniformly dispersed in pores of the inorganic porous material, wherein the inorganic porous material adopts porous silicon dioxide or aluminum oxide, the aperture is 0.5-20 nm, and the specific surface area is 300-500 m＜2＞/g; the organic materials comprise polymers serving as main chains and borane ammonia derivatives, and the borane ammonia derivatives are prepared as follows: side chains and/or end groups of the polymers are subjected to amination by polyamine compounds and grafted to the side chains and/or ends of the polymers through reaction with a borohydride. The invention further discloses a preparation method of the high-capacity organic-inorganic composite hydrogen storage material. The high-capacity organic-inorganic composite hydrogen storage material prepared with the method has the following advantages: mutual agglomeration of the polymers can be inhibited effectively, the hydrogen storage and release efficiency is high, little environmental pollution is produced, the material can be regenerated and recycled, and the cost is saved.
Description
Technical field
The present invention relates to macromolecular material, hydrogen storage material and energy field, specifically refer to a kind of high power capacity organic and inorganic
Composite hydrogen storage material and preparation method thereof.
Background technology
It is hydrogen rich reserves, high combustion efficiency, pollution-free, it is described as the green energy resource carrier of 21 century.The exploitation of Hydrogen Energy
Using being related to the preparation of hydrogen, store, transport and using four big key technologies.However, due to hydrogen be in all elements it is most light
, it is at normal temperatures and pressures gaseous state, density is only 0.0899kg/m3, it is a ten thousandth of water, therefore the high density storage of hydrogen
An always one world-class difficult problem.Efficiently, safe, economic hydrogen storage technology has become hydrogen utilization and has moved towards practical, rule
The bottleneck of modelling, limits the utilization of Hydrogen Energy.
At present, except metal hydride beyond the region of objective existence, substantial amounts of complex system, such as chemical hydride, complex hydrides, ammonia borine chemical combination
Thing and mesoporous material etc. are received as object of study.Wherein, ammonia borane compound (NH3BH3, AB) and it is to be closed closely in recent years
A kind of new chemical hydride hydrogen-storing material of note.It has superelevation hydrogen density (19.6wt%), have concurrently heat stability it is moderate and
The advantages of chemical stability is good, has much on-board hydrogen source application prospect.Pure NH3BH3Pyrolysis put hydrogen exist hydrogen desorption kineticses delay
Slowly, the key issue such as foreign gas pollutant release.Metal institute of Chinese Academy of Sciences Wang Ping researcher is successfully prepared using solid reaction process
Go out substituted type metal ammonia borane compound LiNH2BH3.The compound keep high hydrogen storage capability while (>10wt%), have
Excellent controllable hydrogen discharging performance, can quickly put hydrogen at 100 DEG C>6wt%, while effectively suppressing foreign gas pollutant to generate.
Patent 201210347088 discloses a kind of high-capacity high-molecular polymer hydrogen storage material and preparation method thereof, and it is wrapped
Include as main chain linear high molecular polymer and by its side chain and/or end group Jing after polyamine compounds are aminated again and
Boron hydride reacts and grafts on its side chain and/or the ammonia borane derivative on end.But these polymer are easier group
Poly-, hydrogen discharging rate is slower during hydrogen is put.Patent 200680021474 discloses a kind of composite hydrogen storage material and associated therewith
Method, this material includes a kind of active material particle and binding agent, and this binding agent can be abundant by active material particle
Fix to maintain the relative space relation between the active material particle.Active material used by this composite hydrogen storage material
Grain is mainly metal hydride and its conjugate, porous mineral etc..Its active material determines this composite hydrogen storage material
Hydrogen storage capability is relatively low, limits its application in the industry, and these all limit the development of hydrogen storage material.
The content of the invention
A technical problem to be solved by this invention is to provide a kind of high power capacity Organic-inorganic composite hydrogen storage material, with
Overcome poor existing hydrogen storage material dispersive property, easy reunion, the defect that hydrogen storage efficiency is low, hydrogen discharging rate is slow.
Second technical problem to be solved by this invention is to provide the above-mentioned preparation method for having a composite hydrogen storage material.
To solve above-mentioned first technical problem, the technical solution used in the present invention is：
A kind of high power capacity Organic-inorganic composite hydrogen storage material, by inorganic porous material and to be dispersed in this inorganic porous
Organic material composition in material hole, the inorganic porous material is porous silica or aluminium oxide, aperture is 0.5~
20nm, specific surface area is 300~500m2/ g, the organic material is included as the high molecular polymer of main chain and by its side chain
And/or end group reacts again with boron hydride Jing after polyamine compounds are aminated and grafts on its side chain and/or end
Ammonia borane derivative.
By such scheme, in Organic-inorganic composite hydrogen storage material, the percentage by weight of organic material is：20~80%, it is remaining
Measure as inorganic porous material.
By such scheme, the described high molecular polymer as main chain is the amphipathic polymer containing amido, described
The amphipathic polymer containing amido includes but is not limited to PEI (polyethyleneimine), PEO (poly(ethylene oxide))-PEI, PEI-
PEO-PEI and PAH (polycyclic aromatic hydrocarbon), the PEI can be it is linear can also be branched chain type；The high molecular polymer side
Chain and/or the aminated polyamine compounds used of end group are included but is not limited to：Guanidine, ethylenediamine, diethylenetriamine.
By such scheme, the molecular weight of the described high molecular polymer as main chain is 5000~50000；The ammonia boron
Content of the alkane derivatives in Organic-inorganic composite hydrogen storage material is 10~60wt%.
By such scheme, being shaped as the inorganic porous material is spherical, aperture be 5~10nm, pore volume be 0.1~
1.5cm3/ g, specific surface area is 350~450m2/g。
To solve above-mentioned second technical problem, the technical solution used in the present invention comprises the steps：
1) raw material is chosen：Choose inorganic porous material presoma and template is standby, the inorganic porous material presoma
For tetraethyl orthosilicate or aluminum nitrate, the template is the cetyl bromination of the amphipathic polymer containing amino and small molecule
Ammonium；
2) template is dissolved in alcohol solvent, is then added in above-mentioned solution at 25~100 DEG C inorganic porous
Material precursor, constant temperature is stirred 3~24 hours, is crossed and is filtered to remove filtrate；
3) aqueous solution of bromoethanol and alkali metal salt is added in filtering residue, at pH value 7~8.5,25~100 DEG C of temperature,
Constant temperature is stirred 1~3 hour；
4) drying obtains hybrid inorganic-organic materials after the completion of above-mentioned reaction；
5) aminated reaction is carried out to high molecular polymer in hybrid inorganic-organic materials using polyamine compounds, is obtained
Amido fluidized polymer；
6) by step 5) the amido fluidized polymer that obtains and boron hydride be stoichiometrically in organic solvent suspension
The stirring at 5~50 DEG C is collected by filtration lower floor's organic faciess after 1~12 hour, vacuum distillation removes solvent, scrubbed, extracting, dry
Organic-inorganic composite hydrogen storage material is obtained after dry.
The step 1) in the amphipathic polymer containing amido include but is not limited to PEI, PEO-PEI, PEI-PEO-
PEI and PAH, polyethyleneimine PEI can be it is linear can also be branched chain type.
The step 3) in, pH value is adjusted with alkali metal salt soln or carried out with the mixed solution of ammonia with alkali metal salt
Adjust.
The step 5) in polyamine compounds include but is not limited to：Guanidine, ethylenediamine, diethylenetriamine.
The step 6) in organic solvent include but is not limited to：Tetrahydrofuran, acetonitrile, dimethyl sulfoxide；Described boron
Hydride is selected from sodium borohydride, lithium borohydride and potassium borohydride.
Present invention sol-gel method grows porous material in template situ, and this template is by amphipathic
Small molecule cetyl ammonium bromide and the amphipathic composition of the polymer containing amino.Then amphipathic small molecule 16 is removed
Alkyl bromination ammonium, obtains hybrid inorganic-organic materials of the present invention.Again by the amphipathic polymer containing amino
The side chain so as to polyamine compounds to be bonded polymer and/or end are chemically modified, the function containing amido is obtained
Fluidized polymer, ammonia borane derivative is formed finally by suitable chemical reaction in polymer lateral chain and/or end, obtains this
Bright high power capacity Organic-inorganic composite hydrogen storage material.By selecting the different amphipathic polymer containing amino, can adjust
The hydrogen storage capability of section Organic-inorganic composite hydrogen storage material, effectively reduces its pyrolysis hydrogen discharging temperature, and effectively suppresses borazole, second boron
The generation of the harmful gaseous impurities such as alkane, ammonia.By adding Wilkinson catalyst during hydrogen is put, can also improve it and put
Hydrogen amount, improves hydrogen discharging performance.
Therefore, the present invention compared with prior art, with following beneficial effect：
1) component that high power capacity Organic-inorganic composite hydrogen storage material of the invention plays main hydrogen storage effect is amphipathic containing
Have the polymer of amido, in theory for, in the case of dispersion identical, the content of amido is higher, and hydrogen storage ability is stronger.But
If the load capacity of the polymer containing amido is excessive, it is easy to assemble agglomerating, the absorption effect of carbon dioxide can be reduced on the contrary
Rate.In the present invention, porous material is solved into this problem in the growth of organogel template situ using sol-gel method.
By selecting suitable template, response time and the amount of reactant, can obtain shape, particle diameter and aperture it is controllable it is organic-
Inorganic composite materials, due to the polymer containing amido it is dispersed in the porous material, it is suppressed that the mutual reunion of polymer,
It is favorably improved hydrogen releasing efficient.Meanwhile, polymer load capacity in the porous material can be adjusted according to practical situation.
2) present invention is carrier loaded a certain amount of two by the porous material from special pore size distribution, pore volume and specific surface area
The polymer containing amido of parent's property is adjusting the hydrogen storage capability of hydrogen.Because active group amido is highly dispersed at porous material
Hole in, during hydrogen is put, hydrogen is easier to be discharged in relatively low temperature, therefore hydrogen storage capability is high, stable
And scalable, hydrogen discharging temperature is low, produces when aperture of porous material is in 0.5~20nm without objectionable impurities gas during hydrogen is put,
Specific surface area is in 300~500m2During/g, the release of hydrogen is more beneficial for.
3) organic-inorganic hybrid material for high power capacity storage hydrogen material of porous material confinement according to the present invention is logical
Sol-gal process in-situ preparation is crossed, the polymers compositionss containing amido are not only and formed during the course of the reaction ammonia borane derivative
Important substance, while be also a kind of good pore former, thus the polymers compositionss containing amido and the porous material as carrier
Material can synchronized compound, preparation flow is simple, is easy to operation, with preferable stability, is more suitable for industrialized production.Simultaneously because
The organic amine that the present invention is adopted is the high molecular polymer of long-chain, be may be uniformly dispersed between porous material and and porous material
Between have stronger interaction, be not easily disconnected from away, thus do not result in the pollution of environment.It is successfully realized repeatedly regeneration to follow
Ring is utilized, cost-effective.Thus have the prospect of large-scale production.
Description of the drawings
Fig. 1 is the hydrogen desorption kineticses curve of the composite hydrogen storage material in embodiment 2.
Fig. 2 is the temperature programmed desorption figure of the composite hydrogen storage material in embodiment 2.
Fig. 3 is the synthetic route chart of composite hydrogen storage material in embodiment 6.
Fig. 4 is the molecular structural formula of composite hydrogen storage material in embodiment 2.
Specific embodiment
In order to preferably explain the present invention, below in conjunction with the drawings and specific embodiments the main interior of the present invention is further elucidated
Hold, but present disclosure is not limited solely to following examples.
Embodiment 1：
The polyethyleneimine (molecular weight 10000) of 10g and the cetyl ammonium bromide of 10g are weighed, will at a temperature of 80 DEG C
It is dissolved in 100mL ethanol, and stirring is allowed to fully dissolving.25g tetraethyl orthosilicates are added in reactant liquor after constant temperature stirring 2h,
And continue in the stirring 12 hours of 25 DEG C of temperature；To filtering after the completion of above-mentioned reaction, hybrid inorganic-organic materials are obtained；
Then the bromoethanol of stoichiometric proportion is added in the hybrid inorganic-organic materials of gained, is stirred at 80 DEG C of potassium carbonate
Mix and precipitation filtered after reaction 24h, is washed, being dried, then dried polymer is dissolved in anhydrous methylene chloride, add
The methylsufonyl chloride of 1.5 equivalents, triethylamine react are spin-dried for solvent after 2 hours, dichloromethane extraction, be dried after add guanidine, three
Ethamine obtains the polymer of functional amido after filtration after reaction overnight, washing at 25 DEG C, finally aminated by what is obtained
Polymer and potassium borohydride are more organic than lower floor is collected by filtration after stirring 6h at 50 DEG C in dimethyl sulfoxide suspension by metering
Phase, vacuum distillation removes solvent, and the organic inorganic hybridization material obtained containing polymer hydrogen storage material is finally washed twice with ether
Material.Finally above-mentioned organic-inorganic hybrid material ethanolic extraction is dried to obtain into organic and inorganic of the present invention after 24 hours
Composite.
The hydrogen peak temperature of putting of the Organic-inorganic composite hydrogen storage material is 115 DEG C, can about release 6.7wt%'s at 110 DEG C
Pure hydrogen.And without the generation of objectionable impurities gas during hydrogen is put.
Embodiment 2：
The polyethyleneimine (molecular weight 50000) of 10g and the cetyl ammonium bromide of 10g are weighed, will at a temperature of 80 DEG C
It is dissolved in 100mL ethanol, and stirring is allowed to fully dissolving.25g tetraethyl orthosilicates are added in reactant liquor after constant temperature stirring 2h,
And continue in the stirring 12 hours of 105 DEG C of temperature；To filtering after the completion of above-mentioned reaction, hybrid inorganic-organic materials are obtained；
Then the bromoethanol of stoichiometric proportion is added in the hybrid inorganic-organic materials of gained, is stirred at 80 DEG C of potassium carbonate
Mix and precipitation filtered after reaction 24h, is washed, being dried, then dried polymer is dissolved in anhydrous methylene chloride, add
The methylsufonyl chloride of 1.5 equivalents, triethylamine react are spin-dried for solvent after 2 hours, dichloromethane extraction, be dried after add guanidine, three
Ethamine obtains the polymer of functional amido after filtration after reaction overnight, washing at 25 DEG C, finally aminated by what is obtained
Polymer and potassium borohydride are more organic than lower floor is collected by filtration after stirring 6h at 50 DEG C in dimethyl sulfoxide suspension by metering
Phase, vacuum distillation removes solvent, and the organic inorganic hybridization material obtained containing polymer hydrogen storage material is finally washed twice with ether
Material.Finally above-mentioned organic-inorganic hybrid material ethanolic extraction is dried to obtain into organic and inorganic of the present invention after 24 hours
Composite.
The hydrogen peak temperature of putting of the Organic-inorganic composite hydrogen storage material is 115 DEG C, can about release 6.7wt%'s at 110 DEG C
Pure hydrogen.And without the generation of objectionable impurities gas during hydrogen is put.
The hydrogen storage material polymer d is carried out into hydrogen discharging performance test, Fig. 1 and Fig. 2 is respectively the polymer hydrogen storage material
Hydrogen desorption kineticses curve and temperature programmed desorption figure.As seen from the figure, hydrogen storage material polymer d has relatively low starting
Hydrogen discharging temperature (about 50 DEG C), as temperature is raised, hydrogen discharge reaction is closely carried out with a step, and it is 100 DEG C to put hydrogen peak temperature, and hydrogen desorption capacity is
8wt% or so.And produce without any harmful gass material during hydrogen is entirely put.
Separately, add Wilkinson catalyst to carry out the test of hydrogen discharging performance during hydrogen is put, as comparative test, see
Fig. 2.Figure it is seen that add after Wilkinson catalyst, the hydrogen discharging performance of polymer hydrogen storage material be improved significantly.
Embodiment 3：
The cetyl ammonium bromide of the PAH and 10g of 10g is weighed, is dissolved at a temperature of 80 DEG C in 100mL ethanol,
Stirring is allowed to fully dissolving.25g tetraethyl orthosilicates are added in reactant liquor after constant temperature stirring 2h, and continuation is stirred for 110 DEG C in temperature
Mix 12 hours；To filtering after the completion of above-mentioned reaction, hybrid inorganic-organic materials are obtained；
Then the bromoethanol of stoichiometric proportion is added in the hybrid inorganic-organic materials of gained, is stirred at 80 DEG C of potassium carbonate
Mix and precipitation filtered after reaction 24h, is washed, being dried, then dried polymer is dissolved in anhydrous methylene chloride, add
The methylsufonyl chloride of 1.5 equivalents, triethylamine react are spin-dried for solvent after 2 hours, dichloromethane extraction, be dried after add guanidine, three
Ethamine obtains the polymer of functional amido after filtration after reaction overnight, washing at 25 DEG C, finally aminated by what is obtained
Polymer and potassium borohydride are more organic than lower floor is collected by filtration after stirring 6h at 50 DEG C in dimethyl sulfoxide suspension by metering
Phase, vacuum distillation removes solvent, and the organic inorganic hybridization material obtained containing polymer hydrogen storage material is finally washed twice with ether
Material.Finally above-mentioned organic-inorganic hybrid material ethanolic extraction is dried to obtain into organic and inorganic of the present invention after 24 hours
Composite.
The hydrogen peak temperature of putting of the Organic-inorganic composite hydrogen storage material is 115 DEG C, can about release 6.7wt%'s at 110 DEG C
Pure hydrogen.And without the generation of objectionable impurities gas during hydrogen is put.
Embodiment 4：
The cetyl ammonium bromide of the PEO-PEI and 10g of 10g is weighed, 100mL ethanol is dissolved at a temperature of 80 DEG C
In, stirring is allowed to fully dissolving.25g tetraethyl orthosilicates are added in reactant liquor after constant temperature stirring 2h, and is continued in 120 DEG C of temperature
Stirring 8 hours；To filtering after the completion of above-mentioned reaction, hybrid inorganic-organic materials are obtained；
Then the bromoethanol of stoichiometric proportion is added in the hybrid inorganic-organic materials of gained, is stirred at 80 DEG C of potassium carbonate
Mix and precipitation filtered after reaction 24h, is washed, being dried, then dried polymer is dissolved in anhydrous methylene chloride, add
The methylsufonyl chloride of 1.5 equivalents, triethylamine react are spin-dried for solvent after 2 hours, dichloromethane extraction, be dried after add guanidine, three
Ethamine obtains the polymer of functional amido after filtration after reaction overnight, washing at 25 DEG C, finally aminated by what is obtained
Polymer and potassium borohydride are more organic than lower floor is collected by filtration after stirring 6h at 50 DEG C in dimethyl sulfoxide suspension by metering
Phase, vacuum distillation removes solvent, and the organic inorganic hybridization material obtained containing polymer hydrogen storage material is finally washed twice with ether
Material.Finally above-mentioned organic-inorganic hybrid material ethanolic extraction is dried to obtain into organic and inorganic of the present invention after 24 hours
Composite.
The hydrogen peak temperature of putting of the Organic-inorganic composite hydrogen storage material is 115 DEG C, can about release 6.7wt%'s at 110 DEG C
Pure hydrogen.And without the generation of objectionable impurities gas during hydrogen is put.
Embodiment 5：
The cetyl ammonium bromide of the PEI-PEO-PEI and 10g of 10g is weighed, at a temperature of 80 DEG C 100mL is dissolved in
In ethanol, stirring is allowed to fully dissolving.25g tetraethyl orthosilicates are added in reactant liquor after constant temperature stirring 2h, and is continued in temperature
150 DEG C are stirred 12 hours；To filtering after the completion of above-mentioned reaction, hybrid inorganic-organic materials are obtained；
Then the bromoethanol of stoichiometric proportion is added in the hybrid inorganic-organic materials of gained, is stirred at 80 DEG C of potassium carbonate
Mix and precipitation filtered after reaction 24h, is washed, being dried, then dried polymer is dissolved in anhydrous methylene chloride, add
The methylsufonyl chloride of 1.5 equivalents, triethylamine react are spin-dried for solvent after 2 hours, dichloromethane extraction, be dried after add guanidine, three
Ethamine obtains the polymer of functional amido after filtration after reaction overnight, washing at 25 DEG C, finally aminated by what is obtained
Polymer and potassium borohydride are more organic than lower floor is collected by filtration after stirring 6h at 50 DEG C in dimethyl sulfoxide suspension by metering
Phase, vacuum distillation removes solvent, and the organic inorganic hybridization material obtained containing polymer hydrogen storage material is finally washed twice with ether
Material.Finally above-mentioned organic-inorganic hybrid material ethanolic extraction is dried to obtain into organic and inorganic of the present invention after 24 hours
Composite.
The hydrogen peak temperature of putting of the Organic-inorganic composite hydrogen storage material is 115 DEG C, can about release 6.7wt%'s at 110 DEG C
Pure hydrogen.And without the generation of objectionable impurities gas during hydrogen is put.
Embodiment 6：
The polyethyleneimine of 10g and the cetyl ammonium bromide of 10g are weighed, at a temperature of 80 DEG C 100mL is dissolved in
In ethanol, stirring is allowed to fully dissolving.25g tetraethyl orthosilicates are added in reactant liquor after constant temperature stirring 2h, and is continued in temperature
50 DEG C are stirred 8 hours；To filtering after the completion of above-mentioned reaction, hybrid inorganic-organic materials are obtained；
Then the bromoethanol of stoichiometric proportion is added in the hybrid inorganic-organic materials of gained, is stirred at 80 DEG C of potassium carbonate
Mix and precipitation filtered after reaction 24h, is washed, being dried, then dried polymer is dissolved in anhydrous methylene chloride, add
The methylsufonyl chloride of 1.5 equivalents, triethylamine react are spin-dried for solvent after 2 hours, dichloromethane extraction, be dried after add guanidine, three
Ethamine obtains the polymer of functional amido after filtration after reaction overnight, washing at 25 DEG C, finally aminated by what is obtained
Polymer and potassium borohydride are more organic than lower floor is collected by filtration after stirring 6h at 50 DEG C in dimethyl sulfoxide suspension by metering
Phase, vacuum distillation removes solvent, and the organic inorganic hybridization material obtained containing polymer hydrogen storage material is finally washed twice with ether
Material.Finally above-mentioned organic-inorganic hybrid material ethanolic extraction is dried to obtain into organic and inorganic of the present invention after 24 hours
Composite.
The hydrogen peak temperature of putting of the Organic-inorganic composite hydrogen storage material is 115 DEG C, can about release 6.7wt%'s at 110 DEG C
Pure hydrogen.And without the generation of objectionable impurities gas during hydrogen is put.
Claims (9)
1. a kind of high power capacity Organic-inorganic composite hydrogen storage material, it is characterised in that：The Organic-inorganic composite hydrogen storage material is by nothing
Machine porous material and the organic material composition being dispersed in the inorganic porous material hole, the inorganic porous material is many
Hole silicon dioxide or aluminium oxide, aperture is 0.5~20nm, and specific surface area is 300~500m2/ g, the organic material includes making
High molecular polymer for main chain and by its side chain and/or end group Jing after polyamine compounds are aminated again and boron hydride
React and graft on its side chain and/or the ammonia borane derivative on end, the described high molecular polymer as main chain is two
The polymer containing amido of parent's property, the amphipathic polymer containing amido is PEI, PEO-PEI, PEI-PEO-PEI
Or PAH, the PEI can be it is linear can also be branched chain type；The high molecular polymer side chain and/or end group amine
Polyamine compounds used by base are guanidine, ethylenediamine or diethylenetriamine.
2. high power capacity Organic-inorganic composite hydrogen storage material according to claim 1, it is characterised in that：The organic and inorganic
In composite hydrogen storage material, the percentage by weight of organic material is：20~80%, balance of inorganic porous material.
3. high power capacity Organic-inorganic composite hydrogen storage material according to claim 1 and 2, it is characterised in that：Described conduct
The molecular weight of the high molecular polymer of main chain is 5000~50000；The ammonia borane derivative is in Organic-inorganic composite hydrogen storage material
Weight percent content in material is 10~60%.
4. high power capacity Organic-inorganic composite hydrogen storage material according to claim 1 and 2, it is characterised in that：It is described inorganic many
Being shaped as Porous materials is spherical, and aperture is 5~10nm, and pore volume is 0.1~1.5cm3/ g, specific surface area is 350~450m2/g。
5. a kind of preparation method of high power capacity Organic-inorganic composite hydrogen storage material, it is characterised in that：The method includes following step
Suddenly：
1) raw material is chosen：Choose inorganic porous material presoma and template is standby, the inorganic porous material presoma is for just
Silester or aluminum nitrate, the template is the cetyl bromination of the amphipathic polymer containing amido and small molecule
Ammonium；
2) template is dissolved in alcohol solvent, then adds inorganic porous material in above-mentioned solution at 25~100 DEG C
Presoma, constant temperature is stirred 3~24 hours, is crossed and is filtered to remove filtrate；
3) aqueous solution of bromoethanol and alkali metal salt, at pH value 7~8.5,25~100 DEG C of temperature, constant temperature are added in filtering residue
Stirring 1~3 hour；
4) drying obtains hybrid inorganic-organic materials after the completion of above-mentioned reaction；
5) aminated reaction is carried out to high molecular polymer in hybrid inorganic-organic materials using polyamine compounds, obtains amido
Fluidized polymer；
6) by step 5) the amido fluidized polymer that obtains and boron hydride stoichiometrically in organic solvent suspension in 5~
Be collected by filtration lower floor's organic faciess after stirring 1~12 hour at 50 DEG C, vacuum distillation removes solvent, scrubbed, extracting, be dried after
To Organic-inorganic composite hydrogen storage material.
6. the preparation method of high power capacity Organic-inorganic composite hydrogen storage material according to claim 5, it is characterised in that：Institute
State step 1) in the amphipathic polymer containing amido be PEI, PEO-PEI, PEI-PEO-PEI and PAH, the PEI is
It is linear or branched chain type.
7. the preparation method of the high power capacity Organic-inorganic composite hydrogen storage material according to claim 5 or 6, it is characterised in that：
The step 3) in, pH value alkali metal salt soln is adjusted or is adjusted with the mixed solution of ammonia with alkali metal salt.
8. the preparation method of the high power capacity Organic-inorganic composite hydrogen storage material according to claim 5 or 6, it is characterised in that：
The step 5) in polyamine compounds be guanidine, ethylenediamine or diethylenetriamine.
9. the preparation method of the high power capacity Organic-inorganic composite hydrogen storage material according to claim 5 or 6, it is characterised in that：
The step 6) in organic solvent be tetrahydrofuran, acetonitrile or dimethyl sulfoxide；Described boron hydride is sodium borohydride, boron
Lithium hydride or potassium borohydride.
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| CN103613068A (en) * | 2013-11-26 | 2014-03-05 | 河南理工大学 | Ammonia borane composite hydrogen storage material and preparation method thereof |
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