CN105062033A - 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
- Publication number
- CN105062033A CN105062033A CN201510418505.4A CN201510418505A CN105062033A CN 105062033 A CN105062033 A CN 105062033A CN 201510418505 A CN201510418505 A CN 201510418505A CN 105062033 A CN105062033 A CN 105062033A
- Authority
- CN
- China
- Prior art keywords
- organic
- hydrogen storage
- storage material
- inorganic
- inorganic composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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, particularly refer to a kind of heavy body Organic-inorganic composite hydrogen storage material and preparation method thereof.
Background technology
Hydrogen rich reserves, efficiency of combustion are high, pollution-free, are described as the green energy resource carrier of 21 century.The exploitation of Hydrogen Energy relate to hydrogen preparation, store, transport and apply four large gordian techniquies.But because hydrogen is the lightest in all elements, be gaseous state at normal temperatures and pressures, density is only 0.0899kg/m
3, be water ten thousand/, therefore the high density storage of hydrogen is a world-class difficult problem always.Efficiently, safe, economic hydrogen storage technology become that hydrogen utilization moves towards practical, the bottleneck of mass-producing, limits the utilization of Hydrogen Energy.
At present, except metal hydride beyond the region of objective existence, a large amount of complex systems, as chemical hydride, complex hydrides, ammonia borane compound and mesoporous material etc. are all received as research object.Wherein, ammonia borane compound (NH
3bH
3, AB) and be a kind of new chemical hydride hydrogen-storing material paid close attention in recent years.It has superelevation hydrogen density (19.6wt%), has the advantages such as the moderate and chemical stability of thermostability is good concurrently, has much on-board hydrogen source application prospect.Pure NH
3bH
3pyrolysis put hydrogen exist hydrogen desorption kinetics slowly, the key issue such as foreign gas pollutent release.Metal institute of Chinese Academy of Sciences Wang Ping researcher adopts solid reaction process successfully to prepare substituted type metal ammonia borane compound LiNH
2bH
3.This compound, while the high hydrogen storage capability of maintenance (>10wt%), has excellent controlled hydrogen discharging performance, can put hydrogen >6wt% fast at 100 DEG C, and effectively inhibition of impurities gas pollutant generates simultaneously.
Patent 201210347088 discloses a kind of high-capacity high-molecular polymer hydrogen storage material and preparation method thereof, and it comprises linear high molecular polymer as main chain and the ammonia borane derivative that reacted with hydroborate after polyamine compounds is aminated by its side chain and/or end group again and graft on its side chain and/or end.But these polymkeric substance ratios are easier to reunite, and putting, hydrogen discharging rate in hydrogen process is slower.Patent 200680021474 discloses a kind of composite hydrogen storage material and relative method, this material comprises a kind of active material particle and tackiness agent, and this tackiness agent can be fully fixing to maintain the relative space relation between described active material particle by active material particle.Active material particle mainly metal hydride and binding substances, the porous mineral etc. that this composite hydrogen storage material is used.The hydrogen storage capability that its active material determines this composite hydrogen storage material is lower, and limit its application in the industry, these all limit the development of hydrogen storage material.
Summary of the invention
A technical problem to be solved by this invention is to provide a kind of heavy body Organic-inorganic composite hydrogen storage material, to overcome poor, the easy reunion of existing hydrogen storage material dispersing property, to store up the defect that hydrogen 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 having composite hydrogen storage material.
For solving above-mentioned first technical problem, the technical solution used in the present invention is:
A kind of heavy body Organic-inorganic composite hydrogen storage material, be made up of inorganic porous material and the organic materials be dispersed in this inorganic porous material hole, described inorganic porous material is porous silica or aluminum oxide, and aperture is 0.5 ~ 20nm, and specific surface area is 300 ~ 500m
2/ g, described organic materials comprises high molecular polymer as main chain and the ammonia borane derivative that reacted with hydroborate after polyamine compounds is aminated by its side chain and/or end group again and graft on its side chain and/or end.
By such scheme, in Organic-inorganic composite hydrogen storage material, the weight percent of organic materials is: 20 ~ 80%, and surplus is inorganic porous material.
By such scheme, the described high molecular polymer as main chain is the amphipathic polymkeric substance containing amido, the described amphipathic polymkeric substance containing amido includes but not limited to PEI (polymine), PEO (polyethylene oxide)-PEI, PEI-PEO-PEI and PAH (polycyclic aromatic hydrocarbons), described PEI can be linear also can be branched chain types; Described high molecular polymer side chain and/or the aminated polyamine compounds used of end group include but not limited to: guanidine, quadrol, diethylenetriamine.
By such scheme, the molecular weight of the described high molecular polymer as main chain is 5000 ~ 50000; The content of described ammonia borane derivative in Organic-inorganic composite hydrogen storage material is 10 ~ 60wt%.
By such scheme, the shape of described inorganic porous material is spherical, and aperture is 5 ~ 10nm, and pore volume is 0.1 ~ 1.5cm
3/ g, specific surface area is 350 ~ 450m
2/ g.
For solving 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 for subsequent use, described inorganic porous material presoma is tetraethoxy or aluminum nitrate, and described template is amphipathic containing amino polymkeric substance and micromolecular hexadecyl brometo de amonio;
2) be dissolved in alcohol solvent by template, then at 25 ~ 100 DEG C, add inorganic porous material presoma in above-mentioned solution, constant temperature stirs 3 ~ 24 hours, crosses and filters to remove filtrate;
3) in filter residue, add the aqueous solution of bromoethanol and an alkali metal salt, in pH value 7 ~ 8.5, at temperature 25 ~ 100 DEG C, constant temperature stirs 1 ~ 3 hour;
4) above-mentioned reaction obtains hybrid inorganic-organic materials through drying after completing;
5) adopt polyamine compounds to carry out aminated reaction to high molecular polymer in hybrid inorganic-organic materials, obtain aminated polymkeric substance;
6) by step 5) the aminated polymkeric substance that obtains and hydroborate stoichiometrically stir collecting by filtration lower floor organic phase after 1 ~ 12 hour in organic solvent suspension at 5 ~ 50 DEG C, underpressure distillation, except desolventizing, obtains Organic-inorganic composite hydrogen storage material after washing, extracting, drying.
Described step 1) in the amphipathic polymkeric substance containing amido include but not limited to PEI, PEO-PEI, PEI-PEO-PEI and PAH, polymine PEI can be linear also can be branched chain type.
Described step 3) in, pH value alkali metal salt soln regulates or regulates with the mixing solutions of an alkali metal salt and ammoniacal liquor.
Described step 5) in polyamine compounds include but not limited to: guanidine, quadrol, diethylenetriamine.
Described step 6) in organic solvent include but not limited to: tetrahydrofuran (THF), acetonitrile, dimethyl sulfoxide (DMSO); Described hydroborate is selected from sodium borohydride, lithium borohydride and POTASSIUM BOROHYDRIDE.
The present invention's sol-gel method is by porous material in the growth of template situ, and this template is by amphipathic small molecules hexadecyl brometo de amonio and amphipathic forming containing amino polymkeric substance.Then remove amphipathic small molecules hexadecyl brometo de amonio, obtain hybrid inorganic-organic materials of the present invention.Again by carrying out chemically modified to amphipathic containing amino polymkeric substance thus polyamine compounds key linked side chain and/or the end of polymkeric substance, obtain the functionalized polymer containing amido, form ammonia borane derivative finally by suitable chemical reaction at polymer lateral chain and/or end, obtain heavy body Organic-inorganic composite hydrogen storage material of the present invention.By selecting the different amphipathic polymkeric substance containing amino, the hydrogen storage capability of Organic-inorganic composite hydrogen storage material can be regulated, effectively reduce its pyrolysis hydrogen discharging temperature, and effectively suppress the generation of the harmful gaseous impurities such as borazole, diborane, ammonia.Putting in hydrogen process by adding Wilkinson catalyzer, also can improve its hydrogen desorption capacity, improving hydrogen discharging performance.
Therefore, the present invention compared with prior art, has following beneficial effect:
1) heavy body Organic-inorganic composite hydrogen storage material of the present invention plays the component of main storage hydrogen effect is the amphipathic polymkeric substance containing amido, and in theory, when dispersity is identical, the content of amido is higher, and hydrogen storage ability is stronger.If but the charge capacity of polymkeric substance containing amido is excessive, then and be easy to assemble agglomerating, the assimilated efficiency of carbonic acid gas can be reduced on the contrary.In the present invention, utilize sol-gel method that porous material is solved this problem in the growth of organogel template situ.By selecting the amount of suitable template, reaction times and reactant, the composite organic-inorganic material that shape, particle diameter and aperture are controlled can be obtained, because the polymkeric substance containing amido is dispersed in the porous material, inhibit the mutual reunion of polymkeric substance, contribute to improving hydrogen releasing efficient.Meanwhile, can according to practical situation, telomerized polymer charge capacity in the porous material.
2) the present invention is the hydrogen storage capability that carrier loaded a certain amount of amphipathic polymkeric substance containing amido regulates hydrogen by selecting the porous material of special pore size distribution, pore volume and specific surface area.Because active group amido is highly dispersed in the hole of porous material, in the process of putting hydrogen, hydrogen discharges than the temperature be easier to lower, therefore hydrogen storage capability is high, stable and adjustable, hydrogen discharging temperature is low, put in hydrogen process without detrimental impurity gas produce when aperture of porous material at 0.5 ~ 20nm, specific surface area is at 300 ~ 500m
2during/g, be more conducive to the release of hydrogen.
3) organic-inorganic hybrid material for high power capacity storage hydrogen material of the porous material confinement that the present invention relates to is by sol-gel method in-situ preparation, polymeric constituent containing amido is not only the important substance forming ammonia borane derivative in reaction process, also be a kind of well pore former simultaneously, thus the polymeric constituent containing amido and the porous material as carrier can synchronized compound, preparation flow is simple, convenient operation, has good stability, is more suitable for suitability for industrialized production.The organic amine simultaneously adopted due to the present invention is the high molecular polymer of long-chain, can be dispersed between porous material and also and between porous material have stronger interaction, not easily depart from away, thus can not cause the pollution of environment.Successfully achieve repeatedly recycling utilization, cost-saving.Thus the prospect of scale operation is had.
Accompanying drawing explanation
Fig. 1 is the hydrogen desorption kinetics curve of the composite hydrogen storage material in embodiment 2.
Fig. 2 is the temperature programmed desorption(TPD) 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.
Embodiment
In order to explain the present invention better, illustrate main contents of the present invention further below in conjunction with the drawings and specific embodiments, but content of the present invention is not only confined to following examples.
Embodiment 1:
Take the polymine (molecular weight 10000) of 10g and the hexadecyl brometo de amonio of 10g, be dissolved in 100mL ethanol at 80 DEG C of temperature, stir and make it abundant dissolving.25g tetraethoxy adds in reaction solution after stirring 2h by constant temperature, and continues to stir 12 hours temperature 25 DEG C; Filtration after completing above-mentioned reaction, obtains hybrid inorganic-organic materials;
Then in the hybrid inorganic-organic materials of gained, add the bromoethanol of stoichiometric ratio, at 80 DEG C, salt of wormwood after stirring reaction 24h by sedimentation and filtration, washing, dry, then by dried polymer dissolution in anhydrous methylene chloride, add the Methanesulfonyl chloride of 1.5 equivalents, triethylamine is spin-dried for solvent after reacting 2 hours, dichloromethane extraction, guanidine is added again after drying, triethylamine filters after reacting at 25 DEG C and spending the night, the polymkeric substance of functional amido is obtained after washing, finally by the aminated polymkeric substance obtained and POTASSIUM BOROHYDRIDE by metering than collecting by filtration lower floor organic phase after stir 6h at 50 DEG C in dimethyl sulfoxide (DMSO) suspension, underpressure distillation is except desolventizing, finally obtain the organic-inorganic hybrid material containing polymkeric substance hydrogen storage material for twice with washed with diethylether.Finally by above-mentioned organic-inorganic hybrid material ethanolic extraction after 24 hours drying obtain composite organic-inorganic material of the present invention.
The hydrogen peak temperature of putting of this Organic-inorganic composite hydrogen storage material is 115 DEG C, approximately can release the pure hydrogen of 6.7wt% at 110 DEG C.And putting the generation not having detrimental impurity gas in hydrogen process.
Embodiment 2:
Take the polymine (molecular weight 50000) of 10g and the hexadecyl brometo de amonio of 10g, be dissolved in 100mL ethanol at 80 DEG C of temperature, stir and make it abundant dissolving.25g tetraethoxy adds in reaction solution after stirring 2h by constant temperature, and continues to stir 12 hours temperature 105 DEG C; Filtration after completing above-mentioned reaction, obtains hybrid inorganic-organic materials;
Then in the hybrid inorganic-organic materials of gained, add the bromoethanol of stoichiometric ratio, at 80 DEG C, salt of wormwood after stirring reaction 24h by sedimentation and filtration, washing, dry, then by dried polymer dissolution in anhydrous methylene chloride, add the Methanesulfonyl chloride of 1.5 equivalents, triethylamine is spin-dried for solvent after reacting 2 hours, dichloromethane extraction, guanidine is added again after drying, triethylamine filters after reacting at 25 DEG C and spending the night, the polymkeric substance of functional amido is obtained after washing, finally by the aminated polymkeric substance obtained and POTASSIUM BOROHYDRIDE by metering than collecting by filtration lower floor organic phase after stir 6h at 50 DEG C in dimethyl sulfoxide (DMSO) suspension, underpressure distillation is except desolventizing, finally obtain the organic-inorganic hybrid material containing polymkeric substance hydrogen storage material for twice with washed with diethylether.Finally by above-mentioned organic-inorganic hybrid material ethanolic extraction after 24 hours drying obtain composite organic-inorganic material of the present invention.
The hydrogen peak temperature of putting of this Organic-inorganic composite hydrogen storage material is 115 DEG C, approximately can release the pure hydrogen of 6.7wt% at 110 DEG C.And putting the generation not having detrimental impurity gas in hydrogen process.
Described hydrogen storage material polymkeric substance d is carried out hydrogen discharging performance test, Fig. 1 and Fig. 2 is respectively hydrogen desorption kinetics curve and the temperature programmed desorption(TPD) figure of this polymkeric substance hydrogen storage material.As seen from the figure, this hydrogen storage material polymkeric substance d has lower initial hydrogen discharging temperature (about 50 DEG C), and along with temperature raises, hydrogen discharge reaction closely carries out with a step, and putting hydrogen peak temperature is 100 DEG C, and hydrogen desorption capacity is about 8wt%.And produce without any obnoxious flavour material whole putting in hydrogen process.
Separately, add the test that Wilkinson catalyzer carries out hydrogen discharging performance putting in hydrogen process, as comparison test, see Fig. 2.As can be seen from Figure 2, after adding Wilkinson catalyzer, the hydrogen discharging performance of polymkeric substance hydrogen storage material be improved significantly.
Embodiment 3:
Take the hexadecyl brometo de amonio of PAH and 10g of 10g, be dissolved in 100mL ethanol at 80 DEG C of temperature, stir and make it abundant dissolving.25g tetraethoxy adds in reaction solution after stirring 2h by constant temperature, and continues to stir 12 hours temperature 110 DEG C; Filtration after completing above-mentioned reaction, obtains hybrid inorganic-organic materials;
Then in the hybrid inorganic-organic materials of gained, add the bromoethanol of stoichiometric ratio, at 80 DEG C, salt of wormwood after stirring reaction 24h by sedimentation and filtration, washing, dry, then by dried polymer dissolution in anhydrous methylene chloride, add the Methanesulfonyl chloride of 1.5 equivalents, triethylamine is spin-dried for solvent after reacting 2 hours, dichloromethane extraction, guanidine is added again after drying, triethylamine filters after reacting at 25 DEG C and spending the night, the polymkeric substance of functional amido is obtained after washing, finally by the aminated polymkeric substance obtained and POTASSIUM BOROHYDRIDE by metering than collecting by filtration lower floor organic phase after stir 6h at 50 DEG C in dimethyl sulfoxide (DMSO) suspension, underpressure distillation is except desolventizing, finally obtain the organic-inorganic hybrid material containing polymkeric substance hydrogen storage material for twice with washed with diethylether.Finally by above-mentioned organic-inorganic hybrid material ethanolic extraction after 24 hours drying obtain composite organic-inorganic material of the present invention.
The hydrogen peak temperature of putting of this Organic-inorganic composite hydrogen storage material is 115 DEG C, approximately can release the pure hydrogen of 6.7wt% at 110 DEG C.And putting the generation not having detrimental impurity gas in hydrogen process.
Embodiment 4:
Take the hexadecyl brometo de amonio of PEO-PEI and 10g of 10g, be dissolved in 100mL ethanol at 80 DEG C of temperature, stir and make it abundant dissolving.25g tetraethoxy adds in reaction solution after stirring 2h by constant temperature, and continues to stir 8 hours temperature 120 DEG C; Filtration after completing above-mentioned reaction, obtains hybrid inorganic-organic materials;
Then in the hybrid inorganic-organic materials of gained, add the bromoethanol of stoichiometric ratio, at 80 DEG C, salt of wormwood after stirring reaction 24h by sedimentation and filtration, washing, dry, then by dried polymer dissolution in anhydrous methylene chloride, add the Methanesulfonyl chloride of 1.5 equivalents, triethylamine is spin-dried for solvent after reacting 2 hours, dichloromethane extraction, guanidine is added again after drying, triethylamine filters after reacting at 25 DEG C and spending the night, the polymkeric substance of functional amido is obtained after washing, finally by the aminated polymkeric substance obtained and POTASSIUM BOROHYDRIDE by metering than collecting by filtration lower floor organic phase after stir 6h at 50 DEG C in dimethyl sulfoxide (DMSO) suspension, underpressure distillation is except desolventizing, finally obtain the organic-inorganic hybrid material containing polymkeric substance hydrogen storage material for twice with washed with diethylether.Finally by above-mentioned organic-inorganic hybrid material ethanolic extraction after 24 hours drying obtain composite organic-inorganic material of the present invention.
The hydrogen peak temperature of putting of this Organic-inorganic composite hydrogen storage material is 115 DEG C, approximately can release the pure hydrogen of 6.7wt% at 110 DEG C.And putting the generation not having detrimental impurity gas in hydrogen process.
Embodiment 5:
Take the hexadecyl brometo de amonio of PEI-PEO-PEI and 10g of 10g, be dissolved in 100mL ethanol at 80 DEG C of temperature, stir and make it abundant dissolving.25g tetraethoxy adds in reaction solution after stirring 2h by constant temperature, and continues to stir 12 hours temperature 150 DEG C; Filtration after completing above-mentioned reaction, obtains hybrid inorganic-organic materials;
Then in the hybrid inorganic-organic materials of gained, add the bromoethanol of stoichiometric ratio, at 80 DEG C, salt of wormwood after stirring reaction 24h by sedimentation and filtration, washing, dry, then by dried polymer dissolution in anhydrous methylene chloride, add the Methanesulfonyl chloride of 1.5 equivalents, triethylamine is spin-dried for solvent after reacting 2 hours, dichloromethane extraction, guanidine is added again after drying, triethylamine filters after reacting at 25 DEG C and spending the night, the polymkeric substance of functional amido is obtained after washing, finally by the aminated polymkeric substance obtained and POTASSIUM BOROHYDRIDE by metering than collecting by filtration lower floor organic phase after stir 6h at 50 DEG C in dimethyl sulfoxide (DMSO) suspension, underpressure distillation is except desolventizing, finally obtain the organic-inorganic hybrid material containing polymkeric substance hydrogen storage material for twice with washed with diethylether.Finally by above-mentioned organic-inorganic hybrid material ethanolic extraction after 24 hours drying obtain composite organic-inorganic material of the present invention.
The hydrogen peak temperature of putting of this Organic-inorganic composite hydrogen storage material is 115 DEG C, approximately can release the pure hydrogen of 6.7wt% at 110 DEG C.And putting the generation not having detrimental impurity gas in hydrogen process.
Embodiment 6:
Take the polymine of 10g and the hexadecyl brometo de amonio of 10g, be dissolved in 100mL ethanol at 80 DEG C of temperature, stir and make it abundant dissolving.25g tetraethoxy adds in reaction solution after stirring 2h by constant temperature, and continues to stir 8 hours at temperature 50 C; Filtration after completing above-mentioned reaction, obtains hybrid inorganic-organic materials;
Then in the hybrid inorganic-organic materials of gained, add the bromoethanol of stoichiometric ratio, at 80 DEG C, salt of wormwood after stirring reaction 24h by sedimentation and filtration, washing, dry, then by dried polymer dissolution in anhydrous methylene chloride, add the Methanesulfonyl chloride of 1.5 equivalents, triethylamine is spin-dried for solvent after reacting 2 hours, dichloromethane extraction, guanidine is added again after drying, triethylamine filters after reacting at 25 DEG C and spending the night, the polymkeric substance of functional amido is obtained after washing, finally by the aminated polymkeric substance obtained and POTASSIUM BOROHYDRIDE by metering than collecting by filtration lower floor organic phase after stir 6h at 50 DEG C in dimethyl sulfoxide (DMSO) suspension, underpressure distillation is except desolventizing, finally obtain the organic-inorganic hybrid material containing polymkeric substance hydrogen storage material for twice with washed with diethylether.Finally by above-mentioned organic-inorganic hybrid material ethanolic extraction after 24 hours drying obtain composite organic-inorganic material of the present invention.
The hydrogen peak temperature of putting of this Organic-inorganic composite hydrogen storage material is 115 DEG C, approximately can release the pure hydrogen of 6.7wt% at 110 DEG C.And putting the generation not having detrimental impurity gas in hydrogen process.
Claims (10)
1. a heavy body Organic-inorganic composite hydrogen storage material, it is characterized in that: this Organic-inorganic composite hydrogen storage material is made up of inorganic porous material and the organic materials be dispersed in this inorganic porous material hole, described inorganic porous material is porous silica or aluminum oxide, aperture is 0.5 ~ 20nm, and specific surface area is 300 ~ 500m
2/ g, described organic materials comprises high molecular polymer as main chain and the ammonia borane derivative that reacted with hydroborate after polyamine compounds is aminated by its side chain and/or end group again and graft on its side chain and/or end.
2. heavy body Organic-inorganic composite hydrogen storage material according to claim 1, it is characterized in that: in described Organic-inorganic composite hydrogen storage material, the weight percent of organic materials is: 20 ~ 80%, and surplus is inorganic porous material.
3. heavy body Organic-inorganic composite hydrogen storage material according to claim 1 and 2, it is characterized in that: the described high molecular polymer as main chain is the amphipathic polymkeric substance containing amido, the described amphipathic polymkeric substance containing amido is PEI, PEO-PEI, PEI-PEO-PEI or PAH, and described PEI can be linear also can be branched chain type; Described high molecular polymer side chain and/or the aminated polyamine compounds used of end group are guanidine, quadrol or diethylenetriamine.
4. heavy body Organic-inorganic composite hydrogen storage material according to claim 1 and 2, is characterized in that: the molecular weight of the described high molecular polymer as main chain is 5000 ~ 50000; The weight percent content of described ammonia borane derivative in Organic-inorganic composite hydrogen storage material is 10 ~ 60%.
5. heavy body Organic-inorganic composite hydrogen storage material according to claim 1 and 2, is characterized in that: the shape of described inorganic porous material is spherical, and aperture is 5 ~ 10nm, and pore volume is 0.1 ~ 1.5cm
3/ g, specific surface area is 350 ~ 450m
2/ g.
6. a preparation method for heavy body Organic-inorganic composite hydrogen storage material, is characterized in that: the method comprises the steps:
1) raw material is chosen: choose inorganic porous material presoma and template for subsequent use, described inorganic porous material presoma is tetraethoxy or aluminum nitrate, and described template is amphipathic containing amino polymkeric substance and micromolecular hexadecyl brometo de amonio;
2) be dissolved in alcohol solvent by template, then at 25 ~ 100 DEG C, add inorganic porous material presoma in above-mentioned solution, constant temperature stirs 3 ~ 24 hours, crosses and filters to remove filtrate;
3) in filter residue, add the aqueous solution of bromoethanol and an alkali metal salt, in pH value 7 ~ 8.5, at temperature 25 ~ 100 DEG C, constant temperature stirs 1 ~ 3 hour;
4) above-mentioned reaction obtains hybrid inorganic-organic materials through drying after completing;
5) adopt polyamine compounds to carry out aminated reaction to high molecular polymer in hybrid inorganic-organic materials, obtain aminated polymkeric substance;
6) by step 5) the aminated polymkeric substance that obtains and hydroborate stoichiometrically stir collecting by filtration lower floor organic phase after 1 ~ 12 hour in organic solvent suspension at 5 ~ 50 DEG C, underpressure distillation, except desolventizing, obtains Organic-inorganic composite hydrogen storage material after washing, extracting, drying.
7. the preparation method of heavy body Organic-inorganic composite hydrogen storage material according to claim 6, it is characterized in that: described step 1) in the amphipathic polymkeric substance containing amido be PEI, PEO-PEI, PEI-PEO-PEI and PAH, described PEI is linear or branched chain type.
8. the preparation method of the heavy body Organic-inorganic composite hydrogen storage material according to claim 6 or 7, is characterized in that: described step 3) in, pH value alkali metal salt soln regulates or regulates with the mixing solutions of an alkali metal salt and ammoniacal liquor.
9. the preparation method of the heavy body Organic-inorganic composite hydrogen storage material according to claim 6 or 7, is characterized in that: described step 5) in polyamine compounds be guanidine, quadrol or diethylenetriamine.
10. the preparation method of the heavy body Organic-inorganic composite hydrogen storage material according to claim 6 or 7, is characterized in that: described step 6) in organic solvent be tetrahydrofuran (THF), acetonitrile or dimethyl sulfoxide (DMSO); Described hydroborate is sodium borohydride, lithium borohydride or POTASSIUM BOROHYDRIDE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418505.4A CN105062033B (en) | 2015-07-16 | 2015-07-16 | high-capacity organic-inorganic composite hydrogen storage material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418505.4A CN105062033B (en) | 2015-07-16 | 2015-07-16 | high-capacity organic-inorganic composite hydrogen storage material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105062033A true CN105062033A (en) | 2015-11-18 |
| CN105062033B CN105062033B (en) | 2017-05-17 |
Family
ID=54491569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510418505.4A Active CN105062033B (en) | 2015-07-16 | 2015-07-16 | high-capacity organic-inorganic composite hydrogen storage material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105062033B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731378A (en) * | 2016-01-26 | 2016-07-06 | 北京科技大学 | Organic polymer/AB5 or AB2 composite hydrogen storage material and preparation method thereof |
| CN108884330A (en) * | 2016-03-15 | 2018-11-23 | 住友电气工业株式会社 | Conductive layer, which is formed, uses coating fluid, the manufacturing method of conductive layer and conductive layer |
| CN109467047A (en) * | 2018-10-24 | 2019-03-15 | 东莞理工学院 | A kind of Ti3C2The preparation method of MXene composite hydrogen storage material |
| CN115488988A (en) * | 2022-09-15 | 2022-12-20 | 江苏神鹭农业发展有限公司 | Non-woven fiber board and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008118437A2 (en) * | 2007-03-26 | 2008-10-02 | Millennium Cell, Inc. | Compositions, devices and methods for hydrogen generation |
| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
| CN102838085A (en) * | 2012-09-18 | 2012-12-26 | 武汉凯迪工程技术研究总院有限公司 | High-capacity high-molecular polymer hydrogen storing material and preparation method thereof |
| CN103613068A (en) * | 2013-11-26 | 2014-03-05 | 河南理工大学 | Ammonia borane composite hydrogen storage material and preparation method thereof |
-
2015
- 2015-07-16 CN CN201510418505.4A patent/CN105062033B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008118437A2 (en) * | 2007-03-26 | 2008-10-02 | Millennium Cell, Inc. | Compositions, devices and methods for hydrogen generation |
| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
| CN102838085A (en) * | 2012-09-18 | 2012-12-26 | 武汉凯迪工程技术研究总院有限公司 | High-capacity high-molecular polymer hydrogen storing material and preparation method thereof |
| CN103613068A (en) * | 2013-11-26 | 2014-03-05 | 河南理工大学 | Ammonia borane composite hydrogen storage material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731378A (en) * | 2016-01-26 | 2016-07-06 | 北京科技大学 | Organic polymer/AB5 or AB2 composite hydrogen storage material and preparation method thereof |
| CN105731378B (en) * | 2016-01-26 | 2018-07-24 | 北京科技大学 | A kind of organic polymer/AB5Or AB2Composite hydrogen storage material and preparation method |
| CN108884330A (en) * | 2016-03-15 | 2018-11-23 | 住友电气工业株式会社 | Conductive layer, which is formed, uses coating fluid, the manufacturing method of conductive layer and conductive layer |
| CN108884330B (en) * | 2016-03-15 | 2020-05-15 | 住友电气工业株式会社 | Coating liquid for forming conductive layer, method for producing conductive layer, and conductive layer |
| CN109467047A (en) * | 2018-10-24 | 2019-03-15 | 东莞理工学院 | A kind of Ti3C2The preparation method of MXene composite hydrogen storage material |
| CN115488988A (en) * | 2022-09-15 | 2022-12-20 | 江苏神鹭农业发展有限公司 | Non-woven fiber board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105062033B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lee et al. | Recent advances in preparations and applications of carbon aerogels: A review | |
| Hu et al. | Hierarchical assemblies of conjugated ultrathin COF nanosheets for high-sulfur-loading and long-lifespan lithium–sulfur batteries: fully-exposed porphyrin matters | |
| Saka | Highly active and durable hydrogen release in NaBH4 methanolysis reaction with sulphur and phosphorus-doped metal-free microalgal carbon nanoparticles | |
| Park et al. | Straightforward and controllable synthesis of heteroatom-doped carbon dots and nanoporous carbons for surface-confined energy and chemical storage | |
| Li et al. | Green conversion of bamboo chips into high-performance phenol adsorbent and supercapacitor electrodes by simultaneous activation and nitrogen doping | |
| CN101823705B (en) | Method for preparing high-surface-area nitrogenous mesoporous carbon material | |
| CN102838085B (en) | High-capacity high-molecular polymer hydrogen storing material and preparation method thereof | |
| Xie et al. | Porous carbons synthesized by templating approach from fluid precursors and their applications in environment and energy storage: A review | |
| CN112038648B (en) | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
| Zhao et al. | Solvent-free and mechanochemical synthesis of N-doped mesoporous carbon from tannin and related gas sorption property | |
| CN105062033A (en) | High-capacity organic-inorganic composite hydrogen storage material and preparation method thereof | |
| CN111876160B (en) | Carbon aerogel material, preparation method thereof and application of carbon aerogel material as heavy metal contaminated soil remediation material | |
| CN105883748A (en) | Highly-graphitized carbon nanowire ball material and preparation method thereof | |
| CN104909351A (en) | Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof | |
| CN113307250B (en) | Preparation method and application of ordered lignin carbon-carbon nanotube composite material | |
| CN107954483B (en) | Alpha-phase nickel hydroxide ultrathin nanosheet and preparation method thereof | |
| Wang et al. | Green fabrication of hierarchically porous carbon microtubes from biomass waste via self-activation for high-energy-density supercapacitor | |
| Wang et al. | Polyethyleneimine-functionalized mesoporous carbon nanosheets as metal-free catalysts for the selective oxidation of H2S at room temperature | |
| CN107837821A (en) | A kind of carbon dioxide electroreduction electrode and its preparation and application | |
| Zhang et al. | A heterogeneous FeP-CoP electrocatalyst for expediting sulfur redox in high-specific-energy lithium-sulfur batteries | |
| Shi et al. | Fabrication of nitrogen doped and hierarchically porous carbon flowers for CO2 adsorption | |
| Liu et al. | Controllable fabrication of 3D porous carbon nitride with ultra-thin nanosheets templated by ionic liquid for highly efficient water splitting | |
| Ramadass et al. | Morphologically tunable nanoarchitectonics of mixed kaolin-halloysite derived nitrogen-doped activated nanoporous carbons for supercapacitor and CO2 capture applications | |
| CN109179379B (en) | Carbon material with nano-network structure and carbon nanotube core @ functional amorphous carbon shell unit, and preparation method and application thereof | |
| CN111939878A (en) | Ternary composite aerogel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |