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
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 124
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 124
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011232 storage material Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000011368 organic material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- -1 borane ammonia derivatives Chemical class 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- 125000003368 amide group Chemical group 0.000 claims description 21
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 10
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 10
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- WZMUUWMLOCZETI-UHFFFAOYSA-N azane;borane Chemical class B.N WZMUUWMLOCZETI-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 238000003860 storage Methods 0.000 abstract description 11
- 229910000085 borane Inorganic materials 0.000 abstract 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000005576 amination reaction Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910021426 porous silicon Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 14
- 238000000605 extraction Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000003795 desorption Methods 0.000 description 7
- 230000001627 detrimental effect Effects 0.000 description 7
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- 239000011147 inorganic material Substances 0.000 description 7
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 6
- 229960004132 diethyl ether Drugs 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Compounds (AREA)
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.
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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 |
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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 |
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