CN100421781C - Production of porous molecular-sieve hydrogen-storage material - Google Patents
Production of porous molecular-sieve hydrogen-storage material Download PDFInfo
- Publication number
- CN100421781C CN100421781C CNB2006100483318A CN200610048331A CN100421781C CN 100421781 C CN100421781 C CN 100421781C CN B2006100483318 A CNB2006100483318 A CN B2006100483318A CN 200610048331 A CN200610048331 A CN 200610048331A CN 100421781 C CN100421781 C CN 100421781C
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- sieve
- molecular sieve
- storage material
- metal
- 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.)
- Expired - Fee Related
Links
Abstract
A process for preparing a hydrogen-bearing meso-porous molecular sieve which is a Mg-base metal-meso-porous molecular sieve composition includes such steps as immersing the meso-porous molecular sieve in the aqueous solution of metallic salt, drying, calcining to obtain the composition of meso-porous molecular sieve and metallic oxide, programmed raising temp in hydrogen atmosphere in high-temp furnace, to obtain the composition of metal and meso-porous molecular sieve, and diffusing between it and magnesium hydride in hydrogen atmosphere.
Description
One, technical field
The preparation method of a kind of porous molecular-sieve hydrogen-storage material of the present invention belongs to the inorganic porous material application, specifically is exactly to adopt load and hydrogen reducing and method of diffusion to prepare a kind of method of nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material.
Two, technical background
The magnesium-base metal hydrogen storage material is big, in light weight owing to its hydrogen storage amount, low price, and aboundresources is the hydrogen storage material that is considered to desirable always.But magnesium and alloy thereof are as also there being three shortcomings: (1) speed for hydrogen absorbing and releasing is slower, the kinetics poor performance; (2) hydride is more stable, and putting hydrogen needs higher temperature; (3) surface of magnesium and alloy thereof forms easily the oxide-film of one deck densification, more than these shortcomings seriously hindered the practicalization of magnesium-base metal hydrogen storage material.
For this reason, the various countries scientist is at above-mentioned shortcoming, by studying around the preparation of magnesium base hydrogen-storing material, nanometer and compound etc., both keeping hydrogen storage amount big, obtained gratifying progress under the low situation of hydrogen discharging temperature.
Because conventional preparation method is difficult to the particle diameter of magnesium base hydrogen-storing material is further dwindled, and develops the crux that the mg-based material that really has the nano material physical effect becomes the magnesium-base metal hydrogen storage material of the good hydrogen storage performance of preparation.
Meso-porous molecular sieve material such as M41S, SBA series, because of its aperture can be adjustable continuously in 1.5nm arrives the 30nm scope, arrange in order and high excellent performances such as specific area in the duct, has caused subject researchers' such as chemistry, material, physics in the world very big interest and carried out exploration widely.The mesoporous composite material of Yan Shening has also become a new subject forward position in Industrial Catalysis field and Condensed Matter Physics and material subject field as another kind of new material on this basis.Because mesoporous composite material is the nano particle in the order mesoporous solid, and good dispersiveness is arranged, a little less than the coupling between the particle, there is coupling effect etc. at the interface of particle and mesoporous solid wall, makes it present some new performances.
Oxide and salt can spontaneous formation atomic level in molecular sieve surfaces externally and internally and hole dispersion [Xie Youchang etc., Chinese science, 1993,23 (2): 113-119; Zhang Xuezheng etc. SCI, 2003,24 (1): 121～124], disperse the entropy of back system to increase greatly, generate new key on the surface simultaneously, cause total free energy of system to descend.With metallic reducing in the molecular sieve, can further improve the character in internal and external surface of molecular sieve and hole.Utilize oxide or salt in molecular sieve surfaces externally and internally and hole, to disperse and to carry out modification to molecular sieve, can make catalyst and adsorbent and other new materials of high activity, high selectivity.
Up to the present, people modify mesoporous material with a lot of elements such as Mn, Zn, Cu etc., but the research of this respect are mainly concentrated in its influence to the chemical catalysis effect in the past, and the research that relates to other field such as magnetism characteristic is also arranged.
The present inventor is through further investigation, performances such as the good duct of the good hydrogen storage performance of magnesium-base metal and molecular sieve and surface combine by the salt diffusion and intend oxide diffusion means prepared one and be assembled with metal (magnesium-base metal hydrogen storage material activating catalyst) such as Fe, Ni, Cu and hydrogen storage amount than the nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material of excellent performance greatly.
Three, summary of the invention
The preparation method of a kind of porous molecular-sieve hydrogen-storage material of the present invention, but its purpose is to provide a kind of mesopore molecular sieve of aperture modulation that utilizes is carrier, magnesium-base metal is inserted in the molecule sieve aperture technical scheme of the nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material method that is composited by load and hydrogen reducing and method of diffusion.
The preparation method of a kind of porous molecular-sieve hydrogen-storage material of the present invention, it is characterized in that it being a kind of preparation method of nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material, but utilize the mesopore molecular sieve of aperture modulation to be carrier, by load and hydrogen reducing and method of diffusion magnesium-base metal is inserted in the molecule sieve aperture, nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material is composited, particularly be exactly at first the carrier mesopore molecular sieve to be impregnated in the aqueous metal salt, dipping, drying, roasting obtain the mesopore molecular sieve metal oxide compounds; Then the mesopore molecular sieve metal oxide compounds that makes is adopted temperature programmed reduction in high temperature furnace, under the hydrogen atmosphere, the metal mesoporous molecular screen composite; Metal mesoporous molecular screen composite and magnesium hydride are spread under hydrogen atmosphere again, get nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material, its specific operation process is:
I, mesopore molecular sieve be impregnated in the aqueous metal salt at a certain temperature, dipping 12-48h, in the 373-473K drying, 773-823K roasting 3-5h, the mesopore molecular sieve metal oxide compounds;
II, mesopore molecular sieve metal oxide compounds under the hydrogen atmosphere, adopt the about 3-5h of temperature programmed reduction in high temperature furnace, reduction temperature is adjusted with TPR result, gets the mesopore molecular sieve metal composite;
III, the metal mesoporous molecular screen composite after will reducing and magnesium hydride are in 1: the ratio of 0.1-1 is mixed, and carries out inhaling for 1-3 time under 473-673K and put hydrogen, forms and spreads, and promptly gets nanoscale magnesium-base metal porous molecular-sieve hydrogen-storage material.
The preparation method of above-mentioned a kind of porous molecular-sieve hydrogen-storage material is characterized in that: described carrier mesopore molecular sieve is SBA-15 and MCM-41.
The preparation method of above-mentioned a kind of porous molecular-sieve hydrogen-storage material is characterized in that: described slaine is nitrate, acetate or the hydrochloride of Fe, Ni or Cu metal.
The preparation method of above-mentioned a kind of porous molecular-sieve hydrogen-storage material is characterized in that: described slaine quality is calculated with the 1-10% (weight ratio) of mesoporous molecular sieve carried metallic atom weight.
Its advantage of the preparation method of a kind of porous molecular-sieve hydrogen-storage material of the present invention is: by load and hydrogen reducing and method of diffusion magnesium-base metal is inserted in the molecule sieve aperture, performances such as the good duct of the good hydrogen storage performance of magnesium-base metal and molecular sieve and surface are combined, prepare a class nanoscale magnesium-base metal porous molecular-sieve hydrogen-storage material.
Four, the specific embodiment
Embodiment 1
The first step at room temperature impregnated in the 2g mesoporous molecular sieve SBA-15 among nine water ferric nitrate (1.4g) aqueous solution 40ml, dipping 24h, and in the 373K drying, 773K roasting 3h gets 2.2g mesoporous molecular sieve SBA-15 iron oxide compound.
Second the step, with mesoporous molecular sieve SBA-15 iron oxide compound in high temperature furnace, H
2Under the atmosphere (flow 40ml/min), adopt temperature programming under 1023K, to reduce 5h, 2.1g Fe/SBA-15 mesoporous molecular screen composite.
The 3rd step, Fe/SBA-15 mesoporous molecular screen composite and magnesium hydride is evenly mixed by the ratio of 1: 0.3 (weight ratio), and put among the hydrogen production device P-C-T in the hydrogen suction in 673K and to spread 3 times, promptly get 2.7gMgH
2The Fe/SBA-15 porous molecular-sieve hydrogen-storage material.
Embodiment 2
The first step at room temperature impregnated in the 2g mesoporous molecular sieve SBA-15 among six water nickel chloride (0.8g) aqueous solution 40ml, dipping 48h, and in the 423K drying, 773K roasting 3h gets 2.2g mesoporous molecular sieve SBA-15 nickel oxide compound.
Second the step, with mesoporous molecular sieve SBA-15 nickel oxide compound in high temperature furnace, H
2Under the atmosphere (flow 25ml/min), adopt temperature programming under 923K, to reduce 4h, 2.1g Ni/SBA-15 mesoporous molecular screen composite.
The 3rd step, Ni/SBA-15 mesoporous molecular screen composite and magnesium hydride is evenly mixed by the ratio of 1: 0.5 (weight ratio), and put among the hydrogen production device P-C-T in the hydrogen suction in 673K and to spread 2 times, promptly get 2.9gMgH
2The Ni/SBA-15 porous molecular-sieve hydrogen-storage material.
Embodiment 3
The first step at room temperature impregnated in the 2g mesoporous molecular sieve SBA-15 among six water nickel chloride (0.8g) aqueous solution 40ml, dipping 24h, and in the 3733K drying, 773K roasting 3h gets 2.2g mesoporous molecular sieve SBA-15 nickel oxide compound.
Second the step, with mesoporous molecular sieve SBA-15 nickel oxide compound in high temperature furnace, H
2Under the atmosphere (flow 25ml/min), adopt temperature programming under 923K, to reduce 4h, 2.1g Ni/SBA-15 mesoporous molecular screen composite.
The 3rd step, Ni/SBA-15 mesoporous molecular screen composite and magnesium hydride is evenly mixed by the ratio of 1: 1 (weight ratio), and put among the hydrogen production device P-C-T in the hydrogen suction in 673K and to spread 4 times, promptly get 4gMgH
2The Ni/SBA-15 porous molecular-sieve hydrogen-storage material.
Embodiment 4
The first step impregnated in 2g mesopore molecular sieve MCM-41 among nine water ferric nitrate (1.4g) aqueous solution 40ml under 303K, dipping 48h, and in the 373K drying, 773K roasting 4h must get 2.2g mesopore molecular sieve MCM-41 iron oxide compound.
Second the step, with mesopore molecular sieve MCM-41 iron oxide compound in high temperature furnace, H
2Under the atmosphere (flow 10ml/min), adopt temperature programming under 1023K, to reduce 5h, 2.1g Fe/MCM-41 mesoporous molecular screen composite.
The 3rd step, Fe/MCM-41 mesoporous molecular screen composite and magnesium hydride is evenly mixed by the ratio of 1: 0.1 (weight ratio), and put among the hydrogen production device P-C-T in the hydrogen suction in 673K and to spread 3 times, promptly get 2.2gMgH
2The Fe/MCM-41 porous molecular-sieve hydrogen-storage material.
Embodiment 5
The first step at room temperature impregnated in 2g mesopore molecular sieve MCM-41 among one water copper acetate (0.6g) aqueous solution 40ml, dipping 36h, and in the 373K drying, 773K roasting 3h gets 2.2g mesopore molecular sieve MCM-41 cupric oxide compound.
Second the step, with mesopore molecular sieve MCM-41 iron oxide compound in high temperature furnace, H
2Under the atmosphere (flow 40ml/min), adopt temperature programming under 1023K, to reduce 3h, 2.1g Cu/MCM-41 mesoporous molecular screen composite.
The 3rd step, Fe/MCM-41 mesoporous molecular screen composite and magnesium hydride is evenly mixed by the ratio of 1: 0.4 (weight ratio), and put among the hydrogen production device P-C-T in the hydrogen suction in 673K and to spread 4 times, promptly get 2.8MgH
2The Cu/MCM-41 porous molecular-sieve hydrogen-storage material.
Claims (3)
1. the preparation method of a porous molecular-sieve hydrogen-storage material, but it is characterized in that it being to utilize the mesopore molecular sieve of aperture modulation to be carrier, by load and hydrogen reducing and method of diffusion magnesium-base metal is inserted in the molecule sieve aperture, nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material is composited, particularly be exactly at first the carrier mesopore molecular sieve to be impregnated in the aqueous metal salt of iron, nickel or copper, dipping, drying, roasting obtain the mesopore molecular sieve metal oxide compounds; Then the mesopore molecular sieve metal oxide compounds that makes is adopted temperature programmed reduction in high temperature furnace, under the hydrogen atmosphere, the metal mesoporous molecular screen composite; Metal mesoporous molecular screen composite and magnesium hydride are spread under hydrogen atmosphere again, get nanoscale magnesium-base metal mesoporous molecular screen composite hydrogen storage material, its operating process is:
I, mesopore molecular sieve be impregnated in the aqueous metal salt at a certain temperature, dipping 12-48h, in the 373-473K drying, 773-823K roasting 3-5h, the mesopore molecular sieve metal oxide compounds;
II, mesopore molecular sieve metal oxide compounds under the hydrogen atmosphere, adopt temperature programmed reduction 3-5h in high temperature furnace, reduction temperature is adjusted with TPR result, gets the mesopore molecular sieve metal composite;
III, the metal mesoporous molecular screen composite after will reducing and magnesium hydride are in 1: the ratio of 0.1-1 is mixed, and carries out inhaling for 1-3 time under 473-673K and put hydrogen, forms and spreads, and promptly gets nanoscale magnesium-base metal porous molecular-sieve hydrogen-storage material.
2. according to the preparation method of the described a kind of porous molecular-sieve hydrogen-storage material of claim 1, it is characterized in that: described carrier mesopore molecular sieve is SBA-15 and MCM-41.
3. according to the preparation method of the described a kind of porous molecular-sieve hydrogen-storage material of claim 1, it is characterized in that: described slaine is nitrate, acetate or the hydrochloride of Fe, Ni or Cu metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100483318A CN100421781C (en) | 2006-09-20 | 2006-09-20 | Production of porous molecular-sieve hydrogen-storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100483318A CN100421781C (en) | 2006-09-20 | 2006-09-20 | Production of porous molecular-sieve hydrogen-storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1939583A CN1939583A (en) | 2007-04-04 |
| CN100421781C true CN100421781C (en) | 2008-10-01 |
Family
ID=37958267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100483318A Expired - Fee Related CN100421781C (en) | 2006-09-20 | 2006-09-20 | Production of porous molecular-sieve hydrogen-storage material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100421781C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269317B (en) * | 2007-03-23 | 2011-06-08 | 中国科学院大连化学物理研究所 | Load type stephanoporate metal organic compound hydrogen storing material |
| PL422782A1 (en) * | 2017-09-07 | 2019-03-11 | Politechnika Lubelska | Mesoporous silica, modified with metal compounds and method for modification of mesoporous silica with metal compounds |
| CN109485060B (en) * | 2017-09-13 | 2020-12-18 | 中国石油化工股份有限公司 | SBA-16 molecular sieve modified by nano iron and preparation method and application thereof |
| CN111003687A (en) * | 2019-12-31 | 2020-04-14 | 世能氢电科技有限公司 | Molecular sieve hydrogen storage composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248649A (en) * | 1992-08-21 | 1993-09-28 | Mosley Jr Wilbur C | Palladium/kieselguhr composition and method |
| US5958098A (en) * | 1997-10-07 | 1999-09-28 | Westinghouse Savannah River Company | Method and composition in which metal hydride particles are embedded in a silica network |
| US20020187896A1 (en) * | 2001-04-30 | 2002-12-12 | Ryong Ryoo | Carbon molecular sieve and process for preparing the same |
| WO2005014469A1 (en) * | 2003-07-16 | 2005-02-17 | Studiengesellschaft Kohle Mbh | Materials encapsulated in porous matrices for the reversible storage of hydrogen |
| CN1743066A (en) * | 2004-08-31 | 2006-03-08 | 中国科学院金属研究所 | A kind of nanocomposite hydrogen storage material and preparation method thereof |
-
2006
- 2006-09-20 CN CNB2006100483318A patent/CN100421781C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248649A (en) * | 1992-08-21 | 1993-09-28 | Mosley Jr Wilbur C | Palladium/kieselguhr composition and method |
| US5958098A (en) * | 1997-10-07 | 1999-09-28 | Westinghouse Savannah River Company | Method and composition in which metal hydride particles are embedded in a silica network |
| US20020187896A1 (en) * | 2001-04-30 | 2002-12-12 | Ryong Ryoo | Carbon molecular sieve and process for preparing the same |
| WO2005014469A1 (en) * | 2003-07-16 | 2005-02-17 | Studiengesellschaft Kohle Mbh | Materials encapsulated in porous matrices for the reversible storage of hydrogen |
| CN1743066A (en) * | 2004-08-31 | 2006-03-08 | 中国科学院金属研究所 | A kind of nanocomposite hydrogen storage material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Microporous Metal Organic Materials: Promising CandidatesasSorbents for Hydrogen Storage. Long Pan et al.Journal of American Chemical Society,Vol.126 No.5. 2004 |
| Microporous Metal Organic Materials: Promising CandidatesasSorbents for Hydrogen Storage. Long Pan et al.Journal of American Chemical Society,Vol.126 No.5. 2004 * |
| Strong H2 Binding and Selective Gas Adsorption withinthe Microporous Coordination SolidMg3(O2C-C10H6-CO2)3. Mircea Dincǎ et al.Journal of American Chemical Society,Vol.127 No.26. 2005 |
| Strong H2 Binding and Selective Gas Adsorption withinthe Microporous Coordination SolidMg3(O2C-C10H6-CO2)3. Mircea Dincǎ et al.Journal of American Chemical Society,Vol.127 No.26. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1939583A (en) | 2007-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100421781C (en) | Production of porous molecular-sieve hydrogen-storage material | |
| Liu et al. | A facile fabrication of nanoflower-like Co3O4 catalysts derived from ZIF-67 and their catalytic performance for CO oxidation | |
| CN113422073B (en) | Preparation method of cobalt-modified carbon-supported superfine platinum nano alloy catalyst | |
| Guo et al. | Enhanced hydrogen storage capacity and reversibility of LiBH4 encapsulated in carbon nanocages | |
| CN107973352B (en) | Method for degrading tetracycline by using iron/copper bimetallic oxide | |
| Chen et al. | High loading nanoconfinement of V-decorated Mg with 1 nm carbon shells: hydrogen storage properties and catalytic mechanism | |
| CN105289603A (en) | Method for preparing high-dispersibility gold-loading catalyst | |
| CN107345282A (en) | Magnesium-base nanometer composite hydrogen-storing material of catalytic phase Dispersed precipitate and preparation method thereof | |
| Yang et al. | Characteristics of Mg2Ni0. 75M0. 25 (M= Ti, Cr, Mn, Fe, Co, Ni, Cu and Zn) alloys after surface treatment | |
| CN106390957A (en) | High-performance dye adsorbent and preparation method thereof | |
| Ren et al. | Improved tolerance of Pd/Cu-treated metal hydride alloys towards air impurities | |
| CN115155611A (en) | Single-phase spinel type magnetic high-entropy oxide catalyst and preparation method and application thereof | |
| CN108927201B (en) | AgBr/g-C3N4Preparation method and application of composite powder | |
| CN108832138A (en) | A kind of fuel cell ordered laminar magnesium base alloy hydrogen storage material and preparation method | |
| CN103740210B (en) | A kind of microporous nano coating | |
| CN103756488A (en) | Preparation method of microporous nano-coating | |
| CN103756487A (en) | Microporous nano-coating | |
| CN103740211A (en) | Method for preparing microporous type nano coating | |
| CN114950385A (en) | Preparation method and application of mesoporous carbon nanosphere with polyurethane sponge-supported yolk core-shell structure | |
| Lototsky et al. | Palladium mixed-metal surface-modified AB5-type intermetallides enhance hydrogen sorption kinetics | |
| CN114906801A (en) | MgH 2 @ Fe-ZIF hydrogen storage material and preparation method thereof | |
| Yan et al. | Enhanced hydrogen storage properties of magnesium hydride by multifunctional carbon-based materials: A review | |
| CN103773150B (en) | A kind of microporous nano coating | |
| Chen et al. | Improved dehydrogenation of LiBH4 supported on nanoscale SiO2 via liquid phase method | |
| CN110756186A (en) | Au/CN-H nano composite material with large specific surface area, 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081001 Termination date: 20091020 |