CN115367700A - Zinc-copper bimetallic MOF catalyzed MgH 2 Hydrogen storage material, method for the production thereof and use thereof - Google Patents
Zinc-copper bimetallic MOF catalyzed MgH 2 Hydrogen storage material, method for the production thereof and use thereof Download PDFInfo
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- CN115367700A CN115367700A CN202211053007.0A CN202211053007A CN115367700A CN 115367700 A CN115367700 A CN 115367700A CN 202211053007 A CN202211053007 A CN 202211053007A CN 115367700 A CN115367700 A CN 115367700A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 82
- 239000001257 hydrogen Substances 0.000 title claims abstract description 82
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000013246 bimetallic metal–organic framework Substances 0.000 title claims abstract description 51
- 239000011232 storage material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001879 copper Chemical class 0.000 claims abstract description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 150000003751 zinc Chemical class 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- PTSZYEWEQITNAC-UHFFFAOYSA-N zinc dinitrate dihydrate Chemical compound O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O PTSZYEWEQITNAC-UHFFFAOYSA-N 0.000 claims description 6
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 3
- VWYGTDAUKWEPCZ-UHFFFAOYSA-L dichlorocopper;hydrate Chemical compound O.Cl[Cu]Cl VWYGTDAUKWEPCZ-UHFFFAOYSA-L 0.000 claims description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 3
- CHSMNMOHKSNOKO-UHFFFAOYSA-L zinc;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Zn+2] CHSMNMOHKSNOKO-UHFFFAOYSA-L 0.000 claims description 3
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000006872 improvement Effects 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000006399 behavior Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The invention discloses MgH catalyzed by zinc-copper bimetallic MOF 2 The hydrogen storage material comprises the following components in parts by weight: 14 to 29 parts of copper salt, 12 to 27 parts of zinc salt, 30 to 60 parts of organic ligand, 16 to 31 parts of supporting solvent, 17 to 32 parts of organic solvent and 13 to 28 parts of water. The invention also discloses the MgH 2 The preparation method of the hydrogen storage material comprises the following steps: s1, uniformly mixing a supporting solvent, an organic solvent and water of the components to obtain a mixture solvent; s2, sequentially adding copper salt, zinc salt and organic ligand of the components into the mixture solvent, stirring and reacting for 2-5 h at room temperature, and performing centrifugal separation to obtain a solid substance; s3, washing and drying the obtained solid matter to obtain zinc-copper bimetallic MOF; s4, drying to obtain the zinc-copper doubleMetal MOF and commercial MgH 2 Mixing and ball milling to obtain the magnesium-based composite hydrogen storage material catalyzed by MOF. The invention also discloses the MgH 2 Use of a hydrogen storage material.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to MgH catalyzed by zinc-copper bimetal MOF 2 Hydrogen storage material, method for the production and use thereof.
Background
At present, hydrogen is considered one of the most promising energy carriers. The safe and efficient storage of hydrogen is a major requirement for the practical application of hydrogen energy. Therefore, a safety is designedAn effective hydrogen storage material is of great importance for the application of hydrogen fuel cell vehicles. MgH, a simple metal hydride representative of this metal for decades 2 Has the advantages of large hydrogen storage density (7.6 percent by weight), good reversibility, environmental protection, good economic performance and the like. However, due to its thermodynamic stability and slow kinetics, mgH 2 The temperature at which hydrogen is absorbed/released is high, which hinders practical use thereof in fuel cells.
The MgH can be reduced by doping the catalyst 2 The working temperature of hydrogen adsorption/release effectively alleviates the high temperature problem. At present, various catalysts have been reported for increasing MgH 2 Including transition metals, transition metal oxides, hydrides, carbon materials, alloys, and the like. However, the catalyst is prone to aggregation during continuous, vigorous ball milling and subsequent cycling, resulting in a reduction in exposed catalytic sites, which severely affects catalytic performance. Therefore, the development of a superior catalyst having uniform distribution is of great significance for maintaining high catalytic activity of the hydrogen storage material.
Disclosure of Invention
The invention aims to: providing zinc-copper bimetallic MOF catalyzed MgH 2 Hydrogen storage material, method for producing same and use thereof for improving MgH 2 The reversible hydrogen storage performance of the invention is simple in synthesis process, mild in reaction condition, and effectively improves MgH by introducing the zinc-copper bimetallic MOF 2 The hydrogen absorption and desorption behaviors of the hydrogen storage material reduce the hydrogen desorption working temperature, and the preparation method of the catalyst is simple and easy to implement and can be widely applied to most hydrogen storage systems.
In order to achieve the purpose, the invention adopts the following technical scheme:
zinc-copper bimetallic MOF catalyzed MgH 2 The hydrogen storage material comprises the following components in parts by weight: 14 to 29 parts of copper salt, 12 to 27 parts of zinc salt, 30 to 60 parts of organic ligand, 16 to 31 parts of supporting solvent, 17 to 32 parts of organic solvent and 13 to 28 parts of water.
The above-mentioned zinc-copper bimetallic MOF catalyzed MgH 2 A method for preparing a hydrogen storage material,the method comprises the following steps:
s1, uniformly mixing a supporting solvent, an organic solvent and water of the components to obtain a mixture solvent;
s2, sequentially adding copper salt, zinc salt and organic ligand of the components into the mixture solvent, stirring and reacting for 2-5 h at room temperature, and performing centrifugal separation to obtain a solid substance;
s3, washing and drying the obtained solid matter to obtain zinc-copper bimetallic MOF;
s4, mixing the dried zinc-copper bimetallic MOF with commercial MgH 2 Mixing and ball milling to obtain the magnesium-based composite hydrogen storage material catalyzed by MOF.
Further, the copper salt is one of cupric nitrate hydrate, copper sulfate hydrate and copper chloride hydrate;
the zinc salt is one of zinc nitrate dihydrate, zinc acetate dihydrate, zinc sulfate hydrate and zinc chloride hydrate;
the organic ligand is one of benzimidazole, trimesic acid, 1,3,5-tri (4-carboxyl phenyl) benzene and 2-methylimidazole;
the supporting solvent is one of ammonia water solution and dimethylformamide;
the organic solvent is one of methanol, ethanol, dichloromethane and acetone.
Further, the copper salt, the zinc salt, the organic ligand, the supporting solvent and the organic solvent are respectively copper nitrate hydrate, zinc nitrate dihydrate, trimesic acid, dimethylformamide and ethanol.
Further, the mixture ratio of the copper salt, the zinc salt, the organic ligand, the supporting solvent, the organic solvent and the water is as follows: 1.
Further, the centrifugal separation conditions in S2 are as follows: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled at 8-15 min.
Further, the washing and drying conditions in S3 are as follows: washing the obtained solid with ethanol and deionized water for 3 times respectively, and finally carrying out vacuum drying through an oven, wherein the drying temperature is 180-250 ℃, and the drying time is 5-8 h.
Further, mgH in S4 2 The mass ratio of the metal MOF to the zinc-copper bimetal MOF is 7-12.
Further, the ball milling time in the S4 is 4.5-5.5 h, and the ball milling rotating speed is controlled at 400-500 rpm.
Further, the zinc-copper bimetal MOF and MgH in S4 2 The ball milling is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-to-material ratio is 40-60.
The invention also provides MgH catalyzed by zinc-copper bimetallic MOF prepared by the preparation method 2 A hydrogen storage material.
The invention also provides MgH catalyzed by zinc-copper bimetallic MOF prepared by the preparation method 2 Use of a hydrogen storage material in a fuel cell.
The invention has at least the following beneficial effects:
in the invention, the synthesis process of the bimetallic MOF catalyst is simple, the reaction condition is mild, and the introduction of the zinc-copper bimetallic MOF effectively improves MgH 2 The hydrogen absorption and desorption behaviors of the hydrogen storage material reduce the hydrogen desorption working temperature, and the preparation method of the catalyst is simple and easy to implement and can be widely applied to most hydrogen storage systems.
Drawings
FIG. 1 shows MgH catalyzed by zinc-copper bimetallic MOF according to the invention 2 A PXRD pattern for the hydrogen storage material;
FIG. 2 is MgH catalyzed by zinc-copper bimetallic MOF according to the invention 2 Hydrogen storage material and pure MgH 2 H of (A) to (B) 2 Drawing;
FIG. 3 is MgH catalyzed by zinc-copper bimetallic MOF according to the invention 2 DSC curves of the hydrogen storage material at different temperature rising speeds and corresponding fitting;
FIG. 4 is for pure MgH 2 DSC curves at different ramp rates, and corresponding fits.
Detailed Description
In order that those skilled in the art can better understand the present invention, the following technical solutions are further described with reference to the accompanying drawings and examples.
Example 1
The zinc-copper bimetallic MOF catalyzed MgH of the invention 2 The hydrogen storage material comprises the following raw materials: 22g of a copper salt, 21g of a zinc salt, 43g of an organic ligand, 20g of a supporting solvent, 19g of an organic solvent and 18g of water.
The above-mentioned zinc-copper bimetallic MOF catalyzed MgH 2 The preparation method of the hydrogen storage material comprises the following steps:
s1, uniformly mixing a supporting solvent, an organic solvent and water to obtain a mixture solvent;
s2, sequentially adding copper salt, zinc salt and organic ligand into the mixture solvent, stirring and reacting for 2 hours at room temperature, and performing centrifugal separation to obtain a solid substance;
s3, washing and drying the obtained solid matter to obtain zinc-copper bimetallic MOF;
s4, mixing the dried zinc-copper bimetallic MOF with commercial MgH 2 Mixing and ball milling to obtain the magnesium-based composite hydrogen storage material catalyzed by MOF.
Example 2
The zinc-copper bimetallic MOF catalyzed MgH of the invention 2 The hydrogen storage material comprises the following raw materials: 14g of a copper salt, 12g of a zinc salt, 30g of an organic ligand, 16g of a supporting solvent, 17g of an organic solvent and 13g of water.
The above-described zinc-copper bimetallic MOF catalyzed MgH 2 The preparation method of the hydrogen storage material comprises the following steps:
s1, uniformly mixing a supporting solvent, an organic solvent and water to obtain a mixture solvent;
s2, sequentially adding copper salt, zinc salt and organic ligand into the mixture solvent, stirring and reacting for 4 hours at room temperature, and performing centrifugal separation to obtain a solid substance;
s3, washing and drying the obtained solid matter to obtain zinc-copper bimetallic MOF;
s4, mixing the dried zinc-copper bimetallic MOF with commercial MgH 2 Mixing and ball milling to obtain the MOF catalyzed magnesium-based composite hydrogen storage material.
Example 3
The zinc-copper bimetallic MOF catalyzed MgH of the invention 2 Hydrogen storage materialThe method comprises the following raw materials: 29g of a copper salt, 27g of a zinc salt, 60g of an organic ligand, 31g of a supporting solvent, 32g of an organic solvent and 28g of water.
The above-described zinc-copper bimetallic MOF catalyzed MgH 2 The preparation method of the hydrogen storage material comprises the following steps:
s1, uniformly mixing a supporting solvent, an organic solvent and water to obtain a mixture solvent;
s2, sequentially adding copper salt, zinc salt and organic ligand into the mixture solvent, stirring and reacting for 5 hours at room temperature, and performing centrifugal separation to obtain a solid substance;
s3, washing and drying the obtained solid matter to obtain zinc-copper bimetallic MOF;
s4, mixing the dried zinc-copper bimetallic MOF with commercial MgH 2 Mixing and ball milling to obtain the magnesium-based composite hydrogen storage material catalyzed by MOF.
Example 4
The improvement is based on the embodiment 2:
further, the copper salt is one of copper nitrate hydrate, copper sulfate hydrate or copper chloride hydrate;
the zinc salt is one of zinc nitrate dihydrate, zinc acetate dihydrate, zinc sulfate hydrate or zinc chloride hydrate;
the organic ligand is one of benzimidazole, trimesic acid, 1,3,5-tri (4-carboxyl phenyl) benzene and 2-methylimidazole;
the supporting solvent is one of ammonia water solution and dimethylformamide;
the organic solvent is one of methanol, ethanol, dichloromethane or acetone.
Example 5
The improvement is based on the embodiment 4:
the copper salt, the zinc salt, the organic ligand, the supporting solvent and the organic solvent are respectively copper nitrate hydrate, zinc nitrate dihydrate, trimesic acid, dimethylformamide and ethanol.
Example 6
The improvement is based on the embodiment 2:
further, the mixture ratio of the copper salt, the zinc salt, the organic ligand, the supporting solvent, the organic solvent and the water is as follows: 1.
Example 7
The improvement is carried out on the basis of the embodiment 6:
the mixture ratio of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water is as follows: 1:1:0.80:1.8:0.9:1.
Example 8
The improvement is based on the embodiment 6:
the mixture ratio of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water is as follows: 1:0.83:2:1:100.
Example 9
The improvement is based on the embodiment 6:
the mixture ratio of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water is as follows: 1:1:0.85:2.2:1.1:1.
Example 10
The improvement is based on the embodiment 2:
further, the conditions of the centrifugal separation were: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled to be 8-15 min.
Example 11
The improvement is based on the embodiment 10:
the conditions of the centrifugal separation were: the centrifugal speed is 7000rpm, and the centrifugal time length is controlled at 8min.
Example 12
The improvement is based on the embodiment 10:
the conditions of the centrifugal separation were: the centrifugal speed is 8000rpm, and the centrifugal time is controlled at 10min.
Example 13
The improvement is based on the embodiment 10:
the conditions of the centrifugal separation were: the centrifugal speed is 10000rpm, and the centrifugal time is controlled at 15min.
Example 14
The improvement is based on the embodiment 2:
further, the washing and drying conditions are as follows: washing the obtained solid with ethanol and deionized water for 3 times respectively, and finally carrying out vacuum drying through an oven, wherein the drying temperature is 180-250 ℃, and the drying time is 5-8 h.
Example 15
The improvement is based on the example 14:
the washing and drying conditions are as follows: washing the obtained solid with ethanol and deionized water for 3 times, and vacuum drying in oven at 180 deg.C for 5 hr.
Example 16
The improvement is based on the embodiment 14:
the washing and drying conditions are as follows: washing the obtained solid with ethanol and deionized water for 3 times respectively, and finally performing vacuum drying in an oven at the drying temperature of 200 ℃ for 6h.
Example 17
The improvement is based on the example 14:
the washing and drying conditions are as follows: washing the obtained solid with ethanol and deionized water for 3 times respectively, and finally performing vacuum drying in an oven at the drying temperature of 250 ℃ for 8h.
Example 18
The improvement is based on the embodiment 2:
further, mgH 2 The mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7-12.
Example 19
The improvement is based on the example 18:
MgH 2 the mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7:1.
Example 20
The improvement is based on the example 18:
MgH 2 the mass ratio of the metal MOF to the zinc-copper double metal is 10.
Example 21
The improvement is based on the example 18:
MgH 2 the mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 12.
Example 22
The improvement is based on the embodiment 2:
furthermore, the ball milling time is 4.5 to 5.5 hours, and the ball milling rotating speed is controlled to be 400 to 500rpm.
Example 23
The improvement is based on the embodiment 22:
the ball milling time is 4.5h, and the ball milling rotating speed is controlled at 400rpm.
Example 24
The improvement is based on the embodiment 22:
the ball milling time is 5h, and the ball milling rotating speed is controlled at 450rpm.
Example 25
The improvement is based on the embodiment 22:
the ball milling time is 5.5h, and the ball milling rotating speed is controlled at 500rpm.
Example 26
The improvement is based on the embodiment 2:
further, zinc-copper bimetal MOF and MgH 2 The ball milling is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-to-material ratio is 40-60.
Example 27
The improvement is based on the embodiment 26:
zinc-copper bimetal MOF and MgH 2 The ball milling of (2) was carried out in a hydrogen atmosphere, and the pressure of hydrogen was 1.8MPa, the ball-to-feed ratio was 40.
Example 28
The improvement is based on the embodiment 26:
zinc-copper bimetal MOF and MgH 2 The ball milling of (2) is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 2MPa, and the ball-to-material ratio is 50.
Example 29
The improvement is based on the embodiment 26:
zinc-copper bimetal MOF and MgH 2 The ball milling of (2) was carried out in a hydrogen atmosphere, and the pressure of hydrogen was 2.2MPa, the ball-to-feed ratio was 60.
Example 30
On the basis of example 8:
in a 250mL glass beaker, dimethylformamide, ethanol, and water were mixed in a volume of 1. Subsequently, 5g of trimesic acid (H3 BTC), 5g of Zn (NO 3) 2. 2.5H2O and 5g of Cu (NO 3) 2. 2.5H2O were dissolved in the solvent mixture with continuous stirring. The resulting solution was then transferred to a glass vial, sealed and placed in an oven heated at 85 ℃ for 20 hours. And washing the obtained solid precipitate with ethanol and deionized water for 3 times respectively, then placing the solid precipitate in an oven at 80 ℃ for vacuum drying to obtain the zinc-copper bimetallic MOF material, and sealing and storing the zinc-copper bimetallic MOF material for later use.
Respectively weighing 0.9gMgH 2 And 0.1g of the zinc-copper bimetallic MOF prepared above was placed in a ball mill, followed by addition of 50g of ball milling beads. Ball milling is carried out for 5h at the rotating speed of 450rpm under the hydrogen pressure of 2 MPa. Obtaining MgH catalyzed by zinc-copper bimetal MOF after ball milling 2 A hydrogen storage material. Testing of MgH catalyzed by Zinc-copper bimetallic MOF 2 PXRD of the hydrogen storage material is shown in FIG. 1.
MgH prepared in inventive example 30 2 The hydrogen storage material is compounded, and the hydrogen absorption dynamic behavior of the compound material is tested: under the condition that the initial hydrogen pressure is 2.5MPa, the dynamic behavior of hydrogen absorption in 3600s of the composite material after complete dehydrogenation is tested by adopting Sievert type PCT testing equipment at 300 ℃, and the result is shown in figure 2, and MgH catalyzed by bimetallic MOF 2 The hydrogen absorption amount of the hydrogen storage material is far larger than that of pure MgH 2 At 60s, the maximum hydrogen absorption can reach 4.5wt%, and pure MgH at this time 2 Only 0.7wt.%, bimetallic MOF catalyzed MgH 2 The hydrogen storage material has better hydrogen absorption reaction rate, can complete hydrogen absorption in 60s, and has shorter hydrogen absorption time than pure MgH 2 The material shows that the introduction of the bimetallic MOF can effectively improve MgH 2 Hydrogen sorption kinetics of the hydrogen storage material.
In the embodiment of the invention, different samples are studied on the hydrogen evolution performance by adopting a differential scanning calorimeter at different temperature rising speeds, the obtained data are fitted by using a Kissinger method, the fitting result is shown in figures 3 and 4, and MgH catalyzed by ZnCu bimetal MOF 2 The hydrogen storage material has lower hydrogen desorption activation energy, and shows that the introduction of the bimetallic MOF can improve MgH 2 Hydrogen storage materialAnd the hydrogen release temperature is reduced, and in addition, the invention also proves that the catalytic effect of the bimetallic site is superior to that of a single catalytic site.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (12)
1. Zinc-copper bimetallic MOF catalyzed MgH 2 The hydrogen storage material is characterized by comprising the following components in parts by weight: 14 to 29 parts of copper salt, 12 to 27 parts of zinc salt, 30 to 60 parts of organic ligand, 16 to 31 parts of supporting solvent, 17 to 32 parts of organic solvent and 13 to 28 parts of water.
2. The zinc-copper bimetallic MOF catalyzed MgH of claim 1 2 The preparation method of the hydrogen storage material is characterized by comprising the following steps:
s1, uniformly mixing a supporting solvent, an organic solvent and water of the components to obtain a mixture solvent;
s2, sequentially adding copper salt, zinc salt and organic ligand of the components into the mixture solvent, stirring and reacting for 2-5 h at room temperature, and performing centrifugal separation to obtain a solid substance;
s3, washing and drying the obtained solid matter to obtain zinc-copper bimetallic MOF;
s4, mixing the dried zinc-copper bimetallic MOF with commercial MgH 2 Mixing and ball milling to obtain the magnesium-based composite hydrogen storage material catalyzed by MOF.
3. The method according to claim 2, wherein the copper salt is one of copper nitrate hydrate, copper sulfate hydrate, and copper chloride hydrate;
the zinc salt is one of zinc nitrate dihydrate, zinc acetate dihydrate, zinc sulfate hydrate and zinc chloride hydrate;
the organic ligand is one of benzimidazole, trimesic acid, 1,3,5-tri (4-carboxyl phenyl) benzene and 2-methylimidazole;
the supporting solvent is one of ammonia water solution and dimethylformamide;
the organic solvent is one of methanol, ethanol, dichloromethane and acetone.
4. The method according to claim 3, wherein the copper salt, the zinc salt, the organic ligand, the supporting solvent and the organic solvent are respectively copper nitrate hydrate, zinc nitrate dihydrate, trimesic acid, dimethylformamide and ethanol.
5. The method according to claim 2, wherein the copper salt, the zinc salt, the organic ligand, the supporting solvent, the organic solvent and the water are mixed in a ratio of: 1.
6. The method according to claim 2, wherein the conditions for the centrifugation in S2 are: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled to be 8-15 min.
7. The method according to claim 2, wherein the washing and drying conditions in S3 are as follows: washing the obtained solid with ethanol and deionized water for 3 times respectively, and finally carrying out vacuum drying through an oven, wherein the drying temperature is 180-250 ℃, and the drying time is 5-8 h.
8. The method of claim 2, wherein: mgH in S4 2 The mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7-12.
9. The method of claim 2, wherein: the ball milling time in the S4 is 4.5-5.5 h, and the ball milling rotating speed is controlled at 400-500 rpm.
10. The method of claim 2, wherein: the zinc-copper bimetal MOF and MgH in S4 2 The ball milling is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-to-material ratio is 40-60.
11. Zinc-copper bimetallic MOF catalyzed MgH prepared by the preparation method of any one of claims 2 to 10 2 A hydrogen storage material.
12. Zinc-copper bimetallic MOF catalyzed MgH prepared by the preparation method of any one of claims 2 to 10 2 Use of a hydrogen storage material in a fuel cell.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116174041A (en) * | 2022-12-01 | 2023-05-30 | 理工清科(重庆)先进材料研究院有限公司 | Graphene-supported Ni-MOF hydrogen storage catalyst, and preparation method and application thereof |
| CN117402023A (en) * | 2023-10-17 | 2024-01-16 | 安徽理工大学 | Active damage material with both mechanical strength and deflagration performance and preparation method thereof |
| CN117658061A (en) * | 2023-12-05 | 2024-03-08 | 中国船舶集团有限公司第七一八研究所 | Catalyst doped magnesium-based hydrogen storage material and preparation method thereof |
| CN118954427A (en) * | 2024-07-15 | 2024-11-15 | 兰州理工大学 | A binary and multi-component TM-MOFs@MgH2 composite hydrogen storage material and preparation method thereof |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050126663A1 (en) * | 2003-12-11 | 2005-06-16 | Fetcenko Michael A. | Catalyzed hydrogen desorption in Mg-based hydrogen storage material and methods for production thereof |
| 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 |
| US7201789B1 (en) * | 1997-10-22 | 2007-04-10 | Hydro-Quebec | Nanocomposites with activated interfaces prepared by mechanical grinding of magnesium hydrides and use for storing hydrogen |
| KR20080024976A (en) * | 2006-09-13 | 2008-03-19 | 재단법인서울대학교산학협력재단 | Organic-transition metal complex as hydrogen storage material and preparation method thereof |
| US20100044478A1 (en) * | 2008-08-25 | 2010-02-25 | Industrial Technology Research Institute | Nanotization of magnesium-based hydrogen storage material |
| US20100160149A1 (en) * | 2008-12-19 | 2010-06-24 | Gkss-Forschungszentrum Geesthacht Gmbh | Method of activating or regenerating a hydrogen storage material |
| US20100266488A1 (en) * | 2007-12-10 | 2010-10-21 | Universite Joseph Fourier | Hydrogen storage material made from magnesium hydride |
| CN103668070A (en) * | 2013-12-05 | 2014-03-26 | 中盈长江国际新能源投资有限公司 | Magnesium-base hydrogen storage film and preparation method thereof |
| WO2015032158A1 (en) * | 2013-09-05 | 2015-03-12 | 华南理工大学 | Magnesium-based hydrogen storage material and preparation method therefor |
| CN106809803A (en) * | 2017-02-22 | 2017-06-09 | 长沙理工大学 | A kind of MgH2Base hydrogen storage composite and preparation method thereof |
| US9828245B1 (en) * | 2017-02-07 | 2017-11-28 | Kuwait Institute For Scientific Research | Method of synthesizing MgH2/Ni nanocomposites |
| CN107573233A (en) * | 2017-09-05 | 2018-01-12 | 桂林电子科技大学 | A kind of cobalt-based MOFs materials and its preparation method and application |
| CN110526208A (en) * | 2019-09-04 | 2019-12-03 | 上海交通大学 | The preparation method of Mg-based composite hydrogen storage material based on MOFs material nano confinement |
| KR20200111317A (en) * | 2019-03-18 | 2020-09-29 | 현대자동차주식회사 | Solid state hydrogen storage system |
| CN112850640A (en) * | 2021-01-16 | 2021-05-28 | 南开大学 | Preparation method of metal organic framework doped magnesium-based hydride |
| US20210198107A1 (en) * | 2019-04-10 | 2021-07-01 | Zhejiang University | Nano magnesium hydride and in-situ preparation method thereof |
| EP3932540A2 (en) * | 2020-07-01 | 2022-01-05 | Indian Oil Corporation Limited | Zinc based metal organic frameworks (zit) with mixed ligands for hydrogen storage |
| CN114479094A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Metal-organic framework hydrogen storage material and preparation method and application thereof |
-
2022
- 2022-08-31 CN CN202211053007.0A patent/CN115367700B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7201789B1 (en) * | 1997-10-22 | 2007-04-10 | Hydro-Quebec | Nanocomposites with activated interfaces prepared by mechanical grinding of magnesium hydrides and use for storing hydrogen |
| US20050126663A1 (en) * | 2003-12-11 | 2005-06-16 | Fetcenko Michael A. | Catalyzed hydrogen desorption in Mg-based hydrogen storage material and methods for production thereof |
| 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 |
| KR20080024976A (en) * | 2006-09-13 | 2008-03-19 | 재단법인서울대학교산학협력재단 | Organic-transition metal complex as hydrogen storage material and preparation method thereof |
| US20100266488A1 (en) * | 2007-12-10 | 2010-10-21 | Universite Joseph Fourier | Hydrogen storage material made from magnesium hydride |
| US20100044478A1 (en) * | 2008-08-25 | 2010-02-25 | Industrial Technology Research Institute | Nanotization of magnesium-based hydrogen storage material |
| US20100160149A1 (en) * | 2008-12-19 | 2010-06-24 | Gkss-Forschungszentrum Geesthacht Gmbh | Method of activating or regenerating a hydrogen storage material |
| WO2015032158A1 (en) * | 2013-09-05 | 2015-03-12 | 华南理工大学 | Magnesium-based hydrogen storage material and preparation method therefor |
| CN103668070A (en) * | 2013-12-05 | 2014-03-26 | 中盈长江国际新能源投资有限公司 | Magnesium-base hydrogen storage film and preparation method thereof |
| US9828245B1 (en) * | 2017-02-07 | 2017-11-28 | Kuwait Institute For Scientific Research | Method of synthesizing MgH2/Ni nanocomposites |
| CN106809803A (en) * | 2017-02-22 | 2017-06-09 | 长沙理工大学 | A kind of MgH2Base hydrogen storage composite and preparation method thereof |
| CN107573233A (en) * | 2017-09-05 | 2018-01-12 | 桂林电子科技大学 | A kind of cobalt-based MOFs materials and its preparation method and application |
| KR20200111317A (en) * | 2019-03-18 | 2020-09-29 | 현대자동차주식회사 | Solid state hydrogen storage system |
| US20210198107A1 (en) * | 2019-04-10 | 2021-07-01 | Zhejiang University | Nano magnesium hydride and in-situ preparation method thereof |
| CN110526208A (en) * | 2019-09-04 | 2019-12-03 | 上海交通大学 | The preparation method of Mg-based composite hydrogen storage material based on MOFs material nano confinement |
| EP3932540A2 (en) * | 2020-07-01 | 2022-01-05 | Indian Oil Corporation Limited | Zinc based metal organic frameworks (zit) with mixed ligands for hydrogen storage |
| CN114479094A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Metal-organic framework hydrogen storage material and preparation method and application thereof |
| CN112850640A (en) * | 2021-01-16 | 2021-05-28 | 南开大学 | Preparation method of metal organic framework doped magnesium-based hydride |
Non-Patent Citations (3)
| Title |
|---|
| 卢国俭;周仕学;雷桂芹;吴峻青;: "大容量镁基储氢材料及其储氢性能", 现代化工, no. 04 * |
| 王海晨: "Cu掺杂MgH2与Ti/Vli修饰LiBH4及纯LiCa(AlH4)3的储氢性能理论研究", 中国博士学位论文全文数据库, pages 1 - 140 * |
| 蔡浩;顾昊;朱云峰;李李泉;: "催化剂对镁基储氢材料储氢性能影响的研究进展", 材料导报, no. 11 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116174041A (en) * | 2022-12-01 | 2023-05-30 | 理工清科(重庆)先进材料研究院有限公司 | Graphene-supported Ni-MOF hydrogen storage catalyst, and preparation method and application thereof |
| CN117402023A (en) * | 2023-10-17 | 2024-01-16 | 安徽理工大学 | Active damage material with both mechanical strength and deflagration performance and preparation method thereof |
| CN117658061A (en) * | 2023-12-05 | 2024-03-08 | 中国船舶集团有限公司第七一八研究所 | Catalyst doped magnesium-based hydrogen storage material and preparation method thereof |
| CN118954427A (en) * | 2024-07-15 | 2024-11-15 | 兰州理工大学 | A binary and multi-component TM-MOFs@MgH2 composite hydrogen storage material and preparation method thereof |
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