CN115367700B - MgH catalyzed by zinc-copper bimetallic MOF 2 Hydrogen storage material, preparation method and application thereof - Google Patents
MgH catalyzed by zinc-copper bimetallic MOF 2 Hydrogen storage material, preparation method and application thereof Download PDFInfo
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- CN115367700B CN115367700B CN202211053007.0A CN202211053007A CN115367700B CN 115367700 B CN115367700 B CN 115367700B CN 202211053007 A CN202211053007 A CN 202211053007A CN 115367700 B CN115367700 B CN 115367700B
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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
- 239000013246 bimetallic metal–organic framework Substances 0.000 title claims abstract description 70
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011232 storage material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 150000001879 copper Chemical class 0.000 claims abstract description 27
- 239000013110 organic ligand Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 150000003751 zinc Chemical class 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 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 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 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 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 7
- 238000000034 method Methods 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 4
- VWYGTDAUKWEPCZ-UHFFFAOYSA-L dichlorocopper;hydrate Chemical compound O.Cl[Cu]Cl VWYGTDAUKWEPCZ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 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 4
- CHSMNMOHKSNOKO-UHFFFAOYSA-L zinc;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Zn+2] CHSMNMOHKSNOKO-UHFFFAOYSA-L 0.000 claims description 4
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 description 27
- 238000005119 centrifugation Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000004913 activation Effects 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
- 239000010949 copper Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000007789 sealing 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
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Abstract
The invention discloses MgH catalyzed by zinc-copper bimetallic MOF 2 The hydrogen storage material comprises the following components in parts by weight: 14-29 parts of copper salt, 12-27 parts of zinc salt, 30-60 parts of organic ligand, 16-31 parts of supporting solvent, 17-32 parts of organic solvent and 13-28 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 a mixture solvent, stirring at room temperature for reaction for 2-5 h, and centrifugally separating to obtain a solid substance; s3, washing and drying the obtained solid substance to obtain the zinc-copper bimetallic MOF; s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing and ball milling to obtain the MOF catalyzed magnesium-based composite hydrogen storage material. The invention also discloses the MgH 2 The application of the 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 bimetallic MOF 2 Hydrogen storage materials, methods of making and uses thereof.
Background
Hydrogen is currently considered one of the most promising energy carriers. The safe and efficient hydrogen storage is a main requirement for realizing the practical application of hydrogen energy. Therefore, it is important to design a safe and effective hydrogen storage material for hydrogen fuel cell automotive applications. For decades, as a representative simple goldIs a hydride, mgH 2 Has the advantages of high hydrogen storage density (7.6 wt%), good reversibility, environmental friendliness, good economic performance and the like. However, mgH due to its thermodynamic stability and slow kinetics 2 The high temperature of hydrogen absorption/release prevents its practical use in fuel cells.
Catalyst doping can reduce MgH 2 The working temperature for absorbing/releasing hydrogen effectively relieves 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, etc. However, the catalyst tends to agglomerate during continuous, intense ball milling and subsequent cycles, resulting in reduced exposed catalytic sites and severely impacted catalytic performance. Therefore, the development of an excellent catalyst having a uniform distribution is of great importance for maintaining a high catalytic activity of the hydrogen storage material.
Disclosure of Invention
The invention aims at: mgH providing zinc copper bimetallic MOF catalysis 2 Hydrogen storage material, preparation method and application thereof for realizing improvement of MgH 2 The synthesis process of the bimetallic MOF catalyst provided by the invention is simple, the reaction condition is mild, and the introduction of the zinc-copper bimetallic MOF effectively improves MgH 2 The hydrogen absorbing and releasing behavior of the hydrogen storage material reduces the working temperature of hydrogen releasing, and the preparation method of the catalyst is simple and feasible, and can be widely applied to most hydrogen storage systems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
MgH catalyzed by zinc-copper bimetallic MOF 2 The hydrogen storage material comprises the following components in parts by weight: 14-29 parts of copper salt, 12-27 parts of zinc salt, 30-60 parts of organic ligand, 16-31 parts of supporting solvent, 17-32 parts of organic solvent and 13-28 parts of water.
MgH catalyzed by the zinc-copper bimetallic MOF 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 a mixture solvent, stirring at room temperature for reaction for 2-5 h, and centrifugally separating to obtain a solid substance;
s3, washing and drying the obtained solid substance to obtain the zinc-copper bimetallic MOF;
s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing and ball milling to obtain the MOF catalyzed magnesium-based composite hydrogen storage material.
Further, 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-carboxyphenyl) benzene and 2-methylimidazole;
the supporting solvent is one of ammonia water solution and dimethylformamide;
the organic solvent is one of methanol, ethanol, methylene dichloride and acetone.
Further, the copper salt, zinc salt, organic ligand, supporting solvent and organic solvent are copper nitrate hydrate, zinc nitrate dihydrate, trimesic acid, dimethylformamide and ethanol, respectively.
Further, the proportions of the copper salt, the zinc salt, the organic ligand, the supporting solvent, the organic solvent and the water are as follows: 1:1:0.80-0.85:1.8-2.2:0.9-1.1:1.
Further, the conditions for centrifugation in S2 are: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled to 8-15 min.
Further, the conditions of washing and drying in S3 are as follows: and respectively washing the obtained solid with ethanol and deionized water for 3 times, and finally drying in vacuum through an oven at the drying temperature of 180-250 ℃ for 5-8 hours.
Further, mgH in the S4 2 Quality of MOF with zinc copper bimetalThe weight ratio is 7-12:1.
Further, the ball milling time in the step S4 is 4.5-5.5 hours, and the ball milling rotating speed is controlled at 400-500 rpm.
Further, the zinc-copper bimetallic MOF and MgH in the S4 2 The ball milling of the ball mill is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-material ratio is 40-60:1.
The invention also provides MgH catalyzed by the zinc-copper bimetallic MOF prepared by the preparation method 2 A hydrogen storage material.
The invention also provides MgH catalyzed by the zinc-copper bimetallic MOF prepared by the preparation method 2 The 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 absorbing and releasing behavior of the hydrogen storage material reduces the working temperature of hydrogen releasing, and the preparation method of the catalyst is simple and feasible, and can be widely applied to most hydrogen storage systems.
Drawings
FIG. 1 shows MgH catalyzed by the zinc-copper bimetallic MOF of the invention 2 PXRD pattern of hydrogen storage material;
FIG. 2 shows MgH catalyzed by the zinc-copper bimetallic MOF of the invention 2 Hydrogen storage material and pure MgH 2 H of (2) 2 Sucking the attached drawings;
FIG. 3 shows MgH catalyzed by the zinc-copper bimetallic MOF of the invention 2 DSC curves of the hydrogen storage material at different heating speeds and corresponding fitting;
FIG. 4 is a diagram of para-pure MgH 2 DSC curves at different ramp rates, and corresponding fits.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following technical scheme of the present invention will be further described with reference to the accompanying drawings and examples.
Example 1
MgH catalyzed by zinc-copper bimetallic MOF of the invention 2 The hydrogen storage material comprises the following raw materials: 22g copper salt, 21g zinc salt, 43g organic ligand, 20g supporting solvent, 19g organic solvent and 18g water.
MgH catalyzed by the zinc-copper bimetallic MOF 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 at room temperature for reaction for 2 hours, and centrifugally separating to obtain a solid substance;
s3, washing and drying the obtained solid substance to obtain the zinc-copper bimetallic MOF;
s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing and ball milling to obtain the MOF catalyzed magnesium-based composite hydrogen storage material.
Example 2
MgH catalyzed by zinc-copper bimetallic MOF of the invention 2 The hydrogen storage material comprises the following raw materials: 14g copper salt, 12g zinc salt, 30g organic ligand, 16g supporting solvent, 17g organic solvent and 13g water.
MgH catalyzed by the zinc-copper bimetallic MOF 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 at room temperature for reaction for 4 hours, and centrifugally separating to obtain a solid substance;
s3, washing and drying the obtained solid substance to obtain the zinc-copper bimetallic MOF;
s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing and ball milling to obtain the MOF catalyzed magnesium-based composite hydrogen storage material.
Example 3
MgH catalyzed by zinc-copper bimetallic MOF of the invention 2 The hydrogen storage material comprises the following raw materials: 29g copper salt, 27g zinc salt, 60g organic ligand, 31g supporting solvent, 32g organic solvent and 28g water.
MgH catalyzed by the zinc-copper bimetallic MOF 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 at room temperature for reaction for 5 hours, and centrifugally separating to obtain a solid substance;
s3, washing and drying the obtained solid substance to obtain the zinc-copper bimetallic MOF;
s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing and ball milling to obtain the MOF catalyzed magnesium-based composite hydrogen storage material.
Example 4
Improvement on the basis of example 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-carboxyphenyl) 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 respectively.
Example 5
Improvement on the basis of example 4:
the copper salt, zinc salt, organic ligand, supporting solvent and organic solvent are copper nitrate hydrate, zinc nitrate dihydrate, trimesic acid, dimethylformamide and ethanol respectively.
Example 6
Improvement on the basis of example 2:
further, the proportions of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water are as follows: 1:1:0.80-0.85:1.8-2.2:0.9-1.1:1.
Example 7
Improvement over example 6:
the proportions of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water are as follows: 1:1:0.80:1.8:0.9:1.
Example 8
Improvement over example 6:
the proportions of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water are as follows: 1:0.83:2:1:100.
Example 9
Improvement over example 6:
the proportions of copper salt, zinc salt, organic ligand, supporting solvent, organic solvent and water are as follows: 1:1:0.85:2.2:1.1:1.
Example 10
Improvement on the basis of example 2:
further, the conditions for centrifugation were: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled to 8-15 min.
Example 11
Improvement over example 10:
the conditions for centrifugation were: the centrifugation speed was 7000rpm and the centrifugation time was controlled at 8min.
Example 12
Improvement over example 10:
the conditions for centrifugation were: the centrifugal speed is 8000rpm, and the centrifugal time is controlled to be 10min.
Example 13
Improvement over example 10:
the conditions for centrifugation were: the centrifugation speed was 10000rpm and the centrifugation time was controlled at 15min.
Example 14
Improvement on the basis of example 2:
further, the conditions of washing and drying are: the obtained solid is washed for 3 times by ethanol and deionized water respectively, and finally is dried in vacuum by an oven at the drying temperature of 180-250 ℃ for 5-8 hours.
Example 15
Improvement over example 14:
the washing and drying conditions are as follows: the obtained solid is washed for 3 times by ethanol and deionized water respectively, and finally is dried in vacuum by an oven at the drying temperature of 180 ℃ for 5 hours.
Example 16
Improvement over example 14:
the washing and drying conditions are as follows: the obtained solid was washed with ethanol and deionized water for 3 times, respectively, and finally dried in vacuum by an oven at 200℃for 6 hours.
Example 17
Improvement over example 14:
the washing and drying conditions are as follows: the obtained solid was washed with ethanol and deionized water for 3 times, respectively, and finally dried in vacuum by an oven at a drying temperature of 250 ℃ for 8 hours.
Example 18
Improvement on the basis of example 2:
further, mgH 2 The mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7-12:1.
Example 19
Improvement over example 18:
MgH 2 the mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7:1.
Example 20
Improvement over example 18:
MgH 2 the mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 10:1.
Example 21
Improvement over example 18:
MgH 2 the mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 12:1.
Example 22
Improvement on the basis of example 2:
further, the ball milling time is 4.5-5.5 h, and the ball milling rotating speed is controlled at 400-500 rpm.
Example 23
Improvement over example 22:
the ball milling time was 4.5 hours, and the ball milling rotational speed was controlled at 400rpm.
Example 24
Improvement over example 22:
the ball milling time was 5 hours and the ball milling rotational speed was controlled at 450rpm.
Example 25
Improvement over example 22:
the ball milling time was 5.5 hours, and the ball milling rotational speed was controlled at 500rpm.
Example 26
Improvement on the basis of example 2:
further, zinc-copper bimetallic MOF and MgH 2 The ball milling of the ball mill is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-material ratio is 40-60:1.
Example 27
Improvement over example 26:
zinc-copper bimetallic MOF and MgH 2 The ball milling of (2) is carried out in a hydrogen atmosphere, the pressure of hydrogen is 1.8MPa, and the ball-to-material ratio is 40:1.
Example 28
Improvement over example 26:
zinc-copper bimetallic MOF and MgH 2 The ball milling of (2) is carried out in a hydrogen atmosphere, the pressure of hydrogen is 2MPa, and the ball-to-material ratio is 50:1.
Example 29
Improvement over example 26:
zinc-copper bimetallic MOF and MgH 2 The ball milling of (2) is carried out in a hydrogen atmosphere, the pressure of hydrogen is 2.2MPa, and the ball-to-material ratio is 60:1.
Example 30
Based on example 8:
in a 250mL glass beaker, dimethylformamide, ethanol, and water were mixed in a volume of 1:1:1 to prepare a solvent mixture. 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 bottle, sealed and placed in an oven and heated at 85 ℃ for 20 hours. And respectively washing the obtained solid precipitate with ethanol and deionized water for 3 times, and then placing the solid precipitate in an oven at 80 ℃ for vacuum drying to obtain the zinc-copper bimetallic MOF material, and sealing and preserving the zinc-copper bimetallic MOF material for standby.
Weighing 0.9g MgH respectively 2 And 0.1g of the zinc copper bimetallic MOF prepared above were placed in a ball mill followed by 50g of ball-milling beads. Ball milling was carried out at 450rpm for 5h under a hydrogen pressure of 2 MPa. Ball milling to obtain MgH catalyzed by zinc-copper bimetallic MOF 2 A hydrogen storage material. Testing zinc copper bimetallic MOF catalyzed MgH 2 PXRD of the hydrogen storage material is shown in fig. 1.
MgH prepared in example 30 of the present invention 2 And (3) carrying out a composite hydrogen absorption kinetic behavior test on the composite hydrogen storage material: under the condition of initial hydrogen pressure of 2.5MPa, the composite material after complete dehydrogenation is tested for hydrogen absorption kinetics in 3600s at 300 ℃ by using Sievert PCT test equipment, and the result is shown in figure 2, wherein the MgH is catalyzed by bimetallic MOF 2 The hydrogen absorption amount of the hydrogen storage material is far greater than that of pure MgH 2 At 60s, the maximum hydrogen absorption amount can reach 4.5wt percent, and the pure MgH can be obtained 2 Only 0.7wt.% of bimetallic MOF catalyzed MgH 2 The hydrogen storage material shows better hydrogen absorption reaction rate, can absorb hydrogen in 60s, and has shorter hydrogen absorption time than pure MgH 2 Material shows that the introduction of the bimetallic MOF can effectively improve MgH 2 Kinetics of hydrogen absorption of hydrogen storage materials.
In the embodiment of the invention, under different heating rates, different samples are researched by adopting a differential scanning calorimeter, 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 bimetallic MOF is used 2 The hydrogen storage material has lower hydrogen release activation energy, which indicates that the introduction of the bimetallic MOF can improve MgH 2 The invention also proves that the catalysis effect of the bimetallic site is superior to that of a single catalysis siteAnd (5) a dot.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and 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 and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (5)
1. MgH catalyzed by zinc-copper bimetallic MOF 2 The hydrogen storage material is characterized by comprising the following components in parts by weight: 14-29 parts of copper salt, 12-27 parts of zinc salt, 30-60 parts of organic ligand, 16-31 parts of supporting solvent, 17-32 parts of organic solvent and 13-28 parts of water;
MgH catalyzed by the zinc-copper bimetallic MOF 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 a mixture solvent, 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-carboxyphenyl) benzene and 2-methylimidazole; the supporting solvent is one of ammonia water solution and dimethylformamide; the organic solvent is one of methanol, ethanol, methylene dichloride and acetone; the copper salt, the zinc salt, the organic ligand, the supporting solvent, the organic solvent and the water are prepared from the following components: 1:1:0.80-0.85:1.8-2.2:0.9-1.1:1; stirring and reacting for 2-5 h at room temperature, and centrifugally separating the mixture: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled to 8-15 min; obtaining a solid substance;
s3, washing and drying the obtained solid substance, respectively washing the obtained solid substance with ethanol and deionized water for 3 times, and finally drying the solid substance in vacuum through an oven at the drying temperature of 180-250 ℃ for 5-8 hours; obtaining a zinc-copper bimetallic MOF;
s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing ball milling, mgH 2 The mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7-12:1; zinc-copper bimetallic MOF and MgH 2 The ball milling of the ball mill is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-material ratio is 40-60:1; the ball milling time is 4.5-5.5 h, and the ball milling rotating speed is controlled at 400-500 rpm; thus obtaining the MOF catalyzed magnesium-based composite hydrogen storage material.
2. Zinc copper bimetallic MOF catalyzed MgH according to 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 a mixture solvent, 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-carboxyphenyl) benzene and 2-methylimidazole; the supporting solvent is one of ammonia water solution and dimethylformamide; the organic solvent is one of methanol, ethanol, methylene dichloride and acetone; the copper salt, the zinc salt, the organic ligand, the supporting solvent, the organic solvent and the water are prepared from the following components: 1:1:0.80-0.85:1.8-2.2:0.9-1.1:1; stirring and reacting for 2-5 h at room temperature, and centrifugally separating the mixture: the centrifugal speed is 7000-10000 rpm, and the centrifugal time is controlled to 8-15 min; obtaining a solid substance;
s3, washing and drying the obtained solid substance, respectively washing the obtained solid substance with ethanol and deionized water for 3 times, and finally drying the solid substance in vacuum through an oven at the drying temperature of 180-250 ℃ for 5-8 hours; obtaining a zinc-copper bimetallic MOF;
s4, drying the obtained zinc-copper bimetallic MOF and commercialized MgH 2 Mixing ball milling, mgH 2 The mass ratio of the zinc-copper bimetallic MOF to the zinc-copper bimetallic MOF is 7-12:1; zinc-copper bimetallic MOF and MgH 2 The ball milling of the ball mill is carried out in a hydrogen atmosphere, the pressure of the hydrogen is 1.8-2.2 MPa, and the ball-material ratio is 40-60:1; the ball milling time is 4.5-5.5 h, and the ball milling rotating speed is controlled at 400-500 rpm; thus obtaining the MOF catalyzed magnesium-based composite hydrogen storage material.
3. The method of claim 2, wherein the copper salt, zinc salt, organic ligand, supporting solvent and organic solvent are copper nitrate hydrate, zinc nitrate dihydrate, trimesic acid, dimethylformamide and ethanol, respectively.
4. The zinc-copper bimetallic MOF catalyzed MgH prepared by the preparation method of claim 2 2 A hydrogen storage material.
5. The zinc-copper bimetallic MOF catalyzed MgH prepared by the preparation method of claim 2 2 The use of a hydrogen storage material in a fuel cell.
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