CN117430082A - Magnesium-based hydrogen storage material and preparation method thereof - Google Patents
Magnesium-based hydrogen storage material and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000001257 hydrogen Substances 0.000 title claims abstract description 72
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 72
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011232 storage material Substances 0.000 title claims abstract description 51
- 239000011777 magnesium Substances 0.000 title claims abstract description 49
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 33
- 239000002071 nanotube Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000001238 wet grinding Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims 1
- 238000000498 ball milling Methods 0.000 description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000002105 nanoparticle Substances 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910012375 magnesium hydride Inorganic materials 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910019080 Mg-H Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of magnesium-based hydrogen storage materials, in particular to a magnesium-based hydrogen storage material and a preparation method thereof. The invention provides a magnesium-based hydrogen storage material, which comprises MgH 2 And a modifying agent; the modifier comprises TiO 2 Nanotubes or bismuth oxyhalides. The magnesium-based hydrogen storage material provided by the invention can be dehydrogenated at a lower temperature.
Description
Technical Field
The invention relates to the technical field of magnesium-based hydrogen storage materials, in particular to a magnesium-based hydrogen storage material and a preparation method thereof.
Background
Hydrogen is widely focused by people as a renewable energy source with high efficiency, cleanliness and high energy density, plays a very critical role in energy conversion in China, is considered as one of secondary energy sources with research and development potential, and the technical problem of hydrogen energy storage restricts the large-scale application of the hydrogen energy source. MgH (MgH) 2 As a solid hydrogen storage material, the material has the advantages of higher hydrogen storage capacity (7.6 wt%), low cost, rich magnesium element storage and the like, and is a hydrogen storage material with very development and research prospects. However, magnesium hydride has higher thermodynamic stability, and the high activation energy required for dehydrogenation reaction, so that magnesium hydride as a hydrogen storage material needs higher dehydrogenation temperature, which limits the practical application of the magnesium hydride.
Disclosure of Invention
In view of the above, the present invention aims to provide a magnesium-based hydrogen storage material and a preparation method thereof. The magnesium-based hydrogen storage material provided by the invention has low dehydrogenation temperature.
In order to achieve the above object, the present invention provides a magnesium-based hydrogen storage material;
the invention provides a magnesium-based hydrogen storage material, which comprises MgH 2 And a modifying agent;
the modifier comprises TiO 2 Nanotubes or bismuth oxyhalides.
Preferably, the MgH 2 And the mass ratio of the modifier is 100: 1-12.
Preferably, the TiO 2 The specific surface area of the nanotube is 200-350 m 2 /g。
Preferably, the average particle size of the bismuth oxyhalide is 1-3 mu m.
Preferably, the magnesium-based hydrogen storage material has an average particle diameter of 1-3 μm.
The invention also provides a preparation method of the magnesium-based hydrogen storage material, which comprises the following steps:
MgH is processed 2 And mixing with a modifier, and sequentially carrying out wet grinding and drying to obtain the magnesium-based hydrogen storage material.
Preferably, the wet-grinding medium is one or two of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether.
Preferably, the ball material ratio of the wet grinding is (30-60): 1.
preferably, the ball milling rotating speed of the wet milling is 400-800 r/min, and the ball milling time is 3-24 h.
The invention provides a magnesium-based hydrogen storage material, which comprises MgH 2 And a modifying agent; the modifier comprises TiO 2 Nanotubes or bismuth oxyhalides. The external surface of the bismuth oxyhalide molecule exposes a large amount of Bi atoms, and the strong electronegativity of the atoms between the bismuth oxyhalide molecule and halogen can reduce the electron density of the Bi surface, so that the empty orbitals of Bi can provide rich polar active sites more easily, and the adsorption and catalytic performances of the bismuth oxyhalide molecule are improved, therefore, the BiOX has stronger binding capacity on magnesium hydride, promotes the breakage of Mg-H bonds, and promotes the decomposition of the magnesium hydride to release hydrogen.
Furthermore, the invention provides TiO 2 The nano-tube titanium dioxide nano-tube hollow structure hasHigh specific surface area, making TiO 2 Catalyst and MgH 2 The contact is more compact, and the interface of the nanotube surface is rich to expose atoms, which is used for catalyzing MgH 2 Cracking decomposition provides rich active sites; the highly open pore structure of the nano tube is beneficial to H in the catalytic reaction process 2 The transmission of the catalyst is enhanced; tiO (titanium dioxide) 2 The surface has rich oxygen vacancies, and electrons are changed from Mg-H to TiO in the dehydrogenation process 2 Transfer promotes the breakage of Mg-H bond, and is beneficial to dehydrogenation.
Drawings
FIG. 1 is a TiO film prepared in example 1 2 XRD pattern of nanotubes;
FIG. 2 is a graph of MgH of comparative example 1 2 8K/min DSC;
FIG. 3 is a comparative example 2 MgH 2 -TiO 2 8K/min DSC;
FIG. 4 is a schematic diagram of MgH of example 4 2 -TiO 2 (magnesium-based hydrogen storage material) 8K/min DSC;
FIG. 5 is a schematic diagram of MgH of example 4 2 -TiO 2 (magnesium-based hydrogen storage material) hydrogen desorption profile;
FIG. 6 is a BiOBr XRD pattern prepared in example 6;
FIG. 7 is a BiOBr SEM image of the preparation of example 6;
FIG. 8 shows BiOBr-MgH prepared in example 6 2 (magnesium-based hydrogen storage material) 8K/min DSC;
FIG. 9 shows BiOBr-MgH prepared in example 6 2 (magnesium-based hydrogen storage material) hydrogen desorption profile.
Detailed Description
The invention provides a magnesium-based hydrogen storage material, which comprises MgH 2 And a modifying agent; the modifier comprises TiO 2 Nanotubes or bismuth oxyhalides.
In the present invention, unless otherwise specified, the reagents used are commercially available products well known to those skilled in the art.
In the present invention, the MgH 2 And the mass ratio of the modifier is preferably 100:1 to 12, more preferably 100: 1-10.
In the present invention, the TiO 2 The specific surface area of the nanotube is preferably 200-350 m 2 Preferably 250 to 300 m 2 And/g. The TiO 2 The inner diameter of the nanotube is preferably 5-12 nm, more preferably 8-10 nm; the length is preferably 200 to 400 nm, more preferably 300 to nm.
In the present invention, the average particle diameter of the magnesium-based hydrogen storage material is 1 to 3. Mu.m, more preferably 2. Mu.m.
In the present invention, the TiO 2 The preparation method of the nanotube preferably comprises the following steps:
stirring and mixing a titanium source, water, acid and ethanol to form sol;
aging the obtained sol to obtain titanium-based gel;
drying and first roasting the obtained titanium-based gel in sequence to obtain TiO 2 A nanoparticle;
TiO is mixed with 2 Dispersing nano particles in a strong alkali solution, performing hydrothermal reaction, washing the obtained hydrothermal product to be neutral, then washing with acid again, washing with deionized water to be neutral, drying and performing second roasting to obtain TiO 2 A nanotube.
The invention mixes the titanium source, water, acid and ethanol, and the obtained sol is aged to obtain the titanium-based gel.
In the present invention, the titanium source preferably comprises TiCl 4 、Ti(SO 4 ) 2 、TiOSO 4 And C 16 H 36 O 4 One or more of Ti, more preferably TiCl 4 . In the present invention, the acid includes one or more of nitric acid, hydrochloric acid, sulfuric acid and acetic acid, and more preferably hydrochloric acid. In the invention, the ratio of the mass of the titanium source, the volume of water, the volume of ethanol and the volume of acid is preferably 4-8 g: 1-3 mL: 5-12 mL:1 to 5 mL, more preferably 6 g:2 mL:10 mL:3 mL.
After the titanium-based gel is obtained, the titanium-based gel obtained by the method is sequentially dried and roasted for the first time to obtain TiO 2 And (3) nanoparticles.
In the invention, the drying temperature is preferably 100 ℃, the time is preferably 24 hours, the first roasting temperature is preferably 400-600 ℃, and the time is preferably 3-6 hours.
Obtaining TiO 2 After nano particles, the invention uses TiO 2 Dispersing nano particles in a strong alkali solution, performing hydrothermal reaction, washing the obtained hydrothermal product to be neutral, then washing with acid again, washing with deionized water to be neutral, drying and performing second roasting to obtain TiO 2 A nanotube.
In the present invention, the strong alkali solution is preferably NaOH solution and/or KOH solution; the concentration of the strong alkali solution is preferably 5-10 mol/L, more preferably 10 mol/L. In the present invention, the TiO 2 The dosage ratio of the nano particles to the strong alkali solution is preferably 1-2 g:40mL.
In the invention, the temperature of the hydrothermal reaction is preferably 120-200 ℃, more preferably 150 ℃; the time is preferably 16 to 24 hours, more preferably 20 hours.
The pickling reagent is preferably nitric acid; the concentration of the nitric acid is preferably 1mol/L; the drying temperature is preferably 100 ℃ and the drying time is preferably 12 hours.
In the invention, the temperature of the second roasting is preferably 300-600 ℃, more preferably 400-500 ℃; the time is preferably 2 to 6 hours, more preferably 4 to 5 hours.
In the present invention, the average particle diameter of the bismuth oxyhalide is preferably 1 to 3. Mu.m, more preferably 1. Mu.m.
In the present invention, the bismuth oxyhalide is preferably commercially available or self-made, and the self-made method preferably comprises the following steps: bi (NO) 3 ) 2 ·5H 2 O and halide are dispersed in deionized water, the pH value of the obtained dispersion liquid is regulated to 5.5-6.5 by sodium hydroxide solution, and then halogenation reaction is carried out to obtain bismuth oxyhalide.
In the present invention, the halide includes one or more of KCl, KI, KBr, naCl, naI and NaBr, more preferably KBr. In the present invention, the Bi (NO 3 ) 2 ·5H 2 The molar ratio of O to halide is preferably 1: 1-1: 2, more preferably 1: 1-1: 1.5.
in the invention, the temperature of the halogenation reaction is preferably 120-200 ℃, more preferably 150 ℃; the reaction time is preferably 20 to 26 hours, more preferably 24 hours.
The invention also provides a preparation method of the magnesium-based hydrogen storage material, which comprises the following steps:
MgH is processed 2 And mixing with a modifier, and sequentially carrying out wet grinding and drying to obtain the magnesium-based hydrogen storage material.
In the present invention, the wet-milling medium is preferably one or two of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, more preferably tetrahydrofuran; the ball material ratio of the wet grinding is preferably (30-60): 1, more preferably (40 to 50): 1, a step of; the ball milling rotating speed of the wet milling is preferably 400-800 r/min, more preferably 500-600 r/min; the ball milling time is preferably 3-24 hours, more preferably 5-20 hours.
In the invention, the diameter of the wet-grinding ball is preferably 4-8 mm, more preferably the grinding ball with the diameter of 4mm and the diameter of 8mm is mixed, and the material of the grinding ball is preferably stainless steel.
In the present invention, the drying is not particularly limited, and the wet-milling medium may be removed.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
4 g of C 16 H 36 O 4 Mixing Ti, 1 mL water, 5 mL ethanol and 1.5 mL acetic acid uniformly, stirring at room temperature for 6h, standing for 24 hr to form gel, drying at 100deg.C for 24h, and roasting at 400deg.C in air for 4h to obtain TiO 2 And (3) nanoparticles.
1.2 g TiO 2 The nanoparticles were dispersed in 40mL of 8 mol/L NaOH solution, followed by reaction at 130℃in a reaction vessel at 18. 18 h, followed by washing of the hydrothermal reaction product with deionized water to neutrality, followed by dissolution with 1mol/L nitric acidStirring the solution 2h, washing with deionized water to neutrality, drying at 100deg.C 12h, and calcining at 400deg.C 2.5 h to obtain a specific surface area of 300 m 2 TiO/g 2 A nanotube.
The ball milling tank was transferred into a glove box filled with argon, and 0.3. 0.3 g magnesium hydride and 3% TiO by mass of the magnesium hydride were added to the ball milling tank 2 The nanotubes and 10 mL tetrahydrofuran are then transferred to a planetary ball mill in a sealing way for ball milling (the diameter of the grinding balls is 4mm and 8mm, the material is stainless steel), the ball milling speed is 450 r/min, the total ball milling speed is 6h, and then the ball milled sample is dried, so that the magnesium-based hydrogen storage material with the average particle diameter of 1 μm is obtained.
FIG. 1 is a TiO film prepared in example 1 2 The XRD pattern of the nanotubes can be seen from FIG. 1: tiO (titanium dioxide) 2 The nanotube synthesis was successful.
Example 2
5 g TiCl 4 Mixing 2 mL water, 6 mL ethanol and 2 mL nitric acid, stirring at room temperature for 6h, standing for 24h to form gel, drying at 100deg.C for 24h, and calcining at 500deg.C in air for 3 h to obtain TiO 2 And (3) nanoparticles.
2.0 g of TiO is taken 2 The nanoparticles were dispersed in 40mL of 10 mol/L NaOH solution, followed by reaction in a reaction kettle at 130 ℃ for 18 h, washing the hydrothermal reaction product to neutrality with deionized water, then stirring with 1mol/L nitric acid solution for 2h, and washing with deionized water to neutrality. Finally, drying 12. 12h at 100deg.C, and subsequently calcining at 400deg.C for 2.5. 2.5 h to obtain a specific surface area of 200. 200 m 2 TiO/g 2 A nanotube.
The ball mill pot was then transferred to a glove box filled with argon, and 0.3 g magnesium hydride, 3% TiO by mass of magnesium hydride, was added to the ball mill pot 2 The nanotubes and 10 mL tetrahydrofuran are then transferred to a planetary ball mill in a sealing way for ball milling (the diameter of the grinding balls is 4mm and 8mm, the material is stainless steel), the ball milling speed is 450 r/min, the total ball milling speed is 6h, and then the ball milled sample is dried, so that the magnesium-based hydrogen storage material with the average particle diameter of 0.5 μm is obtained.
Example 3
4 g of Ti (SO) 4 ) 2 3, mL Water, 6mixing mL ethanol and 4 mL sulfuric acid uniformly, stirring at room temperature for 8 h, standing for 20h to form gel, drying at 100deg.C for 24h, and calcining at 600deg.C in air for 4h to obtain TiO 2 And (3) nanoparticles. Weigh 4.0 g TiO 2 The nanoparticles were dispersed in 40mL of 6 mol/L NaOH solution, followed by reaction in a reaction kettle at 180 ℃ for 12h, washing the hydrothermal product deionized water to neutrality, then stirring with 1mol/L nitric acid solution for 2h, and washing with deionized water to neutrality. Finally, drying 12. 12h at 100deg.C, and subsequently calcining 6. 6h at 400deg.C to give a specific surface area of 250. 250 m 2 TiO/g 2 A nanotube.
The ball mill pot was then transferred to a glove box filled with argon, and 0.3 g magnesium hydride, 5% TiO by mass of magnesium hydride, was added to the ball mill pot 2 The nanotubes and 10 mL diethylene glycol dimethyl ether are then transferred to a planetary ball mill in a sealing manner for ball milling (the diameter of the grinding balls is 4mm and 8mm, the material is stainless steel), 600r/min is carried out, 10 h is carried out in total, and then the ball-milled sample is dried, so that the magnesium-based hydrogen storage material with the average particle diameter of 1.5 μm is obtained.
Example 4
6 g of TiOSO 4 Mixing 3 mL water, 8 mL ethanol and 5 mL hydrochloric acid, stirring at room temperature for 10 h, standing for 24h to form gel, drying at 100deg.C for 24h, and calcining at 400deg.C in air for 6h to obtain TiO 2 And (3) nanoparticles. Weigh 6.0 g TiO 2 The nanoparticles were dispersed in 40mL of 10 mol/L NaOH solution, followed by reaction in a reaction kettle at 200 ℃ for 8 h, washing the hydrothermal product deionized water to neutrality, then stirring with 1mol/L nitric acid solution for 2h, and washing with deionized water to neutrality. Finally, drying 12h at 100deg.C, and subsequently calcining at 600deg.C for 3 h to obtain a specific surface area of 300 m 2 TiO/g 2 A nanotube.
Then the ball milling tank is transferred into a glove box filled with argon, and 0.3 g magnesium hydride and 3 mass percent TiO are added into the ball milling tank 2 The nano tube and 10 mL triethylene glycol dimethyl ether are then transferred into a planetary ball mill in a sealing way for ball milling (the diameter of a grinding ball is 4mm and 8mm, and the material is stainless steel), the ball milling is carried out for 5h in a total of 800 r/min, and then the ball milled sample is dried to obtainTo a magnesium-based hydrogen storage material having an average particle diameter of 2 μm.
Example 5
Mixing 6 g, 3 mL water, 10 mL ethanol and 5 mL acetic acid, stirring at room temperature to obtain 6h, standing 48 h to form gel, drying 24h at 100deg.C, and calcining 4h in air at 500deg.C to obtain TiO 2 And (3) nanoparticles. Weigh 2.5 g TiO 2 The nanoparticles were dispersed in 40mL of 10 mol/L NaOH solution, followed by reaction in a reaction kettle at 150 ℃ for 20h, washing the hydrothermal product deionized water to neutrality, then stirring with 1mol/L nitric acid solution for 2h, and washing with deionized water to neutrality. Finally, drying 12. 12h at 100deg.C, and subsequently calcining at 400deg.C for 2.5. 2.5 h to obtain a specific surface area of 350. 350 m 2 TiO/g 2 A nanotube.
Then the ball milling tank is transferred into a glove box filled with argon, and 0.3 g magnesium hydride and 5 mass percent TiO are added into the ball milling tank 2 The nanotubes and 10 mL tetrahydrofuran are then transferred to a planetary ball mill in a sealing way for ball milling (the diameter of the grinding balls is 4mm and 8mm, the material is stainless steel), the ball milling is carried out for 15 h in a total time of 450 r/min, and then the ball milled sample is dried to obtain the magnesium-based hydrogen storage material with the average particle diameter of 2.5 mu m.
Example 6
5 mmol Bi (NO) 3 ) 2 ·5H 2 O and 5 mmol KBr are dissolved by 60 mL deionized water, then 1mol/L NaOH solution is added to adjust the pH to 6, the mixture is stirred uniformly and poured into a reaction kettle, the mixture is reacted at 150 ℃ in the reaction kettle for 24h, the mixture is washed to be neutral by the deionized water, and then the mixture is dried at 80 ℃ for 12h, so that the BiOBr catalyst with the average particle size of 1 μm is obtained.
Then transferring the ball milling tank into a glove box filled with argon, adding 0.3 g magnesium hydride, 5% BiOCl and 10 mL tetrahydrofuran by mass ratio into the ball milling tank, then transferring the ball milling tank into a planetary ball mill in a sealing way for ball milling (the diameter of a grinding ball is 4mm and 8mm, and the material is stainless steel), performing total ball milling for 8 h at 500 r/min, and then drying the ball-milled sample to obtain the magnesium-based hydrogen storage material with the average particle diameter of 2.8 mu m.
FIG. 6 is a chart of BiOBr XRD prepared in example 6, as can be seen from FIG. 6: biOBr was successfully synthesized. FIG. 7 is a BiOBr SEM image of the preparation of example 6, as seen in FIG. 6: biOBr is a sheet structure.
FIG. 8 shows BiOBr-MgH prepared in example 6 2 (magnesium-based hydrogen storage material) 8K/min DSC chart, as can be seen from FIG. 8: biOBr-MgH 2 (magnesium-based hydrogen storage material) the initial hydrogen desorption temperature was 253.2℃and the hydrogen desorption peak temperature was 300.5 ℃.
Example 7
3 mmol Bi (NO) 3 ) 2 ·5H 2 O and 6 mmol NaI are dissolved by 40mL deionized water, then 2 mol/L NaOH solution is added to adjust the pH value to 6.5, the mixture is stirred uniformly and then poured into a reaction kettle, the mixture is reacted at 180 ℃ in the reaction kettle for 22 h, and the mixture is dried at 80 ℃ for 12h after washing for many times, so as to obtain the BiOI catalyst with the average particle size of 1 mu m.
Then transferring the ball milling tank into a glove box filled with argon, adding 0.3 g magnesium hydride, 8% of BiOI and 15 mL tetrahydrofuran into the ball milling tank, then transferring the ball milling tank into a planetary ball mill in a sealing way for ball milling (the diameter of a grinding ball is 4mm and 8mm, and the material is stainless steel), performing ball milling for 10 h in total at 800 r/min, and then drying the ball milled sample to obtain the magnesium-based hydrogen storage material with the average particle size of 2.5 mu m.
Example 8
8 mmol Bi (NO) 3 ) 2 ·5H 2 O and 8 mmol KCl are dissolved by 80 mL deionized water, then 3 mol/L NaOH solution is added to adjust the pH to 5.5, the mixture is stirred uniformly and then poured into a reaction kettle, the mixture is reacted at 180 ℃ in the reaction kettle for 26 h, and the mixture is dried at 80 ℃ for 12h after washing for many times, so as to obtain the BiOCl catalyst with the average particle diameter of 1 mu m. Then transferring the ball milling tank into a glove box filled with argon, adding 0.3 g magnesium hydride, 10% BiOCl and 15 mL tetrahydrofuran by mass ratio into the ball milling tank, then transferring the ball milling tank into a planetary ball mill in a sealing way for ball milling (the diameter of a grinding ball is 4mm and 8mm, the material is stainless steel), performing total ball milling for 15 h at 400 r/min, and then drying the ball-milled sample to obtain the magnesium-based hydrogen storage material with the average particle size of 2.1 mu m.
Comparative example 1
The ball mill jar was transferred to an argon filled glove box, 0.3 g magnesium hydride and 10 mL tetrahydrofuran were added to the ball mill jar, and then sealed for transferThe mixture was transferred to a planetary ball mill for ball milling (ball milling diameters of 4mm and 8mm, stainless steel), 450. 450 r/min, total ball milling of 6. 6h, and then the ball milled sample was dried and transferred to a vial. Adding no catalyst, ball milling to obtain MgH 2 And (5) performing hydrogen discharge performance test.
FIG. 2 is a graph of MgH of comparative example 1 2 8K/min DSC; as can be seen from fig. 2: mgH (MgH) 2 The initial hydrogen release temperature was 364.0 ℃ and the peak hydrogen release temperature was 375.7 ℃.
Comparative example 2
3 g of C 16 H 36 O 4 Mixing Ti and 5 mL acetic acid uniformly, stirring at room temperature for 6h, standing for 24 hr to form gel, drying at 100deg.C for 24h, and calcining at 400deg.C in air for 4h to obtain TiO 2 And (3) nanoparticles. Then the ball milling tank is transferred into a glove box filled with argon, and 0.3 g magnesium hydride and 3 mass percent TiO are added into the ball milling tank 2 And (3) transferring the nano particles and 10 mL tetrahydrofuran into a planetary ball mill in a sealing way, performing ball milling at 450 r/min for 6h total ball milling, and drying the ball-milled sample to obtain the magnesium-based hydrogen storage material.
FIG. 3 is a comparative example 2 MgH 2 -TiO 2 A DSC graph of the nano-particles at 8K/min; as can be seen from fig. 3: mgH (MgH) 2 -TiO 2 The initial hydrogen desorption temperature of the nano-particles is 294.4 ℃, and the peak hydrogen desorption temperature is 349.7 ℃.
FIG. 4 is a schematic diagram of MgH of example 4 2 -TiO 2 8K/min DSC graph of nanotube (magnesium-based hydrogen storage material), mgH 2 -TiO 2 The initial hydrogen release temperature of the nanotube is 232.3 ℃, the hydrogen release peak temperature is 284.5 ℃, and the comparison shows that MgH 2 -TiO 2 Nanotubes can significantly lower the dehydrogenation temperature, and tubular structures have significant advantages over nanoparticles.
The invention also relates to MgH prepared in example 4 and example 6 2 -TiO 2 The hydrogen desorption performance of the nano tube (magnesium-based hydrogen storage material) is tested by the following steps: in a glove box, loading a sample to be tested into a reactor, sealing, taking out the reactor, assembling the reactor on a Sieverts hydrogen storage performance tester, connecting an empty volume with an expanded volume, and loadingVacuum was placed, the temperature and pressure recording device was turned on, and heating was started. The temperature ranges from room temperature to 500 ℃. The temperature rising rate is 2 ℃/min.
FIG. 5 is a schematic diagram of MgH of example 4 2 -TiO 2 As can be seen from fig. 5, the total hydrogen release amount (mass of hydrogen gas generated/mass of magnesium-based hydrogen storage material) of the nanotubes (magnesium-based hydrogen storage material) was 6.7%.
FIG. 9 shows BiOBr-MgH prepared in example 6 2 As can be seen from fig. 9, the hydrogen desorption profile (of the magnesium-based hydrogen storage material): the hydrogen release amount at 500 ℃ is 6.5 percent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A magnesium-based hydrogen storage material is characterized by comprising MgH 2 And a modifying agent;
the modifier comprises TiO 2 Nanotubes or bismuth oxyhalides.
2. The magnesium-based hydrogen storage material of claim 1, wherein said MgH 2 And the mass ratio of the modifier is 100: 1-12.
3. The magnesium-based hydrogen storage material of claim 1, wherein said TiO 2 The specific surface area of the nanotube is 200-350 m 2 /g。
4. The magnesium-based hydrogen storage material according to claim 1, wherein the average particle diameter of the bismuth oxyhalide is 1-3 μm.
5. The magnesium-based hydrogen storage material according to claim 1 or 2, wherein the average particle diameter of the magnesium-based hydrogen storage material is 1-3 μm.
6. The method for preparing a magnesium-based hydrogen storage material according to any one of claims 1 to 5, comprising the steps of:
MgH is processed 2 And mixing with a modifier, and sequentially carrying out wet grinding and drying to obtain the magnesium-based hydrogen storage material.
7. The method according to claim 6, wherein the wet-milling medium is one or two of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether.
8. The method according to claim 6, wherein the wet-milled balls have a material ratio of (30 to 60): 1.
9. the preparation method according to claim 6, wherein the wet milling is performed at a milling speed of 400-800 r/min for 3-24 hours.
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| US20200299130A1 (en) * | 2008-07-30 | 2020-09-24 | Brilliant Light Power, Inc. | Heterogeneous hydrogen-catalyst reactor |
| CN113479934A (en) * | 2021-07-28 | 2021-10-08 | 中国科学院上海硅酸盐研究所 | BiOCl nanosheet and preparation method and application thereof |
| CN114620676A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Titanium-containing material catalytic modified magnesium-based hydrogen storage material and preparation method and application thereof |
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| US20200299130A1 (en) * | 2008-07-30 | 2020-09-24 | Brilliant Light Power, Inc. | Heterogeneous hydrogen-catalyst reactor |
| CN114620676A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Titanium-containing material catalytic modified magnesium-based hydrogen storage material and preparation method and application thereof |
| CN113479934A (en) * | 2021-07-28 | 2021-10-08 | 中国科学院上海硅酸盐研究所 | BiOCl nanosheet and preparation method and application thereof |
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