CN115475661A - MgH reduction 2 Ni-loaded MOF catalyst with hydrogen desorption activation energy and preparation method and application thereof - Google Patents
MgH reduction 2 Ni-loaded MOF catalyst with hydrogen desorption activation energy and preparation method and application thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000012918 MOF catalyst Substances 0.000 title claims abstract description 37
- 230000004913 activation Effects 0.000 title claims abstract description 27
- 238000003795 desorption Methods 0.000 title claims abstract description 27
- 230000009467 reduction Effects 0.000 title claims description 8
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011232 storage material Substances 0.000 claims abstract description 23
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 15
- 230000005684 electric field Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000012922 MOF pore Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000005556 structure-activity relationship Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
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- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- 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
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Abstract
The invention discloses a method for reducing MgH 2 The invention discloses a Ni-loaded MOF catalyst with hydrogen discharge activation energy, and also discloses a preparation method of the Ni-loaded MOF catalyst, which comprises the following steps: a. preparing a Co-MOF carrier; b. preparing a Co-MOF carrier loaded with Ni; the invention also discloses an application of the Ni-loaded MOF catalyst. According to the invention, a Co-MOF catalyst loaded by metal Ni is designed by virtue of the advantages of porous MOF material, large specific surface area, simple preparation and the like; in one aspect the pore structure of MOFs can be used to limit to MgH 2 The hydrogen storage material avoids the agglomeration of active materials in the hydrogen absorption and desorption process, and on the other hand, the introduced metal Ni can be used as a catalytic site to improve MgH 2 The hydrogen absorption and desorption kinetics of the hydrogen storage material reduce the hydrogen desorption activation energy of the hydrogen storage material; the catalyst has simple preparation method and better performanceThe metal supported MOF catalyst can be prepared by changing the type of metal salt during metal loading, is favorable for researching the structure-activity relationship between the type of the catalyst and the hydrogen storage performance, and provides theoretical guidance and experimental reference for the design and preparation of the catalyst.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage, and particularly relates to a method for reducing MgH 2 Ni-loaded MOF catalyst with hydrogen desorption activation energy and a preparation method and application thereof.
Background
The magnesium-based hydrogen storage material hasThe advantages of low cost, excellent reversibility, high hydrogen storage capacity (7.6 wt%, 110 g/L), and abundant elemental reserves are considered to be one of the most studied and promising hydrogen storage materials. But MgH 2 The hydrogen storage material has a high thermodynamic stability, resulting in a high operating temperature thereof. In the process of absorbing and desorbing hydrogen, mg/MgH 2 The material is easy to agglomerate, the number of active sites is reduced, and the performance is attenuated. Furthermore, mgH 2 The slow kinetics of hydrogen storage materials have also hindered the practical use of magnesium-based hydrogen storage materials.
Disclosure of Invention
The technical task of the invention is as follows: aiming at the defects, the method for reducing MgH is provided 2 A Ni-loaded MOF catalyst with hydrogen desorption activation energy, a preparation method and application thereof, which solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
MgH reduction 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy specifically comprises the following steps:
a. preparation of Co-MOF support:
mixing Co (NO) 3 ) 2 ·6H 2 Dissolving O and 2-methylimidazole in ethanol respectively, mixing, aging for 12-36 h, and finally centrifugally separating and washing a product;
b. preparation of Ni-supported Co-MOF carrier:
(1) soaking the prepared Co-MOF carrier in nickel nitrate water solution, standing for 6-24 h at normal temperature or soaking for 2-8 h in intermittently opened high-voltage electric field to ensure that Ni 2+ Combining with an organic ligand on a Co-MOF carrier, and drying to obtain a sample;
(2) adding the sample into a hydrazine hydrate aqueous solution, transferring the obtained solution into a stainless steel hydrothermal kettle, heating for 2-4 h at 100-150 ℃, then cooling to room temperature, washing the obtained solid with water and ethanol for three times respectively, and drying in a vacuum drying oven at 50-80 ℃ for 12-24 h to obtain the Ni-loaded MOF catalyst.
Further, step a is Co (NO) used for preparing Co-MOF carrier 3 ) 2 ·6H 2 The mass ratio of O to 2-methylimidazole is 1:3-7.
Furthermore, the weight of the nickel nitrate used for preparing the Ni-loaded Co-MOF carrier in the step b is 2-8% of that of the Co-MOF carrier.
Furthermore, the concentration of the hydrazine hydrate aqueous solution used for preparing the Ni-supported Co-MOF carrier in the step b is 0.5-3 mol/L.
Further, the vacuum drying conditions in step b are as follows: the vacuum degree is-0.06-0.09 MPa, the drying temperature is 50-80 ℃, and the drying time is 12-24 h.
Further, after the Co-MOF carrier is soaked in the nickel nitrate aqueous solution in the step b, the Co-MOF carrier is soaked in a high-voltage electric field which is intermittently opened for 2 to 8 hours, and the voltage of the high-voltage electric field is 1650 to 2050V. Under the environment of high-voltage electric field, the Co-MOF carrier and Ni are carried under the action of the electric field 2+ Carrying positive charge, making it generate directional movement in solution under the action of DC electric field, collecting it to negative electrode, and making it enter into network structure of Co-MOF carrier to make Ni 2+ Fully contacting with a Co-MOF carrier; intermittent periods of time, negative very high concentration of Ni 2 + Fully combines with organic ligand on Co-MOF carrier, accelerates ion Ni 2+ The loading on the Co-MOF carrier improves the loading rate and the loading efficiency. The whole bubble invasion process can be carried out according to four periods of T1, T2, T3 and T4, wherein the T1 and T3 periods are stably electrified, the T2 and T4 periods are not electrified, and standing treatment is carried out.
The invention also provides the MgH reducing agent 2 The Ni-loaded MOF catalyst prepared by the preparation method of the Ni-loaded MOF catalyst with hydrogen desorption activation energy.
The invention also provides the MgH reduction method 2 The Ni-loaded MOF catalyst prepared by the preparation method of the Ni-loaded MOF catalyst with hydrogen desorption activation energy is applied to magnesium-based hydrogen storage materials.
Compared with the prior art, the invention has the advantages and positive effects that:
1. according to the invention, a Co-MOF catalyst loaded with metal Ni is designed by virtue of the advantages of porous MOF material, large specific surface area, simple preparation and the like; in one aspect the pore structure of the MOF can be used to confineIn MgH 2 The hydrogen storage material avoids the agglomeration of active materials in the hydrogen absorption and desorption process, and on the other hand, the introduced metal Ni can be used as a catalytic site to improve MgH 2 The hydrogen absorption and desorption kinetics of the hydrogen storage material reduce the hydrogen desorption activation energy of the hydrogen storage material.
2. The preparation method of the catalyst is simple, has better universality, can prepare the MOF catalyst loaded by different metals by changing the types of the metal salts during metal loading, is favorable for researching the structure-activity relationship between the types of the catalyst and the hydrogen storage performance, and provides theoretical guidance and experimental reference for the design and preparation of the catalyst.
Drawings
FIG. 1 shows a process for reducing MgH according to the present invention 2 SEM image of Ni-loaded MOF catalyst with hydrogen desorption activation energy
FIG. 2 shows a process for reducing MgH according to the present invention 2 Pxrd pattern of the Ni-supported MOF catalyst at the hydrogen evolution activation energy;
FIG. 3 shows a process for reducing MgH according to the present invention 2 An infrared spectrogram of the Ni-loaded MOF catalyst with hydrogen desorption activation energy;
FIG. 4 is MgH prepared in example 8 of the invention 2 N of composite hydrogen storage material 2 Sucking and removing the attached drawings;
FIG. 5 shows MgH prepared in example 8 of the present invention 2 The hydrogen release curve of the composite hydrogen storage material at different temperatures;
FIG. 6 shows MgH prepared in example 8 of the present invention 2 DSC curves of the composite hydrogen storage material at different heating rates and corresponding fitting;
FIG. 7 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
MgH reduction method 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy specifically comprises the following steps:
a. preparation of Co-MOF support:
2.5g of Co (NO) 3 ) 2 ·6H 2 Dissolving O and 2.1g2-methylimidazole in 250ml of ethanol respectively, mixing, aging for 12 hours, and finally centrifugally separating and washing a product;
b. preparation of Ni-supported Co-MOF carrier:
(1) soaking the prepared Co-MOF carrier in a nickel nitrate aqueous solution, standing for 6h, and drying to obtain a sample, wherein the weight of the used nickel nitrate is 2% of that of the Co-MOF carrier;
(2) adding the sample into a 0.5mol/L hydrazine hydrate aqueous solution, transferring the obtained solution into a stainless steel hydrothermal kettle, heating for 2h at 100 ℃, then cooling to room temperature, respectively washing the obtained solid with water and ethanol for three times, and drying for 12h in a vacuum drying oven at 50 ℃ under-0.06 MPa to obtain the Ni-loaded MOF catalyst.
Example 2
MgH reduction method 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy specifically comprises the following steps:
a. preparation of Co-MOF Carrier:
2.5g of Co (NO) 3 ) 2 ·6H 2 Dissolving O and 3.8g2-methylimidazole in 250ml of ethanol respectively, mixing, aging for 24 hours, and finally centrifugally separating and washing a product;
b. preparation of Ni-supported Co-MOF carrier:
(1) soaking the prepared Co-MOF carrier in a nickel nitrate aqueous solution, standing for 18h, and drying to obtain a sample, wherein the weight of the used nickel nitrate is 5% of that of the Co-MOF carrier;
(2) adding the sample into 1.5mol/L hydrazine hydrate aqueous solution, transferring the obtained solution into a stainless steel hydrothermal kettle, heating for 3h at 120 ℃, then cooling to room temperature, respectively washing the obtained solid with water and ethanol for three times, and drying for 18h in a vacuum drying oven at 60 ℃ under-0.07 MPa to obtain the Ni-loaded MOF catalyst.
Example 3
MgH reduction 2 Preparation method of Ni-loaded MOF catalyst with hydrogen desorption activation energy, and specific packageThe method comprises the following steps:
a. preparation of Co-MOF Carrier:
2.5g of Co (NO) 3 ) 2 ·6H 2 Dissolving O and 4.95g of 2-methylimidazole in 250ml of ethanol respectively, mixing, aging for 36 hours, and finally centrifugally separating and washing a product;
b. preparation of Ni-loaded Co-MOF carrier:
(1) soaking the prepared Co-MOF carrier in a nickel nitrate aqueous solution, standing for 24h, and drying to obtain a sample, wherein the weight of the used nickel nitrate is 8% of that of the Co-MOF carrier;
(2) adding the sample into a 3mol/L hydrazine hydrate aqueous solution, transferring the obtained solution into a stainless steel hydrothermal kettle, heating for 4h at 150 ℃, cooling to room temperature, respectively washing the obtained solid with water and ethanol for three times, and drying for 24h in a vacuum drying oven at 80 ℃ under-0.09 MPa to obtain the Ni-loaded MOF catalyst.
In order to characterize the microstructure of the Ni-supported MOF catalyst material, the product obtained in example 1 was SEM characterized and the results are shown in fig. 1.
In order to confirm the crystal structure of the synthesized sample, XRD characterization and infrared characterization were performed on the sample synthesized in example 1, and the results are shown in fig. 2 and 3.
Example 4
The method is improved on the basis of the embodiment 1,
further, after the Co-MOF carrier is soaked in the nickel nitrate aqueous solution in the step b, soaking for 2-8 h in an intermittently opened high-voltage electric field, wherein the voltage of the high-voltage electric field is 1650-2050V, the whole soaking process can be carried out according to four periods of T1, T2, T3 and T4, wherein the T1 and the T3 are stably electrified in the period, and the T2 and the T4 are not electrified and stand.
Example 5
The improvement is carried out on the basis of the embodiment 4,
and c, soaking the Co-MOF carrier in the nickel nitrate aqueous solution for 2h in an intermittently opened high-voltage electric field with the voltage of 1650V, wherein the whole soaking process can be carried out according to four periods of T1, T2, T3 and T4, wherein the T1 period and the T3 period are respectively electrified for 0.5h stably, the T2 period and the T4 period are not electrified, and the Co-MOF carrier is respectively kept stand for 0.5h.
Example 6
The improvement is carried out on the basis of the embodiment 4,
and c, soaking the Co-MOF carrier in the nickel nitrate aqueous solution for 6h in an intermittently opened high-voltage electric field with the voltage of 1850V, wherein the whole soaking process can be carried out according to four periods of T1, T2, T3 and T4, wherein the power is stably and respectively switched on for 1h in the period of T1 and the period of T3, the power is not switched on for T2 and the period of T4, and the Co-MOF carrier is respectively kept stand for 2h.
Example 7
The improvement is carried out on the basis of the embodiment 4,
and b, soaking the Co-MOF carrier in the nickel nitrate aqueous solution for 8h in an intermittently opened high-voltage electric field with the voltage of 2050V, wherein the whole soaking process can be carried out according to four periods of T1, T2, T3 and T4, wherein the T1 period and the T3 period are respectively electrified for 2h stably, the T2 period and the T4 period are not electrified, and the Co-MOF carrier is respectively kept stand for 2h.
Example 8
MgH 2 Preparing a composite hydrogen storage material: respectively weighing 0.7gMgH 2 And 0.3g of the catalyst prepared in example 1 were placed in a ball mill, followed by addition of 40g of ball milling beads. Ball milling is carried out for 8 hours at the rotating speed of 500rpm under the hydrogen pressure of 2MPa to obtain MgH 2 A composite hydrogen storage material. MgH obtained after ball milling 2 The composite hydrogen storage material is placed in a glove box for storage and standby.
Pair of different catalyst materials MgH 2 Hydrogen storage material kinetic performance characterization:
the adsorption performance of the product obtained in example 8 on nitrogen was tested by using a Micromeritics ASAP 2020 apparatus, and a nitrogen adsorption/desorption curve at 77K was measured at 298K for the sample synthesized in example 4, as shown in FIG. 4.
The sample prepared in example 8 was characterized by the hydrogen evolution performance study using differential scanning calorimetry, and the hydrogen evolution curves obtained at different temperature rising rates are shown in fig. 5.
The Kissinger method (differential method is used to differentiate heat) is adoptedMethod for kinetic analysis of analytical curve by using peak temperature T of thermal analysis curve p Relationship with temperature rise rate β) were fitted to the obtained data, and the fitting results are shown in fig. 6 and 7. Co-MOF catalyzed MgH supported by metallic Ni 2 Shows the lowest hydrogen-releasing activation energy and improves MgH 2 Hydrogen evolution kinetics of hydrogen storage materials.
Wherein, kissinger equation:
wherein, beta is the heating rate, K/min;
T p -capping temperature, K;
A-Arrhenius means pro-factor, l/s;
E k -expression activation energy, J/mol;
r-ideal gas constant, 8.314J. Mol -1 ·K -1 。
In conclusion, the metal Ni loaded Co-MOF catalyst is designed by the advantages of porous MOF material, large specific surface area, simple preparation and the like; in one aspect the pore structure of MOFs can be used to limit to MgH 2 The hydrogen storage material avoids the agglomeration of active materials in the hydrogen absorption and desorption process, and on the other hand, the introduced metal Ni can be used as a catalytic site to improve MgH 2 The hydrogen absorption and desorption kinetics of the hydrogen storage material reduce the hydrogen desorption activation energy; the preparation method of the catalyst is simple, the catalyst has better universality, and the MOF catalyst with different metal loads can be prepared by changing the types of metal salts during metal loading, thereby being beneficial to researching the structure-activity relationship between the types of the catalyst and the hydrogen storage performance, and providing theoretical guidance and experimental reference for the design and preparation of the catalyst.
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 (8)
1. MgH reduction 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy is characterized by comprising the following steps:
a. preparation of Co-MOF support:
mixing Co (NO) 3 ) 2 ·6H 2 Dissolving O and 2-methylimidazole in ethanol respectively, mixing, aging for 12-36 h, and finally centrifugally separating and washing a product;
b. preparation of Ni-loaded Co-MOF carrier:
(1) soaking the prepared Co-MOF carrier in a nickel nitrate aqueous solution, standing for 6-24 h at normal temperature or soaking for 2-8 h in an intermittently opened high-voltage electric field, and then drying to obtain a sample;
(2) adding the sample into a hydrazine hydrate aqueous solution, transferring the obtained solution into a stainless steel hydrothermal kettle, heating for 2-4 h at 100-150 ℃, then cooling to room temperature, respectively washing the obtained solid with water and ethanol for three times, and vacuum drying to obtain the Ni-loaded MOF catalyst.
2. The method of claim 1 for reducing MgH 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy is characterized in that the Co (NO) used for preparing the Co-MOF carrier in the step a 3 ) 2 ·6H 2 The mass ratio of O to 2-methylimidazole is 1:3-7.
3. The method of claim 1 for reducing MgH 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen discharge activation energy is characterized in that the weight of nickel nitrate used for preparing the Ni-loaded Co-MOF carrier in the step b is 2-8% of that of the Co-MOF carrier.
4. The method of claim 1 for reducing MgH 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen discharge activation energy is characterized in that the concentration of a hydrazine hydrate aqueous solution used for preparing the Ni-loaded Co-MOF carrier in the step b is 0.5-3 mol/L.
5. The method of claim 1 for reducing MgH 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy is characterized in that the vacuum drying conditions in the step b are as follows: the vacuum degree is-0.06-0.09 MPa, the drying temperature is 50-80 ℃, and the drying time is 12-24 h.
6. The method of claim 1 for reducing MgH 2 The preparation method of the Ni-loaded MOF catalyst with the hydrogen desorption activation energy is characterized in that the Co-MOF carrier is soaked in the nickel nitrate aqueous solution in the step b and then soaked in a high-voltage electric field which is intermittently opened for 2-8 h, and the voltage of the high-voltage electric field is 1650-2050V.
7. A method of reducing MgH according to any one of claims 1 to 6 2 The Ni-loaded MOF catalyst prepared by the preparation method of the Ni-loaded MOF catalyst with hydrogen desorption activation energy.
8. A method of reducing MgH according to any one of claims 1 to 6 2 The Ni-loaded MOF catalyst prepared by the preparation method of the Ni-loaded MOF catalyst with hydrogen desorption activation energy is applied to magnesium-based hydrogen storage materials.
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