CN107021527B - High-activity chemical-chain hydrogen storage material and preparation method thereof - Google Patents

High-activity chemical-chain hydrogen storage material and preparation method thereof Download PDF

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CN107021527B
CN107021527B CN201710219102.6A CN201710219102A CN107021527B CN 107021527 B CN107021527 B CN 107021527B CN 201710219102 A CN201710219102 A CN 201710219102A CN 107021527 B CN107021527 B CN 107021527B
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肖睿
曾德望
陈超
高远
张志鹏
胡胤博
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    • 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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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses a high-activity chemical chain hydrogen storage material and a preparation method thereof2·4H2O，MgCl2·6H2O，AlCl3·6H2Dissolving O and urea in methanol according to the molar ratio of 1-3: 1:1:7, carrying out solvent heat treatment on the obtained solution in a high-pressure kettle, and carrying out vacuum drying on the obtained product to obtain the high-activity chemical-chain hydrogen storage material with a Layered Double Hydroxide (LDH) structure. The material adopts a chemical chain circulation oxygen hydrogen storage principle, indirectly stores hydrogen by creating oxygen vacancies and then generating hydrogen by oxygen vacancy inversion, theoretically one oxygen vacancy is inverted to obtain two hydrogen, and the hydrogen storage density is twice of that of the traditional hydrogen vacancy. The material has a petal-shaped LDH structure, has a large specific surface area and is Fe3+Providing more attachment sites; adsorption of crystalline aluminum-containing laminates in the material to make Mg2+、Fe3+The uniform and stable distribution in the laminate ensures that reactants can fully contact with the active center, and the factors greatly improve the reactivity of the material.

Description

High-activity chemical-chain hydrogen storage material and preparation method thereof
Technical Field
The invention relates to the field of material preparation and chemical-looping hydrogen storage, in particular to a high-activity chemical-looping hydrogen storage material and a preparation method thereof.
Background
The hydrogen energy is a renewable energy source with large combustion heat value and no pollution, and is regarded as the clean energy source with the most development potential in the 21 st century. The key to effectively utilize hydrogen energy is to develop a hydrogen storage technology which is efficient and can be applied in a large scale.
Common hydrogen storage technologies at present are classified into physical hydrogen storage and chemical hydrogen storage. High-pressure hydrogen storage and hydraulic hydrogen storage in physical hydrogen storage can realize large-scale commercialized hydrogen energy storage, but potential safety hazards brought by high pressure still restrict the application of the two hydrogen storage technologies, and in addition, the high-pressure hydrogen storage and the hydraulic hydrogen storage also have the defects of high energy consumption, large occupied area and the like; the main implementation modes of chemical hydrogen storage include hydrogen storage alloy, metal hydride, organic hydrogen storage and the like. The chemical hydrogen storage material has the advantages of high hydrogen storage density, mild reaction conditions, good safety and the like. However, due to the high preparation cost, the chemical hydrogen storage material is still in the laboratory research stage and has not been reported commercially. The defects of easy environmental pollution and the like also bring difficulty to the popularization of the chemical hydrogen storage technology.
The chemical chain circulation oxygen hydrogen storage technology is a novel hydrogen storage technology and is innovative in that oxygen vacancies are used for indirectly storing hydrogen, and because one oxygen vacancy corresponds to two hydrogen, the theoretical hydrogen storage density of a circulation oxygen vacancy hydrogen storage material is twice that of the traditional hydrogen vacancy hydrogen storage material. The principle of hydrogen storage is illustrated by taking a cobalt-iron oxygen carrier as an example:
the hydrogen storage process comprises the following steps:
Figure GDA0002328142720000011
hydrogen release process:
Figure GDA0002328142720000012
the active ingredient in the oxygen carrier is iron oxide. During the hydrogen storage process, oxygen in the iron oxide is combined with hydrogen to form water, and the iron oxide is reduced into low-valent iron oxide. Every 1 oxygen atom is bonded to 2 hydrogen atoms, corresponding to the creation of an oxygen vacancy. In the hydrogen release process, 1 oxygen vacancy cracks 1 molecule of water, oxygen in water is left in the oxygen vacancy, hydrogen is released in the form of hydrogen, meanwhile, the low-valence iron oxide is oxidized, and the oxygen carrier can be used for storing hydrogen again, so that reversible storage of the hydrogen is realized.
Today, the design and manufacture of high performance chemical-looping hydrogen storage materials is an important issue. The existing chemical chain hydrogen storage material is generally prepared by a sol-gel method, a mechanical mixing method, an immersion method and other methods, and the materials prepared by the methods have low hydrogen charging and discharging speed and long hydrogen storage and releasing time. Therefore, the research and development of a preparation method of the high-activity chemical-chain hydrogen storage material is of great significance.
Disclosure of Invention
The technical problem is as follows: in order to solve the problem of weak reaction activity of the existing chemical-chain hydrogen storage material, the invention provides a high-activity chemical-chain hydrogen storage material and a preparation method thereof.
The technical scheme is as follows: the chemical formula of the high-activity chemical-chain hydrogen storage material is FexMgAlO1.5X+2.5Wherein X is more than or equal to 1 and less than or equal to 3, and the hydrogen storage material has petal-shaped layered bimetalHydroxide compound(LDH) structure, wherein a layered laminate in the hydrogen storage material is formed by combining oxygen ions and metal ions through electrostatic interaction. Under the action of electrostatic force, the metal ions form active centers which are uniformly and stably distributed in the layered laminate.
Wherein:
the metal ion is Fe3+、Mg2+、Al3+。
The specific surface area of the hydrogen storage material is 200-300 m2/g。
The preparation method of the high-activity chemical-chain hydrogen storage material adopts a solvothermal method to prepare the high-activity chemical-chain hydrogen storage material, and the method comprises the following steps of mixing hydrated chloride salts of iron, magnesium and aluminum with urea in a molar ratio of (1-3) to 1:1: dissolving in methanol, treating the mixture with solvent, centrifuging, washing with deionized water and ethanol for several times, and drying.
In the preparation process, the solvothermal treatment step is to transfer the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heat the mixture in an oil bath for 24 hours at 170-190 ℃.
And centrifuging and washing the product, and drying the product in a drying oven at 70-80 ℃ for 12-14 hours.
Has the advantages that: compared with the prior art, the invention has at least the following beneficial effects:
1. the novel hydrogen storage material prepared by the invention adopts the chemical chain circulation hydrogen storage principle, creates oxygen vacancies in the material and uses the oxygen vacanciesThe hydrogen is indirectly stored by a position inversion hydrogen production mode, theoretically, one oxygen vacancy can be inverted to obtain two hydrogen, and therefore, the hydrogen storage density is twice of that of the traditional hydrogen vacancy. The mass fraction of hydrogen stored in the material can reach more than 4.8 percent, and the volume hydrogen storage density can reach 120kg/m3The above
2. The high-activity chemical chain hydrogen storage material prepared by the invention has a petal-shaped LDH structure and a large specific surface area (200-300 m)2And/g), the active centers are uniformly and stably distributed in the laminate, so that the reaction activity of the material is greatly improved. The hydrogen storage process of the material takes 5-10 min, and the hydrogen release process only takes 25-40% of the common oxygen carrier material and takes 2-3 min.
3. The invention adopts cheap chlorine metal salt as raw material, and the preparation process is simple and can be used for large-scale production.
Drawings
FIG. 1 is an SEM image of a highly active chemical-looping hydrogen storage material prepared in example 1.
Fig. 2 is an XRD pattern of the highly active chemical-looping hydrogen storage material prepared in example 1.
FIG. 3 is an SEM image of the highly active chemical-looping hydrogen storage material prepared in example 2.
Fig. 4 is an XRD pattern of the highly active chemical-looping hydrogen storage material prepared in example 2.
FIG. 5 shows the hydrogen storage density of the material in different Fe-Mg-Al molar ratios during the hydrogen charging and discharging cycle, and the reaction temperature is 900 ℃.
FIG. 6 is a graph of hydrogen release rate of the material in hydrogen release process with different Fe-Mg-Al molar ratios, and the reaction temperature is 900 ℃.
Detailed Description
In order to achieve the aim, the high-activity chemical chain hydrogen storage material adopted by the invention adopts the hydrogen storage principle of chemical chain circulating oxygen hydrogen storage, and adopts the mode of manufacturing oxygen vacancies in the material and then generating hydrogen by oxygen vacancy inversion to indirectly store the hydrogen. The material has a petal-shaped LDH structure and a large specific surface area (200-300 m)2/g) can be Fe3+Provide more attachment sites and allow Mg to adsorb due to the adsorption of the crystalline aluminum-containing layer2+、Fe3+Into a laminar stateIn the laminate, active centers are formed in the laminate in a uniform and stable distribution.
The preparation method of the high-activity chemical-chain hydrogen storage material adopts a solvothermal method for preparation, and the preparation method comprises the steps of2·4H2O，MgCl2·6H2O，AlCl3·6H2Dissolving O and urea in methanol according to the stoichiometric ratio of (1-3) to 1:1:7, uniformly stirring, transferring to a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heating in an oil bath at 170-190 ℃ for 24 hours under a sealed condition. And centrifuging the product, washing the product with deionized water and ethanol for several times, and drying the product in a drying oven at 70-80 ℃ for 12-14 hours to obtain the target material.
The material was prepared at different reactant concentrations:
example 1:
0.2mol/L FeCl with the solution amount of 0.03L2·4H2O, 0.1mol/l MgCl2·6H2O, 0.1mol/l AlCl3·6H2O and 0.7mol/l urea were dissolved in 30mL of methanol. The mixture was stirred and then transferred to a teflon lined autoclave, heated at 180 ℃ for 24 hours under closed conditions, the product centrifuged, washed several times with deionized water and ethanol, and dried in an electric oven at 70 ℃ for 12 hours. Obtaining the flower-shaped FeMgAl-LDH ball.
Example 2:
FeCl with the molar concentration of 0.1mol/L and the solution amount of 0.03L2·4H2O, 0.05mol/l MgCl2·6H2O, 0.05mol/l AlCl3·6H2O and 0.35mol/l urea were dissolved in 30mL of methanol. The mixture was stirred and then transferred to a teflon lined autoclave, heated at 180 ℃ for 24 hours under closed conditions, the product centrifuged, washed several times with deionized water and ethanol, and dried in an electric oven at 70 ℃ for 12 hours. Obtaining the flower-shaped FeMgAl-LDH ball.
As can be seen from the XRD and SEM characterization results of example 1 and example 2, under both the working conditions, the material forms obvious petal-shaped LDH structures, and the XRD characterization results also show characteristic peaks of the LDH structures.
FIG. 5 shows the hydrogen storage density of the material in different Fe-Mg-Al molar ratios during the hydrogen charging and discharging cycle. It can be seen that the hydrogen storage density of the material after 20 cycles is basically kept stable, wherein the hydrogen storage density of the three materials with the molar ratio of 3:1:1,5:1:1 and 7:1:1 is basically stabilized at 5000umol g-1。
FIG. 6 is a graph showing the change of hydrogen release rate of the material in hydrogen release process when the hydrogen release rate is less than 10umol g for different Fe-Mg-Al molar ratios-1·s-1When the reaction is considered to be complete, the time consumed for hydrogen release of the three materials is about 2min, and the time consumed in the hydrogen release process is far lower than that of the conventional hydrogen storage material.
The above detailed description of the embodiments of the present invention and the description of the product phenomena of the different embodiments are only examples, and the present invention is not limited to the above described embodiments. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (3)

1. A high-activity chemical-chain hydrogen storage material is characterized in that the chemical formula of the hydrogen storage material is FexMgAlO1.5X+2.5Wherein X is more than or equal to 1 and less than or equal to 3, and the hydrogen storage material has petal-shaped layered bimetalHydroxide compoundThe structure is that the layered laminate in the hydrogen storage material is formed by combining oxygen ions and metal ions through electrostatic force, and the metal ions form active centers which are uniformly and stably distributed in the layered laminate under the action of the electrostatic force; the specific surface area of the material is 200-300 m2The hydrogen storage process takes 5-10 min, and the hydrogen release process takes 2-3 min; the metal ion is Fe3+、Mg2+、Al3+。
2. The preparation method of the high-activity chemical-looping hydrogen storage material as claimed in claim 1, characterized in that the preparation method is a solvothermal method, and the preparation method is characterized in that the molar ratio of hydrated chloride salts of iron, magnesium and aluminum to urea is (1-3): 1:1:7 dissolving in methanol, treating the mixture by solvothermal method, centrifuging the product, washing with deionized water and ethanol for several times, and drying;
in the preparation process, the solvothermal treatment step is to transfer the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heat the mixture in an oil bath for 24 hours at 170-190 ℃.
3. The method for preparing a high-activity chemical-looping hydrogen storage material according to claim 2, wherein the method comprises the following steps: and centrifuging and washing the product, and drying the product in a drying oven at 70-80 ℃ for 12-14 hours.
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CN108716007A (en) * 2018-05-30 2018-10-30 天津大学 The method for improving hydroxide electrocatalytic hydrogen evolution reactivity worth by Lacking oxygen engineering
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