CN109368589B - Two-dimensional load type nano aluminum hydride and preparation method thereof - Google Patents
Two-dimensional load type nano aluminum hydride and preparation method thereof Download PDFInfo
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910021389 graphene Inorganic materials 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 150000002902 organometallic compounds Chemical class 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 14
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- -1 graphene nitride Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229910000091 aluminium hydride Inorganic materials 0.000 description 40
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 19
- 230000008569 process Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 10
- 238000002524 electron diffraction data Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007709 nanocrystallization Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
the invention discloses a two-dimensional load type nano aluminum hydride, which comprises a two-dimensional carbon material and an aluminum hydride distributed on the two-dimensional carbon material, wherein the mass fraction of the aluminum hydride is 20-90%, the crystal form of the aluminum hydride is one or two of alpha crystal form and β crystal form.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a two-dimensional load type nano aluminum hydride and a preparation method thereof.
Technical Field
Along with social development and population growth, the human demand for energy sources will be larger and larger. Fossil energy is currently the main energy source, but it is a non-renewable energy source, with limited reserves and rapid depletion. Meanwhile, the use of fossil fuels has a great impact on the environment. On the other hand, as a clean renewable energy source, hydrogen energy has the characteristics of high calorific value and wide sources. As a key technology for hydrogen energy application, storage and transportation of hydrogen gas have received extensive attention and research in the field of energy storage materials. Liquid hydrogen, high pressure hydrogen storage and metal hydrides in hydrogen storage and transportation technology have been successfully used in fuel cell vehicles to date. Among them, the metal hydride is the most safe and has the highest volumetric hydrogen storage density.
Compared with the traditional ABnThe metal hydrides in the form of light metal hydrides having a relatively high gravimetric hydrogen storage density, e.g. MgH2(7.8 wt.%) and AlH3(10.1 wt.%). Wherein, AlH3Has lower hydrogen releasing temperature (100-200 ℃), and can realize hydrogen releasing at the temperature lower than 100 ℃ after mechanical ball milling and modification by adding additives. Early, documents g.stecher, e.wiberg, ber.dtsch.chem.ges.,1942,75B,2003-2012, reported amine complexes AlH3The purity and yield of the product are low. Thereafter, documents a.e. finholt, a.c. bond, h.i. schleisinger, JAm. chem. soc.,1947,69(5),1199-1203, invented LiAlH in ether solution4With AlCl3Reaction for preparing AlH3The method of ether complex of (1).
At present, AlH is prepared3The method mainly adopts the documents F.M.Brower, N.E.Matzek, P.F.Reigler, H.W.Rinn, C.B.Roberts, D.L.Schmidt, J.A.Snover, Soc.,1976,98(9) and 2450-2453, but the process is complex, the influence of the raw material ratio and the process conditions on the crystal form is large, and the prepared AlH has the advantages of high yield, high purity, high yield and low cost3Often in a polycrystalline phase. On the other hand, documents [ h.saitoh, a.machida, y.katayama, k.aoki, Applied Physics Letters,2008,93(15),2450.]Reports that metallic Al simple substance is directly hydrogenated under the conditions of high hydrogen pressure and high temperature to prepare AlH3However, the reaction conditions are severe, the hydrogen pressure is up to 10GPa and the temperature needs to be higher than 600 ℃. Although various improved technologies exist at present, the various disadvantages, such as complicated process flow or harsh preparation conditions, cannot be overcome.
The nano-method is to control the material in nano scale, and the high specific surface area of the nano-material enables hydrogen atoms to have shorter diffusion paths in a solid phase, so that the kinetic barrier and the thermodynamic stability of the hydrogen storage material are reduced, the nano-method is an effective means for improving the performance of the hydrogen storage material, and excellent results are achieved in other systems of hydrides. However, due to the complex preparation conditions of alanate, no good alanate nanocrystallization method exists at present.
Documents [ c.w.duan, l.x.hu, d.xue.green chem.,2015,17,3466-3474]Provides a method for utilizing other hydrides and AlCl3Reaction ball milling, solid phase synthesis of nano-scale AlH3The method of (2) but other metal atoms and chlorine atoms introduced in the preparation process exist in the final product all the time, and the impurity elements which do not participate in the hydrogen releasing process not only greatly influence the hydrogen storage performance of the material, but also greatly reduce the hydrogen storage capacity of the whole material. At the same time, there is still no correlation with the production of nanoscale AlH under relatively mild conditions3And a report loaded on a nanocarrier.
Disclosure of Invention
The invention aims to provide a two-dimensional load type nano aluminum hydride, which realizes AlH3The nanocrystallization of the particles on the two-dimensional material. The invention also provides a preparation method of the two-dimensional load type nano aluminum hydride, and solves the problem of AlH3The method has the advantages of solving the problem of difficult direct preparation and nanocrystallization, greatly reducing the cost, simplifying the synthesis method and obtaining the nano-scale alanate by direct synthesis through room temperature one-step reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
the two-dimensional supported nano aluminum hydride comprises a two-dimensional carbon material and aluminum hydrides distributed on the two-dimensional carbon material, wherein the mass fraction of the aluminum hydrides is 20-90%, and the crystal forms of the aluminum hydrides are one or two of alpha crystal forms and β crystal forms.
An alanate is supported as an active ingredient on a two-dimensional carbon material. The chemical formula of the alanate is AlH3in one or both of the alpha and beta crystal forms.
The two-dimensional carbon material is selected from one of thin-layer graphite (the thickness is less than 4nm), graphene oxide, graphene nitride or graphene fluoride.
The grain size of the aluminum hydride is 20 nm-400 nm.
The invention also provides a preparation method of the two-dimensional load type nano aluminum hydride, which comprises the following steps:
(1) taking an Al-containing metal organic compound and a two-dimensional carbon material as raw materials, carrying out ball milling at room temperature under hydrogen atmosphere under the protection of argon, hydrogenating the Al-containing metal organic compound to generate alanate, and distributing the alanate on the two-dimensional carbon material to obtain a reaction product suspension;
(2) and (2) carrying out suction filtration and drying on the reaction product suspension obtained in the step (1) to obtain the two-dimensional supported nano aluminum hydride.
In the step (1), the purity of argon is 99.999%, and the ball-to-material ratio in the ball milling process is 10-40: 1.
In the step (1), the Al-containing metal organic compound is dissolved in hexane or heptane solution with the concentration of 0.6-1.3M to be used as a raw material, and the weight fraction is 90-99%.
The interaction between the two-dimensional carbon material and the aluminum-containing metal organic compound with a specific proportion leads the synthesized nano aluminum hydride to be capable of nucleating and growing on the two-dimensional carrier uniformly, and a very large specific surface area is obtained.
In the step (1), the molar ratio of the Al-containing metal organic compound to the two-dimensional carbon material is 1: 0.25-10, and the Al-containing metal organic compound is triethylaluminum.
In the step (1), the ball milling reaction time t is as follows: t is more than or equal to 10h and less than or equal to 100h, and the hydrogen pressure P is as follows: p is more than or equal to 2MPa and less than or equal to 10MPa, the purity of hydrogen is 99.0-99.99%, and the ball milling speed is 200-500 rpm.
In the invention, hydrogen is used as protective gas of reactants in the ball milling tank and is also used as a chemical synthesis reaction substance participating in the reaction; the hydrogen pressure is important as a chemical synthesis reaction substance participating in the reaction. If the concentration of hydrogen participating in the reaction is insufficient, the reaction driving force is small, and AlH is generated in the hydrogenation reaction process3The nucleation driving force of the product is weak, and AlH cannot be directly synthesized3Or synthesis of AlH3The yield of (a) is low. When the reaction hydrogen pressure is higher than 10MPa, the synthesis process is carried out under high pressure, the production cost is increased, and the operation safety is reduced. The hydrogen pressure P is thus controlled at: p is more than or equal to 2MPa and less than or equal to 10 MPa.
The ball milling time of the traditional ball milling synthesis of the coordination hydride is not more than 100h, and the AlH in the synthesized product is caused by slow reaction kinetics and insufficient ball milling reaction time in the hydrogenation reaction process3Little or no AlH3And (4) generating. On the other hand, the ball milling time is too long, so that the ball and the tank are abraded in the milling process, and impurities are introduced. Therefore, the ball milling time t is controlled to be more than or equal to 10h and less than or equal to 100 h.
Energy is required to provide when Al in the metal organic compound reacts with hydrogen, and the collision between the ball balls or the ball tanks in the ball milling process can provide local instantaneous high heat to drive the hydrogenation reaction. When the rotation speed of the mechanical ball mill is too low, the energy generated by collision is difficult to drive the hydrogenation reaction, and then AlH3It is difficult to synthesize. On the other hand, too high a rotational speed may increase the wear of the balls and the canister, resulting in moreImpurities are introduced, and the potential safety hazard is large. Therefore, the ball milling speed is controlled to be 200rpm to 500 rpm.
In the step (2), the drying temperature is 10-200 ℃, and the air pressure is 100 pa-1 × 105pa。
The metal organic compound is dissolved in a specific organic solution, the temperature is too low or the air pressure is too high in the drying process, the organic solution is incompletely volatilized, and the metal organic compound still serves as an impurity to be remained in the nano aluminum hydride. On the other hand, AlH3Has lower hydrogen releasing temperature (100-200 ℃), further reduces the hydrogen releasing temperature after ball milling, and ensures AlH at overhigh temperature3Decomposed during the drying process. Therefore, the drying temperature is controlled to be 10-200 ℃, and the air pressure is controlled to be 100 pa-1 × 105pa。
Preferably, the molar ratio of the Al-containing metal organic compound to the two-dimensional carbon material is 1: 2.5-3.5; the ball milling reaction time t is as follows: 20-30 h, wherein the hydrogen pressure P is as follows: 5-6 Mpa, and the ball milling rotating speed is 300-400 rpm; the drying temperature is 50-60 ℃, and the air pressure is 1 multiplied by 103～1×104pa. In the two-dimensional supported nano aluminum hydride prepared under the conditions, the aluminum hydride accounts for 42-50 wt% of the total mass, and the particle size is 20-200 nm. The two-dimensional supported alanate prepared under the conditions is uniformly distributed on the two-dimensional carbon material, and the hydrogen release temperature is obviously reduced compared with commercial massive alanate.
More preferably, the molar ratio of the Al-containing metal organic compound to the two-dimensional carbon material is 1: 2.5; the ball milling reaction time t is as follows: 20h, hydrogen pressure P is: 5Mpa, the ball milling rotating speed is 300 rpm; drying at 50 deg.C under 1 × 103pa. The aluminum hydride in the prepared two-dimensional supported nano aluminum hydride accounts for 50 wt% of the total mass, and the particle size is 50 nm-200 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional chemical reaction synthesis method, the synthesis method has the advantages of simple raw materials, simple operation, high production efficiency and low energy consumption, only has the participation of three elements of Al, C and H, and does not have impurity elements such as Li, Cl, B and the like, the process flow is greatly simplified, and the subsequent treatment such as impurity removal, precipitation and the like is not needed;
(2) compared with a direct synthesis method by utilizing Al under high-pressure hydrogen (10GPa) and high temperature (600 ℃), the method only needs to be carried out under medium hydrogen pressure (P is more than or equal to 2MPa and less than or equal to 10MPa) and room temperature, and has the advantages of simple temperature requirement, high safety, lower cost and less energy consumption;
(3) with other AlH3Compared with a nano method, the method has no impurity element introduced, and the final product only contains nano AlH3And the two-dimensional carbon material carrier ensures high purity;
(4) the invention firstly loads the nano particles with the particle size of 20 nm-200 nm on the surface of the two-dimensional carbon material uniformly by a liquid phase ball milling method, and realizes the AlH for the first time3Nano-loading of particles on a two-dimensional material; meanwhile, the excellent structure stability generated by the strong mutual combination of the nano aluminum hydride and the two-dimensional carbon material can inhibit the agglomeration and growth of nano particles.
Drawings
FIG. 1 is a transmission electron micrograph, a particle size distribution and an electron diffraction pattern of the two-dimensional supported nano aluminum hydride prepared in example 1;
FIG. 2 is a transmission electron micrograph, a particle size distribution and an electron diffraction pattern of the two-dimensional supported nano aluminum hydride prepared in example 2;
FIG. 3 is a transmission electron micrograph and an electron diffraction pattern of the two-dimensional supported nano-aluminum hydride prepared in example 3;
FIG. 4 is a transmission electron micrograph and an electron diffraction pattern of the two-dimensional supported nano-aluminum hydride prepared in example 3;
fig. 5 is an XRD spectrum of the two-dimensional supported nano aluminum hydride prepared in example 1 and example 3;
FIG. 6 is a transmission electron micrograph and a particle size distribution of the two-dimensional supported nano-aluminum hydride prepared in example 4;
fig. 7 is a transmission electron micrograph and a particle size distribution of the two-dimensional supported nano-aluminum hydride prepared in example 5.
Detailed Description
The present invention will now be described more fully and in detail with reference to the accompanying drawings and examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1
Two-dimensional load type nano aluminum hydride AlH3Preparation of @50 wt.% GR.
Dissolving 95% triethyl aluminum in 0.6M heptane solution as raw material, Graphene (GR) as two-dimensional carrier, according to AlH3The amount of the raw materials was calculated in a mass ratio of 1:1 (molar ratio: 1: 2.5). Under the protection of high-purity argon (99.999%), triethyl aluminum and a two-dimensional carbon material are placed in a ball milling tank of a ball mill, and the ball-to-material ratio in the ball milling process is 40: 1. Before ball milling, the ball tank is evacuated and exhausted to a vacuum degree of 1 × 103And pa, recharging hydrogen with the purity of more than or equal to 99% and the pressure of 5.0MPa, and then performing ball milling at room temperature for 20 hours at the ball milling rotating speed of 300rpm to obtain a product suspension. Filtering and drying the suspension of the ball-milling reaction product at 50 deg.C under 1 × 103pa to obtain two-dimensional load type nano aluminum hydride AlH3@50wt.％GR(300rpm)。
The two-dimensional supported nano-aluminum hydride AlH prepared by the embodiment3The transmission electron micrograph, particle size distribution and electron diffraction pattern of @50 wt.% GR (300rpm) are shown in FIG. 1, a-c, and it is clear from FIG. 1 that the product is only AlH3the graphene oxide has no other impurities, exists in α and beta crystal forms, and has the particle size of 50-200 nm, wherein the aluminum hydride particles are uniformly distributed on the graphene.
Example 2
Two-dimensional load type nano aluminum hydride AlH3Preparation of @50 wt.% GR.
Dissolving 95% triethyl aluminum in 0.6M heptane solution as raw material, Graphene (GR) as two-dimensional carrier, according to AlH3The amount of the raw materials was calculated in a mass ratio of 1:1 (molar ratio: 1: 2.5). Under the protection of high-purity argon (99.999%), triethyl aluminum and a two-dimensional carbon material are placed in a ball milling tank of a ball mill, and the ball-to-material ratio in the ball milling process is 40: 1. Before ball milling, the ball tank is evacuated and exhausted to a vacuum degree of 1 × 103pa, then filling hydrogen with the purity of more than or equal to 99 percent and the pressure of 5.0MPa, and then performing ball milling for 20 hours at room temperature, wherein the ball milling rotating speed is 400rpm, thus obtaining the productAnd (4) suspension of the product. Filtering and drying the suspension of the ball-milling reaction product at 50 deg.C under 1 × 103pa to obtain two-dimensional load type nano aluminum hydride AlH3@50wt.％GR(400rpm)。
The two-dimensional supported nano-aluminum hydride AlH prepared by the embodiment3The transmission electron micrograph, particle size distribution and electron diffraction pattern of @50 wt.% GR (400rpm) are shown in FIG. 2, a-c. As can be seen, the product is single-phase AlH3No other impurities exist, and only one crystal form exists; the aluminum hydride particles are uniformly distributed on the graphene, and the particle size is 20-100 nm.
Example 3
AlH of two-dimensional load type nano aluminum hydride3@75 wt.% GR preparation.
Dissolving 95% triethyl aluminum in 0.6M heptane solution as raw material, Graphene (GR) as two-dimensional carrier, according to AlH3The amount of the raw materials was calculated in a mass ratio of 1:3 (molar ratio of 1: 7.5). Under the protection of high-purity argon (99.999%), triethyl aluminum and a two-dimensional carbon material are placed in a ball milling tank of a ball mill, and the ball-to-material ratio in the ball milling process is 40: 1. Before ball milling, the ball tank is evacuated and exhausted to a vacuum degree of 1 × 103And pa, recharging hydrogen with the purity of more than or equal to 99% and the pressure of 5.0MPa, and then performing ball milling for 30 hours at room temperature, wherein the ball milling rotating speed is 300rpm, so as to obtain a product suspension. Filtering and drying the suspension of the ball-milling reaction product at 100 deg.c and 1 × 10 pressure5pa to obtain two-dimensional load type nano aluminum hydride AlH3@75wt.％GR。
The two-dimensional supported nano-aluminum hydride AlH prepared by the embodiment3The transmission electron microscope pattern and the electron diffraction pattern of @75 wt.% GR varying with the duration of electron beam irradiation are shown in FIGS. 3 and 4. As can be seen from the figure, a large amount of Al as a simple substance and a part of AlH are present3(ii) a The particles are wrapped with graphene and have a particle size of about 150 nm. It was found that AlH was contained in the sample under the dry condition of 100 ℃3Decomposition has occurred to generate an Al simple substance; also describes the nano AlH3The hydrogen release temperature of the reactor is lower than 100 ℃; compared with commercial bulk AlH3(the hydrogen releasing temperature is higher than 100 ℃), the hydrogen releasing temperature is obviously reduced, and the hydrogen releasing performance is good. The other partyThe graphene curls under the irradiation of electron beams, particles do not change obviously, and the components of a sample are Al and AlH3。
The XRD patterns of the products prepared in example 1 and example 3 under the same ball milling conditions and different drying conditions are shown in fig. 5. Due to AlH3In the form of nanoparticles and with a particle size too small to allow determination of AlH by XRD analysis3Presence of (a); in the sample prepared in example 3, the drying temperature of 100 ℃ was set to allow nano-AlH3Decomposition takes place, AlH3The thermal decomposition product of (3) is simple substance Al which can be detected by XRD. From this it is also demonstrated that nano-AlH3Can decompose and release hydrogen at a lower temperature, and has good hydrogen release performance.
Example 4
Two-dimensional load type nano aluminum hydride AlH3Preparation of @9 wt.% GR.
Dissolving 95% triethyl aluminum in 0.6M heptane solution as raw material, Graphene (GR) as two-dimensional carrier, according to AlH3The amount of the raw materials was calculated in a 10:1 mass ratio (molar ratio: 1: 0.25). Under the protection of high-purity argon (99.999%), triethyl aluminum and a two-dimensional carbon material are placed in a ball milling tank of a ball mill, and the ball-to-material ratio in the ball milling process is 40: 1. Before ball milling, the ball tank is evacuated and exhausted to a vacuum degree of 1 × 103And pa, recharging hydrogen with the purity of more than or equal to 99% and the pressure of 10.0MPa, and then performing ball milling for 10 hours at room temperature at the ball milling rotating speed of 200rpm to obtain a product suspension. Filtering and drying the suspension of the ball-milling reaction product at 200 deg.C under 1 × 105pa to obtain two-dimensional load type nano aluminum hydride AlH3@9wt.％GR。
The two-dimensional supported nano-aluminum hydride AlH prepared by the embodiment3The transmission electron micrograph and the electron diffraction pattern of @9 wt.% GR are shown in FIG. 6. As can be seen from the figure, the agglomeration of the aluminum hydride particles on the graphene is obvious, and the particle size is 100-400 nm.
Example 5
Two-dimensional load type nano aluminum hydride AlH3Preparation of @80 wt.% GR.
Taking 95% triethyl aluminum dissolved in 0.6M heptane solution as raw material, graphene (G)R) is a two-dimensional support according to AlH3The amount of the raw materials was calculated in a mass ratio of 1:4 (molar ratio: 1: 10). Under the protection of high-purity argon (99.999%), triethyl aluminum and a two-dimensional carbon material are placed in a ball milling tank of a ball mill, and the ball-to-material ratio in the ball milling process is 40: 1. Before ball milling, the ball tank is evacuated and exhausted to a vacuum degree of 1 × 103And pa, recharging hydrogen with the purity of more than or equal to 99% and the pressure of 2.0MPa, and then performing ball milling for 100 hours at room temperature at the ball milling rotation speed of 500rpm to obtain a product suspension. Carrying out suction filtration and drying on the suspension of the ball-milling reaction product at the drying temperature of 10 ℃ and the air pressure of 100pa to obtain the two-dimensional load type nano aluminum hydride AlH3@80wt.％GR。
The two-dimensional supported nano-aluminum hydride AlH prepared by the embodiment3The transmission electron micrograph and the electron diffraction pattern of @80 wt.% GR are shown in FIG. 7. As can be seen from the figure, the distribution of the aluminum hydride particles on the graphene is less, and the particle size is 40-100 nm.
Example 6
The preparation method of two-dimensional supported nano aluminum hydride as provided in example 1 is as follows3The amount of the raw materials was calculated in a ratio of 1:1.4 by mass (molar ratio: 1: 3.5). Hydrogen with the purity of more than or equal to 99 percent and 6.0MPa is filled before ball milling, and then the ball milling is carried out for 30 hours at room temperature, wherein the ball milling rotating speed is 350 rpm; drying at 60 deg.C under 1 × 104pa。
The two-dimensional supported nano-aluminum hydride AlH prepared by the embodiment3Products of @42 wt.% GR are AlH only3No other impurities, exists in two crystal forms; the aluminum hydride particles are uniformly distributed on the graphene, and the particle size is 50-200 nm. Drying at 100 deg.C to obtain nano AlH3Decomposition occurs, and thus it is also demonstrated that nano AlH3Can decompose and release hydrogen at a lower temperature, and has good hydrogen release performance.
Claims (6)
1. the preparation method of the two-dimensional supported nano aluminum hydride is characterized in that the two-dimensional supported nano aluminum hydride comprises a two-dimensional carbon material and aluminum hydrides distributed on the two-dimensional carbon material, the mass fraction of the aluminum hydrides is 20-90%, and the crystal forms of the aluminum hydrides are one or two of alpha crystal forms and beta crystal forms;
the preparation method comprises the following steps:
(1) taking an Al-containing metal organic compound and a two-dimensional carbon material as raw materials, carrying out ball milling at room temperature under hydrogen atmosphere under the protection of argon, hydrogenating the Al-containing metal organic compound to generate alanate, and distributing the alanate on the two-dimensional carbon material to obtain a reaction product suspension; the Al-containing metal organic compound is triethyl aluminum; the ball milling reaction time t is as follows: t is more than or equal to 10h and less than or equal to 100h, and the hydrogen pressure P is as follows: p is more than or equal to 2MPa and less than or equal to 10MPa, and the ball milling rotating speed is 200 rpm-500 rpm;
(2) and (2) carrying out suction filtration and drying on the reaction product suspension obtained in the step (1) to obtain the two-dimensional supported nano aluminum hydride.
2. The method for preparing two-dimensional supported nano aluminum hydride according to claim 1, wherein the two-dimensional carbon material is selected from one of graphite, graphene oxide, graphene nitride or graphene fluoride.
3. The method for preparing the two-dimensional supported nano aluminum hydride according to claim 1, wherein the particle size of the aluminum hydride is 20nm to 400 nm.
4. The method for preparing two-dimensional supported nano aluminum hydride according to claim 1, wherein in the step (1), the molar ratio of the metal organic compound containing Al to the two-dimensional carbon material is 1: 0.25-10.
5. The method for preparing two-dimensional supported nano aluminum hydride according to claim 1, wherein in the step (2), the drying temperature is 10 ℃ to 200 ℃ and the air pressure is 100pa to 1 x 105pa。
6. The method for preparing two-dimensional supported nano aluminum hydride according to claim 5, wherein in the step (1), the molar ratio of the Al-containing metal organic compound to the two-dimensional carbon material is 1: 2.5-3.5; ball with ball-shaped sectionThe milling reaction time t is: 20-30 h, wherein the hydrogen pressure P is as follows: 5-6 Mpa, and the ball milling rotating speed is 300-400 rpm; in the step (2), the drying temperature is 50-60 ℃, and the air pressure is 1 multiplied by 103～1×104pa。
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