CN117654484A - Metal doped titanium dioxide nanotube and preparation method and application thereof - Google Patents
Metal doped titanium dioxide nanotube and preparation method and application thereof Download PDFInfo
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- CN117654484A CN117654484A CN202311668766.2A CN202311668766A CN117654484A CN 117654484 A CN117654484 A CN 117654484A CN 202311668766 A CN202311668766 A CN 202311668766A CN 117654484 A CN117654484 A CN 117654484A
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- titanium dioxide
- doped titanium
- dioxide nanotube
- aluminum hydride
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 239000002071 nanotube Substances 0.000 title claims abstract description 42
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 sodium aluminum hydride Chemical compound 0.000 claims abstract description 43
- 239000011232 storage material Substances 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001238 wet grinding Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 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
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of hydrogen storage materials, in particular to a titanium dioxide nanotube catalyst and a preparation method and application thereof. The metal doped titanium dioxide nanotube provided by the invention comprises TiO 2 Nanotubes and metal elements substituted for part of the Ti element; the metal element includes a transition metal element and/or a rare earth metal element. The invention adds low-valence variable metal by doping transition metal or rare earth metal, and the metal has excellent propertiesIs easy to be matched with NaAlH by oxidation-reduction property of (C) 4 Charge transfer occurs between the two, and NaAlH is quickened 4 Dehydrogenation reaction, tiO 2 Lattice distortion occurs, and surface oxygen is removed to form more oxygen vacancies, so that rich active sites are obtained, and the catalytic effect is enhanced. Therefore, the metal doped titanium dioxide nanotube provided by the invention can obviously reduce the decomposition temperature of sodium aluminum hydride.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a metal doped titanium dioxide nanotube and a preparation method and application thereof.
Background
The hydrogen is taken as a renewable energy source, and the practical application comprises three links of preparation, transportation and application, wherein the storage and transportation link is a key link for efficiently utilizing the hydrogen energy, is also an important link influencing the development direction of the hydrogen energy, is a key for improving the storage and transportation efficiency of the hydrogen energy and reducing the cost, and has great difficulty. Among solid hydrogen storage materials, alkali metal or alkaline earth metal alanates and borohydrides have the highest hydrogen storage mass density, can be a carrier for carrying a large amount of hydrogen, have stability in the storage process, and do not react easily at normal temperature. NaAlH 4 As a common aluminum hydride, the content of hydrogen is up to 7.4%, meets the standard of novel hydrogen storage materials, and is widely studied by people.
The decomposition process of sodium aluminum hydride is divided into three steps, namely, the sodium aluminum hydride is decomposed in the first step at 182 ℃ to 230 ℃ to generate Na 3 AlH 6 And Al, and releases hydrogen, then Na 3 AlH 6 The second step of decomposition occurs when the temperature reaches about 240 ℃, naH and Al are generated by decomposition, hydrogen is released, and the third step of decomposition reaction occurs when the temperature reaches 425 ℃, so that the practical application value of the NaH is seriously reduced.
To reduce the decomposition temperature, naAlH is increased 4 Many methods have been used, such as adding catalysts or additives, using nanorestraint techniques, to mix with reactive hydride composites. Currently, commonly used catalysts or additives are metals/transition metals, metal/transition metal oxides, metal/transition metal halides, alloys and carbon-based materials. However, the catalyst pair reduces NaAlH 4 The decomposition temperature effect of (c) is not good.
Disclosure of Invention
In view of the above, the present invention aims to provide a metal doped titanium dioxide nanotube and a preparation method thereof. The metal doped titanium dioxide nanotube provided by the invention can obviously reduce NaAlH 4 Decomposition temperature of (2).
In order to achieve the above object, the present invention provides a technical solution.
The invention provides a metal doped titanium dioxide nanotube, which comprises TiO 2 Nanotubes and metal elements substituted for part of the Ti element; the metal element comprises a transition metal element and/or a rare earth metal element; the molar ratio of the metal element to the Ti element in the metal doped titanium dioxide nanotube is 0.02-0.04:1.
Preferably, the transition metal is one or more of Mn, zr, co and V; the rare earth metal is one or more of Y, la, ce, sc and Sm.
The invention also provides a preparation method of the metal doped titanium dioxide nanotube, which comprises the following steps:
TiO is mixed with 2 Mixing powder, metal-containing salt, surfactant and alkali solution, performing hydrothermal reaction, sequentially performing first water washing, acid washing and filtering on a system obtained by the hydrothermal reaction, and performing second water washing on a solid phase obtained by filtering to obtain a hydrothermal product;
and drying and roasting the hydrothermal product to obtain the metal doped titanium dioxide nanotube.
Preferably, the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 16-24 hours.
Preferably, the roasting temperature is 300-600 ℃ and the roasting time is 2-6 hours.
The invention also provides an application of the metal doped titanium dioxide nanotube or the metal doped titanium dioxide nanotube prepared by the preparation method in sodium aluminum hydride based hydrogen storage materials.
The invention also provides a sodium aluminum hydride-based hydrogen storage material, which comprises sodium aluminum hydride and the metal doped titanium dioxide nanotube or the metal doped titanium dioxide nanotube prepared by the preparation method.
Preferably, the mass of the metal doped titanium dioxide nanotube is 1% -10% of the mass of the sodium aluminum hydride.
Preferably, the invention also provides a preparation method of the sodium aluminum hydride-based hydrogen storage material, which comprises the following steps:
mixing the metal doped titanium dioxide nanotube with sodium aluminum hydride, and sequentially carrying out wet grinding and drying to obtain the sodium aluminum hydride-based hydrogen storage material.
Preferably, the wet grinding medium is one or two of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; the ball milling rotating speed of wet milling is 400-800 r/min, and the time is 3-24 h.
The invention provides a metal doped titanium dioxide nanotube, which comprises TiO 2 Nanotubes and metal elements substituted for part of the Ti element; the metal element comprises a transition metal element and/or a rare earth metal element; the molar ratio of Ti to metal elements in the metal doped titanium dioxide nanotube is 1:0.05 to 0.15. The invention adds low-valence variable metal by doping transition metal or rare earth metal, and the metal has excellent oxidation-reduction characteristic and is easy to be matched with NaAlH 4 Charge transfer occurs between the two, so that Al-H bond breakage is promoted, and TiO 2 The lattice distortion occurs, more oxygen vacancies are formed, so that rich active sites are obtained, and the catalytic effect is enhanced, therefore, the metal doped titanium dioxide nanotube provided by the invention can obviously reduce the decomposition temperature of sodium aluminum hydride.
Drawings
FIG. 1 is a view showing Mn-TiO as prepared in example 1 2 An XRD pattern of (b);
FIG. 2 is a view of Mn-TiO as prepared in example 1 2 A TEM image of (a);
FIG. 3 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in example 1;
FIG. 4 is a graph showing the hydrogen desorption profile of the sodium aluminum hydride based hydrogen storage material prepared in example 1;
FIG. 5 is a DSC of the sodium aluminum hydride based hydrogen storage material prepared in example 2;
FIG. 6 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in comparative example 1;
FIG. 7 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in comparative example 2.
Detailed Description
The invention provides a metal doped titanium dioxide nanotube, which comprises TiO 2 Nanotubes and metal elements substituted for part of the Ti element; the metal element comprises a transition metal element and/or a rare earth metal element; the molar ratio of the metal element to the Ti element in the metal doped titanium dioxide nanotube is 0.02-0.04:1.
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 metal element includes a transition metal element and/or a rare earth metal element; the transition metal is preferably one or more of Mn, zr, co and V, more preferably Mn, zr or Co; the rare earth metal is preferably one or more of Y, la, ce, sc and Sm, more preferably Y, la or Ce.
In the invention, the molar ratio of the metal element to the Ti element in the metal doped titanium dioxide nanotube is 0.02-0.04:1, preferably 0.03:1.
the invention also provides a preparation method of the metal doped titanium dioxide nanotube, which comprises the following steps:
TiO is mixed with 2 Mixing the powder, the metal-containing salt, the surfactant and the strong alkali solution, and performing hydrothermal reaction to obtain a hydrothermal product;
TiO is mixed with 2 Mixing powder, metal-containing salt, surfactant and alkali solution, performing hydrothermal reaction, sequentially performing first water washing, acid washing and filtering on a system obtained by the hydrothermal reaction, and performing second water washing on a solid phase obtained by filtering to obtain a hydrothermal product;
and drying and roasting the hydrothermal product to obtain the metal doped titanium dioxide nanotube.
In the present invention, the metal-containing salt is preferably a metal nitrate salt, a metal chloride salt, or a metal sulfate salt; the nitrate metal salt is preferably Y (NO) 3 ) 2 、Mn(NO 3 ) 2 Or Ce (NO) 3 ) 2 。
In the present invention, the TiO 2 The particle size of the powder is preferably 20 to 100 nm, more preferably 20 nm. In the present inventionIn the light, the strong alkali solution is preferably a NaOH solution; the concentration of the NaOH solution is preferably 5-10 mol/L, more preferably 8mol/L. In the present invention, the surfactant is preferably cetyl trimethylammonium bromide (CTAB).
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.
In the present invention, the first water washing is preferably washed to neutrality; the pickling solvent is preferably nitric acid, and the nitric acid concentration is preferably 1mol/L. In the present invention, the second water washing is preferably washed to neutrality.
After the hydrothermal product is obtained, the method dries and bakes the hydrothermal product to obtain the metal doped titanium dioxide nanotube.
In the present invention, the temperature of the drying is preferably 100℃and the time is preferably 12 hours.
In the invention, the roasting temperature is preferably 300-600 ℃, more preferably 400 ℃; the time is preferably 2 to 6 hours, more preferably 4 to 5 hours.
The invention also provides application of the metal doped titanium dioxide nanotube in sodium aluminum hydride based hydrogen storage materials.
The invention also provides a sodium aluminum hydride-based hydrogen storage material, which comprises sodium aluminum hydride and the metal doped titanium dioxide nanotube.
In the invention, the mass of the metal doped titanium dioxide nanotube is preferably 1% -10% of the mass of the sodium aluminum hydride, and more preferably 2% -5%.
The invention also provides a preparation method of the sodium aluminum hydride based hydrogen storage material, which comprises the following steps:
mixing the metal doped titanium dioxide nanotube with sodium aluminum hydride, and sequentially carrying out wet grinding and drying to obtain the sodium aluminum hydride-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 drying temperature is preferably 50-80 ℃, more preferably 70 ℃, and the drying time is preferably 20-60 min, more preferably 30 min.
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
Weigh 0.8 g TiO 2 Powder and Mn (NO) 3 ) 2 Dispersing in 30 mL of 10mol/L NaOH solution according to the mol ratio of Ti to Mn=1:0.05, then reacting in a reaction kettle at 150 ℃ for 20h, washing with water to be neutral, stirring (acid washing) in 1mol/L nitric acid for 2h, and washing with deionized water to be neutral. 100. Drying at a temperature of 12℃ h, followed by calcination at a temperature of 350 ℃ for 4 h to obtain Mn-doped TiO 2 （Mn-TiO 2 ）；Mn-TiO 2 The molar ratio of Mn to Ti was 0.03:1. The bowl was then transferred to an argon filled glove box and 0.3 g NaAlH was added to the bowl 4 Mass ratio 5% (Mn-TiO) 2 Ratio NaAlH 4 5%) Mn-TiO 2 And 15 mL tetrahydrofuran, then sealing and transferring the mixture into a planetary ball mill for ball milling, wherein the total ball milling is carried out for 8 h at 500 r/min, and then drying the ball-milled sample to obtain the sodium aluminum hydride-based hydrogen storage material.
Example 2
1.0 g of TiO is weighed 2 Powder and Y (NO) 3 ) 2 Dispersing in 40 mL of 10mol/L NaOH solution according to the molar ratio of Ti to Y=1:0.08, then reacting 18 to h at 180 ℃ in a reaction kettle, washing to be neutral, stirring 2 to h in 1mol/L nitric acid, and washing to be neutral by deionized water. 100. Drying at a temperature of 12℃ h, and subsequently calcining at a temperature of 450 ℃ for 5h to obtain Y-doped TiO 2 （Y-TiO 2 ）；Y-TiO 2 The molar ratio of Y to Ti was 0.02:1. The bowl was then transferred to an argon filled glove box and 0.3 g NaAlH was added to the bowl 4 Mass ratio of 8% (Y-TiO) 2 Ratio NaAlH 4 5%) of Y-TiO 2 And 10 mL tetrahydrofuran, then sealing and transferring the mixture into a planetary ball mill for ball milling, wherein the total ball milling speed is 600r/min, the total ball milling speed is 10 h, and then drying the ball-milled sample to obtain the sodium aluminum hydride-based hydrogen storage material.
Example 3
1.8 g of TiO was weighed 2 Powder and Mn (NO) 3 ) 2 、Y(NO 3 ) 2 Dispersing in 50 mL of 8mol/L NaOH solution according to the ratio of Ti to Mn to Y=1:0.09:0.01, then reacting in a reaction kettle at 200 ℃ for 16 h, washing with water to be neutral, stirring in 1mol/L nitric acid for 2h, and washing with deionized water to be neutral. 100. Drying at a temperature of 12 ℃ h, and then roasting at a temperature of 500 ℃ for 5h to obtain Mn and Y co-doped TiO 2 （MnY-TiO 2 ）。MnY-TiO 2 The molar ratio of Y to Mn to Ti is 0.04:1; the bowl was then transferred to an argon filled glove box and 0.3 g NaAlH was added to the bowl 4 Mass ratio 5% (MnY-TiO) 2 Ratio NaAlH 4 5%) of MnY-TiO 2 And 10 mL tetrahydrofuran, then sealing and transferring the mixture into a planetary ball mill for ball milling, wherein the total ball milling speed is 800 r/min, the total ball milling speed is 12h, and then drying the ball-milled sample to obtain the sodium aluminum hydride-based hydrogen storage material.
Example 4
1.8 g of TiO was weighed 2 Powder and Ce (NO) 3 ) 2 Dispersing in 50 mL of 7 mol/L NaOH solution according to the ratio of Ti to Ce=1 to 0.15, then reacting in a reaction kettle at 180 ℃ for 24 h, washing to be neutral, stirring in 1mol/L nitric acid for 2h, and washing to be neutral by deionized water. 100. Drying at a temperature of 12 ℃ h, and then roasting at a temperature of 400 ℃ for 5h to obtain Ce-doped TiO 2 （Ce-TiO 2 ）；Ce-TiO 2 The molar ratio of Ce to Ti was 0.03:1. The bowl was then transferred to an argon filled glove box and 0.3 g NaAlH was added to the bowl 4 Mass ratio of 8% (MnY-TiO) 2 Ratio NaAlH 4 8%) of MnY-TiO 2 And 8 mL tetrahydrofuran, then sealing and transferring the mixture into a planetary ball mill for ball milling, wherein the total ball milling speed is 600r/min, the total ball milling speed is 12h, and then drying the ball-milled sample to obtain the sodium aluminum hydride-based hydrogen storage material.
Comparative example 1
The ball mill jar was transferred to an argon filled glove box and 0.3 g NaAlH was added to the ball mill jar 4 And 10 mL tetrahydrofuran, then transferring the mixture into a planetary ball mill in a sealing way for ball milling, wherein the ball milling speed is 450 r/min, the total ball milling speed is 8 h, and then drying the ball-milled sample to obtain the sodium aluminum hydride-based hydrogen storage material.
Comparative example 2
1.8 g of TiO was weighed 2 Dispersing the powder in 50 mL of 7 mol/L NaOH solution, then reacting 24 h at 180 ℃ in a reaction kettle, drying 12h at 100 ℃ after washing for multiple times, and then roasting 5h at 400 ℃ to obtain TiO 2 A catalyst. The bowl was then transferred to an argon filled glove box and 0.3 g NaAlH was added to the bowl 4 Mass ratio 5% (TiO) 2 Ratio NaAlH 4 8%) of TiO 2 And (3) hermetically transferring the nano particles and 10 mL tetrahydrofuran into a planetary ball mill for ball milling, wherein the total ball milling speed is 450 r/min, the total ball milling speed is 6 h, and then drying the ball-milled sample to obtain the sodium aluminum hydride-based hydrogen storage material.
The sodium aluminum hydride based hydrogen storage materials prepared in the examples and the comparative examples are subjected to hydrogen release performance test, wherein the test methods are a Differential Scanning Calorimeter (DSC) and a programmed temperature desorption Test (TPD).
FIG. 1 is a view showing Mn-TiO as prepared in example 1 2 As can be seen from fig. 1: after Mn doping, diffraction peaks corresponding to Mn do not appear, and original TiO is still maintained 2 Since Mn is uniformly dispersed in the interior of the crystal lattice, substituting for Ti having +4 valence, causing lattice distortion to form an amorphous state.
FIG. 2 is a view of Mn-TiO as prepared in example 1 2 As can be seen from the TEM image of fig. 2: mn-TiO 2 The appearance is nano-tube shape.
FIG. 3 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in example 1, as can be seen from FIG. 3: 164.1 Hydrogen is discharged at the temperature of 265.0 ℃ twice before the temperature is increased; peak temperatures were 182.7 ℃,226.8 ℃,364.2 ℃, respectively.
Fig. 4 is a graph showing the hydrogen desorption profile of the sodium aluminum hydride based hydrogen storage material prepared in example 1, as can be seen from fig. 4: the hydrogen release amount at 300 ℃ is 6.0 percent.
FIG. 5 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in example 2, as can be seen from FIG. 5: 178.6 Hydrogen is discharged at the temperature of 258.1 ℃ and discharged twice before the temperature is finished; the peak temperatures were 188.4 ℃,237.1 ℃ and 369.0 ℃, respectively.
FIG. 6 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in comparative example 1, beginning hydrogen desorption at 179.6℃and ending twice hydrogen desorption at 300.0 ℃; the peak temperatures were 184.3 ℃,280.0 ℃ and 373.7 ℃, respectively.
FIG. 7 is a DSC chart of the sodium aluminum hydride based hydrogen storage material prepared in comparative example 2, as can be seen from FIG. 7: 178.6 Hydrogen is discharged at the temperature of 294.4 ℃ twice before the end; peak temperatures were 186.6 ℃,270.8 ℃,376.2 ℃, respectively.
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 (10)
1. A metal doped titanium dioxide nanotube is characterized by comprising TiO 2 Nanotubes and metal elements substituted for part of the Ti element; the metal element comprises a transition metal element and/or a rare earth metal element; the molar ratio of the metal element to the Ti element in the metal doped titanium dioxide nanotube is 0.02-0.04:1.
2. The metal-doped titanium dioxide nanotube according to claim 1, wherein the transition metal is one or more of Mn, zr, co and V; the rare earth metal is one or more of Y, la, ce, sc and Sm.
3. The method for preparing the metal-doped titanium dioxide nanotube according to claim 1 or 2, comprising the following steps:
TiO is mixed with 2 Mixing powder, metal-containing salt, surfactant and alkali solution, performing hydrothermal reaction, sequentially performing first water washing, acid washing and filtering on a system obtained by the hydrothermal reaction, and performing second water washing on a solid phase obtained by filtering to obtain a hydrothermal product;
and drying and roasting the hydrothermal product to obtain the metal doped titanium dioxide nanotube.
4. The method according to claim 3, wherein the hydrothermal reaction is carried out at a temperature of 120-200 ℃ for 16-24 hours.
5. The method according to claim 4, wherein the baking temperature is 300-600 ℃ and the baking time is 2-6 hours.
6. The metal-doped titanium dioxide nanotube according to claim 1 or 2 or the application of the metal-doped titanium dioxide nanotube prepared by the preparation method according to any one of 3-5 in sodium aluminum hydride-based hydrogen storage materials.
7. The sodium aluminum hydride-based hydrogen storage material is characterized by comprising sodium aluminum hydride and the metal-doped titanium dioxide nanotube prepared by the preparation method of any one of claims 1 or 2 or 3-5.
8. The sodium aluminum hydride based hydrogen storage material of claim 7, wherein the mass of the metal doped titanium dioxide nanotubes is 1% -10% of the mass of the sodium aluminum hydride.
9. The method for producing a sodium aluminum hydride-based hydrogen storage material as claimed in claim 7 or 8, characterized by comprising the steps of:
mixing the metal doped titanium dioxide nanotube with sodium aluminum hydride, and sequentially carrying out wet grinding and drying to obtain the sodium aluminum hydride-based hydrogen storage material.
10. The method according to claim 9, wherein the wet-milling medium is one or two of tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether; the ball milling rotating speed of wet milling is 400-800 r/min, and the time is 3-24 h.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007930A1 (en) * | 1998-08-06 | 2000-02-17 | University Of Hawaii | Novel hydrogen storage materials and method of making by dry homogenation |
| JP2002234701A (en) * | 2001-02-07 | 2002-08-23 | Toyota Central Res & Dev Lab Inc | Method and apparatus for generating hydrogen |
| JP2006051473A (en) * | 2004-08-16 | 2006-02-23 | Toyota Central Res & Dev Lab Inc | Hydrogen storing/releasing catalyst and hydrogen storing compound material using the same |
| KR100814951B1 (en) * | 2006-09-27 | 2008-03-19 | 한양대학교 산학협력단 | Production method of transition metal doped titanate dioxide nano-tube |
| WO2008094007A1 (en) * | 2007-02-01 | 2008-08-07 | Seoul National University Industry Foundation | Polymer-metal hydride complexes containing aromatic group as hydrogen storage materials and a method of preparing the same |
| US20090242382A1 (en) * | 2008-03-06 | 2009-10-01 | Lipinska-Kalita Kristina E | Hollow glass microsphere candidates for reversible hydrogen storage, particularly for vehicular applications |
| US20120003146A1 (en) * | 2010-07-02 | 2012-01-05 | Microbes Unlimited, Llc | Naturally-occurring nanomatrix biomaterials as catalysts |
| CN102950009A (en) * | 2012-10-12 | 2013-03-06 | 南京大学 | Load type CoB catalyst for process of preparing hydrogen through hydrolysis of sodium borohydride and preparation method of load type CoB catalyst |
| CN103183314A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Composite hydrogen storage material with foamed structure and preparation method thereof |
| CN105800680A (en) * | 2016-03-14 | 2016-07-27 | 武汉理工大学 | Preparation method of titanium dioxide nanotube doped with transition metal |
| CN108439331A (en) * | 2018-05-28 | 2018-08-24 | 桂林电子科技大学 | A kind of preparation method and application of the sodium aluminum hydride hydrogen storage material of metatitanic acid additive Mn |
-
2023
- 2023-12-07 CN CN202311668766.2A patent/CN117654484B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007930A1 (en) * | 1998-08-06 | 2000-02-17 | University Of Hawaii | Novel hydrogen storage materials and method of making by dry homogenation |
| JP2002234701A (en) * | 2001-02-07 | 2002-08-23 | Toyota Central Res & Dev Lab Inc | Method and apparatus for generating hydrogen |
| JP2006051473A (en) * | 2004-08-16 | 2006-02-23 | Toyota Central Res & Dev Lab Inc | Hydrogen storing/releasing catalyst and hydrogen storing compound material using the same |
| KR100814951B1 (en) * | 2006-09-27 | 2008-03-19 | 한양대학교 산학협력단 | Production method of transition metal doped titanate dioxide nano-tube |
| WO2008094007A1 (en) * | 2007-02-01 | 2008-08-07 | Seoul National University Industry Foundation | Polymer-metal hydride complexes containing aromatic group as hydrogen storage materials and a method of preparing the same |
| US20090242382A1 (en) * | 2008-03-06 | 2009-10-01 | Lipinska-Kalita Kristina E | Hollow glass microsphere candidates for reversible hydrogen storage, particularly for vehicular applications |
| US20120003146A1 (en) * | 2010-07-02 | 2012-01-05 | Microbes Unlimited, Llc | Naturally-occurring nanomatrix biomaterials as catalysts |
| CN103183314A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Composite hydrogen storage material with foamed structure and preparation method thereof |
| CN102950009A (en) * | 2012-10-12 | 2013-03-06 | 南京大学 | Load type CoB catalyst for process of preparing hydrogen through hydrolysis of sodium borohydride and preparation method of load type CoB catalyst |
| CN105800680A (en) * | 2016-03-14 | 2016-07-27 | 武汉理工大学 | Preparation method of titanium dioxide nanotube doped with transition metal |
| CN108439331A (en) * | 2018-05-28 | 2018-08-24 | 桂林电子科技大学 | A kind of preparation method and application of the sodium aluminum hydride hydrogen storage material of metatitanic acid additive Mn |
Non-Patent Citations (3)
| Title |
|---|
| 花朵;施春红;袁蓉芳;周北海;马丽;: "金属掺杂对纳米管TiO_2光催化性能的影响", 功能材料, vol. 44, no. 21, 31 December 2013 (2013-12-31), pages 3163 - 3168 * |
| 董发勤等: "生态功能基元材料及其复合建材集成技术", 31 October 2008, 电子科技大学出版社, pages: 77 * |
| 郑雪萍;刘状壮;冯鑫;董艳丽;张刚;: "过渡金属氧化物掺杂NaAlH_4放氢性能", 稀有金属材料与工程, vol. 41, no. 09, 30 September 2012 (2012-09-30), pages 1619 - 1622 * |
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