CN1215980C - Method of catalyst synthesis nanometer lanthanide metal hydride - Google Patents
Method of catalyst synthesis nanometer lanthanide metal hydride Download PDFInfo
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- CN1215980C CN1215980C CN021417350A CN02141735A CN1215980C CN 1215980 C CN1215980 C CN 1215980C CN 021417350 A CN021417350 A CN 021417350A CN 02141735 A CN02141735 A CN 02141735A CN 1215980 C CN1215980 C CN 1215980C
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- lanthanide metal
- hydride
- nanometer
- hydrogen
- metal hydride
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- -1 lanthanide metal hydride Chemical class 0.000 title claims abstract description 26
- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 24
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims description 8
- 230000015572 biosynthetic process Effects 0.000 title claims description 7
- 238000003786 synthesis reaction Methods 0.000 title claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The nanometer science and technology becomes one of main science and technologies focused all over the world. The preparation of nanometer materials is the base of the nanometer science and technology, and is a researched core. The present invention provides a new method for synthesizing nanometer lanthanide metal hydrides through catalysis under normal pressure and at a temperature of 0 to 60 DEG C, and the method is used for synthesizing various lanthanide metal hydrides. The results measured by a transmission electron microscope indicate that the grain diameter of lanthanide metal hydrides is from 10 to 40 nm. The method has the advantages of mild reaction conditions, simple required equipment, easy control of operating conditions, high product yield and low production cost.
Description
Technical Field
The invention relates to a preparation method of nano lanthanide metal hydride. Specifically, under mild condition, in organic solvent, nano size lanthanide metal hydride is synthesized through catalytic process.
Background
Research in nanoscience and technology has become one of the most important technological fronts of worldwide interest. The nanometer material has very high dispersivity, very large specific surface area and very high surface energy owing to its size of nanometer order of magnitude (1-100nm), and its chemical reaction activity is 2-4 orders of magnitude higher than that of its corresponding conventional matter. They will have wide application value in the fields of catalytic chemistry, synthetic chemistry, material science, energy and environmental protection, resulting in direct economic benefits. The hydride composed of lanthanide metal and transition metal alloy is a hydrogen storage material, and has wide application prospect in modern science and industry fields.
The preparation of nano materials is the basis of nanotechnology and is a core research problem. The preparation of nanomaterials is generally divided into physical and chemical methods. Chemical methods are mainly used for preparing nanomaterials from molecules and atoms through appropriate chemical reactions (including liquid phase, gas phase and solid phase reactions). The synthesis of lanthanide metal hydride is usually prepared by direct reaction of lanthanide metal and hydrogen at high temperature, the reaction conditions are relatively harsh, and the productparticles are in the order of microns. At present, no literature report on a synthesis method of nano-size lanthanide metal hydride is found.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for catalytically synthesizing nano-sized lanthanide metal hydride in an organic solvent at 0-60 ℃ and normal pressure.
The method for catalytically synthesizing the nano lanthanide metal hydride can be represented by the following reaction formula:
the organic solvent is any one of tetrahydrofuran, 1, 4-dioxane, pyridine or toluene. Tetrahydrofuran is preferred.
The catalyst is any one of titanium tetrachloride, zirconium tetrachloride, ferric trichloride, cobalt dichloride, copper dichloride, titanocene dichloride or nickelocene. Titanium tetrachloride is preferred.
The nano lanthanide metal hydride synthesized by the invention has the particle size within the range of 10-40nm, and compared with lanthanide metal hydride with micron size, the nano lanthanide metal hydride has extremely high dispersity, extremely large specific surface area, extremely high surface energy and extremely high chemical reaction activity.
Detailed Description
The method for catalytically synthesizing nano lanthanide metal hydride provided by the present invention is further illustrated by the following examples.
EXAMPLE 1 catalytic Synthesis of Nano lanthanum hydride
Bulk lanthanum (purity>99.99%from Peking institute for nonferrous metals), sawing into chips with a steel saw, weighing 3.47g (25mmol) of lanthanum, adding into a reaction bottle, connecting the reaction bottle with a constant pressure hydrogen burette (pure hydrogen>99.99%), adding 15.0mL of THF (tetrahydrofuran) and 0.015mL of TiCl4The magnetic stirrer was turned on, the temperature was controlled by an oil bath, and immediately after counting, the hydrogen absorption amount of the reaction was directly read by a constant pressure hydrogen burette. And stopping the hydrogenation reaction of the metal lanthanum for 58 hours, transferring the whole reaction liquid into a single-mouth centrifuge bottle, centrifuging to separate a liquid phase (5000 r/min, 15min), washing a solid phase twice by using THF, and carrying out oil bath vacuum drying at the temperature of 80 ℃ for 1 hour to obtain black solid powder lanthanum hydride. The catalyst has high catalytic activity and can quantitatively convert lanthanum into lanthanized hydrogen. Determining the molecular formula as LaH according to the hydrogen absorption amount2.84. The composition of the nanometer rare earth metal hydride is a non-stoichiometric value, the composition of the large-particle rare earth metal hydride prepared by the traditional method is also a non-stoichiometric value, and the m value in LnHm is between 2 and 3. The particle size of the crystal is in the range of 10-40nm as determined by JEM-1200 EX transmission electron microscope, and the crystal is cubic as determined by XRD with D/Max-rb X-ray diffractometer.
EXAMPLE 2 catalytic Synthesis of Neodymium Nanohydride
The catalytic synthesis of nano neodymium hydride was performed according to the experimental method of example 1. The hydrogenation of metallic neodymium was stopped for 68 hours. The molecular formula is NdH determined according to the hydrogen absorption amount2.80. The particle size is within 10-40nm as determined by transmission electron microscope.
EXAMPLE 3 catalytic Synthesis of Nanohydrosamarium
The synthesis of nano-samarium hydride was catalyzed according to the experimental procedure of example 1. And stopping the hydrogenation reaction of the metal samarium for 120 hours. Determining molecular formula as SmH according to hydrogen absorption amount2.72. The particle size is within 10-40nm as determined by transmission electron microscope.
EXAMPLE 4 catalytic Synthesis of Nanohydrodysprosium
Nano dysprosium hydride was catalytically synthesized according to the experimental method of example 1. The hydrogenation reaction of metallic dysprosium is stopped for 173 hours. Determining molecular formula as DyH according to hydrogen absorption amount2.82. The particle size is within 10-40nm as determined by transmission electron microscope.
EXAMPLE 5 catalytic Synthesis of NanoYtterbrium hydride
The nano ytterbium hydride was catalytically synthesized according to the experimental method of example 1. The ytterbium metal hydrogenation reaction was stopped for 262 hours. Molecular formula of YbH according to hydrogen absorption2.55. The particle size is within 10-40nm as determined by transmission electron microscope.
On the whole, the synthesis of the hydride of the light rare earth lanthanum and neodymium has no induction period, and after the reagent is added, the hydrogen is absorbed immediately, so that the reaction is carried out quickly; the heavy rare earth ytterbium hydride has longer synthesis induction period and slower reaction. The catalyst has high catalytic activity and can quantitatively convert lanthanide metal into corresponding lanthanide metal hydride.
It can be seen from the above examples that the lanthanide can quantitatively synthesize nano lanthanide metal hydride under the action of catalyst in organic solvent at 0-60 deg.C and normal pressure by using the catalytic synthesis method of the present invention. The catalytic synthesis method has the advantages of mild reaction conditions, simple required equipment, easy control of operation conditions, high product yield, high catalyst efficiency and the like.
Claims (5)
1. The catalytic synthesis process of nanometer lanthanide metal hydride features that different lanthanide metal powder and hydrogen react at 0-60 deg.c and normal pressure in one organic solvent of tetrahydrofuran, 1, 4-dioxane, pyridine or toluene and in the presence of one catalyst of titanium tetrachloride, zirconium tetrachloride, ferric trichloride, cobalt dichloride, copper dichloride, titanocene dichloride or nickocene for 58-262 hr to synthesize lanthanide metal hydride powder with particle size of 10-40 nm.
2. The process of claim 1 wherein the catalyst is titanium tetrachloride.
3. The process according to claim 1, wherein the organic solvent is tetrahydrofuran.
4. The method of claim 1, wherein the hydrogen has a purity greater than 4 and 9.
5. The method of claim 1 wherein the synthesis of nanosized lanthanum hydride by lanthanum and hydrogen takes 58 hours and the synthesis of nanosized neodymium hydride by neodymium and hydrogen takes 68 hours; the ytterbium and hydrogen are reacted to synthesize nanometer size ytterbium hydride for 262 hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN021417350A CN1215980C (en) | 2002-08-29 | 2002-08-29 | Method of catalyst synthesis nanometer lanthanide metal hydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN021417350A CN1215980C (en) | 2002-08-29 | 2002-08-29 | Method of catalyst synthesis nanometer lanthanide metal hydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1478723A CN1478723A (en) | 2004-03-03 |
| CN1215980C true CN1215980C (en) | 2005-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN021417350A Expired - Fee Related CN1215980C (en) | 2002-08-29 | 2002-08-29 | Method of catalyst synthesis nanometer lanthanide metal hydride |
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| Country | Link |
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| CN (1) | CN1215980C (en) |
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| CN1478723A (en) | 2004-03-03 |
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