CN1212974C - Zeolite-based nano metal oxide composite material and its preparing method - Google Patents
Zeolite-based nano metal oxide composite material and its preparing method Download PDFInfo
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- CN1212974C CN1212974C CN 03129239 CN03129239A CN1212974C CN 1212974 C CN1212974 C CN 1212974C CN 03129239 CN03129239 CN 03129239 CN 03129239 A CN03129239 A CN 03129239A CN 1212974 C CN1212974 C CN 1212974C
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Abstract
The present invention belongs to a functional material class, particularly to a novel zeolite-base nano metal oxide composite material. The composite material is prepared by immersing a zeolite molecular sieve in a metal salt solution and steaming and roastingthe mixture to form a nano metal oxide on the surface of the zeolite. The novel zeolite-base nano metal oxide composite material has the characteristics of simple preparation, low price, no toxicity, etc., and the novel zeolite-base nano metal oxide composite material is suitable for large-scale production.
Description
Technical field
The invention belongs to technical field of function materials, being specifically related to a kind of is the nano-metal-oxide composite functional material and preparation method thereof of substrate with the zeolite.
Background technology
Many metal oxides have electricity, optics, magnetics and the chemical feature of many uniquenesses, are widely used in technical fields such as information storage, transmitter, catalysis, photocell.When the particle of these metal oxides is in nanometer range, the variation of matter has appearred in their many character, these character for The application of new technique provide wide space [Adv.Funct.Mater.2003,13,9.].About the existing many pieces of bibliographical informations of the preparation of nano-metal-oxide, Tao Shi chemical company has invented a kind of metal-salt and has contained the method (Chinese patent of the amphipathic copolymer nano metal based powders of oxyethane, application number 99809832.9), this method is multipolymer to be mixed with metal-salt form metal-salt/multipolymer and stick with paste, and should stick with paste afterwards being enough to dewater and organic temperature lower calcination formation metal oxide.People such as Zhang Lide invent a kind of preparation method's (Chinese patent of nanometre titanium dioxide/silicon dioxide mesic hole compound, application number 98111113.0), they prepare the mesoporous SiO 2 solid with the gel-sol method, make solvent preparation butyl (tetra) titanate solution with dehydrated alcohol again, the mesoporous SiO 2 solid is put into butyl (tetra) titanate solution soak hydrolysis, it is 500～740m that the oven dry of taking-up back prepares specific surface area through hot-water cure again
2/ g, titanium dioxide nano-particle is less than the titanium dioxide/silicon dioxide mesic hole compound of 5nm in the complex body.People such as Gao Shanmin have invented a kind of preparation method's (Chinese patent of metal oxide nano-material, application number 00111310.0), mixed grinding metal-salt and alkali metal hydroxide in ball mill, make them that solid-solid phase moment chemical reaction take place, wash dissolving then with water removing an alkali metal salt that dereaction generates, after the filtration metal oxide and metal hydroxides blending filter cake at high temperature calcined and carry out secondary reaction and make.World patent (WO2003014011-A1) has been reported with metal alkylide alkoxide pyrolytic method in solvent and has been come the controlled nano-metal-oxide of preparation size.World patent (WO200071465-A, WO200071465-A1), German Patent (DE19923625-A1) be reported in poly-carboxylic acid exist add down alkali increase that pH value is settled out from the aqueous solution of metal-salt can be at the dispersive metal oxide nanoparticles, then nano-metal-oxide is separated from the aqueous solution, with the size of particles of the metal oxide of this method preparation at 1-20nm.World patent (WO200125367-A, WO200125367-A1), French Patent (FR2799392-A1) report is handled under hydrothermal condition with metal-salt and is obtained metal oxide nanoparticles, it is that precursor precipitates with hydroxide form in acidity or alkaline aqueous solution that this method is taked metal-salt, oxyhydroxide is formed oxide compound under certain pressure, this oxide nano-particles can be by redispersion in water or alcohol.It is that precursor joins in the aqueous solution of silicate suspension that world patent (WO2003004412-A1) has been reported with nonionogenic tenside and tart metal hydrate, produces a kind of preparation method of metal oxide nanoparticles as catalyzer in exfoliate silicate.
Zeolite molecular sieve is the inorganic poromerics of a class that is widely used in fields such as absorption, heterocatalysis, gas delivery and ion-exchange.In recent years, the zeolitization scholar chooses zeolite molecular sieve as main body, with pure substance as having the nanometer object that functional organism, inorganic salt, metal and metal oxide go out to have controlled microtexture as object in zeolite cavity interior orientation growth or assembly arranged evenly, thereby be built into new zeolite-nano composite material [Chem.Mater.1992,4,511.], as imperial outstanding person etc. LiCl is assembled into the STI zeolite and forms a kind of wet sensitive sensing material [Chem.Lett.2001,8,810], or the like.But these results only are confined to assemble nanometer clustered materials in the duct of zeolite and cage, and do not appear in the newspapers so far at the outside surface growing nano sized metal oxide of zeolite, and load on the nanoparticle of outer surface of zeolite, contact easilier, be suitable as very much catalyzer and sensing material with reactant molecule.
Summary of the invention
The object of the present invention is to provide a kind of is that the surface growth of substrate has advanced composite material of nano-metal-oxide and preparation method thereof with the zeolite molecular sieve, and this material has wide application prospects in fields such as light, electricity, magnetic, catalysis.
The matrix material of the Zeolite-based nano metal oxide that the present invention proposes is immersed in the soluble metallic salt by zeolite molecular sieve, roasting and obtaining in air then; Used zeolite base material can be the natural or synthesis zeolite of 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structural approaches, as the MFI (ZSM-5) of 10 oxygen unit ring, TON (ZSM-22), FER (ZSM-35), natural zeolite STI, the FAU of 12 oxygen unit ring (Y, X), LAL (L), MTN (ZSM-12), BEA (β), MOR, AlPO
4-5, (SO such as MTW
2/ Al
2O
3Scope 3～∞), and the presoma of metal oxide is the soluble metal salt, as metal halide, nitrate, vitriol, acetate, metal alkoxide class etc.
The concrete preparation method of above-mentioned Zeolite-based nano metal oxide is: soluble metal salt is dissolved in the corresponding solvent, be made into the solution of concentration at 1-5mol/L, then zeolite molecular sieve is immersed in wherein, soluble salt is 0.1-1 with the ratio of zeolite molecular sieve, after the oven dry, 300-700 ℃ of following roasting, the time of roasting was generally 1-10 hour, get final product nano-metal-oxide/Zeolite composite materials.
Novel material provided by the invention can be tested with the following method:
1.X-ray diffraction.This material is the matrix material that zeolite molecular sieve and nano-metal-oxide are formed, and can provide the strong diffraction peak of zeolite molecular sieve and the broadening characteristic diffraction peak of metal oxide in x-ray diffraction pattern, judges with this whether nano-metal-oxide forms.
2. transmission electron microscope.Can be clear that existence and the size of nano-metal-oxide by transmission electron microscope on the zeolite molecular sieve surface.
Be the test result of example explanation material of the present invention below with NaY zeolite molecular sieve and nano-stannic oxide.
Among Fig. 1, A is the x-ray diffraction pattern of typical NaY zeolite molecular sieve, B is the x-ray diffraction pattern of nano-stannic oxide and the formed matrix material of NaY zeolite, the weak peak of three broadenings belongs to 110 of tindioxide among the figure, 101, the diffraction peak of 211 3 crystal faces from the broadening of three diffraction peaks the strongest of tindioxide, illustrates that the nanoparticle of tindioxide forms.The result of transmission electron microscope has confirmed that further nano-stannic oxide forms (Fig. 2) at zeolite surface, and from transmission electron microscope photo, rod-like nano tindioxide particle is of a size of and is about is 60 nanometers, wide 12 nanometers that are about, and long-width ratio is 5.
Description of drawings
Among Fig. 1, A is the x-ray diffraction pattern of NaY zeolite molecular sieve, and B is the x-ray diffraction pattern of nano-stannic oxide and the formed matrix material of NaY zeolite.
Fig. 2 is the electromicroscopic photograph of above-mentioned matrix material.
Embodiment
Further describe the present invention below by examples Example:
Embodiment 1: the SnCl that takes by weighing 0.5g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1g NaY zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 600 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, both got product, be designated as SnO
2-NaY.This product characterizes with X-ray diffraction, transmission electron microscope: nano-stannic oxide forms at the NaY zeolite surface, and the nano-stannic oxide particle is of a size of and is about is 60 nanometers, wide 12 nanometers that are about, and long-width ratio is 5.
Embodiment 2: the SnCl that takes by weighing 0.4g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1g EFR zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 600 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-FER.This product characterizes with X-ray diffraction, transmission electron microscope: the size at EFR zeolite surface nano-stannic oxide particle is about 20 nanometers.
Embodiment 3: the SnCl that takes by weighing 0.4g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1g TON zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 600 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-TON.This product characterizes with X-ray diffraction, transmission electron microscope: the size at TON zeolite surface nano-stannic oxide particle is about 20 nanometers.
Embodiment 4: the SnCl that takes by weighing 0.5g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1g BEA zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water is put into muffle furnace with the magnetic boat, 600 ℃ of (roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-BEA.This product characterizes with X-ray diffraction, transmission electron microscope: the size at BEA zeolite Nanosurface tindioxide particle is about 15 nanometers.
Embodiment 5: the SnCl that takes by weighing 0.5g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1gZSM-5 zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 600 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-ZSM-5.This product characterizes with X-ray diffraction, transmission electron microscope: the size at ZSM-5 zeolite surface tindioxide particle is about 15 nanometers.
Embodiment 6: the TiCl that takes by weighing 2g
3Solution (contain 15%TiCl
3) be positioned in the magnetic boat, with 1g NaY zeolite molecular sieve dipping wherein, stir, 100 ℃ of heating, evaporating water is put into muffle furnace with the magnetic boat, 500 ℃ of roastings 2 hours, when treating that sample is reduced to room temperature, sample is taken out, and can get product, is designated as TiO
2-NaY.This product characterizes with X-ray diffraction, transmission electron microscope: the size at NaY zeolite surface TiO 2 particles is about 20 nanometers.
Embodiment 7: the FeCl that takes by weighing 0.5g
36H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1gNaY zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 600 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as Fe
2O
3-NaY.This product characterizes with X-ray diffraction, transmission electron microscope: the size at NaY zeolite surface ferric oxide particle is about 20 nanometers.
Claims (3)
1, a kind of Zeolite-based nano metal oxide composite is characterized in that it being to be immersed in the soluble metallic salt by zeolite molecular sieve, roasting and obtaining in air then; Used zeolite base material is the natural or synthesis zeolite of 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structural approaches, and this zeolite molecular sieve is a kind of of NaY, BEA, and used soluble metallic salt is metal-salt a kind of of Sn, Ti and Fe.
2, matrix material according to claim 1 is characterized in that said soluble metallic salt is a kind of of metal halide, nitrate, vitriol, acetate, metal alkoxide class.
3, a kind of preparation method of matrix material as claimed in claim 1, it is characterized in that concrete steps are as follows: soluble metal salt is dissolved in the corresponding solvent, be made into the solution that concentration is 1-5mol/L, then zeolite molecular sieve is immersed in wherein, soluble salt is 0.1-1 with the ratio of zeolite molecular sieve, and oven dry is 300-700 ℃ of following roasting, roasting time is 1-10 hour, get final product product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1297478C (en) * | 2003-11-28 | 2007-01-31 | 上海家化联合股份有限公司 | Molecular sieve based nano composite anti-ultraviolet material, its preparation method and use |
| CN1308243C (en) * | 2004-09-16 | 2007-04-04 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
| CN1295149C (en) * | 2004-12-01 | 2007-01-17 | 长春理工大学 | MCM-41 molecular sieve and titanium nanometer composite material, preparation thereof |
| CN101966465B (en) * | 2010-09-02 | 2012-05-30 | 中国科学院上海有机化学研究所 | Molecular sieve catalyst for use in preparation of isopulegol |
| CN104056657B (en) * | 2014-07-11 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Multi-stage porous SnO 2/ ZSM-5 methanol fuel cell anode catalyzer and preparation method thereof |
| CN106946268B (en) * | 2016-01-07 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method |
| CN106334576B (en) * | 2016-10-10 | 2018-10-23 | 大连民族大学 | A kind of auxiliary agent loaded photocatalyst and preparation method and application |
| CN106811200B (en) * | 2017-01-13 | 2020-04-24 | 环保桥（湖南）生态环境修复有限公司 | Composite repairing agent for reducing arsenic content in crops in arsenic-polluted area and preparation method thereof |
| CN109092351A (en) * | 2017-06-21 | 2018-12-28 | 江苏华伦化工有限公司 | A kind of preparation method and application of the support type composite molecular screen based on microwave technology |
| CN108341425A (en) * | 2018-02-05 | 2018-07-31 | 大连理工大学 | The preparation method and application of tin oxide/nano-ZSM-5 composite material |
| CN110330033A (en) * | 2019-07-19 | 2019-10-15 | 江苏理工学院 | A kind of preparation method and application of -22 molecular sieve of modified ZSM-5 |
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