CN101723332B - Complex oxide nanophase material, nanophase structure and method for preparing same - Google Patents
Complex oxide nanophase material, nanophase structure and method for preparing same Download PDFInfo
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- CN101723332B CN101723332B CN2008102254100A CN200810225410A CN101723332B CN 101723332 B CN101723332 B CN 101723332B CN 2008102254100 A CN2008102254100 A CN 2008102254100A CN 200810225410 A CN200810225410 A CN 200810225410A CN 101723332 B CN101723332 B CN 101723332B
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Abstract
The invention provides a complex nanophase structure. The nanophase structure is formed by a compound of a molecular formula AwBxCyOz, wherein A is Mn, Fe, Co, Ni, In or Zn; B is Mo; C is Cu; the summation of wa, xb and yc is 2z; and a, b and c are the valence states of metallic elements A, B and C respectively. The invention also provides a method for preparing the nanophase structure and a nanophase material comprising the nanophase structure. Compared with a binary oxide nanophase material, the complex oxide nanophase structure and the nanophase material of the invention usually have complex and special crystalline structures so as to show some special physical and chemical properties that the binary oxide nanophase material does not have. The preparation of the nanophase structure of the invention does not need any catalyst and is simple and low in cost.
Description
Technical field
The nanostructure that the present invention relates to a kind of multivariant oxide nano material and form by this nano material and the preparation method of this nanostructure.
Background technology
Along with nano science and technology rapid development, the preparation of one dimension Nano structure array and application thereof more and more receive extensive concern.This one dimension Nano structure array or accurate array have many-sided purposes according to material system is different, can be used as feds, various biologies and gas sensor, nanometer generating device and magnetic storage components and parts etc.Therefore, extensively carried out research in the world, become one of nanometer material science and Study on Technology focus various one dimension Nano structure array growth methods explorations and performance thereof.
At present, the method for preparing the one dimension Nano structure array mainly comprises solution method and chemical vapor deposition (CVD) method.The former mainly utilizes some medium with holes as template, after processing one dimension Nano structure, removes template, thereby obtains array structure.Yet, more be to adopt chemical Vapor deposition process.Flow process is as the one of which: at first on substrate deposition certain have the catalyst film of certain thickness (depend on will prepare nanostructure diameter); The certain hour of then under suitable temperature, annealing; Obtain the size homogeneous as far as possible and finely dispersed granules of catalyst (has certain selectivity; Different nanostructures needs dissimilar catalyzer), and then adopt CVD method deposition growing.It is generally acknowledged that chemical Vapor deposition process prepares nanostructure to carry out with two kinds of mechanism usually, promptly gas-solid (VS) and gas-liquid-solid (VLS) mechanism.VS mechanism is to need sedimentary material to form gas phase with the distillation form in the high-temperature zone, then through gas transmission, condenses when arriving cold zone, forms nanostructure.This mechanism generally need not used catalyzer, but is difficult to form the one dimension Nano structure array.And being the deposition material gas phase, VLS mechanism in liquid state or semi-solid state granules of catalyst, dissolves;, concentration separates out forming core when meeting or exceeding its saturation solubility; Form one dimension Nano structure or array through continuous growth, catalyzer often is present in the end or the root of one dimension Nano structure.This shows that it has certain limitation and deficiency the characteristics of traditional C VD method growth of one-dimensional nano structure and process decision: 1. different types of nanostructure has stronger selectivity to catalyzer; 2. nanostructure size depends on catalyst particle size; 3. need special catalyzer plated film and growth apparatus, cost is higher; 4. be difficult to grow ternary or the above nano wire of ternary; 5. the existence of granules of catalyst is remarkable to the performance impact of nano-structure array, limited use; 6. large-area preparation receives the restriction of filming equipment and growth apparatus size, and cost is increased sharply, and growth technique is complicated.
In order to overcome the limitation of traditional C VD method growth of one-dimensional nano array of structures or accurate array, improve and additional this growth method, but we have proposed the method for a kind of large area deposition nano material and nanostructure thereof.Product has the form of one dimension Nano structure array or accurate array.This method need not to use catalyzer, simple, cost is low.Simultaneously, the oxide nano structure among the present invention is quaternary and the above oxide nano structure of quaternary.
Summary of the invention
The present invention's one purpose provides a kind of oxide-based nanomaterial.
Another purpose of the present invention provides a kind of multivariant oxide nanostructure.
Still a further object of the present invention also provides a kind of method for preparing the multivariant oxide nanostructure.
One aspect of the present invention provides a kind of multivariant oxide nanostructure, and this nanostructure is by molecular formula A
wB
xC
yO
zCompound formation, A is Mn, Fe, Co, Ni, In or Zn in the formula, B is Mo, C is Cu, and wa+xb+yc=2z, a, b and c are respectively the valence state of metal element A, B and C.Because Mn, Fe, Co, Ni, In and Zn and oxide compound thereof all can react at certain condition with CuO with Mo with low sublimation temperature and the oxide compound of Mo, the formation multi-element metal oxide.Therefore, these pairing metallic elements of MOX with higher sublimation temperature all can be the A in the molecular formula.
Preferably, described nanostructure is nano wire, nanometer rod or nanometer sheet.
The present invention also provides a kind of method for preparing described nanostructure on the other hand, and this method may further comprise the steps:
The container that a. will fill A metal or its oxide compound places body of heater 1000-1400 ℃ warm area; The container that fills B metal or its oxide compound is placed body of heater 600-1000 ℃ warm area, and C tinsel or the substrate that is coated with the C metallic membrane are placed body of heater 400-600 ℃ warm area;
B. the mixed gas of aerating oxygen and rare gas element in body of heater; Make 1) A metal or its oxide vapor and 2) B metal or its oxide vapor be simultaneously to the C tinsel or be coated with on the substrate of C metallic membrane and transmit; And kept 2-40 hour, at the C tinsel or be coated with on the substrate of C metallic membrane and obtain described nanostructure;
Wherein said A metal is Mn, Fe, Co, Ni, In or Zn, and described B metal is Mo, and described C metal is Cu.
Because different metal or its MOX have different saturated vapor pressures under differing temps, and Cu just can grow nanostructure under proper temperature.So, fill 1 among the present invention) and the container, 2 of A metal or its oxide compound) container and 3 of B metal or its oxide compound) C tinsel or the substrate that is coated with the C metallic membrane should place the differing temps district of body of heater respectively.The present invention is at 1000-1400 ℃ warm area, and the A metallic element is oxidized to after the oxide compound of A metal distillation or the A MOX directly distils, and produces oxide compound steam; At 600-1000 ℃ warm area, the B metallic element is oxidized to the distillation afterwards of B MOX or the B MOX directly distils, and produces oxide vapor; Warm area at 400-600 ℃; At the C tinsel or be coated with that the C direct oxidation forms its corresponding oxide nano structure on the substrate of C metallic membrane; The steam of A MOX and B MOX is also reacted with it by the oxide nano structure place of the mixed gas delivery of oxygen and rare gas element to C, has formed A
wB
xC
yO
zNanostructure.
Preferably, in described step b, the mixed gas of the rare gas element of the oxygen of feeding 15%-25% volume parts and surplus in body of heater, the flow velocity of this mixed gas is 10-200sscm.This proportioning is that oxygen content approaches its aerial content in the mixed gas in order to make.
Preferably, wherein the thickness of the C tinsel described in the step a is 50-100 μ m, and the substrate of the described C of being coated with metallic membrane is the substrate that is coated with the C metallic membrane of 50-100 μ m thickness.
Preferably, wherein the thickness of the C tinsel described in the step a is 50-80 μ m, and the substrate of the described C of being coated with metallic membrane is the substrate that is coated with the C metallic membrane of 50-80 μ m thickness.
Preferably, wherein in described step a, the substrate of the described C of being coated with metallic membrane is that the method through thermal evaporation, electron beam evaporation plating or magnetron sputtering plates the C metallic membrane on substrate, forms the substrate that is coated with the C metallic membrane.
Further aspect of the present invention also provides a kind of nano material, and this nano material comprises described nanostructure.
Preferably, wherein said nanostructure is the on-chip nanostructure that evenly is grown in the C tinsel or is coated with the C metallic membrane, and described C metal is Cu.
Different with prior art is that nano material among the present invention and nanostructure are the nano material and the nanostructure of multivariant oxide, the i.e. nano material of quaternary oxide compound and structure.And the nano material among the present invention, promptly evenly being grown in the C tinsel or being coated with the on-chip nanostructure of C metallic membrane is the form of array or accurate array.Existing common oxide nano structure and be mainly binary oxide nano wire and nano-array thereof by the array that nanostructure forms, as: tungsten oxide nano and nano-array thereof, nickel oxide nano line and nano-array thereof, TiOx nano line and nano-array thereof.Quaternary oxide nano structure among the present invention and quaternary oxide-based nanomaterial can be applied to many different fields, like preparation feds, various biology, gas sensor, nanometer generating device, magnetic storage components and parts, energy conversion component and as catalyzer.Different with binary oxide nanostructure and nano material is; Quaternary oxide nano structure and nano material are compared with the binary oxide nano material and are had comparatively complicated and special crystalline structure usually among the present invention; Therefore also show binary oxide nano material not available some specific physics and chemical property, perhaps some performance is improved and improves.During for example equally as nanocatalyst; Valence state takes place and changes in the multiple metals ion in the quaternary oxide-based nanomaterial among the present invention in some carbonaceous organic material process of catalysis; Mutually promote and make that catalyzed reaction more is prone to carry out; And then catalytic performance significantly improves, and this is that wherein arbitrary metal and corresponding binary oxide nano material are not available.In addition, these quaternary oxide-based nanomaterials are according to the different different field that can be applicable to kind of type, like catalysis, spintronics, magnetic recording storage, an emission components and parts and gas sensing components and parts etc.The common relative narrower in field that many binary oxide nano materials can be used, and performance often is difficult to satisfy the real world applications requirement.Simultaneously, the multivariant oxide nanostructure that adopts among the present invention and the growth preparation method of nano material also are different from existing chemical vapour deposition, promptly are different from traditional gas-solid and gas-liquid-solid growth mechanism.At first, rely on the stress that produces in self internal stress and the oxidising process of the C mf that forms on C tinsel or the substrate to become the motivating force of nano-array nucleation.The growth of nano-array of the present invention need not to use any catalyzer.Method of the present invention also is applicable to the nanostructure and the nano material of the MOX that the preparation quaternary is above simultaneously.The distribution density of nano-array and length can be controlled through the amount of Heating temperature, gas flow rate, heat-up time and A among the preparation technology and B metal or its oxide compound and the Heating temperature of C metal among the present invention.Because the present invention prepares in the complex oxide nanostructure process and need not use catalyzer, so also there is not the problem of catalysts influence product property.The area of the quaternary oxide-based nanomaterial among the present invention only receives the size of heat resource equipment and the restriction of tinsel and film size thereof to it is provided, and does not receive the restriction of other growth factor.
Description of drawings
Fig. 1 representes the embodiment of the invention 1 preparation Cu
2Zn
1.75Mo
3O
12The schematic flow sheet of nanostructure.
Fig. 2 representes the Cu of the embodiment of the invention 1 preparation
2Zn
1.75Mo
3O
12
Embodiment
Following examples are used to explain the present invention, and are not used in restriction the present invention.
Embodiment 1
Body of heater in the present embodiment is available from the commodity of the Cole instrument company in BeiJing ZhongKe high-temperature tubular process furnace by name, and its article number is F54540CM-33.
In body of heater, place the Copper Foil of 100 micron thickness in 500 ℃ the warm area,, will fill MoO filling the warm area that ZnO particulate crucible places 1200 ℃ in process furnace
3The particulate crucible places the warm area of 600 ℃ in process furnace.In body of heater, feed O
2With the mixed gas of Ar, wherein O
2With the volume ratio of Ar be 1:4, the flow velocity of mixed gas is 50sscm.After 10 hours, take out Copper Foil, on Copper Foil, grow the nano-array of the quaternary oxide compound that contains Cu, Mo, Zn element.
The X-ray diffraction result confirms that this oxide nano thread is Cu
2Zn
1.75Mo
3O
12
Claims (10)
1. polynary nanometer structure, this nanostructure is A by molecular formula
wB
xC
yO
zCompound formation, A is Mn, Fe, Co, Ni, In or Zn in the formula, B is Mo, C is Cu, and wa+xb+yc=2z, a, b and c are respectively the valence state of metal element A, B and C.
2. nanostructure according to claim 1, wherein said nanostructure are nano wire, nanometer rod or nanometer sheet.
3. method for preparing claim 1 or 2 described nanostructures, this method may further comprise the steps:
The container that a. will fill A metal or its oxide compound places body of heater 1000-1400 ℃ warm area; The container that fills B metal or its oxide compound is placed body of heater 600-1000 ℃ warm area, and C tinsel or the substrate that is coated with the C metallic membrane are placed body of heater 400-600 ℃ warm area;
B. the mixed gas of aerating oxygen and rare gas element in body of heater; Make 1) A metal or its oxide vapor and 2) B metal or its oxide vapor be simultaneously to the C tinsel or be coated with on the substrate of C metallic membrane and transmit; And kept 2-40 hour, at the C tinsel or be coated with on the substrate of C metallic membrane and obtain described nanostructure;
Wherein said A metal is Mn, Fe, Co, Ni, In or Zn, and described B metal is Mo, and described C metal is Cu.
4. method according to claim 3, in described step b, the mixed gas of the rare gas element of the oxygen of feeding 15%-25% volume parts and surplus in body of heater, the flow velocity of this mixed gas is 10-200sscm.
5. method according to claim 4, wherein said rare gas element are argon gas.
6. according to each described method among the claim 3-5, the thickness of wherein said C tinsel is 50-100 μ m, and the substrate of the described C of being coated with metallic membrane is the substrate that is coated with the C metallic membrane of 50-100 μ m thickness.
7. according to each described method among the claim 3-5, wherein the thickness of the C tinsel described in the step a is 50-80 μ m, and the substrate of the described C of being coated with metallic membrane is the substrate that is coated with the C metallic membrane of 50-80 μ m thickness.
8. according to each described method among the claim 3-5; Wherein in described step a; The substrate of the described C of being coated with metallic membrane is that the method through thermal evaporation, electron beam evaporation plating or magnetron sputtering plates the C metallic membrane on substrate, forms the substrate that is coated with the C metallic membrane.
9. nano material, this nano material comprises claim 1 or 2 described nanostructures.
10. nano material according to claim 9, wherein said nanostructure are the on-chip nanostructures that evenly is grown in the C tinsel or is coated with the C metallic membrane, and described C metal is Cu.
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| CN101723332B true CN101723332B (en) | 2012-04-18 |
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