CN101412541B - Method for synthesizing rod-like and echinoid molybdena-based nano-material - Google Patents
Method for synthesizing rod-like and echinoid molybdena-based nano-material Download PDFInfo
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Abstract
The invention relates to a quick and efficient non-template agent hydro-thermal synthesizing method. The system can synthesize an alpha-molybdenum trioxide nanometer rod and a high-density echinoid molybdenum oxide based nanometer materials. Molybdenum peroxide acid prepared from molybdenum trioxide and aqueous hydrogen peroxide solution is used as a precursor, is produced into scattered alpha-molybdenum trioxide nanometer rod by hydro-thermal synthesis at a temperature of between 80 and 180 DEG C, and is produced into the peroxide modified molybdenum oxide hydrate by hydro-thermal synthesis at a temperature of between 65 and 75 DEG C. The hydrate is a multiscale structure; a nanometer thin slice, a micron prism and a nanometer rod-shaped structure unit are divergently assembled into a micron-size high-density echinoid structure. The hydrate is roasted to obtain high-density echinoid alpha-molybdenum trioxide. Modulation of the synthesizing condition can realize fine adjustment for appearance of the nanometer rod, the micron-size echinoid structure and the structure unit thereof. The method uses raw materials with low cost, has the advantages of simple technical process, controllable conditions and the like, and can promote research and application of the molybdenum oxide in the fields of sensors, field transmission, electrode materials and so on.
Description
Technical field
The present invention relates to the hydrothermal preparing process of α-molybdenum trioxide nano rod and high-density sea urchin shape molybdenum oxide based nano-material, specifically a kind of no template, the method of effectively synthesizing bar-shaped and high-density sea urchin shape molybdenum oxide based nano-material fast, it effectively prepares α-molybdenum trioxide nano rod and high-density sea urchin shape molybdenum oxide based nano-material fast by no template water-heat process.
Background technology
In recent years, pattern anisotropy nano structural material (comprising nanotube, nano wire, nanometer rod, nano belt) and multiple dimensioned assembly thereof receive increasing concern in the investigation of materials field.On the one hand, the material of Nano grade itself can show and the distinct physicochemical property of respective masses rank material; On the other hand, the anisotropy of pattern helps the functionalization of nano material, array, self-assembly operation, the multiple dimensioned assembly of realization and then can find potential to use in preparation functionalized nano devices field.In the nano material of numerous researchs, molybdenum oxide based nano-material, especially α-molybdic oxide have attracted the considerable interest of investigator.Unique physical, the chemical property that the molybdenum oxide based nano-material is had makes it to be widely used as the active ingredient of active ingredient, the chemical sensor of supported catalyst, the cathode material and the fluorescence display material of the ionization cell that can repeat to discharge and recharge.Recently, α-molybdenum trioxide nano rod is used as the positive template that is adopted when synthesizing other nano-oxides.And α-molybdenum trioxide nano band can be as the active ingredient of field emission device.
The preparation method of pattern anisotropy molybdenum oxide based nano-material and multiple dimensioned assembly thereof mainly contains physical method, Subjective and Objective/hard template method and hydrothermal synthesis method at present.
Physical method adopts under high temperature, inert gas or the vacuum and heats molybdenum, arrays such as the nano wire of growth molybdenum dioxide, nanometer rod, nanotube on substrate.With array thermal treatment under oxygenous gas mixture, obtain molybdic oxide array (WO2005040455, JP2004175619, JP2004203720).Physical method also can adopt under the rough vacuum residual oxygen condition, and the infrared radiation heating molybdenum is to high temperature, the growth accurate array of molybdenum trioxide nano pipe (Chem.Phys.Lett.2002,364,484) on substrate.Physical method needs high temperature more, and conditions such as vacuum are higher to equipment requirements.
In Subjective and Objective/hard template method, the carbon nanotube of fused molybdic oxide and opening can be mixed, heat in the pipe of finding time to seal is at the inner filling nano wire (Chem.Commun.1996,2489) that generates molybdic oxide of carbon nanotube.Use the functionalized carbon nanotube of molybdic acid solution immersion, template is removed in dry back high-temperature roasting can obtain the molybdenum trioxide nano rod, can obtain molybdenum trioxide nano pipe (J.Mater.Chem.2000,10,2115) in some cases simultaneously.There is the research worker to adopt alkaline molybdate solution, generates the molybdenum oxide array (Science 2000,290,2120) that is parallel to substrate in fresh graphite surface electrolysis of peeling off.Also having the research worker to adopt anodised aluminium is template, uses the hydrogen high temperature reduction after the thermal treatment in solid-state molybdic oxide powder, utilizes the restriction of template to prepare molybdenum oxide nano-tube array (Acta Phys.-Chim.Sin.2004,20,637).
Hydrothermal synthesis method can use the synthetic width of different organic guiding die plate agent to be the fiber of nanoscale, multiple dimensioned structure, multilayer mesoscopic structure.Aqua oxidation molybdenum and long-chain primary amine stirring at room in mixed solvent generates the white precipitate of pre-intercalation.This post precipitation of hydrothermal treatment consists is sloughed primary amine with it in salpeter solution, can obtain parallel bundles of nanofibers (WO9826871, WO200259042).Ammonium molybdate, cetyl trimethylammonium bromide, the mixed back of aqueous nitric acid hydrothermal treatment consists can generate nano belt and radial multiple dimensioned structure (Solid State Commun.2005,136,283).The mixed back of molybdic oxide and tensio-active agent hydrothermal treatment consists can generate multilayer Jie and see nanometer rod or nano belt (J.Phys.Chem.B2005,109,22758).Use different nitrate as template, regulate the water-heat process of acidifying ammonium paramolybdate and also can regulate and control (J.Phys.Chem.B 2006,110,2006) the pattern that the molybdenum trioxide nano material carries out to a certain degree.
Do not use any template also can synthesize the molybdenum trioxide nano material under the hydro-thermal synthetic system, this becomes hydro-thermal synthetic focus on the one hand gradually.Hydrothermal treatment consists can low-temperature synthesis of nanometer band, still reaction generation virose perchlorate (CN1155524C) after using high chloro acid solution's acidifying sodium molybdate aqueous solution.The acidifying ammonium paramolybdate aqueous solution, aged at room temperature is after one month, using nitric acid to regulate after the acidity of aged solution hydrothermal treatment consists can synthesis of nano band/nanometer rod (Chem.Mater.2002,14,4781, CN1962461A).Solvent heat treatment can single stage method synthesizing submicron fiber under acid or nearly neutrallty condition to use the aqua oxidation molybdenum, but must preparation before the reaction be difficult for the solid precursor two hydration molybdic oxides (Chem.Mater.2004,16,1126) preserved.The two kinds of methods in back all need to grow the generated time of (about 1 month).The mixed mazarine slurries of molybdenum at a low price that generate of excess metal molybdenum and lower concentration superoxol, this slurry water thermal treatment can be obtained different valence state molybdenum oxide material according to time length, present shape (J.Phys.Chem.B2006 such as spirrillum nanometer sheet, cross nanometer flower and isolating nano belt respectively, 110,24472).CN1762831A discloses the narrow method of a kind of synthesis condition variation range, with molybdenum oxide or the molybdate and the excess hydrogen peroxide aqueous solution mixed (mol ratio of patent requirement molybdenum and hydrogen peroxide 1: 500), obtain colloidal sol after vigorous stirring 30-50 hour, 150-180 ℃ obtained molybdenum trioxide laminated nanometer bar in hydrothermal treatment consists 4-6 days.
Summary of the invention
The purpose of this invention is to provide a kind of hydrothermal synthesis method, do not use any template, do not produce unwanted or deleterious chemical waste, effectively synthetic fast α-molybdenum trioxide nano rod and high-density sea urchin shape molybdenum oxide based nano-material.
For achieving the above object, the invention provides a kind of no template, effectively synthesize the method for bar-shaped and sea urchin shape molybdenum oxide based nano-material fast, adopt hydrothermal synthesis method, its operation steps is as follows,
1) with molybdic oxide and aqueous hydrogen peroxide solution prepared in reaction peroxidation molybdenum acid solution, be presoma with this solution; The volumetric molar concentration of molybdenum ion is 1.0-0.2mol/L in the peroxidation molybdic acid precursor water solution; Molybdenum ion and peroxide ionic mol ratio are 1: 10; Till stirring reaction to solution is clarified;
2) A. is precursor solution in 80-180 ℃ of following hydro-thermal synthetic 1-48 hour, in drying at room temperature, obtains α-molybdenum trioxide nano rod after centrifugal, washing;
Or B. in drying at room temperature, obtains the molybdenum oxide hydrate of high-density sea urchin shape peroxide modification through suction filtration, washing back with precursor solution in 65-75 ℃ of following hydro-thermal synthetic 10-48 hour.
Described step 2) hydrate that obtains of B can obtain high-density sea urchin shape α-molybdic oxide after 200-600 ℃ of roasting 1-6 hour;
When the product that generates is α-molybdenum trioxide nano rod, in precursor solution, can add additive nitric acid, the volumetric molar concentration of nitric acid is 0-2mol/L;
When the product that generates is the molybdenum oxide hydrate of high-density sea urchin shape peroxide modification, in precursor solution, can add additive nitric acid or lithium nitrate, the volumetric molar concentration of nitric acid or lithium nitrate is 0-1mol/L.
Compared with former hydrothermal synthesis method, the hydrothermal synthesis method of this invention does not use any template, and does not produce unwanted or deleterious chemical waste.Synthesis material is with low cost, only need commercial aqueous hydrogen peroxide solution and molybdic oxide as reaction raw materials, and the mol ratio of molybdenum and peroxide is low.Operation large-scale, complex appts that technology does not relate to, process is simple.Reaction conditions is controlled, the nano material yardstick homogeneous of generation, and good repetitiveness, proterties is stable.It is short to obtain the presoma required time in this invention, and the reaction soln clarification can be carried out hydro-thermal reaction and generate product.The hydro-thermal time is short, can effectively synthesize the molybdenum oxide hydrate that α-molybdenum trioxide nano rod and high-density sea urchin shape peroxide are modified fast, and the roasting hydrate can obtain high-density sea urchin shape α-molybdic oxide.
The product of the present invention's preparation can promote research and the application of molybdenum oxide in fields such as transmitter, an emission, electrode materialss.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 product;
Fig. 2 is the SEM figure of embodiment 1 product;
Fig. 3 is the TEM figure of embodiment 1 product;
Fig. 4 is the TEM figure of embodiment 2 products;
Fig. 5 is the TEM figure of embodiment 3 products;
Fig. 6 is the TEM figure of embodiment 4 products;
Fig. 7 is the TEM figure of embodiment 5 products;
Fig. 8 is the XRD figure of embodiment 6 products;
Fig. 9 is the SEM figure of embodiment 6 products;
Figure 10 is the SEM figure of embodiment 7 products;
Figure 11 is the SEM figure of embodiment 8 products;
Figure 12 is the SEM figure of embodiment 9 products;
Figure 13 is the SEM figure of embodiment 10 products;
Figure 14 is the SEM figure of embodiment 11 products;
Figure 15 is the SEM figure of embodiment 12 products;
Figure 16 is the XRD figure of the product after embodiment 13 roastings;
Figure 17 is the SEM figure of the product after embodiment 13 roastings;
Figure 18 is the TEM figure of Comparative Examples product;
Fig. 1, the position of diffraction peak conforms to JCPDS card No.35-609 in the XRD spectra of 16 explanation synthetic products, illustrates that product is rhombic system α-molybdic oxide (spacer is Pbnm).Do not have the assorted peak of diffraction of other thing phases in the XRD figure spectrum, show that product is pure phase α-molybdic oxide.
Fig. 8 illustrates that the position and the JCPDS card No.26-1449 of diffraction peak in the XRD spectra of synthetic product is approaching, but composing the peak has certain deviation, and product is the molybdenum oxide hydrate that peroxide is modified.
Embodiment
Hydrothermal synthesis method provided by the present invention only relates to conventional test operation, and process is simple, and required condition obtains and control easily.
Below in conjunction with preferred embodiment the present invention is further elaborated.
The preparation of α-molybdenum trioxide nano rod, its concrete steps are:
A) 1.44 gram molybdic oxides (10mmol) are joined in 10ml 30% aqueous hydrogen peroxide solution, outside temperature remains 30 ℃, stirs.React after 6 hours, molybdic oxide dissolves fully, obtains the clarifying yellow-green colour peroxidation molybdic acid aqueous solution (wherein the concentration of molybdenum is 1.0mol/L).
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 180 ℃, add the thermal recovery electric furnace, kept 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The centrifugation solid product thoroughly cleans repeatedly with deionized water, and solid product places drying at room temperature, obtains α-molybdenum trioxide nano rod.
By Fig. 2-3 as can be known, α-molybdenum trioxide nano rod length is 6-10 μ m, and width is 200-330nm, and major part is about 250nm, and thickness is 60-90nm.The dispersed nano rod that generates is straight along its length, the yardstick homogeneous.
Embodiment 2
The preparation of α-molybdenum trioxide nano rod, its concrete steps are:
A) with embodiment 1A)
B) be 0.2mol/L with the peroxidation molybdic acid aqueous solution with the concentration that deionized water is diluted to molybdenum, as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 180 ℃, add the thermal recovery electric furnace, kept 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The centrifugation solid product thoroughly cleans repeatedly with deionized water, and solid product places drying at room temperature, obtains α-molybdenum trioxide nano rod.
As shown in Figure 4, α-molybdenum trioxide nano rod length is 5.5-7.5 μ m, and width is 200-330nm, and major part is about 250nm.The dispersed nano rod that generates is straight along its length, the yardstick homogeneous.
Embodiment 3
The preparation of α-molybdenum trioxide nano rod, its concrete steps are:
A) with embodiment 1A)
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 80 ℃, add the thermal recovery electric furnace, kept 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The centrifugation solid product thoroughly cleans repeatedly with deionized water, and solid product places drying at room temperature, obtains α-molybdenum trioxide nano rod.
As shown in Figure 5, α-molybdenum trioxide nano rod length is 1-3 μ m, and width is 200-300nm, and major part is about 250nm.The nanometer rod thickness that generates is little, and yardstick is than homogeneous.
Embodiment 4
The preparation of α-molybdenum trioxide nano rod, its concrete steps are:
A) with embodiment 1A)
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 180 ℃, add the thermal recovery electric furnace, kept 1 hour.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The centrifugation solid product thoroughly cleans repeatedly with deionized water, and solid product places drying at room temperature, obtains α-molybdenum trioxide nano rod.
As shown in Figure 6, α-molybdenum trioxide nano rod length is 1-2.2 μ m, and width is 180-250nm.The nanometer rod that generates is short and small, and yardstick is than homogeneous.
Embodiment 5
The preparation of α-molybdenum trioxide nano rod, its concrete steps are:
A) with embodiment 1A)
B) be 0.2mol/L with the peroxidation molybdic acid aqueous solution with the concentration that rare nitric acid is diluted to molybdenum, as precursor solution, the concentration of nitric acid is 2mol/L in the solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 180 ℃, add the thermal recovery electric furnace, kept 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The centrifugation solid product thoroughly cleans repeatedly with deionized water, and solid product places drying at room temperature, obtains α-molybdenum trioxide nano rod.
As shown in Figure 7, α-molybdenum trioxide nano rod length is 4.5-7.5 μ m, and width is 170-330nm, and thickness is 150nm.The nanometer rod that generates is straight along its length, and thickness is big, the yardstick homogeneous.
Embodiment 6
When synthesis temperature is 65 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nano flake that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 65 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 9, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 25-45 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a nano flake, and width is 900nm, and thickness is about 70-95nm.Microstructure and structural unit size thereof are than homogeneous.
Embodiment 7
When synthesis temperature is 70 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nanoprisms that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 70 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 10, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 50-55 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is that micron is prismatic, and width is 1.4 μ m, and thickness is about 850nm.Microstructure and structural unit size homogeneous thereof.
When synthesis temperature is 75 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nanometer rod that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 75 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 11, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 35-40 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a nanometer rod, and width is 300-400nm, and thickness is about 190nm.Microstructure and structural unit size homogeneous thereof.
Embodiment 9
When synthesis temperature is 75 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nanometer rod that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) be 0.2mol/L with the peroxidation molybdic acid aqueous solution with the concentration that deionized water is diluted to molybdenum, as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 75 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 12, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 350-400 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a micron bar, and width/thickness is 400-500nm.Microstructure and structural unit size homogeneous thereof.
When synthesis temperature is 75 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nano flake that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) with the peroxidation molybdic acid aqueous solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 75 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 10 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 13, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 10 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a nanometer rod, and width is 180nm, and thickness is about 50nm.Microstructure and structural unit size thereof are than homogeneous.
When synthesis temperature is 75 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nanometer rod that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) add concentrated nitric acid in the peroxidation molybdic acid aqueous solution, as precursor solution, the concentration of nitric acid is 1mol/L in the solution with it.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 75 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 14, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 20 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a nanometer rod, and width is 200nm, and thickness is about 130nm.Microstructure and structural unit size homogeneous thereof.
When synthesis temperature is 75 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nanometer rod that the nanometer of molybdenum oxide hydrate constitutes primitive.Its concrete steps are:
A) with embodiment 1A)
B) add lithium nitrate in the peroxidation molybdic acid aqueous solution, making the concentration of lithium nitrate in the solution is 1mol/L, with it as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 75 ℃, add the thermal recovery constant temperature water bath, Beckman temperature regulator controlled temperature, minimum scale are 0.5 ℃ thermometer measure temperature.Water keeps the complete submergence of hydro-thermal synthesis reactor 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The suction filtration isolated solid product is thoroughly cleaned repeatedly with deionized water, and solid product places drying at room temperature, obtains the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified.
As shown in Figure 15, the molybdenum oxide hydrate that peroxide is modified is a high-density sea urchin shape, and diameter is 20 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a nanometer rod, and width/thickness is 100nm.Microstructure and structural unit size homogeneous thereof.
When synthesis temperature is 75 ℃, the preparation of the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified, it is nanometer rod that the nanometer of molybdenum oxide hydrate constitutes primitive.Obtain the α-molybdic oxide of high-density sea urchin shape after the roasting.Its concrete steps are:
A) with embodiment 1A)
B) with embodiment 8B)
C) at the be maintained α-molybdic oxide of pattern of 250 ℃ of roasting hydrates.
As shown in Figure 17, α-molybdic oxide that the molybdenum oxide hydrate of modifying by the roasting peroxide obtains is a high-density sea urchin shape, and diameter is 35-40 μ m, and the nano-scale structures unit that constitutes micron order high-density sea urchin shape structure is a nanometer rod, width is 300-400nm, and thickness is about 190nm.Microstructure and structural unit size homogeneous thereof.
Comparative Examples
The α for preparing-molybdic oxide micron bar size heterogeneity, its concrete steps are:
A) with embodiment 1A)
B) be 0.036mol/L with the peroxidation molybdic acid aqueous solution with the concentration that deionized water is diluted to molybdenum, surpass this concentration range of 1.0-0.2mol/L.With this solution as precursor solution.It is the stainless steel water thermal synthesis still of lining that this solution is moved into Teflon.With the sealing of hydro-thermal synthesis reactor, place 180 ℃, add the thermal recovery electric furnace, kept 48 hours.After heating finishes, take out the hydro-thermal synthesis reactor, kettle places in the laboratory, the room temperature naturally cooling.The centrifugation solid product thoroughly cleans repeatedly with deionized water, and solid product places drying at room temperature, obtains the inhomogenous α of size-molybdic oxide micron bar.
As shown in Figure 18, α-molybdic oxide length surpasses 15 μ m, and width is 570nm-1.3 μ m.Be of a size of micron bar, and the unusual heterogeneity of size.
Claims (3)
1. the method for the molybdenum oxide hydrate modified of a synthetic high-density sea urchin shape peroxide, it is characterized in that: adopt hydrothermal synthesis method, its operation steps is as follows,
1) with molybdic oxide and aqueous hydrogen peroxide solution prepared in reaction peroxidation molybdenum acid solution, be presoma with this solution; The volumetric molar concentration of molybdenum ion is 1.0-0.2mol/L in the peroxidation molybdic acid precursor water solution; Molybdenum ion and peroxide ionic mol ratio are 1: 10; Till stirring reaction to solution is clarified;
2) precursor solution was synthesized 10-48 hour in 65-75 ℃ of following hydro-thermal, after suction filtration, washing,, obtain the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified in drying at room temperature.
2. in accordance with the method for claim 1, it is characterized in that: add additive nitric acid or lithium nitrate in precursor solution, the volumetric molar concentration of nitric acid or lithium nitrate is 0-1mol/L.
3. the method for a synthetic sea urchin shape molybdenum oxide based nano-material is characterized in that: adopt hydrothermal synthesis method, its operation steps is as follows,
1) with molybdic oxide and aqueous hydrogen peroxide solution prepared in reaction peroxidation molybdenum acid solution, be presoma with this solution; The volumetric molar concentration of molybdenum ion is 1.0-0.2mol/L in the peroxidation molybdic acid precursor water solution; Molybdenum ion and peroxide ionic mol ratio are 1: 10; Till stirring reaction to solution is clarified;
2) precursor solution was synthesized 10-48 hour in 65-75 ℃ of following hydro-thermal, after suction filtration, washing,, obtain the molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified in drying at room temperature;
The molybdenum oxide hydrate that high-density sea urchin shape peroxide is modified can obtain high-density sea urchin shape α-molybdic oxide after 200-600 ℃ of roasting 1-6 hour.
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| CN103198991B (en) * | 2013-03-30 | 2015-10-14 | 福州大学 | Based on field emission cathode structure and the manufacture method of sea urchin type nickel particles template |
| CN103449524B (en) * | 2013-08-23 | 2015-10-28 | 东华大学 | A kind of molybdenum oxide nanometer optical-thermal conversion material and preparation method thereof |
| US10130937B2 (en) | 2014-08-29 | 2018-11-20 | Lg Chem, Ltd. | Preparation method for rod-shaped molybdenum oxide and preparation method for molybdenum oxide composite |
| CN105753051A (en) * | 2016-02-02 | 2016-07-13 | 济南大学 | Au nano particle/MoO3 nanorod heterojunction material with trimethylamine sensitizing effect |
| CN105776347A (en) * | 2016-02-02 | 2016-07-20 | 济南大学 | Ferric oxide nano-particle/molybdenum trioxide nano-rod heterojunction material sensitive to trimethylamine |
| CN105540670A (en) * | 2016-02-02 | 2016-05-04 | 济南大学 | Preparation method of In2O3 nanoparticles/MoO3 nanorod composite materials |
| CN105845449B (en) * | 2016-03-24 | 2017-06-30 | 清华大学深圳研究生院 | A kind of electrode material and preparation method thereof and ultracapacitor |
| CN106622210B (en) * | 2016-11-16 | 2019-10-18 | 任昊琦 | A method of synthesis sea urchin shape tungsten oxide |
| CN108658127B (en) * | 2017-04-01 | 2020-07-14 | 中国科学院上海硅酸盐研究所 | Molybdenum oxide nano powder and preparation method and application thereof |
| CN107799758A (en) * | 2017-11-02 | 2018-03-13 | 齐鲁工业大学 | A kind of utilize sacrifices the method that template prepares the bar-shaped Zinc ion battery positive electrode of manganese sulfide/graphene oxide composite Nano |
| CN109970103B (en) * | 2019-04-22 | 2021-04-02 | 郑州大学 | Method for preparing amorphous molybdenum oxide nanosheet with LSPR effect by doping bulk molybdenum oxide with metal molybdenum atoms |
| CN112374538A (en) * | 2019-09-27 | 2021-02-19 | 德州学院 | Molybdenum trioxide micron rod with adjustable size and preparation method thereof |
| CN113697857B (en) * | 2021-09-14 | 2023-01-24 | 河北地质大学 | Preparation method and application of two-dimensional flaky molybdenum oxide nano material |
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