CN105712392B - Molten-salt template method for preparation of Zn＜1-x＞Mg＜x＞O nanorod - Google Patents
Molten-salt template method for preparation of Zn＜1-x＞Mg＜x＞O nanorod Download PDFInfo
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Abstract
The invention provides a molten-salt template method for preparation of a Zn＜1-x＞Mg＜x＞O nanorod. The method comprises the following steps: S1, adding a ZnO nanorod and oxalic acid into a Mg＜2+＞ solution so as to obtain a mixed solution with a pH value of less than 6, then adding ammonia water into the mixed solution so as to obtain a precipitate and drying the precipitate so as to obtain a precursor; and S2, mixing the precursor with molten salt, heating the mixture at a heating temperature higher than the melting temperature of the molten salt and then carrying out cooling and washing so as to obtain the Zn＜1-x＞Mg＜x＞O nanorod. The method provided by the invention is easy to control and has good operationality.
Description
Technical field
The present invention relates to field of nanometer material technology, more particularly to it is a kind of by fused salt template preparation Zn1-xMgxO nanometer rods
Method.
Background technology
Zinc oxide (ZnO) sill is a kind of direct band gap material, its in visible region substantially transparent, but ultraviolet
Spectral regions have strong absorption, significant to producing UV photodetector with high s/n ratio.Mg2+Doping
ZnO can adjust its energy band, and the material non-toxic, aboundresources；Further, since ZnO is prepared simply, and there is the base of matching
Piece, so that preparing the high performance Zn of high efficiency1-xMgxO ultraviolet light photo devices are possibly realized.
Zn1-xMgxO has the good chemical stability of ZnO and MgO simultaneously, and its performance depends on the base of ZnO and MgO
This performance, zinc ion radius (Zn2+=0.060nm) and magnesium ion radius (Mg2+=0.057nm) very close, zinc ion and magnesium
Ion can mutually replace in respective lattice and form Zn1-xMgxO substituted alloys.Keeping the original hexagonal wurtzites of ZnO
On the premise of structure is constant, Zn1-xMgxO alloy materials can realize that in theory the energy gap of ZnO broadens, and the taboo of MgO
Bandwidth is 7.9eV, it is possible to by the incorporation for changing Mg, make Zn1-xMgxThe energy gap of O materials 3.3eV～
Continuously adjustabe is realized on 7.9eV, but because solid solubility is limited in ZnO by MgO, keeps the Zn of single hexagonal phase1- xMgxThe bandgap range of O need further to be studied.
In atmospheric conditions, to keep the hexagonal wurtzite structure of zinc oxide not change, MgO can be obtained by calculating and existed
Thermodynamics solid solubility limit in ZnO will be less than 4at%.But, if in the case where thermodynamical equilibrium is deviateed, MgO-ZnO
The solid solubility of system will be improved, and deviate that the degree of thermodynamic equilibrium state is bigger, and MgO is solid-solution in ZnO systems
It is higher.So, it is possible to use non-equilibrium technology of preparing breaks through the Zn of solid solubility limit to prepare1-xMgxO materials.At present, state
Inside and outside the more commonly used technical method have pulsed laser deposition (PLD), metal-organic chemical vapor deposition equipment method (MOCVD or
Person MOVPE), molecular beam epitaxy (MBE), magnetron sputtering method (MS), thermal evaporation, sol-gal process (Sol-gel), molten-salt growth method
Deng.Various methods have the merits and demerits of its own, and can be prepared using different methods according to different purposes
Zn1-xMgxO materials.Pulsed laser deposition is adapted to prepare has multi-component complicated film, easily prepares hetero-junctions
Or a variety of multilayer films；And mocvd method growing film is best in quality, but it is relatively costly；Molecular beam epitaxy needs
Ultra-high vacuum environment, is not suitable for large area film forming；Magnetron sputtering method is a kind of film-forming method of comparative maturity, it can be difficult to finding out
The target of matching.Comparatively cost is relatively low for thermal evaporation, simple to operate, it can be difficult to the stoichiometry of the composition of control material
Than.Molten-salt growth method (Molten-salt Growth Method) is the salt that solute or reactant are added one or more low melting point
In, at relatively high temperatures, the salt of low melting point can be melted, and solute or reactant can accelerate dissolving and then complete synthetic reaction
Process.The method adopts the salt of low melting point for medium, and at high temperature the salt of low melting point can occur melting transition into liquid phase,
Solute or reactant have wherein certain solubility, accelerate the diffusion rate of atom, make to be contacted between atom and more fill
Point, realize that atomic scale mixes.The method has operating procedure simple relative to general solid phase reaction, low cost, synthesis temperature
Degree is low, and temperature retention time is short, and raw material is simple, and the powder crystal pattern of synthesis is good, and chemical composition is uniform, the advantages of purity is high；In addition,
Reacted salt medium is easily removed, and can also be reused, it is possible to achieve large-scale production.At present, also not over fused salt
Method prepares Zn1-xMgxThe method of O nanometer rods.
Meanwhile, in order to realize Zn1-xMgxApplication of the O materials on ultraviolet detector, Zn1-xMgxO materials will have wider
Energy gap and electric conductivity.And Zn1-xMgxThe energy gap of O materials can be by controlling Mg2+Adulterate to realize broadening, so as to
Ultraviolet light range can be covered.And Zn1-xMgxThe electric conductivity of O materials depends on the carrier concentration and carrier mobility of material
Two factors of rate.Obtain high carrier mobility and require that material has preferable heterogeneous microstructure.Therefore, should be as far as possible
Scattering center and electron trap during the carrier mobility of ground reduction material, needs Zn1-xMgxO nanometer rods have appropriate crystal grain
Size, better crystallinity degree, the heterogeneous microstructure of dense uniform, and with high c-axis preferred orientation, i.e. ZnO crystal grain<
002>Crystal face is perpendicular to substrate into columnar growth.C-axis orientation is higher, and meaning degree of crystallinity is high.Complete crystallization, it is meant that in crystal grain
The defect in portion less, crystal boundary number it is fewer, so as to be conducive to carrier mobility.However, at present, also one kind can be not easily
Prepare c-axis orientation high, the Zn of complete crystallization1-xMgxThe preparation method of O nanometer rods.
The content of the invention
The present invention is at present one kind can not easily prepare c-axis orientation height, the Zn of complete crystallization1-xMgxO
The problem of the preparation method of nanometer rods, there is provided one kind prepares Zn by fused salt template1-xMgxThe method of O nanometer rods.
The invention provides one kind prepares Zn1-xMgxThe method of O nanometer rods, comprises the following steps：
Step S1, ZnO nanorod and oxalic acid are added to into Mg2+In solution, mixed liquor of the pH value less than 6 is obtained；Then to
Ammoniacal liquor is added in the mixed liquor, to be precipitated；Then by the precipitation drying, to obtain presoma；
Step S2, the presoma is mixed with fused salt, and together under the heating-up temperature higher than fused salt melt temperature plus
Heat, then cooling, washing, so as to obtain Zn1-xMgxO nanometer rods.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, the fused salt for NaCl and KCl complex salt,
In NaCl salt and KCl salt any one.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, the heating-up temperature in 800 DEG C -900 DEG C it
Between.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, the ZnO nanorod and the Mg2+In solution
Mg2+Mol ratio between the 1-4.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, add before ammoniacal liquor in mixed liquor, pass through
Ultrasonic wave disperses and/or stirs the mixed liquor.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, ammoniacal liquor is added to mixed by dropwise addition or injection system
In closing liquid so as to which pH is between 6-7.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, the ZnO nanorod by vapour deposition process or
Hydro-thermal method is prepared.
The above-mentioned preparation Zn of the present invention1-xMgxIn the method for O nanometer rods, the Mg2+Solution is Mg (NO3)2Solution or
MgCl2Solution.
The present invention using molten-salt growth method by realizing Zn1-xMgxO nanometer rods complete crystallizations, are also received by employing in ZnO
Rice rod wraps up one layer of magnesium oxalate and causes Zn1-xMgxThe c-axis orientation of O nanometer rods is high, and present invention process is easily controlled, operability
By force.
Description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 is product A, product B, the XRD spectrum of product C and product D of the present invention；
Fig. 2 is the Zn (NO with 0.01mol/L of the present invention3)2·6H2O, is incubated 4h and is prepared under 95 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 3 is the Zn (NO with 0.02mol/L of the present invention3)2·6H2O, is incubated 4h and is prepared under 95 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 4 is the Zn (NO with 0.04mol/L of the present invention3)2·6H2O, is incubated 4h and is prepared under 95 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 5 is the Zn (NO with 0.05mol/L of the present invention3)2·6H2O, is incubated 4h and is prepared under 95 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 6 is the present invention in Zn (NO3)2·6H2The concentration of O is 0.05mol/L, is prepared under 80 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 7 is the present invention in Zn (NO3)2·6H2The concentration of O is 0.05mol/L, is prepared under 85 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 8 is the present invention in Zn (NO3)2·6H2The concentration of O is 0.05mol/L, is prepared under 95 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Fig. 9 is the present invention in Zn (NO3)2·6H2The concentration of O is 0.05mol/L, is prepared under 120 DEG C of hydrothermal temperature
The SEM pictures of the ZnO nanorod for arriving；
Figure 10 be the present invention the first sample a, the second sample b, the 3rd sample c, the 4th sample d, the 5th sample e and
The XRD spectrum of ZnO nanorod；
Figure 11 be the present invention the first sample a, the second sample b, the 3rd sample c, the 4th sample d, the 5th sample e and
ZnO nanorod is in the XRD spectrum that 2 θ are 33.5 ° -35.0 °；
Figure 12 is the 6th sample f, the 7th sample g, the 8th sample h and the 9th sample i and the ZnO nanorod of the present invention
XRD spectrum；
Figure 13 is the 6th sample f, the 7th sample g, the 8th sample h and the 9th sample i and the ZnO nanorod of the present invention
In the XRD spectrum that 2 θ are 33.5 ° -35.0 °；
Figure 14 is the SEM spectrum of the 5th sample e of the present invention；
Figure 15 is the SEM spectrum of the ZnO nanorod of the present invention.
Specific embodiment
Most starting, inventor mixes in proportion with ZnO nanorod and MgO powders as raw material, obtains mixture；Again
With NaCl, KCl complex salt as fused salt, and the fused salt is mixed with mixture, and then cool down, wash in 800 DEG C of insulation 4h together
Wash, so as to obtain product；Then, inventor carries out XRD analysis to product.
Specifically, ZnO nanorod and MgO powders are mixed respectively with mol ratio as 9,4,1.5 and 1, corresponding,
Inventor has obtained product A, product B, product C and product D.As shown in figure 1, Fig. 1 is product A, product B, product C and product
The XRD spectrum of thing D.As seen from the figure, the principal crystalline phase of product A, product B, product C and product D is the hexagonal wurtzite knot of ZnO
Structure, and also include the larger Emission in Cubic MgO structures of peak intensity；Contrast product A, product B, the XRD spectrum of product C and product D,
It is also found that when even if the mol ratio of ZnO nanorod and MgO powders is 9, the peak of MgO is also relatively strong, this explanation MgO solid solution is entered
The limitation of ZnO.
In order to improve this situation, inventor is template using ZnO nanorod, by chemical method in ZnO nanorod table
Bread covers one layer of MgC2O4Obtain precursor；Then, Zn is prepared by molten-salt growth method by raw material of presoma1-xMgxO nanometer rods.
Specifically, the invention provides one kind prepares Zn1-xMgxThe method of O nanometer rods, comprises the following steps：
Step S1, ZnO nanorod and oxalic acid are added to into Mg2+In solution, mixed liquor of the pH value less than 6 is obtained；Then to
Ammoniacal liquor is added in the mixed liquor, to be precipitated；Then by the precipitation drying, to obtain presoma；
In this step, ZnO nanorod can be prepared by vapour deposition process or hydro-thermal method；The present invention adopts hydro-thermal
Method prepares ZnO nanorod；Specifically, with Zn (NO3)2·6H2O, pregnancy urotropine are raw material, by control reactant concentration, instead
Between seasonable, the technological parameter such as reaction temperature, hydro-thermal prepares ZnO nanorod.Wherein, Zn (NO3)2·6H2O concentration increases, hydro-thermal temperature
Degree is high, the hydro-thermal time is long, and the diameter that can make ZnO nanorod becomes big, and draw ratio diminishes, and yield is higher；Conversely, low reaction thing is dense
Degree, suitable temperature and time, the diameter of ZnO nanorod attenuates, and draw ratio becomes big.Prepared by vapour deposition process or hydro-thermal method
ZnO nanorod is prior art, is not just specifically repeated here.
Fig. 2-5 is respectively with the Zn (NO of variable concentrations3)2·6H2O, the ZnO nano prepared under identical hydrothermal temperature
The SEM pictures of rod.As shown in Figures 2 and 3, as Zn (NO3)2·6H2When the concentration of O is 0.01mol/L or 0.02mol/L, can be with
Obtain ZnO nanorod.As shown in Figure 4 and Figure 5, as Zn (NO3)2·6H2When O concentration increases to 0.04mol/L or 0.05mol/L,
The diameter of ZnO nanorod up to 400nm, length about 10um or so.
Fig. 6-9 is respectively in Zn (NO3)2·6H2The concentration of O is 0.05mol/L, is prepared under different hydrothermal temperatures
The SEM pictures of ZnO nanorod, it can be seen that hydrothermal temperature is too high, it may appear that flower-shaped aggregate, and hydrothermal temperature is produced when relatively low
Thing pattern is evenly.
Consider of both comprehensive high yield, little yardstick, the present invention adopts the Zn by concentration for 0.05mol/L
(NO3)2·6H2O, in 85 DEG C or so the ZnO nanorods for preparing, as template, for follow-up Zn is prepared1-xMgxO nanometers
Rod.
ZnO nanorod and Mg2+Mg in solution2+Mol ratio between the 1-4, this makes Zn1-xMgxX in O nanometer rods
No more than 0.5, so as to the microstructure that ensure that the original hexagonal wurtzites of ZnO is constant.
Further, Mg2+Solution is Mg (NO3)2Solution or MgCl2Solution, due to presoma after the heating, the Mg of residual
(NO3)2And MgCl2Can react and vapor away, in this way, it is possible to obtain pure Zn1-xMgxO nanometer rods.
Due to oxalic acid is added to into Mg2+When in solution, oxalic acid and Mg2+Solution can generate the magnesium oxalate for being slightly soluble in water；To
Add in mixed liquor before ammoniacal liquor, disperse and/or stir mixed liquor by ultrasonic wave.
Further, in this step, ammoniacal liquor is slowly added in mixed liquor by dropwise addition or injection system so as to which pH is in
Between 6-7.So so that magnesium oxalate can be slowly wrapped on ZnO nanorod.In order to control the addition speed of ammoniacal liquor, this
In invention, the addition speed of ammoniacal liquor is less than 0.1mL/s.In order to ensure not affect the parcel effect of magnesium oxalate parcel ZnO nanorod
Really, ammoniacal liquor of the ammoniacal liquor using concentration less than 15wt%.And in order to ensure the addition efficiency of ammoniacal liquor, ammoniacal liquor can be more than using concentration
The ammoniacal liquor of 5wt%.
Step S2, presoma is mixed with fused salt, and heated under the heating-up temperature higher than fused salt melt temperature together, so
Cooling, washing afterwards, so as to obtain Zn1-xMgxO nanometer rods.
In this step, fused salt is the complex salt of NaCl and KCl, in NaCl salt and KCl salt any one；And at heating-up temperature
Between 800 DEG C -900 DEG C.
For the ease of skilled artisan understands that and implement the present invention, below in conjunction with accompanying drawing and specific embodiment
The present invention will be further described in detail.
First embodiment
First, ZnO nanorod, the Mg (NO of the 2mol/L of 0.5L of 81g are prepared3)2Solution and oxalic acid, by the ZnO of 81g
Nanometer rods are added to the Mg (NO of the 2mol/L of 0.5L3)2In solution, meanwhile, also oxalic acid is also added to into the Mg (NO3)2In solution
To obtain mixed liquor；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction completely generates grass
Sour magnesium, at this moment, the pH value of mixed liquor is 1.Now, ZnO nanorod and Mg (NO3)2Mg in solution2+Mol ratio be 1；In order to
Oxalic acid magnesium precipitate is avoided, here, ultrasonic wave dispersion is carried out to mixed liquor, and stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 200g；Will
The 200g fused salts and presoma mixing resulting before, heat and protect under 900 DEG C of heating-up temperature together as reactant
Warm 4h, then cooling, washing, so as to obtain the first sample a, i.e. Zn1-xMgx(x=0.5, x are by ZnO nanorod and Mg for O
(NO3)2Mg in solution2+Mol ratio calculate), here, cooling procedure is referred to and for reactant to be cooled to normal temperature, the present embodiment
In, washing process is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters,
Fused salt can automatic dissolving in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and use absolute ethyl alcohol centrifuge washing
1 time, finally 24h is dried at 70 DEG C, obtains the first sample a of white.
Second embodiment
First, ZnO nanorod, the Mg (NO of the 2mol/L of 0.5L of 121.5g are prepared3)2Solution and oxalic acid, by 121.5g
ZnO nanorod be added to 0.5L 2mol/L Mg (NO3)2In solution, meanwhile, also oxalic acid is also added to into the Mg (NO3)2
Obtaining mixed liquor in solution；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+React completely
Magnesium oxalate is generated, at this moment, the pH value of mixed liquor is 6.Now, ZnO nanorod and Mg (NO3)2Mg in solution2+Mol ratio be
1.5；In order to avoid oxalic acid magnesium precipitate, here, ultrasonic wave dispersion is carried out to mixed liquor, and stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.08mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation
It is to be dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 200g；Will
The 200g fused salts and presoma mixing resulting before, heat and protect under 900 DEG C of heating-up temperature together as reactant
Warm 4h, then cooling, washing, so as to obtain the second sample b, i.e. Zn1-xMgx(x=0.4, x are by ZnO nanorod and Mg for O
(NO3)2Mg in solution2+Mol ratio calculate).Here, cooling procedure is referred to and for reactant to be cooled to normal temperature, the present embodiment
In, washing process is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters,
Fused salt can automatic dissolving in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and use absolute ethyl alcohol centrifuge washing
1 time, finally 24h is dried at 70 DEG C, obtains the second sample b of white.
3rd embodiment
First, ZnO nanorod, the Mg (NO of the 2mol/L of 0.5L of 186.3g are prepared3)2Solution and oxalic acid, by 186.3g
ZnO nanorod be added to 0.5L 2mol/L Mg (NO3)2In solution, meanwhile, also oxalic acid is also added to into the Mg (NO3)2
Obtaining mixed liquor in solution；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+React completely
Magnesium oxalate is generated, at this moment, the pH value of mixed liquor is 5.Now, ZnO nanorod and Mg (NO3)2Mg in solution2+Mol ratio be
2.3；In order to avoid oxalic acid magnesium precipitate, here, ultrasonic wave dispersion is carried out to mixed liquor, and stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 8, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 300g；Will
The 300g fused salts and presoma mixing resulting before, heat and protect under 900 DEG C of heating-up temperature together as reactant
Warm 4h, then cooling, washing, so as to obtain the 3rd sample c, i.e. Zn1-xMgx(x=0.3, x are by ZnO nanorod and Mg for O
(NO3)2Mg in solution2+Mol ratio calculate).Here, cooling procedure is referred to and for reactant to be cooled to normal temperature, the present embodiment
In, washing process is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters,
Fused salt can automatic dissolving in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and washed with absolute ethyl alcohol centrifugation
Wash 1 time, be finally dried 24h at 70 DEG C, obtain the 3rd sample c of white.
Fourth embodiment
First, ZnO nanorod, the Mg (NO of the 2mol/L of 0.5L of 243g are prepared3)2Solution and oxalic acid, by 243g's
ZnO nanorod is added to the Mg (NO of the 2mol/L of 0.5L3)2In solution, meanwhile, also oxalic acid is also added to into the Mg (NO3)2It is molten
Obtaining mixed liquor in liquid；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction life completely
Into magnesium oxalate, at this moment, the pH value of mixed liquor is 6.Now, ZnO nanorod and Mg (NO3)2Mg in solution2+Mol ratio be 3；
In order to avoid oxalic acid magnesium precipitate, here, ultrasonic wave dispersion is carried out to mixed liquor, and stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 400g；Will
The 400g fused salts and presoma mixing resulting before, heat and protect under 900 DEG C of heating-up temperature together as reactant
Warm 4h, then cooling, washing, so as to obtain the 4th sample d, i.e. Zn1-xMgx(x=0.25, x are by ZnO nanorod and Mg for O
(NO3)2Mg in solution2+Mol ratio calculate).Here, cooling procedure is referred to and for reactant to be cooled to normal temperature, the present embodiment
In, washing process is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters,
Fused salt can automatic dissolving in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and use absolute ethyl alcohol centrifuge washing
1 time, finally 24h is dried at 70 DEG C, obtains the 4th sample d of white.
5th embodiment
First, ZnO nanorod, the Mg (NO of the 2mol/L of 0.5L of 324g are prepared3)2Solution and oxalic acid, by 324g's
ZnO nanorod is added to the Mg (NO of the 2mol/L of 0.5L3)2In solution, meanwhile, also oxalic acid is also added to into the Mg (NO3)2It is molten
Obtaining mixed liquor in liquid；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction life completely
Into magnesium oxalate, at this moment, the pH value of mixed liquor is 1.Now, ZnO nanorod and Mg (NO3)2Mg in solution2+Mol ratio be 4；
In order to avoid oxalic acid magnesium precipitate, here, ultrasonic wave dispersion is carried out to mixed liquor, and stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 400g；Will
The 400g fused salts and presoma mixing resulting before, heat and protect under 900 DEG C of heating-up temperature together as reactant
Warm 4h, then cooling, washing, so as to obtain the 5th sample e, i.e. Zn1-xMgx(x=0.2, x are by ZnO nanorod and Mg for O
(NO3)2Mg in solution2+Mol ratio calculate).Here, cooling procedure is referred to and for reactant to be cooled to normal temperature, the present embodiment
In, washing process is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters,
Fused salt can automatic dissolving in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and use absolute ethyl alcohol centrifuge washing
1 time, finally 24h is dried at 70 DEG C, obtains the 5th sample e of white.
Sixth embodiment
First, ZnO nanorod, the MgCl of the 2mol/L of 0.5L of 324g are prepared2Solution and oxalic acid, by the ZnO of 324g
Nanometer rods are added to the MgCl of the 2mol/L of 0.5L2In solution, meanwhile, also oxalic acid is also added to into the MgCl2Obtaining in solution
Mixed liquor；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction completely generates magnesium oxalate, this
When, the pH value of mixed liquor is 1.Now, ZnO nanorod and MgCl2Mg in solution2+Mol ratio be 4；In order to avoid magnesium oxalate
Precipitation, here, to mixed liquor ultrasonic wave dispersion is carried out, and is stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 400g；Will
The 400g fused salts and presoma mixing resulting before, heat and protect under 900 DEG C of heating-up temperature together as reactant
Warm 4h, then cooling, washing, so as to obtain the 6th sample f, i.e. Zn1-xMgx(x=0.2, x are by ZnO nanorod and MgCl for O2It is molten
Mg in liquid2+Mol ratio calculate).Here, cooling procedure refers to and for reactant to be cooled to normal temperature, washed in the present embodiment
Journey is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters, fused salt can be certainly
It is dynamic to be dissolved in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and with absolute ethyl alcohol centrifuge washing 1 time, finally
24h is dried at 70 DEG C, the 6th sample f of white is obtained.
7th embodiment
First, ZnO nanorod, the MgCl of the 2mol/L of 0.5L of 324g are prepared2Solution and oxalic acid, by the ZnO of 324g
Nanometer rods are added to the MgCl of the 2mol/L of 0.5L2In solution, meanwhile, also oxalic acid is also added to into the MgCl2Obtaining in solution
Mixed liquor；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction completely generates magnesium oxalate, this
When, the pH value of mixed liquor is 1.Now, ZnO nanorod and MgCl2Mg in solution2+Mol ratio be 4；In order to avoid magnesium oxalate
Precipitation, here, to mixed liquor ultrasonic wave dispersion is carried out, and is stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 400g；Will
The 400g fused salts and presoma mixing resulting before, heat and protect under 800 DEG C of heating-up temperature together as reactant
Warm 2h, then cooling, washing, so as to obtain the 7th sample g, i.e. Zn1-xMgx(x=0.2, x are by ZnO nanorod and MgCl for O2It is molten
Mg in liquid2+Mol ratio calculate).Here, cooling procedure refers to and for reactant to be cooled to normal temperature, washed in the present embodiment
Journey is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters, fused salt can be certainly
It is dynamic to be dissolved in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and with absolute ethyl alcohol centrifuge washing 1 time, finally
24h is dried at 70 DEG C, the 7th sample g of white is obtained.
8th embodiment
First, ZnO nanorod, the MgCl of the 2mol/L of 0.5L of 324g are prepared2Solution and oxalic acid, by the ZnO of 324g
Nanometer rods are added to the MgCl of the 2mol/L of 0.5L2In solution, meanwhile, also oxalic acid is also added to into the MgCl2Obtaining in solution
Mixed liquor；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction completely generates magnesium oxalate, this
When, the pH value of mixed liquor is 2.Now, ZnO nanorod and MgCl2Mg in solution2+Mol ratio be 4；In order to avoid magnesium oxalate
Precipitation, here, to mixed liquor ultrasonic wave dispersion is carried out, and is stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 400g；Will
The 400g fused salts and presoma mixing resulting before, heat and protect under 700 DEG C of heating-up temperature together as reactant
Warm 2h, then cooling, washing, so as to obtain the 8th sample h, i.e. Zn1-xMgx(x=0.2, x are by ZnO nanorod and MgCl for O2It is molten
Mg in liquid2+Mol ratio calculate).Here, cooling procedure refers to and for reactant to be cooled to normal temperature, washed in the present embodiment
Journey is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters, fused salt can be certainly
It is dynamic to be dissolved in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and with absolute ethyl alcohol centrifuge washing 1 time, finally
24h is dried at 70 DEG C, the 8th sample h of white is obtained.
9th embodiment
First, ZnO nanorod, the MgCl of the 2mol/L of 0.5L of 324g are prepared2Solution and oxalic acid, by the ZnO of 324g
Nanometer rods are added to the MgCl of the 2mol/L of 0.5L2In solution, meanwhile, also oxalic acid is also added to into the MgCl2Obtaining in solution
Mixed liquor；Here, oxalic acid can be excessive, so, by adding oxalic acid, can make Mg2+Reaction completely generates magnesium oxalate, this
When, the pH value of mixed liquor is 2.Now, ZnO nanorod and MgCl2Mg in solution2+Mol ratio be 4；In order to avoid magnesium oxalate
Precipitation, here, to mixed liquor ultrasonic wave dispersion is carried out, and is stirred.
Then, then by syringe slowly injection adds the ammoniacal liquor of 10wt% in mixed liquor, and pH value is adjusted to into 7, from
And be precipitated；Here, the addition speed of ammoniacal liquor is 0.1mL/s；Then, by the precipitation drying, to obtain presoma；Precipitation is
It is dried 24 hours in 80 DEG C of baking oven；
Then, with the complex salt that mol ratio is 1 configuration NaCl and KCl, it is used as fused salt, and prepares fused salt 400g；Will
The 400g fused salts and presoma mixing resulting before, heat and protect under 1000 DEG C of heating-up temperature together as reactant
Warm 3h, then cooling, washing, so as to obtain the 9th sample i, i.e. Zn1-xMgx(x=0.2, x are by ZnO nanorod and MgCl for O2It is molten
Mg in liquid2+Mol ratio calculate).Here, cooling procedure refers to and for reactant to be cooled to normal temperature, washed in the present embodiment
Journey is comprised the following steps：Reactant after cooling is added and is cleaned in the beaker equipped with 90 DEG C of deionized waters, fused salt can be certainly
It is dynamic to be dissolved in 90 DEG C of deionized waters, then again with distilled water centrifuge washing 3 times, and with absolute ethyl alcohol centrifuge washing 1 time, finally
24h is dried at 70 DEG C, the 9th sample i of white is obtained.
Sample testing
To ZnO nanorod, the first sample a, the second sample b, the 3rd sample c, the 4th sample d, the 5th sample e, the 6th examination
Sample f, the 7th sample g, the 8th sample h and the 9th sample i do XRD diffraction analysis, obtain the collection of illustrative plates as shown in Figure 10-Figure 13.
Wherein, Figure 10 is that the first sample a, the second sample b, the 3rd sample c, the 4th sample d, the 5th sample e and ZnO receive
The XRD spectrum of rice rod；And Figure 11 be the first sample a, the second sample b, the 3rd sample c, the 4th sample d, the 5th sample e and
ZnO nanorod is in the XRD spectrum that 2 θ are 33.5 ° -35.0 °；
Can be seen by Figure 10：First sample a, the second sample b, the 3rd sample c, the 4th sample d and the 5th sample e
Principal crystalline phase be the hexagonal wurtzite structure of ZnO, and have the mutually presence of a small amount of cube of MgO structure；Can be seen by Figure 11
Arrive：3rd sample c (Zn1-xMgxO, x=0.3), the 4th sample d (Zn1-xMgxO, x=0.25), the 5th sample e (Zn1-xMgxO,x
=0.2) and ZnO nanorod (Zn1-xMgxO, x=0) spectral line with the increase of x values, (200) peak position of ZnO offsets to the right
Offset to high angle, the c-axis orientation of ZnO uprises, while also illustrating as the raising of x values is melting in ZnO Mg contents just admittedly
It is bigger.And work as x and continue increase when reaching 0.4,0.5, the peak position of (200) keeps identical position with the diffraction peak of x=0.3,
There is no the shift phenomenon to high angle, illustrate that, when x >=0.3, the doping of Mg reaches saturation.
Figure 12 is the XRD of the 6th sample f, the 7th sample g, the 8th sample h and the 9th sample i and ZnO nanorod
Spectrum；Figure 13 be the 6th sample f, the 7th sample g, the 8th sample h and the 9th sample i and ZnO nanorod 2 θ be 33.5 °-
35.0 ° of XRD spectrum；
By Figure 12 it is known that：6th sample f, the 7th sample g, the 8th sample h and the 9th sample i principal crystalline phase it is equal
For the wurtzite structure of ZnO, can be seen by Figure 13：When heating-up temperature is in 700 DEG C to 900 DEG C, Zn0.8Mg0.2O exists
34.4 ° of XRD diffraction maximums there occurs and significantly move to right, and as the rising of temperature moves to right more obvious, but peak position when 1000 DEG C
Peak position with 900 DEG C is identical, without further skew, illustrates with the rising of temperature, Mg2+Solid solution replaces Zn2+Amount it is more,
The Mg to after 900 DEG C2+For Zn2+Replacement almost saturation.
Further, the present invention is also to the 5th sample e (Zn1-xMgxO, x=0.2) and ZnO nanorod do sem analysis, such as
Shown in Figure 14 and Figure 15.As shown in figure 14, the 5th sample e (Zn1-xMgxO, x=0.2) still remain template ZnO nanorod
Club shaped structure, also has not seen nano particle in Figure 14, illustrate surface coated MgC2O4There is high diffusivity under high-temperature molten salt environment
Speed, it is easier to which solid solution is entered in ZnO, so, the 5th sample e (Zn1-xMgxO, x=0.2) it is Zn1-xMgxO (x=0.2) nanometer
Rod, the Zn1-xMgxO (x=0.2) nanorod diameter about 200nm, about several microns to tens microns of length, Zn1-xMgxO (x=0.2)
Nanorod surfaces are smooth, and growth is complete.With reference to Figure 10-15, Zn can prepared by the method for the 5th embodiment1-xMgxO
(x=0.2) on the basis of nanometer rods, improve x in the case of or heating-up temperature impact it is less when, i.e., using first-the four,
The method of the 6th-the nine embodiment can be prepared by Zn1-xMgxO nanometer rods.
The present invention using molten-salt growth method by realizing Zn1-xMgxO nanometer rods complete crystallizations, are also received by employing in ZnO
Rice rod wraps up one layer of magnesium oxalate and causes Zn1-xMgxThe c-axis orientation of O nanometer rods is high, and present invention process is easily controlled, operability
By force.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or be converted,
And all these modifications and variations should all belong to the protection domain of claims of the present invention.
Claims (8)
1. one kind prepares Zn1-xMgxThe method of O nanometer rods, it is characterised in that comprise the following steps：
Step S1, ZnO nanorod and oxalic acid are added to into Mg2+In solution, mixed liquor of the pH value less than 6 is obtained；Then it is mixed to this
Close in liquid and add ammoniacal liquor, to be precipitated；Then by the precipitation drying, to obtain presoma；
Step S2, the presoma is mixed with fused salt, and heated under the heating-up temperature higher than fused salt melt temperature together, so
Cooling, washing afterwards, so as to obtain Zn1-xMgxO nanometer rods.
2. preparation Zn according to claim 11-xMgxThe method of O nanometer rods, it is characterised in that the fused salt be NaCl and
In the complex salt of KCl, NaCl salt and KCl salt any one.
3. preparation Zn according to claim 21-xMgxThe method of O nanometer rods, it is characterised in that the heating-up temperature is in
Between 800 DEG C -900 DEG C.
4. preparation Zn according to claim 11-xMgxThe method of O nanometer rods, it is characterised in that the ZnO nanorod and institute
State Mg2+Mg in solution2+Mol ratio between the 1-4.
5. preparation Zn according to claim 11-xMgxThe method of O nanometer rods, it is characterised in that add in mixed liquor
Before ammoniacal liquor, disperse and/or stir the mixed liquor by ultrasonic wave.
6. preparation Zn according to claim 51-xMgxThe method of O nanometer rods, it is characterised in that ammoniacal liquor is by being added dropwise or noting
The mode of penetrating is added in mixed liquor so as to which pH is between 6-7.
7. preparation Zn according to claim 11-xMgxThe method of O nanometer rods, it is characterised in that the ZnO nanorod passes through
Vapour deposition process or hydro-thermal method are prepared.
8. preparation Zn according to claim 11-xMgxThe method of O nanometer rods, it is characterised in that the Mg2+Solution is Mg
(NO3)2Solution or MgCl2Solution.
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