CN106219599A - F/Mn codope SnO2nano-powder and preparation method thereof - Google Patents

F/Mn codope SnO2nano-powder and preparation method thereof Download PDF

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CN106219599A
CN106219599A CN201610559659.XA CN201610559659A CN106219599A CN 106219599 A CN106219599 A CN 106219599A CN 201610559659 A CN201610559659 A CN 201610559659A CN 106219599 A CN106219599 A CN 106219599A
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CN106219599B (en
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吕维忠
吴志军
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Shenzhen University
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Abstract

The present invention provides a kind of F/Mn codope SnO2Nano-powder and preparation method thereof, belongs to codope SnO2Nano-powder technical field.The method step is as follows: add water in reactor, adds Fructus Citri Limoniae acid for adjusting pH, and stirring simultaneously is warming up to 40 60 DEG C, adds SnCl afterwards4·5H2O extremely dissolves, then by MnSO4·H2O and NH4F adds in above-mentioned solution, it is added gradually to precipitant in above-mentioned solution after continuing stirring 10 min continue stirring 30 min, rear regulation pH to 5 11, add dispersant, gained mixed liquor carries out hydro-thermal reaction at 140 200 DEG C, after reacting 2 36h, product distilled water and absolute ethanol washing do not had Cl to until detection‑Till, by after being dried, calcine, grinding and get final product.It is about 12nm and finely dispersed F/Mn codope SnO that the method can prepare particle diameter2Nano-powder.

Description

F/Mn codope SnO2Nano-powder and preparation method thereof
Technical field
The invention belongs to codope SnO2Nano-powder technical field, particularly relates to a kind of F/Mn codope SnO2Nano powder Body and preparation method thereof.
Background technology
Nano-stannic oxide is as the metal oxide semiconductor nano-material of a kind of N-shaped broad-band gap, the most by greatly Amount is used in each different field, such as fields such as catalyst, conductivity ceramics, sensor, display, solaodes.Owing to receiving Rice tin dioxide powder has the biggest reference area, and Surface Oxygen defect is the biggest, and oxygen ligancy ratio is relatively low, is very beneficial for electricity The generation of sub-carrier, is thus advantageous to improve the optical band gap of tin ash, is simultaneously also beneficial to improve its electric conductivity.
Owing to nano tin dioxide material possesses special pattern and special nanostructured, it is at optics, catalysis, gas The aspects such as quick, electricity possess superior performance, and therefore, domestic and international substantial amounts of experts and scholars have carried out numerous studies to it.Nanometer SnO2Preparation method have a variety of, each of which synthetic method has its respective pluses and minuses, and at present the method for preparation has Vapor phase method, solid-phase synthesis, liquid phase method.Wherein the application of liquid phase method is the most, including chemical precipitation method, microemulsion Method, sol-gel process, microwave process for synthesizing, hydro-thermal method etc..
Hydro-thermal method refers to, inside a pressure vessel closed, use water as solvent, the water that at high temperature water produces A kind of chemical reaction carried out under the condition of high voltage that steam is formed.The feature of hydro-thermal reaction is to react, instead in hermetic container Can't see the growth course of crystal during Ying, the purity of the nanoparticle that the method prepares is higher, and crystal formation is good, particle diameter It is evenly distributed, good dispersion, it is not necessary to high-temperature calcination, it is possible to reduce particle agglomeration in calcination process, this method Reaction temperature need not the highest, so being a kind of more satisfactory preparation method of nano material, but have no relevant use at present Hydro-thermal method prepares F/Mn codope SnO2The relevant report of nano-powder.At present, hydro-thermal method prepares F/Mn codope SnO2Nano powder The difficult point of body is synthetic powder scattering problem and size, therefore, at the F/Mn synthesizing a kind of uniform particle sizes, good dispersion Codope SnO2In the method for nano-powder, hydro-thermal method has clear superiority, and the present invention solves hydro-thermal method and prepares F/Mn altogether Doping SnO2Scattering problem and particle diameter shortcoming pockety in nano-powder.
Summary of the invention
It is an object of the invention to provide a kind of F/Mn codope SnO2Nano-powder and preparation method thereof, the method is permissible Preparing particle diameter is about 12nm and finely dispersed FxMnySn(1-x-y)O2Nano-powder.
The present invention adopts the following technical scheme that
F/Mn codope SnO2The preparation method of nano-powder, step is as follows:
Adding water in reactor, addition Fructus Citri Limoniae acid for adjusting pH is to 1-2, and stirring simultaneously is warming up to 40-60 DEG C, and rear addition is appropriate SnCl4·5H2O extremely dissolves, then by MnSO4·H2O and NH4F adds in above-mentioned solution, will precipitation after continuing stirring 10-30 min Agent is added gradually in above-mentioned solution continue stirring 10-30 min, rear regulation pH to 5-11, adds dispersant, and gained mixes Liquid proceeds to water heating kettle and carries out hydro-thermal reaction at 140-200 DEG C, after reaction 2-36h, by hydro-thermal reaction product distilled water and nothing Water-ethanol washing is not to until detection has Cl-Till, by i.e. obtaining described F/Mn codope SnO after being dried, calcine, grinding2Nanometer Powder body.
Further, described F/Mn codope SnO2The preparation method of nano-powder, wherein said NH4F、MnSO4· H2O and SnCl4·5H2The mol ratio of O is x:y:(1-x-y), wherein 0 ＜ x≤0.09,0 ＜ y≤0.11.
Further, described F/Mn codope SnO2The preparation method of nano-powder, wherein said precipitant is ammonia One in water, sodium hydroxide or potassium hydroxide.
Further, described F/Mn codope SnO2The preparation method of nano-powder, wherein said precipitant is hydrogen Sodium oxide.
Further, described F/Mn codope SnO2The preparation method of nano-powder, wherein said dispersant is CTAB。
Further, described F/Mn codope SnO2The preparation method of nano-powder, adding of wherein said dispersant Entering amount is the SnCl added4·5H2The 1%-5% of the quality of O.
Further, described F/Mn codope SnO2The preparation method of nano-powder, wherein said being dried is specially Toasting 10h at 110 DEG C in drying baker, described calcining heat is 800 DEG C.
Further, above-mentioned F/Mn codope SnO2The preparation method of nano-powder, during wherein said hydro-thermal reaction Temperature be 200 DEG C, the hydro-thermal reaction time is 12h, and pH value is 10.
The present invention also provides for a kind of F/Mn codope SnO2Nano-powder.
Compared with prior art the invention has the beneficial effects as follows: the F/Mn codope SnO of (1) present invention synthesis2Nano powder The even particle size distribution of body, easily disperses, low cost；(2) the F/Mn codope SnO of present invention synthesis2The particle diameter ratio of nano-powder More uniform, and size meets industrial requirements；(3) the whole technological process of the present invention is simple and easy to do, and does not has in course of reaction There are use toxic solvent, environmental protection.
Accompanying drawing explanation
Fig. 1 is F prepared by different precipitant0.05Mn0.05Sn0.90O2The XRD figure of nano-powder: wherein a is that NaOH, b are KOH, c are NH3·H2O；
Fig. 2 is F prepared by different dispersant0.05Mn0.05Sn0.90O2The SEM figure of powder body, wherein a: be not added with dispersant；B:PEG- 600；C:CTAB；D:SDS；E: sodium stearate；F:TPAB；
Fig. 3 is F prepared by different pH valuexMnySn(1-x-y)O2The XRD figure of nano-powder；
Fig. 4 is the F of preparation under different hydrothermal temperature0.05Mn0.05Sn0.90O2The XRD figure of powder body；
Fig. 5 is the F of preparation under the different hydro-thermal time0.05Mn0.05Sn0.90O2The XRD figure of powder body；
Fig. 6 is different hydro-thermal time F0.05Mn0.05Sn0.90O2The XRD of powder body；
Fig. 7 is hydrothermal temperature F/Mn codope SnO when being 200 DEG C2For the crystal grain curve under the different hydro-thermal time；
Fig. 8 is different additive Mn amount (mol ratio) FxMnySn(1-x-y)O2The XRD figure of nano-powder
Fig. 9 is additive Mn amount (mol ratio) FxMnySn(1-x-y)O2The grain size curve of nano-powder；
Figure 10 is different Fluorin doped amount (mol ratio) and FxMnySn(1-x-y)O2The XRD figure of nano-powder；
The F that Figure 11 is at 200 DEG C, prepared by hydro-thermal reaction 12h0.05Mn0.05Sn0.90O2The TEM figure of powder body；
Figure 12 is FxMnySn(1-x-y)O2Powder body Fourier infrared absorption spectrum；
Figure 13 is F under different calcining heat0.05Mn0.05Sn0.90O2Nano-powder XRD figure；
Figure 14 is F0.05Mn0.05Sn0.90O2Diameter of particle and the curve chart of calcining heat relation；
Figure 15 is F0.05Mn0.05Sn0.90O2Nano-powder calcines the two-dimensional map of the atomic force microscope of 3h at 900 DEG C；
Figure 16 is F0.05Mn0.05Sn0.90O2Nano-powder calcines the three-dimensional collection of illustrative plates of 3h at 900 DEG C；
Figure 17 is F0.05Mn0.05Sn0.90O2The calcination time XRD figure that nano-powder is different at 900 DEG C；
Figure 18 is F0.05Mn0.05Sn0.90O2Particle diameter of nanometer powder and the curve chart of calcination time relation；
Figure 19 is F0.05Mn0.05Sn0.90O2SEM figure (a=1h and b=5h) of different calcination times at powder body 900 DEG C；
F prepared by the adulterant that Figure 20 is different0.05Mn0.05Sn0.90O2The XRD figure of powder body；
F prepared by the adulterant that Figure 21 is different0.05Mn0.05Sn0.90O2The XRD figure of powder body；
F prepared by the adulterant that Figure 22 is different0.05Mn0.05Sn0.90O2The XRD figure of powder body；
F prepared by the adulterant that Figure 23 is different0.05Mn0.05Sn0.90O2The XRD figure of powder body；
Figure 24 is F prepared by different dopant0.05Mn0.05Sn0.90O2The SEM figure of powder body, wherein a:HF ＆ Mncl2·4H2O；B: HF ＆ MnSO4·H2O；C:KF ＆ Mncl2·4H2O；D:KF ＆ MnSO4·H2O；E:NaF ＆ Mncl2·4H2O；F:NaF ＆ MnSO4·H2O；G:NH4F ＆ Mncl2·4H2O；
Figure 25 is F0.05Mn0.05Sn0.90O2The SEM-EDS test figure of nano-powder.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
Hydro-thermal method is used to prepare F/Mn codope SnO2Nano-powder, specifically comprises the following steps that the deionized water first measuring 50 ml In beaker, add citric acid and pH value is transferred to 1-2, be heated to 50 DEG C by magnetic stirrer simultaneously and keep constant temperature；So The SnCl that rear addition is appropriate4·5H2O is to dissolving；Again by the MnSO of different dopings4·H2O and NH4F adds in above-mentioned solution.Continue It is added gradually in above-mentioned solution continue to stir by precipitant (ammonia, sodium hydroxide or potassium hydroxide) after continuous stirring 10-30 min Mix 10-30 min regulation pH value to 5-11, add dispersant (addition of dispersant 1% to 5%, according to SnCl4· 5H2O mass calculates), gained mixed liquor proceeds to water heating kettle and carries out hydro-thermal reaction the most at different temperatures；Then hydro-thermal is anti- Product distilled water and absolute ethanol washing is answered not to have Cl to detection-Till, under 110 ° of C, toast 10h at drying baker afterwards.After A part of powder body is carried out high-temperature calcination, ground after i.e. obtain F/Mn prepared by hydro-thermal method and adulterate SnO2Nano-particle, will system The nano-powder got ready carries out various sign.
The selection of embodiment 2 precipitant
NaOH, KOH and ammonia is used to prepare doping F as precipitant respectively0.05Mn0.05Sn0.90O2Nano-powder, through XRD Test characterizes its result as shown in Figure 1.
Fig. 1 is the doping SnO prepared with different precipitant2The XRD figure spectrum of nano-powder, passes through and SnO2Standard card (PDF#-1445) contrast, NaOH, KOH and ammonia are all four directions rutile structures as the sample prepared by precipitant.Wherein with Ammonia is that the sample of precipitant is not apparent from the diffraction maximum of (220) and (002) crystal face, and KOH is that the sample of precipitant exists (220) and (002) crystal face diffraction maximum somewhat substantially a bit, but the spreading out at the two crystal face of the sample with NaOH as precipitant Penetrating peak the most clear, the height at peak is the highest, and the diffraction maximum at characteristic peak (110), (101) and (211) these three crystal face is also 3 simultaneously Plant in precipitant the strongest, the doping SnO prepared for precipitant with NaOH is described2Degree of crystallinity the highest, crystallize the most perfect, so It is optimal precipitant with NaOH.
The selection of embodiment 3 dispersant
Other conditions of experiment are certain, and (each atomic molar compares: F:Mn:Sn=0.05:0.05:0.90, pH=9, hydrothermal temperature is 180 DEG C, the hydro-thermal time is 6 h, and precipitant is NaOH), use different dispersant preparation doping SnO2Nano-powder, is surveyed by SEM Examination is as shown in Figure 2.
As shown in Figure 2, not adding the sample reunion especially severe of dispersant, wherein stearic acid sodium is not only not reaching to point Dissipating effect, the sample that it is prepared is reunited more serious than the sample not adding dispersant, is substantially block structure, adds SDS(ten Dialkyl sulfonates) and TPAB(4-propyl bromide) it is that the pattern of the sample of dispersant is all somewhat like coralliform, but dispersion Effect is not it is obvious that the sample surfaces that PEG-600 is dispersant to be prepared is as there being a tunic to cover the table at powder body Face, this macromolecule being probably PEG-600 itself covers on powder body, wherein CTAB(cetyl trimethylammonium bromide) be Sample prepared by dispersant is as it can be seen, the particle size ratio of powder body is more uniform, and dispersion effect is best.So this experimental selection CTAB is as dispersant.
The selection of embodiment 4 pH
Other conditions of experiment certain (for F:Mn:Sn=0.05:0.05:0.90, hydrothermal temperature is 180 DEG C to each atomic molar ratio, The hydro-thermal time is 6h, precipitant be NaOH, CTAB be dispersant), regulate different pH value prepare doping SnO2Nano-powder, Characterized as shown in Figure 3 by XRD.
According to compareing SnO after the sign of XRD2The peak position of standard card (PDF#-1445), crystal is all four directions golden red Stone structure, pH value is to F/Mn codope SnO2The degree of crystallinity of crystal have some impact, but impact is little, the crystallization of crystal is strong Degree difference is little, and under conditions of pH=10 with pH=11, each characteristic peak of the powder body of preparation is relative sharp-pointed, and half-peak breadth is the most relative Little.
The selection of embodiment 5 hydrothermal temperature
Other conditions of experiment are certain, and (for F:Mn:Sn=0.05:0.05:0.90, the hydro-thermal time is 6 h to each atomic molar ratio, heavy Shallow lake agent be NaOH, CTAB be dispersant, pH value is 10), regulate different hydrothermal temperatures prepare doping SnO2Nano-powder is logical Cross XRD to characterize as shown in Figure 4.
Fig. 4 is the different hydrothermal temperatures XRD diffraction pattern at the adulterated powder that the hydro-thermal time is 6 hours.XRD figure shows For hydrothermal temperature is 140 DEG C when, (110), (101) relative with (211) three characteristic peaks substantially outside, other positions Diffraction maximum the most unintelligible, illustrate the when that hydrothermal temperature being 140 DEG C, SnO2The degree of crystallinity imperfection of crystal, nano-powder is Non-crystal structure.When hydrothermal temperature 160 DEG C of samples made above diffraction maximum all with SnO2Standard card (PDF#-1445) Peak position match, crystal be all four directions rutile structure.Hydrothermal temperature is 160 DEG C and 180 DEG C when, each position The intensity of diffraction maximum and half-peak breadth difference be not the most clearly.But, when hydrothermal temperature is 200 DEG C when, sample (110), the intensity at the peak of (101) and (211) three crystal faces be all remarkably reinforced, the peak of the crystal face in (200) direction is obvious especially, And the fuzzyyest at the sample of 160 DEG C and the 180 DEG C crystal face in this direction, simultaneously the peak of (002) and (202) crystal face also than The crystal face of sample prepared by other temperature clear, this explanation is advantageous for SnO along with the rising of temperature2The growth of crystal.Root SnO can be calculated by Scherrer formula according to the width of more than half peak height of diffraction maximum2The average grain size of crystal, is all at 8-10 About nm, warm problem is little on the impact of grain size, considers the synthesis temperature selecting 200 DEG C to be the later stage afterwards.
The selection of embodiment 6 hydro-thermal reaction time
The reaction temperature of experiment is 200 DEG C, and each atomic molar ratio is for F:Mn:Sn=0.05:0.05:0.90 (F0.05Mn0.05Sn0.90O2), precipitant be NaOH, CTAB be dispersant, pH value is 10, under the different response time, makes Standby doping SnO2Nano-powder, is characterized as shown in Figure 5 by XRD.
As figure 5 illustrates, the hydro-thermal reaction time at 200 DEG C that represents respectively is 2 h, 4 h, 6 h, 8 h, 12 h, 18 h, 24 H, 36 h, along with the increase of hydro-thermal time, the degree of crystallinity of crystal gradually strengthens, and 12 h when, the degree of crystallinity of crystal compares Perfect, after 12h under conditions of the degree of crystallinity of crystal be not remarkably reinforced than 12 h, SnO is described2Crystal can't be with The prolongation of time and infinitely strengthen, but the most perfect 12 h when.Fig. 6 is SnO2The three of the XRD of powder body Dimension, the peak of each crystal face of the powder body finding out 24 h that can become apparent from according to Fig. 6 is not prepared than under conditions of 12 h The powder body come makes a big difference.
Fig. 7 is F/Mn codope SnO2Hydrothermal temperature is at 200 DEG C, the different crystal grain curves under the hydro-thermal time, works as water The heat time, the size being calculated crystal grain by Scherrer formula was to drop to from 63.45 nm during 2 h extend to 8 h 15.54 nm, it may be possible to the tin ash produced when the hydro-thermal time is 2 h is not the most a complete crystal, is just to have started The tin ash crystal formed is female, and along with the prolongation of hydro-thermal time, it slowly melts, after the hydro-thermal time is 12 h, brilliant Body just crystallization is fairly perfect, and the grain size of 18 h, 24 h, 36 h, 48 h and 60 h is the most the same with during 12 h, this Just it coincide with the acuity of each characteristic peak of XRD, further illustrate after the hydro-thermal time reaches 12 h, crystal structure degree Fairly perfect.So, this considers that selecting the hydro-thermal time is that 12 h are optimal.
The embodiment 7 Mn doping crystal structure on powder body and the impact of particle diameter
Experiment reaction condition is: hydrothermal temperature is 200 DEG C, and the hydro-thermal time is 12h, pH=10, and dispersant is CTAB, and precipitant is The doping of NaOH, F is fixed as the F of the doping ratio preparation difference doping of 0.05 change MnxMnySn(1-x-y)O2Nano-powder, Characterizing through XRD test, XRD figure is composed as shown in Figure 8.
XRD figure spectrum according to Fig. 8, all corresponding SnO of the doping ratio of Mn diffraction maximum below 0.092Standard card (PDF#-1445) peak position, crystal is all four directions rutile structure, does not has the appearance of other thing phases, and the position of diffraction maximum is also The most significantly offseting, illustrate that the doping ratio of Mn is then added to 0.07 from 0.01, the doping of Mn does not change SnO2Lattice. But, along with the doping of Mn, SnO2Diffraction maximum type gradually wideization such as (110), (101) and (211) of crystal, the intensity of diffraction maximum Weaken, illustrate to reduce SnO along with the doping of Mn2Degree of crystallinity, strongly fragrant made SnO2The growth of crystal.But the doping as Mn The when that ratio reaching 0.09, occur that impurity occurs mutually, have MnO2Impurity.Illustrate that the doping of Mn not can exceed that 0.09.
Fig. 9 is that the doping ratio of Mn is to SnO2Grain size curve graph of a relation, owing to the doping of Mn reduces SnO2Crystallization Degree, strongly fragrant has made SnO2The growth of crystal, particle diameter also tapers into, and particle diameter gradually decreases to 9.22nm from 12.32nm.This is because Mn is doped into SnO2After crystal, Mn2+Account for the position of part Sn, due to Mn2+Radius be that 0.067nm compares Sn4+The half of ion Footpath is the smaller of 0.069nm, causes a part of crystal defect, and the strongly fragrant growth having made crystal, so causing particle diameter to diminish.According to XRD is the most provable, when the doping ratio of Mn reaches 0.09 when, and SnO2Lattice is seriously damaged, say, that bright is not Mn Doping The more the better.
The impact on the crystal structure of powder body of the embodiment 8 F doping
Experiment reaction condition is: hydrothermal temperature is 200 DEG C, and the hydro-thermal time is 12h, pH=10, and dispersant is CTAB, and precipitant is The doping of NaOH, Mn is fixed as the F of the doping preparation difference doping of 0.05 change FxMnySn(1-x-y)O2Nano-powder, warp Crossing XRD test to characterize, XRD figure is composed as shown in Figure 10.
XRD figure spectrum according to Figure 10, the doping of F prepares sample FxMnySn(1-x-y)O2The all corresponding SnO of diffraction maximum2Mark The peak position of quasi-card (PDF#-1445), crystal is all four directions rutile structure, does not has the appearance of other impurity peaks, diffraction maximum Position somewhat occur a little offseting.But, along with the doping of F, SnO2The characteristic diffraction peak type of crystal somewhat occurs the widest Change and strength reduction, illustrate to reduce SnO along with the doping of F element2Degree of crystallinity, strongly fragrant made SnO2The growth of crystal.May It is because F-Substituted for part O2-Position, cause that segmental defect occurs, thus inhibit the crystalline growth of crystal.The doping of F Amount is to the most not occurring impurity phase peak when of 0.11, it may be possible to the reason little to the structural deterioration of lattice of adulterating of F element.
Embodiment 9
1、F0.05Mn0.05Sn0.90O2The transmission electron microscope analysis of nano-powder
Hydrothermal temperature is 200 DEG C, and the hydro-thermal time is 12h, pH=10, and dispersant is CTAB, and precipitant is NaOH, preparation F0.05Mn0.05Sn0.90O2Nano-powder, characterizes through TEM test, and TEM is as shown in figure 11.As shown in Figure 11, make under this condition Standby F out0.05Mn0.05Sn0.90O2The pattern of nano-powder is random blockage shape, and mean diameter is about 12nm, particle diameter It is distributed more dispersed, this crystal particle diameter size ratio tested with XRD above and calculate through Scherrer formula It is closer to.
、F0.05Mn0.05Sn0.90O2The infrared spectrum analysis of nano-powder
SnO2Crystal is a kind of four directions rutile structure, and its each structure cell is containing 4 oxygen atoms and 2 tin atoms. Figure 12 is the SnO that undopes2Sample and doping SnO2(F0.05Mn0.05Sn0.90O2) the FTIR spectrum figure of sample, according to figure 12 understand, at 3414.0cm-1And 1647.20cm-1For SnO2-OH group stretching vibration peak or powder body table on Nanosurface -OH the group of face absorption water.At 2920.1cm-1And 2854.6cm-1It is C-H stretching vibration peak, 1394.53 cm-1It it is C-H deformation Vibration peak, occurs that C-H peak is to have used citric acid during preparing sample, the sample also residual minim causing preparing Citric acid causes on surface.F0.05Mn0.05Sn0.90O2Sample is pure and SnO2All there is C-H peak and-OH peak in nano-powder, does not has Have and occur significantly to offset because of the doping of fluorine manganese element.2355.08cm-1Peak be due to powder surface absorption trace water with Carbon dioxide jointly acts on and occurs, 1004.91cm-1Peak is the vibration at the peak, Sn=O and Sn-O position of powder surface, but After being doped with fluorine manganese element, the peak of this position occurs in that and significantly weakens or almost disappear.SnO2The spy of crystal Levying peak is at 400 cm-1-700cm-1Between, pure sample occurs 514.9 cm-1With 650 cm-1The two characteristic peak is SnO2The Sn-O-Sn vibration of crystal, this two peak structure is exactly that water and stannum oxide are to SnO2The conversion of crystal.Doped with fluorine manganese SnO2 Crystal occurs in that 507 cm-1With 665 cm-1The peak of the two position, with 514.9 cm of plain tin ash-1With 650 cm-1Closely, do not find substantially skew, illustrate that doped with fluorine manganese element does not change SnO2The structure of crystal, this with The analysis result of XRD above is consistent.
, EDS analyze
The F prepared by hydro-thermal method0.05Mn0.05Sn0.90O2Powder body carries out power spectrum (SEM-EDS) and is characterized as below shown in Figure 25.
As can be seen from Figure 25 the EDS power spectrum test figure of fluorine/manganese codoped stannic oxide nano powder detects F, Mn, The peak of Sn, O, does not has other to find the peak of other impurity elements, illustrates to have been adulterated entrance tin ash by hydro-thermal method F and Mn Suffer.
Embodiment 10 calcining heat is to F0.05Mn0.05Sn0.90O2The impact of nano-powder
Calcining heat is to F0.05Mn0.05Sn0.90O2The impact of nano-powder is bigger, due to the rising of temperature, nano-powder The energy obtained also can increase, and promotes powder body further growth crystallization, simultaneously because the rising of calcining heat, also results in and receive Rice flour body generation hard aggregation phenomenon.So being not that calcining heat is the highest more good, and it is intended to select a suitable temperature.
The F that hydro-thermal method prepares0.05Mn0.05Sn0.90O2Nano-powder is calcined, calcining heat is 500 DEG C respectively, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, calcination time is all to be fixed as 3h, and the sample after calcining is carried out XRD sign Test, test collection of illustrative plates is as shown at 13.
The XRD figure spectrum contrast of Figure 13 and SnO2The peak position of standard card (PDF#-1445) is corresponding, does not has after calcining Occur impurity peaks, so the powder body after Duan Shao is all SnO2Crystal.Calcining heat is understood from 500 DEG C to 800 DEG C from XRD figure Each characteristic peak of sample be all gradually to sharpen, half-peak breadth also tapers into, and illustrates that crystal the following is along with temperature at 800 DEG C The rising of degree is grown into, and degree of crystallinity is also the most perfect.But, when calcining heat is raised to 900 DEG C and 1000 DEG C when, respectively Individual characteristic peak is all substantially sharp-pointed a lot, and half-peak breadth the most substantially diminishes, and illustrates that the degree of crystallinity of sample is substantially to increase after 900 DEG C By force, degree of crystallinity tends to more perfect, particle diameter fast-growth, between particle be also reunite more serious.Illustrate that temperature is the highest, more have It is beneficial to the growth of crystal, but owing to considering reunion and grain size size issue, is not that calcining heat is the highest more good.
Calculate (calculating, be all according to 101 peaks in full) according to 101 peaks according to Scherrer formula to go out under each calcining heat F0.05Mn0.05Sn0.90O2Diameter of particle as shown in figure 14, according to figure understand calcining heat below 800 DEG C, the particle diameter of powder body Size is not increase clearly, but after 900 DEG C, particle diameter increases 44.43nm rapidly from 14.45nm, to 1000 DEG C When, particle diameter increases to 78.87nm, and this is the most identical with the analysis of XRD, so considering, selection calcining heat is 800 DEG C more suitable.
Figure 15-16 is the two and three dimensions figure that the sample after calcining 900 DEG C carries out AFM test, understands when forging according to figure The when that burning temperature reaching 900 DEG C, F0.05Mn0.05Sn0.90O2The growth of powder body is that the most uniformly particle diameter is distributed in 30-50 Between nm, this size calculated with XRD standard above and Scherrer formula is basically identical.
Embodiment 11 calcination time is to F0.05Mn0.05Sn0.90O2Powder body crystal structure and the impact of particle diameter
F calcining heat is 900 DEG C when is understood according to experiment above0.05Mn0.05Sn0.90O2The particle diameter of nano-powder goes out Now mushroom out, so probing into when 900 DEG C, the calcination time impact on crystal.Experiment condition is that calcining heat is fixed as 900 DEG C, calcination time is respectively 1 h, 3 h, 5 h and 7 h.Sample after calcining is carried out XRD characterization test, tests collection of illustrative plates such as 3- Shown in 16.
The XRD figure spectrum of Figure 17 and SnO2The peak position of standard card (PDF#-1445) is corresponding, does not go out after calcining Existing impurity.As we know from the figure at 900 DEG C after calcining, SnO2Each diffraction peak intensity of crystal the most significantly strengthens, and says Bright affect SnO2The impact of the growth of crystal most importantly temperature, calcination time is little on its impact, calcines 1 h and calcining 7 Degree of crystallinity difference after h is little.
Figure 18 is the relation of calcination time and particle diameter, calculates the different calcination times grain to crystal according to Scherrer formula The impact in footpath, along with the prolongation of calcination time, particle diameter is constantly to increase, because calcination time extends during the increase of particle diameter, The reunion of particle is more serious, causes particle diameter to be gradually increased, but particle diameter increases inconspicuous, and this is consistent with the analysis of XRD.
Figure 19 is the scanning electron microscope (SEM) photograph calcined under the conditions of 900 DEG C and calcined 1h and 5h respectively, as seen from the figure, and calcining 5h's The sample reunion than 3h is more serious, the polyhedron that the pattern of particle is just as, and peripheral outline is very clear, illustrates 900 Under conditions of DEG C, the sample grown after calcining is the most perfect.
The impact on crystalline structure of embodiment 12 adulterant
Figure 20 be HF as F element adulterant respectively with Mncl2·4H2O and MnSO4·H2Prepared by additive Mn agent different for O F0.05Mn0.05Sn0.90O2The XRD figure of powder body；Figure 21 be KF as F element adulterant respectively with MnCl2·4H2O and MnSO4· H2F prepared by additive Mn agent different for O0.05Mn0.05Sn0.90O2The XRD figure of powder body；Figure 22 is NaF to be divided as the adulterant of F element Not and Mncl2·4H2O and MnSO4·H2F prepared by additive Mn agent different for O0.05Mn0.05Sn0.90O2The XRD figure of powder body；Figure 23 It is NH4F as F element adulterant respectively with MnCl2·4H2O and MnSO4·H2Prepared by additive Mn agent different for O F0.05Mn0.05Sn0.90O2The XRD figure of powder body.XRD figure spectrum according to following four series can be apparent from finding out each sample Each principal character peak the most clearly, other impurity phase peaks do not occur, illustrate that different adulterants does not affects dioxy Change the crystallization of stannum crystal.
The impact on morphology microstructure of embodiment 13 adulterant
Such as the F for preparing of adulterant that Figure 24 is different0.05Mn0.05Sn0.90O2The SEM figure of powder body, wherein figure a is HF ＆ MnCl2· 4H2The a lot of spicule of X rays topographs of the sample that O prepares is piled up, and figure b, d and figure f is MnSO4·H2O respectively with HF, KF The sample prepared with NaF, its pattern is all somewhat like spongy.The powder body that different adulterants prepares is understood according to figure Pattern the most different, there is no special pattern yet, this is likely due to synthesis when different adulterants causes preparing sample The result of interior condition impact.All samples is all irregular pattern, and this is consistent with the result of SEM and TEM above.
Above in conjunction with accompanying drawing, embodiments of the present invention are explained in detail, but the present invention is not limited to above-mentioned enforcement Mode, in the ken that those of ordinary skill in the art are possessed, it is also possible on the premise of without departing from present inventive concept Make a variety of changes.

Claims (9)

1.F/Mn codope SnO2The preparation method of nano-powder, it is characterised in that step is as follows:
Adding water in reactor, addition Fructus Citri Limoniae acid for adjusting pH is to 1-2, and stirring simultaneously is warming up to 40-60 DEG C, and rear addition is appropriate SnCl4·5H2O extremely dissolves, then by MnSO4·H2O and NH4F adds in above-mentioned solution, will precipitation after continuing stirring 10-30 min Agent is added gradually in above-mentioned solution continue stirring 10-30 min, rear regulation pH to 5-11, adds dispersant, and gained mixes Liquid proceeds to water heating kettle and carries out hydro-thermal reaction at 140-200 DEG C, after reaction 2-36h, by hydro-thermal reaction product distilled water and nothing Water-ethanol washing is not to until detection has Cl-Till, by i.e. obtaining described F/Mn codope SnO after being dried, calcine, grinding2Nanometer Powder body.
F/Mn codope SnO the most according to claim 12The preparation method of nano-powder, it is characterised in that described NH4F、 MnSO4 ·H2O and SnCl4·5H2The mol ratio of O is x:y:(1-x-y), wherein 0 ＜ x≤0.09,0 ＜ y≤0.11.
F/Mn codope SnO the most according to claim 12The preparation method of nano-powder, it is characterised in that described precipitant For the one in ammonia, sodium hydroxide or potassium hydroxide.
F/Mn codope SnO the most according to claim 32The preparation method of nano-powder, it is characterised in that described precipitant For sodium hydroxide.
F/Mn codope SnO the most according to claim 12The preparation method of nano-powder, it is characterised in that described dispersant For CTAB.
F/Mn codope SnO the most according to claim 12The preparation method of nano-powder, it is characterised in that described dispersant Addition be add SnCl4·5H2The 1%-5% of the quality of O.
F/Mn codope SnO the most according to claim 12The preparation method of nano-powder, it is characterised in that described dry tool Body is for toast 10 h at 110 DEG C in drying baker, and described calcining heat is 800 DEG C.
8. according to the F/Mn codope SnO described in any one of claim 1 to 72The preparation method of nano-powder, it is characterised in that Temperature during described hydro-thermal reaction is 200 DEG C, and the hydro-thermal reaction time is 12h, and pH value is 10.
9. by the F/Mn codope SnO described in claim 82The F/Mn codope SnO that the preparation method of nano-powder prepares2Receive Rice flour body.
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CN108342749A (en) * 2018-02-01 2018-07-31 太原理工大学 A kind of modified SnO2The preparation method and applications of electrode restore CO in photoelectrocatalysis2Formic acid processed
CN109704394A (en) * 2019-01-28 2019-05-03 广州奥松电子有限公司 A kind of preparation method of doped tin dioxide powder body and the doped tin dioxide powder body obtained by this method

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CN104150528A (en) * 2014-08-28 2014-11-19 攀枝花学院 Preparation method of doped stannic oxide conductive nano powder
CN104402042A (en) * 2014-10-22 2015-03-11 安徽科技学院 Method for direct synthesis of Mn<+>-doped SnO2 nanocrystals with one-step hydrothermal method
CN105152202A (en) * 2015-07-17 2015-12-16 济南大学 Preparation method for antimony-doped flower-ball-shaped tin dioxide gas-sensing material

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CN104402042A (en) * 2014-10-22 2015-03-11 安徽科技学院 Method for direct synthesis of Mn<+>-doped SnO2 nanocrystals with one-step hydrothermal method
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* Cited by examiner, † Cited by third party
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CN108342749A (en) * 2018-02-01 2018-07-31 太原理工大学 A kind of modified SnO2The preparation method and applications of electrode restore CO in photoelectrocatalysis2Formic acid processed
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