CN109485090A - A kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth and preparation method - Google Patents
A kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth and preparation methods, and the chemical composition of the chromium doping barium stannate nano-powder is BaSn1‑xCrxO3, wherein 0 x≤0.5 <, the chromium doping adjustment powder forbidden bandwidth.
Description
Technical field
The present invention relates to a kind of adjustable materials of forbidden bandwidth -- and chromium adulterates barium stannate nano-powder and preparation method thereof, belongs to
In conductor oxidate nano-powder material technical field.
Background technique
Explore high conversion efficiency, high stability, low cost novel photoelectric transition material be photovoltaic material research it is eternal
Theme.For current most popular solar battery when belonging to perovskite solar battery (PSC), succession is simultaneously derived from dye sensitization
Solar battery (DSSC) is dedicated to solving several disadvantages of crystal silicon, the solar batteries such as cadmium telluride, as transfer efficiency is lower,
The problems such as precious metal dye price is higher, liquid electrolyte volatile leakage.
Currently, the light-absorption layer of perovskite solar battery is still with Organic-inorganic composite halogen perovskite material (methylamine lead
Iodine: CH3NH3PbI3) based on, however, unstability, the toxicity of methylamine lead iodine material limit it in photovoltaic solar cell device
The application in part field, so, low energy gap, high stable, full-inorganic perovskite light absorbing material will become research hotspot.Alkaline earth
Metal stannate is the composite oxide material of a kind of typical perovskite structure, and forbidden band is wide (3.18-4.5eV), and resistance is big, high
Warm nature matter is stablized, and has optics abundant, electricity, magnetism characteristic, has obtained extensive research.Britain K.P.Marshall et al. is adopted
With iodine tin caesium (CsSnI3) it is used as light absorbing material, prepare the perovskite solar battery that photoelectric conversion efficiency is 3.56%.
Therefore, stannic acid salt material is expected to push the development of perovskite solar cell device.
In stannate preparation, since its forbidden bandwidth is wider, it is difficult to realize the level-density parameter with hole transmission layer.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of energy Effective Regulation forbidden bandwidth and widening light absorption range
Perovskite light absorbent chromium doping barium stannate nano-powder and preparation method thereof.
Herein, on the one hand, the present invention provides a kind of chromium doping barium stannate nano-powder, and the chromium adulterates barium stannate nano powder
The chemical composition of body is BaSn1-xCrxO3, wherein 0 x≤0.5 <, the chromium doping adjustment powder forbidden bandwidth.
According to foregoing invention, doped chemical chromium, the perovskite extinction material being consequently formed are introduced in alkaline-earth metal barium stannate
Expect that chromium adulterates barium stannate nano-powder, realize the Effective Regulation of energy band band gap and has widened light absorption range.For example, of the invention
The adjustable chromium doping barium stannate nano-powder energy band band gap width of the forbidden bandwidth of one implementation form is to effectively reduced to from 3.15eV
2.74eV, light absorption range are widened from 400nm to 600nm.
Chromium doping barium stannate nano-powder has adjustable optical in the visible light wave range of 400-600nm in the present invention
Energy.The optical energy band band gap width that the chromium adulterates barium stannate nano-powder realizes controllable adjustment, passes through the doping of elemental chromium, band gap
Width is 3.15~2.74eV.Preferably, the chemical composition BaSn of the chromium doping barium stannate nano-powder1-xCrxO3In, 0.01
≤ x≤0.05, band gap width are 3.02~2.74eV.
Preferably, the chromium doping barium stannate particle diameter of nanometer powder is evenly distributed, partial size is 25~30nm.
On the other hand, the present invention also provides a kind of methods for preparing above-mentioned chromium doping barium stannate nano-powder, comprising:
Using water-soluble pink salt, water soluble barium salt, water-soluble chromic salts as raw material, using peroxide aqueous solution as solvent, using peroxide
The compound precipitation method prepare precursor powder；And
The precursor powder is heat-treated 1~24 hour in 700~1300 DEG C, obtains the chromium doping barium stannate nano-powder.
The present invention is to precipitate legal system by peroxide using water-soluble pink salt, water soluble barium salt, water-soluble chromic salts as raw material
Standby precursor powder out, then high-temperature heat treatment obtains that the uniform crystallinity of particle diameter distribution is good, optics is prohibited at a certain temperature by it
The chromium of bandwidth controllable adjustment adulterates barium stannate nano-powder, can be widely applied to semiconductor photoelectric device, photocatalysis, solar energy
The fields such as battery.Compared with the conventional powders preparation method such as solid-phase sintering, collosol and gel, the peroxide precipitation method prepare powder tool
There are the outstanding features such as particle diameter distribution is uniformly tiny, crystalline quality is high.
The water solubility pink salt can be tin tetrachloride (SnCl4), stannic chloride pentahydrate (SnCl4·5H2O) stannic iodide
(SnI4), tin acetate (C8H12O8At least one of Sn).
The water soluble barium salt can be barium chloride (BaCl2), barium chloride (BaCl2·2H2O), barium iodide
(BaI2), two water barium iodide (BaI2·2H2O), barium nitrate (Ba (NO3)2), barium acetate (C4H6O4At least one of Ba).
The water solubility chromic salts can be chromium trichloride (CrCl3), chromium chloride hexahydrate (CrCl3·6H2O), chromic nitrate
(Cr(NO3)3), nine water chromic nitrate (Cr (NO3)3·9H2O), chromium acetate (C6H9O6At least one of Cr).
The peroxide aqueous solution is hydrogen peroxide (H2O2) aqueous solution, sodium carbonate peroxide (2Na2CO3·3H2O2) water-soluble
Liquid, benzoyl hydroperoxide (C6H7O3At least one of) aqueous solution, the concentration of the peroxide aqueous solution can be 10~50%
(mass fraction).
The ratio of water-soluble pink salt and solvent can be (0.001-0.1) mol:(100-2000) ml.
Preferably, using the peroxide precipitation method prepare precursor powder include: according to stoichiometric ratio by water-soluble pink salt,
Water soluble barium salt, water-soluble chromic salts are dissolved in peroxide aqueous solution, and chelating agent is then added, is mixed to get clear solution,
Then it is 8~14 that precipitating reagent to solution ph, which is added dropwise, and stirring obtains precursor powder in 1~120 minute.
The chelating agent can be oxalic acid (C2H2O4), tartaric acid (C4H6O6), citric acid (C6H8O7), gluconic acid
(C6H12O7), aminotriacetic acid (C6H9NO6), ethylenediamine tetra-acetic acid (C10H16N2O8At least one of).
The molar ratio of water-soluble pink salt and chelating agent can be (0.001-0.1): (0.001-0.1).
The precipitating reagent can be ammonium hydroxide (NH3·H2O), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate
(Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), saleratus (KHCO3At least one of).Wherein ammonium hydroxide
Concentration can be 10~50% (mass fractions).
Preferably, the temperature of heat treatment is 700~900 DEG C, the time is 1~2 hour.
The present invention use the peroxide precipitation method, be prepared for mixing the barium stannate nano-powder of chromium, obtain partial size 25~
The chromium of 30nm adulterates barium stannate nano-powder, has widened barium stannate nano-powder in the absorption region of visible light, has realized chromium and mix
The controllable adjustment of miscellaneous barium stannate nano-powder energy band band gap.Compared with the conventional powders preparation method such as solid-phase sintering, collosol and gel,
The peroxide precipitation method prepare the outstanding features such as powder is uniformly tiny with particle diameter distribution, crystalline quality is high.
Detailed description of the invention
Fig. 1 is that the adjustable chromium of forbidden bandwidth of an implementation form of the invention adulterates the preparation flow of barium stannate nano-powder
Figure；
Fig. 2 (a) is that the adjustable chromium of forbidden bandwidth of different dopings according to the present invention adulterates barium stannate nano-powder (BaSn1- xCrxO3, x=0.01,0.03,0.05,0.1,0.15) and undoped sour barium nano-powder XRD spectrum；
Fig. 2 (b) is that the adjustable chromium of forbidden bandwidth of different dopings according to the present invention adulterates barium stannate nano-powder (BaSn1- xCrxO3, x=0.01,0.03,0.05,0.1,0.15) and XRD of the undoped sour barium nano-powder in 30 °≤2 θ≤32 °
Map；
Fig. 3 (a) is undoped barium stannate nano-powder (BaSnO3) field emission scanning electron microscope (FESEM) photo；
Fig. 3 (b) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 3 adulterates barium stannate nano-powder (BaSn0.99Cr0.01O3)
Field emission scanning electron microscope (FESEM) photo；
Fig. 3 (c) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 4 adulterates barium stannate nano-powder (BaSn0.97Cr0.03O3)
Field emission scanning electron microscope (FESEM) photo；
Fig. 3 (d) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 2 adulterates barium stannate nano-powder (BaSn0.95Cr0.05O3)
Field emission scanning electron microscope (FESEM) photo；
Fig. 3 (e) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 5 adulterates barium stannate nano-powder (BaSn0.9Cr0.1O3)
Field emission scanning electron microscope (FESEM) photo；
Fig. 3 (f) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 6 adulterates barium stannate nano-powder (BaSn0.85Cr0.15O3)
Field emission scanning electron microscope (FESEM) photo；
Fig. 4 (a) is that undoped chromium adulterates barium stannate nano-powder (BaSnO3) particle diameter distribution picture；
Fig. 4 (b) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 3 adulterates barium stannate nano-powder (BaSn0.99Cr0.01O3)
Particle diameter distribution picture；
Fig. 4 (c) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 4 adulterates barium stannate nano-powder (BaSn0.97Cr0.03O3)
Particle diameter distribution picture；
Fig. 4 (d) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 2 adulterates barium stannate nano-powder (BaSn0.95Cr0.05O3)
Particle diameter distribution picture；
Fig. 4 (e) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 5 adulterates barium stannate nano-powder (BaSn0.9Cr0.1O3)
Particle diameter distribution picture；
Fig. 4 (f) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 6 adulterates barium stannate nano-powder (BaSn0.85Cr0.15O3)
Particle diameter distribution picture；
Fig. 5 (a) is undoped barium stannate nano-powder (BaSnO3) energy loss spectroscopy (EDS) picture；
Fig. 5 (b) is that the adjustable chromium of forbidden bandwidth of the embodiment of the present invention 2 adulterates barium stannate nano-powder (BaSn0.95Cr0.05O3)
Energy loss spectroscopy (EDS) picture；
Fig. 6 is that the adjustable chromium of forbidden bandwidth of different dopings according to the present invention adulterates barium stannate nano-powder (BaSn1- xCrxO3, x=0.01,0.03,0.05,0.1,0.15) and undoped sour barium nano-powder ultraviolet-visible light (UV-Vis)
Absorb map；
Fig. 7 is that the adjustable chromium of forbidden bandwidth of different dopings according to the present invention adulterates barium stannate nano-powder (BaSn1- xCrxO3, x=0.01,0.03,0.05,0.1,0.15) and undoped sour barium nano-powder optical energy band band gap map.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The present invention relates to a kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth and preparation method, the chromium doped tins
The constitutional chemistry formula of sour barium nano-powder is BaSn1-xCrxO3, wherein 0 x≤0.5 <, wherein Cr atom replaces BaSnO3In Sn
Position.Preparation method may include: using water-soluble pink salt, water soluble barium salt, water-soluble chromic salts as raw material, it is water-soluble with peroxide
Liquid is solvent, prepares precursor powder using the peroxide precipitation method, is heat-treated, obtains at a certain temperature to the precursor powder of preparation
To the uniform crystallinity of particle diameter distribution, good, optical energy gap controllable adjustment chromium adulterates barium stannate nano-powder, can be used as
Perovskite light absorbent.Passing through element doping, thus it is possible to vary electronic structure realizes the regulation to stannate materials optical band gap,
Make it be changed into light absorption by intrinsic wide-band gap material to match with solar spectrum, there is high carrier mobility, high stability
Novel, full-inorganic perovskite light absorbing material.Nano-powder is prepared with chromium doping barium stannate, widens chromium doping barium stannate
The light absorption range of nano-powder and its band gap width of reduction, to realize in fields such as photoelectric device, photocatalysis, solar batteries
Using.
In the present invention, the constitutional chemistry formula that chromium adulterates barium stannate nano-powder is BaSn1-xCrxO3, 0 x≤0.5 <.Wherein
Chromium atom replaces the tin position in barium stannate.Since the band gap width reduction of the nano-powder of highly doped amount is limited, while preparing difficulty
Spend larger, of the invention chromium doping barium stannate nano-powder BaSn1-xCrxO3In, make 0 x≤0.5 <, preferably 0.01≤x≤
0.05.The chromium doping barium stannate nano-powder, which can be, prepares precursor powder by the peroxide precipitation method, then it is high
Warm handles to obtain.
Following exemplary illustrates the controllable method for preparing of chromium doping barium stannate nano-powder of the invention.
Firstly, using water-soluble pink salt, water soluble barium salt, water-soluble chromic salts as raw material, using peroxide aqueous solution as solvent,
Prepare precursor powder using the peroxide precipitation method (chromium adulterates barium stannate Nano-powder body).It may include: to be counted according to chemistry
Amount than by water-soluble pink salt, water soluble barium salt, water solubility chromic salts be dissolved in peroxide aqueous solution, chelating agent is then added,
It is mixed to get clear solution, precipitating reagent is then added dropwise, stirs to get precursor powder.Wherein selected water-soluble pink salt include but
It is not limited to: tin tetrachloride (SnCl4), stannic chloride pentahydrate (SnCl4·5H2O), stannic iodide (SnI4), tin acetate (C8H12O8Sn)
Deng one or more of water-soluble pink salt.Selected water soluble barium salt includes but is not limited to: barium chloride (BaCl2), two water
Barium chloride (BaCl2·2H2O), barium iodide (BaI2), two water barium iodide (barium iodide dihydrates；BaI2·2H2O), barium nitrate
(Ba(NO3)2), barium acetate (C4H6O4One or more of the water soluble barium salts such as Ba).Selected water-soluble chromic salts include but
It is not limited to: chromium trichloride (CrCl3), chromium chloride hexahydrate (CrCl3·6H2O), chromic nitrate (Cr (NO3)3), nine water chromic nitrate (nitre
Sour chromium nonahydrate；Cr(NO3)3·9H2O), chromium acetate (C6H9O6One or more of the water-soluble chromic salts such as Cr).It is selected
Peroxide aqueous solution include but is not limited to: hydrogen peroxide (H2O2) aqueous solution, sodium carbonate peroxide (2Na2CO3·3H2O2) water
Solution, benzoyl hydroperoxide (C6H7O3One or more of) peroxide aqueous solutions such as aqueous solution.Peroxide aqueous solution it is dense
Degree can be 10~50% (mass fractions).Selected chelating agent includes but is not limited to: oxalic acid (C2H2O4), tartaric acid
(C4H6O6), citric acid (C6H8O7；Including Citric Acid Mono C6H8O7·H2O), gluconic acid (C6H12O7), aminotriacetic acid
(C6H9NO6), ethylenediamine tetra-acetic acid (C10H16N2O8) etc..Wherein selected precipitating reagent can be alkaline precipitating agent, including but not
It is limited to: ammonium hydroxide (NH3·H2O), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), sodium bicarbonate
(NaHCO3), potassium carbonate (K2CO3), saleratus (KHCO3) etc..Wherein the concentration of ammonium hydroxide can be 10~50% (quality point
Number).
The ratio of water-soluble pink salt and solvent can be (0.001-0.1) mol:(100-2000) ml.It can will be water-soluble
Pink salt, water soluble barium salt, water-soluble chromic salts are dissolved in peroxide aqueous solution under 20~80 DEG C of water-bath magnetic agitations, thus
Be conducive to the formation of dissolution of raw material and precursor powder.The molar ratio of water-soluble pink salt and chelating agent can be (0.001-0.1):
(0.001-0.1).Clear solution can be mixed to get by stirring after chelating agent is added, time of stirring can be with
It is 1~60 minute, preferably 1~20 minute.It is 8~14, preferably 8~10 that precipitating reagent to solution ph, which can be added dropwise, to promote
Precursor powder is precipitated out, then reaction (precipitation reaction) 1~120 minute under 20~80 DEG C of water-bath magnetic agitations, and preferably 60
Obtain precursor powder within~120 minutes.
In a preferred embodiment, the peroxide precipitation method include: by water-soluble pink salt, water soluble barium salt, water soluble chromium
Salt is successively dissolved in 10~50% peroxide aqueous solutions under 20~80 DEG C of water-bath magnetic agitations, and chelating agent is then added,
Stirring 1~obtain clear solution after twenty minutes, it is 8~10 that precipitating reagent to solution ph, which is then added dropwise, finally in 20~80 DEG C of water
It is reacted 60~120 minutes under bath magnetic agitation and obtains precursor powder (such as Fig. 1).Precursor powder is prepared using the peroxide precipitation method
Have the advantages that further to make that the reaction time is shorter, cost is relatively low, the precursor powder partial size of preparation is smaller and is evenly distributed.
Centrifuging treatment appropriate can be carried out to the precursor powder of preparation.Centrifuging treatment may include: will be preceding
Driving powder, successively simultaneously eccentric cleaning is multiple for ultrasound in deionized water, dehydrated alcohol, 1~30 minute each time, finally 60
(such as Fig. 1) is dried at~80 DEG C.
Then, resulting chromium doping barium stannate Nano-powder body is heat-treated at a certain temperature.Heat treatment
Temperature can be 700~1300 DEG C, and the time can be 1~24 hour.Since the crystallization temperature of precursor powder is at 800 DEG C or so,
It is preferred that the temperature being heat-treated is 700 DEG C~900 DEG C, the time is 1-2 hours.Heat treatment can carry out in air.Heat treatment
Heating rate can be 1~10 DEG C/min.By being heat-treated, further increase the crystallinity of the powder of preparation, simultaneously
Eliminate the remaining organic matter adsorbed in powder preparation process.In a preferred embodiment, in air, forged at 700 DEG C~900 DEG C
It burns 1~2 hour, is then cooled to room temperature (such as Fig. 1).Cooling rate can be 1~10 DEG C/min.
Chromium doping barium stannate nano-powder is obtained as a result,.The chromium doping barium stannate particle diameter of nanometer powder of preparation is evenly distributed,
Partial size is in 25~30nm.There is chromium doping barium stannate nano-powder prepared by the present invention good crystallinity to remove if Fig. 2 (a) shows
BaSnO3Outside the diffraction maximum of cubic phase, no other diffraction maximums exist, and chromium doping does not influence crystal structure, chromium ion (Cr3+)
Radius is less than tin ion (Sn4+) radius, doping concentration increase diffraction peak to high angle deviate.The doping of chromium in the present invention
The crystalline quality that chromium doping barium stannate nano-powder can be weakened to a certain extent, changes the appearance structure of powder, to influence
The performances such as its optical absorptivity, optical energy band band gap width.The adjustable chromium of forbidden bandwidth of the invention adulterates barium stannate nano powder
The controllable preparation of body can be implemented as the key technology that photoelectric device forbidden bandwidth is effectively adjusted, with important scientific value and
Widely use prospect.
Advantages of the present invention:
Chromium doping barium stannate nano-powder prepared by the present invention has adjustable optical property in the visible light wave range of 400-600nm
(as shown in Figure 6)；
The optical energy band band gap width of chromium doping barium stannate nano-powder prepared by the present invention realizes controllable adjustment, passes through elemental chromium
Doping, band gap width be 2.74~3.15eV；
Preparation method of the invention can realize the optical absorptivity and energy band band gap width to chromium doping barium stannate nano-powder
Controllable adjustment；This method has the characteristics that process stabilizing is reliable, low in cost, easy to operate simultaneously, application easy to spread.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
In the following embodiments, reagent, material and the instrument used such as not special explanation, is conventional examination
Agent, conventional material and conventional instrument, it is commercially available, involved in reagent can also be synthesized by conventional synthesis process
It obtains.
Embodiment 1
(1) prepared by precursor powder.Stannic chloride pentahydrate (the SnCl of 10mmol is weighed respectively4·5H2O), barium chloride
(BaCl2·2H2O), 30% hydrogen peroxide (H of 170ml is successively dissolved under 50 DEG C of water-bath magnetic agitations2O2) in aqueous solution,
Chelating agent 5mmol Citric Acid Mono (C is then added6H8O7·H2O), clear solution is obtained after stirring 15 minutes, it is heavy to be then added dropwise
Shallow lake agent ammonium hydroxide (NH3·H2O it is) 10 to solution ph, is finally reacted 60 minutes under 50 DEG C of water-bath magnetic agitations and obtain front axle shell
Body；
(2) precursor powder centrifugal treating.By precursor powder, successively simultaneously eccentric cleaning is more for ultrasound in deionized water, dehydrated alcohol
Secondary, until supernatant pH value is 7, each centrifugation time 10 minutes is finally dried at 70 DEG C；
(3) it is heat-treated.The dry precursor powder of gained is heat-treated for 800 DEG C in Muffle furnace, the time is 2 hours, cooling
Afterwards up to BaSnO3Nano-powder.
To above-mentioned BaSnO3The structure and morphology and performance of nano-powder are tested and are analyzed.Fig. 5 (a) indicates that barium stannate is received
Rice flour body (BaSnO3) energy loss spectroscopy (EDS) picture.As seen from the figure, the BaSnO of preparation3Nano-powder free from admixture element, only
Contain tri- kinds of elements of corresponding Ba, Sn, O.
Embodiment 2
Prepare BaSn0.95Cr0.05O3Nano-powder
9.5mmol stannic chloride pentahydrate (SnCl is weighed respectively4·5H2O), 10mmol barium chloride (BaCl2·2H2O) and
0.5mmol chromium chloride hexahydrate (CrCl3·6H2O) successively it is dissolved in 30% hydrogen peroxide (H of 170ml2O2) in aqueous solution.Its
Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
By Fig. 2 (a) as it can be seen that BaSn prepared by embodiment 20.95Cr0.05O3The crystal structure and cubic phase of nano-powder
BaSnO3It is identical.Its field emission scanning electron microscope photo such as Fig. 3 (d), particle diameter distribution picture such as Fig. 4 (d), embodiment 2
BaSn0.95Cr0.05O3The partial size of nano-powder is 30nm.By Fig. 5 (b) it is found that the BaSn of preparation0.95Cr0.05O3Nano-powder
Free from admixture element only contains tetra- kinds of elements of corresponding Ba, Sn, Cr, O.By Fig. 6,7 as it can be seen that gained nano-powder in visible region
There is certain optical absorption, optical energy band band gap is 2.74eV.
Embodiment 3
Prepare BaSn0.99Cr0.01O3Nano-powder
9.9mmol stannic chloride pentahydrate (SnCl is weighed respectively4·5H2O), 10mmol barium chloride (BaCl2·2H2O) and
0.1mmol chromium chloride hexahydrate (CrCl3·6H2O) successively it is dissolved in 30% hydrogen peroxide (H of 170ml2O2) in aqueous solution.Its
Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
By Fig. 2 (a) as it can be seen that BaSn prepared by embodiment 30.99Cr0.01O3The crystal structure and cubic phase of nano-powder
BaSnO3It is identical.Its field emission scanning electron microscope photo such as Fig. 3 (b), particle diameter distribution picture such as Fig. 4 (b), embodiment 3
BaSn0.99Cr0.01O3The partial size of nano-powder is 25nm.By Fig. 6,7 as it can be seen that gained nano-powder has centainly in visible region
Optical absorption, optical energy band band gap be 3.02eV.
Embodiment 4
Prepare BaSn0.97Cr0.03O3Nano-powder
9.7mmol stannic chloride pentahydrate (SnCl is weighed respectively4·5H2O), 10mmol barium chloride (BaCl2·2H2O) and
0.3mmol chromium chloride hexahydrate (CrCl3·6H2O) successively it is dissolved in 30% hydrogen peroxide (H of 170ml2O2) in aqueous solution.Its
Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
By Fig. 2 (a) as it can be seen that BaSn prepared by embodiment 40.97Cr0.03O3The crystal structure and cubic phase of nano-powder
BaSnO3It is identical.Its field emission scanning electron microscope photo such as Fig. 3 (c), particle diameter distribution picture such as Fig. 4 (c), embodiment 4
BaSn0.99Cr0.01O3The partial size of nano-powder is 25nm.By Fig. 6,7 as it can be seen that gained nano-powder has centainly in visible region
Optical absorption, optical energy band band gap be 2.86eV.
Embodiment 5
Prepare BaSn0.9Cr0.1O3Nano-powder
9mmol stannic chloride pentahydrate (SnCl is weighed respectively4·5H2O), 10mmol barium chloride (BaCl2·2H2O) and
1mmol chromium chloride hexahydrate (CrCl3·6H2O) successively it is dissolved in 30% hydrogen peroxide (H of 170ml2O2) in aqueous solution.Remaining
Step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
By Fig. 2 (a) as it can be seen that BaSn prepared by embodiment 50.9Cr0.1O3The crystal structure and cubic phase BaSnO of nano-powder3
It is identical.Its field emission scanning electron microscope photo such as Fig. 3 (e), particle diameter distribution picture such as Fig. 4 (e), embodiment 5
BaSn0.9Cr0.1O3The partial size of nano-powder is 30nm.By Fig. 6,7 as it can be seen that gained nano-powder has certain light in visible region
It learns and absorbs, optical energy band band gap is 2.79eV.
Embodiment 6
Prepare BaSn0.85Cr0.15O3Nano-powder
8.5mmol stannic chloride pentahydrate (SnCl is weighed respectively4·5H2O), 10mmol barium chloride (BaCl2·2H2O) and
1.5mmol chromium chloride hexahydrate (CrCl3·6H2O) successively it is dissolved in 30% hydrogen peroxide (H of 170ml2O2) in aqueous solution.Its
Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
By Fig. 2 (a) as it can be seen that BaSn prepared by embodiment 20.85Cr0.15O3The crystal structure and cubic phase of nano-powder
BaSnO3It is identical.Its field emission scanning electron microscope photo such as Fig. 3 (f), particle diameter distribution picture such as Fig. 4 (f), embodiment 6
BaSn0.85Cr0.15O3The partial size of nano-powder is 30nm.By Fig. 6,7 as it can be seen that gained nano-powder has centainly in visible region
Optical absorption, optical energy band band gap be 2.79eV.
Embodiment 7
Prepare BaSn0.8Cr0.2O3Nano-powder
Tin acetate (the C of 8mmol is weighed respectively8H12O8Sn), 10mmol barium acetate (C4H6O4Ba), 2mmol chromic nitrate (Cr
(NO3)3) 30% sodium carbonate peroxide (2Na of 170ml is successively dissolved under 50 DEG C of water-bath magnetic agitations2CO3·3H2O2) aqueous solution
In, chelating agent 2.5mmol ethylenediamine tetra-acetic acid (C is then added10H16N2O8), stirring obtained clear solution after 15 minutes, then
It is 10 that precipitating reagent sodium hydroxide (NaOH), which is added dropwise, to solution ph, finally reacts 60 minutes and obtains under 50 DEG C of water-bath magnetic agitations
Precursor powder.Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
BaSn prepared by embodiment 70.8Cr0.2O3The crystal structure and cubic phase BaSnO of nano-powder3It is identical.Its partial size point
Cloth is uniform, partial size 30nm.Gained nano-powder has certain optical absorption in visible region, and optical energy band band gap is 2.7eV
Left and right.
Embodiment 8
Prepare BaSn0.7Cr0.3O3Nano-powder
7mmol stannic chloride pentahydrate (SnCl is weighed respectively4·5H2O), 10mmol barium chloride (BaCl2·2H2O) and
3mmol chromium chloride hexahydrate (CrCl3·6H2O 15% hydrogen peroxide of 170ml) is successively dissolved under 70 DEG C of water-bath magnetic agitations
(H2O2) in aqueous solution, chelating agent 10mmol Citric Acid Mono (C is then added6H8O7·H2O), clarified after stirring 15 minutes
Then precipitating reagent ammonium hydroxide (NH is added dropwise in solution3·H2O it is) 12 to solution ph, is finally reacted under 70 DEG C of water-bath magnetic agitations
Obtain precursor powder within 120 minutes.Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
BaSn prepared by embodiment 80.7Cr0.3O3The crystal structure and cubic phase BaSnO of nano-powder3It is identical.Its partial size point
Cloth is uniform, partial size 30nm.Gained nano-powder has certain optical absorption in visible region, and optical energy band band gap is 2.65eV
Left and right.
Embodiment 9
Prepare BaSn0.5Cr0.5O3Nano-powder
Stannic chloride pentahydrate (the SnCl of 2.5mmol is weighed respectively4·5H2O), the tin acetate (C of 2.5mmol8H12O8Sn)、5mmol
Barium chloride (BaCl2·2H2O), 5mmol barium acetate (C4H6O4Ba), 2.5mmol chromium chloride hexahydrate (CrCl3·6H2O)、
2.5mmol chromic nitrate (Cr (NO3)3), 170ml30% hydrogen peroxide (H is successively dissolved under 50 DEG C of water-bath magnetic agitations2O2)
In aqueous solution, chelating agent 10mmol Citric Acid Mono (C is then added6H8O7·H2O), clear solution is obtained after stirring 15 minutes,
Then precipitating reagent ammonium hydroxide (NH is added dropwise3·H2O it is) 10 to solution ph, is finally reacted 120 minutes under 50 DEG C of water-bath magnetic agitations
Obtain precursor powder.Remaining step is same as Example 1.
The structure and morphology and performance of the adjustable nano-powder of above-mentioned forbidden bandwidth are tested and analyzed.
BaSn prepared by embodiment 90.5Cr0.5O3The crystal structure and cubic phase BaSnO of nano-powder3It is identical.Its partial size point
Cloth is uniform, partial size 30nm.Gained nano-powder has certain optical absorption in visible region, and optical energy band band gap is 2.6eV
Left and right.
Fig. 2 (a), Fig. 2 (b) respectively indicate different dopings chromium doping barium stannate nano-powder X ray diffracting spectrum,
XRD spectrum in 30 °≤2 θ≤32 °.As seen from the figure, gained BaSnO3Nano-powder has and cubic phase BaSnO3The phase isomorphous
Body structure occurs other than cubic phase diffraction maximum without impurity phase.Fig. 3 (a) indicates barium stannate nano-powder (BaSnO3) field
Emit scanning electron microscope (FESEM) photo.As seen from the figure, BaSnO3The particle diameter distribution of nano particle is uniform.Fig. 3 (b)-figure
3 (f) are shown respectively the chromium doping barium stannate nano-powder (BaSn of different dopings1-xCrxO3, x=0.01,0.03,0.05,
0.1,0.15 field emission scanning electron microscope (FESEM) photo).As seen from the figure, these chromium adulterate barium stannate nano-powder
Particle diameter distribution it is uniform.Fig. 4 (a) indicates barium stannate nano-powder (BaSnO3) particle diameter distribution picture.As seen from the figure, BaSnO3
The partial size of nano particle is 25nm.The chromium doping barium stannate nano-powder of different dopings is shown respectively in Fig. 4 (b)-Fig. 4 (f)
(BaSn1-xCrxO3, x=0.01,0.03,0.05,0.1,0.15) particle diameter distribution picture.As seen from the figure, these chromium adulterate stannic acid
The partial size of barium nano-powder is 25~30nm.Fig. 6 indicates the ultraviolet-visible of the chromium doping barium stannate nano-powder of different dopings
Light (UV-Vis) absorbs map.As seen from the figure, BaSnO3Nano-powder in visible region substantially without absorption, and different dopings
Chromium adulterates barium stannate nano-powder (BaSn1-xCrxO3, x=0.01,0.03,0.05,0.1,0.15) have significantly in visible region
It absorbs, and absorption intensity increases with the increase of doping.Fig. 7 indicates the chromium doping barium stannate nano powder of different dopings
The optical energy band band gap map of body.As seen from the figure, BaSnO3The optical energy band band gap of nano-powder is 3.15eV,
BaSn0.99Cr0.01O3The optical energy band band gap of nano-powder is 3.02eV, BaSn0.97Cr0.03O3The optical energy band band of nano-powder
Gap is 2.86eV, BaSn0.95Cr0.05O3The optical energy band band gap of nano-powder is 2.74eV, BaSn0.9Cr0.1O3Nano-powder
Optical energy band band gap is 2.79eV, BaSn0.85Cr0.15O3The optical energy band band gap of nano-powder is 2.79eV.
The present invention is prepared for a kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth using the peroxide precipitation method.
Nano-powder is prepared with chromium doping barium stannate, widened the light absorption range of chromium doping barium stannate nano-powder and reduces its band
Gap width realizes the application in fields such as photoelectric device, photocatalysis, solar batteries.The preparation method, which can be realized, mixes chromium
The controllable adjustment of miscellaneous barium stannate nano-powder optical transmittance and energy band band gap width；This method has process stabilizing can simultaneously
It leans on, is low in cost, feature easy to operate, application easy to spread.
Claims (10)
1. a kind of chromium adulterates barium stannate nano-powder, which is characterized in that the chemical composition of the chromium doping barium stannate nano-powder
For BaSn1-xCrxO3, wherein 0 x≤0.5 <, the chromium doping adjustment powder forbidden bandwidth.
2. chromium according to claim 1 adulterates barium stannate nano-powder, which is characterized in that the chromium adulterates barium stannate nanometer
The partial size of powder is 25~30 nm.
3. a kind of method for preparing chromium doping barium stannate nano-powder of any of claims 1 or 2 characterized by comprising
Using water-soluble pink salt, water soluble barium salt, water-soluble chromic salts as raw material, using peroxide aqueous solution as solvent, using peroxide
The compound precipitation method prepare precursor powder；And
The precursor powder is heat-treated 1~24 hour in 700~1300 DEG C, obtains the chromium doping barium stannate nano-powder.
4. according to the method described in claim 3, it is characterized in that, the water solubility pink salt is tin tetrachloride, five water, four chlorination
At least one of tin, stannic iodide, tin acetate.
5. the method according to claim 3 or 4, which is characterized in that the water soluble barium salt is barium chloride, two water chlorinations
At least one of barium, barium iodide, two water barium iodides, barium nitrate, barium acetate.
6. method according to any one of claim 3 to 5, which is characterized in that it is described water solubility chromic salts be chromium trichloride,
At least one of chromium chloride hexahydrate, chromic nitrate, nine water chromic nitrates, chromium acetate.
7. method according to any one of claim 3 to 6, which is characterized in that the peroxide aqueous solution is peroxide
Change at least one of aqueous solution of hydrogen, peroxycarbonic acid sodium water solution, benzoyl hydroperoxide aqueous solution, the peroxide aqueous solution
Concentration is 10~50%.
8. the method according to any one of claim 3 to 7, which is characterized in that before the preparation of the peroxide precipitation method
Drive powder include: according to stoichiometric ratio by water-soluble pink salt, water soluble barium salt, that water-soluble chromic salts is dissolved in peroxide is water-soluble
In liquid, chelating agent is then added, is mixed to get clear solution, it is 8~14 that precipitating reagent to solution ph, which is then added dropwise, stirring 1~
Obtain precursor powder within 120 minutes.
9. according to the method described in claim 8, it is characterized in that, the chelating agent is oxalic acid, tartaric acid, citric acid, grape
At least one of saccharic acid, aminotriacetic acid, ethylenediamine tetra-acetic acid.
10. method according to claim 8 or claim 9, which is characterized in that the precipitating reagent is ammonium hydroxide, sodium hydroxide, hydroxide
At least one of potassium, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus.
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| US20140017163A1 (en) * | 2012-07-11 | 2014-01-16 | Snu R&Db Foundation | Method of preparing sn-based oxide semiconductor nanopowder and method of manufacturing photoelectric electrode using sn-based oxide semiconductor nanopowder |
| CN104861970A (en) * | 2015-04-03 | 2015-08-26 | 华南理工大学 | Cr-doped near-infrared long-afterglow luminescent material with perovskite structure and preparation method thereof |
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| US20140017163A1 (en) * | 2012-07-11 | 2014-01-16 | Snu R&Db Foundation | Method of preparing sn-based oxide semiconductor nanopowder and method of manufacturing photoelectric electrode using sn-based oxide semiconductor nanopowder |
| CN104861970A (en) * | 2015-04-03 | 2015-08-26 | 华南理工大学 | Cr-doped near-infrared long-afterglow luminescent material with perovskite structure and preparation method thereof |
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