CN109485090B - Chromium-doped barium stannate nano powder with adjustable forbidden bandwidth and preparation method thereof - Google Patents
Chromium-doped barium stannate nano powder with adjustable forbidden bandwidth and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a chromium-doped barium stannate nano powder with adjustable forbidden band width and a preparation method thereofThe chemical composition of the chromium-doped barium stannate nano powder is BaSn1‑xCrxO3Wherein x is more than 0 and less than or equal to 0.5, and the forbidden bandwidth of the powder is adjusted by doping chromium.
Description
Technical Field
The invention relates to a material with adjustable forbidden band width-chromium doped barium stannate nano powder and a preparation method thereof, belonging to the technical field of semiconductor oxide nano powder materials.
Background
The exploration of novel photoelectric conversion materials with high conversion efficiency, high stability and low cost is a constant theme of photovoltaic material research. The most popular solar cell at present belongs to a Perovskite Solar Cell (PSC), which inherits and devotes to a dye-sensitized solar cell (DSSC), and aims to solve several defects of solar cells such as crystalline silicon, cadmium telluride and the like, such as low conversion efficiency, high price of noble metal dye, volatile leakage of liquid electrolyte and the like.
At present, the light absorption layer of the perovskite solar cell is still made of organic-inorganic composite halogen perovskite material (methylamine lead iodide: CH)3NH3PbI3) Mainly, however, the instability and toxicity of methylamine lead iodine materials limit the application of methylamine lead iodine materials in the field of photovoltaic solar cell devices, so narrow-gap, high-stability and all-inorganic perovskite light absorption materials are bound to become research hotspots. The alkaline earth metal stannate is a typical perovskite structure composite oxide material, has wide forbidden band (3.18-4.5eV), large resistance and stable high-temperature property, has rich optical, electrical and magnetic characteristics, and is widely researched. Marshall et al, K.P.in England, uses Cesium iodonium (CsSnI)3) As a light absorbing material, a perovskite solar cell having a photoelectric conversion efficiency of 3.56% was prepared. Thus, stannate materials are expected to drive the development of perovskite solar cell devices.
In stannate preparation, due to the wide forbidden band width, energy level matching with a hole transport layer is difficult to realize.
Disclosure of Invention
Aiming at the problems, the invention aims to provide perovskite light absorption material chromium-doped barium stannate nano powder capable of effectively regulating and controlling the forbidden bandwidth and widening the light absorption range and a preparation method thereof.
In one aspect, the present invention provides a chromium-doped barium stannate nanopowder, the chemical composition of which is BaSn1-xCrxO3Wherein x is more than 0 and less than or equal to 0.5, and the forbidden bandwidth of the powder is adjusted by doping chromium.
According to the invention, the doping element chromium is introduced into the alkaline earth metal barium stannate, so that the formed perovskite light absorption material chromium-doped barium stannate nano powder realizes effective regulation of energy band gap and widens the light absorption range. For example, the energy band gap width of the chromium-doped barium stannate nano powder with adjustable forbidden band width is effectively reduced from 3.15eV to 2.74eV, and the absorption range is widened from 400nm to 600 nm.
The chromium-doped barium stannate nano powder has adjustable optical performance in a visible light wave band of 400-600 nm. The optical energy band gap width of the chromium-doped barium stannate nano powder can be controllably adjusted, and the band gap width is 3.15-2.74 eV by doping element chromium. Preferably, the chemical composition of the chromium-doped barium stannate nano powder is BaSn1-xCrxO3In the formula, x is more than or equal to 0.01 and less than or equal to 0.05, and the band gap width is 3.02-2.74 eV.
Preferably, the chromium-doped barium stannate nano powder has uniform particle size distribution, and the particle size is 25-30 nm.
In another aspect, the present invention further provides a method for preparing the chromium-doped barium stannate nanopowder, comprising:
preparing precursor powder by using water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt as raw materials and using a peroxide aqueous solution as a solvent and adopting a peroxide precipitation method; and
and carrying out heat treatment on the precursor powder at 700-1300 ℃ for 1-24 hours to obtain the chromium-doped barium stannate nano powder.
The invention takes water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt as raw materials, prepares precursor powder by a peroxide precipitation method, and then carries out high-temperature heat treatment at a certain temperature to obtain chromium-doped barium stannate nano powder with uniform particle size distribution, good crystallinity and controllable and adjustable optical forbidden bandwidth, and can be widely applied to the fields of semiconductor photoelectric devices, photocatalysis, solar cells and the like. Compared with the traditional powder preparation methods such as solid phase sintering, sol-gel and the like, the powder prepared by the peroxide precipitation method has the outstanding characteristics of uniform and fine particle size distribution, high crystallization quality and the like.
The water-soluble tin salt may be tin tetrachloride (SnCl)4) Tin tetrachloride pentahydrate (SnCl)4·5H2O) tin iodide (SnI)4) Tin acetate (C)8H12O8Sn).
The water-soluble barium salt may be barium chloride (BaCl)2) Barium chloride dihydrate (BaCl)2·2H2O), barium iodide (BaI)2) Barium iodide dihydrate (BaI)2·2H2O), barium nitrate (Ba (NO)3)2) Barium acetate (C)4H6O4Ba).
The water-soluble chromium salt may be chromium trichloride (CrCl)3) Chromium trichloride hexahydrate (CrCl)3·6H2O), chromium nitrate (Cr (NO)3)3) Chromium nitrate nonahydrate (Cr (NO)3)3·9H2O), chromium acetate (C)6H9O6Cr).
The peroxide aqueous solution is hydrogen peroxide (H)2O2) Aqueous solution, sodium carbonate peroxide (2 Na)2CO3·3H2O2) Aqueous solution, Peroxybenzoic acid (C)6H7O3) At least one of the aqueous solutions, and the concentration of the peroxide aqueous solution may be 10 to 50% (mass fraction).
The ratio of the water-soluble tin salt to the solvent may be (0.001-0.1) mol: (100-.
Preferably, the preparation of the precursor powder by the peroxide precipitation method comprises the following steps: dissolving water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt in a peroxide aqueous solution according to a stoichiometric ratio, then adding a chelating agent, mixing to obtain a clear solution, then dropwise adding a precipitating agent until the pH value of the solution is 8-14, and stirring for 1-120 minutes to obtain precursor powder.
The chelating agent may be oxalic acid (C)2H2O4) Tartaric acid (C)4H6O6) Citric acid (C)6H8O7) Gluconic acid (C)6H12O7) Nitrilotriacetic acid (C)6H9NO6) Ethylenediaminetetraacetic acid (C)10H16N2O8) At least one of (1).
The molar ratio of water-soluble tin salt to chelating agent may be (0.001-0.1): (0.001-0.1).
The precipitant may be ammonia (NH)3·H2O), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na)2CO3) Sodium bicarbonate (NaHCO)3) Potassium carbonate (K)2CO3) Potassium bicarbonate (KHCO)3) At least one of (1). Wherein the concentration of the ammonia water can be 10-50% (mass fraction).
Preferably, the temperature of the heat treatment is 700-900 ℃ and the time is 1-2 hours.
According to the invention, the chromium-doped barium stannate nano powder is prepared by adopting a peroxide precipitation method, the chromium-doped barium stannate nano powder with the particle size of 25-30 nm is obtained, the absorption range of the barium stannate nano powder in visible light is widened, and the controllable adjustment of the band gap of the chromium-doped barium stannate nano powder is realized. Compared with the traditional powder preparation methods such as solid phase sintering, sol-gel and the like, the powder prepared by the peroxide precipitation method has the outstanding characteristics of uniform and fine particle size distribution, high crystallization quality and the like.
Drawings
FIG. 1 is a flow chart of the preparation of chromium-doped barium stannate nanopowder with adjustable forbidden band width according to one embodiment of the present invention;
FIG. 2(a) is a diagram of different doping amounts of adjustable forbidden band width chromium dopingBarium metastannate nano powder (BaSn)1-xCrxO3X is 0.01,0.03,0.05,0.1,0.15) and the XRD pattern of the undoped barium acid nano powder;
FIG. 2(b) is a diagram of chromium-doped barium stannate nano-powder (BaSn) with different doping amounts and adjustable forbidden band widths1-xCrxO3X is 0.01,0.03,0.05,0.1,0.15) and the XRD pattern of the undoped barium acid nano powder within the range of more than or equal to 30 degrees and less than or equal to 2 theta and less than or equal to 32 degrees;
FIG. 3(a) is an undoped barium stannate nanopowder (BaSnO)3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a);
fig. 3(b) shows a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 3 of the present invention0.99Cr0.01O3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a);
fig. 3(c) shows a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 4 of the present invention0.97Cr0.03O3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a);
FIG. 3(d) is a diagram of a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 2 of the present invention0.95Cr0.05O3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a);
fig. 3(e) shows the chromium-doped barium stannate nanopowder (BaSn) with adjustable forbidden band width in embodiment 5 of the present invention0.9Cr0.1O3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a);
fig. 3(f) shows a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 6 of the present invention0.85Cr0.15O3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a);
FIG. 4(a) is an undoped chromium-doped barium stannate nanopowder (BaSnO)3) The particle size distribution picture of (1);
fig. 4(b) is a chromium-doped barium stannate nano-powder (BaSn) with adjustable forbidden band width in embodiment 3 of the present invention0.99Cr0.01O3) The particle size distribution picture of (1);
FIG. 4(c) shows the present inventionExample 4 chromium-doped barium stannate nanopowder (BaSn) with adjustable forbidden bandwidth0.97Cr0.03O3) The particle size distribution picture of (1);
FIG. 4(d) is a diagram of a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 2 of the present invention0.95Cr0.05O3) The particle size distribution picture of (1);
FIG. 4(e) is a diagram of chromium-doped barium stannate nanopowder (BaSn) with adjustable forbidden band width in embodiment 5 of the present invention0.9Cr0.1O3) The particle size distribution picture of (1);
fig. 4(f) shows a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 6 of the present invention0.85Cr0.15O3) The particle size distribution picture of (1);
FIG. 5(a) is an undoped barium stannate nanopowder (BaSnO)3) An energy loss spectroscopy (EDS) picture of;
FIG. 5(b) is a diagram of a chromium-doped barium stannate nano-powder (BaSn) with an adjustable forbidden band width in embodiment 2 of the present invention0.95Cr0.05O3) An energy loss spectroscopy (EDS) picture of;
FIG. 6 shows different doping amounts of chromium-doped barium stannate nanopowder (BaSn) with adjustable forbidden band widths1-xCrxO3X ═ 0.01,0.03,0.05,0.1,0.15) and the ultraviolet-visible light (UV-Vis) absorption spectrum of the undoped barium acid nanopowder;
FIG. 7 shows different doping amounts of chromium-doped barium stannate nanopowder (BaSn) with adjustable forbidden band widths1-xCrxO3X ═ 0.01,0.03,0.05,0.1,0.15) and undoped barium acid nanopowder.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are intended to illustrate and not to limit the present invention.
The invention relates to a chromium-doped barium stannate nano powder with adjustable forbidden band width and a preparation method thereof, wherein the chemical formula of the chromium-doped barium stannate nano powder is BaSn1-xCrxO3Wherein x is more than 0 and less than or equal to 0.5, and Cr atom replaces BaSnO3At the Sn site. The preparation method comprises the following steps: the method comprises the steps of taking water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt as raw materials, taking a peroxide aqueous solution as a solvent, preparing precursor powder by adopting a peroxide precipitation method, and carrying out heat treatment on the prepared precursor powder at a certain temperature to obtain chromium-doped barium stannate nano powder which is uniform in particle size distribution, good in crystallinity and controllable and adjustable in optical forbidden band width, wherein the chromium-doped barium stannate nano powder can be used as a perovskite light absorption material. By element doping, the electronic structure can be changed, the regulation and control of the optical band gap of the stannate material are realized, and the stannate material is converted from an intrinsic wide-bandgap material into a novel all-inorganic perovskite light absorption material which has light absorption, solar spectrum matching, high carrier mobility and high stability. The chromium-doped barium stannate is used for preparing the nano powder, so that the light absorption range of the chromium-doped barium stannate nano powder is widened, the band gap width of the chromium-doped barium stannate nano powder is reduced, and the chromium-doped barium stannate nano powder can be applied to the fields of photoelectric devices, photocatalysis, solar cells and the like.
In the invention, the chemical formula of the chromium-doped barium stannate nano powder is BaSn1-xCrxO3X is more than 0 and less than or equal to 0.5. Wherein the chromium atom replaces the tin site in the barium stannate. Because the reduction of the band gap width of the nano powder with high doping amount is limited, and the preparation difficulty is larger, the chromium-doped barium stannate nano powder BaSn is prepared by the method1-xCrxO3In this case, x is 0 < x.ltoreq.0.5, preferably 0.01. ltoreq.x.ltoreq.0.05. The chromium-doped barium stannate nano powder can be obtained by preparing precursor powder by a peroxide precipitation method and then carrying out high-temperature heat treatment on the precursor powder.
The following is an exemplary illustration of the controllable preparation method of chromium-doped barium stannate nanopowder of the present invention.
Firstly, water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt are used as raw materials, aqueous solution of peroxide is used as a solvent, and a peroxide precipitation method is adopted to prepare precursor powder (chromium-doped barium stannate nano precursor powder). The method can comprise the following steps: dissolving water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt in a peroxide aqueous solution according to a stoichiometric ratio, then adding a chelating agent, mixing to obtain a clear solution, then dropwise adding a precipitating agent, and stirringStirring to obtain precursor powder. Wherein the water soluble tin salts selected include, but are not limited to: tin tetrachloride (SnCl)4) Tin tetrachloride pentahydrate (SnCl)4·5H2O), tin iodide (SnI)4) Tin acetate (C)8H12O8Sn) and the like. Selected water-soluble barium salts include, but are not limited to: barium chloride (BaCl)2) Barium chloride dihydrate (BaCl)2·2H2O), barium iodide (BaI)2) Barium iodide dihydrate (barium iodide dihydrate; BaI2·2H2O), barium nitrate (Ba (NO)3)2) Barium acetate (C)4H6O4Ba), and the like. Selected water-soluble chromium salts include, but are not limited to: chromium trichloride (CrCl)3) Chromium trichloride hexahydrate (CrCl)3·6H2O), chromium nitrate (Cr (NO)3)3) Chromium nitrate nonahydrate (chromium nitrate nonahydrate; cr (NO)3)3·9H2O), chromium acetate (C)6H9O6Cr), and the like. Aqueous peroxide solutions selected include, but are not limited to: hydrogen peroxide (H)2O2) Aqueous solution, sodium carbonate peroxide (2 Na)2CO3·3H2O2) Aqueous solution, Peroxybenzoic acid (C)6H7O3) Aqueous solution, etc. of peroxide. The concentration of the peroxide aqueous solution may be 10 to 50 mass%. Selected chelating agents include, but are not limited to: oxalic acid (C)2H2O4) Tartaric acid (C)4H6O6) Citric acid (C)6H8O7(ii) a Comprises citric acid C monohydrate6H8O7·H2O), gluconic acid (C)6H12O7) Nitrilotriacetic acid (C)6H9NO6) Ethylenediaminetetraacetic acid (C)10H16N2O8) And the like. Wherein the selected precipitating agent may be an alkaline precipitating agent, including but not limited to: ammonia (NH)3·H2O), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na)2CO3) Sodium bicarbonate (NaHCO)3) Potassium carbonate (K)2CO3) Potassium bicarbonate (KHCO)3) And the like. Wherein the concentration of the ammonia water can be 10-50% (mass fraction).
The ratio of the water-soluble tin salt to the solvent may be (0.001-0.1) mol: (100-. The water-soluble tin salt, the water-soluble barium salt and the water-soluble chromium salt can be dissolved in the peroxide water solution under the magnetic stirring of a water bath at the temperature of 20-80 ℃, so that the raw material dissolution and the precursor powder formation are facilitated. The molar ratio of water-soluble tin salt to chelating agent may be (0.001-0.1): (0.001-0.1). The chelating agent can be added and then mixed by stirring to obtain a clear solution, and the stirring time can be 1-60 minutes, preferably 1-20 minutes. The precipitant can be added dropwise until the pH value of the solution is 8-14, preferably 8-10, so as to promote the precipitation of the precursor powder, and then the precursor powder is obtained by reacting (precipitation reaction) for 1-120 minutes, preferably 60-120 minutes, under the magnetic stirring of a water bath at 20-80 ℃.
In a preferred embodiment, the peroxide precipitation method comprises: sequentially dissolving water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt in 10-50% peroxide aqueous solution under the magnetic stirring of water bath at 20-80 ℃, then adding a chelating agent, stirring for 1-20 minutes to obtain a clear solution, then dropwise adding a precipitator until the pH value of the solution is 8-10, and finally reacting for 60-120 minutes under the magnetic stirring of water bath at 20-80 ℃ to obtain precursor powder (as shown in figure 1). The method for preparing the precursor powder by adopting the peroxide precipitation method has the advantages of shorter reaction time, lower cost, smaller particle size of the prepared precursor powder and uniform distribution.
The prepared precursor powder may be subjected to an appropriate centrifugal separation treatment. The centrifugation process may include: and (2) sequentially carrying out ultrasonic and centrifugal cleaning on the precursor powder in deionized water and absolute ethyl alcohol for multiple times, wherein the time is 1-30 minutes each time, and finally drying at 60-80 ℃ (as shown in figure 1).
And then, carrying out heat treatment on the obtained chromium-doped barium stannate nano precursor powder at a certain temperature. The temperature of the heat treatment can be 700-1300 ℃, and the time can be 1-24 hours. Because the crystallization temperature of the precursor powder is about 800 ℃, the temperature of the heat treatment is preferably 700-900 ℃ and the time is 1-2 hours. The heat treatment may be performed in air. The heating rate of the heat treatment can be 1-10 ℃/min. By carrying out heat treatment, the crystallinity of the prepared powder is further improved, and residual organic matters adsorbed in the powder preparation process are eliminated. In a preferred scheme, the catalyst is calcined in air at 700-900 ℃ for 1-2 hours and then cooled to room temperature (as shown in figure 1). The cooling rate can be 1-10 ℃/min.
Thus, the chromium-doped barium stannate nano powder is obtained. The prepared chromium-doped barium stannate nano powder has uniform particle size distribution, and the particle size is 25-30 nm. The chromium-doped barium stannate nano powder prepared by the invention has good crystallinity, as shown in figure 2(a), except BaSnO3No other diffraction peak exists outside the diffraction peak of the cubic phase, the chromium doping does not influence the crystal structure, and chromium ions (Cr)3+) Radius less than tin ion (Sn)4+) Radius, doping concentration increases the diffraction peak position towards high angles. The doping of the chromium element can weaken the crystallization quality of the chromium-doped barium stannate nano powder to a certain extent and change the shape and structure of the powder, thereby influencing the optical absorption rate, the optical energy band gap width and other properties of the powder. The controllable preparation of the chromium-doped barium stannate nano powder with adjustable forbidden bandwidth can be used as a key technology for realizing the effective adjustment of the forbidden bandwidth of a photoelectric device, and has important scientific value and wide application prospect.
The invention has the advantages that:
the chromium-doped barium stannate nano powder prepared by the invention has adjustable optical performance in a visible light waveband of 400-600nm (as shown in figure 6);
the optical energy band gap width of the chromium-doped barium stannate nano powder prepared by the invention can be controllably adjusted, and the band gap width is 2.74-3.15 eV by doping element chromium;
the preparation method can realize the controllable adjustment of the optical absorption rate and the band gap width of the chromium-doped barium stannate nano powder; meanwhile, the method has the characteristics of stable and reliable process, low cost and simple operation, and is easy to popularize and apply.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
In the following examples, reagents, materials and instruments used are all conventional reagents, conventional materials and conventional instruments, which are commercially available, if not specifically mentioned, and the reagents involved therein can also be synthesized by conventional synthesis methods.
Example 1
(1) And (3) preparing precursor powder. 10mmol of tin tetrachloride pentahydrate (SnCl) were weighed out separately4·5H2O), barium chloride dihydrate (BaCl)2·2H2O), dissolved in 170ml of 30% hydrogen peroxide (H) in turn under magnetic stirring in a water bath at 50 DEG C2O2) To the aqueous solution, the chelating agent 5mmol citric acid monohydrate (C) was subsequently added6H8O7·H2O), stirring for 15 min to obtain a clear solution, and then dropwise adding ammonia water (NH) serving as a precipitator3·H2O) until the pH value of the solution is 10, and finally reacting for 60 minutes under the magnetic stirring of water bath at 50 ℃ to obtain precursor powder;
(2) and (4) centrifuging the precursor powder. Sequentially carrying out ultrasonic and centrifugal cleaning on the precursor powder in deionized water and absolute ethyl alcohol for multiple times until the pH value of a supernatant is 7, wherein the centrifugation time is 10 minutes each time, and finally drying at 70 ℃;
(3) and (6) heat treatment. Carrying out heat treatment on the obtained dry precursor powder in a muffle furnace at 800 ℃ for 2 hours, and cooling to obtain BaSnO3And (3) nano powder.
For the above BaSnO3And testing and analyzing the structural morphology and the performance of the nano powder. FIG. 5(a) shows barium stannate nanopowder (BaSnO)3) Energy ofLoss spectra (EDS) pictures. As can be seen, BaSnO prepared3The nano powder has no impurity elements and only contains three corresponding elements of Ba, Sn and O.
Example 2
Preparation of BaSn0.95Cr0.05O3Nano powder
9.5mmol of stannic chloride pentahydrate (SnCl) were weighed out separately4·5H2O), 10mmol of barium chloride dihydrate (BaCl)2·2H2O) and 0.5mmol of chromium trichloride hexahydrate (CrCl)3·6H2O) was dissolved in 170ml of 30% hydrogen peroxide (H) in turn2O2) In aqueous solution. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
As can be seen from FIG. 2(a), BaSn prepared in example 20.95Cr0.05O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The SEM photograph is shown in FIG. 3(d), the particle size distribution is shown in FIG. 4(d), and BaSn of example 20.95Cr0.05O3The particle size of the nano powder is 30 nm. As can be seen from FIG. 5(b), BaSn was produced0.95Cr0.05O3The nano powder has no impurity elements and only contains corresponding Ba, Sn, Cr and O four elements. As can be seen from fig. 6 and 7, the obtained nano powder has a certain optical absorption in the visible light region, and the optical band gap is 2.74 eV.
Example 3
Preparation of BaSn0.99Cr0.01O3Nano powder
9.9mmol of stannic chloride pentahydrate (SnCl) were weighed out separately4·5H2O), 10mmol of barium chloride dihydrate (BaCl)2·2H2O) and 0.1mmol of chromium trichloride hexahydrate (CrCl)3·6H2O) was dissolved in 170ml of 30% hydrogen peroxide (H) in turn2O2) In aqueous solution. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
As can be seen from FIG. 2(a), BaSn prepared in example 30.99Cr0.01O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The SEM photograph is shown in FIG. 3(b), the particle size distribution is shown in FIG. 4(b), and BaSn of example 30.99Cr0.01O3The particle size of the nano powder is 25 nm. As can be seen from fig. 6 and 7, the obtained nano powder has a certain optical absorption in the visible light region, and the optical band gap is 3.02 eV.
Example 4
Preparation of BaSn0.97Cr0.03O3Nano powder
9.7mmol of stannic chloride pentahydrate (SnCl) were weighed out separately4·5H2O), 10mmol of barium chloride dihydrate (BaCl)2·2H2O) and 0.3mmol of chromium trichloride hexahydrate (CrCl)3·6H2O) was dissolved in 170ml of 30% hydrogen peroxide (H) in turn2O2) In aqueous solution. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
As can be seen from FIG. 2(a), BaSn prepared in example 40.97Cr0.03O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The SEM photograph is shown in FIG. 3(c), the particle size distribution is shown in FIG. 4(c), and BaSn of example 40.99Cr0.01O3The particle size of the nano powder is 25 nm. As can be seen from fig. 6 and 7, the obtained nano powder has a certain optical absorption in the visible light region, and the optical band gap is 2.86 eV.
Example 5
Preparation of BaSn0.9Cr0.1O3Nano powder
9mmol of tin tetrachloride pentahydrate (SnCl) were weighed out separately4·5H2O), 10mmol of barium chloride dihydrate (BaCl)2·2H2O) and 1mmol of chromium trichloride hexahydrate (CrCl)3·6H2O) was dissolved in 170ml of 30% hydrogen peroxide (H) in turn2O2) In aqueous solution. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
As can be seen from FIG. 2(a), BaSn prepared in example 50.9Cr0.1O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The SEM photograph is shown in FIG. 3(e), the particle size distribution is shown in FIG. 4(e), and BaSn of example 50.9Cr0.1O3The particle size of the nano powder is 30 nm. As can be seen from fig. 6 and 7, the obtained nano powder has a certain optical absorption in the visible light region, and the optical band gap is 2.79 eV.
Example 6
Preparation of BaSn0.85Cr0.15O3Nano powder
8.5mmol of tin tetrachloride pentahydrate (SnCl) were weighed out separately4·5H2O), 10mmol of barium chloride dihydrate (BaCl)2·2H2O) and 1.5mmol of chromium trichloride hexahydrate (CrCl)3·6H2O) was dissolved in 170ml of 30% hydrogen peroxide (H) in turn2O2) In aqueous solution. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
As can be seen from FIG. 2(a), BaSn prepared in example 20.85Cr0.15O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The SEM photograph is shown in FIG. 3(f), the particle size distribution is shown in FIG. 4(f), and BaSn of example 60.85Cr0.15O3The particle size of the nano powder is 30 nm. As can be seen from fig. 6 and 7, the obtained nano powder has a certain optical absorption in the visible light region, and the optical band gap is 2.79 eV.
Example 7
Preparation of BaSn0.8Cr0.2O3Nano powder
Separately, 8mmol of tin acetate (C) was weighed8H12O8Sn), 10mmol of barium acetate (C)4H6O4Ba), 2mmol of chromium nitrate (Cr (NO)3)3) At 50 deg.C waterDissolved in 170ml of 30% sodium percarbonate (2 Na) in turn under magnetic stirring in a bath2CO3·3H2O2) To the aqueous solution, 2.5mmol of chelating agent (C) of ethylenediaminetetraacetic acid was added10H16N2O8) Stirring for 15 minutes to obtain a clear solution, then dropwise adding a precipitator sodium hydroxide (NaOH) until the pH value of the solution is 10, and finally reacting for 60 minutes in a water bath at 50 ℃ under magnetic stirring to obtain precursor powder. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
BaSn prepared in example 70.8Cr0.2O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The particle size distribution is uniform, and the particle size is 30 nm. The obtained nano powder has certain optical absorption in a visible light region, and the band gap of an optical energy band is about 2.7 eV.
Example 8
Preparation of BaSn0.7Cr0.3O3Nano powder
7mmol of tin tetrachloride pentahydrate (SnCl) were weighed out separately4·5H2O), 10mmol of barium chloride dihydrate (BaCl)2·2H2O) and 3mmol of chromium trichloride hexahydrate (CrCl)3·6H2O) was dissolved in 170ml of 15% hydrogen peroxide (H) in sequence under magnetic stirring in a 70 ℃ water bath2O2) To the aqueous solution, the chelating agent 10mmol citric acid monohydrate (C) was subsequently added6H8O7·H2O), stirring for 15 min to obtain a clear solution, and then dropwise adding ammonia water (NH) serving as a precipitator3·H2O) until the pH value of the solution is 12, and finally reacting for 120 minutes under the magnetic stirring of water bath at 70 ℃ to obtain precursor powder. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
BaSn prepared in example 80.7Cr0.3O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The particle size distribution is uniform, and the particle size is 30 nm. The obtained nano powder has the characteristics of visible light regionThe optical band gap is about 2.65eV at a certain optical absorption.
Example 9
Preparation of BaSn0.5Cr0.5O3Nano powder
2.5mmol of stannic chloride pentahydrate (SnCl) were weighed out separately4·5H2O), 2.5mmol of tin acetate (C)8H12O8Sn), 5mmol barium chloride dihydrate (BaCl)2·2H2O), 5mmol of barium acetate (C)4H6O4Ba), 2.5mmol chromium trichloride hexahydrate (CrCl)3·6H2O), 2.5mmol chromium nitrate (Cr (NO)3)3) Dissolved in 170ml of 30% hydrogen peroxide (H) in turn under magnetic stirring in a water bath at 50 DEG C2O2) To the aqueous solution, the chelating agent 10mmol citric acid monohydrate (C) was subsequently added6H8O7·H2O), stirring for 15 min to obtain a clear solution, and then dropwise adding ammonia water (NH) serving as a precipitator3·H2O) until the pH value of the solution is 10, and finally reacting for 120 minutes in a water bath at 50 ℃ under magnetic stirring to obtain precursor powder. The rest of the procedure was the same as in example 1.
And testing and analyzing the structural morphology and the performance of the nano powder with adjustable forbidden band width.
BaSn prepared in example 90.5Cr0.5O3Crystal structure and cubic phase BaSnO of nano powder3The same is true. The particle size distribution is uniform, and the particle size is 30 nm. The obtained nano powder has certain optical absorption in a visible light region, and the band gap of an optical energy band is about 2.6 eV.
FIGS. 2(a) and 2(b) show X-ray diffraction patterns and XRD patterns of chromium-doped barium stannate nanopowder with different doping amounts within 30-2 theta-32 deg. As can be seen, the BaSnO obtained3The nano powder has a cubic phase of BaSnO3The same crystal structure, except for the cubic phase diffraction peak, no impurity phase appears. FIG. 3(a) shows barium stannate nanopowder (BaSnO)3) A Field Emission Scanning Electron Microscope (FESEM) photograph of (a). As can be seen, BaSnO3The particle size distribution of the nano particles is uniform. FIGS. 3(b) to 3(f) show different amounts of chromium-doped stannic acidBarium nanopowder (BaSn)1-xCrxO3And x ═ 0.01,0.03,0.05,0.1,0.15) by Field Emission Scanning Electron Microscopy (FESEM). As can be seen from the figure, the particle size distribution of these chromium-doped barium stannate nanopowders was uniform. FIG. 4(a) shows barium stannate nanopowder (BaSnO)3) The particle size distribution of (1). As can be seen, BaSnO3The particle size of the nanoparticles was 25 nm. FIGS. 4(b) and 4(f) show chromium-doped barium stannate nanopowder (BaSn) with different doping amounts1-xCrxO3And x is 0.01,0.03,0.05,0.1, 0.15). As can be seen from the figure, the particle size of the chromium-doped barium stannate nano powder is 25-30 nm. Fig. 6 shows ultraviolet-visible light (UV-Vis) absorption spectra of chromium-doped barium stannate nanopowders with different doping amounts. As can be seen, BaSnO3The nano powder basically has no absorption in a visible light region, and chromium doped barium stannate nano powder (BaSn) with different doping amounts1-xCrxO3X ═ 0.01,0.03,0.05,0.1,0.15) has significant absorption in the visible region, and the absorption intensity increases with increasing doping amount. FIG. 7 shows the band gap spectrum of the optical energy band of the chromium-doped barium stannate nanopowder with different doping amounts. As can be seen, BaSnO3The optical band gap of the nano powder is 3.15eV, BaSn0.99Cr0.01O3The optical band gap of the nano powder is 3.02eV, BaSn0.97Cr0.03O3The optical band gap of the nano powder is 2.86eV, BaSn0.95Cr0.05O3The optical band gap of the nano powder is 2.74eV, BaSn0.9Cr0.1O3The optical band gap of the nano powder is 2.79eV, and the BaSn0.85Cr0.15O3The optical band gap of the nano powder is 2.79 eV.
The invention adopts a peroxide precipitation method to prepare chromium-doped barium stannate nano powder with adjustable forbidden band width. The chromium-doped barium stannate is used for preparing the nano powder, so that the light absorption range of the chromium-doped barium stannate nano powder is widened, the band gap width of the chromium-doped barium stannate nano powder is reduced, and the application in the fields of photoelectric devices, photocatalysis, solar cells and the like is realized. The preparation method can realize the controllable adjustment of the optical transmittance and the band gap width of the chromium-doped barium stannate nano powder; meanwhile, the method has the characteristics of stable and reliable process, low cost and simple operation, and is easy to popularize and apply.
Claims (9)
1. A method for regulating and controlling the forbidden bandwidth of a barium stannate nano powder material is characterized in that the material is composed of chromium-doped barium stannate nano powder, and the chemical composition of the chromium-doped barium stannate nano powder is BaSn1-xCrxO3Wherein x is more than or equal to 0.01 and less than or equal to 0.5, the forbidden bandwidth of the powder is adjusted by chromium doping, and Cr atoms replace BaSnO3The Sn site in the (C) is,
the method for preparing the chromium-doped barium stannate nano powder comprises the following steps: dissolving water-soluble tin salt, water-soluble barium salt and water-soluble chromium salt in a peroxide aqueous solution according to a stoichiometric ratio, then adding a chelating agent, mixing to obtain a clear solution, then dropwise adding a precipitating agent until the pH value of the solution is 8-14, and stirring for 1-120 minutes to obtain precursor powder; heat-treating the precursor powder at 700-900 ℃ for 1-24 hours to obtain the chromium-doped barium stannate nano powder,
the forbidden band width of the chromium-doped barium stannate nano powder is adjustable within 2.74-3.02 eV.
2. The method of claim 1, wherein 0.2 ≦ x ≦ 0.5.
3. The method of claim 1, wherein the chromium-doped barium stannate nanopowder has a particle size of 25-30 nm.
4. The method of claim 1, wherein the water-soluble tin salt is at least one of tin tetrachloride, tin tetrachloride pentahydrate, tin iodide, and tin acetate.
5. The method of claim 1, wherein the water-soluble barium salt is at least one of barium chloride, barium chloride dihydrate, barium iodide dihydrate, barium nitrate, and barium acetate.
6. The method of claim 1, wherein the water-soluble chromium salt is at least one of chromium trichloride, chromium trichloride hexahydrate, chromium nitrate nonahydrate, and chromium acetate.
7. The method according to claim 1, wherein the aqueous peroxide solution is at least one of an aqueous hydrogen peroxide solution, an aqueous sodium carbonate peroxide solution and an aqueous perbenzoic acid solution, and the aqueous peroxide solution has a concentration of 10 to 50% by mass.
8. The method of claim 1, wherein the chelating agent is at least one of oxalic acid, tartaric acid, citric acid, gluconic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid.
9. The method according to any one of claims 1 to 8, wherein the precipitant is at least one of ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate.
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