CN108975396B - Method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material - Google Patents
Method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material Download PDFInfo
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Abstract
A method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material relates to a preparation method of bismuth oxybromide photoelectric material. The invention aims to solve the problems of low photo-generated charge separation efficiency and poor photoelectric performance of the bismuth oxybromide photoelectric material prepared by the existing method. The method comprises the following steps: firstly, preparing a mixed solution of bismuth salt and stannate; secondly, preparing a bromine salt solution; thirdly, preparing a precursor; and fourthly, carrying out hydrothermal reaction on the precursor to obtain the silver/tin oxide/bismuth oxybromide photoelectric material. The photovoltaic response intensity of the silver/tin oxide/bismuth oxybromide photoelectric material prepared by the invention can reach 16.62mV, the photovoltaic response is stronger, the charge separation efficiency is better, and the photoelectric characteristic is better. The method is suitable for preparing silver/tin oxide/bismuth oxybromide photoelectric materials.
Description
Technical Field
The invention relates to a preparation method of a bismuth oxybromide photoelectric material.
Background
The reserves of bismuth resources in China are rich, and the research prospect for developing bismuth-series materials is wide. The bismuth-based material has unique electronic structure, optical and electrical properties, stable chemical properties, low price and safety, and has wide application in photoelectric conversion, military industry and other aspects due to good physicochemical properties. Therefore, the potential for developing the research on the photoelectric characteristics of bismuth-based materials is huge.
BiOBr in bismuth-based material is easy to synthesize, controllable in energy band, stable in visible light response and chemical property, and is a narrow-band semiconductor with high anisotropyUnique [ Bi ] thereof2O2]The two-dimensional layered structure alternately arranged with the double halogen is beneficial to the separation and transmission of electron-hole, and shows good optical and electrical properties. Therefore, the research on the photoelectric performance of the BiOBr is of great significance. However, the BiOBr conduction band position is low, so that the photo-generated electron-hole recombination probability is high, the photoelectric property is poor, and the photovoltaic intensity of the bismuth oxybromide is about 1.08 mV. In order to solve the problem, methods such as surface modification and heterojunction construction are generally adopted to modify the BiOBr, surface modification such as acetic acid and phosphate can change surface chemical properties and defects, but the crystallization degree of the BiOBr is reduced; common BiOBr-ZnFe2O4、BiOBr-Bi2WO6And the heterojunction complex such as BiOBr-BiOI, etc. has poor photo-generated charge separation effect.
Disclosure of Invention
The invention aims to solve the problems of low photo-generated charge separation efficiency and poor photoelectric performance of the bismuth oxybromide photoelectric material prepared by the existing method, and provides a method for in-situ synthesis of a silver/tin oxide/bismuth oxybromide photoelectric material.
A method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material is completed according to the following steps:
firstly, preparing a mixed solution of bismuth salt and stannate: dissolving bismuth salt into deionized water at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min, adding stannate, and stirring at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min until the stannate is dissolved into the deionized water to obtain a mixed solution of the bismuth salt and the stannate;
the volume ratio of the bismuth salt substance in the step one to the deionized water is (1-3) mol:2500m L;
the mass ratio of the bismuth salt to the stannate in the first step is (1-3) to (0.01-0.05);
secondly, preparing a bromine salt solution: dissolving bromine salt into deionized water at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min to obtain a bromine salt aqueous solution;
the volume ratio of the bromine salt substance in the second step to the deionized water is (1-3) mol:5000m L;
thirdly, dropwise adding the mixed solution of bismuth salt and stannate into the bromine salt aqueous solution at a dropwise adding speed of 3-4 drops/min, and stirring and reacting for 10-40 min under the conditions that the temperature is 25-35 ℃ and the stirring speed is 100-300 r/min to obtain a tin-containing bismuth oxybromide solution; adding silver salt into a tin-containing bismuth oxybromide solution, and stirring for 20-30 min at a stirring speed of 100-300 r/min to obtain a precursor;
the volume ratio of the mixed solution of the bismuth salt and the stannate to the bromine salt water solution in the third step is (1-2) to (1-4);
the volume ratio of the silver salt substance in the step three to the tin-containing bismuth oxybromide solution is (0.001-0.01) mol (5000-10000) m L;
fourthly, carrying out hydro-thermal reaction on the precursor in a forced air drying oven at the temperature of 120-160 ℃ for 10-12 h, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product with absolute ethyl alcohol for 3-5 times, then washing with deionized water for 3-5 times, finally, drying in vacuum at the temperature of 60-80 ℃, and then grinding to obtain a silver/tin oxide/bismuth oxybromide photoelectric material, namely completing the method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material.
The principle of the invention is as follows:
firstly, the SnO is constructed by optimizing synthesis conditions through an in-situ hydrothermal method2The high-energy-level electronic platform improves the utilization efficiency of photo-generated electrons, further enhances the transfer of the photo-generated electrons by silver modification, and controls and synthesizes the silver/tin oxide/bismuth oxybromide photoelectric material with strong photoelectric response; the hydrothermal in-situ growth method has the advantages of mild reaction conditions, high crystallization degree, good dispersibility and simple operation.
The invention has the advantages that:
compared with the existing bismuth oxybromide photoelectric material, the photovoltaic intensity of the bismuth oxybromide photoelectric material prepared by the invention is about 1.08mV, and the photovoltaic response intensity of the silver/tin oxide/bismuth oxybromide photoelectric material prepared by the invention can reach 16.62mV, so that the photovoltaic response is stronger, the charge separation efficiency is better, and the photoelectric characteristic is better;
secondly, the silver/tin oxide/bismuth oxybromide photoelectric material prepared by the invention has better crystallization degree.
The method is suitable for preparing silver/tin oxide/bismuth oxybromide photoelectric materials.
Drawings
FIG. 1 is an SEM image of a bismuth oxybromide photoelectric material prepared according to the first embodiment;
FIG. 2 is an enlarged view taken at A in FIG. 1;
FIG. 3 is an X-ray diffraction pattern of a bismuth oxybromide photoelectric material prepared in accordance with the first example;
FIG. 4 is SnO prepared according to example two2X-ray photoelectron spectroscopy of the tin element of the/BiOBr composite material;
FIG. 5 is an X-ray diffraction diagram, in which 1 is the bismuth oxybromide photoelectric material prepared in the first embodiment, and 2 is SnO prepared in the second embodiment2a/BiOBr composite material;
FIG. 6 is a surface photo-voltage spectrum, in which 1 is a surface photo-voltage curve of the bismuth oxybromide photoelectric material prepared in example one, and 2 is SnO prepared in example two2The surface photovoltage curve of the/BiOBr composite material;
FIG. 7 is an X-ray diffraction diagram, in which 1 is SnO prepared by example two2The Ag/BiOBr photoelectric material prepared in the third embodiment is 2;
FIG. 8 is a surface photovoltage spectrum, in which FIG. 1 is SnO prepared by example two2The surface photovoltage curve of the/BiOBr composite material is shown in 2, which is the surface photovoltage curve of the Ag/BiOBr photoelectric material prepared in the third embodiment;
FIG. 9 is Ag/SnO prepared in example four2SEM image of/BiOBr photoelectric material;
FIG. 10 is an enlarged view taken at A in FIG. 9;
FIG. 11 is an X-ray diffraction diagram in which 1 is the bismuth oxybromide photoelectric material prepared in example one and 2 is Ag/SnO prepared in example four2a/BiOBr photoelectric material;
FIG. 12 is a surface photo-voltage spectrum, in which 1 is a surface photo-voltage curve of the bismuth oxybromide photoelectric material prepared in example one, and 2 is a surface photo-voltage curve of the bismuth oxybromide photoelectric material prepared in example twoSnO of2The surface photovoltage curve of the/BiOBr composite material is shown in 3, which is the surface photovoltage curve of the Ag/BiOBr photoelectric material prepared in the third embodiment, and 4, which is the Ag/SnO prepared in the fourth embodiment2The surface photovoltage curve of the/BiOBr photoelectric material.
Detailed Description
The first embodiment is as follows: the embodiment is a method for in-situ synthesis of a silver/tin oxide/bismuth oxybromide photoelectric material, which is completed according to the following steps:
firstly, preparing a mixed solution of bismuth salt and stannate: dissolving bismuth salt into deionized water at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min, adding stannate, and stirring at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min until the stannate is dissolved into the deionized water to obtain a mixed solution of the bismuth salt and the stannate;
the volume ratio of the bismuth salt substance in the step one to the deionized water is (1-3) mol:2500m L;
the mass ratio of the bismuth salt to the stannate in the first step is (1-3) to (0.01-0.05);
secondly, preparing a bromine salt solution: dissolving bromine salt into deionized water at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min to obtain a bromine salt aqueous solution;
the volume ratio of the bromine salt substance in the second step to the deionized water is (1-3) mol:5000m L;
thirdly, dropwise adding the mixed solution of bismuth salt and stannate into the bromine salt aqueous solution at a dropwise adding speed of 3-4 drops/min, and stirring and reacting for 10-40 min under the conditions that the temperature is 25-35 ℃ and the stirring speed is 100-300 r/min to obtain a tin-containing bismuth oxybromide solution; adding silver salt into a tin-containing bismuth oxybromide solution, and stirring for 20-30 min at a stirring speed of 100-300 r/min to obtain a precursor;
the volume ratio of the mixed solution of the bismuth salt and the stannate to the bromine salt water solution in the third step is (1-2) to (1-4);
the volume ratio of the silver salt substance in the step three to the tin-containing bismuth oxybromide solution is (0.001-0.01) mol (5000-10000) m L;
fourthly, carrying out hydro-thermal reaction on the precursor in a forced air drying oven at the temperature of 120-160 ℃ for 10-12 h, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product with absolute ethyl alcohol for 3-5 times, then washing with deionized water for 3-5 times, finally, drying in vacuum at the temperature of 60-80 ℃, and then grinding to obtain a silver/tin oxide/bismuth oxybromide photoelectric material, namely completing the method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material.
The principle of the present embodiment:
firstly, the SnO is constructed by optimizing synthesis conditions through an in-situ hydrothermal method2The high-energy-level electronic platform improves the utilization efficiency of photo-generated electrons, further enhances the transfer of the photo-generated electrons by silver modification, and controls and synthesizes the silver/tin oxide/bismuth oxybromide photoelectric material with strong photoelectric response; the hydrothermal in-situ growth method has the advantages of mild reaction conditions, high crystallization degree, good dispersibility and simple operation.
The advantages of this embodiment:
compared with the existing bismuth oxybromide photoelectric material, the photovoltaic intensity of the bismuth oxybromide photoelectric material prepared by the embodiment is about 1.08mV, the photovoltaic response intensity of the silver/tin oxide/bismuth oxybromide photoelectric material prepared by the embodiment can reach 16.62mV, the photovoltaic response is stronger, the charge separation efficiency is better, and the photoelectric characteristic is better;
secondly, the silver/tin oxide/bismuth oxybromide photoelectric material prepared by the embodiment has better crystallization degree.
The method is suitable for preparing silver/tin oxide/bismuth oxybromide photoelectric materials.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the bismuth salt in the step one is one or a mixture of more of bismuth nitrate, bismuth chloride and bismuth sulfate. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the stannate in the step one is stannous chloride dihydrate, sodium stannate trihydrate or crystallized stannic chloride. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: and the bromine salt in the second step is one or a mixture of more of cetyl trimethyl ammonium bromide, sodium bromide and potassium bromide. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the silver salt in the third step is silver nitrate. The other steps are the same as those in the first to fourth embodiments.
Sixth embodiment A difference between the first to fifth embodiments is that the volume ratio of the bismuth salt substance to the deionized water in the first step is (1.5 to 2.5) mol:2500m L, and the other steps are the same as in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the mass ratio of the bismuth salt to the stannate in the step one is (1.5-2.5): (0.015-0.03). The other steps are the same as those in the first to sixth embodiments.
Eighth embodiment, the difference between this embodiment and one of the first to seventh embodiments is that the volume ratio of the bromine salt to the deionized water in the second step is (1 to 1.5) mol:5000m L, and the other steps are the same as those in the first to seventh embodiments.
Ninth embodiment the present embodiment is different from the first to eighth embodiments in that the volume ratio of the amount of the silver salt to the tin-containing bismuth oxybromide solution in the third step is (0.001 to 0.005) mol (5000 to 7500) m L.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: in the fourth step, the precursor is subjected to hydrothermal reaction for 11-12 hours in a forced air drying oven at the temperature of 150-160 ℃, and then is naturally cooled to room temperature to obtain a reaction product; firstly, washing a reaction product with absolute ethyl alcohol for 3-5 times, then washing with absolute ethyl alcohol for 3-5 times, finally, drying in vacuum at the temperature of 60-80 ℃, and then grinding to obtain a silver/tin oxide/bismuth oxybromide photoelectric material, namely completing the method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material. The other steps are the same as those in the first to ninth embodiments. The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the bismuth oxybromide photoelectric material is completed according to the following steps:
firstly, dissolving bismuth salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min to obtain a bismuth salt solution;
the bismuth salt in the step one is Bi (NO)3)3·5H2O；
The volume ratio of the bismuth salt substance in the step one to the deionized water is 1mol:2500m L;
secondly, dissolving bromine salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min to obtain a bromine salt aqueous solution;
the bromine salt in the second step is potassium bromide;
the volume ratio of the bromine salt substance in the step two to the deionized water is 1mol:5000m L;
thirdly, dropwise adding the bismuth salt solution into the bromine salt aqueous solution at a dropwise adding speed of 4 drops/min, and stirring and reacting for 30min under the conditions that the temperature is 25 ℃ and the stirring speed is 200r/min to obtain a mixed solution;
the volume ratio of the bismuth salt solution to the bromine salt solution in the third step is 1: 2;
fourthly, carrying out hydro-thermal reaction on the mixed solution in a forced air drying oven at the temperature of 160 ℃ for 12 hours, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, finally, carrying out vacuum drying at the temperature of 80 ℃, and then grinding to obtain the bismuth oxybromide photoelectric material.
The photogenerated charge separation of the BiOBr photovoltaic material prepared in example one was about 1.08 mV.
The microscopic morphology of the bismuth oxybromide photoelectric material prepared in the first example was tested by a scanning electron microscope, and the result is shown in fig. 1;
FIG. 1 is an SEM image of a bismuth oxybromide photoelectric material prepared according to the first embodiment;
FIG. 2 is an enlarged view taken at A in FIG. 1;
as can be seen from fig. 1 to 2, the bismuth oxybromide photoelectric material (BiOBr) prepared in the first embodiment has a sheet structure, and the length thereof is about 2 to 3 μm.
The detection result of the bismuth oxybromide photoelectric material prepared in the first embodiment by using an X-ray diffractometer is shown in fig. 3.
FIG. 3 is an X-ray diffraction pattern of a bismuth oxybromide photoelectric material prepared in accordance with the first example;
as can be seen from fig. 3, characteristic diffraction peaks of the flake bismuth oxybromide photoelectric material prepared in example one at 2 θ angles of 10.9 °, 21.9 °, 25.2 °, 31.7 °, 32.2 °, 33.2 °, 44.7 °, 50.7 °, 56.2 °, 57.1 ° and the like correspond to (001), (002), (101), (102), (110), (003), (004), (104), (114) and (212) crystal planes of the tetragonal phase of BiOBr, respectively, and the diffraction peaks also correspond to those of the standard data Card JCPDS Card number: 09-0393, which demonstrates that the bismuth oxybromide photovoltaic material prepared in example one was bibbr.
Example two: SnO2The preparation method of the/BiOBr composite material is completed according to the following steps:
firstly, preparing a mixed solution of bismuth salt and stannate: dissolving bismuth salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min, adding stannate, and stirring at the temperature of 25 ℃ and the stirring speed of 200r/min until the stannate is dissolved into the deionized water to obtain a mixed solution of the bismuth salt and the stannate;
the bismuth salt in the step one is Bi (NO)3)3·5H2O；
The volume ratio of the bismuth salt substance in the step one to the deionized water is 1mol:2500m L;
the mass ratio of the bismuth salt to the stannate in the first step is 1: 0.015;
the stannate in the step one is sodium stannate trihydrate;
secondly, preparing a bromine salt solution: dissolving bromine salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min to obtain a bromine salt aqueous solution;
the volume ratio of the bromine salt substance in the step two to the deionized water is 1mol:5000m L;
the bromine salt in the second step is potassium bromide;
thirdly, dropwise adding the mixed solution of bismuth salt and stannate into the bromine salt aqueous solution at a dropwise adding speed of 4 drops/min, and stirring and reacting for 30min under the conditions that the temperature is 25 ℃ and the stirring speed is 200r/min to obtain a tin-containing bismuth oxybromide solution;
the volume ratio of the mixed solution of the bismuth salt and the stannate to the bromine salt aqueous solution in the step three is 1: 2;
fourthly, carrying out hydrothermal reaction on the tin-containing bismuth oxybromide solution in a forced air drying oven at the temperature of 160 ℃ for 12 hours, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, finally, drying in vacuum at the temperature of 80 ℃, and then grinding to obtain SnO2a/BiOBr composite material.
SnO prepared in example II2The photogenerated charge of the/BiOBr photoelectric material is separated by about 4.42 mV.
The existence form of tin is verified by adopting X-ray photoelectron spectroscopy, and the detection result is shown in figure 4;
FIG. 4 is SnO prepared according to example two2X-ray photoelectron spectroscopy of the tin element of the/BiOBr composite material;
as can be seen from FIG. 4, the tin is SnO2Exist in the form of (1).
SnO prepared in example two was detected by X-ray diffractometer2a/BiOBr composite material, as shown in FIG. 5;
FIG. 5 is an X-ray diffraction diagram, in which 1 is the bismuth oxybromide photoelectric material prepared in the first embodiment, and 2 is SnO prepared in the second embodiment2a/BiOBr composite material;
as can be seen from FIG. 5, SnO2Does not change the crystalline phase of bismuth oxybromide.
SnO prepared in example two is detected by adopting surface photovoltage technology2The photo-generated charge separation condition of the/BiOBr composite material is shown in FIG. 6;
FIG. 6 is a surface photo-voltage spectrum, in which 1 is a surface photo-voltage curve of the bismuth oxybromide photoelectric material prepared in example one, and 2 is SnO prepared in example two2The surface photovoltage curve of the/BiOBr composite material;
as can be seen from FIG. 6, SnO prepared in example two2The photoproduction charge separation of the/BiOBr composite material is obviously improved. This indicates that SnO2The introduction of (2) facilitates the separation and transport of photogenerated electron-hole pairs.
Example three: the preparation method of the Ag/BiOBr photoelectric material is completed according to the following steps:
firstly, dissolving bismuth salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min to obtain a bismuth salt solution;
the bismuth salt in the step one is Bi (NO)3)3·5H2O；
The volume ratio of the bismuth salt substance in the step one to the deionized water is 1mol:25000m L;
secondly, dissolving bromine salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min to obtain a bromine salt aqueous solution;
the bromine salt in the second step is potassium bromide;
the volume ratio of the bromine salt substance in the step two to the deionized water is 1mol:5000m L;
thirdly, dropwise adding the bismuth salt solution into the bromine salt aqueous solution at a dropwise adding speed of 4 drops/min, and stirring and reacting for 10min under the conditions that the temperature is 25 ℃ and the stirring speed is 200r/min to obtain a mixed solution; adding silver salt into the mixed solution, and stirring for 20min at the stirring speed of 200r/min to obtain a precursor;
the silver salt in the third step is silver nitrate;
the volume ratio of the bismuth salt solution to the bromine salt solution in the third step is 1: 2;
the volume ratio of the silver salt substance in the third step to the mixed solution is 0.005mol:7500m L;
fourthly, carrying out hydro-thermal reaction on the precursor in a forced air drying oven at the temperature of 160 ℃ for 12 hours, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, finally, carrying out vacuum drying at the temperature of 80 ℃, and then grinding to obtain the Ag/BiOBr photoelectric material.
The photo-generated charge of the Ag/BiOBr photovoltaic material prepared in example three was separated by about 12.77 mV.
Detecting the Ag/BiOBr photoelectric material prepared in the third embodiment by using an X-ray diffractometer, wherein the detection result is shown in FIG. 7;
FIG. 7 is an X-ray diffraction diagram, in which 1 is SnO prepared by example two2The Ag/BiOBr photoelectric material prepared in the third embodiment is 2;
as can be seen from fig. 7, the introduction of Ag did not change the crystalline phase of bismuth oxybromide.
Detecting the photo-generated charge separation condition of the Ag/BiOBr photoelectric material prepared in the third embodiment by adopting a surface photovoltage technology, as shown in FIG. 8;
FIG. 8 is a surface photovoltage spectrum, in which FIG. 1 is SnO prepared by example two2The surface photovoltage curve of the/BiOBr composite material is shown in 2, which is the surface photovoltage curve of the Ag/BiOBr photoelectric material prepared in the third embodiment;
as can be seen from the data in fig. 8, the photo-generated charge separation of the Ag/BiOBr photoelectric material prepared in the third embodiment is also significantly improved, and the introduction of Ag improves the transfer of photo-generated electrons of BiOBr.
Example four: Ag/SnO2The preparation method of the/BiOBr photoelectric material is completed according to the following steps:
firstly, preparing a mixed solution of bismuth salt and stannate: dissolving bismuth salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min, adding stannate, and stirring at the temperature of 25 ℃ and the stirring speed of 200r/min until the stannate is dissolved into the deionized water to obtain a mixed solution of the bismuth salt and the stannate;
the bismuth salt in the step one is Bi (NO)3)3·5H2O；
The stannate in the step one is sodium stannate trihydrate;
the volume ratio of the bismuth salt substance in the step one to the deionized water is 1mol:2500m L;
the mass ratio of the bismuth salt to the stannate in the first step is 1: 0.015;
secondly, preparing a bromine salt solution: dissolving bromine salt into deionized water at the temperature of 25 ℃ and the stirring speed of 200r/min to obtain a bromine salt aqueous solution;
the bromine salt in the second step is potassium bromide;
the volume ratio of the bromine salt substance in the step two to the deionized water is 1mol:5000m L;
thirdly, dropwise adding the mixed solution of bismuth salt and stannate into the bromine salt aqueous solution at a dropwise adding speed of 4 drops/min, and stirring and reacting for 10min under the conditions that the temperature is 25 ℃ and the stirring speed is 200r/min to obtain a tin-containing bismuth oxybromide solution; adding silver salt into a bismuth oxybromide solution containing tin, and stirring for 20min at the stirring speed of 200r/min to obtain a precursor;
the silver salt in the third step is silver nitrate;
the volume ratio of the mixed solution of the bismuth salt and the stannate to the bromine salt aqueous solution in the step three is 1: 2;
the volume ratio of the silver salt substance in the step three to the tin-containing bismuth oxybromide solution is 0.005mol:7500m L;
fourthly, carrying out hydro-thermal reaction on the precursor in a forced air drying oven at the temperature of 160 ℃ for 12 hours, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, finally, drying in vacuum at the temperature of 80 ℃, and then grinding to obtain Ag/SnO2a/BiOBr photoelectric material.
Ag/SnO prepared in example four2The photogenerated charge of the/BiOBr photovoltaic material is separated by about 16.62 mV.
Testing of the Ag/SnO prepared in example four by scanning Electron microscopy2a/BiOBr photoelectric material, a porous material,as shown in fig. 9 and 10;
FIG. 9 is Ag/SnO prepared in example four2SEM image of/BiOBr photoelectric material;
FIG. 10 is an enlarged view taken at A in FIG. 9;
the presence of SnO on the BiOBr surface is clearly seen in FIGS. 9 and 102And small particles of Ag exist, and the thickness is about 30-60 nm.
Detection of the Ag/SnO prepared in example four by means of an X-ray diffractometer2The detection result of the/BiOBr photoelectric material is shown in figure 11;
FIG. 11 is an X-ray diffraction diagram in which 1 is the bismuth oxybromide photoelectric material prepared in example one and 2 is Ag/SnO prepared in example four2a/BiOBr photoelectric material;
as can be seen from FIG. 11, Ag and SnO2Does not change the crystalline phase of bismuth oxybromide.
Ag/SnO prepared by adopting surface photovoltage technology as detection example four2a/BiOBr photovoltaic material, as shown in fig. 12;
FIG. 12 is a surface photo-voltage spectrum, in which 1 is a surface photo-voltage curve of the bismuth oxybromide photoelectric material prepared in example one, and 2 is SnO prepared in example two2The surface photovoltage curve of the/BiOBr composite material is shown in 3, which is the surface photovoltage curve of the Ag/BiOBr photoelectric material prepared in the third embodiment, and 4, which is the Ag/SnO prepared in the fourth embodiment2The surface photovoltage curve of the/BiOBr photoelectric material.
As can be seen from the data in FIG. 12, Ag/SnO was prepared in example four2The photoproduction charge separation of the/BiOBr photoelectric material is greatly improved, namely SnO2The separation and transmission of the BiOBr photoproduction electron-hole pairs and the Ag are facilitated, and the transfer effect of the BiOBr photoproduction electrons is improved.
Claims (10)
1. A method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material is characterized in that the method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material is completed according to the following steps:
firstly, preparing a mixed solution of bismuth salt and stannate: dissolving bismuth salt into deionized water at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min, adding stannate, and stirring at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min until the stannate is dissolved into the deionized water to obtain a mixed solution of the bismuth salt and the stannate;
the volume ratio of the bismuth salt substance in the step one to the deionized water is (1-3) mol:2500m L;
the mass ratio of the bismuth salt to the stannate in the first step is (1-3) to (0.01-0.05);
secondly, preparing a bromine salt solution: dissolving bromine salt into deionized water at the temperature of 25-35 ℃ and the stirring speed of 100-300 r/min to obtain a bromine salt aqueous solution;
the volume ratio of the bromine salt substance in the second step to the deionized water is (1-3) mol:5000m L;
thirdly, dropwise adding the mixed solution of bismuth salt and stannate into the bromine salt aqueous solution at a dropwise adding speed of 3-4 drops/min, and stirring and reacting for 10-40 min under the conditions that the temperature is 25-35 ℃ and the stirring speed is 100-300 r/min to obtain a tin-containing bismuth oxybromide solution; adding silver salt into a tin-containing bismuth oxybromide solution, and stirring for 20-30 min at a stirring speed of 100-300 r/min to obtain a precursor;
the volume ratio of the mixed solution of the bismuth salt and the stannate to the bromine salt water solution in the third step is (1-2) to (1-4);
the volume ratio of the silver salt substance in the step three to the tin-containing bismuth oxybromide solution is (0.001-0.01) mol (5000-10000) m L;
fourthly, carrying out hydro-thermal reaction on the precursor in a forced air drying oven at the temperature of 120-160 ℃ for 10-12 h, and then naturally cooling to room temperature to obtain a reaction product; firstly, washing a reaction product with absolute ethyl alcohol for 3-5 times, then washing with deionized water for 3-5 times, finally, drying in vacuum at the temperature of 60-80 ℃, and then grinding to obtain a silver/tin oxide/bismuth oxybromide photoelectric material, namely completing the method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material.
2. The method of claim 1, wherein the bismuth salt in the first step is one or a mixture of bismuth nitrate, bismuth chloride and bismuth sulfate.
3. The method of claim 1, wherein the stannate in step one is sodium stannate trihydrate.
4. The method of claim 1, wherein the bromide salt in step two is one or a mixture of cetyl trimethyl ammonium bromide, sodium bromide and potassium bromide.
5. The method of claim 1, wherein the silver salt is silver nitrate in step three.
6. The method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material according to claim 1, wherein the volume ratio of the bismuth salt substance to the deionized water in the step one is (1.5-2.5) mol:2500m L.
7. The method of claim 1, wherein the ratio of bismuth salt to stannate in step one is (1.5-2.5): (0.015-0.03).
8. The method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material according to claim 1, wherein the volume ratio of the bromine salt to the deionized water in the second step is (1-1.5) mol:5000m L.
9. The method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material according to claim 1, wherein the volume ratio of the silver salt to the tin-containing bismuth oxybromide solution in step three is (0.001-0.005) mol (5000-7500) m L.
10. The method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material according to claim 1, wherein the fourth step is that the precursor undergoes a hydrothermal reaction in a forced air drying oven at a temperature of 150-160 ℃ for 11-12 h, and then is naturally cooled to room temperature to obtain a reaction product; firstly, washing a reaction product with absolute ethyl alcohol for 3-5 times, then washing with absolute ethyl alcohol for 3-5 times, finally, drying in vacuum at the temperature of 60-80 ℃, and then grinding to obtain a silver/tin oxide/bismuth oxybromide photoelectric material, namely completing the method for in-situ synthesis of the silver/tin oxide/bismuth oxybromide photoelectric material.
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| CN105036436A (en) * | 2015-06-25 | 2015-11-11 | 上海师范大学 | Ag/BiOBr photocatalysis-membrane distillation reaction system |
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