CN109761266B - Preparation method of self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material - Google Patents
Preparation method of self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material Download PDFInfo
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Abstract
The invention discloses a preparation method of a self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material, which comprises the following steps: at room temperature, regulating and controlling the proportion of each metal salt through a self-doping strategy according to the basic proportion that the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and stannic chloride pentahydrate is 2:1:1 to obtain a metal salt mixture, adding oleylamine, heating to remove oxygen and water, filling argon and heating to 230-; and then injecting an oleylamine solution of sulfur by a hot injection method, fully reacting, cooling to stop the reaction, adding a centrifugal solvent after the mixture reaches the room temperature, and centrifugally separating the solution to precipitate the nano crystals to obtain the quaternary nano crystal photoelectric material. The nanocrystalline photoelectric material prepared by the method can be applied to the fields of photovoltaics, photoelectrochemistry, photocatalytic hydrogen production and the like, and the performance is obviously improved.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a preparation method of a self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material.
Background
The non-renewable nature and environmental pollution caused by burning of traditional fossil energy forces people to find new renewable pollution-free clean energy. Hydrogen is an emerging renewable energy source that is of great interest because of its high calorific value and the fact that the combustion product is water, which is not polluting to the environment. The method for producing hydrogen by utilizing solar photocatalysis and photoelectrochemistry to decompose water is an ideal way for producing hydrogen with high efficiency and is one of hot spots for research in the field of energy sources. The key point of the goal is to research, develop and prepare efficient, stable, nontoxic and low-cost photoelectric materials.
The optical bandgap of the Copper Zinc Tin Sulfide (CZTS) catalyst is 1.5eV close to the optimal optical bandgap of the solar cell; has a light absorption coefficient of more than 104cm-1The material has a relatively wide absorption band in an ultraviolet-visible light wave band; the CZTS does not contain highly toxic elements, is safe and environment-friendly, and has rich element reserves; the CZTS is a direct band gap semiconductor, has good light failure resistance, and is suitable for preparing efficient and stable solar thin film batteries and photoelectrochemistry hydrogen production photoelectrode. However, the CZTS quaternary compound has many binary or ternary impurity phases and defects, such as vacancies, substitutions, and gaps, which adversely affect the photoelectrochemical properties and reduce the photoelectric efficiency thereof. This has led to the related research of CZTS entering the bottleneck period, which restricts the way of large-scale industrial application.
In the study of CZTS thin film solar cells, there is oneEmpirical rule, namely, the CZTS battery prepared in the environment poor in Cu, Sn and Zn is higher in efficiency. This is due to the deeper levels of Cu in the sample under such growth conditionsZnAnd SnZnThe defect concentration will be reduced, and the defective cluster [2Cu ] will be unfavorableZn+SnZn]Is also inhibited. However, at present, a powerful means for component regulation and defect control of the CZTS is still lacked, and the method is more empirical, and the physical nature and the action mechanism existing in the method are lacked of deep experimental research, which is an important factor for limiting the improvement of the performance of the CZTS photoelectric device. Therefore, developing a proper modification means to reduce harmful defects, optimizing components and structures, and researching the action mechanism of the modification means is an important means for improving the photoelectric property of CZTS. The project provides that the self-doping strategy based on the colloid chemical preparation technology is utilized to regulate and control the components and defects of the CZTS material, the energy band structure is optimized, and the photoelectric performance is further improved.
Disclosure of Invention
The invention aims to provide a preparation method of a self-doped Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst, and provides a novel preparation method of a photoelectric material, wherein the preparation method can regulate and control components and defects of the photocatalyst so as to regulate and control an energy band structure of the photocatalyst and further optimize photoelectrochemical properties of the photocatalyst. Can be applied to the fields of photovoltaics, photoelectrochemistry, photocatalytic hydrogen production and the like, and the performance is obviously improved.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material comprises the following steps:
at room temperature, regulating and controlling the proportion of each metal salt through a self-doping strategy according to the basic proportion that the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and stannic chloride pentahydrate is 2:1:1 to obtain a metal salt mixture, adding oleylamine, heating to remove oxygen and water, filling argon and heating to 230-;
then injecting sulfur oleylamine solution by a hot injection method, fully reacting, cooling to stop the reaction, adding a centrifugal solvent after the mixture reaches the room temperature, and centrifugally separating the solution to precipitate the nano-crystals to obtain the quaternary nano-crystal photoelectric material;
the self-doping strategy includes:
s1, under the premise that the total metal salt mole number is not changed, replacing one metal cation contained in the quaternary nanocrystal photoelectric material by another metal cation contained in the quaternary nanocrystal photoelectric material: replacing monohydrate copper acetate with dihydrate zinc acetate, wherein the replaced amount accounts for 0-100% of the original copper metal salt, and synthesizing a series of single-element self-doped copper-zinc-tin-sulfur nanocrystals; or replacing tin chloride pentahydrate with zinc acetate dihydrate, wherein the replaced amount accounts for 0-100% of the original tin metal salt, and synthesizing a series of single-element self-doped copper-zinc-tin-sulfur nanocrystals; or,
s2, under the premise that the mole number of the total metal salt is not changed, replacing the other two metal cations contained in the material by one metal cation contained in the quaternary nanocrystal photoelectric material: firstly, replacing copper acetate monohydrate with zinc acetate dihydrate in an amount accounting for 0-50% of the original copper metal salt, and then replacing tin chloride pentahydrate with zinc acetate dihydrate in an amount accounting for 0-50% of the original tin metal salt to synthesize a series of multi-element self-doped copper-zinc-tin-sulfur nanocrystals; or replacing tin chloride pentahydrate with zinc acetate dihydrate in an amount of 0-50% of the original tin metal salt, and replacing copper acetate monohydrate with zinc acetate dihydrate in an amount of 0-50% of the original copper metal salt to synthesize a series of multi-element self-doped copper-zinc-tin-sulfur nanocrystals. And the substitution ratio is not equal to 0.
As a further improvement of the invention, the molar ratio of the copper acetate monohydrate, the zinc acetate dihydrate and the stannic chloride pentahydrate is (1-2): 1-2.4): 0.5-1.
As a further improvement of the invention, the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and tin chloride pentahydrate is 1.2:1.8: 1.
As a further improvement of the invention, the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and tin chloride pentahydrate is 1.2:2.2: 0.6.
As a further improvement of the invention, the conditions of removing oxygen and water are that the temperature is kept at 135 ℃ for 60-120 minutes under a vacuum state.
As a further improvement of the invention, the temperature of the oleylamine solution of sulfur powder is 230-250 ℃ when the solution is heated.
As a further improvement of the invention, the full reaction time is 50 to 80 minutes.
As a further improvement of the invention, the centrifugation solvent is isopropanol.
As a further improvement of the present invention, in step 1), the prepared quaternary nanocrystals are dispersed in hexane.
As a further improvement of the invention, in the step 1), zinc is used for replacing copper and tin to obtain the nano-crystalline photoelectric material, and after the nano-crystalline photoelectric material is prepared into a film by an electrophoretic deposition method, under the illumination of a xenon lamp, the photocurrent is 0.01-0.6mA/cm-2。
Compared with the prior art, the invention has the following advantages:
the invention realizes the preparation of the self-doped Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst with different component proportions under the simple and easy condition; by adjusting the proportional components of the metal salts in the reactants, the defects and the energy band structure of the CZTS nanocrystalline photocatalyst can be regulated and controlled, so that the photoelectric performance of the CZTS nanocrystalline photocatalyst is optimized. In addition, the invention has simple experimental device and simple experimental operation steps, and is very beneficial to the popularization of the synthesis method. The self-doping CZTS nanocrystalline prepared by the method regulates and controls the defects and the energy band structure of the nanocrystalline by regulating and controlling self elements to replace other elements to form self doping, so that the photoelectrochemical property of the nanocrystalline is improved, and the nanocrystalline is beneficial to popularization and application of the copper-zinc-tin-sulfur market. By researching the action mechanism of the self-doped modified copper-zinc-tin-sulfur (CZTS) material, the optimization of the CZTS component and structure can be promoted, the photoelectric property of CZTS is improved, and a foundation is laid for the high-efficiency application of CZTS in the fields of solar cells, photoelectrocatalysis water decomposition hydrogen production, photocatalysis and the like. The method and theory of semiconductor autodoping modification can be enriched, technical and theoretical guidance is provided for developing novel high-efficiency photoelectric functional materials, and the method and theory are applied to industries such as photovoltaics and the like to generate considerable economic benefits.
Drawings
FIG. 1a is a transmission electron micrograph of a CZTS nanocrystalline photocatalyst with a molar ratio of 2:1:1 of metal salts (copper acetate monohydrate, zinc acetate dihydrate, tin chloride pentahydrate) obtained in example 1 of the present invention; FIG. 1b is a TEM image of a CZTS nanocrystalline photocatalyst with a molar ratio of 1.6:1.4:1 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) obtained in example 2 of the present invention; FIG. 1c is a transmission electron micrograph of a CZTS nanocrystalline photocatalyst with a molar ratio of 1.2:1.8:1 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, tin chloride pentahydrate) obtained in example 2 of the present invention.
FIG. 2a is a transmission electron micrograph of a CZTS nanocrystalline photocatalyst with a molar ratio of 2:1:1 of metal salts (copper acetate monohydrate, zinc acetate dihydrate, tin chloride pentahydrate) obtained in example 1 of the present invention; FIG. 2b is a TEM image of the CZTS nanocrystalline photocatalyst obtained in example 2 of the present invention (copper acetate monohydrate, zinc acetate dihydrate, tin chloride pentahydrate) in a molar ratio of 2:1.2: 0.8; FIG. 2c is a TEM image of the CZTS nanocrystalline photocatalyst with a molar ratio of 2:1.4:0.6 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) obtained in example 2 of the present invention.
FIG. 3a is a TEM image of CZTS nanocrystalline photocatalyst with molar ratio of metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) 1.4:2.0:0.6 obtained in example 3 of the present invention; FIG. 3b is a TEM image of the CZTS nanocrystalline photocatalyst with a molar ratio of 1.2:2.2:0.6 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) obtained in example 3 of the present invention; FIG. 3c is a TEM image of the CZTS nanocrystalline photocatalyst with a molar ratio of 1.0:2.4:0.6 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) obtained in example 3 of the present invention.
FIG. 4a is a TEM image of CZTS nanocrystalline photocatalyst with molar ratio of metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) 1.2:2.1:0.7 obtained in example 3 of the present invention; FIG. 4b is a TEM image of the CZTS nanocrystalline photocatalyst with a molar ratio of 1.2:2.2:0.6 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) obtained in example 3 of the present invention; FIG. 4c is a TEM image of the CZTS nanocrystalline photocatalyst with a molar ratio of 1.2:2.3:0.5 of the metal salt (copper acetate monohydrate, zinc acetate dihydrate, stannic chloride pentahydrate) obtained in example 3 of the present invention.
Detailed Description
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
The invention relates to a preparation method of a self-doped Copper Zinc Tin Sulfide (CZTS) nanocrystalline photoelectric material, which comprises the following steps:
1) weighing 1.6mmol of total metal salt at room temperature according to the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and stannic chloride pentahydrate of 2:1:1, adding the weighed metal salt into a three-neck round-bottom flask, adding 30mL of oleylamine, heating the reaction flask to 135 ℃, keeping the temperature under vacuum for 60-120 minutes to remove oxygen and water, filling argon into the flask, and heating the flask to 230-. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane;
2) on the basis of the step 1), a material self-doping method is provided, and on the premise that the mole number of the total metal salt is not changed, one metal cation contained in the material is used for replacing the other metal cation contained in the material; replacing monohydrate copper acetate with dihydrate zinc acetate, wherein the replaced amount accounts for 0-50% of the original copper metal salt, and synthesizing a series of single-element self-doped copper-zinc-tin-sulfur nanocrystals; or replacing tin chloride pentahydrate with zinc acetate dihydrate, wherein the replaced amount accounts for 0-50% of the original tin metal salt, and synthesizing a series of single-element self-doped copper-zinc-tin-sulfur nanocrystals;
3) on the basis of the step 2), increasing the self-doping element species, and replacing the other two metal cations contained in the material with one metal cation contained in the material on the premise of keeping the mole number of the total metal salt unchanged; firstly, replacing copper acetate monohydrate with zinc acetate dihydrate in an amount accounting for 0-50% of the original copper metal salt, and then replacing tin chloride pentahydrate with zinc acetate dihydrate in an amount accounting for 0-50% of the original tin metal salt to synthesize a series of multi-element self-doped copper-zinc-tin-sulfur nanocrystals; or zinc acetate dihydrate is used for replacing tin chloride pentahydrate, the replaced amount accounts for one proportion of 0-50% of the original tin metal salt, the zinc acetate dihydrate is used for replacing copper acetate monohydrate, the replaced amount accounts for 0-50% of the original copper metal salt, and a series of multi-element self-doped copper-zinc-tin-sulfur nanocrystalline target products are synthesized.
Preferably, in the step 1), the molar ratio of the copper acetate monohydrate, the zinc acetate dihydrate and the stannic chloride pentahydrate is 2:1: 1; preferably, the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and tin chloride pentahydrate is 1.2:1.8: 1; preferably, copper acetate monohydrate, zinc acetate dihydrate, tin chloride pentahydrate 1.2:2.2: 0.6.
Preferably, in the step 1), the time for removing water and oxygen from the mixed solution under vacuum condition is 60-120 minutes; when the oleylamine solution of sulfur powder is added into a three-necked bottle, the temperature is 230-250 ℃; the growth time of CZTS is 50-80 minutes.
Preferably, in step 1), 1.6mmol of sulfur powder is dissolved in 2mL of oleylamine, and the solution is rapidly injected into a flask containing a metal salt solution.
Preferably, in step 1), the centrifugation solvent is isopropanol, and the volume of the solution during centrifugation is 20-40 mL.
Preferably, in the step 2), the amount of the total metal salt is not changed in the process of the single element self-doping, and one metal salt is substituted for the other metal salt in proportion, wherein the substitution proportion is 0-100%.
Preferably, in step 2), one metal salt is selected to be substituted for the other metal salt in proportion of 0 to 100%, and the remaining metal salt is substituted with the first metal salt in proportion of 0 to 100%.
Preferably, the Copper Zinc Tin Sulfide (CZTS) nanocrystal prepared by the synthesis method of the self-doped Copper Zinc Tin Sulfide (CZTS) nanocrystal is characterized in that: the nanocrystalline is obtained by replacing other elements with existing elements, and replacing copper and tin with zinc, and the nanocrystalline is made into film by electrodeposition method, and under xenon lamp illumination, the photocurrent is 0.01-0.6mA/cm-2。
Preferably, the speed of the centrifugal separation is 7000r/min, and the time is 10 min.
Preferably, the centrifugal solvent is isopropanol.
Preferably, the resulting quaternary crystals of CZTS are finally dispersed in 30mL of hexane.
In the step 1), the reaction device is a three-neck round-bottom flask, and the heating device is a temperature-programmed controllable heating device.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following description of the embodiments of the present invention with reference to the accompanying drawings and examples is given by way of illustration and not limitation.
Example 1a
1. 1.6mmol of total metal salts were weighed at room temperature in a 2:1:1 molar ratio of copper acetate monohydrate (0.8mmol), zinc acetate dihydrate (0.4mmol) and tin chloride pentahydrate (0.4mmol) into a three-necked round bottom flask, 30mL of oleylamine was added, the reaction flask was heated to 135 ℃ and kept under vacuum for 120 minutes to remove oxygen and water, the flask was charged with argon and heated to 230 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 1b
1. 1.6mmol of total metal salts were weighed at room temperature in the proportions copper acetate monohydrate (0.64mmol), zinc acetate dihydrate (0.56mmol), tin chloride pentahydrate (0.4mmol) in the molar ratio 1.6:1.4:1, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and held under vacuum for 80 minutes to remove oxygen and water, the flask charged with argon and heated to 245 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 1c
1. 1.6mmol of total metal salts were weighed at room temperature in the proportions copper acetate monohydrate (0.48mmol), zinc acetate dihydrate (0.72mmol), tin chloride pentahydrate (0.4mmol) in a molar ratio of 1.2:1.8:1, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and held under vacuum for 100 minutes to remove oxygen and water, the flask charged with argon and heated to 245 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Fig. 1a, 1b, and 1c show transmission electron micrographs of Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalysts obtained in examples 1a, 1b, and 1c, respectively, from which it can be seen that particles of the CZTS nanocrystals are clearly transformed from small to large, gradually from circular to polygonal, and it is presumed that the particle size changes due to the difference in the reaction rate of the two cations Cu and Zn with sulfur when the oleylamine solution of sulfur is injected by the hot injection method, and the particle size changes when the ratio of Cu/Zn element is changed.
Example 2a
1. 1.6mmol of total metal salts were weighed at room temperature in a 2:1:1 molar ratio of copper acetate monohydrate (0.8mmol), zinc acetate dihydrate (0.4mmol) and tin chloride pentahydrate (0.4mmol) into a three-necked round bottom flask, 30mL of oleylamine was added, the reaction flask was heated to 135 ℃ and kept under vacuum for 60 minutes to remove oxygen and water, the flask was charged with argon and heated to 250 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 2b
1. 1.6mmol of total metal salts were weighed at room temperature in the proportions copper acetate monohydrate (0.8mmol), zinc acetate dihydrate (0.48mmol), tin chloride pentahydrate (0.32mmol) in a molar ratio of 2:1.2:0.8, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and held under vacuum for 90 minutes to remove oxygen and water, the flask charged with argon and heated to 240 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 2c
1. At room temperature, 1.6mmol of total metal salts were weighed out as copper acetate monohydrate (0.8mmol), zinc acetate dihydrate (0.56mmol), tin chloride pentahydrate (0.24mmol) in a molar ratio of 2:1.4:0.6, into a three-necked round-bottomed flask, 30mL of oleylamine were added, the reaction flask was heated to 135 ℃ and kept under vacuum for 65 minutes to remove oxygen and water, the flask was charged with argon and heated to 230 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
FIGS. 2a, 2b, and 2c show TEM photographs of the Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst obtained in examples 2a, 2b, and 2c, respectively. As can be seen from the figure, there is no significant change in the morphology of the nanocrystals. This is probably because the reaction rates of Zn element and Sn element with sulfur are not much different.
Example 3a
1. At room temperature, 1.6mmol of total metal salts were weighed out in the proportions copper acetate monohydrate (0.56mmol), zinc acetate dihydrate (0.8mmol), tin chloride pentahydrate (0.24mmol) in the molar ratio 1.4:2.0:0.6, into a three-necked round bottom flask, 30mL of oleylamine were added, the reaction flask was heated to 135 ℃ and kept under vacuum for 110 minutes to remove oxygen and water, the flask was charged with argon and heated to 240 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 3b
1. 1.6mmol of total metal salts were weighed at room temperature in the proportions copper acetate monohydrate (0.48mmol), zinc acetate dihydrate (0.88mmol), tin chloride pentahydrate (0.24mmol) in the molar ratio 1.2:2.2:0.6, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and held under vacuum for 70 minutes to remove oxygen and water, the flask charged with argon and heated to 245 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 3c
1. At room temperature, 1.6mmol of total metal salts were weighed out in the proportions copper acetate monohydrate (0.4mmol), zinc acetate dihydrate (0.96mmol), tin chloride pentahydrate (0.24mmol) in the molar ratio 1.0:2.4:0.6, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and held under vacuum for 80 minutes to remove oxygen and water, the flask charged with argon and heated to 250 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth, the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
FIGS. 3a, 3b, and 3c show TEM photographs of the Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst obtained in examples 3a, 3b, and 3c, respectively. As can be seen from the figure, the nanocrystals gradually changed from round particles to elongated particles, and the particles gradually thickened.
Example 4a
1. At room temperature, 1.6mmol of total metal salts were weighed out in the proportions copper acetate monohydrate (0.48mmol), zinc acetate dihydrate (0.84mmol), tin chloride pentahydrate (0.28mmol) in the molar ratio 1.2:2.1:0.7, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and held under vacuum for 60 minutes to remove oxygen and water, the flask charged with argon and heated to 230 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth (80 min), the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 4b
1. At room temperature, 1.6mmol of total metal salts were weighed out in the proportions copper acetate monohydrate (0.48mmol), zinc acetate dihydrate (0.88mmol), tin chloride pentahydrate (0.24mmol) in the molar ratio 1.2:2.2:0.6, into a three-necked round bottom flask, 30mL of oleylamine were added, the reaction flask was heated to 135 ℃ and kept under vacuum for 100 minutes to remove oxygen and water, the flask was charged with argon and heated to 240 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth (60 minutes), the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
Example 4c
1. At room temperature, 1.6mmol of total metal salts were weighed out in the proportions copper acetate monohydrate (0.48mmol), zinc acetate dihydrate (0.92mmol), tin chloride pentahydrate (0.2mmol) in the molar ratio 1.2:2.3:0.5, added to a three-necked round bottom flask, 30mL of oleylamine added, the reaction flask heated to 135 ℃ and kept under vacuum for 120 minutes to remove oxygen and water, the flask charged with argon and heated to 250 ℃.
2. An oleylamine solution of sulfur powder (1.6mmol of sulfur powder dissolved in 2mL of oleylamine) was quickly charged into the flask. After a certain time of growth (50 minutes), the reaction was terminated by removing the heating mantle.
3. After the mixture reached room temperature, isopropanol was added and the solution was centrifuged at 7000rpm for 10 minutes to precipitate the nanocrystals. The quaternary nanocrystals were finally dispersed in 30mL of hexane.
FIGS. 4a, 4b, and 4c show TEM photographs of the Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst obtained in examples 4a, 4b, and 4c, respectively. As can be seen from the figure, the nanocrystals gradually changed from elongated stripe-shaped particles to circular large particles, which indicates that the self-doping has an effect on the morphology of the nanocrystals.
The method realizes the preparation of the self-doped Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst by using a simpler experimental device under a very mild condition, and the prepared CZTS nanocrystalline photocatalyst can regulate and control the shape, defects and energy band structure of the nanocrystalline by regulating and controlling the proportion of reactants, thereby optimizing the photoelectrochemical property of the nanocrystalline photocatalyst. In the whole reaction process, no toxic chemical reagent is involved, so that the pollution to the environment can be effectively avoided. The whole preparation process is simple to operate, strong in controllability, good in repeatability, green and environment-friendly, and suitable for large-scale production.
The invention realizes the preparation of the self-doped Copper Zinc Tin Sulfide (CZTS) nanocrystalline photocatalyst with different component proportions under the simple and easy condition; by adjusting the proportional components of the metal salts in the reactants, the defects and the energy band structure of the CZTS nanocrystalline photocatalyst can be regulated and controlled, so that the photoelectric performance of the CZTS nanocrystalline photocatalyst is optimized. In addition, the invention has simple experimental device and simple experimental operation steps, and is very beneficial to the popularization of the synthesis method. The self-doping CZTS nanocrystalline prepared by the method regulates and controls the defects and the energy band structure of the nanocrystalline by regulating and controlling self elements to replace other elements to form self doping, so that the photoelectrochemical property of the nanocrystalline is improved, and the nanocrystalline is beneficial to popularization and application of the copper-zinc-tin-sulfur market.
The foregoing is merely illustrative of the present invention. Various modifications and additions may be made to the described examples by those skilled in the art without departing from the spirit of the invention, which is defined by the scope of the following claims.
Although specific embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the specific embodiments described above, which are intended to be illustrative, instructive, and not restrictive. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material is characterized by comprising the following steps:
at room temperature, regulating and controlling the proportion of each metal salt through a self-doping strategy according to the basic proportion that the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and stannic chloride pentahydrate is 2:1:1 to obtain a metal salt mixture, adding oleylamine, heating to remove oxygen and water, filling argon and heating to 230-;
then injecting sulfur oleylamine solution by a hot injection method, fully reacting, cooling to stop the reaction, adding a centrifugal solvent after the mixture reaches room temperature, centrifugally separating the solution to precipitate the nano-crystals, and adjusting the proportion of metal salt in reactants to realize the adjustment and control of the defects and the energy band structure of the CZTS nano-crystal photocatalyst; obtaining a quaternary nanocrystal photoelectric material;
the self-doping strategy includes:
s1, under the premise that the total metal salt mole number is not changed, replacing one metal cation contained in the quaternary nanocrystal photoelectric material by another metal cation contained in the quaternary nanocrystal photoelectric material: replacing monohydrate copper acetate with dihydrate zinc acetate, wherein the replaced amount accounts for 0-100% of the original copper metal salt, and synthesizing a series of single-element self-doped copper-zinc-tin-sulfur nanocrystals; or replacing tin chloride pentahydrate with zinc acetate dihydrate, wherein the replaced amount accounts for 0-100% of the original tin metal salt, and synthesizing a series of single-element self-doped copper-zinc-tin-sulfur nanocrystals; or,
s2, under the premise that the total metal salt mole number is not changed, replacing the other two metal cations contained in the material by one metal cation contained in the quaternary nanocrystal photoelectric material: firstly, replacing copper acetate monohydrate with zinc acetate dihydrate in an amount accounting for 0-50% of the original copper metal salt, and then replacing tin chloride pentahydrate with zinc acetate dihydrate in an amount accounting for 0-50% of the original tin metal salt to synthesize a series of multi-element self-doped copper-zinc-tin-sulfur nanocrystals; or zinc acetate dihydrate is used for replacing tin chloride pentahydrate, the replaced amount accounts for one proportion of 0-50% of the original tin metal salt, the zinc acetate dihydrate is used for replacing copper acetate monohydrate, the replaced amount accounts for 0-50% of the original copper metal salt, and a series of multi-element self-doped copper-zinc-tin-sulfur nanocrystals are synthesized;
adjusting the self element to replace other elements to form self doping to adjust the defect and the energy band structure, wherein the molar ratio of the copper acetate monohydrate, the zinc acetate dihydrate and the tin chloride pentahydrate is (1-2): 1-2.4): 0.5-1;
the nano-crystalline photoelectric material is obtained by replacing copper element and tin element with zinc element, and after the nano-crystalline photoelectric material is prepared into a film by an electrophoretic deposition method, under the illumination of a xenon lamp, the photocurrent is 0.01-0.6mA/cm-2。
2. The method for preparing the self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material according to claim 1, wherein the molar ratio of copper acetate monohydrate, zinc acetate dihydrate and tin chloride pentahydrate is 1.2:1.8: 1.
3. The method according to claim 1, wherein the molar ratio of copper acetate monohydrate, zinc acetate dihydrate to tin chloride pentahydrate is 1.2:2.2: 0.6.
4. The method for preparing the self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material according to claim 1, wherein the conditions of removing oxygen and water are that the temperature is kept at 135 ℃ for 60-120 minutes in a vacuum state.
5. The method as claimed in claim 1, wherein the temperature of the oleylamine solution of sulfur powder is 230-250 ℃ when it is heated.
6. The method for preparing the self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material according to claim 1, wherein the sufficient reaction time is 50-80 minutes.
7. The method for preparing the self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material according to claim 1, wherein the centrifugal solvent is isopropanol.
8. The method for preparing the self-doped copper-zinc-tin-sulfur nanocrystalline photovoltaic material according to claim 1, wherein in the step 1), the prepared quaternary nanocrystals are dispersed in hexane.
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