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
- Publication number
- CN109761266B CN109761266B CN201811612190.7A CN201811612190A CN109761266B CN 109761266 B CN109761266 B CN 109761266B CN 201811612190 A CN201811612190 A CN 201811612190A CN 109761266 B CN109761266 B CN 109761266B
- Authority
- CN
- China
- Prior art keywords
- zinc
- tin
- copper
- self
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 39
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 150000003839 salts Chemical class 0.000 claims abstract description 62
- 239000002159 nanocrystal Substances 0.000 claims abstract description 59
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 52
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 50
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 229910052786 argon Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 14
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 14
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000011833 salt mixture Substances 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 48
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 32
- 239000011941 photocatalyst Substances 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 13
- 230000007547 defect Effects 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001652 electrophoretic deposition Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000003917 TEM image Methods 0.000 description 13
- 230000006872 improvement Effects 0.000 description 10
- 239000011135 tin Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910005728 SnZn Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811612190.7A CN109761266B (en) | 2018-12-27 | 2018-12-27 | Preparation method of self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811612190.7A CN109761266B (en) | 2018-12-27 | 2018-12-27 | Preparation method of self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109761266A CN109761266A (en) | 2019-05-17 |
| CN109761266B true CN109761266B (en) | 2021-01-19 |
Family
ID=66450898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811612190.7A Active CN109761266B (en) | 2018-12-27 | 2018-12-27 | Preparation method of self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109761266B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113044813B (en) * | 2019-12-26 | 2022-06-10 | 温州大学 | Copper-zinc-tin-selenium nanocrystal and synthesis method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060338A (en) * | 2015-07-29 | 2015-11-18 | 武汉理工大学 | Preparation method of phase-selective copper-zinc-tin-sulfur nano crystal |
| CN106629820B (en) * | 2016-09-09 | 2019-05-24 | 武汉理工大学 | Cu2ZnSnS4The controllable method for preparing of nanocrystalline material |
| CN106395886B (en) * | 2016-09-13 | 2018-03-06 | 昆明理工大学 | A kind of buergerite Cu2ZnSnS4Nanocrystalline large-scale producing method |
-
2018
- 2018-12-27 CN CN201811612190.7A patent/CN109761266B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109761266A (en) | 2019-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Cadmium sulfide-based nanomaterials for photocatalytic hydrogen production | |
| JP6883799B2 (en) | A method for producing a metal compound, a method for producing a photocatalyst, and a method for producing a photocatalyst complex. | |
| WO2014099842A1 (en) | Photo-catalytic systems for the production of hydrogen | |
| CN105289690B (en) | A kind of CuS@g C3N4Composite visible light catalyst and its preparation method and application | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| TWI421214B (en) | Fabrication method for ibiiiavia-group amorphous compound and ibiiiavia-group amorphous precursor for thin-film solar cell | |
| CN110624563A (en) | Preparation method of silver ion doped zinc thioindate heterojunction photocatalyst | |
| CN112875755A (en) | Preparation method of bismuth tungstate nano powder | |
| Jiang et al. | Visible light photocatalytic H2-production activity of epitaxial Cu2ZnSnS4/ZnS heterojunction | |
| CN109761266B (en) | Preparation method of self-doped copper-zinc-tin-sulfur nanocrystalline photoelectric material | |
| CN104810159B (en) | Preparation method for tin-doped indium phosphide quantum dot sensitized solar cell | |
| CN113643902B (en) | Copper indium selenium tellurium/cadmium sulfide core-shell structure quantum dot and preparation method thereof, and preparation method of photo-anode | |
| Li et al. | Regulating deep and shallow defects of CuInS2 quantum dots to enhance photocatalytic hydrogen production | |
| Ikhioya et al. | Optimization of erbium percentage molarity on cobalt selenide semiconductor material via spray pyrolysis deposition technique for photovoltaic application | |
| CN117585912A (en) | Preparation method of metal ion doped sulfur indium zinc/cadmium sulfide heterojunction nanorod array | |
| CN112978795B (en) | BaZrS3Preparation method and application of nanocrystalline | |
| CN116603541A (en) | Preparation method of photocatalyst for producing ethylene by reducing carbon dioxide | |
| CN112158879A (en) | Method for preparing CdS by low-temperature molten salt method and application of prepared CdS in photocatalysis field | |
| CN102191038A (en) | Method for preparing CdTe quantum dots in aqueous phase and at low temperature | |
| CN114653382B (en) | P-n type stannous sulfide-zinc stannate semiconductor material and preparation method and application thereof | |
| CN103586051B (en) | Composite metal sulfide photocatalyst, and preparation method and application thereof | |
| CN111013562B (en) | ZnO/In (OH) with different shapes 3 Preparation method of composite photocatalyst | |
| CN113122224B (en) | Quantum dot with core-shell structure, and preparation method and application thereof | |
| CN103877969B (en) | In (I) 2 O 3 ·InVO 4 Heterostructure composites and methods of making and using same | |
| CN104692450A (en) | Preparation method for solar battery materials with three-zone gap tin doped with copper, gallium and sulphur |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |