CN108842159B - Preparation method and application of cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity - Google Patents
Preparation method and application of cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity Download PDFInfo
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- CN108842159B CN108842159B CN201810632306.7A CN201810632306A CN108842159B CN 108842159 B CN108842159 B CN 108842159B CN 201810632306 A CN201810632306 A CN 201810632306A CN 108842159 B CN108842159 B CN 108842159B
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 230000000694 effects Effects 0.000 title claims abstract description 22
- 239000002070 nanowire Substances 0.000 title claims abstract description 22
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 150000001661 cadmium Chemical class 0.000 claims abstract description 9
- 150000001413 amino acids Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 46
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 46
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 45
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 45
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 27
- 235000018417 cysteine Nutrition 0.000 claims description 27
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 27
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 235000001014 amino acid Nutrition 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical group [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000003828 vacuum filtration Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 46
- 238000009210 therapy by ultrasound Methods 0.000 description 46
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 24
- 239000004471 Glycine Substances 0.000 description 23
- 238000005119 centrifugation Methods 0.000 description 23
- 239000011541 reaction mixture Substances 0.000 description 23
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention discloses a preparation method of a cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity, which comprises the following steps: a, dissolving cadmium salt in an organic solvent at room temperature, adding CNT with the mole percentage of 0-5%, uniformly mixing, adding a certain amount of amino acid, uniformly stirring, transferring into a microwave reaction kettle, and reacting for 0.5-2 hours at the temperature of 150-; after cooling to room temperature, washing with water and ethanol, centrifuging, and drying to obtain a sample A; b: preparing a sample A into an aqueous solution, dripping a proper amount of aqueous solution on a clean flexible substrate, performing suction filtration through a vacuum pump, and loading a catalyst on the surface of the flexible substrate; after drying, the mixture is placed into a muffle furnace for roasting at the temperature of 150-350 ℃, so that the interaction between the catalyst and the substrate is enhanced.
Description
Technical Field
The invention relates to a preparation method of a cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity and application of the electrode.
Background
Environmental and energy issues are one of the major challenges currently facing the world. Hydrogen is widely considered as a clean energy carrier in the future in many applications, such as environmental vehicles, home heating, and power plants. The photocatalytic hydrolysis hydrogen production is a most promising way for realizing hydrogen economic benefits because the photocatalytic hydrolysis hydrogen production utilizes inexhaustible solar energy in nature as an energy source. The photocatalysis technology has the advantages of mild reaction conditions, low energy consumption, less secondary pollution and the like, and has very important application prospects in the aspects of environment and energy. However, in the process of producing hydrogen by photocatalysis of a common photocatalyst, photo-generated electron-hole pairs are easy to recombine in the process of transferring the photo-generated electron-hole pairs to the surface in the catalyst, and reverse reaction of producing hydrogen by photocatalysis is easy to occur, so that the total efficiency of converting light energy into hydrogen energy is low. Most of the commonly used catalysts in the prior art are powder systems, and have the defects of difficult recovery and fixation and difficult practical application.
Disclosure of Invention
The invention aims to solve the technical problems that photocatalytic hydrogen production electron holes are easy to compound and the hydrogen production efficiency is low in the prior art, and provides a preparation method of a cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity.
The technical problem to be solved can be implemented by the following technical scheme.
A preparation method of a cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity comprises the following steps:
a, dissolving cadmium salt in an organic solvent at room temperature to prepare a solution (preferably 0.025M) with the concentration of 0.01-0.1M, adding CNT with the molar percentage of 0-5%, uniformly mixing, adding a certain amount of amino acid with the molar ratio of 1: 1-3: 1 to the added cadmium salt, uniformly stirring, transferring the mixture into a microwave reaction kettle for 0.5-2 hours at the reaction temperature of 150-300 ℃; after cooling to room temperature, washing with water and ethanol, centrifuging, and drying to obtain a sample A;
b, preparing a sample A into L aqueous solution with the concentration of 1-5 mg/m (preferably 2mg/m L), dripping a proper amount of aqueous solution on a clean flexible substrate, performing suction filtration through a vacuum pump, and loading the synthesized cadmium sulfide nanowire and carbon nanotube composite material on the surface of the flexible substrate;
wherein the organic solvent is ethylenediamine or triethanolamine, preferably ethylenediamine;
the amino acid is cysteine.
As a further improvement of the technical scheme, the cadmium salt is selected from one of cadmium sulfate, cadmium nitrate and cadmium acetate, and cadmium nitrate is preferred.
As a further improvement of the present invention, the molar percentage of the CNTs is 1%, 1.5%, 2%, 3%, 4% or 5%, preferably 1.5%.
Further, the flexible substrate is a stainless steel mesh, copper foam, nickel foam, or titanium sheet, preferably a stainless steel mesh.
In addition, in step A, the molar ratio of amino acid to added cadmium salt is 1:1, or 2:1, or 3: 1.
The invention also aims to provide an application of the composite flexible electrode obtained by the preparation method.
The method comprises the following steps:
1) mounting the prepared flexible electrode on the anode of an electrochemical double-cell, wherein the cathode adopts a platinum sheet, and the reference electrode is silver chloride;
2) respectively adding 30-60ml (preferably 50 ml) of sodium sulfate solution and 5-20ml (preferably 20 ml) of methanol at two sides of the double pool;
3) introducing nitrogen into the double tanks to drive off air, and then sealing;
4) irradiating anode with xenon lamp source with wavelength of 420nm or more for 1H, measuring gas in 0.2-0.8m L (preferably 0.5 ml) with gas sampler via sealed silicon rubber plug, and detecting H with gas chromatograph2The amount of (c).
The cadmium sulfide nanowire and CNT flexible electrode provided by the invention is used for synthesizing a composite material of the cadmium sulfide nanowire and the CNT in situ by a microwave method, has good crystallinity and provides more transmission channels for rapid conduction of photo-generated electrons. The catalyst is loaded on a stainless steel substrate, forms a three-dimensional net structure with a stainless steel net, has more electron transmission channels, is manufactured into a flexible electrode for photoelectrocatalysis hydrogen production, has higher photoelectrocatalysis hydrogen production activity, and has the highest hydrogen production amount of the catalyst per unit time and unit mass in the current searched literature. Greatly improves the hydrogen production activity and has great application prospect.
The product prepared by the invention is subjected to structural characterization by adopting the following means of carrying out structural analysis on a sample by adopting X-ray diffraction measured on a Rigaku D2000 model X-ray diffractometer in Japan, and analyzing the morphological structure of the sample by adopting a scanning electron microscope photo obtained by a HITACHI S4800 model scanning electron microscope in Japan and a transmission electron microscope photo obtained by a high-resolution transmission electron microscope in JEM 2010 model Japan JEO L.
Compared with the prior art, the invention has the following advantages and outstanding effects: the chemical reagents used in the invention are all common reagents, and are cheap and easy to obtain.
Drawings
The following detailed description of embodiments of the invention refers to the accompanying drawings.
FIG. 1 is a scanning electron microscope image of the CdS and CNT composite material; from the figure, it can be seen that the cadmium sulfide nanowires synthesized in situ by the microwave method have very uniform morphological characteristics.
FIG. 2 is a transmission electron microscope image of the CdS and CNT composite material; the transmission electron microscope image shows that the synthesized cadmium sulfide nano-wire and the carbon nano-tube are mutually interwoven and closely contacted.
FIG. 3 is an XRD pattern of the resulting highly hydrogen producing active material; the abscissa is angle, and the ordinate is intensity, and the XRD spectrum shows that the cadmium sulfide nanowire and carbon nanotube composite material synthesized in situ by the microwave method has good crystallinity.
Detailed Description
The invention will now be described in greater detail, clearly and completely, with reference to specific examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
In the specific embodiment of the invention, the uniform cadmium sulfide and CNT composite material with the shape of a nanowire structure is obtained by optimizing the reaction temperature, the reaction time, the microwave power, the CNT content, the ethylenediamine content and the cysteine content, and the composite material has good crystallinity, and the photocatalytic hydrogen production test also proves that the composite material has good activity. The reaction temperature, the reaction time and the microwave power mainly influence the growth process of the cadmium sulfide crystal, and the contents of CNT, ethylenediamine and cysteine mainly influence the appearance and hydrogen production activity of the cadmium sulfide. The specific embodiment content is as follows:
example 1
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 2
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 180 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 3
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 200 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 4
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 220 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 5
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 70min at 220 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 6
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 80min at 220 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 7
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 90min at 220 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 8
Dissolving 0.013g CNT and 0.3g cadmium sulfate or cadmium nitrate in 40ml ethylene diamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g glycine or cysteine, and continuing ultrasonic treatment and stirring until the solution is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 9
Dissolving 0.026g CNT and 0.3g cadmium sulfate or cadmium nitrate in 40ml ethylene diamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g glycine or cysteine, and continuing ultrasonic treatment and stirring until dissolving. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 10
Dissolving 0.039g CNT and 0.3g cadmium sulfate or cadmium nitrate in 40ml ethylene diamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g glycine or cysteine, and continuing ultrasonic treatment and stirring until the components are dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 11
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 50ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 12
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 60ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 13
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 70ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 14
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 80ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 15
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.6g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 16
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.7g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 17
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.8g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 18
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.9g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 19
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 1.0g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1200W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 20
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1000W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 21
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and microwave power of 1400W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 22
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1600W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
Example 23
Dissolving 0.3g of cadmium sulfate or cadmium nitrate in 40ml of ethylenediamine or triethanolamine, directly performing ultrasonic treatment and stirring in a microwave reaction kettle, adding 0.5g of glycine or cysteine, and continuously performing ultrasonic treatment and stirring until the cadmium sulfate or the cadmium nitrate is dissolved. Carrying out microwave reaction for 60min at 150 deg.C and 1800W. After the reaction was finished and cooled to room temperature, the reaction mixture was washed with water and ethanol by centrifugation and dried in vacuum.
The invention discloses a preparation method and application of a cadmium sulfide nanowire/carbon nanotube composite flexible electrode with high hydrogen production activity. The composite material of cadmium sulfide (CdS) nanowires and Carbon Nano Tubes (CNTs) is synthesized in situ by a microwave method, and is loaded on a stainless steel substrate by a suction filtration method, and a three-dimensional net structure is constructed between two materials with one-dimensional structures and a stainless steel net, so that the interaction between the materials is enhanced, more transmission channels are provided for the conduction of photo-generated electrons, the electron conduction efficiency is improved, and the higher photoelectrocatalytic hydrogen production activity is obtained. The flexible electrode of the cadmium sulfide and CNT composite material prepared by the invention has high hydrogen production activity and good flexibility, and has wide application prospects in the aspects of hydrogen production, energy storage, pollutant degradation, batteries and the like.
The obtained flexible electrode is used for producing hydrogen through photoelectrocatalysis, electrons are guided to the cathode by using external bias voltage, the recombination of the electrons and holes is effectively inhibited, and the hydrogen production activity is greatly improved.
Claims (8)
1. A preparation method of a cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity is characterized by comprising the following steps:
a, dissolving cadmium salt in an organic solvent at room temperature to prepare a solution with the concentration of 0.01-0.1M, adding CNT with the mole percentage of 0-5%, uniformly mixing, adding a certain amount of amino acid with the mole ratio of 1: 1-3: 1, uniformly stirring, transferring into a microwave reaction kettle for 0.5-2 hours at the reaction temperature of 150-; after cooling to room temperature, washing with water and ethanol, centrifuging, and drying to obtain a sample A;
b, preparing a sample A into L aqueous solution with the concentration of 1-5 mg/m, dripping a proper amount of aqueous solution on a clean flexible substrate, loading the synthesized cadmium sulfide nanowire and carbon nanotube composite material on the surface of the flexible substrate through vacuum filtration, drying, and roasting in a muffle furnace at the temperature of 150-350 ℃;
the organic solvent is one of ethylenediamine and triethanolamine;
the amino acid is cysteine.
2. The method for preparing the cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity as recited in claim 1, wherein the cadmium salt is selected from one of cadmium sulfate, cadmium nitrate and cadmium acetate.
3. The method for preparing the cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity as claimed in claim 1, wherein the molar percentage of the CNT is 1%, 1.5%, 2%, 3%, 4% or 5%.
4. The method for preparing the cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity as claimed in claim 1, wherein the flexible substrate is a stainless steel mesh, copper foam, nickel foam, copper mesh or titanium sheet.
5. The method for preparing the cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity as recited in claim 1, wherein in the step A, cadmium salt is dissolved in an organic solvent at room temperature to prepare a solution with a concentration of 0.025M, and in the step B, a sample A is prepared into an aqueous solution with a concentration of 2mg/M L.
6. The preparation method of the cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity as claimed in claim 1, wherein in the step A, the molar ratio of the amino acid to the added cadmium salt is 1:1 or 2:1 or 3: 1.
7. The application of the composite flexible electrode prepared by the preparation method of any one of claims 1 to 6 in a photoelectrocatalysis hydrogen production activity experiment comprises the following steps:
1) mounting the prepared flexible electrode on the anode of an electrochemical double-cell, wherein the cathode adopts a platinum sheet, and the reference electrode is silver chloride;
2) respectively adding 30-60ml of sodium sulfate solution and 5-20ml of methanol into two sides of the double pool;
3) introducing nitrogen into the double tanks to drive off air, and then sealing;
4) irradiating anode with xenon lamp source with wavelength of 420nm or more for 1H, measuring gas in 0.2-0.8m L reactor with gas sampler via sealed silicon rubber plug, and detecting H with gas chromatograph2The amount of (c).
8. Use according to claim 7, characterized in that it comprises the following steps:
1) mounting the prepared flexible electrode on the anode of an electrochemical double-cell, wherein the cathode adopts a platinum sheet, and the reference electrode is silver chloride;
2) respectively adding 50ml of sodium sulfate solution and 20ml of methanol into two sides of the double pool;
3) introducing nitrogen into the double tanks to drive off air, and then sealing;
4) irradiating anode with 420nm xenon lamp for 1H, measuring gas in 0.5m L reactor with gas sampler via sealed silicon rubber plug, and detecting H with gas chromatograph2The amount of (c).
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