CN114807969B - Preparation method of snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with near-infrared thermal enhancement electrocatalytic hydrogen production function - Google Patents
Preparation method of snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with near-infrared thermal enhancement electrocatalytic hydrogen production function Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 241000533950 Leucojum Species 0.000 title claims description 35
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 8
- 229920006362 Teflon® Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 150000003460 sulfonic acids Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004687 hexahydrates Chemical class 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 molybdenum sulfide compound Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 description 22
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of snowflake-shaped cuprous sulfide/molybdenum sulfide/platinum heterostructure with near infrared thermal enhancement electro-catalytic hydrogen production, which constructs the snowflake-shaped cuprous sulfide/molybdenum sulfide/platinum heterostructure through a two-step hydrothermal method and an electrochemical deposition method, and the determined cuprous sulfide composite material with the addition mass of 45 mg of cuprous sulfide/molybdenum sulfide is the catalyst with the best performance, and shows the photo-thermal enhancement electro-catalytic hydrogen evolution performance under near infrared irradiation. After a small amount of platinum is electrochemically deposited, a Schottky barrier is formed between the platinum nano particles and the molybdenum sulfide nano sheets, so that the photo-thermal effect and hydrogen evolution performance of the composite material are further enhanced. The use of cuprous sulfide/molybdenum sulfide/platinum as an electrocatalyst allows for a low overpotential of 78 mV (@ 10 mV cm ‑2) with the aid of near infrared radiation.
Description
Technical Field
The invention relates to a preparation method of snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with near infrared thermal enhancement electro-catalytic hydrogen production, relates to a hydrogen evolution technology of a photo-thermal effect enhanced cuprous sulfide/molybdenum sulfide/platinum nano-composite generated under near infrared, and belongs to the technical field of preparation of glassy carbon electrodes modified by the cuprous sulfide/molybdenum sulfide/platinum nano-composite.
Background
Environmental problems caused by the emission of large amounts of carbon have currently attracted considerable attention in the world. China has formally decided to reduce the use of fossil fuels, and has greatly developed clean energy, thereby reducing carbon emissions. Hydrogen energy, one of the important members of clean energy, has received great attention over the last few years as a high heating value and zero carbon emissions. New hydrogen production and storage technologies have attracted increasing attention and have become a subject of hot spot research. Electrochemical and photoelectrochemical decomposition of aqueous hydrogen is an economical and green production route in addition to industrial processes that rely on fossil fuels. However, at present, noble metal catalysts such as platinum-based catalysts are expensive, and an inexpensive, efficient and stable electrocatalyst is highly desirable as an alternative product. Searching for efficient non-noble metal catalysts or reducing the amount of noble metal used has become the key point in the development of new catalysts at present. At the same time, magnetic or thermal assistance is also becoming a new solution to further increase the efficiency of catalytic hydrogen production.
Metal sulfides, including molybdenum sulfide (MoS 2), tungsten sulfide (WS 2), and copper sulfide (CuS x), have been widely used in hydrogen-producing catalysts. Among them, the composite material based on MoS 2 and Cu 2 S has been proven to be an excellent hydrogen-generating electrocatalyst because of its low hydrogen evolution overpotential. While some materials can convert near infrared light energy to thermal energy, including polymers, noble metal nanoparticles, metal sulfides, and metal oxides. Wherein, molybdenum sulfide and cuprous sulfide have excellent photo-thermal effect, and can be used for photo-thermal treatment, water purification and photo-catalytic degradation.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a preparation method of snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with near-infrared thermal enhancement electro-catalytic hydrogen production.
The purpose of the invention is realized in the following way: the preparation method of the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with the near-infrared thermal enhanced electrocatalytic hydrogen production effect is characterized by comprising the following steps of:
(1) Adding 2-6 mmol of copper chloride dihydrate and 6-10 mmol of thiourea into 60-80 ml of ethylenediamine solution, and mixing for 2-4 hours under magnetic stirring to obtain a first mixed solution;
(2) Filling the first mixed solution obtained in the step (1) into a 100 ml Teflon stainless steel reactor, heating in an oven at 60-100 ℃ for 8-10 hours, and then naturally cooling to room temperature;
(3) Centrifugally washing the product obtained in the step (2) with water and ethanol for several times respectively, and drying in a vacuum oven at 60 ℃ for 8-12 hours to obtain snowflake cuprous sulfide;
(4) Adding 60-100 mg of ammonium tetrathiomolybdate into a mixed solution consisting of 40-60 ml of dimethylformamide and 20-30 ml of deionized water, and performing ultrasonic dispersion for 30 minutes to obtain a second mixed solution;
(5) Adding 45 mg of snowflake-shaped cuprous sulfide obtained in the step (3) into the second mixed solution obtained in the step (4), performing ultrasonic dispersion for 30 minutes, and magnetically stirring for 30 minutes to obtain a third mixed solution;
(6) Filling the third mixed solution obtained in the step (5) into a 100 ml Teflon stainless steel reactor, heating in an oven at 200-210 ℃ for 18-22 hours, and then naturally cooling to room temperature;
(7) Centrifugally washing the product obtained in the step (6) with water and ethanol for several times respectively, and drying in a vacuum oven at 60 ℃ for 8-12 hours to obtain snowflake cuprous sulfide/molybdenum sulfide compound;
(8) Weighing 2-10 mg of snowflake cuprous sulfide/molybdenum sulfide composite powder obtained in the step (7), and adding the snowflake cuprous sulfide/molybdenum sulfide composite powder into a mixed solution composed of ionized water, ethanol and perfluorinated sulfonic acid resin to obtain a fourth mixed solution; uniformly mixing the fourth mixed solution by ultrasonic, dripping 3-6 microliters on the surface of a clean glassy carbon electrode, and drying for 30 minutes at room temperature;
(9) And (3) connecting the glassy carbon electrode treated in the step (8) into a three-electrode system consisting of a saturated calomel reference electrode and a stone mill rod counter electrode, and performing electrodeposition for 50-150 seconds under the potential of 0V (SCE) by taking a mixture consisting of 0.5 mol/L sulfuric acid and 0.001 mol/L chloroplatinic acid hexahydrate as electrolyte to prepare the snowflake cuprous sulfide/molybdenum sulfide/platinum nano-composite.
In the step (3), the solution is centrifuged at 6000-9000 rpm and washed for 4-6 times.
In the step (7), the solution is centrifuged at 8000-9000 rpm and washed for 4-6 times.
A method for detecting hydrogen evolution performance of snowflake cuprous sulfide/molybdenum sulfide/platinum nano-composite under acidic condition comprises the following steps:
a) Weighing 2-10 mg of snowflake cuprous sulfide/molybdenum sulfide/platinum nano-composite powder prepared in the method of claim 1, adding the snowflake cuprous sulfide/molybdenum sulfide/platinum nano-composite powder into a mixed solution composed of deionized water, ethanol and perfluorinated sulfonic acid resin, uniformly mixing the mixed solution by ultrasonic waves, dripping the mixed solution on the surface of a clean glassy carbon electrode, and drying at room temperature;
b) Forming a three-electrode system by the glassy carbon electrode treated in the step a), the saturated calomel electrode and the graphite rod counter electrode;
c) Placing the three-electrode system into a sulfuric acid solution of 0.5-1M, respectively determining the photoelectrocatalysis hydrogen evolution performance of the graphene-molybdenum sulfide/molybdenum oxide composite by a linear sweep voltammetry under two different conditions of darkness and near infrared light, and preparing a overpotential map of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite under different light conditions;
Under the condition of near infrared light irradiation, the hydrogen evolution performance of the snowflake cuprous sulfide/molybdenum sulfide/platinum nano-composite is obviously enhanced.
In the step a), the volume of deionized water is 0.5-1.1 milliliters, the volume of ethanol is 0.1-0.3 milliliters, and the volume of perfluorosulfonic acid is 20-80 milliliters.
In step c), the potential range of the linear sweep voltammetry is-0.8 to 0.1V.
The cuprous sulfide/molybdenum sulfide/platinum nanocomposite capable of generating a photo-thermal effect under near infrared so as to enhance hydrogen evolution provides a new thought for the design of high-efficiency electrocatalytic hydrogen evolution materials.
Compared with the prior art, the invention has the following beneficial effects:
1. The too high and too low amount of the cuprous sulfide in the step 5) is unfavorable for the electrocatalytic hydrogen evolution reaction, and the best electrochemical hydrogen evolution performance is obtained by adopting 45 mg of the cuprous sulfide to prepare the composite cuprous sulfide/molybdenum sulfide/platinum.
2. In the step c), under the condition of near infrared light irradiation, the hydrogen evolution performance of the cuprous sulfide/molybdenum sulfide/platinum nano-composite is obviously enhanced.
The snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure is constructed through a two-step hydrothermal method and an electrochemical deposition method. The determined cuprous sulfide/molybdenum sulfide composite material with the addition mass of 45 mg is the catalyst with the best performance, and the catalyst shows the photo-thermal enhanced electrocatalytic hydrogen evolution performance under near infrared irradiation. After a small amount of platinum is electrochemically deposited, a Schottky barrier is formed between the platinum nano particles and the molybdenum sulfide nano sheets, so that the photo-thermal effect and hydrogen evolution performance of the composite material are further enhanced. The use of cuprous sulfide/molybdenum sulfide/platinum as an electrocatalyst allows for a low overpotential of 78 mV (@ 10 mV cm -2) with the aid of near infrared radiation.
Drawings
FIG. 1 is a scanning transmission electron microscope image of a cuprous sulfide/molybdenum sulfide/platinum nanocomposite of example 1 of the present invention.
Figure 2 is an X-ray diffraction pattern of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite of example 2 of the present invention.
FIG. 3 is a graph showing the change of the surface temperature of the electrode surface with time under irradiation of near infrared light in 0.5 mol/liter of sulfuric acid of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite of example 3 of the present invention.
FIG. 4 is a graph showing the overpotential of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite of example 4 of the present invention under various light conditions in alkali.
Detailed Description
The preparation of graphene-molybdenum sulfide/molybdenum oxide composites is further described in connection with specific examples.
Example 1:
(1) Adding 2 mmol of copper chloride dihydrate and 6 mmol of thiourea into 60 ml of ethylenediamine solution, and mixing for 2 hours under magnetic stirring to obtain a first mixed solution;
(2) Charging the first mixed solution obtained in the step (1) into a 100 ml Teflon stainless steel reactor, heating the reactor in an oven at 80 ℃ for 8 hours, and then naturally cooling the reactor to room temperature;
(3) Centrifugally washing the product obtained in the step (2) with water and ethanol for 3 times respectively, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain snowflake cuprous sulfide;
(4) Adding 100 mg of ammonium tetrathiomolybdate into a mixed solution consisting of 50 ml of dimethylformamide and 25ml of deionized water, and performing ultrasonic dispersion for 30 minutes to obtain a second mixed solution;
(5) Adding 45 mg of snowflake-shaped cuprous sulfide into the second mixed solution obtained in the step (4), performing ultrasonic dispersion for 30 minutes, and magnetically stirring for 30 minutes to obtain a third mixed solution;
(6) Filling the third mixed solution obtained in the step (5) into a 100 ml Teflon stainless steel reactor, heating the mixed solution in an oven at 210 ℃ for 18 hours, and then naturally cooling the mixed solution to room temperature;
(7) Centrifugally washing the product obtained in the step (6) with water and ethanol for several times respectively, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain snowflake cuprous sulfide/molybdenum sulfide compound;
(8) 5 mg of snowflake-shaped cuprous sulfide/molybdenum sulfide composite powder obtained in the step (7) is weighed and added into a mixed solution composed of ionized water, ethanol and perfluorinated sulfonic acid resin to obtain a fourth mixed solution. And uniformly mixing the fourth mixed solution by ultrasonic, taking 5 microliters to be dripped on the surface of the clean glassy carbon electrode, and drying for 30 minutes at room temperature.
(9) And (3) connecting the glassy carbon electrode treated in the step (8) into a three-electrode system consisting of a saturated calomel reference electrode and a stone mill rod counter electrode, and electrodepositing for 100 seconds at a potential of 0V (SCE) by taking a mixture consisting of 0.5 mol/L sulfuric acid and 0.001 mol/L chloroplatinic acid hexahydrate as electrolyte to prepare the snowflake cuprous sulfide/molybdenum sulfide/platinum nanocomposite.
FIG. 1 is a scanning electron microscope image of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite prepared in example 1.
Example 2:
(1) Adding 2 mmol of copper chloride dihydrate and 6 mmol of thiourea into 60 ml of ethylenediamine solution, and mixing for 2 hours under magnetic stirring to obtain a first mixed solution;
(2) Charging the first mixed solution obtained in the step (1) into a 100 ml Teflon stainless steel reactor, heating the reactor in an oven at 80 ℃ for 8 hours, and then naturally cooling the reactor to room temperature;
(3) Centrifugally washing the product obtained in the step (2) with water and ethanol for 3 times respectively, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain snowflake cuprous sulfide;
(4) Adding 100 mg of ammonium tetrathiomolybdate into a mixed solution consisting of 50 ml of dimethylformamide and 25ml of deionized water, and performing ultrasonic dispersion for 30 minutes to obtain a second mixed solution;
(5) Adding 45 mg of snowflake-shaped cuprous sulfide into the second mixed solution in the step (4), performing ultrasonic dispersion for 30 minutes, and magnetically stirring for 3 minutes to obtain a third mixed solution;
(6) Filling the third mixed solution obtained in the step (5) into a 100ml Teflon stainless steel reactor, heating the third mixed solution in a baking oven at 210 ℃ for 18 hours, and then naturally cooling the third mixed solution to room temperature;
(7) Centrifugally washing the product obtained in the step (6) with water and ethanol for several times respectively, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain snowflake cuprous sulfide/molybdenum sulfide compound;
(8) 6 mg of snowflake-shaped cuprous sulfide/molybdenum sulfide composite powder obtained in the step (7) is weighed and added into a mixed solution composed of ionized water, ethanol and perfluorinated sulfonic acid resin to obtain a fourth mixed solution. And uniformly mixing the fourth mixed solution by ultrasonic, taking 5 microliters to be dripped on the surface of the clean glassy carbon electrode, and drying for 30 minutes at room temperature.
(9) Connecting the glassy carbon electrode treated in the step (8) into a three-electrode system consisting of a saturated calomel reference electrode and a stone mill rod counter electrode, and performing electrodeposition for 100 seconds under the potential of 0V (SCE) by taking a mixture consisting of 0.5 mol/L sulfuric acid and 0.001 mol/L chloroplatinic acid hexahydrate as electrolyte to prepare snowflake cuprous sulfide/molybdenum sulfide/platinum nano-composite;
The crystal structure of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite is shown in fig. 2, from which it can be determined that the composite is composed of cuprous sulfide, molybdenum sulfide and platinum.
The method for providing the cuprous sulfide/molybdenum sulfide/platinum nanocomposite with excellent electrochemical hydrogen evolution performance in the present invention is further described with reference to specific examples.
Example 3
A) 4 mg of snowflake cuprous sulfide/molybdenum sulfide/platinum nanocomposite powder was weighed and added to a mixed solution composed of deionized water, ethanol and perfluorosulfonic acid resin. And uniformly mixing the mixed solution by ultrasonic, dripping the mixed solution on the surface of a clean glassy carbon electrode, and drying at room temperature.
B) Forming a three-electrode system by the glassy carbon electrode obtained in the step a), the saturated calomel electrode and the stone mill rod counter electrode;
c) The three electrode system was placed in a 0.5M sulfuric acid solution, the electrode surface was irradiated with near infrared light and the electrode surface temperature was measured.
Fig. 3 shows the change curves of the electrode surface temperature increase with time under near infrared light irradiation of the surface of cuprous sulfide, molybdenum sulfide, cuprous sulfide/platinum and bare glassy carbon electrode.
Example 4
A) 5 mg of snowflake cuprous sulfide/molybdenum sulfide/platinum nanocomposite powder was weighed and added to a mixed solution composed of deionized water, ethanol and perfluorosulfonic acid resin. And uniformly mixing the mixed solution by ultrasonic, dripping the mixed solution on the surface of a clean glassy carbon electrode, and drying at room temperature.
B) Forming a three-electrode system by the glassy carbon electrode treated in the step a), the saturated calomel electrode and the stone mill rod counter electrode;
c) And placing the three-electrode system into a 0.5M sulfuric acid solution, respectively determining the photoelectrocatalysis hydrogen evolution performance of the graphene-molybdenum sulfide/molybdenum oxide composite by a linear sweep voltammetry under two different conditions of darkness and near infrared light, and preparing a overpotential map of the cuprous sulfide/molybdenum sulfide/platinum nanocomposite under different light conditions.
Fig. 4 shows the overpotential map for the presence or absence of near infrared radiation of cuprous sulfide, molybdenum sulfide, cuprous sulfide/molybdenum sulfide and cuprous sulfide/molybdenum sulfide/platinum in 0.5M sulfuric acid. As can be seen from fig. 4, cuprous sulfide, molybdenum sulfide, cuprous sulfide/molybdenum sulfide and cuprous sulfide/molybdenum sulfide/platinum show better electrocatalytic hydrogen production performance under near infrared irradiation than under darkness, and the cuprous sulfide/molybdenum sulfide/platinum can achieve a low overpotential of 78 mV (@ 10 mV cm -2) with the aid of near infrared irradiation.
Claims (6)
1. The preparation method of the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with the near-infrared thermal enhanced electrocatalytic hydrogen production effect is characterized by comprising the following steps of:
(1) Adding 2-6 mmol of copper chloride dihydrate and 6-10 mmol of thiourea into 60-80 ml of ethylenediamine solution, and mixing for 2-4 hours under magnetic stirring to obtain a first mixed solution;
(2) Filling the first mixed solution obtained in the step (1) into a 100 ml Teflon stainless steel reactor, heating in an oven at 60-100 ℃ for 8-10 hours, and then naturally cooling to room temperature;
(3) Centrifugally washing the product obtained in the step (2) with water and ethanol for several times respectively, and drying in a vacuum oven at 60 ℃ for 8-12 hours to obtain snowflake cuprous sulfide;
(4) Adding 60-100 mg of ammonium tetrathiomolybdate into a mixed solution consisting of 40-60 ml of dimethylformamide and 20-30 ml of deionized water, and performing ultrasonic dispersion for 30 minutes to obtain a second mixed solution;
(5) Adding 45 mg of snowflake-shaped cuprous sulfide obtained in the step (3) into the second mixed solution obtained in the step (4), performing ultrasonic dispersion for 30 minutes, and magnetically stirring for 30 minutes to obtain a third mixed solution;
(6) Filling the third mixed solution obtained in the step (5) into a 100 ml Teflon stainless steel reactor, heating in an oven at 200-210 ℃ for 18-22 hours, and then naturally cooling to room temperature;
(7) Centrifugally washing the product obtained in the step (6) with water and ethanol for several times respectively, and drying in a vacuum oven at 60 ℃ for 8-12 hours to obtain snowflake cuprous sulfide/molybdenum sulfide compound;
(8) Weighing 2-10 mg of snowflake cuprous sulfide/molybdenum sulfide composite powder obtained in the step (7), and adding the snowflake cuprous sulfide/molybdenum sulfide composite powder into a mixed solution composed of ionized water, ethanol and perfluorinated sulfonic acid resin to obtain a fourth mixed solution; uniformly mixing the fourth mixed solution by ultrasonic, dripping 3-6 microliters on the surface of a clean glassy carbon electrode, and drying for 30 minutes at room temperature;
(9) And (3) connecting the glassy carbon electrode treated in the step (8) into a three-electrode system consisting of a saturated calomel reference electrode and a stone mill rod counter electrode, and performing electrodeposition for 50-150 seconds under the potential of 0V (SCE) by taking a mixture consisting of 0.5mol/L sulfuric acid and 0.001 mol/L chloroplatinic acid hexahydrate as electrolyte to prepare the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure.
2. The preparation method of the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with the near-infrared thermal enhanced electrocatalytic hydrogen production effect, which is disclosed in claim 1, is characterized in that in the step (3), the solution centrifugation condition is 6000-9000 rpm, and the washing times are 4-6 times.
3. The preparation method of the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure with the near-infrared thermal enhanced electrocatalytic hydrogen production effect, which is disclosed in claim 1, is characterized in that in the step (7), the solution centrifugation condition is 8000-9000 rpm, and the washing times are 4-6 times.
4. The method for detecting the hydrogen evolution performance of the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure under the acidic condition is characterized by comprising the following steps of:
a) Weighing 2-10 mg of snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure powder prepared in the method of claim 1, adding the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure powder into a mixed solution composed of deionized water, ethanol and perfluorinated sulfonic acid resin, uniformly mixing the mixed solution by ultrasonic, dripping the mixed solution on the surface of a clean glassy carbon electrode, and drying at room temperature;
b) Forming a three-electrode system by the glassy carbon electrode treated in the step a), the saturated calomel electrode and the graphite rod counter electrode;
c) Placing the three-electrode system into a sulfuric acid solution of 0.5-1M, respectively determining the photoelectrocatalysis hydrogen evolution performance of the cuprous sulfide/molybdenum sulfide/platinum heterostructure by a linear sweep voltammetry under two different conditions of darkness and near infrared light, and preparing a overpotential map of the cuprous sulfide/molybdenum sulfide/platinum heterostructure under different light conditions;
Under the condition of near infrared light irradiation, the hydrogen evolution performance of the snowflake cuprous sulfide/molybdenum sulfide/platinum heterostructure is obviously enhanced.
5. The method according to claim 4, wherein in the step a), the deionized water has a volume of 0.5 to 1.1 ml, the ethanol has a volume of 0.1 to 0.3 ml, and the perfluorosulfonic acid resin has a volume of 20to 80 μl.
6. The method according to claim 4, wherein in the step c), the potential range of the linear sweep voltammetry is-0.8 to 0.1V.
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| CN107262116A (en) * | 2017-05-31 | 2017-10-20 | 武汉理工大学 | A kind of hierarchy MoS2/Cu2S composites and preparation method thereof |
| CN109524677A (en) * | 2018-12-03 | 2019-03-26 | 浙江师范大学 | The preparation method and applications of molybdenum sulfide Supported Pt Nanoparticles electrocatalysis material |
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| CN107262116A (en) * | 2017-05-31 | 2017-10-20 | 武汉理工大学 | A kind of hierarchy MoS2/Cu2S composites and preparation method thereof |
| CN109524677A (en) * | 2018-12-03 | 2019-03-26 | 浙江师范大学 | The preparation method and applications of molybdenum sulfide Supported Pt Nanoparticles electrocatalysis material |
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