CN111450848A - Preparation method of CuS nano-dot material and application of CuS nano-dot material in electrocatalytic carbon dioxide reduction - Google Patents
Preparation method of CuS nano-dot material and application of CuS nano-dot material in electrocatalytic carbon dioxide reduction Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002096 quantum dot Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 32
- 230000009467 reduction Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 23
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 17
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 sulfur ions Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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Abstract
The invention belongs to the technical field of new energy materials and electrochemical catalysis, and aims to improve the activity and selectivity of a copper-based catalyst in electrocatalytic carbon dioxide reduction. On the one hand, relates to a preparation method of a CuS nano-dot material, which comprises the following steps: (1) dissolving copper chloride and polyvinylpyrrolidone in deionized water, and stirring until the solution is clear; (2) dissolving sodium sulfide in the clear solution in the step (1) under stirring; (3) and (3) reacting the mixed solution in the step (2), centrifuging and drying to obtain the CuS nanodots. Another aspect also relates to the use of the CuS nanodot material as a catalyst in electrocatalytic carbon dioxide reduction. The CuS nanodot material is prepared from copper chloride, polyvinylpyrrolidone and sodium sulfide as raw materials by a hydrothermal method, the operation is simple, the implementation is easy, and the obtained CuS nanodot materialThe material has excellent catalytic activity and selectivity for carbon dioxide reduction, and can be used as a catalyst for electrocatalytic carbon dioxide reduction on CH4Has higher selectivity.
Description
Technical Field
The invention belongs to the technical field of new energy materials and electrochemical catalysis, and particularly relates to a preparation method of a CuS nano-dot material and application of the CuS nano-dot material in electrocatalysis of carbon dioxide reduction.
Background
In recent decades, with the progress and development of science and technology and the excessive development and consumption of fossil fuels, the global temperature is continuously raised due to the over-standard emission of carbon dioxide, and the global climate is continuously worsened by the greenhouse effect, so that the problem of carbon dioxide is urgently needed to be solved. Meanwhile, carbon dioxide is a rich C1 resource, and if it can be fully utilized, it can relieve the pressure on energy and environment. Electrocatalysis of carbon dioxide is also widely concerned because of the advantages of simple operation, environmental friendliness and the like. At present, the electrocatalytic carbon dioxide reduction focuses on preparing electrode materials with high catalytic activity, selectivity and stability. Therefore, finding a suitable electrode catalyst material has been a way to solve the problem.
At present, metal catalysts for electrocatalytic carbon dioxide reduction can be roughly classified into four types according to the difference in reduction products. The first type: lead, mercury, indium, tin, cadmium and other metals, and HCOO is easily generated in the reaction process－The reduced product mainly comprises formic acid and formate; the second type: metals such as gold, silver, zinc, palladium, gallium and the like, and the catalyst has the characteristics of poor stability on CO, and the product is mainly CO; in the third category: nickel, iron, platinum and titanium, and the main product of the catalyst is H due to the low hydrogen evolution over potential of the catalyst2(ii) a The fourth type: metallic copper, the products of which are mainly hydrocarbons and alcohols. Copper is by far the only single metal catalyst that can electrochemically reduce carbon dioxide to a high value and high energy density product.
In recent years, the development of new non-copper based catalysts has shown electrocatalytic reduction of carbon dioxide to C2+The product capacity, but the product yield is low, limiting the further use of these catalysts. Copper is unique as a carbon dioxide reduction electrocatalyst in that it is the only metal that has negative adsorption energy for CO (an important carbon dioxide reduction intermediate) and positive adsorption energy for H (an intermediate in the hydrogen evolution reaction). Studies have shown that poly-crystalline copper foil produces over 16 different products, which is a huge challenge to its selectivity. Therefore, how to change the structure of the copper-based catalyst to increase the activity and selectivity of electrocatalytic carbon dioxide reduction has important practical significance.
Disclosure of Invention
The invention aims to improve the activity and selectivity of a copper-based catalyst in electrocatalytic carbon dioxide reduction, and provides a preparation method of a CuS nanodot material and application of the CuS nanodot material in electrocatalytic carbon dioxide reduction. The CuS nano-dot material provided by the invention has high activity and selectivity.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a CuS nanodot material specifically comprises the following steps:
(1) dissolving copper chloride and polyvinylpyrrolidone in deionized water, and stirring until the solution is clear;
(2) dissolving sodium sulfide in the clear solution in the step (1) under stirring;
(3) and (3) reacting the mixed solution in the step (2), centrifuging and drying to obtain the CuS nanodots.
Furthermore, the adding amount ratio of the copper chloride, the polyvinylpyrrolidone and the deionized water in the step (1) is (20-30) mg, (50-70) mg, (2-8) m L.
Further, in the step (1), the adding amount ratio of the copper chloride to the polyvinylpyrrolidone to the deionized water is 21mg:60mg:5m L.
Further, the molecular weight of the polyvinylpyrrolidone in the step (1) is one of 8000, 24000, 40000 and 90000.
Furthermore, the adding amount ratio of the copper chloride, the polyvinylpyrrolidone, the sodium sulfide and the deionized water in the step (2) is (20-30) mg, (50-70) mg, (20-40) mg, (2-8) m L.
Further, in the step (2), the adding amount ratio of the copper chloride to the polyvinylpyrrolidone to the sodium sulfide to the deionized water is 21mg to 60mg to 30mg to 5m L.
Further, the reaction temperature of the mixed solution in the step (3) is 70-120 ℃, and the reaction time is 10-60 min.
Further, the product obtained by the reaction in the step (3) is centrifuged by ethanol.
Further, the drying temperature in the step (3) is 30-80 ℃, and the drying time is 2-6 h.
The invention also provides application of the CuS nano-dot material as a catalyst in electrocatalysis of carbon dioxide reduction.
The CuS nanodot material is prepared from copper chloride, polyvinylpyrrolidone and sodium sulfide serving as raw materials by a hydrothermal method, the operation is simple, the implementation is easy, the obtained CuS nanodot material has excellent carbon dioxide reduction catalytic activity and selectivity, and the CuS nanodot material is used as a catalyst for electrocatalysis of carbon dioxide reduction to CH4Has higher selectivity, and the highest Faraday efficiency can reach 27.7 percent.
Drawings
Fig. 1 is an SEM image of the catalytic CuS nanodots of example 1;
FIG. 2 is a TEM image of CuS nanodots as a catalyst in example 1;
FIG. 3 is an XRD pattern of CuS nanodots of the catalyst of example 1;
fig. 4 is an XPS diagram of the 2p orbitals of Cu of the catalytic CuS nanodots of example 1;
fig. 5 is an XPS diagram of the 2p orbitals of the S of the catalytic CuS nanodots of example 1;
FIG. 6 is a time and current curve at-1.4V vs. Ag/AgCl for the catalyst CuS nanodot catalyst of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and the accompanying drawings.
Example 1:
a preparation method of a CuS nanodot material comprises the following steps:
(1) adding 21mg of copper chloride and 60mg of polyvinylpyrrolidone with molecular weight of 40000 into 5m L deionized water, and stirring at room temperature for 30min to uniformly disperse the copper chloride and the polyvinylpyrrolidone;
(2) adding 30mg of sodium sulfide into the mixed solution in the step (1), and stirring at room temperature for 60min to uniformly disperse the sodium sulfide;
(3) and (3) transferring the uniformly dispersed mixed solution in the step (2) into a single-neck flask with the diameter of 20m L, stirring and reacting for 15min at the temperature of 90 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging by using ethanol, and washing for 3 times.
(4) And (4) drying the product which is centrifuged and washed in the step (3) for 4h at 60 ℃ under a vacuum condition to obtain the CuS nanodot material.
Preparation of a working electrode:
weighing 5mg of CuS nanodot catalyst, adding the CuS nanodot catalyst into a solution of isopropanol (1 m L) and Nafion (15 mu L), performing ultrasonic dispersion for half an hour to prepare catalyst ink, weighing 100 mu L ink by using a liquid transfer gun, uniformly dripping the ink on carbon paper (1 cm x 1 cm), and drying under an infrared lamp to obtain a working electrode for electrocatalysis carbon dioxide reduction.
Electrochemical testing:
the process was tested on an electrochemical workstation (CHI660E) using a standard three-electrode system, a custom H-cell separated by a Nafion117 proton exchange membrane, and a 0.1MKHCO of 30m L in each of the two cells of the cell3And (3) introducing high-purity carbon dioxide for half an hour before testing the electrolyte, and driving away other dissolved gases in the electrolyte to saturate the solubility of the carbon dioxide in the system.
In the carbon dioxide reduction test, high-purity carbon dioxide gas with the flow rate of 20m L/min is continuously introduced into a reaction system to ensure the saturation solubility of the carbon dioxide in the system, the electrochemical test method of a time-current curve is used to enable a catalyst to carry out electrochemical test for 2 hours under the potential of-1.4V vs. Ag/AgCl, an air bag is used to collect redundant carbon dioxide gas and generated gas products in the system, gas chromatography is used to detect and analyze the gas products, and the products are H2And CH4Working electrode was tested at-1.4V vs. Ag/AgCl and found to be on CH4Has higher selectivity, and the highest Faraday efficiency can reach 27.7 percent.
Fig. 1 is an SEM image of the catalyst CuS nanodots of embodiment 1, and it can be seen from fig. 1 that the CuS nanodots obtained in this embodiment are very uniform; FIG. 2 is a TEM image of CuS nanodots of the catalyst of example 1, and it can be seen from FIG. 2 that the particle size of the CuS nanodots obtained in this example is 10-20 nm; FIG. 3 XRD pattern, X, of catalyst CuS nanodots of example 1The diffraction peak energy of RD corresponds to the diffraction peak of CuS. Fig. 4 to 5 are XPS graphs of Cu and S of the catalyst CuS nanodots of example 1, and the composition of the catalyst surface can be clearly seen by XPS as bivalent copper ions and negatively bivalent sulfur ions. FIG. 6 is a graph of the time and current curves at-1.4V vs. Ag/AgCl of the CuS nanodot catalyst of example 1, which shows that H can be calculated2The Faraday efficiency of (1) is 72.3%, CH4The Faraday efficiency of (2) was 27.7%.
Example 2:
a preparation method of a CuS nanodot material comprises the following steps:
(1) adding 21mg of copper chloride and 60mg of polyvinylpyrrolidone with molecular weight of 8000 into 5m L deionized water, and stirring at room temperature for 30min to uniformly disperse the copper chloride and the polyvinylpyrrolidone;
(2) adding 30mg of sodium sulfide into the mixed solution in the step (1), and stirring at room temperature for 60min to uniformly disperse the sodium sulfide;
(3) and (3) transferring the uniformly dispersed mixed solution in the step (2) into a single-neck flask with the diameter of 20m L, stirring and reacting for 15min at the temperature of 90 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging by using ethanol, and washing for 3 times.
(4) And (4) drying the product which is centrifuged and washed in the step (3) for 4h at 60 ℃ under a vacuum condition to obtain the CuS nanodot material.
Electrochemical tests of the CuS nanodots obtained in the present application were performed in the same manner as in example 1, and the results showed activity and selectivity comparable to those of example 1.
Example 3:
a preparation method of a CuS nanodot material comprises the following steps:
(1) adding 21mg of copper chloride and 60mg of polyvinylpyrrolidone with molecular weight of 24000 into 5m L deionized water, and stirring at room temperature for 30min to uniformly disperse the copper chloride and the polyvinylpyrrolidone;
(2) adding 30mg of sodium sulfide into the mixed solution in the step (1), and stirring at room temperature for 60min to uniformly disperse the sodium sulfide;
(3) and (3) transferring the uniformly dispersed mixed solution in the step (2) into a single-neck flask with the diameter of 20m L, stirring and reacting for 15min at the temperature of 90 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging by using ethanol, and washing for 3 times.
(4) And (4) drying the product which is centrifuged and washed in the step (3) for 4h at 60 ℃ under a vacuum condition to obtain the CuS nanodot material.
Electrochemical tests of the CuS nanodots obtained in the present application were performed in the same manner as in example 1, and the results showed activity and selectivity comparable to those of example 1.
Example 4:
a preparation method of a CuS nanodot material comprises the following steps:
(1) adding 21mg of copper chloride and 60mg of polyvinylpyrrolidone with the molecular weight of 90000 into 5m L deionized water, and stirring at room temperature for 30min to uniformly disperse the copper chloride and the polyvinylpyrrolidone;
(2) adding 30mg of sodium sulfide into the mixed solution in the step (1), and stirring at room temperature for 60min to uniformly disperse the sodium sulfide;
(3) and (3) transferring the uniformly dispersed mixed solution in the step (2) into a single-neck flask with the diameter of 20m L, stirring and reacting for 15min at the temperature of 90 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging by using ethanol, and washing for 3 times.
(4) And (4) drying the product which is centrifuged and washed in the step (3) for 4h at 60 ℃ under a vacuum condition to obtain the CuS nanodot material.
Electrochemical tests of the CuS nanodots obtained in the present application were performed in the same manner as in example 1, and the results showed activity and selectivity comparable to those of example 1.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a CuS nanodot material is characterized by comprising the following steps:
(1) dissolving copper chloride and polyvinylpyrrolidone in deionized water, and stirring until the solution is clear;
(2) dissolving sodium sulfide in the clear solution in the step (1) under stirring;
(3) and (3) reacting the mixed solution in the step (2), centrifuging and drying to obtain the CuS nanodots.
2. The method for preparing a CuS nanodot material according to claim 1, wherein the ratio of the addition amount of the copper chloride, the polyvinylpyrrolidone and the deionized water in step (1) is (20-30) mg, (50-70) mg, (2-8) m L.
3. The method for preparing a CuS nanodot material according to claim 2, wherein the ratio of the addition amount of copper chloride, polyvinylpyrrolidone and deionized water in step (1) is 21mg:60mg:5m L.
4. The method for preparing a CuS nanodot material according to claim 1, wherein the molecular weight of polyvinylpyrrolidone in step (1) is one of 8000, 24000, 30000, 90000.
5. The method for preparing the CuS nanodot material of claim 1, wherein the ratio of the addition amounts of the copper chloride, the polyvinylpyrrolidone, the sodium sulfide and the deionized water in step (2) is (20-30) mg, (50-70) mg, (20-40) mg, (2-8) m L.
6. The method for preparing a CuS nanodot material according to claim 5, wherein the adding amount ratio of the copper chloride, the polyvinylpyrrolidone, the sodium sulfide and the deionized water in the step (2) is 21mg:60mg:30mg:5m L.
7. The method for preparing a CuS nanodot material according to claim 1, wherein the reaction temperature of the mixed solution in the step (3) is 70-120 ℃ and the reaction time is 10-60 min.
8. The method for preparing a CuS nanodot material according to claim 1, wherein the product obtained from the reaction in step (3) is centrifuged with ethanol.
9. The method for preparing a CuS nanodot material for electrocatalytic carbon dioxide reduction according to claim 1, wherein the drying temperature in the step (3) is 30-80 ℃ and the drying time is 2-6 h.
10. Use of the CuS nanodot material of claims 1-9 as a catalyst in electrocatalytic carbon dioxide reduction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111974415A (en) * | 2020-08-31 | 2020-11-24 | 北京化工大学 | Copper sulfide/brass mesh electrode material with nanosheet array structure and preparation method and application thereof |
| CN116237063A (en) * | 2023-02-17 | 2023-06-09 | 兰州大学 | Yttrium promoted carbon dioxide reduction catalyst and its preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056234A (en) * | 2015-09-01 | 2015-11-18 | 郑州大学 | Active targeting nano ball for photo-thermally treating tumor and preparation method and appliance thereof |
| CN108524935A (en) * | 2018-05-17 | 2018-09-14 | 山东大学 | A kind of Quercetin drug-loading system based on copper sulfide-metal-organic framework material |
-
2020
- 2020-05-09 CN CN202010386323.4A patent/CN111450848A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056234A (en) * | 2015-09-01 | 2015-11-18 | 郑州大学 | Active targeting nano ball for photo-thermally treating tumor and preparation method and appliance thereof |
| CN108524935A (en) * | 2018-05-17 | 2018-09-14 | 山东大学 | A kind of Quercetin drug-loading system based on copper sulfide-metal-organic framework material |
Non-Patent Citations (2)
| Title |
|---|
| 蒋伟: ""基于硫化铜-金厲有机框架材料的槲皮素载药系统的构建和研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 赵喆: ""基于硫化铜纳米片的电化学还原CO2研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111974415A (en) * | 2020-08-31 | 2020-11-24 | 北京化工大学 | Copper sulfide/brass mesh electrode material with nanosheet array structure and preparation method and application thereof |
| CN116237063A (en) * | 2023-02-17 | 2023-06-09 | 兰州大学 | Yttrium promoted carbon dioxide reduction catalyst and its preparation method |
| CN116237063B (en) * | 2023-02-17 | 2023-08-15 | 兰州大学 | Yttrium promoted carbon dioxide reduction catalyst and its preparation method |
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