CN116495770A - Plasmon enhanced copper-based sulfide semiconductor and preparation method and application thereof - Google Patents
Plasmon enhanced copper-based sulfide semiconductor and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- 239000004065 semiconductor Substances 0.000 title claims abstract description 55
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- OVRQXQSDQWOJIL-UHFFFAOYSA-N 1,1-dibutylthiourea Chemical compound CCCCN(C(N)=S)CCCC OVRQXQSDQWOJIL-UHFFFAOYSA-N 0.000 claims abstract description 24
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000002096 quantum dot Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—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
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a plasmon enhanced copper-based sulfide semiconductor, a preparation method and application thereof, wherein N, N-dibutyl thiourea and copper stearate are added into oleylamine, stirred under inert atmosphere, and a dispersion liquid containing the plasmon enhanced copper-based sulfide semiconductor is obtained in an oil bath reaction. The invention realizes the effective regulation and control of plasmon resonance absorption peak by controlling the sulfur-copper ratio. Mild synthesis condition, easy realization and better photocatalysis of CO 2 Reducing performance and the like, is hopeful to solve the problem of limiting the catalysis of CO by the traditional photocatalyst 2 The reduction technology bottleneck has important experimental and theoretical guiding significance for realizing the 'double carbon' target in China.
Description
Technical Field
The invention belongs to the technical field of synthesis and photocatalysis of copper-based sulfide semiconductors, and particularly relates to a plasmon enhanced copper-based sulfide semiconductor. The invention also relates to a preparation method of the plasmon enhanced copper-based sulfide semiconductor. The invention further relates to application of the plasmon enhanced copper-based sulfide semiconductor.
Background
Continuous consumption of fossil fuels results in CO 2 High emissions and severe energy shortages. Photocatalytic technology, which can convert CO by solar energy 2 The conversion into high added value chemicals and/or solar energy fuels is considered to be a novel green carbon reduction technology with great potential. However, the traditional photocatalyst is used for photocatalysis of CO 2 The key scientific problems of narrow photoresponse wave band, low catalytic activity, difficult carrier separation and transportation regulation and control and the like still exist in the reduction process. Therefore, it is important to select a suitable photocatalyst, which must have a suitable band gap and band edge position, such as a positive potential of the valence band higher than O 2 /H 2 Oxidation-reduction potential of O, negative potential of conduction band ratio product/CO 2 Is more negative. A great deal of literature at home and abroad proves that the plasmon catalyst is used for photocatalysis of CO 2 The following advantages are achieved in the reduction (Nature Photonics,2014,8,95-103;Nature Nanotechnology,2015,10,25-34;ACS Nano,2021,15,3529-3539): (1) A large amount of hot carriers with extremely high energy are generated to efficiently participate in the chemical reaction of the surface of the catalyst; (2) Remarkably broadens the light response wave band and improves the solar energy utilization rate; (3) Has more defects, is used as an active site, and improves the catalytic property. For example, mou et al (Small, 2015,11,2275-2283) successfully prepared Cu by the thermal implantation method 1.2 S series Cu 2-x S plasmon catalyst; studies have shown that: the atomic metering ratio of the catalyst is optimized by changing the injection amount of sulfur powder-oleic acid, the spectral absorption range of the catalyst can be effectively regulated and controlled, and the photocatalytic CO of the catalyst is obviously improved 2 Performance of reduction. Shen et al (Energy)&Fuels,2022,36,11515-11523) preparation of WO for defective state by chemical reduction 3-y /TiO 2-x A plasmonic catalyst; studies have shown that: the synergistic effect of defects and heterojunction promotes photo-generated current carryingSeparation and transmission of the seed; and photocatalytic CO by loading 0.8% Pd 2 The selectivity of the reduction product is improved to 100%. Wang et al (Journal of Materials Chemistry A,2016,4,5314-5322) prepared WO by hydrothermal method 3 A plasmonic catalyst; studies have shown that: the ultraviolet visible absorption spectrum of the ultraviolet visible absorption spectrum increases along with the reduction temperature, and obvious plasmon characteristic absorption appears in a visible light region; under the combined action of heating and illumination, the photocatalyst is used for catalyzing CO after 12 hours 2 Reduction to CH 4 The yield of (C) is as high as 26. Mu. Mol/g. Therefore, the plasmon catalyst is designed and developed to solve the problem of limiting the traditional photocatalyst to catalyze CO 2 Efficient method for reducing key scientific problems of technical bottlenecks, and simultaneously converting CO 2 The novel double-carbon-assisted power generation device is converted into high-added-value chemicals, and the assistance of the assistance to achieve the double-carbon target has great significance.
Disclosure of Invention
The invention aims to provide a plasmon enhanced copper-based sulfide semiconductor, which can realize effective regulation and control of plasmon resonance absorption peaks by controlling experimental conditions.
The invention further aims to provide a preparation method of the plasmon enhanced copper-based sulfide semiconductor, which is mild in synthesis condition and easy to realize.
Still another object of the present invention is to provide a copper-based sulfide semiconductor with enhanced plasmons and better photocatalytic CO 2 Reduction performance.
The first technical scheme adopted by the invention is as follows: the plasmon enhanced copper-based sulfide semiconductor has the morphology of quantum dots, the plasmon absorption peak can regulate and control blue shift, and the absorption peak position is above 1500 nm.
The first technical solution of the invention is also characterized in that,
the diameter of the quantum dot is about 10nm.
The second technical scheme adopted by the invention is as follows: the preparation method of the plasmon enhanced copper-based sulfide semiconductor comprises the following steps:
step 1, weighing N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and copper stearate in a three-neck flask, and adding oleylamine to obtain a mixed solution;
step 2, building a closed reaction device, introducing inert gas, and stirring to uniformly stir the mixed solution;
step 3, connecting a condensing pipe on the three-neck flask and introducing condensed water;
step 4, placing the three-neck flask into an oil bath, heating to a reaction temperature, and stirring at the reaction temperature to perform a reaction;
stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a mixed solution containing the copper-based sulfide semiconductor with enhanced plasmons;
and 6, centrifugally separating the mixed solution, and washing the precipitate to obtain the nano-porous titanium dioxide.
The second technical proposal of the invention is also characterized in that,
the concentration of N, N-dibutyl thiourea in the mixed solution in the step 1 is 0.2-1.0mol/L, and the concentration of copper stearate is 0.1-0.95mol/L.
The inert gas in step 2 comprises nitrogen or argon.
The reaction temperature in the step 4 is 30-100 ℃ and the reaction time is 0.5-5h.
The step 6 is specifically as follows: and (3) centrifugally separating the mixed solution, washing the obtained precipitate with ethanol to obtain colorless supernatant, separating, and washing with deionized water to obtain the dispersion liquid containing the plasmon enhanced copper-based sulfide semiconductor.
The third technical scheme adopted by the invention is as follows: application of plasmon enhanced copper-based sulfide semiconductor, coating the plasmon enhanced copper-based sulfide semiconductor on quartz sheet, drying in oven at 30-60deg.C for 5-10 hr, and placing in reaction vessel for photocatalytic CO 2 And (5) reduction.
The beneficial effects of the invention are as follows: the plasmon enhanced copper-based sulfide semiconductor, the preparation method and the application thereof realize effective regulation and control of plasmon resonance absorption peaks by controlling experimental conditions, and have mild synthesis conditions, easy realization and better photocatalysis of CO 2 Reducing performance and the like, is hopeful to solve the problem of limiting the catalysis of the traditional photocatalystCO 2 Reducing technical bottlenecks.
Drawings
FIG. 1 is a 50nm scale transmission electron microscope image of a plasmon enhanced copper-based sulfide semiconductor of the present invention;
FIG. 2 is a graph of the plasmon ultraviolet visible absorption spectrum of the plasmon enhanced copper-based sulfide semiconductor of the present invention;
FIG. 3 is a schematic view of a plasmon enhanced copper-based sulfide semiconductor of the present invention for photocatalytic CO 2 Performance map of reduction.
Detailed Description
The invention will be described in detail with reference to the accompanying drawings and detailed description.
The invention provides a preparation method of a plasmon enhanced copper-based sulfide semiconductor, which comprises the following steps:
step 1, weighing a certain amount of N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and the copper stearate in a three-neck flask, and adding a certain volume of oleylamine to obtain a mixed oleylamine solution with the concentration of the N, N-dibutyl thiourea of 0.2-1.0mol/L and the concentration of the copper stearate of 0.1-0.95 mol/L;
step 2, building a closed reaction device, introducing inert gas, opening stirring and adjusting to a proper rotating speed, and uniformly mixing the solutions;
step 3, connecting a condensing pipe to the other bottle mouth of the three-mouth bottle in the step 1, introducing condensed water, and placing the whole mixed solution reaction system in inert atmosphere;
step 4, placing the mixed solution obtained in the step 3 into an oil bath, stirring at the reaction temperature of 30-100 ℃, and controlling the reaction time to be 0.5-5h;
stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a brownish-black mixed solution containing the copper-based sulfide semiconductor with enhanced plasmons;
and 6, centrifugally separating and washing the brownish-black mixed solution containing the plasmon enhanced copper-based sulfide semiconductor obtained in the step 5 to obtain brownish-black precipitate, and dispersing the precipitate in an aqueous solution to obtain the brownish-black dispersion liquid containing the plasmon enhanced copper-based sulfide semiconductor. Wherein, the washing process is as follows: and washing the precipitate centrifugally separated from the mixed solution by deionized water until the supernatant is clear, and preserving for later use.
Through the mode, the preparation method of the plasmon enhanced copper-based sulfide semiconductor successfully obtains the copper-based sulfide semiconductor with adjustable plasmon resonance absorption peak by controlling experimental conditions. As shown in FIG. 1, the prepared material shows the appearance of quantum dots, and the diameter of the quantum dots is about 10 nanometers; as shown in figure 2, by regulating the molar ratio of sulfur to copper, the plasmon resonance absorption peak of the prepared material shows a blue shift phenomenon, and the absorption peak position is more than 1500nm, which shows that the material can remarkably widen the light absorption range and is expected to improve the catalytic performance of the photocatalyst.
The invention also provides application of the plasmon enhanced copper-based sulfide semiconductor, which comprises the steps of coating the plasmon enhanced copper-based sulfide semiconductor on a clean quartz plate, drying in an oven at 30-60 ℃ for 5-10h, and then placing in a self-made cube reaction container for photocatalysis of CO 2 And (5) reduction. As can be seen from fig. 3, CO increases with the catalytic time 2 The yield of the reduction product CO is gradually increased, and the yield of methane is increased to a smaller extent. Meanwhile, the catalyst has higher selectivity to CO, the product mainly comprises CO, and the yield is higher than 10 mu mol/g after 4 hours of reaction.
Example 1
Weighing a certain amount of N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and copper stearate in a three-neck flask, adding a certain volume of oleylamine to obtain a mixed oleylamine solution with the concentration of N, N-dibutyl thiourea of 0.2mol/L and the concentration of copper stearate of 0.8mol/L, building a closed reaction device, introducing inert gas nitrogen, opening stirring to adjust to a proper rotating speed, and uniformly mixing the solution; connecting a condensing tube on the other bottle mouth of the three-mouth bottle, introducing condensed water, placing the obtained mixed solution into an oil bath, stirring at a reaction temperature of 40 ℃, controlling the reaction time to be 0.5h, stopping heating after the reaction is finished, cooling the product to room temperature in an inert atmosphere to obtain the copper-based vulcanized product containing plasmon enhancementA brown-black mixed solution of the compound semiconductor; and (3) centrifugally separating and washing the brown-black mixed solution to obtain brown-black precipitate, and dispersing the precipitate in an aqueous solution to obtain a brown-black dispersion liquid containing the copper-based sulfide semiconductor with enhanced plasmons. Coating a brown-black dispersion liquid of a copper-based sulfide semiconductor with plasmon enhancement on a clean quartz sheet, drying in an oven at 30 ℃ for 10 hours, and then placing in a self-made cube reaction container for photocatalysis of CO 2 Reduction, reduction products are CO and CH 4 With the extension of the catalytic time, the CO yield of the product is far higher than that of CH 4 After 4 hours of reaction, the CO yield was CH 4 3.2 times of (3).
Example 2
Weighing a certain amount of N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and copper stearate in a three-neck flask, adding a certain volume of oleylamine to obtain a mixed oleylamine solution with the concentration of N, N-dibutyl thiourea of 0.5mol/L and the concentration of copper stearate of 0.1mol/L, building a closed reaction device, introducing inert gas argon, stirring and adjusting to a proper rotating speed, and uniformly mixing the solution; connecting a condensing tube on the other bottle mouth of the three-mouth bottle, introducing condensed water, placing the obtained mixed solution into an oil bath, stirring at the reaction temperature of 100 ℃, controlling the reaction time to be 1h, stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a brownish-black mixed solution containing a plasmon enhanced copper-based sulfide semiconductor; and (3) centrifugally separating and washing the brown-black mixed solution to obtain brown-black precipitate, and dispersing the precipitate in an aqueous solution to obtain a brown-black dispersion liquid containing the copper-based sulfide semiconductor with enhanced plasmons. Coating a brown-black dispersion liquid of a copper-based sulfide semiconductor with enhanced plasmons on a clean quartz sheet, drying for 5 hours in a baking oven at 40 ℃, and then placing in a self-made cube reaction container for photocatalysis of CO 2 Reduction, reduction products are CO and CH 4 With the extension of the catalytic time, the CO yield of the product is far higher than that of CH 4 After 4 hours of reaction, the CO yield was CH 4 Is 2 times as large as the above.
Example 3
Weighing a certain amount of N, N-dibutylThiourea and copper stearate are placed in a three-neck flask, a certain volume of oleylamine is added to obtain a mixed oleylamine solution with the concentration of N, N-dibutyl thiourea of 0.8mol/L and the concentration of copper stearate of 0.95mol/L, a closed reaction device is built, inert gas nitrogen is introduced, stirring is started and adjusted to a proper rotating speed, and the solution is uniformly mixed; connecting a condensing tube on the other bottle mouth of the three-mouth bottle, introducing condensed water, placing the obtained mixed solution into an oil bath, stirring at the reaction temperature of 80 ℃, controlling the reaction time to be 02h, stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a brownish-black mixed solution containing a plasmon enhanced copper-based sulfide semiconductor; and (3) centrifugally separating and washing the brown-black mixed solution to obtain brown-black precipitate, and dispersing the precipitate in an aqueous solution to obtain a brown-black dispersion liquid containing the copper-based sulfide semiconductor with enhanced plasmons. Coating a brown-black dispersion liquid of a copper-based sulfide semiconductor with enhanced plasmons on a clean quartz sheet, drying for 6 hours in an oven at 60 ℃, and then placing in a self-made cube reaction container for photocatalysis of CO 2 Reduction, reduction products are CO and CH 4 With the extension of the catalytic time, the CO yield of the product is far higher than that of CH 4 After 4 hours of reaction, the CO yield was CH 4 1.5 times of (2).
Example 4
Weighing a certain amount of N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and copper stearate in a three-neck flask, adding a certain volume of oleylamine to obtain a mixed oleylamine solution with the concentration of N, N-dibutyl thiourea of 1.0mol/L and the concentration of copper stearate of 0.5mol/L, building a closed reaction device, introducing inert gas nitrogen, opening stirring to adjust to a proper rotating speed, and uniformly mixing the solution; connecting a condensing tube on the other bottle mouth of the three-mouth bottle, introducing condensed water, placing the obtained mixed solution into an oil bath, stirring at the reaction temperature of 30 ℃, controlling the reaction time to be 5 hours, stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a brownish-black mixed solution containing a plasmon enhanced copper-based sulfide semiconductor; centrifugally separating and washing the brown-black mixed solution to obtain brown-black precipitate, and dispersing the precipitate in water solution to obtainTo a brownish black dispersion containing a plasmon-enhanced copper-based sulfide semiconductor. Coating a brown-black dispersion liquid of a copper-based sulfide semiconductor with plasmon enhancement on a clean quartz sheet, drying in an oven at 50 ℃ for 8 hours, and then placing in a self-made cube reaction container for photocatalysis of CO 2 Reduction, reduction products are CO and CH 4 With the extension of the catalytic time, the CO yield of the product is far higher than that of CH 4 After 4 hours of reaction, the CO yield was CH 4 Is 2.5 times as large as the above.
Example 5
Weighing a certain amount of N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and copper stearate in a three-neck flask, adding a certain volume of oleylamine to obtain a mixed oleylamine solution with the concentration of N, N-dibutyl thiourea of 0.4mol/L and the concentration of copper stearate of 0.2mol/L, building a closed reaction device, introducing inert gas argon, stirring and adjusting to a proper rotating speed, and uniformly mixing the solution; connecting a condensing tube on the other bottle mouth of the three-mouth bottle, introducing condensed water, placing the obtained mixed solution into an oil bath, stirring at the reaction temperature of 50 ℃, controlling the reaction time to be 3 hours, stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a brownish-black mixed solution containing a plasmon enhanced copper-based sulfide semiconductor; and (3) centrifugally separating and washing the brown-black mixed solution to obtain brown-black precipitate, and dispersing the precipitate in an aqueous solution to obtain a brown-black dispersion liquid containing the copper-based sulfide semiconductor with enhanced plasmons. Coating a brown-black dispersion liquid of a copper-based sulfide semiconductor with enhanced plasmons on a clean quartz sheet, drying for 8 hours in a baking oven at 45 ℃, and then placing in a self-made cube reaction container for photocatalysis of CO 2 Reduction, reduction products are CO and CH 4 With the extension of the catalytic time, the CO yield of the product is far higher than that of CH 4 After 4 hours of reaction, the CO yield was CH 4 3 times of (3).
Claims (8)
1. The plasmon enhanced copper-based sulfide semiconductor is characterized in that the morphology is quantum dots, the plasmon absorption peak can be adjusted and controlled to be blue-shifted, and the absorption peak position is above 1500 nm.
2. The plasmonic enhanced copper-based sulfide semiconductor of claim 1, wherein the quantum dot diameter is 10nm.
3. The preparation method of the plasmon enhanced copper-based sulfide semiconductor is characterized by comprising the following steps of:
step 1, weighing N, N-dibutyl thiourea and copper stearate, placing the N, N-dibutyl thiourea and copper stearate in a three-neck flask, and adding oleylamine to obtain a mixed solution;
step 2, building a closed reaction device, introducing inert gas, and stirring to uniformly stir the mixed solution;
step 3, connecting a condensing pipe on the three-neck flask and introducing condensed water;
step 4, placing the three-neck flask into an oil bath, heating to a reaction temperature, and stirring at the reaction temperature to perform a reaction;
stopping heating after the reaction is finished, and cooling the product to room temperature in an inert atmosphere to obtain a mixed solution containing the copper-based sulfide semiconductor with enhanced plasmons;
and 6, centrifugally separating the mixed solution, and washing the precipitate to obtain the nano-porous titanium dioxide.
4. The method for producing a plasmon enhanced copper-based sulfide semiconductor according to claim 1, wherein the concentration of N, N-dibutylthiourea in the mixed solution of step 1 is 0.2 to 1.0mol/L and the concentration of copper stearate is 0.1 to 0.95mol/L.
5. The method for producing a plasmon enhanced copper-based sulfide semiconductor of claim 1 wherein said inert gas in step 2 comprises nitrogen or argon.
6. The method for producing a plasmon enhanced copper-based sulfide semiconductor according to claim 1, wherein the reaction temperature in step 4 is 30 to 100 ℃ and the reaction time is 0.5 to 5 hours.
7. The method for preparing a plasmon enhanced copper-based sulfide semiconductor according to claim 1, wherein the step 6 is specifically: and (3) centrifugally separating the mixed solution, washing the obtained precipitate with ethanol to obtain colorless supernatant, separating, and washing with deionized water to obtain the dispersion liquid containing the plasmon enhanced copper-based sulfide semiconductor.
8. The application of the copper-based sulfide semiconductor with enhanced plasmons is characterized in that the copper-based sulfide semiconductor with enhanced plasmons is coated on a quartz plate, is dried for 5-10h in an oven with the temperature of 30-60 ℃ and is then placed in a reaction container for photocatalysis of CO 2 And (5) reduction.
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CN113981481A (en) * | 2021-09-27 | 2022-01-28 | 西安电子科技大学 | Preparation method and application of copper nanoparticle-loaded one-dimensional carbon-based nano material |
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CN113981481A (en) * | 2021-09-27 | 2022-01-28 | 西安电子科技大学 | Preparation method and application of copper nanoparticle-loaded one-dimensional carbon-based nano material |
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