CN108686685B - Copper nanoparticle/black phosphorus nanosheet composite material and preparation method and application thereof - Google Patents
Copper nanoparticle/black phosphorus nanosheet composite material and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 83
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 63
- 239000002135 nanosheet Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 11
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical group O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- -1 copper hexafluorophosphate Chemical compound 0.000 claims description 4
- 239000002055 nanoplate Substances 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000007630 basic procedure Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
The invention discloses a copper nanoparticle/black phosphorus nanosheet composite material and a preparation method and application thereof, wherein the composite material comprises a carrier black phosphorus nanosheet and copper nanoparticles loaded on the carrier; the preparation method comprises the steps of dispersing black phosphorus and sodium hydroxide in an organic solvent to prepare a mixed solution, placing the mixed solution in a supercritical reaction kettle, reacting for 3-4 hours at 40-70 ℃ and 15-20 MPa to prepare black phosphorus nanosheets, mixing the black phosphorus nanosheets with a copper phase solution, and reacting for 10-120 minutes at 50-60 ℃ to prepare the composite material. The composite material is applied to electrochemical catalytic reduction of carbon dioxide. The invention has the following remarkable advantages: the composite material has large specific surface area, large loading capacity of copper nanoparticles and excellent crystallization performance and catalytic performance; the preparation method is simple, low in cost and environment-friendly; simultaneously applied to electrochemical catalytic reduction of CO2High catalytic activity, high stability and low applied voltage.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a copper nanoparticle/black phosphorus nanosheet composite material and a preparation method and application thereof.
Background
CO2It is thermodynamically stable (standard molar enthalpy of formation-393.51 kJ · mol-1), inert and not readily activatable (C ═ O bond energy 750kJ · mol-1). Thus, CO is realized2Chemical conversion under mild conditions is a very challenging study. CO22The electrochemical reduction can further convert electric energy converted from renewable energy sources such as solar energy, wind energy and the like into chemical energy, and the chemical energy is stored in fuel and chemicals with high added values. Despite CO2Electrochemical reduction gradually draws attention and research interest of scientists in various countries, but there still exist many problems to be solved in this field, such as: (1) for treatingHigh applied potential (or low energy efficiency); (2) slow electron transfer kinetics; (3) the selectivity of the product is not ideal; (4) the bias current density is too low (only a few tens of milliamps per square centimeter); (5) poor stability and durability (less than 100 hours) of the catalyst, and the like. The above problems greatly limit the practical application and commercialization of the existing electrode catalytic materials. Based on the method, a high-performance catalytic material is developed to reduce CO2The overpotential of electrochemical reduction and the improvement of the activity, selectivity and stability of the catalytic material have important scientific significance and industrial value.
Although some two-dimensional nanomaterials such as graphene are applied to CO2The electrochemical reduction field (atomic dispersed Ni (i) as the active site for electrochemical CO2reduction, Natureenergy, 2018,3,140 and 147), but the experimental process of the method is complex, and the popularization and application are limited.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a copper nanoparticle/black phosphorus nanosheet composite material with excellent crystallization performance, large specific surface area and large copper loading;
the second purpose of the invention is to provide a preparation method of the composite material, which is simple, low in cost, short in time and environment-friendly;
the third purpose of the invention is to provide the application of the composite material, which is applied to electrocatalytic CO2And the catalytic performance is superior.
The technical scheme is as follows: the copper nanoparticle/black phosphorus nanosheet composite material comprises a carrier black phosphorus nanosheet and copper nanoparticles loaded on the carrier.
The composite material of the invention takes the black phosphorus nanosheet as the carrier and loads the copper nanoparticles, so that the specific surface area is large, the copper nanoparticles are sufficiently loaded, the crystallization performance and the catalyst performance are excellent, and the stability is strong. Furthermore, the particle size of the copper nanoparticles in the composite material is 2-5 nm. The composite material can load copper nanoparticles with the particle size of 2-5 nm, and the catalytic activity of the composite material is further enhanced by the copper nanoparticles with the particle size range.
The method for preparing the copper nanoparticle/black phosphorus nanosheet composite material comprises the following steps:
(1) preparing black phosphorus nanosheets: dispersing black phosphorus and sodium hydroxide in an organic solvent to prepare a mixed solution, then placing the mixed solution in a supercritical reaction kettle, reacting for 3-4 h at 40-70 ℃ and 15-20 MPa, and carrying out centrifugal washing to prepare black phosphorus nanosheets;
(2) preparing a composite material: and mixing the black phosphorus nanosheet with the copper phase solution, reacting for 10-120 min at 50-60 ℃, and centrifugally washing to obtain the copper nanoparticle/black phosphorus nanosheet composite material.
Furthermore, in the step (1) of the preparation method, the mass ratio of the black phosphorus to the sodium hydroxide is 1: 1-2. The organic solvent may preferably be N-cyclohexyl-2-pyrrolidone, N-cyclohexylpyrrolidone or isopropanol. By adopting the anhydrous and oxygen-free organic solvent of N-cyclohexyl-2-pyrrolidone, N-cyclohexyl pyrrolidone or isopropanol, the oxidative degradation of the black phosphorus can be effectively prevented.
Furthermore, in the step (2) of the preparation method of the present invention, the copper phase solution may include a solute and a solvent in a mass volume ratio of 1:1 to 1:0.5, wherein the solute may be a monovalent copper compound, and more preferably may be tetraacetonitrilopiroxyphosphate. According to the invention, a monovalent copper compound is adopted, divalent copper ions and nano copper particles are generated in the reaction, and after centrifugal washing, the copper particles are finally loaded in the black phosphorus nanosheets, and the particle size of the copper particles is 2-5 nm. The solvent may preferably be n-butanol or acetone. The centrifugal speed is preferably 9000-13000 r/min.
The copper nanoparticle/black phosphorus nanosheet composite material is applied to electrochemical catalytic reduction of carbon dioxide.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the copper nanoparticle/black phosphorus nanosheet composite material takes the black phosphorus nanosheet as a carrier to load the copper nanoparticles, the thickness of the copper nanoparticle/black phosphorus nanosheet composite material can reach several nanometers to dozens of nanometers, the specific surface area is large, the loading capacity of the copper nanoparticles is large, and the crystallization performance and the catalytic performance are excellent; meanwhile, the preparation method is simple, short in time, low in cost and environment-friendly; furthermore, the composite material should beFor electrochemical catalytic reduction of CO2The composite material has high catalytic activity, strong stability and lower applied voltage, the particle size of the copper nanoparticles loaded in the black phosphorus nanosheets in the composite material can reach about 2nm, and the copper nanoparticles in the particle size range further enhance the catalytic performance of the composite material.
Drawings
FIG. 1 is a low power transmission electron micrograph of a copper nanoparticle/black phosphorus nanosheet composite of the present invention;
FIG. 2 is a high resolution transmission electron micrograph of the copper nanoparticle/black phosphorus nanosheet composite of the present invention;
FIG. 3 is a graph showing the electrochemical performance test of the copper-copper nanoparticle/black phosphorus nanosheet composite material of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Example 1
The copper nanoparticle/black phosphorus nanosheet composite material comprises a black phosphorus nanosheet carrier and copper nanoparticles loaded on the carrier, wherein the particle size of the copper nanoparticles is 2-4 nm.
The preparation method of the composite material comprises the following steps:
(1) weighing 10mg of blocky black phosphorus and 10mg of sodium hydroxide, and dispersing the blocky black phosphorus and the 10mg of sodium hydroxide in 30ml of N-cyclohexyl-2-pyrrolidone to obtain a mixed solution for later use;
(2) putting the mixed solution into a high-pressure reaction kettle of a supercritical device, and adding CO when the temperature of the high-pressure reaction kettle reaches 40 DEG C2Pumping into a high-pressure reaction kettle, and maintaining the system in a supercritical state for 3 hours when the pressure of the high-pressure reaction kettle reaches 15 MPa;
(3) after the reaction is finished, discharging CO in the high-pressure reaction kettle2Cooling to room temperature, then carrying out ultrasonic treatment on the mixed solution for 6h under the condition of 100W, centrifuging and washing to obtain black polyatomic layer black phosphorus nanosheets;
(4) fully mixing the obtained black phosphorus nanosheet layer with the copper phase mixed solution, preheating to react for 20min at 50 ℃, centrifuging and washing to obtain the composite material; wherein the copper phase mixed solution consists of 4mg of copper tetraacetonitrile hexafluorophosphate and 6ml of n-butanol. Wherein the centrifugation speed is 10000 r/min.
The copper nanoparticle/black phosphorus nanosheet composite material prepared in this example was observed, and the results obtained are shown in fig. 1 and 2. As can be seen from fig. 1 and 2, a large number of copper nanoparticles are attached to the multi-layer black phosphorus layer, the lattice of the multi-atomic layer black phosphorus is 0.25nm, and the lattice of the copper particles is 0.18nm, so that the copper nanoparticles are successfully supported on the black phosphorus layer.
The copper nanoparticle/black phosphorus nanosheet composite material prepared in the embodiment is applied to electrochemical catalytic reduction of carbon dioxide, and specifically comprises the following steps:
(1) performed on an electrochemical workstation, using a three-electrode cell configuration, a glassy carbon electrode (RDE) with a diameter of 5mm as the working electrode, a platinum foil as the counter electrode and saturated calomel as the reference electrode (SCE). For preparing the catalyst, 50-100 mul of 5% Nafion solution used as a conductive adhesive is introduced into 100-300 mul of water-ethanol solution with equal volume of water and ethanol and is subjected to ultrasonic treatment for 0.5-1 h;
(2) the composite material prepared by the invention is applied to glassy carbon RDE and dried in air to obtain the material with the thickness of 0.1-0.2 mgcm-2By introducing CO into the catalyst2(99.99%) purge to 0.5MKHCO3Preparation of CO2Saturated in aqueous electrolyte solution for 30min and maintaining CO on the electrolyte throughout the electrochemical measurement2Flowing;
(3) all potentials were calculated according to nernst equation (ere ═ ESCE +0.0591 × pH +0.241V at 25 ℃) on a Reversible Hydrogen Electrode (RHE) scale linear sweep voltammogram (L SVs) at 5mVs-1The scan rate of (2).
Comparative assay 1
Essentially the same electrolysis procedure as in example 1 was used except that the glassy carbon RDE was not covered with any material.
Essentially the same electrolytic procedure as in example 1 was used except that black phosphorus nanoplatelets were applied on the glassy carbon RDE.
The results of example 1 and comparative tests 1-2 are shown in FIG. 3. The figure shows that compared with blank carbon cloth and carbon cloth-black phosphorus nanosheets, the carbon cloth-copper nanoparticles/black phosphorus nanosheets have the smallest applied voltage, which indicates that the catalytic performance is superior.
Example 2
The copper nanoparticle/black phosphorus nanosheet composite material comprises a black phosphorus nanosheet carrier and copper nanoparticles loaded on the carrier. The particle size of the copper nanoparticles is 2-5 nm.
The preparation method of the composite material comprises the following steps:
(1) weighing 10mg of blocky black phosphorus and 15mg of sodium hydroxide, and dispersing the blocky black phosphorus and the 15mg of sodium hydroxide in 30ml of N-cyclohexyl-2-pyrrolidone to obtain a mixed solution for later use;
(2) putting the mixed solution into a high-pressure reaction kettle of a supercritical device, and adding CO when the temperature of the high-pressure reaction kettle reaches 40 DEG C2Pumping into a high-pressure reaction kettle, and maintaining the system in a supercritical state for 3 hours when the pressure of the high-pressure reaction kettle reaches 15 MPa;
(3) after the reaction is finished, discharging CO in the high-pressure reaction kettle2Cooling to room temperature, then carrying out ultrasonic treatment on the mixed solution for 4h under the condition of 150W, centrifuging and washing to obtain black polyatomic layer black phosphorus nanosheets;
(4) mixing the obtained black phosphorus nanosheet layer with a copper phase mixed solution, preheating to react for 40min at 50 ℃, centrifuging, and washing to obtain the composite material; wherein the copper phase mixed solution consists of 5mg of copper tetraacetonitrile hexafluorophosphate and 6ml of n-butanol. Wherein the speed of centrifugation is 9000 r/min.
The copper nanoparticle/black phosphorus nanosheet composite material prepared in the embodiment is applied to electrochemical catalytic reduction of carbon dioxide, and has excellent catalytic performance.
Example 3
The copper nanoparticle/black phosphorus nanosheet composite material comprises a black phosphorus nanosheet carrier and copper nanoparticles loaded on the carrier. The particle size of the copper nanoparticles is 2-5 nm.
The preparation method of the composite material comprises the following steps:
(1) weighing 10mg of blocky black phosphorus and 20mg of sodium hydroxide, and dispersing the blocky black phosphorus and the 20mg of sodium hydroxide in 30ml of N-cyclohexyl-2-pyrrolidone to obtain a mixed solution for later use;
(2) putting the mixed solution into a high-pressure reaction kettle of a supercritical device, and adding CO when the temperature of the high-pressure reaction kettle reaches 40 DEG C2Pumping into a high-pressure reaction kettle, and maintaining the system in a supercritical state for 3 hours when the pressure of the high-pressure reaction kettle reaches 15 MPa;
(3) after the reaction is finished, discharging CO in the high-pressure reaction kettle2Cooling to room temperature, then carrying out ultrasonic treatment on the mixed solution for 5h under the condition of 120W, centrifuging and washing to obtain black polyatomic layer black phosphorus nanosheets;
(4) mixing the obtained black phosphorus nanosheet layer with a copper mixed solution, preheating to react for 40min at 60 ℃, centrifuging, and washing to obtain a black phosphorus nanosheet compound attached to copper particles; wherein the copper phase mixed solution consists of 6mg of copper tetraacetonitrile hexafluorophosphate and 6ml of n-butanol. Wherein the speed of centrifugation is 13000 r/min.
The copper nanoparticle/black phosphorus nanosheet composite material prepared in the embodiment is applied to electrochemical catalytic reduction of carbon dioxide, and has excellent catalytic performance.
Example 4
5 sets of parallel tests were designed, the basic procedure was the same as in example 1, except that the mass ratio of black phosphorus to sodium hydroxide was 1:0.5, 1:1, 1:1.5, 1:2, 1: 2.5. The structural representation of the composite material prepared in the embodiment shows that the composite material prepared with the mass ratio of the black phosphorus to the sodium hydroxide being 1: 1-2 has the advantages of large specific surface area, sufficient copper nanoparticle load, strong catalytic performance, and strong crystallization performance and stability. When the mass ratio is 1:0.5, namely the addition amount of sodium hydroxide is small, the stability of the black phosphorus is poor; when the mass ratio is 1:2.5, the sodium hydroxide and the sodium hydroxide are in a supersaturated state as the mass ratio is 1:1.5, and the stability reaches the same expected effect, namely, when the sodium hydroxide is excessive, the sodium hydroxide is also in a supersaturated state, and the resource is not saved.
Example 5
5 sets of parallel experiments are designed, and the basic steps are the same as those of the example 1, except that the mass-to-volume ratio of the solute to the solvent in the copper phase solution is 1:0.3, 1:0.5, 1:1, 1:1.5 and 1:2. The structural representation of the composite material prepared in the embodiment shows that the composite material prepared with the mass-volume ratio of the solute to the solvent of 1: 0.5-1.5 has the advantages of large specific surface area, sufficient copper nanoparticle load, strong catalytic performance, and strong crystallization performance and stability. When the mass-to-volume ratio is 1:0.3, namely the amount of the solute is small, the solute cannot be completely dissolved; and when the mass-to-volume ratio is 1:2, i.e., the solvent amount is high, the concentration of the solution is low, and the content of the copper nanoparticles loaded is low.
Example 6
4 sets of parallel tests are designed, the basic steps are the same as those in the embodiment 1, and the difference is that the reaction temperature after the black phosphorus nanosheets and the copper phase solution are mixed is 40 ℃, 50 ℃, 60 ℃ and 70 ℃. The structural characterization of the composite material prepared by the embodiment shows that the composite material prepared at the temperature of 50-60 ℃ has the advantages of large specific surface area, sufficient copper nanoparticle load, strong catalytic performance, and strong crystallization performance and stability. When the temperature is lower than 50 ℃, the reaction rate is slowed down, and the loading capacity of the copper nanoparticles is reduced, and when the temperature is higher than 60 ℃, copper ions are not easily converted into the copper nanoparticles, and the loading capacity of the copper nanoparticles is reduced.
Example 7
6 groups of parallel tests are designed, the basic steps are the same as those of the example 1, and the difference is that the reaction time after the black phosphorus nanosheets and the copper phase solution are mixed is 5min, 10min, 50min, 100min, 120min and 130 min. The structural representation of the composite material prepared in the embodiment shows that the composite material prepared by reacting for 10-120 min not only has large specific surface area, sufficient copper nanoparticle load, strong catalytic performance, but also has strong crystallization performance and stability. When the reaction time is less than 10min, the reaction time is short, the reduction number of copper ions is small, and the loading capacity of the copper nanoparticles is reduced; above 120min, if the copper particles are exposed for too long, they will be further oxidized into copper oxide.
Example 8
The basic procedure was as in example 1, except that the organic solvent was N-cyclohexylpyrrolidone or isopropanol, the solvent was acetone, and the starting materials used in the present invention were all commercially available. When the black phosphorus nanosheet is prepared, firstly, the black phosphorus and the sodium hydroxide are dispersed in an organic solvent to prepare a mixed solution, then, the mixed solution is placed in a supercritical reaction kettle to react for 4 hours at the temperature of 70 ℃ and under the pressure of 20MPa, and the black phosphorus nanosheet is prepared after centrifugal washing.
According to the embodiment, the composite material has the advantages of large specific surface area, large loading capacity of copper nanoparticles, and excellent crystallization performance and catalytic performance; meanwhile, the preparation method is simple, low in cost and environment-friendly; application to electrochemical catalytic reduction of CO2High catalytic activity, high stability and low applied voltage.
Claims (8)
1. A method for preparing a copper nanoparticle/black phosphorus nanosheet composite is characterized by comprising the following steps:
(1) preparing black phosphorus nanosheets: dispersing black phosphorus and sodium hydroxide in an organic solvent to prepare a mixed solution, then placing the mixed solution in a supercritical reaction kettle, reacting for 3-4 h at 40-70 ℃ and 15-20 MPa, and carrying out centrifugal washing to prepare black phosphorus nanosheets;
(2) preparing a composite material: and mixing the black phosphorus nanosheet with the copper phase solution, reacting at 50-60 ℃ for 10-120 min, and centrifugally washing to obtain the copper nanoparticle/black phosphorus nanosheet composite material.
2. The method of making a copper nanoparticle/black phosphorus nanoplate composite of claim 1, wherein: in the step (1), the mass ratio of the black phosphorus to the sodium hydroxide is 1: 1-2.
3. The method of making a copper nanoparticle/black phosphorus nanoplate composite of claim 1, wherein: in the step (1), the organic solvent is N-cyclohexyl-2-pyrrolidone, N-cyclohexyl-pyrrolidone or isopropanol.
4. The method of making a copper nanoparticle/black phosphorus nanoplate composite of claim 1, wherein: in the step (2), the copper phase solution comprises a solute and a solvent in a mass-to-volume ratio of 1: 0.5-1.5, wherein the solute is a monovalent copper compound, and the solvent is n-butyl alcohol or acetone.
5. The method of making a copper nanoparticle/black phosphorus nanoplate composite of claim 4, wherein: the monovalent copper compound is tetraacetonitrile copper hexafluorophosphate.
6. The method of making a copper nanoparticle/black phosphorus nanoplate composite of claim 1, wherein: in the step (2), the centrifugation speed is 9000-13000 r/min.
7. A copper nanoparticle/black phosphorus nanosheet composite material, characterized in that: the composite material is prepared by the method of claim 1, and comprises a carrier black phosphorus nanosheet and copper nanoparticles loaded on the carrier, wherein the particle size of the copper nanoparticles is 2-5 nm.
8. The copper nanoparticle/black phosphorus nanoplate composite of claim 7 for use in the electrochemical catalytic reduction of carbon dioxide.
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| CN110586954A (en) * | 2019-09-05 | 2019-12-20 | 厦门大学 | Preparation method of copper nanoparticles and copper nanoparticles |
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| CN112892564B (en) * | 2021-01-26 | 2023-07-25 | 深圳市中科墨磷科技有限公司 | Preparation method and application of black phosphorus treated copper-based catalyst |
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