CN113072092A - Crystal face coupled cuprous oxide, and preparation method and application thereof - Google Patents
Crystal face coupled cuprous oxide, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrocatalytic carbon dioxide reduction, in particular to a crystal face coupled cuprous oxide, a preparation method and application thereof; the preparation method of the crystal face coupled cuprous oxide comprises the following steps of A) mixing copper salt, polyvinylpyrrolidone and water, and heating to 50-60 ℃ to obtain a mixed solution; the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 0.56-2.78 g; B) and (3) in the stirred mixed solution, dropwise adding a sodium hydroxide solution for reaction, and then dropwise adding an ascorbic acid solution for reaction to obtain crystal face coupled cuprous oxide. The method uses less reaction raw materials, realizes the adjustment of the shape of the cuprous oxide, can adjust the proportion of the obtained cuprous oxide crystal faces, has more uniform size, excellent carbon dioxide electrocatalysis performance, and higher multi-carbon product Faraday efficiency and current density.
Description
Technical Field
The invention relates to the technical field of electrocatalytic carbon dioxide reduction, in particular to a crystal face coupled cuprous oxide and a preparation method thereof.
Background
With the continuous development of social economy, the excessive consumption of fossil energy and the accompanying environmental problems (such as global warming, haze and the like) become bottlenecks which restrict the development of global economy. Meanwhile, with the use of a large amount of fossil fuels, the carbon emission is remarkably increased, and the concentration of carbon dioxide in the atmosphere is continuously increased. Reducing and converting carbon dioxide not only reduces the carbon dioxide concentration in the atmosphere but also enables the recycling of useful carbon-based fuels.
Among various carbon dioxide conversion strategies, the reaction conditions required by electrocatalytic reduction of carbon dioxide are the mildest, and meanwhile, the reaction system is compact and modular, is easy to realize large-scale popularization and application, and is considered to be the most attractive conversion technology and storage mechanism. Multi-carbon product (CH) from electrocatalytic carbon dioxide reduction3CH2OH、C2H4、CH3CH2CH2OH, etc.) has higher energy density and wider applicability, while being able to improve the energy efficiency of electrocatalytic carbon dioxide reduction. Although a series of breakthroughs are made in the research of electrocatalysis of carbon dioxide reduction into multi-carbon products, the current catalyst still has the problems of low catalytic activity, poor product selectivity, poor long-term stability and the like.
The copper-based material has moderate adsorption energy to key intermediates (CO), and is the only catalyst capable of realizing carbon-carbon coupling to generate multi-carbon products. In a plurality of catalyst design strategies, crystal face coupling adjustment of the copper-based catalyst is a common and effective mode for controlling the form, a boundary obtained by coupling different crystal faces has the activity of efficiently catalyzing carbon dioxide reduction, and the coupling of different crystal faces can realize the catalytic effect of 1+1 & gt 2. However, most of the crystal-coupled copper-based catalysts reported in the literature to date cannot meet the requirements of practical catalytic applications. For example, Gong et al obtained catalysts with coupling properties of copper (100) and (111) planes by electro-reduction of copper-containing precursors on copper foil, and the use of copper foil substrates increased the cost of preparing such catalysts and also limited the use of catalysts in flow cells (see Angew. chem. int. Ed.2021,60, 4879-. Cuprous oxide particles prepared by the Wangzhou rock and the like expose a (100) crystal face and a (111) crystal face at the same time, but the used raw materials are large in dosage and are uneconomical; the prepared cuprous oxide is uneven in size, the proportion of the (100) crystal face and the (111) crystal face is fixed, and the cuprous oxide is single and unadjustable (see Chinese patent CN 201911342476.2).
In addition, stability is also an important indicator of catalyst performance. Most of the stability test systems reported in the literature often face the problem of product crossover, resulting in increasingly lower faradaic efficiency of the product in stability testing. On the other hand, the electrodes are flooded with the electrolyte, so that the electrodes lose hydrophobicity and become poor in stability. For example, the stability of the Yang et al electrocatalytic carbon dioxide reduction test is maintained for only 3 or more hours (see j.am. chem. soc.2020,142,6400-6408), which is far from satisfying the requirements of practical applications.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a crystal-surface-coupled cuprous oxide, a preparation method and an application thereof, wherein a smaller amount of polyvinylpyrrolidone raw material is adopted, and the prepared cuprous oxide has excellent carbon dioxide electrocatalytic performance, and has high multi-carbon product faraday efficiency and current density.
The invention provides a preparation method of crystal face coupled cuprous oxide, which comprises the following steps:
A) mixing copper salt, polyvinylpyrrolidone and water, and heating to 50-60 ℃ to obtain a mixed solution; the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 0.56-2.78 g;
B) and (3) in the stirred mixed solution, dropwise adding a sodium hydroxide solution for reaction, and then dropwise adding an ascorbic acid solution for reaction to obtain crystal face coupled cuprous oxide.
Preferably, in step a), the copper salt is selected from at least one of copper chloride, copper sulfate and copper nitrate;
the dosage ratio of the copper salt to the water is 1 mmol: 80-120 mL;
the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 1.11 g;
the heating rate is 4-6 ℃/min;
the temperature after heating was 55 ℃.
Preferably, in the step B), the stirring speed is 490-510 r/min;
the concentration of the sodium hydroxide solution is 1.5-2.5 mol/L, and the dropping speed of the sodium hydroxide solution is 0.5-2 mL/min;
the dosage ratio of the sodium hydroxide solution to the copper salt is 5-15 mL: 1 mmol.
Preferably, in the step B), the concentration of the ascorbic acid solution is 0.4-0.8 mol/L, and the dripping speed of the ascorbic acid solution is 1-3 mL/min;
the dosage ratio of the ascorbic acid solution to the copper salt is 5-15 mL: 1 mmol.
Preferably, the step B), after the dropwise addition of the ascorbic acid solution is completed, further comprises:
and cooling to 20-40 ℃, centrifuging, washing and drying.
Preferably, the cuprous oxide coupled with the crystal face is formed by coupling a cuprous oxide (100) crystal face with a cuprous oxide (111) crystal face.
The invention also provides the crystal face coupled cuprous oxide prepared by the preparation method.
The invention also provides a flow electrolytic cell, which comprises a cathode electrode, an anode electrode, a diaphragm, anolyte and catholyte;
the cathode electrode includes:
a carbon paper layer;
a cuprous oxide layer compounded on the carbon paper layer;
a polytetrafluoroethylene layer compounded on the cuprous oxide layer;
the composition of the cuprous oxide layer comprises the above-described crystal-coupled cuprous oxide.
Preferably, the preparation method of the cathode electrode comprises the following steps:
a) ultrasonically and uniformly mixing cuprous oxide, ethanol and a Nafion solution with coupled crystal faces to obtain a dispersion liquid;
b) spraying the dispersion liquid on hydrophobic carbon paper, and drying to obtain sprayed carbon paper;
c) and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid for 1-3 min, taking out, and drying to obtain the cathode electrode.
Preferably, the anode electrode is foamed nickel, the diaphragm is a bipolar membrane, the anolyte is a 1mol/L potassium bicarbonate solution, and the catholyte is a 1mol/L potassium bicarbonate solution.
The invention provides a preparation method of crystal face coupled cuprous oxide, which comprises the following steps: A) mixing copper salt, polyvinylpyrrolidone and water, and heating to 50-60 ℃ to obtain a mixed solution; the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 0.56-2.78 g; B) and (3) in the stirred mixed solution, dropwise adding a sodium hydroxide solution for reaction, and then dropwise adding an ascorbic acid solution for reaction to obtain crystal face coupled cuprous oxide. The cuprous oxide is synthesized by using a small amount of polyvinylpyrrolidone as a raw material, the shape of the cuprous oxide is adjusted by a simple method for adjusting the proportion of reactants, the obtained cuprous oxide is more uniform in size, the proportion among crystal faces can be adjusted, and crystal face coupled cuprous oxide provides more high-reaction active sites, so that the cuprous oxide has excellent carbon dioxide electrocatalysis performance and has higher multi-carbon product Faraday efficiency and current density.
The invention also provides a flow electrolytic cell, which comprises a cathode electrode, an anode electrode, a diaphragm, anolyte and catholyte; the cathode electrode includes: a carbon paper layer; a cuprous oxide layer compounded on the carbon paper layer; a polytetrafluoroethylene layer compounded on the cuprous oxide layer; the composition of the cuprous oxide layer comprises the above-described crystal-coupled cuprous oxide. The flow electrolytic cell provided by the invention solves the problem of poor stability of the catalyst, can effectively avoid cross loss of products, keeps the hydrophobicity of the electrode and ensures that the catalyst has excellent stability.
Drawings
Fig. 1 is a schematic structural diagram of a cathode electrode according to an embodiment of the present invention;
FIG. 2 is an SEM image of crystal-face-coupled cuprous oxide of example 1 of the present invention;
FIG. 3 is an XRD pattern of facet-coupled cuprous oxide of example 1 of the present invention, cuprous oxide cubes of comparative example 1 and cuprous oxide octahedra of comparative example 2;
FIG. 4 is a graph of the Faraday efficiencies of a multi-carbon product of facets-coupled cuprous oxide of example 1 of the present invention, cuprous oxide cubes of comparative example 1, and cuprous oxide octahedra of comparative example 2 under different applied currents;
FIG. 5 is a graph of current density for a multi-carbon product of inventive crystal-face coupled cuprous oxide of example 1, cuprous oxide cubes of comparative example 1, and cuprous oxide octahedra of comparative example 2 under different applied currents;
FIG. 6 is a diagram of a high stability electrolysis system according to example 1 of the present invention;
FIG. 7 shows a polycarbonic product (C) of example 1 of the present invention2+) Faraday efficiency and test voltage plot of (a);
FIG. 8 is an SEM image of crystal-face-coupled cuprous oxide of example 2 of the present invention;
FIG. 9 is an SEM image of crystal-face-coupled cuprous oxide of example 3 of the present invention;
FIG. 10 is an SEM image of crystal-face-coupled cuprous oxide of example 4 of the present invention;
FIG. 11 is an SEM image of cuprous oxide cubes of comparative example 1 of the present invention;
fig. 12 is an SEM image of cuprous oxide octahedra of comparative example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of crystal face coupled cuprous oxide, which comprises the following steps:
A) mixing copper salt, polyvinylpyrrolidone and water, and heating to 50-60 ℃ to obtain a mixed solution; the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 0.56-2.78 g;
B) and (3) in the stirred mixed solution, dropwise adding a sodium hydroxide solution for reaction, and then dropwise adding an ascorbic acid solution for reaction to obtain crystal face coupled cuprous oxide.
The preparation method comprises the steps of mixing copper salt, polyvinylpyrrolidone and water, and heating to 50-60 ℃ to obtain a mixed solution.
In certain embodiments of the present invention, the copper salt is selected from soluble inorganic copper salts. In certain embodiments, the copper salt is selected from at least one of copper chloride, copper sulfate, and copper nitrate.
In certain embodiments of the invention, the polyvinylpyrrolidone is polyvinylpyrrolidone k 30.
In certain embodiments of the invention, the copper salt and polyvinylpyrrolidone are used in a ratio of 1 mmol: 1.11g, 1 mmol: 0.56g, 1 mmol: 1.67g or 1 mmol: 2.78 g.
In certain embodiments of the invention, the ratio of the amount of copper salt to water is 1 mmol: 80-120 mL. In certain embodiments of the invention, the ratio of the amount of copper salt to water is 1 mmol: 90-110 mL. In certain embodiments, the copper salt to water is used in a ratio of 1 mmol: 100 mL. In certain embodiments, the water is deionized water.
In some embodiments of the present invention, the mixing of the copper salt, the polyvinylpyrrolidone and the water further comprises: and (4) stirring. In certain embodiments of the invention, the means of stirring is magnetic stirring. In some embodiments, the stirring time is 10-50 min or 20-40 min. In certain embodiments, the time of stirring is 30 min.
In some embodiments of the present invention, the heating rate is 4-6 ℃/min. In certain embodiments, the heating ramp rate is 5 ℃/min.
In certain embodiments of the invention, the heated temperature is 55 ℃. In certain embodiments of the invention, the heating is by oil bath heating.
And after the mixed solution is obtained, firstly dropwise adding a sodium hydroxide solution into the stirred mixed solution for reaction, and then dropwise adding an ascorbic acid solution for reaction to obtain the crystal face coupled cuprous oxide.
In some embodiments of the present invention, the stirring rate is 490 to 510 r/min. In certain embodiments, the rate of stirring is 500 r/min.
In some embodiments of the invention, the concentration of the sodium hydroxide solution is 1.5-2.5 mol/L. In certain embodiments of the invention, the solvent of the sodium hydroxide solution is water. In some embodiments of the invention, the dropping rate of the sodium hydroxide solution is 0.5-2 mL/min. In certain embodiments, the dropping rate of the sodium hydroxide solution is 1 mL/min.
In some embodiments of the present invention, the ratio of the sodium hydroxide solution to the copper salt is 5 to 15 mL: 1 mmol. In certain embodiments, the ratio of the amount of the sodium hydroxide solution to the copper salt is 10 mL: 1 mmol.
In some embodiments of the invention, the temperature for adding the sodium hydroxide solution to carry out the reaction is 50-60 ℃ and the time is 0.5-1 h. In certain embodiments, the temperature at which the reaction is carried out by adding sodium hydroxide solution is 55 ℃. In certain embodiments, the reaction is carried out by adding sodium hydroxide solution for 0.5 h. In certain embodiments of the invention, the pressure at which the reaction is carried out by adding the sodium hydroxide solution is atmospheric pressure.
In certain embodiments of the present invention, the concentration of the ascorbic acid solution is 0.4 to 0.8 mol/L. In certain embodiments of the invention, the solvent of the ascorbic acid solution is water. In certain embodiments of the present invention, the ascorbic acid solution is added dropwise at a rate of 1 to 3 mL/min. In certain embodiments, the ascorbic acid solution is added dropwise at a rate of 2 mL/min.
In some embodiments of the present invention, the ratio of the ascorbic acid solution to the copper salt is 5-15 mL: 1 mmol. In certain embodiments, the ratio of the amount of the ascorbic acid solution to the copper salt is 10 mL: 1 mmol.
In some embodiments of the invention, the ascorbic acid solution is added for reaction at a temperature of 50-60 ℃ for 2-4 hours. In certain embodiments, the temperature at which the ascorbic acid solution is added to carry out the reaction is 55 ℃. In certain embodiments, the reaction is carried out with the addition of ascorbic acid solution for a period of 3 hours. In certain embodiments of the invention, the reaction is carried out at atmospheric pressure with the addition of the ascorbic acid solution. In certain embodiments of the invention, the ascorbic acid solution is added to the reaction mixture and the reaction mixture is stirred. In certain embodiments of the invention, the stirring rate of the stirring reaction is 500 r/min. After the reaction is finished, cuprous oxide with uniform appearance can be obtained.
In certain embodiments of the invention, the reaction in step B) is carried out in an oil bath or hydrothermal reaction kettle.
In some embodiments of the present invention, after the dropwise addition of the ascorbic acid solution is completed, the method further comprises:
and cooling to 20-40 ℃, centrifuging, washing and drying.
In some embodiments of the present invention, the temperature is reduced to 30-40 ℃. In certain embodiments, the temperature is reduced to 35 ℃.
The method and parameters of the centrifugation are not particularly limited in the present invention, and the method and parameters of the centrifugation known to those skilled in the art can be used.
In certain embodiments of the invention, the washing comprises:
the mixture was washed with deionized water and then with ethanol.
In some embodiments, the number of washing with deionized water is 2 to 4, and the number of washing with ethanol is 2 to 4. In certain embodiments, the number of washes with deionized water is 3 and the number of washes with ethanol is 3.
In certain embodiments of the invention, the drying process is vacuum drying.
In certain embodiments of the present invention, the obtained cuprous oxide with coupled crystal planes is cuprous oxide (100) crystal plane coupled with cuprous oxide (111) crystal plane.
When the ratio of the copper salt to the polyvinylpyrrolidone is low (i.e. the polyvinylpyrrolidone content is high), the synthesized cuprous oxide tends to form nano-octahedrons; when the ratio of the copper salt to the polyvinylpyrrolidone is high, the synthesized cuprous oxide tends to form a nanocube shape; when the dosage proportion of the copper salt and the polyvinylpyrrolidone is proper, the crystal face coupled nano cuprous oxide can be synthesized, and the nano morphology of the obtained cuprous oxide can be influenced by the reaction temperature and time.
The invention synthesizes cuprous oxide with coordinated crystal faces by using a polyvinylpyrrolidone raw material with less raw material, realizes the adjustment of the appearance of the cuprous oxide by a simple method for adjusting the proportion of reactants, and the obtained cuprous oxide has uniform size and adjustable crystal face coupling degree series, and the crystal face coupled cuprous oxide provides more high reaction active sites, so the invention has excellent carbon dioxide electrocatalysis performance and has higher multi-carbon product Faraday efficiency and current density.
The invention also provides the crystal face coupled cuprous oxide prepared by the preparation method.
In certain embodiments of the present invention, the cuprous oxide coupled crystal plane is cuprous oxide (100) crystal plane coupled to cuprous oxide (111) crystal plane. In some embodiments of the present invention, the ratio of the crystal plane of the cuprous oxide (100) to the crystal plane of the cuprous oxide (111) is 0 to 9: 1. in certain embodiments, the ratio of the crystal plane of cuprous oxide (100) to the crystal plane of cuprous oxide (111) is 1.73: 1. 8.1: 1. 0.3: 1 or 0.07: 1.
in certain embodiments of the invention, the crystal-face coupled cuprous oxide is in the shape of a truncated cube.
In certain embodiments of the present invention, the crystal-face-coupled cuprous oxide is nanoscale crystal-face-coupled cuprous oxide. In some embodiments, the grain size of the crystal-face-coupled cuprous oxide is 400-600 nm. In some embodiments, the grain size of the crystal-face-coupled cuprous oxide is 450-550 nm. In certain embodiments of the present invention, the grain size of the crystal-face coupled cuprous oxide is uniform.
In certain embodiments of the present invention, the surface of the crystal-face coupled cuprous oxide particles is smooth.
The crystal face coupled cuprous oxide prepared by the method has excellent carbon dioxide electrocatalytic performance and higher multi-carbon product Faraday efficiency and current density.
The preparation method of the cuprous oxide coupled by the crystal face provided by the invention has low cost, uses less polyvinylpyrrolidone raw material, has more uniform size of the prepared cuprous oxide coupled by the crystal face, can carry out a series of adjustments on the proportion between the (100) crystal face and the (111) crystal face, and is suitable for various reaction devices including a flowing electrolytic cell. The high-stability electrolytic system provided by the invention can effectively avoid the problems of product crossing and electrode flooding, and is suitable for various nano-particle catalysts including cuprous oxide.
The invention also provides a flow electrolytic cell which is a double-electrode flow electrolytic cell and comprises a cathode electrode, an anode electrode, a diaphragm, anolyte and catholyte;
the cathode electrode includes:
a carbon paper layer;
a cuprous oxide layer compounded on the carbon paper layer;
a polytetrafluoroethylene layer compounded on the cuprous oxide layer;
the composition of the cuprous oxide layer comprises the above-described crystal-coupled cuprous oxide.
Fig. 1 is a schematic structural diagram of a cathode electrode according to an embodiment of the present invention.
In some embodiments of the present invention, the carbon paper layer has a thickness of 150 to 200 μm. In certain embodiments, the carbon paper layer has a thickness of 170 μm.
In some embodiments of the present invention, the thickness of the cuprous oxide layer is 1-2 μm. In certain embodiments, the thickness of the cuprous oxide layer is 1.5 μm.
In some embodiments of the present invention, the polytetrafluoroethylene layer has a thickness of 50 to 100 nm. In certain embodiments, the polytetrafluoroethylene layer has a thickness of 70 nm.
In certain embodiments of the present invention, the method of preparing the cathode electrode comprises the steps of:
a) ultrasonically and uniformly mixing cuprous oxide, ethanol and a Nafion solution with coupled crystal faces to obtain a dispersion liquid;
b) spraying the dispersion liquid on hydrophobic carbon paper, and drying to obtain sprayed carbon paper;
c) soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid for 1-3 min, taking out, and drying to obtain a cathode electrode;
the cuprous oxide coupled with the crystal face is the cuprous oxide coupled with the crystal face.
The preparation method comprises the steps of firstly, ultrasonically mixing cuprous oxide coupled with crystal faces, ethanol and a Nafion solution to obtain a dispersion liquid.
In certain embodiments of the invention, the Nafion solution has a mass concentration of 4% to 6%. In certain embodiments, the Nafion solution has a mass concentration of 5%.
In some embodiments of the invention, the dosage ratio of the cuprous oxide coupled with the crystal face, the ethanol and the Nafion solution is 8-12 mg: 0.5-1.5 mL: 75-85 μ L. In some embodiments, the dosage ratio of the cuprous oxide coupled with the crystal face, the ethanol and the Nafion solution is 10 mg: 1mL of: 80 μ L.
In some embodiments of the invention, the time for ultrasonic blending is 1-2 hours. In certain embodiments, the time for ultrasonic homogenisation is 1.5 hours.
And after the dispersion liquid is obtained, spraying the dispersion liquid on hydrophobic carbon paper, and drying to obtain the sprayed carbon paper.
In certain embodiments of the present invention, the hydrophobic carbon paper has a model number SGL29 BC.
In certain embodiments of the invention, the hydrophobic carbon paper has dimensions of 3cm by 3 cm.
In certain embodiments of the invention, the method of drying is room temperature drying.
And after the sprayed carbon paper is obtained, soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid for 1-3 min, taking out, and drying to obtain the cathode electrode.
In certain embodiments of the present invention, the mass fraction of the polytetrafluoroethylene dispersion is 0.4% to 0.6%. In certain embodiments, the polytetrafluoroethylene dispersion is 0.5% by mass.
In certain embodiments of the present invention, the 0.5% mass fraction polytetrafluoroethylene dispersion can be obtained by diluting 60% mass fraction commercial polytetrafluoroethylene dispersion with absolute ethanol.
In certain embodiments of the present invention, after the drying, further comprising: and (5) cutting. In certain embodiments of the invention, the cut carbon paper has dimensions of 1.5cm by 1.5 cm.
In certain embodiments of the invention, the dimensions of the cathode electrode are 1.5cm by 1.5 cm.
In certain embodiments of the invention, the anode electrode is foamed nickel, which is folded in a zigzag pattern.
In certain embodiments of the invention, the membrane is a bipolar membrane, and in certain embodiments, the bipolar membrane is of the type FBM-PK.
In certain embodiments of the invention, the anolyte is a 1mol/L potassium bicarbonate solution. In certain embodiments of the invention, the anolyte has a capacity of 500 mL.
In certain embodiments of the invention, the catholyte is a 1mol/L potassium bicarbonate solution. In certain embodiments of the invention, the catholyte has a capacity of 500 mL.
The method of assembling the flow cell is not particularly limited in the present invention, and a flow cell assembly method known to those skilled in the art may be used.
In some embodiments of the invention, in the performance detection of the assembled flow electrolytic cell, the flow rate of the anolyte is 10-20 mL/min; the flow rate of the catholyte is 10-20 mL/min; the gas flow rate of the cathode electrode is 20-30 sccm. In some embodiments, the gas flow rate at the cathode electrode is controlled to 24sccm, the anolyte flow rate is controlled to 15mL/min, and the catholyte flow rate is controlled to 15 mL/min.
The invention adopts a flow electrolytic cell to carry out electrocatalytic carbon dioxide reduction, and the target product of the electrocatalytic carbon dioxide reduction is a multi-carbon compound, specifically comprises C2H4、CH3COO-、CH3CH2OH and CH3CH2CH2And (5) OH. In the invention, the coupling junction of the (111) crystal face and the (100) crystal face has a crystal face coupling effect, so that defects such as steps and the like are more easily generated, and atoms with lower coordination numbers can enhance the adsorption of reactants such as carbon dioxide and an x CO intermediate, reduce the reaction potential barrier of C-C coupling and promote the generation of a multi-carbon product.
The flow electrolytic cell provided by the invention solves the problem of poor stability of the catalyst, can effectively avoid cross loss of products, keeps the hydrophobicity of the electrode and ensures that the catalyst has excellent stability.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further illustrate the invention, the following embodiments are combined to provide a crystal face coupled cuprous oxide, a preparation method and an application thereof; the design of the high stability electrolysis system is described in detail but is not to be construed as limiting the scope of the invention.
Example 1
Dissolving 1mmol of copper chloride and 1.11g of polyvinylpyrrolidone (k30) in 100mL of deionized water, magnetically stirring for 30min to obtain a uniform solution, then placing the uniform solution into an oil bath, heating to 55 ℃ at a speed of 5 ℃/min, controlling the stirring rate to be 500r/min, dropwise adding 10mL of 2mol/L sodium hydroxide solution at a speed of 1mL/min, reacting for 0.5h at 55 ℃ and normal pressure, dropwise adding 10mL of 0.6mol/L ascorbic acid solution at a speed of 2mL/min, reacting for 3h at a stirring rate of 500r/min at 55 ℃ and normal pressure, then cooling to 35 ℃, centrifuging the obtained product, washing for 3 times with deionized water, washing for 3 times with ethanol, and vacuum drying to obtain the crystal-face coupled cuprous oxide.
The crystal-face-coupled cuprous oxide obtained in example 1 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 2. FIG. 2 is an SEM image of crystal-face-coupled cuprous oxide of example 1 of the present invention. As can be seen from fig. 2, the crystal-face-coupled cuprous oxide prepared in example 1 is in the shape of a truncated cube, the particle size is about 500nm, the particle surface is smooth, and the ratio of the (100) crystal face to the (111) crystal face is about 1.73: 1, the prepared crystal face coupled cuprous oxide is uniform in size, and the crystal face coupling proportion is fixed.
The crystal face-coupled cuprous oxide obtained in example 1 was analyzed by X-ray diffraction, and the X-ray crystal diffraction pattern thereof was obtained as shown in fig. 3. FIG. 3 is an XRD pattern of facet-coupled cuprous oxide of example 1 of the present invention, cuprous oxide cubes of comparative example 1 and cuprous oxide octahedra of comparative example 2. As can be seen from fig. 3, the crystal-coupled cuprous oxide phase prepared in example 1 is well matched with the standard card of cubic cuprous oxide, indicating that the sample has good crystallinity, single phase and no impurity phase.
Weighing 10mg of the crystal face coupled cuprous oxide, adding 1mL of ethanol, then adding 80 mu L of Nafion solution with the mass concentration of 5%, and ultrasonically mixing for 1.5h to obtain a dispersion liquid;
spraying the dispersion liquid on 3cm × 3cm hydrophobic carbon paper SGL29BC, and drying at room temperature to obtain sprayed carbon paper;
and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid with the mass fraction of 0.5% for 1min, taking out, airing, and cutting to 1.5cm multiplied by 1.5cm to obtain the cathode electrode.
The cathode electrode includes: the carbon paper comprises a carbon paper layer with the thickness of 170 mu m, a cuprous oxide layer with the thickness of 1.5 mu m and a polytetrafluoroethylene layer with the thickness of 70nm, wherein the cuprous oxide layer is compounded on the carbon paper layer.
The cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, and the flow electrolytic cell is assembled. In the test process, the gas flow rate of the cathode electrode is controlled to be 24sccm, the flow rate of the anolyte is controlled to be 15mL/min, and the flow rate of the catholyte is controlled to be 15 mL/min.
The gas and liquid phase products were analyzed by gas chromatography and liquid nuclear magnetism, respectively, to obtain the faraday efficiency and current density plots of the multi-carbon product under different applied currents, as shown in fig. 4 and 5. Figure 4 is a graph of the faradaic efficiency of a multi-carbon product of facets-coupled cuprous oxide of example 1 of the present invention, cuprous oxide cubes of comparative example 1, and cuprous oxide octahedra of comparative example 2 under different applied currents. FIG. 5 is a graph of current density for a multi-carbon product of inventive facet-coupled cuprous oxide of example 1, cuprous oxide cubes of comparative example 1, and cuprous oxide octahedra of comparative example 2 under different applied currents. As can be seen from FIGS. 4 and 5, the multi-carbon product of example 1 (C) was obtained at different applied currents (-400 to-100 mA)2+) The maximum Faraday efficiency reaches 74%, and the current density of the multi-carbon product can break 296mAcm with the increase of applied current-2. The crystal face coupled cuprous oxide is shown to have higher catalytic activity, and the selectivity of the multi-carbon product is greatly improved.
The flowing electrolytic cell is subjected to stability test, and the specific steps comprise: the cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, a flowing electrolytic cell is assembled, the electrolyte is replaced once every 10 hours, an ice water bath is carried out on the electrolyte in the testing process, and an air outlet is inserted below the liquid level of the catholyte. The assembled high stability electrolysis system is shown in figure 6. FIG. 6 is a diagram of a high stability electrolysis system according to example 1 of the present invention.
The gas and liquid phase products were analyzed by gas chromatography and liquid nuclear magnetism, respectively, and the experimental results are shown in FIG. 7, where FIG. 7 is the multi-carbon product (C) of example 1 of the present invention2+) Faraday efficiency and test voltage profiles. The results show that at an applied current of-300 mA, the polycarbonic product (C)2+) Faradaic efficiency and test electronicsThe pressure is kept stable within 45h, and the multi-carbon product (C) is obtained2+) The Faraday efficiency of the electrode is kept between 72 and 75 percent within 45 hours, and the test voltage is kept between-4.2 and-3.9V (relative to a reference electrode) within 45 hours. The high-stability electrolytic system can effectively avoid product crossing, solve the problem of failure caused by electrode flooding and greatly improve the stability.
Example 2
Dissolving 1mmol of copper chloride and 0.56g of polyvinylpyrrolidone (k30) in 100mL of deionized water, magnetically stirring for 30min to obtain a uniform solution, then placing the uniform solution into an oil bath, heating to 55 ℃ at a speed of 5 ℃/min, controlling the stirring rate to be 500r/min, dropwise adding 10mL of sodium hydroxide solution with the concentration of 2mol/L at a speed of 1mL/min, reacting for 0.5h at 55 ℃ and normal pressure, dropwise adding 10mL of ascorbic acid solution with the concentration of 0.6mol/L at a speed of 2mL/min, reacting for 3h at a stirring rate of 500r/min at 55 ℃ and normal pressure, then cooling to 35 ℃, centrifuging the obtained product, washing for 3 times with deionized water, washing for 3 times with ethanol, and vacuum drying to obtain the crystal-face coupled cuprous oxide.
The crystal-face-coupled cuprous oxide obtained in example 2 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 8. FIG. 8 is an SEM image of crystal-face-coupled cuprous oxide of example 2 of the present invention. As can be seen from fig. 8, the crystal-face-coupled cuprous oxide prepared in this example is in the form of truncated cube, the particle size is about 500nm, the particle surface is smooth, and the ratio of the (100) crystal face to the (111) crystal face is about 8.1: 1, the prepared crystal face coupling cuprous oxide is not uniform in size, and the crystal face coupling proportion is fixed.
Weighing 10mg of the crystal face coupled cuprous oxide, adding 1mL of ethanol, then adding 80 mu L of Nafion solution with the mass concentration of 5%, and ultrasonically mixing for 1.5h to obtain a dispersion liquid;
spraying the dispersion liquid on 3cm × 3cm hydrophobic carbon paper SGL29BC, and drying at room temperature to obtain sprayed carbon paper;
and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid with the mass fraction of 0.5% for 1min, taking out, airing, and cutting to 1.5cm multiplied by 1.5cm to obtain the cathode electrode.
The cathode electrode includes: the carbon paper comprises a carbon paper layer with the thickness of 170 mu m, a cuprous oxide layer with the thickness of 1.5 mu m and a polytetrafluoroethylene layer with the thickness of 70nm, wherein the cuprous oxide layer is compounded on the carbon paper layer.
The cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, and the flow electrolytic cell is assembled. In the test process, the gas flow rate of the cathode electrode is controlled to be 24sccm, the flow rate of the anolyte is controlled to be 15mL/min, and the flow rate of the catholyte is controlled to be 15 mL/min.
Gas chromatography and liquid nuclear magnetism are respectively adopted to analyze gas phase products and liquid phase products, and experimental results show that under different applied currents (-400 to-100 mA), a multi-carbon product (C)2+) The faradaic efficiency of (A) is up to 54%, and the current density of the polycarbonic product is up to 200mAcm with the increase of applied current-2。
Example 3
Dissolving 1mmol of copper chloride and 1.67g of polyvinylpyrrolidone (k30) in 100mL of deionized water, magnetically stirring for 30min to obtain a uniform solution, then placing the uniform solution into an oil bath, heating to 55 ℃ at a speed of 5 ℃/min, controlling the stirring rate to be 500r/min, dropwise adding 10mL of sodium hydroxide solution with the concentration of 2mol/L at a speed of 1mL/min, reacting for 0.5h at 55 ℃ and normal pressure, dropwise adding 10mL of ascorbic acid solution with the concentration of 0.6mol/L at a speed of 2mL/min, reacting for 3h at a stirring rate of 500r/min at 55 ℃ and normal pressure, then cooling to 35 ℃, centrifuging the obtained product, washing for 3 times with deionized water, washing for 3 times with ethanol, and vacuum drying to obtain the crystal-face coupled cuprous oxide.
The crystal-face-coupled cuprous oxide obtained in example 3 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 9. FIG. 9 is an SEM image of crystal-face-coupled cuprous oxide of example 3 of the present invention. As can be seen from fig. 9, the shape of the crystal-face-coupled cuprous oxide prepared in this example is truncated octahedron, the particle size is about 500nm, the particle surface is smooth, and the proportion of the (100) crystal face to the (111) crystal face is about 0.3: 1, the prepared crystal face coupled cuprous oxide is uniform in size, and the crystal face coupling proportion is fixed.
Weighing 10mg of the crystal face coupled cuprous oxide, adding 1mL of ethanol, then adding 80 mu L of Nafion solution with the mass concentration of 5%, and ultrasonically mixing for 1.5h to obtain a dispersion liquid;
spraying the dispersion liquid on 3cm × 3cm hydrophobic carbon paper SGL29BC, and drying at room temperature to obtain sprayed carbon paper;
and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid with the mass fraction of 0.5% for 1min, taking out, airing, and cutting to 1.5cm multiplied by 1.5cm to obtain the cathode electrode.
The cathode electrode includes: the carbon paper comprises a carbon paper layer with the thickness of 170 mu m, a cuprous oxide layer with the thickness of 1.5 mu m and a polytetrafluoroethylene layer with the thickness of 70nm, wherein the cuprous oxide layer is compounded on the carbon paper layer.
The cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, and the flow electrolytic cell is assembled. In the test process, the gas flow rate of the cathode electrode is controlled to be 24sccm, the flow rate of the anolyte is controlled to be 15mL/min, and the flow rate of the catholyte is controlled to be 15 mL/min.
Gas chromatography and liquid nuclear magnetism are respectively adopted to analyze gas phase products and liquid phase products, and experimental results show that under different applied currents (-400 to-100 mA), a multi-carbon product (C)2+) The maximum Faraday efficiency of the composite material reaches 59%, and the current density of the multi-carbon product is 232mAcm at most with the increase of applied current-2。
Example 4
Dissolving 1mmol of copper chloride and 2.78g of polyvinylpyrrolidone (k30) in 100mL of deionized water, magnetically stirring for 30min to obtain a uniform solution, then placing the uniform solution into an oil bath, heating to 55 ℃ at a speed of 5 ℃/min, controlling the stirring rate to be 500r/min, dropwise adding 10mL of 2mol/L sodium hydroxide solution at a speed of 1mL/min, reacting for 0.5h at 55 ℃ and normal pressure, dropwise adding 10mL of 0.6mol/L ascorbic acid solution at a speed of 2mL/min, reacting for 3h at a stirring rate of 500r/min at 55 ℃ and normal pressure, then cooling to 35 ℃, centrifuging the obtained product, washing for 3 times with deionized water, washing for 3 times with ethanol, and vacuum drying to obtain the crystal-face coupled cuprous oxide.
The crystal-face-coupled cuprous oxide obtained in example 4 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 10. FIG. 10 is an SEM image of crystal-face-coupled cuprous oxide of example 4 of the present invention. As can be seen from fig. 10, the shape of the crystal-face-coupled cuprous oxide prepared in this example is truncated octahedron, the particle size is about 500nm, the particle surface is smooth, and the ratio of the (100) crystal face to the (111) crystal face is about 0.07: 1, the prepared crystal face coupled cuprous oxide is uniform in size, and the crystal face coupling proportion is fixed.
Weighing 10mg of the crystal face coupled cuprous oxide, adding 1mL of ethanol, then adding 80 mu L of Nafion solution with the mass concentration of 5%, and ultrasonically mixing for 1.5h to obtain a dispersion liquid;
spraying the dispersion liquid on 3cm × 3cm hydrophobic carbon paper SGL29BC, and drying at room temperature to obtain sprayed carbon paper;
and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid with the mass fraction of 0.5% for 1min, taking out, airing, and cutting to 1.5cm multiplied by 1.5cm to obtain the cathode electrode.
The cathode electrode includes: the carbon paper comprises a carbon paper layer with the thickness of 170 mu m, a cuprous oxide layer with the thickness of 1.5 mu m and a polytetrafluoroethylene layer with the thickness of 70nm, wherein the cuprous oxide layer is compounded on the carbon paper layer.
The cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, and the flow electrolytic cell is assembled. In the test process, the gas flow rate of the cathode electrode is controlled to be 24sccm, the flow rate of the anolyte is controlled to be 15mL/min, and the flow rate of the catholyte is controlled to be 15 mL/min.
Gas chromatography and liquid nuclear magnetism are respectively adopted to analyze gas phase products and liquid phase products, and experimental results show that under different applied currents (-400 to-100 mA), a multi-carbon product (C)2+) The faradaic efficiency of (2) is up to 50%, and the current density of the polycarbonic product is up to 192mAcm with the increase of applied current-2。
Comparative example 1
Dissolving 1mmol of copper chloride and 0g of polyvinylpyrrolidone (k30) in 100mL of deionized water, magnetically stirring for 30min to obtain a uniform solution, then placing the uniform solution into an oil bath pot, heating to 55 ℃ at the speed of 5 ℃/min, dropwise adding 10mL of sodium hydroxide solution with the concentration of 2mol/L at the speed of 1mL/min, reacting for 0.5h at the temperature of 55 ℃ and under normal pressure, dropwise adding 10mL of ascorbic acid solution with the concentration of 0.6mol/L at the speed of 2mL/min, reacting for 3h at the temperature of 55 ℃ and under normal pressure and at the stirring speed of 500r/min, then cooling to 35 ℃, centrifuging the obtained product, then washing for 3 times by using deionized water, washing for 3 times by using ethanol, and drying in vacuum to obtain a cuprous oxide cube.
The cuprous oxide cube obtained in comparative example 1 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 11. Fig. 11 is an SEM image of cuprous oxide cubes of comparative example 1 of the present invention. As can be seen from FIG. 11, when the ratio of the amount of copper salt to polyvinylpyrrolidone (k30) was 1 mol: when 0g of the cuprous oxide is obtained, the obtained cuprous oxide tends to be in a cubic shape, the particle size of the particles is about 500nm, the exposed crystal faces are (100) faces, and the prepared cuprous oxide is uniform in size.
The cuprous oxide cube obtained in comparative example 1 was analyzed by X-ray diffraction, and its X-ray crystal diffraction pattern was obtained, as shown in fig. 3. As can be seen from fig. 3, the cuprous oxide cubic phase prepared in comparative example 1 is well matched with the standard card of cubic cuprous oxide, indicating that the sample has good crystallinity, and the phase is single and has no impurity phase.
Weighing 10mg cuprous oxide cubes, adding 1mL of ethanol, then adding 80 mu L of 5% Nafion solution, and ultrasonically mixing for 1.5h to obtain a dispersion liquid;
spraying the dispersion liquid on 3cm × 3cm hydrophobic carbon paper SGL29BC, and drying at room temperature to obtain sprayed carbon paper;
and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid with the mass fraction of 0.5% for 1min, taking out, airing, and cutting to 1.5cm multiplied by 1.5cm to obtain the cathode electrode.
The cathode electrode includes: the carbon paper comprises a carbon paper layer with the thickness of 170 mu m, a cuprous oxide layer with the thickness of 1.5 mu m and a polytetrafluoroethylene layer with the thickness of 70nm, wherein the cuprous oxide layer is compounded on the carbon paper layer.
The cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, and the flow electrolytic cell is assembled. In the test process, the gas flow rate of the cathode electrode is controlled to be 24sccm, the flow rate of the anolyte is controlled to be 15mL/min, and the flow rate of the catholyte is controlled to be 15 mL/min.
The gas and liquid phase products were analyzed by gas chromatography and liquid nuclear magnetism, respectively, to obtain the faraday efficiency and current density plots of the multi-carbon product under different applied currents, as shown in fig. 4 and 5. As can be seen from FIGS. 4 and 5, the multi-carbon product (C) of comparative example 1 was obtained at different applied currents (-400 to-100 mA)2+) The Faraday efficiency of the composite is 30-45%, and the current density of the multi-carbon product does not exceed 150mAcm along with the increase of the applied current-2. The cuprous oxide cube is shown to have poor selectivity and low catalytic activity to the multi-carbon product.
Comparative example 2
Dissolving 1mmol of copper chloride and 4g of polyvinylpyrrolidone (k30) in 100mL of deionized water, magnetically stirring for 30min to obtain a uniform solution, then placing the uniform solution into an oil bath pot, heating to 55 ℃ at the speed of 5 ℃/min, dropwise adding 10mL of 2mol/L sodium hydroxide solution at the speed of 1mL/min at the temperature of 55 ℃ and normal pressure, reacting for 0.5h at the temperature of 55 ℃ and normal pressure, dropwise adding 10mL of 0.6mol/L ascorbic acid solution at the speed of 2mL/min, reacting for 3h at the stirring speed of 500r/min at the temperature of 55 ℃ and normal pressure, then cooling to 35 ℃, centrifuging the obtained product, then washing for 3 times with deionized water, washing for 3 times with ethanol, and drying in vacuum to obtain the cuprous oxide octahedron.
The cuprous oxide octahedron obtained in comparative example 2 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 12. Fig. 12 is an SEM image of cuprous oxide octahedra of comparative example 2 of the present invention. As can be seen from fig. 12, when the ratio of the amount of copper salt to polyvinylpyrrolidone (k30) is 1 mol: when the weight is 4g, the obtained cuprous oxide tends to be cubic, the particle size of the particles is about 500nm, the exposed crystal faces are (111) faces, and the prepared cuprous oxide is uniform in size.
The cuprous oxide octahedron obtained in comparative example 2 was analyzed by X-ray diffraction, and its X-ray crystal diffraction pattern was obtained, as shown in fig. 3. As can be seen from fig. 3, the cuprous oxide octahedral phase prepared in comparative example 2 is well matched with the cubic cuprous oxide standard card, indicating that the sample is good in crystallinity, and has a single phase and no impurity phase.
Weighing 10mg of cuprous oxide octahedron, adding 1mL of ethanol, then adding 80 mu L of 5% Nafion solution, and ultrasonically mixing for 1.5h to obtain a dispersion liquid;
spraying the dispersion liquid on 3cm × 3cm hydrophobic carbon paper SGL29BC, and drying at room temperature to obtain sprayed carbon paper;
and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid with the mass fraction of 0.5% for 1min, taking out, airing, and cutting to 1.5cm multiplied by 1.5cm to obtain the cathode electrode.
The cathode electrode includes: the carbon paper comprises a carbon paper layer with the thickness of 170 mu m, a cuprous oxide layer with the thickness of 1.5 mu m and a polytetrafluoroethylene layer with the thickness of 70nm, wherein the cuprous oxide layer is compounded on the carbon paper layer.
The cathode electrode is adopted, foamed nickel is used as an anode electrode, the foamed nickel is folded into a zigzag shape, the anode and the cathode are separated by a bipolar membrane FBM-PK, the anolyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, the catholyte is 1mol/L potassium bicarbonate solution, the capacity is 500mL, and the flow electrolytic cell is assembled. In the test process, the gas flow rate of the cathode electrode is controlled to be 24sccm, the flow rate of the anolyte is controlled to be 15mL/min, and the flow rate of the catholyte is controlled to be 15 mL/min.
The gas and liquid phase products were analyzed by gas chromatography and liquid nuclear magnetism, respectively, to obtain the faraday efficiency and current density plots of the multi-carbon product under different applied currents, as shown in fig. 4 and 5. As can be seen from FIGS. 4 and 5, the multi-carbon product (C) of comparative example 2 was obtained at different applied currents (-400 to-100 mA)2+) The Faraday efficiency of the composite is 20-45%, and the current density of the multi-carbon product does not exceed 150mAcm along with the increase of the applied current-2. The cuprous oxide octahedron is shown to have poor selectivity and low catalytic activity on the multi-carbon product.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of crystal face coupled cuprous oxide comprises the following steps:
A) mixing copper salt, polyvinylpyrrolidone and water, and heating to 50-60 ℃ to obtain a mixed solution; the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 0.56-2.78 g;
B) and (3) in the stirred mixed solution, dropwise adding a sodium hydroxide solution for reaction, and then dropwise adding an ascorbic acid solution for reaction to obtain crystal face coupled cuprous oxide.
2. The method according to claim 1, wherein in step a), the copper salt is at least one selected from the group consisting of copper chloride, copper sulfate and copper nitrate;
the dosage ratio of the copper salt to the water is 1 mmol: 80-120 mL;
the dosage ratio of the copper salt to the polyvinylpyrrolidone is 1 mmol: 1.11 g;
the heating rate is 4-6 ℃/min;
the temperature after heating was 55 ℃.
3. The preparation method according to claim 1, wherein in the step B), the stirring speed is 490 to 510 r/min;
the concentration of the sodium hydroxide solution is 1.5-2.5 mol/L, and the dropping speed of the sodium hydroxide solution is 0.5-2 mL/min;
the dosage ratio of the sodium hydroxide solution to the copper salt is 5-15 mL: 1 mmol.
4. The preparation method according to claim 1, wherein in the step B), the concentration of the ascorbic acid solution is 0.4 to 0.8mol/L, and the dripping rate of the ascorbic acid solution is 1 to 3 mL/min;
the dosage ratio of the ascorbic acid solution to the copper salt is 5-15 mL: 1 mmol.
5. The preparation method according to claim 1, wherein the step B), after the dropwise addition of the ascorbic acid solution is completed, further comprises:
and cooling to 20-40 ℃, centrifuging, washing and drying.
6. The preparation method according to claim 1, wherein the cuprous oxide coupled with the crystal face is cuprous oxide (100) coupled with cuprous oxide (111) coupled with the crystal face.
7. The cuprous oxide with coupled crystal face prepared by the preparation method of any one of claims 1 to 6.
8. A flow cell comprising a cathode electrode, an anode electrode, a separator, an anolyte, and a catholyte;
the cathode electrode includes:
a carbon paper layer;
a cuprous oxide layer compounded on the carbon paper layer;
a polytetrafluoroethylene layer compounded on the cuprous oxide layer;
the composition of the cuprous oxide layer comprises crystal-coupled cuprous oxide as claimed in claim 7.
9. The flow cell according to claim 8, characterized in that the preparation method of the cathode electrode comprises the following steps:
a) ultrasonically and uniformly mixing cuprous oxide, ethanol and a Nafion solution with coupled crystal faces to obtain a dispersion liquid;
b) spraying the dispersion liquid on hydrophobic carbon paper, and drying to obtain sprayed carbon paper;
c) and soaking the sprayed carbon paper in a polytetrafluoroethylene dispersion liquid for 1-3 min, taking out, and drying to obtain the cathode electrode.
10. The flow cell of claim 8, wherein the anode electrode is foamed nickel, the membrane is a bipolar membrane, the anolyte is a 1mol/L solution of potassium bicarbonate, and the catholyte is a 1mol/L solution of potassium bicarbonate.
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