CN109518222B - For electrocatalysis of CO2Bismuth-based catalyst for reduction to formic acid, preparation method and application thereof - Google Patents

For electrocatalysis of CO2Bismuth-based catalyst for reduction to formic acid, preparation method and application thereof Download PDF

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CN109518222B
CN109518222B CN201910082704.0A CN201910082704A CN109518222B CN 109518222 B CN109518222 B CN 109518222B CN 201910082704 A CN201910082704 A CN 201910082704A CN 109518222 B CN109518222 B CN 109518222B
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formic acid
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CN109518222A (en
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李彦光
韩娜
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Suzhou University
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Abstract

The invention provides a method for electrocatalysis of CO2Bismuth-based catalyst for reduction to formic acid and preparation thereofA method and an application. In aqueous systems, bismuth catalysts have electrocatalytic CO2The reduction property, the activity and the selectivity are superior to those of the electrode material which produces formic acid in the same category. Compared with bulk metal bismuth, the bismuth-based catalyst with the nano structure has the characteristics of higher specific surface area, abundant surface chemical reaction sites, specific exposed crystal faces, diversified size effect and the like, so that the bismuth-based catalyst can be used for electrocatalysis of CO2The reduction system shows higher catalytic activity. The nano bismuth-based catalyst disclosed by the invention is environment-friendly, low in price, efficient and stable, and the conversion efficiency of the electrocatalytic reduction of carbon dioxide to formic acid can reach more than 98%, so that the nano bismuth-based catalyst has important practical significance for environmental protection and resource utilization.

Description

For electrocatalysis of CO2Bismuth-based catalyst for reduction to formic acid, preparation method and application thereof
Technical Field
The present invention belongs to electrochemical reduction of CO2The field of catalysis, in particular to the application of bismuth-based materials in the electrocatalytic reduction of CO2Reactions for the formation of formic acid, especially involving the electrocatalytic reduction of CO2Bismuth-based catalyst for generating formic acid, and preparation method and application thereof.
Background
Energy is an important material basis for human survival and development. The progress of human society is closely related to the emergence of high-quality energy and the use of advanced energy technologies. In recent years, the acceleration of global industrialization has led to the growth of CO2The emission amount is in a remarkable rising trend, and has a great threat to the global ecological environment. How to remove CO in the atmosphere2The recovery and conversion to various organic compounds or chemical fuels is one of the great challenges facing sustainable development.
Catalytic reduction of CO by electrochemical means2Can realize CO under milder conditions2Reducing to generate chemical products or small molecular fuels with high added values such as carbon monoxide, formic acid and the like. Meanwhile, the process can be directly and effectively combined with renewable energy sources (such as wind energy, tidal energy and solar energy) without other auxiliary energy sources, so that the carbon resource can be recycled in the true sense, and the process is considered to be the CO with the greatest prospect2And (3) a transformation method. However, at present, CO2The development of electrocatalytic reduction technology still faces a series of challenges: slow kinetic processThe problems of low selectivity and conversion efficiency, easy inactivation of electrode materials and the like caused by the competition of hydrogen evolution reaction and the like. In order to solve the above problems, the development of an efficient and stable electrochemical catalyst has become a key to the research in this field.
Numerous products are obtained by electrocatalytic reduction of carbon dioxide. Formic acid is one of basic organic chemical raw materials, and is widely used in the industrial fields of pesticides, leather, dyes, medicines and the like. Formic acid has a higher commercial value than methanol, CO and other long-chain hydrocarbon compounds, and is a more desirable CO2And (4) reducing the product. Some existing metallic materials can be used for CO2Formic acid is generated by catalytic reduction, but the heavy metal materials are difficult to be widely used due to the problems of biotoxicity, environmental pollution, low reaction efficiency and the like.
Disclosure of Invention
To solve CO2The invention aims to provide a bismuth-based catalyst for efficiently electrocatalytically reducing CO2The method for preparing formic acid, in particular to a novel bismuth-based catalyst prepared by a novel synthesis method, which comprises a novel structure, a novel crystal form and the like, combines the excellent properties of nano materials, and applies the nano bismuth-based catalyst to the electrocatalytic reduction of CO2In a system for generating formic acid, the overpotential of the reaction can be greatly reduced, the electrocatalytic performance is effectively improved, and the catalytic conversion efficiency is obviously improved. Compared to other CO2The electrode material reduced to formic acid has formic acid conversion efficiency close to 100%, catalytic current density is obviously improved, and stability is good. The invention adopts the following technical scheme:
for electrocatalysis of CO2Bismuth-based catalyst for reduction to formic acid, useful for electrocatalysis of CO2The preparation method of the bismuth-based catalyst reduced to formic acid comprises a solution synthesis method, a micromechanical force stripping method, an electrostatic spinning method, an electrodeposition method, a magnetron sputtering method, a high-temperature thermal decomposition method, a vapor deposition method, a ball milling methodA method; the bismuth-based catalyst is simple substance bismuth or a substance containing bismuth. The invention is used for obviously improving the catalytic performance of the bismuth-based catalyst by introducing control strategies such as defects, doping atoms, loading other metals or compounds and the like into the bismuth-based catalyst.
For electrocatalysis of CO2The preparation method of the bismuth-based catalyst reduced to formic acid comprises a solution synthesis method, a micromechanical force stripping method, an electrostatic spinning method, an electrodeposition method, a magnetron sputtering method, a high-temperature thermal decomposition method, a vapor deposition method and a ball milling method; the bismuth-based catalyst is simple substance bismuth or a substance containing bismuth. The invention is used for obviously improving the catalytic performance of the bismuth-based catalyst by introducing control strategies such as defects, doping atoms, loading other metals or compounds and the like into the bismuth-based catalyst.
In the technical scheme, the bismuth-based catalyst is in a powder, fiber or film structure; the powder comprises one or more of microparticles, nanoparticles, nanowires, nanotubes and two-dimensional layered nanosheets; the bismuth-containing substance comprises a bismuth compound, a bismuth-based bimetallic material or a bismuth-containing composite material; the bismuth compound comprises bismuth oxide, bismuth hydroxide, bismuth oxyhalide, bismuth carbonate oxide, bismuth halide and bismuth sulfide; the bismuth-based bimetallic material comprises an alloy or bimetallic compound of bismuth and other metals; the bismuth-containing composite material includes a composite material formed of bismuth and a carbon material. In the invention, bismuth alloy refers to that bismuth and other metals form a bimetal structure for adjusting the whole electrocatalytic performance, and the other metals comprise Cu, Au, Sn and the like; the bismuth-containing composite material is characterized in that a bismuth-based material and some carbon materials are compounded, and the performance of the catalytic material is further improved by utilizing the synergistic effect, wherein the carbon materials comprise conductive carbon black, carbon nano fibers, carbon nano tubes, graphene, reduced graphene oxide, carbon polymers and the like.
The invention discloses an electrocatalytic reduction of CO by a bismuth-based catalyst2Use in the production of formic acid, or in the preparation of electrocatalytic reduction of CO2Use in an electrode for the generation of formic acid; the bismuth-based catalyst is prepared by a solution synthesis method, a micromechanical force stripping method, an electrostatic spinning method, an electrodeposition method, a magnetron sputtering method, a high-temperature thermal decomposition method, a vapor deposition method or a ball milling methodAnd (3) preparing.
In the above technical scheme, the CO is reduced by electrocatalysis2When formic acid is generated, a saturated calomel electrode is used as a reference electrode, and a carbon rod is used as an auxiliary electrode; CO 22The saturated aqueous electrolyte comprises CO2Saturated LiHCO3Solution, NaHCO3Solution, KHCO3Solution, RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3The solution comprises a NaCl solution, a KCl solution, a NaOH solution, a KOH solution, a CsOH solution, a LiOH solution, a phosphate buffer solution and a borate buffer solution; the bismuth-based catalyst is used as a working electrode for preparing the working electrode, or the bismuth-based catalyst is combined with an electrode substrate to obtain the working electrode, or the bismuth-based catalyst is mixed with a conductive carbon material and then is combined with the electrode substrate to obtain the working electrode.
The invention discloses an electrocatalytic CO2A method for reducing formic acid comprises the steps of preparing a bismuth-based catalyst by a solution synthesis method, a micromechanical force stripping method, an electrostatic spinning method, an electrodeposition method, a magnetron sputtering method, a high-temperature thermal decomposition method, a vapor deposition method or a ball milling method; then preparing a working electrode by using a bismuth-based catalyst in CO2Electrocatalytic reduction of CO in saturated aqueous electrolyte2Formic acid is generated by the reaction.
In the above technical scheme, the CO is reduced by electrocatalysis2When formic acid is generated, a saturated calomel electrode is used as a reference electrode, and a carbon rod is used as an auxiliary electrode; CO 22The saturated aqueous electrolyte comprises CO2Saturated LiHCO3Solution, NaHCO3Solution, KHCO3Solution, RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3The solution comprises a NaCl solution, a KCl solution, a NaOH solution, a KOH solution, a CsOH solution, a LiOH solution, a phosphate buffer solution and a borate buffer solution; the bismuth-based catalyst is used as a working electrode for preparing the working electrode, or the bismuth-based catalyst is combined with an electrode substrate to obtain the working electrode, or the bismuth-based catalyst is mixed with a conductive carbon material and then is combined with the electrode substrate to obtain the bismuth-based catalystTo the working electrode.
In the present invention, the solution synthesis method is represented by C6H9BiO6Reacting with polyvinylpyrrolidone in a mixed solvent to obtain a bismuth oxide nanotube, and then electrolytically reducing the bismuth oxide nanotube to obtain a bismuth-based catalyst;
the liquid phase stripping method comprises the steps of taking bismuth powder as a raw material, and carrying out probe ultrasonic treatment in a solvent to obtain a bismuth-based catalyst;
the electrostatic spinning method comprises the following steps of using BiCl3Preparing spinning solution with polymer as raw material, then carrying out electrostatic spinning to obtain nano-fiber, and carrying out heat treatment on the nano-fiber to obtain a bismuth-based catalyst;
the electrodeposition method is to use Bi (NO)3)3▪5H2O and p-benzoquinone are used as raw materials, a three-electrode system is adopted, and electrodeposition treatment is carried out to obtain a bismuth-based catalyst;
the magnetron sputtering method is that metal bismuth is used as a target material, and sputtering treatment is carried out on a substrate to obtain a bismuth-based catalyst;
the high-temperature thermal decomposition method comprises the following steps of3Heating the raw materials in an air atmosphere to obtain a bismuth-based catalyst;
the vapor deposition method is that vapor of bismuth precursor is deposited on the surface of a heat-resistant and insulating substrate to generate a layered product, and the bismuth-based catalyst is obtained;
the ball milling method is to ball mill the powdery bismuth compound precursor in the presence of a lubricant to obtain the bismuth-based catalyst.
According to the preparation method, the bismuth material can grow along a two-dimensional plane, the growth of a third dimension is inhibited, so that the two-dimensional ultrathin bismuth-based catalyst with uniform thickness can be obtained, particularly, the initially formed nanocrystals are oriented and connected together under the action of dipole moment, surface charge mutual attraction and the like, and then are crystallized into the large-size bismuth-based material with high orientation, so that the two-dimensional bismuth-based thin slice with ultrathin thickness can be rapidly obtained in a large amount; compared with the existing material, the large specific surface area of the two-dimensional layered material can provide abundant surface catalytic active sites, and the electronic structure of the two-dimensional layered material can be obviously changed, so that a plurality of strange physicochemical properties are brought. More importantly, the material of the invention can easily realize controllable modulation through ways of element doping, surface modification, manufacturing defect, lamella thickness control and the like, which is very key to the construction and performance optimization of high-performance catalytic materials. By changing the chemical bonding and configuration of the material surface interface, the chemical potential is increased, more dangling bonds and more unsaturation are caused, and the interaction with target molecules is promoted, so that the catalytic activity is different from the original catalytic activity.
Further, in the solution synthesis method, the reaction is 195oC, reacting for 15 min; electrolytic reduction of the bismuth oxide nanotube is carried out in electrolyte, and the potential of the electrolytic reduction is lower than-1V; c6H9BiO6The mass ratio of the polyvinyl pyrrolidone to the polyvinyl pyrrolidone is 0.75 (0.5-1); the mixed solvent is a mixed solvent of water and glycol;
in the liquid phase stripping method, a solvent is N-methyl pyrrolidone, and after ultrasonic treatment by a probe, centrifugal separation and freeze drying are carried out to obtain a bismuth-based catalyst;
in the electrostatic spinning method, the polymer is polyacrylonitrile, and the heat treatment is 240 in the air atmosphereoC treating for 2h, and then 500 g in argon atmosphereoC, calcining for 2 h;
in the electrodeposition method, Bi (NO) is added3)3Mixing the solution with a p-benzoquinone ethanol solution, and performing electrodeposition treatment by adopting a three-electrode system to obtain a bismuth-based catalyst; in the three-electrode system, a metal titanium foil is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, and a platinum wire is used as an auxiliary electrode;
in the magnetron sputtering method, the purity of the metal bismuth is more than 99.99 percent, and the substrate is hydrophobic carbon paper;
in the high-temperature thermal decomposition method, the heating temperature is 300 to 600 DEGoC, the time is 1-6 h;
in the vapor deposition method, bismuth precursor is bismuth oxide, heat-resistant and insulating substrate is quartz boat, deposition is carried out in argon and oxygen, and deposition temperature is 105 deg.CoC, the time is 2-5 min;
in the ball milling method, the lubricant comprises one or more of benzyl benzoate, water, ethanol and n-dodecane; the powdery bismuth compound precursor is bismuth powder or bismuth compound, such as bismuth oxide, bismuth chloride, and bismuth sulfide.
Further, in the solution synthesis method, the reaction is carried out under the protection of magnetic stirring and nitrogen; the electrolytic reduction of the bismuth oxide nano tube is carried out for 1-2 h under the potential of-1.5V; the volume ratio of the glycol to the water is (50-100) to 1; preferably, the bismuth oxide nanotube is calcined and then subjected to electrolytic reduction;
in the liquid phase stripping method, the ultrasonic treatment power of the probe is 900W, the time is 4 h, and the temperature is 5oC; centrifuging at 1500 rpm for 2 hr, collecting supernatant, and centrifuging at 8000 rpm for 0.5 hr; the freeze drying is vacuum freeze drying;
in the electrostatic spinning method, the mass concentration of polyacrylonitrile in spinning solution is 10wt%, and Bi is3+The concentration of (A) is 0.1-1 mol/L; during electrostatic spinning, the sample introduction speed is 1mL/h, the positive pressure and high pressure are 15kV, and the heat treatment is 240 ℃ in the air atmosphereoC treating for 2h, and then 500 g in argon atmosphereoC, calcining for 2 h;
in the electrodeposition method, Bi (NO)3)3The concentration of the solution is 0.01-0.1 mol/L, the concentration of the p-benzoquinone ethanol solution is 0.0575-0.575 mol/L, and the electro-deposition treatment is carried out for 3-5 min under the constant voltage of-0.1V;
in the magnetron sputtering method, during sputtering treatment, the background is vacuumized to 4.6x10-3Pa, the sputtering gas is pure argon, the gas pressure during sputtering is 0.3999 Pa, the sputtering power is 240W, the sputtering time is 200 s, and the target base distance is 10 cm;
in the vapor deposition method, according to the gas flow, the ratio of argon to oxygen is 50 sccm to 5 sccm;
in the ball milling method, the rotation speed of the ball mill is 8000 rpm.
The invention prepares the material for electrocatalytic CO by introducing defects, doping atoms, loading other metals or compounding with other materials in the bismuth material (prior art)2Bismuth-based catalysts for reduction to formic acid, this regulation strategy significantly improves their catalytic performance. The solution synthesis method of the invention can be specifically as follows:
will 100mg polyvinylpyrrolidone was dissolved in 10mL of ethylene glycol and 0.1mL of deionized water, and 75 mg C was added at room temperature6H9BiO6And forming a uniform dispersion liquid under the assistance of ultrasound. Subsequently, the temperature of the dispersion was raised to 195oAnd C, keeping the temperature for 15 min under the magnetic stirring and nitrogen protection. Then adding 25 mL of ethanol and 10mL of deionized water for quenching reaction to finally obtain a bismuth oxide nanotube; dispersing bismuth oxide nanotube, ketjen black powder and adhesive in ethanol solvent, ultrasonically treating for 30 min, uniformly dripping on hydrophobic carbon paper as working electrode, and adding NaHCO saturated with carbon dioxide3In the electrolyte, the electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the carbon rod is used as an auxiliary electrode, and the electrolytic reduction is carried out for 1-2 hours under the reduction potential lower than-1V (vs. SCE), so as to obtain the bismuth catalyst rich in the defect structure. As electrocatalytic reduction of CO2Working electrode for formic acid production with a catalyst loading of 1mg/cm2Active area of 1mg/cm2。
The liquid phase stripping method may be specifically:
weighing bismuth powder (50-100 mg) and adding into N-methylpyrrolidone (NMP) to obtain a mixed solution, carrying out probe ultrasonic treatment for 4 h under the condition of sealing with the power of 900W, and controlling the temperature to be kept at 5 ℃ in the whole probe ultrasonic treatment processoCAnd after the stripping is finished, immediately transferring the stripping solution into a centrifugal tube for centrifugal separation at 1500 rpm for 2h, taking the supernatant after the centrifugation is finished, performing centrifugal separation at 8000 rpm for 0.5 h, and performing vacuum freeze drying to obtain the two-dimensional bismuth nanosheet which is the bismuth-based catalyst.
The electrostatic spinning method can be specifically as follows:
weighing Polyacrylonitrile (PAN) powder, dissolving the Polyacrylonitrile (PAN) powder in N, N-dimethylformamide solution to prepare solution with the mass concentration of 10wt%, and then adding BiCl3（Bi3+= 0.1-1 mol/L) is slowly added into the solution, and the solution is continuously stirred until the solution is uniformly mixed, thus obtaining a precursor solution containing bismuth salt and polyacrylonitrile polymer; transferring the prepared precursor solution into a syringe, fixing the syringe on a micro-pump sample injector, and arranging a needle of the syringeThe collecting plate is connected with the positive electrode of the high-voltage direct-current power supply, the collecting plate paved with the aluminum foil is connected with the negative electrode of the high-voltage direct-current power supply, the sample injection speed is controlled to be 1mL/h, and the positive pressure and the high voltage are set to be 15 kV; by adopting an electrostatic spinning technology, the composite nano-fiber of bismuth salt and polyacrylonitrile can be collected; subjecting the obtained composite nanofiber to 240 ℃ in an air atmosphereoCPre-oxidation treatment for 2h, and finally 500 hours of pre-oxidation treatment in argon atmosphereoCAnd 2h of high-temperature calcination to obtain Bi2O3The nano-fiber is a bismuth-based catalyst, is in a fiber felt thin film structure, and can be directly used for electrocatalytic reduction of CO2A working electrode for generating formic acid.
The electrodeposition method may be specifically:
adding Bi (NO)3)3Mixing the solution (0.01-0.1 mol/L) with a p-benzoquinone ethanol solution (0.0575-0.575 mol/L), and uniformly stirring; adopting a three-electrode system, taking a metal titanium foil as a working electrode, a silver/silver chloride electrode as a reference electrode and a platinum wire as an auxiliary electrode, and electrodepositing for 3-5 min at a constant voltage of-0.1V (vs. Ag/AgCl) to finally obtain a bismuth oxyiodide film as a bismuth-based catalyst which can be directly used as an electro-catalytic reduction CO2A working electrode for generating formic acid.
The magnetron sputtering method may specifically be:
high-purity metal bismuth (with the purity of 99.99 percent, the diameter of 50.8 mm and the thickness of 3 mm) is adopted as a target material, and hydrophobic carbon paper is selected as a substrate material; background vacuum pumped to 4.6x10-3Pa, the sputtering gas is pure argon, the gas pressure during sputtering is 0.3999 Pa, the sputtering power is 240W, the sputtering time is 200 s, and the target base distance is 10 cm. After sputtering is finished, the electrode with bismuth nano particles uniformly distributed on the surface layer of the carbon paper can be used as an electrode for electrocatalytic reduction of CO2A working electrode for generating formic acid.
The ball milling method may specifically be:
bismuth powder or precursor powder of bismuth compound is used as raw material, and under the action of benzyl benzoate, water, ethanol, n-dodecane and other lubricating solvents, the bismuth-based catalyst is obtained by utilizing ball milling and shearing action at a certain rotating speed.
The vapor deposition method may be specifically:
putting bismuth oxide powder in the middle of quartz boat, adjusting temperature to 105 deg.CoCKeeping the temperature for 2-5 min to obtain a bismuth-based catalyst; argon and oxygen are introduced in the temperature rise stage and the constant temperature stage, and the gas flow is Ar/O2= 50/5 sccm to act as protective, carrier gas.
The bismuth-based material is used for electrocatalytic reduction of CO2When the cathode electrode of the reaction is prepared, the bismuth-based material can form a film by itself to form a working electrode; or directly depositing or growing on the conductive electrode substrate to form an electrode; or after the soluble bismuth material powder and the conductive carbon material are uniformly mixed and dispersed in a solvent, the mixture is dripped on the surface of an electrode substrate to form an electrode, wherein the conductive carbon material comprises carbon powder, graphite, carbon black, acetylene black, activated carbon, nano carbon, a carbon nano tube and graphene; the conductive electrode substrate comprises a material selected from the group consisting of a glassy carbon electrode, a rotating disk electrode, a gas diffusion electrode, carbon paper, carbon cloth, carbon felt, conductive glass, a metal foil electrode, and a metal foam electrode.
When the bismuth-based catalyst is used for the reaction of generating formic acid by high-efficiency electrocatalytic reduction, an ion exchange membrane separates the anode and the cathode of an H-type electrolytic cell, a three-electrode system is adopted, the electrode modified by the bismuth-based catalyst is used as a working electrode (cathode), and CO is continuously introduced2In the electrolyte of (2) to carry out CO2Carrying out reduction reaction; in electrocatalytic reduction of CO2In the reaction, the catholyte solution used is CO2Saturated aqueous electrolyte mainly containing CO in different concentrations2Saturated LiHCO3Solution, NaHCO3Solution, KHCO3Solution, RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3The solution comprises NaCl solution, KCl solution, NaOH solution, KOH solution, CsOH solution, LiOH solution, phosphate buffer solution and borate buffer solution.
The invention discloses a new prepared bismuth-based catalyst for electrocatalytic reduction of CO2To formic acid, the bismuth-based catalysts are elemental bismuth, compounds of bismuth, polymers, and bismuth-containing composites, such as bismuth oxide, bismuth hydroxide, bismuth oxyhalideBismuth oxycarbonate, bismuth halides, bismuth sulfides and alloys of bismuth, composite materials of bismuth; the bismuth-based catalyst has forms including powder, thin film and fiber. The invention takes the bismuth-based catalyst as the electrocatalytic reduction of CO2The preparation method of the cathode catalyst and the working electrode in the reaction comprises the steps of using the bismuth-based catalyst as the working electrode, for example, forming a film without an additional adhesive and an electrode substrate, and also comprises the step of loading the bismuth-based catalyst on the electrode substrate to form the working electrode. The electrode substrate comprises a material substrate having good electrical conductivity: glassy carbon electrodes, rotating disk electrodes, gas diffusion electrodes, carbon cloth, carbon paper, carbon felt, conductive glass, metal foil electrodes, metal foam electrodes. The combination mode of the bismuth-based catalyst and the electrode substrate comprises deposition, in-situ growth or spin coating on the surface of the electrode substrate, and simultaneously, the bismuth-based catalyst powder and the conductive carbon material can also be uniformly mixed to prepare catalyst slurry which is dripped on the conventional electrode substrate.
The invention takes the bismuth-based catalyst as the electrocatalysis CO2A cathode catalyst for reduction reaction, capable of efficiently converting CO2Reduction to formic acid (or formate ion). Electrocatalytic reduction of CO2The reaction is carried out in an H-type electrolytic cell, with the anode and cathode separated by a Nafion117 diaphragm or an anion exchange membrane. Adopting a three-electrode system, taking an electrode modified by a bismuth-based material as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a carbon rod or an electrode loaded with an oxygen evolution catalyst material as an auxiliary electrode, and continuously introducing CO2Under the atmosphere of (2), a constant potential electrolysis method is adopted to carry out reduction reaction under different voltages. Gas chromatography, ion chromatography and nuclear magnetic resonance are used for qualitative and quantitative analysis of gas and liquid products of the reaction.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention prepares the novel bismuth catalyst with the nano structure, and can realize high-efficiency electro-catalysis of CO under lower overpotential in an aqueous electrolyte system2Formic acid is generated, the Faraday efficiency can be close to 100%, and the bismuth catalyst can maintain good Faraday after long-time electrolysis testEfficiency and current density, and exhibits excellent electrocatalytic stability.
2. Compared with other catalysts, the nano bismuth catalyst prepared by the limited method is environment-friendly, low in price, efficient, stable, high in selectivity and wide in industrial production application value.
Drawings
FIG. 1 is a morphology and structure characterization of commercial bismuth powder, (a) SEM image; (b) an XRD spectrum;
FIG. 2 electrocatalytic CO of commercial bismuth powder2Reduction performance, (a) formic acid faradaic efficiency plot (b) formic acid current density plot;
FIG. 3 is a representation of the morphology and structure of bismuth oxide nanotubes of example one, (a) XRD spectrum; (b) SEM image; (c) STEM-HAADF images; (d) a high resolution TEM image;
FIG. 4 is the electrocatalytic CO of bismuth oxide nanotubes of example one2Reduction performance, (a) formic acid faradaic efficiency plot; (b) formic acid current density plot; (c) a stability test chart;
FIG. 5 is an electrocatalytic CO of two-dimensional monolayer/multilayer bismuth nanoplates of example two2A graph of the faradaic efficiency of reduced formic acid;
FIG. 6 is a morphology and structure characterization of bismuth oxide nanofibers in example III, (a) XRD spectra; (b) SEM image; FIG. 7 is the electrocatalytic CO of bismuth oxide nanofibers in example III2Reducing formic acid Faraday efficiency and formic acid current density diagram;
FIG. 8 is a morphology and structure characterization of the bismuth oxyiodide thin film of example four, (a) SEM image; (b) an XRD spectrum; FIG. 9 is electrocatalytic CO of bismuth oxyiodide thin film in example IV2Reducing formic acid Faraday efficiency and formic acid current density diagram;
fig. 10 is a morphology and structure characterization of the magnetron sputtered bismuth nanoparticles of example five, (a) SEM image; (b) an XRD spectrum;
FIG. 11 is the electrocatalytic CO of magnetron sputtered bismuth nanoparticles of example five2Graph of faradaic efficiency of reduced formic acid.
Detailed Description
Taking commercial bismuth powder (99.99%, 200 molybdenum, mcalin biochemistry ltd, shanghai) as an example, SEM images (fig. 1 a) show that commercial bismuth powder has blocky irregular morphology with non-uniform size. At 0.5M NaHCO3CO in solution2Commercial bismuth powder electrocatalytic CO on reduction test2The initial potential of formic acid generated by reduction is-0.7V vs RHE, the highest faradaic efficiency of formic acid is about 85%, and H gradually moves in a negative way along with the gradual potential2The product is increased, and the yield of formate is sharply reduced. In addition, the highest formic acid catalytic current density is only 6mA/cm in the RHE voltage interval of-0.5 to-1 Vvs2(FIG. 2). The invention obviously improves the catalytic performance of the existing bismuth material by introducing the regulation strategies of defects, doping atoms, loading other metals or compounding with other materials and the like, and can be seen in the following embodiments.
Example 1: preparation of metal bismuth catalyst by solution synthesis method
100mg of polyvinylpyrrolidone was dissolved in 10mL of ethylene glycol and 0.1mL of deionized water. At room temperature, 75 mg of C6H9BiO6Adding into the above solution, and forming uniformly dispersed solution under the assistance of ultrasound for 1 min. Subsequently, the temperature of the reaction solution was rapidly increased to 195oAnd C, keeping the temperature for 15 min under the magnetic stirring and nitrogen protection. The reaction was then quenched by the addition of 25 mL of ethanol and 10mL of deionized water. And after the reaction is finished, centrifugally collecting a solid product, washing the solid product for at least three times by using absolute ethyl alcohol and deionized water, and performing vacuum freeze drying to obtain a solid sample bismuth oxide nanotube. Finally, the bismuth oxide nanotubes were placed in air at 300 deg.foCalcining for 1 h under C to remove possible residual organic matters on the surface to obtain bismuth oxide nanotube powder (marked as Bi)2O3-NT）。
Mixing the above Bi2O3-NT powder 1mg, Ketjen black powder 0.5 mg, 6. mu.L Nafion binder dispersed in 250 uL ethanol solvent, sonicated for 30 min, uniformly drop-coated on hydrophobic carbon paper as a working electrode, and then CO2Saturated NaHCO3By electrolysis ofIn the solution, the electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a carbon rod is used as an auxiliary electrode, electrolytic reduction is carried out for 1.5 h under the reduction potential of-1.5V (vs. SCE), a metal bismuth catalyst rich in a defect structure is obtained, and hydrophobic carbon paper loaded with the bismuth catalyst is used as electro-catalytic reduction CO2Working electrode for formic acid production with a catalyst loading of 1mg/cm2Active area of 1mg/cm2。
Electrode CO in evaluation of the above bismuth catalyst2In the process of reducing the electrocatalysis performance, a standard three-electrode system is adopted in an H-shaped electrolytic cell which is divided into an anode tank and a cathode tank by a proton exchange membrane: the hydrophobic carbon paper with the surface loaded with the nano bismuth catalyst rich in defects is taken as a working electrode (cathode), a carbon rod is taken as an auxiliary electrode (anode), a saturated calomel electrode is taken as a reference electrode, and the hydrophobic carbon paper is fed into a cathode groove to form a 0.5M KHCO solution3Introducing CO into the electrolyte2Until saturated, then controlling the reduction potential range to be-0.28 to-1.05V vs RHE to carry out CO2And (5) testing the reduction reaction.
Bi preparation by controlled hydrolysis of bismuth acetate in the presence of polyvinylpyrrolidone and trace amounts of water with ethylene glycol as the main solvent2O3FIG. 3 is a representation of the morphology and structure of bismuth oxide nanotubes, the product determined by X-ray diffraction pattern from tetragonal β -Bi2O3Composition (fig. 3 a), scanning electron microscopy image showing that it consists of one-dimensional nanotube structures (fig. 3 b), as can be seen from STEM-HAADF image in fig. 3c, one-dimensional nanotube structures with hollow central carbon nanotubes of length 30-60 nm and inner diameter 4.5 ± 0.2 nm, fig. 3d demonstrates that it is predominantly along the tetragonal β -Bi2O3Of crystals<220>The direction grows longitudinally. It is noteworthy that Bi2O3Is covered with highly defective fragments or nanoclusters, which are characterized by electrocatalytic CO2The reduction reaction provides an advantageous structural basis. Bi prepared by the method2O3Clearly distinguished from the samples prepared by other methods, their double-wall character and high defect-state surface coverage provided ideal templates for the cathodic conversion to defective metallic Bi nanostructures.
In CO2Saturated 0.5M KHCO3In the solution, the defect-rich nano Bi is subjected to CO treatment in the potential intervals of-0.28V and-1.05V2And (4) reduction electrolysis testing. Firstly, formic acid can be obviously detected at-0.38V, the initial Faraday efficiency is 4.4%, when the potential reaches-0.64V, the Faraday efficiency rapidly rises to 92%, and the Faraday efficiency is always kept between-0.7V and-1.05V>97 percent. Corresponding CO and H2Is only contained in<3% (fig. 4 a).
The corresponding formate current density reached an unprecedented 60 mA/cm at-1.05V2Values (fig. 4 b). It can be found that the ultra-high formic acid selectivity and the larger current density are far better than other known formate-forming CO under the wider potential window2The electrocatalyst is reduced. Compared with the Bi-based material reported at present, the excellent performance of the material is improved in a breakthrough manner. In particular, the current density is generally less than 8 mA/cm2About (6 mA/cm for experimental testing of catalyst Current Density of example 1 as disclosed in 1079746902About, 107020075 reported that the catalyst of example 2 has a current density of 7mA/cm2And about), which proves the unique advantage of the nano Bi with rich structural defects prepared by the method of the invention.
In addition to good activity and selectivity, the nano-metal Bi of the present invention has excellent long-term durability. CO up to 46 h at-0.82V2And (4) reduction electrolysis. In the reaction process, the total current density of the nano metal Bi is stabilized at 36 mA/cm2Left and right (fig. 4 c). And sucking a small amount of electrolyte every 12 hours, calculating the formic acid Faraday efficiency of the electrolyte, and finding that the value is highly consistent and is always maintained in the range of 98-100%.
Example 2: liquid phase stripping method for preparing two-dimensional bismuth nanosheet
800 mg of bismuth powder was weighed and added to 80 mL of N-methylpyrrolidone (NMP) to obtain a mixed solution. Performing probe ultrasonic treatment at 900W for 4 h under sealed condition, and controlling temperature to be 5 deg.C during the whole probe ultrasonic treatment processoC. Immediately after the end of stripping, the stripping solution was transferred toAnd (3) respectively carrying out 1500 rpm centrifugal separation for 2h in each centrifugal tube (the liquid volume of each tube is about 27 mL), merging supernate after the centrifugation is finished, carrying out 8000 rpm centrifugal separation for 0.5 h, and carrying out vacuum freeze drying to obtain the two-dimensional bismuth nanosheet.
The morphology in the SEM photo of the bismuth nanosheet is an irregular sheet structure. Further using TEM, it can be observed that: after stripping, a small amount of bismuth nanoparticles of smaller size, about 10 nm, was simultaneously produced. AFM characterization test results show that the thickness of the prepared bismuth nanosheet is about 3-4 nm, which corresponds to the thickness of about 2 atomic layers. In addition, the Raman spectra of the bismuth nanosheet and the bulk bismuth after stripping are compared, and the Raman spectra of the bulk bismuth and the bismuth of the thin layer have obvious displacement difference, namely Eg and Ag 1Both characteristic peaks have different degrees of red-shift and the intensity tends to be significantly weaker.
Dispersing 1mg of the above two-dimensional bismuth nanosheet catalyst, 0.5 mg of conductive ketjen black powder and 6 μ L of 5 wt% Nafion (r) binder in 250 μ L of ethanol solvent, subjecting to ultrasonic treatment for 30 min to form a uniform dispersion, and then, uniformly applying the entire slurry to 1 × 1 cm by drop coating in small amounts for several times2And naturally drying the hydrophobic carbon paper to obtain the carbon paper loaded with the two-dimensional ultrathin bismuth nanosheets.
As shown in FIG. 5, in CO2Saturated 0.1M KHCO3In the method, the carbon paper loaded with the two-dimensional ultrathin bismuth nanosheets can be used as a cathode to absorb CO at a lower overpotential2Formic acid is generated by reduction, and when the potential is-1V, the faradaic efficiency of formic acid is as high as 97%, which also indicates that the two-dimensional ultrathin bismuth nanosheet has higher specific surface area, more catalytic active sites are exposed on the surface, and CO is favorably generated2And (3) the transmission and reduction of molecules on the surface.
EXAMPLE 3 preparation of Bi by electrospinning2O3Nano-fiber
Weighing 1g of Polyacrylonitrile (PAN) powder, dissolving the Polyacrylonitrile (PAN) powder in N, N-dimethylformamide solution to prepare solution with the mass concentration of 10wt%, and then adding 0.1g of BiCl3Slowly adding into the above solution, and continuously stirring until the solution is uniformly mixed to obtain the product containing bismuth salt and polypropylenePrecursor solution of an Enenitrile Polymer (Bi)3+= 0.5 mol/L). Transferring the prepared precursor solution into a 10mL injector, fixing the injector on a micro pump injector, connecting a needle of the injector with the positive electrode of a high-voltage direct-current power supply, connecting a collecting plate paved with an aluminum foil with the negative electrode of the high-voltage direct-current power supply, controlling the sample introduction speed to be 1mL/h, and setting the positive pressure and the high pressure to be 15 kV. The composite nano-fiber of the bismuth salt and the polyacrylonitrile can be collected by adopting an electrostatic spinning technology. The obtained composite nano-fiber is subjected to pre-oxidation treatment at 240 ℃ for 2h in the air atmosphere, and finally is subjected to high-temperature calcination at 500 ℃ for 2h in the argon atmosphere to obtain Bi2O3A nanofiber mat.
FIG. 6 is a graphical representation of the morphology and structure of bismuth oxide nanofibers, Bi2O3All diffraction peaks appearing on the XRD pattern of the nanofibers (FIG. 6 a) correspond to β -Bi2O3And no other miscellaneous peak appears, the prepared sample fiber is confirmed to be pure phase Bi2O3. As can be seen from the SEM image (FIG. 6 b), Bi2O3The composite fiber has uniform diameter, smooth surface, nano-fiber shape, uniform size distribution and good dispersibility, the fiber length can reach several micrometers, and the fiber diameter is 200-300 nm. In addition, the FT-IR spectrum analysis shows that the characteristic peak of PAN disappears, indicating that the organic molecules in the system are completely removed after calcination. In addition, the height of the groove is 400-600 cm-1A new characteristic peak appears and can be classified as a regular octahedron BiO6Vibration of the middle Bi-O bond.
Bi obtained in the above-mentioned manner2O3The nanofiber felt directly acts as a flexible working electrode without the need for an additional electrode substrate and binder. At 0.5M NaHCO3Has been subjected to CO in solution of2And (5) reduction testing. The test results are shown in the attached figure 7, and CO is reduced in a RHE voltage range of-0.6 to-1V vs2，CO2The highest Faraday efficiency of the reduction to formic acid is 98 percent, and the catalytic current density is close to 20 mA/cm2。
In conclusion, Bi is successfully prepared by combining the electrostatic spinning technology2O3Nanofiber electrode materials. The electrode pair CO2The electrocatalysis for preparing the formic acid by reduction has higher catalytic activity and better catalytic stability. The method is simple and convenient, has low preparation cost, has universal applicability to the preparation of other single metal or bimetal composite materials, and can be used for preparing CO2Has good application prospect in the research of reduction.
Example 4: preparation of bismuth oxyhalide film by electrodeposition method
50 mL of a solution containing 0.04 mol/L of Bi (NO)3)3Adding 20 ml of 0.23 mol/L p-benzoquinone ethanol solution into 0.4 mol/L KI mixed solution, mixing for 1 min and stirring uniformly. A three-electrode system is adopted, metal titanium foil is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, a platinum wire is used as an auxiliary electrode, and electrodeposition is carried out for 3.5 min at constant voltage of minus 0.1V (vs. Ag/AgCl) to obtain the bismuth oxyiodide thin film electrode.
According to the XRD spectrogram (figure 8 b), the obtained sample is the BiOI of a tetragonal system, the peak type of each characteristic peak is sharp, the intensity is high, and the crystallization performance of the sample is good. As can be seen from the SEM image (fig. 8 a), the prepared Bioi thin films were all composed of thin sheets, and a layer of flaky bismuth oxyhalide was uniformly spread and grown on the surface of the metallic titanium foil, and the thickness of each thin sheet was 200 nm or less, and the thickness of the BiOBr and BiOCl thin sheets prepared by the same method was thinner than that of the Bioi thin sheets.
The lamellar array can be vertically grown on the surface of the conductive substrate (metal titanium foil) uniformly by the electrochemical deposition method. The bismuth oxyiodide film and the metal titanium foil are used as a working electrode together and are added with 0.5M NaHCO3In the electrolyte of (2) to carry out CO2The Faraday efficiency of the formic acid of the product can reach more than 98 percent in a reduction test (figure 9), and the microstructure and the electrocatalytic performance of the product are kept good after a long-time test (-0.8V vs RHE) after 10 hours. The electrocatalytic performance of bismuth oxyiodide is replaced by bismuth oxychloride or bismuth oxybromide, and the faradaic efficiency of formic acid can reach more than 98%.
Example 5: preparation of bismuth nanoparticles by magnetron sputtering method
High-purity metal bismuth (purity 99.99 percent, straight line) is adoptedDiameter 50.8 mm and thickness 3 mm) as target material, and hydrophobic carbon paper as substrate material. Background vacuum pumped to 4.6x10-3Pa, the sputtering gas is pure argon, the gas pressure during sputtering is 0.3999 Pa, the sputtering power is 240W, the sputtering time is 200 s, and the target base distance is 10 cm. After the sputtering is finished, small-sized bismuth nano-particles can be uniformly distributed on the surface layer of the carbon paper.
SEM image shows (fig. 10 a): the average bismuth nanocrystal grain size of the film is firstly increased and then reduced along with the sputtering power, and the compactness of the film is reduced along with the increase of the power. XRD results showed (fig. 10 b): the bismuth nanoparticles prepared by sputtering are all of polycrystalline inclined hexagonal structures.
Subjecting the electrode to electrocatalytic reduction of CO2The test shows that the conversion efficiency of formic acid can reach 93 percent (figure 11), and meanwhile, the sputtering substrate material can be replaced by a silicon wafer and applied to photoelectrocatalysis CO2The catalytic conversion efficiency and stability of the system are also considerable in a reduction system.
The invention obtains the nanometer bismuth-based material with different structures through a specific preparation method, the unique structural characteristics of the nanometer bismuth-based material provide favorable guarantee for improving the electrocatalytic performance, the invention is not only beneficial to improving the number of catalytic active sites, but also can regulate and control the intrinsic electronic structure of the bismuth material to a certain degree, thereby showing excellent electrocatalytic CO2Reducing to the catalytic performance of formic acid, the prepared catalyst has an overpotential less than 0.5V, a Faraday efficiency more than 95% and a current density more than 11 mA/cm2。

Claims (3)

1. For electrocatalysis of CO2A bismuth-based catalyst for reduction to formic acid, characterized in that: the method is used for electrocatalysis of CO2The preparation method of the bismuth-based catalyst reduced to formic acid comprises a solution synthesis method; the bismuth-based catalyst is simple substance bismuth or a substance containing bismuth; the solution synthesis method is as follows6H9BiO6Reacting with polyvinylpyrrolidone in a mixed solvent to obtain a bismuth oxide nanotube, and then electrolytically reducing the bismuth oxide nanotube to obtain a bismuth-based catalyst; in the solution synthesis method, the reaction is 195oC, reacting for 15 min; bismuth oxide nanotubesThe electrolytic reduction is carried out in the electrolyte, and the potential of the electrolytic reduction is lower than-1V; c6H9BiO6The mass ratio of the polyvinyl pyrrolidone to the polyvinyl pyrrolidone is 0.75 (0.5-1); the mixed solvent is a mixed solvent of water and glycol; the ratio of polyvinylpyrrolidone to ethylene glycol to water was 100 mg/10 mL/0.1 mL.
2. The method of claim 1 for electrocatalytic CO2Electrocatalytic reduction of CO with bismuth-based catalysts to formic acid2Use in the production of formic acid, or in the preparation of electrocatalytic reduction of CO2Use in an electrode for the production of formic acid.
3. Use according to claim 2, characterized in that: electrocatalytic reduction of CO2When formic acid is generated, a saturated calomel electrode is used as a reference electrode, and a carbon rod is used as an auxiliary electrode; CO 22The saturated aqueous electrolyte comprises CO2Saturated LiHCO3Solution, NaHCO3Solution, KHCO3Solution, RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3A solution, a NaCl solution, a KCl solution, a NaOH solution, a KOH solution, a CsOH solution, a LiOH solution, a phosphate buffer solution, or a borate buffer solution.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104846397A (en) * 2015-04-21 2015-08-19 盐城工学院 Electrode for electrochemical reduction of CO2 and preparation of formic acid and preparation method and application thereof
CN106735304A (en) * 2017-01-06 2017-05-31 西南科技大学 Metal nano preparation of sections method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104846397A (en) * 2015-04-21 2015-08-19 盐城工学院 Electrode for electrochemical reduction of CO2 and preparation of formic acid and preparation method and application thereof
CN106735304A (en) * 2017-01-06 2017-05-31 西南科技大学 Metal nano preparation of sections method

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