CN109518222A - For electro-catalysis CO2It is restored to the bismuth-based catalysts and its preparation method and application of formic acid - Google Patents
For electro-catalysis CO2It is restored to the bismuth-based catalysts and its preparation method and application of formic acid Download PDFInfo
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Abstract
The present invention provides be used for electro-catalysis CO2It is restored to the bismuth-based catalysts and the preparation method and application thereof of formic acid.In aqueous phase system, bismuth catalyst has electro-catalysis CO2The characteristic of reduction, and activity and selectivity etc. are superior to the similar electrode material for producing formic acid.Compared with bulk metal bismuth, the bismuth-based catalysts with nanostructure are because it is with higher specific surface area, surface chemical reaction site abundant, specifically expose the features such as crystal face and diversified dimensional effect, therefore in electro-catalysis CO2Higher catalytic activity is shown in reduction system.Nanometer bismuth-based catalysts in the present invention are environmental-friendly, cheap, efficient stable, and the transformation efficiency of electro-catalysis reduction carbon dioxide to formic acid can be up to 98% or more, this all has important practical significance for environmental protection and the utilization of resources.
Description
Technical field
The invention belongs to electrochemical reduction CO2Catalytic field, and in particular to bismuthino material is applied to electro-catalysis and restores CO2
The reaction more particularly to electro-catalysis for generating formic acid restore CO2Generate formic acid bismuth-based catalysts and the preparation method and application thereof.
Background technique
The energy is the important material base of human survival and development.The progress of human society and the appearance of high-grade energy and elder generation
Use into energy technology is closely bound up.In recent years, the quickening of global industry process makes CO2Discharge amount is on apparent
The trend of liter causes very big threat to the ecological environment in the whole world.How by the CO in atmosphere2Recycling and be converted into each
Kind organic compound or chemical fuel are one of the huge challenges for maintaining Faced In Sustainable Development.
Utilize the method catalysis reduction CO of electrochemistry2, CO can be realized in relatively mild condition2Reduction generates carbon monoxide,
The chemical products or small molecule fuel of the high added values such as formic acid.Meanwhile the process can directly effectively with renewable energy
(such as wind energy, tide energy, solar energy) combines, and is not necessarily to other supplementary energies, realizes the circulation benefit of carbon resource truly
With, it is considered to be most promising CO2Method for transformation.But CO at present2The development of electro-catalysis reduction technique still faces a system
The challenge of column: dynamic process is slow, reacts higher overpotential, the competition participation of evolving hydrogen reaction cause lower selectivity and
The problems such as transformation efficiency and electrode material are easy inactivation.In order to solve problem above, develop the electrochemical catalysis of efficient stable
Agent becomes the key of the area research.
It is numerous that electro-catalysis restores the obtained product of carbon dioxide.Wherein, formic acid is fired as a kind of liquid of safe and convenient
Material, volume energy density with higher are easy to the advantages that transporting storage, are one of basic organic chemical industry raw materials, are used extensively
In the industrial circles such as pesticide, leather, dyestuff, medicine.Have compared to methanol, CO and other long-chain hydrocarbon compounds, formic acid
Higher commercial value is ideal CO2Reduzate.Though existing some metal materials can be used in CO at this stage2It urges
Change reduction generate formic acid, but due to the bio-toxicity of heavy metal material, environmental pollution and reaction efficiency are low the problems such as, this
Class material is difficult to come into operation extensively.
Summary of the invention
In order to solve CO2Series of challenges existing for electro-catalysis reduction technique, the object of the present invention is to provide a kind of bismuthinos
The efficient electro-catalysis of catalyst restores CO2To the method for formic acid, novel bismuthino is prepared especially by new synthetic method and is catalyzed
Agent, including new structure, new crystal form etc., the excellent properties in conjunction with possessed by nano material, by nanometer bismuth-based catalysts application
CO is restored in electro-catalysis2In the system for generating formic acid, reaction overpotential can be substantially reduced, is effectively improved electrocatalysis characteristic, significantly
Improve catalytic conversion efficiency.Compared to other CO2It is restored to the electrode material of formic acid, the formic acid transformation efficiency of such catalyst connects
Nearly 100%, catalytic current density is significantly improved and is had good stability.The present invention adopts the following technical scheme:
For electro-catalysis CO2The bismuth-based catalysts of formic acid are restored to, it is described to be used for electro-catalysis CO2It is restored to the bismuthino catalysis of formic acid
The preparation method of agent includes solution synthetic method, micromechanical forces stripping method, method of electrostatic spinning, electro-deposition method, magnetron sputtering method, height
Warm decomposition method, vapour deposition process, ball-milling method；The bismuth-based catalysts are the substance of bismuth with elementary or bismuth-containing.The present invention passes through
The regulating strategies such as defect, foreign atom, the other metals of load or compound are introduced in bismuth-based catalysts for significantly improving it
Catalytic performance.
For electro-catalysis CO2It is restored to the preparation method of the bismuth-based catalysts of formic acid, including solution synthetic method, micromechanical forces
Stripping method, method of electrostatic spinning, electro-deposition method, magnetron sputtering method, high temperature thermal decomposition method, vapour deposition process, ball-milling method；The bismuth
Base catalyst is the substance of bismuth with elementary or bismuth-containing.The present invention in bismuth-based catalysts by introducing defect, foreign atom, load
The regulating strategies such as other metals or compound are used to significantly improve their catalytic performance.
In above-mentioned technical proposal, the bismuth-based catalysts are powder, fiber or membrane structure；The powder includes micron
One or more of particle, nano particle, nano wire, nanotube, two-dimensional layer nanometer sheet；The substance of the bismuth-containing includes bismuth
Compound, bismuthino bimetallic material or bismuth-containing composite material；Bismuth compound includes bismuth oxide, bismuth hydroxide, BiOX, carbon
Sour oxygen bismuth, halogenation bismuth, bismuth sulfide；The bismuthino bimetallic material includes the alloy or bimetallic compound of bismuth and other metals；
The bismuth-containing composite material includes the composite material that bismuth and carbon material are formed.In the present invention, bismuth alloy is referred to bismuth and other
Metal forms bimetal structure for adjusting whole electrocatalysis characteristic, other metals include Cu, Au, Sn etc.；Bismuth-containing composite material
It refers to carrying out bismuthino material and some carbon materials compound, synergistic effect is utilized further to promote the performance of catalysis material, carbon
Material includes conductive black, carbon nano-fiber, carbon nanotube, graphene, redox graphene, carbon polymer etc..
The invention discloses bismuth-based catalysts to restore CO in electro-catalysis2The application in formic acid is generated, or is urged preparing electricity
Change reduction CO2Generate the application in formic acid electrode；It is heavy using solution synthetic method, micromechanical forces stripping method, method of electrostatic spinning, electricity
Product method, magnetron sputtering method, high temperature thermal decomposition method, vapour deposition process or ball-milling method prepare bismuth-based catalysts.
In above-mentioned technical proposal, electro-catalysis restores CO2When generating formic acid, using saturated calomel electrode as reference electrode, carbon-point
For auxiliary electrode；CO2The water phase electrolyte of saturation includes CO2The LiHCO of saturation3Solution, NaHCO3Solution, KHCO3Solution,
RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3Solution, NaCl solution, KCl solution, NaOH solution, KOH solution,
CsOH solution, LiOH solution, phosphate buffer solution, borate buffer solution；It is using bismuth-based catalysts preparation work electrode
Using bismuth-based catalysts as working electrode, perhaps combine bismuth-based catalysts with electrode basement to obtain working electrode or by bismuth
Base catalyst combines to obtain working electrode with electrode basement after mixing with conductive carbon material.
The invention discloses a kind of electro-catalysis CO2The method for being restored to formic acid, includes the following steps, is synthesized using solution
Method, micromechanical forces stripping method, method of electrostatic spinning, electro-deposition method, magnetron sputtering method, high temperature thermal decomposition method, vapour deposition process or
Person's ball-milling method prepares bismuth-based catalysts；Then bismuth-based catalysts preparation work electrode is utilized, in CO2In the water phase electrolyte of saturation
It carries out electro-catalysis and restores CO2Reaction generates formic acid.
In above-mentioned technical proposal, electro-catalysis restores CO2When generating formic acid, using saturated calomel electrode as reference electrode, carbon-point
For auxiliary electrode；CO2The water phase electrolyte of saturation includes CO2The LiHCO of saturation3Solution, NaHCO3Solution, KHCO3Solution,
RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3Solution, NaCl solution, KCl solution, NaOH solution, KOH solution,
CsOH solution, LiOH solution, phosphate buffer solution, borate buffer solution；It is using bismuth-based catalysts preparation work electrode
Using bismuth-based catalysts as working electrode, perhaps combine bismuth-based catalysts with electrode basement to obtain working electrode or by bismuth
Base catalyst combines to obtain working electrode with electrode basement after mixing with conductive carbon material.
In the present invention, solution synthetic method is, with C6H9BiO6It is raw material with polyvinylpyrrolidone, in the mixed solvent
Reaction obtains oxidation bismuth nanotube, then will aoxidize bismuth nanotube electroreduction, and obtain bismuth-based catalysts；
Liquid phase stripping method is, using bismuth meal as raw material, carries out Probe Ultrasonic Searching processing in a solvent, obtains bismuth-based catalysts；
Method of electrostatic spinning is, with BiCl3It is raw material with polymer, configures spinning solution, then carries out electrostatic spinning and obtain Nanowire
Dimension, nanofiber obtain bismuth-based catalysts through Overheating Treatment；
Electro-deposition method is with Bi (NO3)3▪5H2O and 1,4-benzoquinone are raw material, and using three-electrode system, electrodeposition process obtains bismuth
Base catalyst；
Magnetron sputtering method is, using bismuth metal as target, the sputter process on substrate obtains bismuth-based catalysts；
High temperature thermal decomposition method is, with BiI3It for raw material, heats in air atmosphere, obtains bismuth-based catalysts；
Vapour deposition process is by the vapor deposition of bismuth predecessor in the substrate surface of high temperature insulation, to generate nonwoven fabric from filaments, obtain bismuthino
Catalyst；
Ball-milling method is, in the presence of lubricant, carries out ball-milling treatment to powdered bismuth compound presoma, obtains bismuthino catalysis
Agent.
In the present invention, preparation method is conducive to bismuth material and grows along two-dimensional surface, inhibits the growth of third dimension, so as to
To obtain the uniform two-dimensional ultrathin bismuth-based catalysts of thickness, the effects of especially attracting each other by dipole moment and surface charge
The nanocrystalline orientation being initially formed is linked together, then crystallization is at height-oriented large scale bismuthino material, it can be fast
Fast a large amount of acquisitions have the two-dimentional bismuthino thin slice of ultrathin；Compared with current material, the big ratio of two-dimensional layer material of the present invention
Surface area can not only provide superficial catalytic activation site abundant, but also its electronic structure may significantly change, and bring
Many unusual physico-chemical properties.More importantly material of the present invention is easy to pass through element doping, surface modification, manufacturing defect
Controllable modulation is realized with approach such as lamellar spacing controls, this extremely closes constructing for high-performance catalysis material with performance optimization
Key.By changing the chemical bonding and configuration of material surface and interface, so that its chemical potential increases, causes more dangling bonds and bigger
Unsaturation, promotion and target molecule interaction, to embody different from original catalytic activity.
Further, in solution synthetic method, reacting is 195oC reacts 15 min；The electroreduction of oxidation bismuth nanotube exists
It is carried out in electrolyte, the current potential of electroreduction is lower than -1V；C6H9BiO6Mass ratio with polyvinylpyrrolidone is 0.75:
(0.5~1)；Mixed solvent is water and ethylene glycol mixed solvent；
In liquid phase stripping method, solvent is N-Methyl pyrrolidone, is centrifuged, is freeze-dried after Probe Ultrasonic Searching processing, obtains
To bismuth-based catalysts；
In method of electrostatic spinning, polymer is polyacrylonitrile, and being heat-treated is in air atmosphere 240oC handles 2 h, then in argon atmospher
500 in enclosingoC calcines 2 h；
In electro-deposition method, by Bi (NO3)3Solution is mixed with 1,4-benzoquinone ethanol solution, using three-electrode system, at electro-deposition
Reason, obtains bismuth-based catalysts；In three-electrode system, metal titanium foil as working electrode, silver/silver chloride electrode be reference electrode,
Platinum filament is as auxiliary electrode；
In magnetron sputtering method, the purity of bismuth metal is greater than 99.99%, and substrate is hydrophobic carbon paper；
In high temperature thermal decomposition method, the temperature of heating is 300~600oC, time are 1~6 h；
In vapour deposition process, bismuth predecessor is bismuth oxide, and the substrate of high temperature insulation is quartz boat, be deposited on argon gas, in oxygen into
Row, the temperature of deposition are 105oC, time are 2~5 min；
In ball-milling method, lubricant includes one or more of Ergol, water, ethyl alcohol and n-dodecane；Powdered bismuth
Close the compound that object presoma is bismuth meal or bismuth, such as bismuth oxide, bismuth chloride, bismuth sulfide.
Further, in solution synthetic method, reaction carries out under magnetic agitation and nitrogen protection；Aoxidize the electricity of bismuth nanotube
Solution is reduced to 1~2 h of electroreduction at -1.5 V of current potential；The volume ratio of ethylene glycol and water is (50 ~ 100): 1；It is preferred that will
Electroreduction is carried out again after oxidation bismuth nanotube calcining；
In liquid phase stripping method, the power of Probe Ultrasonic Searching processing is 900 W, and the time is 4 h, temperature 5oC；Centrifuge separation is 1500
Rpm is centrifugated 2 h, then takes supernatant, carries out 8000 rpm and is centrifugated 0.5 h；Freeze-drying is vacuum freeze drying；
In method of electrostatic spinning, in spinning solution, the mass concentration of polyacrylonitrile is 10 wt%, Bi3+Concentration be 0.1~1 mol/
L；When electrostatic spinning, sample introduction speed is 1mL/h, positive pressure high pressure is 15 kV, and being heat-treated is in air atmosphere 240oC handles 2h, so
Afterwards 500 in argon atmosphereoC calcines 2h；
In electro-deposition method, Bi (NO3)3The concentration of solution is 0.01 ~ 0.1 mol/L, and the concentration of 1,4-benzoquinone ethanol solution is
0.0575 ~ 0.575 mol/L, electrodeposition process 3~5 min of electro-deposition in the case where constant voltage is -0.1 V；
In magnetron sputtering method, when sputter process, base vacuum is evacuated to 4.6x10-3 When Pa, sputter gas are pure argon, sputtering
Air pressure is 0.3999 Pa, sputtering power is 240 W, sputtering time is 200 s, target-substrate distance is from for 10cm；
In vapour deposition process, by gas flow, argon gas: oxygen is 50 sccm:5 sccm；
In ball-milling method, the revolving speed of ball milling is 8000 rpm.
The present invention in bismuth material (existing) by introducing defect, foreign atom, the other metals of load or and other materials
Compound method preparation is used for electro-catalysis CO2The bismuth-based catalysts of formic acid are restored to, this regulating strategy significantly improves theirs
Catalytic performance.Solution synthetic method of the present invention can specifically:
100 mg polyvinylpyrrolidone are dissolved in 10 mL ethylene glycol and 0.1 mL deionized water, at room temperature, are added
75 mg C6H9BiO6, and uniform dispersion liquid is formed under ultrasonic wave added.Then, the temperature of dispersion liquid is risen to 195oC, and
Keep 15 min at such a temperature under magnetic agitation and nitrogen protection.Then be added 25 mL ethyl alcohol and 10 mL deionized waters into
Row quenching reaction, it is final to obtain oxidation bismuth nanotube；Will oxidation bismuth nanotube, Ketjen black powder, that adhesive is dispersed in ethyl alcohol is molten
In agent, after 30 min of ultrasound, equably drop coating is used as working electrode on hydrophobic carbon paper, then in carbon dioxide saturation
NaHCO3Electrolyte in, using above-mentioned electrode as working electrode, saturated calomel electrode is reference electrode, and carbon-point is auxiliary electrode,
1 ~ 2 h of electroreduction in the case where reduction potential is lower than -1 V(vs. SCE), obtains the bismuth catalyst for being rich in defect sturcture.As electricity
Catalysis reduction CO2Generate the working electrode of formic acid, catalyst loadings 1mg/cm2, active area 1mg/cm2。
Liquid phase stripping method can specifically:
It weighs bismuth meal (50 ~ 100 mg) to be added in N-Methyl pyrrolidone (NMP), mixed liquor is obtained, in sealing
4 h of Probe Ultrasonic Searching is carried out with the power of 900 W, and controls temperature during entire Probe Ultrasonic Searching and is maintained at 5 oC, removing terminates
Afterwards, stripper is transferred in centrifuge tube immediately and carries out 1500 rpm, 2 h of centrifuge separation, take supernatant after centrifugation again, into
8000 rpm of row is centrifugated 0.5 h, and vacuum freeze drying obtains two-dimentional bismuth nanometer sheet, is bismuth-based catalysts.
Method of electrostatic spinning can specifically:
It weighs polyacrylonitrile (PAN) powder to be dissolved in n,N-Dimethylformamide solution, being made into mass concentration is the molten of 10 wt%
Liquid, then by BiCl3(Bi3+ =0.1 ~ 1 mol/L) it is slowly added in above-mentioned solution, continuous stirring is until solution mixing is equal
It is even, the precursor solution containing bismuth salt and polyacrylonitrile polymer can be obtained；The precursor solution of preparation is transferred to injection
In device, and syringe is fixed on micro pump sample injector, the syringe needle of syringe is connected with the anode of high-voltage DC power supply, is covered with
The collecting board of aluminium foil is connected with the cathode of high-voltage DC power supply, and control sample introduction speed is 1mL/h, and setting positive pressure high pressure is 15 kV；
Using electrostatic spinning technique, the composite nano fiber of bismuth salt and polyacrylonitrile can be collected into；By composite Nano obtained above
Fiber carries out 240 in air atmosphere oC, 2h pre-oxidation treatment, 500 are finally carried out in argon atmosphere oC, 2h high temperature forge
Bi can be obtained in burning2O3Nanofiber is bismuth-based catalysts, and form is fibrofelt membrane structure, can be restored directly as electro-catalysis
CO2Generate the working electrode of formic acid.
Electro-deposition method can specifically:
By Bi (NO3)3Solution (0.01 ~ 0.1mol/L) is mixed with 1,4-benzoquinone ethanol solution (0.0575 ~ 0.575mol/L), stirring
Uniformly；Using three-electrode system, metal titanium foil is as working electrode, and silver/silver chloride electrode is reference electrode, and platinum filament is as auxiliary
Electrode is -0.1V (vs.Ag/AgCl) electro-deposition 3-5 min in constant voltage, finally obtains bismuth oxyiodide film and urge as bismuthino
Agent can restore CO directly as electro-catalysis2Generate the working electrode of formic acid.
Magnetron sputtering method can specifically:
It is target using high purity metal bismuth (purity 99.99%, 50.8 mm of diameter, 3 mm of thickness), substrate material selects hydrophobic carbon
Paper；Base vacuum is evacuated to 4.6x10-3 Pa, sputter gas are pure argon, and air pressure when sputtering is 0.3999 Pa, and sputtering power is
240 W, sputtering time are 200 s, and target-substrate distance is from for 10 cm.After sputtering, bismuth can be evenly distributed on carbon paper surface layer and received
The electrode of rice grain restores CO as electro-catalysis2Generate the working electrode of formic acid.
Ball-milling method can specifically:
Using the precursor powder of bismuth meal or bismuth compound as raw material, lubricated in Ergol, water, ethyl alcohol and n-dodecane etc.
Under the action of solvent, bismuth-based catalysts are obtained using ball milling shear action under certain revolving speed.
Vapour deposition process can specifically:
Bismuth oxide powder is placed in the middle part of quartz boat, adjustment temperature to 105 oC, constant temperature 2-5 min obtains bismuth-based catalysts；
Argon gas and oxygen, gas flow Ar/O are all passed through in temperature rise period and constant temperature stage2=50/5 sccm, with play protection,
Carrier gas effect.
Bismuthino material of the invention restores CO for electro-catalysis2When the cathode electrode preparation of reaction, bismuthino material can be certainly
Body forms a film to form working electrode；Or it Direct precipitation or is grown in conductive electrode basement and forms electrode；Or it will be soluble
Bismuth material powder is uniformly mixed with conductive carbon material be dispersed in solvent after, drop coating is in electrode basement table surface forming electrode, wherein institute
The conductive carbon material stated includes carbon dust, graphite, carbon black, acetylene black, active carbon, nano-sized carbon, carbon nanotube, graphene；Conductive
Electrode basement includes being selected from glass-carbon electrode, rotating disk electrode (r.d.e), gas-diffusion electrode, carbon paper, carbon cloth, carbon felt, electro-conductive glass, gold
Belong to foil electrode, the material of metal foam electrode.
When bismuth-based catalysts of the invention generate the reaction of formic acid for efficient electro-catalysis reduction, amberplex is by H-type
Yin-yang the two poles of the earth of electrolytic cell separate, using three-electrode system, using the electrode of above-mentioned bismuth-based catalysts modification as working electrode (yin
Pole), it is being continually fed into CO2Electrolyte in carry out CO2Reduction reaction；CO is restored in electro-catalysis2In reaction, cathode electricity used
Electrolyte solution is CO2The water phase electrolyte of saturation, main includes the CO of various concentration2The LiHCO of saturation3Solution, NaHCO3It is molten
Liquid, KHCO3Solution, RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3Solution, NaCl solution, KCl solution, NaOH are molten
Liquid, KOH solution, CsOH solution, LiOH solution, phosphate buffer solution, borate buffer solution.
The invention discloses freshly prepd bismuth-based catalysts to restore CO in electro-catalysis2To the application of formic acid, the bismuthino is urged
Agent is the composite material of bismuth simple substance, the compound of bismuth, polymer and bismuth-containing, such as bismuth oxide, bismuth hydroxide, zirconyl oxyhalides
Bismuth, bismuthyl carbonate, halogenation bismuth, the alloy of bismuth sulfide and bismuth, the composite material of bismuth；The form of the bismuth-based catalysts includes powder
End, film and fiber.Bismuth-based catalysts are restored CO by the present invention2Cathod catalyst in reaction, work electricity
The preparation method of pole includes bismuth-based catalysts itself as working electrode, for example is formed a film, and additional adhesive and electrode are not needed
Substrate also includes that bismuth-based catalysts are supported in electrode basement to form working electrode.Electrode basement includes having good conductive
The material substrate of property: glass-carbon electrode, rotating disk electrode (r.d.e), gas-diffusion electrode, carbon cloth, carbon paper, carbon felt, electro-conductive glass, metal
Foil electrode, metal foam electrode.Mode of the bismuth-based catalysts in conjunction with electrode basement includes deposition, growth in situ or is spin-coated on
Electrode basement surface, while bismuth-based catalysts powder and conductive carbon material can also be uniformly mixed and made into catalyst slurry, drop coating
In conventional electrodes substrate.
The present invention is using bismuth-based catalysts as electro-catalysis CO2The cathod catalyst of reduction reaction, can be efficiently by CO2Also
Primary formic acid (or formate ion).Electro-catalysis restores CO2Reaction carries out in the electrolytic cell of H-type, and yin-yang the two poles of the earth use
Nafion117 diaphragm or anion-exchange membrane are spaced.Using three-electrode system, the electrode of bismuthino material modification is as work electricity
Pole, saturated calomel electrode are being held as reference electrode, carbon-point or the electrode for loading oxygen-separating catalyst material as auxiliary electrode
It is continuous to be passed through CO2Atmosphere under, using potentiostatic electrolysis carry out different voltages under reduction reaction.With gas-chromatography, ion
Chromatography and magnetic nuclear resonance method carry out quantification and qualification to the gas and product liquid of reaction.
Due to the application of the above technical scheme, the invention has the following advantages over the prior art:
1. the present invention is prepared for the novel bismuth catalyst with nanostructure, in water phase electrolyte system, may be implemented compared with
Efficient electro-catalysis CO under low overpotential2Formic acid is generated, faradic efficiency can be close to 100%, test by long-time electrolysis
Afterwards, bismuth catalyst can maintain good faradic efficiency and current density, show excellent electro-catalysis stability.
2. the present invention is environmental-friendly using the nanometer bismuth catalyst of restriction method preparation, price compared with other catalyst
It is cheap, efficient stable and have it is highly selective, have wide industrial production application value.
Detailed description of the invention
Fig. 1 is the pattern and structural characterization of business bismuth meal, (a) SEM image；(b) XRD spectrum；
Fig. 2 is the electro-catalysis CO of business bismuth meal2Reducing property, (a) formic acid faradic efficiency figure (b) formic acid current density figure；
Fig. 3 is the pattern and structural characterization of the oxidation bismuth nanotube in embodiment one, (a) XRD spectrum；(b) SEM image；(c)
STEM-HAADF image；(d) high-resolution TEM image；
Fig. 4 is the electro-catalysis CO of the oxidation bismuth nanotube in embodiment one2Reducing property, (a) formic acid faradic efficiency figure；(b)
Formic acid current density figure；(c) stability test figure；
Fig. 5 is two-dimension single layer/multilayer bismuth nanometer sheet electro-catalysis CO in embodiment two2Also orthoformic acid faradic efficiency figure；
Fig. 6 is the pattern and structural characterization of the bismuth oxide nanofiber in embodiment three, (a) XRD spectrum；(b) SEM image；Figure
7 be the electro-catalysis CO of the bismuth oxide nanofiber in embodiment three2Also orthoformic acid faradic efficiency and formic acid current density figure；
Fig. 8 is the pattern and structural characterization of the bismuth oxyiodide film in example IV, (a) SEM image；(b) XRD spectrum；Fig. 9
It is the electro-catalysis CO of the bismuth oxyiodide film in example IV2Also orthoformic acid faradic efficiency and formic acid current density figure；
Figure 10 is the pattern and structural characterization of the bismuth nano particle of magnetron sputtering in embodiment five, (a) SEM image；(b) XRD diagram
Spectrum；
Figure 11 is the electro-catalysis CO of the bismuth nano particle of magnetron sputtering in embodiment five2Also orthoformic acid faradic efficiency figure.
Specific embodiment
By taking business bismuth meal (Shanghai Mike's woods biochemistry Co., Ltd, 99.99%, 200 molybdenums) as an example, SEM image (Fig. 1 a) display
Business bismuth meal has block-like irregular pattern, and size is inhomogenous.In 0.5 M NaHCO3CO is carried out in solution2When reduction test,
Business bismuth meal electro-catalysis CO2The take-off potential that reduction generates formic acid is -0.7 V vs RHE, and highest formic acid faradic efficiency is about
It is 85%, as gradually bearing for current potential is moved, H2Product increases, and the yield of formates sharply declines.In addition, in -0.5 ~ -1 V
In vs RHE voltage range, the catalytic current density of highest formic acid is only 6 mA/cm2(Fig. 2).The present invention passes through in existing bismuth
Introduced in material defect, foreign atom, the other metals of load or with the regulating strategies such as other materials is compound, significantly improve theirs
Catalytic performance, for details, reference can be made to following examples.
Embodiment 1: solution synthetic method prepares metal bismuth catalyst
100 mg polyvinylpyrrolidone are dissolved in 10 mL ethylene glycol and 0.1 mL deionized water.At room temperature, by 75
mg C6H9BiO61 min forms evenly dispersed solution into above-mentioned solution, and under ultrasonic wave added for addition.It then, will be above-mentioned
The temperature of reaction solution is rapidly increased to 195oC, and keep 15 min at such a temperature under magnetic agitation and nitrogen protection.Then lead to
It crosses and 25 mL ethyl alcohol and 10 mL deionized waters progress quenching reaction is added.After reaction, solid product is collected by centrifugation, and uses nothing
At least three times, vacuum freeze drying obtains solid sample and aoxidizes bismuth nanotube for water-ethanol and deionized water washing.Finally, will oxidation
Bismuth nanotube is in air 300o1 h is calcined under C to remove possible remaining organic matter on surface, is obtained bismuth oxide and is received
Mitron powder (is denoted as Bi2O3- NT).
By above-mentioned Bi2O31 mg of-NT powder, 0.5 mg of Ketjen black powder, 6 μ L Nafion adhesives are dispersed in 250 uL
Alcohol solvent in, after 30 min of ultrasound, equably drop coating on hydrophobic carbon paper be used as working electrode, then in CO2Saturation
NaHCO3Electrolyte in, using above-mentioned electrode as working electrode, saturated calomel electrode is reference electrode, and carbon-point is auxiliary electrode,
In -1.5 V(vs. SCE of reduction potential) under 1.5 h of electroreduction, the metal bismuth catalyst for being rich in defect sturcture is obtained, with negative
The hydrophobic carbon paper for carrying bismuth catalyst restores CO as electro-catalysis2The working electrode of formic acid is generated, catalyst loadings are 1 mg/
cm2, active area is 1 mg/cm2。
In the electrode CO for evaluating above-mentioned bismuth catalyst2When restoring electrocatalysis characteristic, anode slot is divided into proton exchange membrane
In the H-type electrolytic cell of cathode can, the three-electrode system of standard is used: with the rich defective nanometer bismuth catalysis of above-mentioned area load
The hydrophobic carbon paper of agent is working electrode (cathode), and carbon-point is auxiliary electrode (anode), and saturated calomel electrode is reference electrode, Xiang Yin
0.5 M KHCO of pole slot3CO is passed through in electrolyte2To satisfying, then controlling reduction potential range is -0.28 ~ -1.05 V vs RHE
Carry out CO2Reduction reaction test.
In the presence of polyvinylpyrrolidone and trace water, ethylene glycol passes through the water of control bismuth acetate as primary solvent
Solution is to prepare Bi2O3Nanotube.Fig. 3 is the pattern and structural characterization for aoxidizing bismuth nanotube, determines production by X ray diffracting spectrum
Object is by cubic β-Bi2O3Form (Fig. 3 a), scanning electron microscope image show it by 1-dimention nano pipe structure composition (Fig. 3 b),
Can be seen that one-dimensional nano tube structure from the STEM-HAADF image in Fig. 3 c has hollow center carbon nanotube, these
The length of nanotube is 30-60 nm, and internal diameter is 4.5 ± 0.2 nm, and Fig. 3 d proves it mainly along cubic β-Bi2O3Crystal <
The longitudinal growth of 220 > direction.It is worth noting that Bi2O3Outer wall be covered with the fragment or nano-cluster of height defect, this feature
For electro-catalysis CO2The advantageous structure basis that reduction reaction provides.The Bi of this method preparation2O3It is clearly distinguishable from other methods
The surface of the sample of preparation, double-wall feature and height defect state is covered as cathode and is converted into defective metal Bi nanostructure
Provide ideal template.
In CO20.5 M KHCO of saturation3In solution, rich defective nanometer Bi is in -0.28 V and -1.05 V voltage belts
Between carried out CO2Reduction electrolysis test.Firstly, can be clearly detected formic acid in -0.38 V, initial faradic efficiency is
4.4%, when current potential reaches -0.64 V, faradic efficiency rises very rapidly up to 92%, and between -0.7 .05 of V ~ -1 V
Remain > 97%.Corresponding CO and H2Total content only < 3%(Fig. 4 a).
Corresponding formates current density reaches unprecedented 60 mA/cm in -1.05 V2It is worth (Fig. 4 b).It can send out
Existing, under wider potential window, the formic acid selectivity and larger current density of superelevation are far superior to other known life
The CO of formic acid salt2Restore elctro-catalyst.Compared to the Bi sill reported at present, excellent performance has breakthrough mention
It is high.Especially in terms of current density, existing current density is generally less than 8 mA/cm2Left and right is (real as disclosed in 107974690
The catalyst current density experiment test for applying example 1 is 6mA/cm2It controls, the catalyst electric current of the embodiments 2 of 107020075 reports
Density is 7mA/cm2Left and right), this again demonstrate the uniqueness with abundant fault of construction nanometer Bi of the method for the present invention preparation is excellent
Gesture.
Other than good activity and selectivity, nano metal Bi of the present invention also has excellent long durability.-
The CO up to 46 h has been carried out under 0.82 V2Reduction electrolysis.During the reaction, the overall current density of nano metal Bi is stablized
36 mA/cm2Left and right (Fig. 4 c).At interval of drawing a small amount of electrolyte within 12 hours and calculating its formic acid faradic efficiency, the value is found
Height is consistent, maintains in the range of 98% ~ 100% always.
Embodiment 2: liquid phase stripping method prepares two-dimentional bismuth nanometer sheet
It weighs 800 mg bismuth meals to be added in the N-Methyl pyrrolidone (NMP) of 80 mL, obtains mixed liquor.In sealing
4 h of Probe Ultrasonic Searching is carried out with the power of 900 W, and controls temperature during entire Probe Ultrasonic Searching and is maintained at 5oC.Removing terminates
Afterwards, stripper is transferred in 3 centrifuge tubes (every about 27 mL of pipe liquid volume) immediately, carries out 1500 rpm centrifugation point respectively
It from 2 h, takes supernatant to merge again after centrifugation, carries out 8000 rpm and be centrifugated 0.5 h, vacuum freeze drying obtains two dimension
Bismuth nanometer sheet.
Pattern in the SEM photograph of gained bismuth nanometer sheet is irregular laminated structure.Further using TEM can observe
To: a small amount of smaller size of bismuth nano particle is generated after removing simultaneously, partial size is about 10 nm.AFM characterization test the result shows that
Prepared bismuth nanometer sheet thickness is 3-4 nm or so, corresponds to 2 atomic layer level thickness or so.In addition, bismuth is received after comparison removing
The Raman spectrum of rice piece and blocky bismuth, it can be seen that the bismuth Raman spectrum of blocky bismuth and thin layer has apparent displacement difference,
Eg and Ag 1Two characteristic peaks have different degrees of red shift, and intensity has the tendency that obviously dying down.
By the above-mentioned two-dimentional bismuth nanometer sheet catalyst of 1 mg, the 5 wt % of conductive Ketjen black powder and 6 μ L of 0.5 mg
Nafion adhesive is dispersed in the alcohol solvent of 250 μ L, and 30 min of ultrasound form uniform dispersion liquid.Then, by whole slurries
The a small amount of multiple equably drop coating of liquid is in 1 × 1 cm2Hydrophobic carbon paper on, natural drying, obtain load two-dimensional ultrathin bismuth nanometer
The carbon paper of piece.
As shown in Fig. 5, in CO20.1 M KHCO of saturation3In, the carbon paper of above-mentioned load two-dimensional ultrathin bismuth nanometer sheet is made
It can be under lower overpotential by CO for cathode2Reduction generates formic acid, and when current potential is -1V, formic acid faradic efficiency is up to
97%, this also illustrates the bismuth nanometer sheet specific surface areas with higher of two-dimensional ultrathin, and surface exposes more catalytic active sites
Point, is conducive to CO2Transmission and reduction of the molecule on surface.
Embodiment 3: electrostatic spinning technique prepares Bi2O3Nanofiber
It weighs 1 gram of polyacrylonitrile (PAN) powder to be dissolved in n,N-Dimethylformamide solution, being made into mass concentration is 10 wt%'s
Solution, then by 0.1g BiCl3It is slowly added in above-mentioned solution, continuous stirring is uniformly mixed up to solution, be can be obtained and is contained
There is the precursor solution (Bi of bismuth salt and polyacrylonitrile polymer3+ =0.5 mol/L).The precursor solution of preparation is transferred to
In 10 mL syringes, and syringe is fixed on micro pump sample injector, the syringe needle of syringe and the anode of high-voltage DC power supply
It is connected, the collecting board for being covered with aluminium foil is connected with the cathode of high-voltage DC power supply, and control sample introduction speed is 1 mL/h, and setting positive pressure is high
Pressure is 15 kV.Using electrostatic spinning technique, the composite nano fiber of bismuth salt and polyacrylonitrile can be collected into.It is obtained above-mentioned
Composite nano fiber the pre-oxidation treatment of 240oC/2h is carried out in air atmosphere, 500oC/ is finally carried out in argon atmosphere
Bi can be obtained in the high-temperature calcination of 2 h2O3Nanofiber mats.
Fig. 6 is the pattern and structural characterization of bismuth oxide nanofiber, Bi2O3(Fig. 6 a) occurs in the XRD spectrum of nanofiber
All diffraction maximums both correspond to β-Bi2O3, and occur without other miscellaneous peaks, confirm that made sample fiber is pure phase Bi2O3.By
SEM schemes visible (Fig. 6 b), Bi2O3The uniform diameter of composite fibre and surface is smooth, is in nanometer fibrous, even size distribution, point
It is good to dissipate property, fibre length can reach several microns, and fibre diameter is 200~300 nm.In addition, by FT-IR atlas analysis, hair
The characteristic peak of existing PAN disappears, and shows after calcining that organic molecule has completely removed in system.In addition, being located at 400 ~ 600 cm-1
There is new characteristic peak in place, can be attributed to regular octahedron BiO6The vibration of middle Bi-O key.
By Bi obtained above2O3Nanofiber mats do not need additional electrode basement directly as working electrode flexible
And adhesive.In 0.5 M NaHCO3Solution in CO has been carried out to it2Reduction test.The test result such as display of attached drawing 7 ,-
CO is restored under 0.6 ~ -1 V vs RHE voltage range2, CO2It is reduced to the highest faradic efficiency 98% of formic acid, catalytic current is close
Spend nearly 20 mA/cm2。
In conclusion being successfully prepared for Bi in conjunction with electrostatic spinning technique2O3Nano-fiber electrode material.This electrode is to CO2
The electro-catalysis for restoring formic acid processed has higher catalytic activity and preferable catalytic stability.This method is easy, and preparation cost is lower
It is honest and clean, and there is general applicability to the preparation of other monometallics or double metallic composite material, in CO2Have in the research of reduction good
Good application prospect.
Embodiment 4: electro-deposition method prepares BiOX film
Contain the Bi (NO of 0.04 mol/L to 50 mL3)3With 20 mL 0.23 are added in the KI mixed solution of 0.4 mol/L
The 1,4-benzoquinone ethanol solution of mol/L, 1 min of mixing are stirred evenly.Using three-electrode system, metal titanium foil as working electrode,
Silver/silver chloride electrode is reference electrode, and platinum filament is -0.1V (vs.Ag/AgCl) electro-deposition in constant voltage as auxiliary electrode
3.5 min obtain bismuth oxyiodide membrane electrode.
According to XRD spectra (Fig. 8 b), show that gained sample is the BiOI of tetragonal crystal system, the peak type of each characteristic peak is more sharp
Sharp, intensity is larger, shows that the crystal property of sample is good.It can be seen that (Fig. 8 a), prepared BiOI film are equal from SEM figure
It is made of thin slice, and the evenly laid out BiOX for growing a lamellar on the surface of metal titanium foil, the thickness of thin slice exist
200 nm hereinafter, the thin slice of the wherein BiOBr and BiOCl that are prepared using same procedure thin slice of the thickness compared with BiOI
It is thin.
Above by the method for electrochemical deposition, equably can vertically be grown on conductive substrates (metal titanium foil) surface
Lamella array out.With above-mentioned bismuth oxyiodide film and metal titanium foil together as working electrode, in 0.5 M NaHCO3Electrolysis
CO is carried out in liquid2Reduction test, the faradic efficiency of the formic acid of product can be up to 98% or more (Fig. 9), and after 10 h
Test (- 0.8 V vs RHE) for a long time, microstructure and electrocatalysis characteristic all keep good.Bismuth oxyiodide is substituted for chlorine
Bismuth oxide or bismuth oxybromide, electrocatalysis characteristic there is no very big difference, formic acid faradic efficiency can be up to 98% with
On.
Embodiment 5: magnetron sputtering method prepares bismuth nano particle
It is target using high purity metal bismuth (purity 99.99%, 50.8 mm of diameter, 3 mm of thickness), substrate material selects hydrophobic carbon
Paper.Base vacuum is evacuated to 4.6x10-3 Pa, sputter gas are pure argon, and air pressure when sputtering is 0.3999 Pa, and sputtering power is
240 W, sputtering time are 200 s, and target-substrate distance is from for 10 cm.After sputtering, small size can be uniformly distributed on carbon paper surface layer
Bismuth nano particle.
SEM image shows (Figure 10 a): mean sheet bismuth nanocrystalline grain size is with sputtering power first increases and then decreases, film
Consistency reduced with the increase of power.XRD is the result shows that (Figure 10 b): sputtering the bismuth nano particle being prepared is
The oblique hexagonal structure of polycrystalline.
Above-mentioned electrode is subjected to electro-catalysis and restores CO2Test, the transformation efficiency of formic acid is up to 93%(Figure 11), meanwhile, can
It is changed to silicon wafer so that base material will be sputtered, is applied in photoelectrocatalysis CO2In the system of reduction, catalytic conversion efficiency and stabilization
Property is also very considerable.
The present invention obtains the nanometer bismuthino material of different structure by specific preparation method, and unique structure feature is
Improve electrocatalysis characteristic and provide advantageous guarantee, not only facilitates the number for improving active site, it can also certain journey
The native electronic structure of degree ground regulation bismuth material, to show excellent electro-catalysis CO2It is restored to the catalytic performance of formic acid, is made
Standby catalyst overpotential is less than 0.5V, and faradic efficiency is more than 95%, and current density is more than 11 mA/cm2。
Claims (10)
1. one kind is used for electro-catalysis CO2It is restored to the bismuth-based catalysts of formic acid, it is characterised in that: described to be used for electro-catalysis CO2Reduction
Preparation method to the bismuth-based catalysts of formic acid includes solution synthetic method, micromechanical forces stripping method, method of electrostatic spinning, electro-deposition side
Method, magnetron sputtering method, high temperature thermal decomposition method, vapour deposition process or ball-milling method；The bismuth-based catalysts are bismuth with elementary or contain
The substance of bismuth；
Solution synthetic method is, with C6H9BiO6It is raw material with polyvinylpyrrolidone, reacts, aoxidized in the mixed solvent
Then bismuth nanotube will aoxidize bismuth nanotube electroreduction, and obtain bismuth-based catalysts；
Micromechanical forces stripping method is, using bismuth meal as raw material, carries out Probe Ultrasonic Searching processing in a solvent, obtains bismuth-based catalysts；
Method of electrostatic spinning is, with BiCl3It is raw material with polymer, configures spinning solution, then carries out electrostatic spinning and obtain Nanowire
Dimension, nanofiber obtain bismuth-based catalysts through Overheating Treatment；
Electro-deposition method is, with Bi (NO3)3▪5H2O and 1,4-benzoquinone are raw material, and using three-electrode system, electrodeposition process is obtained
Bismuth-based catalysts；
Magnetron sputtering method is, using bismuth metal as target, the sputter process on substrate obtains bismuth-based catalysts；
High temperature thermal decomposition method is, with BiI3It for raw material, heats in air atmosphere, obtains bismuth-based catalysts；
Vapour deposition process is by the vapor deposition of bismuth predecessor in the substrate surface of high temperature insulation, to generate nonwoven fabric from filaments, obtain bismuthino
Catalyst；
Ball-milling method is, in the presence of lubricant, carries out ball-milling treatment to powdered bismuth compound presoma, obtains bismuthino catalysis
Agent.
2. being used for electro-catalysis CO according to claim 12It is restored to the bismuth-based catalysts of formic acid, it is characterised in that: the bismuthino
Catalyst is powder, fiber or membrane structure；The substance of the bismuth-containing includes bismuth compound, bismuthino bimetallic material or contains
Bismuth composite material.
3. being used for electro-catalysis CO according to claim 22It is restored to the bismuth-based catalysts of formic acid, it is characterised in that: the powder
Including one or more of micron particles, nano particle, nano wire, nanotube, two-dimensional layer nanometer sheet；The bismuth compound
Including bismuth oxide, bismuth hydroxide, BiOX, bismuthyl carbonate, halogenation bismuth or bismuth sulfide；The bismuthino bimetallic material includes
The alloy or bimetallic compound that bismuth and other metals are formed；The bismuth-containing composite material include bismuth formed with carbon material it is compound
Material.
4. being used for electro-catalysis CO according to claim 12It is restored to the bismuth-based catalysts of formic acid, it is characterised in that:
In solution synthetic method, reacting is 195oC reacts 15 min；The electroreduction of oxidation bismuth nanotube carries out in the electrolytic solution, electricity
The current potential of solution reduction is lower than -1V；C6H9BiO6Mass ratio with polyvinylpyrrolidone is 0.75:(0.5~1)；Mixed solvent
For water and ethylene glycol mixed solvent；
In liquid phase stripping method, solvent is N-Methyl pyrrolidone, is centrifuged, is freeze-dried after Probe Ultrasonic Searching processing, obtains
To bismuth-based catalysts；
In method of electrostatic spinning, polymer is polyacrylonitrile, and being heat-treated is in air atmosphere 240oC handles 2 h, then in argon atmospher
500 in enclosingoC calcines 2 h；
In electro-deposition method, by Bi (NO3)3Solution is mixed with 1,4-benzoquinone ethanol solution, using three-electrode system, electrodeposition process,
Obtain bismuth-based catalysts；In three-electrode system, metal titanium foil is reference electrode, platinum filament as working electrode, silver/silver chloride electrode
As auxiliary electrode；
In magnetron sputtering method, the purity of bismuth metal is greater than 99.99%, and substrate is hydrophobic carbon paper；
In high temperature thermal decomposition method, the temperature of heating is 300~600oC, time are 1~6 h；
In vapour deposition process, bismuth predecessor is bismuth oxide, and the substrate of high temperature insulation is quartz boat, be deposited on argon gas, in oxygen into
Row, the temperature of deposition are 105oC, time are 2~5 min；
In ball-milling method, lubricant includes one or more of Ergol, water, ethyl alcohol and n-dodecane；Powdered bismuth
Close the compound that object presoma is bismuth meal or bismuth.
5. being used for electro-catalysis CO according to claim 12It is restored to the bismuth-based catalysts of formic acid, it is characterised in that: by bismuth
Defect, foreign atom, the other metals of load or the method preparation compound with other materials are introduced in material is used for electro-catalysis CO2Also
As far as the bismuth-based catalysts of formic acid.
6. being used for electro-catalysis CO2It is restored to the preparation method of the bismuth-based catalysts of formic acid, including the stripping of solution synthetic method, micromechanical forces
From method, method of electrostatic spinning, electro-deposition method, magnetron sputtering method, high temperature thermal decomposition method, vapour deposition process or ball-milling method；It is described
Bismuth-based catalysts are powder, fiber or membrane structure；The substance of the bismuth-containing include bismuth compound, bismuthino bimetallic material or
Person's bismuth-containing composite material；
Solution synthetic method is, with C6H9BiO6It is raw material with polyvinylpyrrolidone, reacts, aoxidized in the mixed solvent
Then oxidation bismuth nanotube is carried out electroreduction, obtains bismuth-based catalysts by bismuth nanotube；
Micromechanical forces stripping method is, using bismuth meal as raw material, carries out Probe Ultrasonic Searching processing in a solvent, obtains bismuth-based catalysts；
Method of electrostatic spinning is, with BiCl3It is raw material with polymer, configures spinning solution, then carries out electrostatic spinning and obtain Nanowire
Dimension, nanofiber obtain bismuth-based catalysts through Overheating Treatment；
Electro-deposition method is, with Bi (NO3)3▪5H2O and 1,4-benzoquinone are raw material, and using three-electrode system, electrodeposition process is obtained
Bismuth-based catalysts；
Magnetron sputtering method is, using bismuth metal as target, the sputter process on substrate obtains bismuth-based catalysts；
High temperature thermal decomposition method is, with BiI3It for raw material, heats in air atmosphere, obtains bismuth-based catalysts；
Vapour deposition process is by the vapor deposition of bismuth predecessor in the substrate surface of high temperature insulation, to generate nonwoven fabric from filaments, obtain bismuthino
Catalyst；
Ball-milling method is, in the presence of lubricant, carries out ball-milling treatment to powdered bismuth compound presoma, obtains bismuthino catalysis
Agent.
7. electro-catalysis CO according to claim 62It is restored to the preparation method of the bismuth-based catalysts of formic acid, it is characterised in that: institute
Stating powder includes one or more of micron particles, nano particle, nano wire, nanotube, two-dimensional layer nanometer sheet；The bismuth
Compound includes bismuth oxide, bismuth hydroxide, BiOX, bismuthyl carbonate, halogenation bismuth or bismuth sulfide；The bismuthino bimetallic material
Material includes the alloy or bimetallic compound that bismuth and other metals are formed；The bismuth-containing composite material includes that bismuth is formed with carbon material
Composite material.
8. electro-catalysis CO according to claim 52It is restored to the preparation method of the bismuth-based catalysts of formic acid, it is characterised in that:
In solution synthetic method, reacting is 195oC reacts 15 min；The electroreduction of oxidation bismuth nanotube carries out in the electrolytic solution, electricity
The current potential of solution reduction is lower than -1V；C6H9BiO6Mass ratio with polyvinylpyrrolidone is 0.75:(0.5~1)；Mixed solvent
For water and ethylene glycol mixed solvent；
In liquid phase stripping method, solvent is N-Methyl pyrrolidone, is centrifuged, is freeze-dried after Probe Ultrasonic Searching processing, obtains
To bismuth-based catalysts；
In method of electrostatic spinning, polymer is polyacrylonitrile, and being heat-treated is in air atmosphere 240oC handles 2 h, then in argon atmospher
500 in enclosingoC calcines 2h；
In electro-deposition method, by Bi (NO3)3Solution is mixed with 1,4-benzoquinone ethanol solution, using three-electrode system, electrodeposition process,
Obtain bismuth-based catalysts；In three-electrode system, metal titanium foil is reference electrode, platinum filament as working electrode, silver/silver chloride electrode
As auxiliary electrode；
In magnetron sputtering method, the purity of bismuth metal is greater than 99.99%, and substrate is hydrophobic carbon paper；
In high temperature thermal decomposition method, the temperature of heating is 300~600oC, time are 1~6 h；
In vapour deposition process, bismuth predecessor is bismuth oxide, and the substrate of high temperature insulation is quartz boat, be deposited on argon gas, in oxygen into
Row, the temperature of deposition are 105oC, time are 2~5 min；
In ball-milling method, lubricant includes one or more of Ergol, water, ethyl alcohol and n-dodecane；Powdered bismuth
Close the compound that object presoma is bismuth meal or bismuth.
9. bismuth-based catalysts restore CO in electro-catalysis2The application in formic acid is generated, or restores CO in preparation electro-catalysis2Generate first
Application in sour electrode；It is characterized by: using solution synthetic method, micromechanical forces stripping method, method of electrostatic spinning, electro-deposition side
Method, magnetron sputtering method, high temperature thermal decomposition method, vapour deposition process or ball-milling method prepare bismuth-based catalysts；
Solution synthetic method is, with C6H9BiO6It is raw material with polyvinylpyrrolidone, reacts, aoxidized in the mixed solvent
Then bismuth nanotube will aoxidize bismuth nanotube electroreduction, and obtain bismuth-based catalysts；
Micromechanical forces stripping method is, using bismuth meal as raw material, carries out Probe Ultrasonic Searching processing in a solvent, obtains bismuth-based catalysts；
Method of electrostatic spinning is, with BiCl3It is raw material with polymer, configures spinning solution, then carries out electrostatic spinning and obtain Nanowire
Dimension, nanofiber obtain bismuth-based catalysts through Overheating Treatment；
Electro-deposition method is, with Bi (NO3)3▪5H2O and 1,4-benzoquinone are raw material, and using three-electrode system, electrodeposition process is obtained
Bismuth-based catalysts；
Magnetron sputtering method is, using bismuth metal as target, the sputter process on substrate obtains bismuth-based catalysts；
High temperature thermal decomposition method is, with BiI3It for raw material, heats in air atmosphere, obtains bismuth-based catalysts；
Vapour deposition process is by the vapor deposition of bismuth predecessor in the substrate surface of high temperature insulation, to generate nonwoven fabric from filaments, obtain bismuthino
Catalyst；
Ball-milling method is, in the presence of lubricant, carries out ball-milling treatment to powdered bismuth compound presoma, obtains bismuthino catalysis
Agent.
10. application according to claim 9, it is characterised in that: electro-catalysis restores CO2When generating formic acid, to be saturated calomel electricity
Extremely reference electrode, carbon-point are auxiliary electrode；CO2The water phase electrolyte of saturation includes CO2The LiHCO of saturation3Solution, NaHCO3
Solution, KHCO3Solution, RbHCO3Solution, CsHCO3Solution, Na2CO3Solution, K2CO3Solution, NaCl solution, KCl solution, NaOH
Solution, KOH solution, CsOH solution, LiOH solution, phosphate buffer solution or borate buffer solution.
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