CN114959761A - Preparation method and application of silver hollow fiber electrode - Google Patents
Preparation method and application of silver hollow fiber electrode Download PDFInfo
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- CN114959761A CN114959761A CN202210480868.0A CN202210480868A CN114959761A CN 114959761 A CN114959761 A CN 114959761A CN 202210480868 A CN202210480868 A CN 202210480868A CN 114959761 A CN114959761 A CN 114959761A
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 209
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 183
- 239000004332 silver Substances 0.000 title claims abstract description 183
- 238000002360 preparation method Methods 0.000 title claims abstract description 90
- 239000000047 product Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 17
- 238000009987 spinning Methods 0.000 claims abstract description 15
- 238000006479 redox reaction Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000007872 degassing Methods 0.000 claims abstract description 8
- 238000007493 shaping process Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 5
- 230000008023 solidification Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 70
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 230000009467 reduction Effects 0.000 claims description 34
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 28
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 330
- 229910002092 carbon dioxide Inorganic materials 0.000 description 165
- 239000001569 carbon dioxide Substances 0.000 description 165
- 230000035484 reaction time Effects 0.000 description 30
- 238000006722 reduction reaction Methods 0.000 description 28
- 239000002994 raw material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009668 long-life test Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a preparation method and application of a silver hollow fiber electrode, wherein the preparation method comprises the following steps: s1, ball-milling and mixing the silver powder, the N-methyl-2-pyrrolidone and the polyethyleneimine according to a certain proportion to obtain uniform slurry, and degassing; s2, extruding the slurry liquid through a spinning head, and allowing the slurry liquid to enter solidification liquid for phase conversion to obtain hollow fiber soft bodies; s3, washing and shaping to obtain a hollow fiber green blank; s4, roasting the hollow fiber blank in an oxidizing gas atmosphere to obtain a first product; s5, placing the first intermediate product in a reducing gas atmosphere for heating and reducing to obtain a second product; and S6, carrying out electrochemical oxidation-reduction reaction on the second product to obtain the silver hollow fiber electrode. The electrode is applied to CO 2 And (4) electrocatalytic conversion. The preparation method of the invention is simple, the cost is low, the prepared electrode has controllable appearance,the electrode has good electrocatalytic activity, high selectivity, high current density and high stability.
Description
Technical Field
The invention belongs to the field of electrochemical reduction and conversion of carbon dioxide, and particularly relates to a preparation method and application of a silver hollow fiber electrode.
Background
The ever-increasing total energy demand and the over-exploitation of fossil fuels have led to a continuous rise in the total global carbon dioxide emissions, creating an ever-increasing environmental problem. Should be treated with carbon dioxide (CO) 2 ) The climate warming caused by the excessive emission of greenhouse gases as main body is particularly urgent, and CO 2 Emission reduction and utilization have become a research hotspot. And CO 2 As one of C1 raw materials widely distributed in nature, CO is used for realizing carbon neutralization 2 The transformation and utilization of (b) become the focus of attention in various countries. At present, CO 2 The conversion and utilization are mainly thermochemical reduction, but the conditions required for this method must be high temperature and high pressure, and CO will be present during the reduction process 2 Regeneration, so that CO is not available 2 The effective utilization and recovery of the waste water. In contrast, electrochemical methods can circumvent these harsh conditions as CO 2 The conversion provides a mild recycling means, has good operability and practicability, and can be used for CO 2 Has wider application prospect in the transformation and recovery.
At present, CO 2 The research on electroreduction is not enough to reach the industrial level, mainly because of the problems of catalytic activity, catalytic selectivity, catalytic efficiency and the like, so the research on the electrode is to solve the problem of CO 2 The key to electroreduction. Due to the electronic structural characteristics of silver element, carbon-oxygen double bonds (C = O) in carbon dioxide molecules can be broken and further converted into more reducing species, such as chemicals like CO. In addition, silver (Ag) electrodes have moderate hydrogen evolution overpotentials and can suitably suppress H 2 Is generated.
Conventional electrode electroreduction of CO 2 Maximum current ofThe density will be affected by CO 2 The hollow fiber electrode can overcome the limitation of substance transfer and can be used under high current density and high voltage, thereby improving the conversion efficiency and selectivity of the electrode, self-supporting firm single metal provides considerable mechanical strength, thereby maintaining stable structure and performance in long-life test, and represents huge application potential, which provides guidance for the practical application of electrocatalysis carbon dioxide and is beneficial to the deepening of theoretical and experimental research.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a method for preparing a silver hollow fiber electrode and its application, which is used to solve the problems of the prior art in the electroreduction of CO by using an electrode 2 Is subjected to CO 2 The problem of low solubility in aqueous solutions and the limitation of slow mass transfer, and CO in the prior art 2 The catalytic activity, catalytic selectivity and catalytic efficiency of the electroreduction are low.
In order to accomplish the above and other related objects, the present invention provides a method for preparing a silver hollow fiber electrode, the method comprising the steps of:
s1, ball-milling silver powder, N-methyl-2-pyrrolidone and polyethyleneimine according to a certain proportion at room temperature, uniformly mixing the silver powder, the N-methyl-2-pyrrolidone and the polyethyleneimine to obtain uniform slurry, and standing the slurry in a vacuum drying oven for degassing;
s2, extruding the degassed slurry through a core liquid and a spinning head at a certain flow rate to form initial fibers, and allowing the initial fibers to enter a coagulating liquid for phase conversion after passing through an air bath to obtain hollow fiber soft bodies;
s3, washing and shaping the hollow fiber soft body to obtain a hollow fiber green body;
s4, placing the hollow fiber blank in an oxidizing gas atmosphere, heating to a certain temperature at a certain heating rate, and roasting and oxidizing to obtain a first product;
s5, placing the first intermediate product in a reducing gas atmosphere, heating to a certain temperature at a certain heating rate, and carrying out heating reduction to obtain a second product;
and S6, carrying out electrochemical redox reaction on the second product to obtain the silver hollow fiber electrode.
Preferably, in the slurry of step S1, the silver powder accounts for 30wt% to 80wt%, the N-methyl-2-pyrrolidone accounts for 5wt% to 65wt%, and the polyethyleneimine accounts for 5wt% to 15wt%, by mass%.
Preferably, the silver powder particles in step S1 have a particle size of 20nm to 10 μm.
Preferably, the silver powder particles in step S1 have one or more of a spherical shape, a spheroidal shape, a chain spherical shape, a dendritic shape, and an irregular shape.
Preferably, the ball milling time in the step S1 is 10-30 h.
Preferably, the degassing time in the step S1 is 2-12 h.
Preferably, the slurry in the step S2 is extruded through the spinning head at a flow rate of 1-20 mL/min.
Preferably, the size of the spinneret in step S2 is one or a combination of Φ 1.0 × 0.3mm, Φ 1.5 × 0.5mm, Φ 2.0 × 1.0 mm.
Preferably, the flow rate of the core liquid in the step S2 is 1-20 mL/min.
Preferably, the air distance between the spinning head and the liquid surface of the coagulating liquid in the step S2 is 0.2-5 cm.
Preferably, the oxidizing gas in step S4 is air or oxygen.
Preferably, the flow rate of the oxidizing gas in step S4 is 10 to 300 mL/min.
Preferably, the temperature rise rate in the step S4 is 1-20 ℃/min.
Preferably, the temperature of the roasting oxidation in the step S4 is 500-1000 ℃.
Preferably, the roasting and oxidation time in the step S4 is 4-10 h.
Preferably, the hollow fiber blank in the step S4 has an outer diameter of 0.5-5 mm and an inner diameter of 0.3-4.5 mm.
Preferably, the reducing gas in step S5 is one of hydrogen, argon, and a hydrogen/argon mixture.
Preferably, the flow rate of the reducing gas in the step S5 is 10 to 300 mL/min.
Preferably, the temperature rise rate in the step S5 is 1-20 ℃/min.
Preferably, the temperature of the heating reduction in the step S5 is 300-800 ℃.
Preferably, the heating reduction time in the step S5 is 2-10 h.
Preferably, the electrochemical redox reaction in step S6 specifically includes the following steps: the second product is anodically oxidized in situ in the electrolyte and subsequently cathodically reduced.
Preferably, the electrolyte in step S6 is KHCO 3 、K 2 SO 4 、KOH、KCl、NaHCO 3 、Na 2 SO 4 And NaCl or a combination thereof.
Preferably, the concentration of the electrolyte in the step S6 is 0.1-3M.
Preferably, the anodic oxidation potential in step S6 is 0.1-10V vs. Ag/AgCl electrode, and the anodic oxidation time is 1-120 min.
Preferably, the potential of the cathode reduction in the step S6 is-0.1 to-10V vs. Ag/AgCl electrode, and the time of the cathode reduction is 1 to 120 min.
Preferably, the silver hollow fiber electrode obtained in step S6 has an outer diameter of 0.2 to 4mm and an inner diameter of 0.15 to 3.5 mm.
Preferably, the electrochemical redox reaction in step S6 specifically comprises the steps of: and scanning for 50 circles by adopting cyclic voltammetry at a scanning speed of 20mV/s and in a potential range of-0.5-2.4V vs.
The application of the silver hollow fiber electrode prepared by the preparation method of the silver hollow fiber electrode in CO 2 Electrocatalytic conversion of said CO 2 The electrocatalytic conversion comprises the following steps: introducing CO 2 Introducing the silver hollow fiber electrode into the electrolyte, placing the silver hollow fiber electrode into the electrolyte, and applying constant potential or constant current to carry out electrochemical reduction on CO 2 Introduction of CO into 2 Electrocatalytic conversion to CO.
Preferably, the electrolyte comprises catholyte and anolyte, and the catholyte is KHCO 3 、K 2 SO 4 、KCl、NaHCO 3 、Na 2 SO 4 And NaCl, and the anolyte is KHCO 3 、K 2 SO 4 、KCl、NaHCO 3 、Na 2 SO 4 And NaCl or a combination thereof.
Preferably, the concentration of the catholyte and the concentration of the anolyte are both 0.1-5M.
Preferably, the potential is-0.25 to-4.0V vs. RHE, and the current is-0.01 to-5A/cm 2 。
As described above, the preparation method and application of the silver hollow fiber electrode of the present invention have the following beneficial effects:
the invention adopts a simple phase conversion method to prepare a hollow fiber blank, the blank is roasted in an oxidizing atmosphere and a reducing atmosphere in sequence to obtain a second product, and the second product is further subjected to electrochemical oxidation reduction to obtain a silver hollow fiber electrode with a reconstructed outer surface, which is used for electrocatalytic reduction of CO 2 The electrode has the advantages of easily available raw materials, low cost and simple preparation, the prepared electrode has controllable appearance, and the prepared silver hollow fiber electrode has good electrocatalytic activity, high selectivity, high current density and high stability.
The silver hollow fiber electrode in the invention can be applied to CO 2 The method can be particularly applied to the reaction of generating CO by the electrocatalytic conversion of carbon dioxide in the electrocatalytic reduction, and can solve the problem of CO in the prior art 2 CO due to solution phase in the reaction of electrocatalytic conversion to CO 2 DissolutionThe silver hollow fiber electrode prepared by the method is applied to CO, and has the problems of low total current density, low CO Faraday selectivity and short electrode service life caused by low degree, slow mass transfer and other factors 2 The CO is generated by electrocatalytic conversion, the Faraday current efficiency of the CO can reach 20-99.9% at normal temperature and normal pressure, and the CO is 2 The conversion rate of CO per pass is 1-90%, and the method has extremely high application prospect.
Drawings
FIG. 1 shows an SEM image of a cross-section of a second product obtained in an embodiment of the present invention.
Fig. 2 is a partially enlarged view of fig. 1.
Fig. 3 is an SEM image showing a cross section of a silver hollow fiber electrode obtained in an example of the present invention.
Fig. 4 is a partially enlarged view of fig. 3.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-4. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
The invention adopts a simple phase conversion method to prepare a hollow fiber blank, the blank is roasted in an oxidizing atmosphere and a reducing atmosphere in sequence to obtain a second product, and the second product is further subjected to electrochemical oxidation reduction to obtain a silver hollow fiber electrode with a reconstructed outer surface, which is used for electrocatalytic reduction of CO 2 The electrode has the advantages of easily obtained raw materials, low cost and simple preparation, and the prepared electrodeThe shape is controllable, and the prepared silver hollow fiber electrode has good electrocatalytic activity, high selectivity, high current density and high stability; the silver hollow fiber electrode in the invention can be applied to CO 2 The method can be particularly applied to the reaction of generating CO by the electrocatalytic conversion of carbon dioxide in the electrocatalytic reduction, and can solve the problem of CO in the prior art 2 CO due to solution phase in the reaction of electrocatalytic conversion to CO 2 The problems of low total current density, low CO Faraday selectivity and short electrode service life caused by low solubility, slow mass transfer and other factors are solved, and the silver hollow fiber electrode prepared by the method is applied to CO 2 The CO is generated by electrocatalytic conversion, the Faraday current efficiency of the CO can reach 20-99.9% at normal temperature and normal pressure, and the CO is 2 The conversion rate of CO per pass is 1-90%, and the method has extremely high application prospect.
The invention provides a preparation method of a silver hollow fiber electrode, which comprises the following steps:
s1, ball-milling the silver powder, the N-methyl-2-pyrrolidone and the polyethyleneimine according to a certain proportion at room temperature, uniformly mixing the silver powder, the N-methyl-2-pyrrolidone and the polyethyleneimine to obtain uniform slurry, and standing the slurry in a vacuum drying oven for degassing.
As an example, in the slurry of step S1, the silver powder accounts for 30wt% to 80wt% in terms of mass percentage, such as 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, etc.; the N-methyl-2-pyrrolidone accounts for 5wt% -65 wt%, such as 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 65wt% and the like; the mass percentage of the polyethyleneimine is 5wt% -15 wt%, such as 5wt%, 8wt%, 10wt%, 12wt%, 15wt% and the like.
As an example, the silver powder particles in step S1 have a particle size of 20nm to 10 μm, such as 20nm, 50nm, 100nm, 200nm, 500nm, 1 μm, 5 μm, 10 μm, and the like.
Preferably, the silver powder particles have a particle size of 50 nm.
As an example, the shape of the silver powder particles in step S1 is one or more of spherical, spheroidal, chain spherical, dendritic, and irregular.
Preferably, the silver powder particles are spherical in shape.
For example, the ball milling time in step S1 is 10-30 h, such as 10h, 15h, 20h, 25h, 30h, and the like.
Preferably, the ball milling time is 18-24 h, such as 18h, 19h, 20h, 21h, 22h, 23h, 24h and the like.
By way of example, the degassing time in step S1 is 2-12 h, such as 2h, 4h, 6h, 8h, 10h, 12h, and the like.
Preferably, the degassing time is 5-10 h, such as 5h, 6h, 7h, 8h, 9h, 10h, and the like.
And S2, extruding the degassed slurry through a core liquid and a spinning head at a certain flow rate, forming initial fibers along with the core liquid (inner coagulation bath), and allowing the initial fibers to pass through an air bath and enter a coagulation liquid (outer coagulation bath) for phase conversion to obtain hollow fiber soft bodies.
For example, in step S2, the slurry is extruded through the spinning head at a flow rate of 1-20 mL/min, such as 1mL/min, 5mL/min, 10mL/min, 15mL/min, 20mL/min, etc.
Preferably, the flow rate of the slurry is 5 mL/min.
As an example, the size of the spinning head in step S2 is one or a combination of Φ 1.0 × 0.3mm, Φ 1.5 × 0.5mm, Φ 2.0 × 1.0 mm.
Preferably, the dimensions of the spinneret are Φ 1.0 × 0.3 mm.
As an example, the flow rate of the core liquid in step S2 is 1-20 mL/min, such as 1mL/min, 5mL/min, 10mL/min, 15mL/min, 20mL/min, etc.
Preferably, the flow rate of the bore fluid is 5 mL/min.
Illustratively, the air distance between the spinning head and the liquid surface of the coagulating liquid in step S2 is 0.2-5 cm, such as 0.2cm, 0.5cm, 1cm, 2cm, 3cm, 4cm, 5cm, etc.
Preferably, the air distance between the spinning head and the surface of the coagulation liquid is 1 cm.
S3, washing and shaping the hollow fiber soft body to obtain the hollow fiber green body.
Specifically, washing with a large amount of tap water, removing the organic solvent (N-methyl-2-pyrrolidone) in the hollow fiber soft body, and shaping, specifically, straightening and fixing the hollow fiber tubular soft body, and then naturally drying in the air.
S4, placing the hollow fiber blank in an oxidizing gas atmosphere, heating to a certain temperature at a certain heating rate, and roasting and oxidizing to obtain a first product.
As an example, the oxidizing gas in step S4 is air or oxygen.
For example, in step S4, the flow rate of the oxidizing gas is 10-300 mL/min, such as 10mL/min, 50mL/min, 100mL/min, 150mL/min, 200mL/min, 250mL/min, 300mL/min, and the like.
Preferably, the flow rate of the oxidizing gas is 100-200 mL/min, such as 100mL/min, 120mL/min, 140mL/min, 160mL/min, 180mL/min, 200mL/min, and the like.
For example, in step S4, the temperature rise rate is 1-20 ℃/min, such as 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, and the like.
Preferably, the heating rate is 1-10 ℃/min, such as 1 ℃/min, 2 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min, 10 ℃/min, and the like.
For example, the temperature of the roasting oxidation in step S4 is 500 to 1000 ℃, such as 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ and the like.
Preferably, the temperature of the roasting oxidation is 500-800 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ and the like.
For example, the time for the roasting oxidation in step S4 is 4-10 h, such as 4h, 5h, 6h, 7h, 8h, 9h, 10h, and the like.
Preferably, the time for roasting and oxidizing is 6-8 h, such as 6h, 6.5h, 7h, 7.5h, 8h and the like.
And S5, placing the first intermediate product in a reducing gas atmosphere, heating to a certain temperature at a certain heating rate, and carrying out heating reduction to obtain a second product.
As an example, the reducing gas in step S5 is one of hydrogen, argon, and a hydrogen/argon mixed gas.
For example, the flow rate of the reducing gas in step S5 is 10-300 mL/min, such as 10mL/min, 50mL/min, 100mL/min, 150mL/min, 200mL/min, 250mL/min, 300mL/min, etc.
Preferably, the flow rate of the reducing gas is 50-200 mL/min, such as 50mL/min, 100mL/min, 120mL/min, 140mL/min, 160mL/min, 180mL/min, 200mL/min, and the like.
For example, in step S5, the temperature rise rate is 1-20 ℃/min, such as 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, and the like.
Preferably, the heating rate is 1-5 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, and the like.
For example, the temperature for the heating reduction in step S5 is 300 to 800 ℃, such as 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ and the like.
Preferably, the temperature for heating reduction is 300-500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and the like.
For example, the heating reduction time in step S5 is 2-10 h, such as 2h, 4h, 6h, 8h, 10h, and the like.
Preferably, the heating reduction time is 6-8 h, such as 6h, 6.5h, 7h, 7.5h, 8h and the like.
And S6, carrying out electrochemical oxidation-reduction reaction on the second product to obtain the silver hollow fiber electrode. The second product is also a silver hollow fiber electrode, after the second product is subjected to electrochemical oxidation-reduction treatment, the components of the hollow fiber electrode are still metallic silver, but the appearance is greatly changed, referring to fig. 1-4, the electrochemical activity and the specific surface area are greatly increased, the number of exposed active sites is also greatly increased, and finally the silver hollow fiber electrode with the reconstructed outer surface is obtained.
The specific embodiment of the invention provides a method for carrying out electrochemical oxidation-reduction reaction on a second product, which specifically comprises the following steps: the second product is anodically oxidized in situ in the electrolyte and subsequently cathodically reduced.
As an example, the electrolyte is KHCO 3 、K 2 SO 4 、KOH、KCl、NaHCO 3 、Na 2 SO 4 And NaCl or a combination thereof.
For example, the concentration of the electrolyte is 0.1-3M, such as 0.1M, 0.5M, 1M, 2M, 3M, etc.
Preferably, the electrolyte is 0.5M KHCO 3 。
As an example, the anodic oxidation potential is 0.1-10V vs. Ag/AgCl electrode, such as 0.1V vs. Ag/AgCl electrode, 0.5V vs. Ag/AgCl electrode, 2V vs. Ag/AgCl electrode, 4V vs. Ag/AgCl electrode, 6V vs. Ag/AgCl electrode, 8V vs. Ag/AgCl electrode, 10V vs. Ag/AgCl electrode, etc., and the anodic oxidation time is 1-120 min, such as 1min, 10min, 20min, 40min, 60min, 80min, 100min, 120min, etc.
Preferably, the anodic oxidation potential is 2.0V vs. Ag/AgCl electrode and the anodic oxidation time is 4 min.
By way of example, the potential of the cathodic reduction is-0.1 to-10V vs. Ag/AgCl electrode, such as-0.1V vs. Ag/AgCl electrode, -0.5V vs. Ag/AgCl electrode, -1V vs. Ag/AgCl electrode, -2V vs. Ag/AgCl electrode, -4V vs. Ag/AgCl electrode, -6V vs. Ag/AgCl electrode, -8V vs. Ag/AgCl electrode, -10V vs. Ag/AgCl electrode, etc., and the cathodic reduction time is 1 to 120min, such as 1min, 10min, 20min, 40min, 60min, 80min, 100min, 120min, etc.
Preferably, the potential of cathodic reduction is-0.5V vs. Ag/AgCl electrode, and the cathodic reduction time is 10 min.
The specific embodiment of the present invention further provides a method for performing an electrochemical oxidation-reduction reaction on the second product, which specifically includes the following steps: and scanning for 50 circles by adopting cyclic voltammetry at a scanning speed of 20mV/s and in a potential range of-0.5-2.4V vs.
Specifically, the roughness of the reconstructed thickness of the silver hollow fiber outer layer is controlled by controlling different scanning speeds, different scanning voltage ranges and the number of scanning circles.
The invention provides a silver hollow fiber electrode prepared by the preparation method of the silver hollow fiber electrode, wherein the outer diameter of the hollow fiber blank obtained in the step S3 is 0.5-5 mm, such as 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm and the like, and the inner diameter is 0.3-4.5 mm, such as 0.3mm, 0.5mm, 1mm, 2mm, 3mm, 4mm, 4.5mm and the like; the silver hollow fiber electrode obtained in step S6 has an outer diameter of 0.2 to 4mm, such as 0.2mm, 0.5mm, 1mm, 2mm, 3mm, 4mm, etc., and an inner diameter of 0.15 to 3.5mm, such as 0.15mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, etc.
Specifically, the prepared silver hollow fiber electrode has a plurality of pores on the surface, the average value of the pore diameter is 2-10 mu m, and the silver hollow fiber electrode is used for electrocatalytic reduction of CO 2 The catalytic activity is high.
The invention also provides an application of the silver hollow fiber electrode in CO 2 Electrocatalytic conversion of CO 2 The electrocatalytic conversion comprises the following steps: introducing CO 2 Introducing into silver hollow fiber electrode, placing the silver hollow fiber electrode in electrolyte, and applying constant potential or constant current to perform electrochemical reduction of CO 2 Introduction of CO 2 Electrocatalytic conversion to CO.
Specifically, the silver hollow fiber electrode is placed in electrolyte, the bottom end of the silver hollow fiber electrode is sealed, and CO is introduced into the top end of the silver hollow fiber electrode 2 ，CO 2 The raw material gas CO is emitted from the porous wall of the silver hollow fiber electrode and is forced to react 2 The electrolyte contacts with the electrolyte, so that a gas-liquid-solid three-phase reaction interface is enhanced, and the mass transfer process of reactants and products is enhanced.
Specifically, CO 2 The total flow rate is 1-100 mL/min, and CO 2 The temperature of electrocatalytic conversion is 10-60 ℃.
As an example, the electrolyte comprises catholyte and anolyte, and the catholyte is KHCO 3 、K 2 SO 4 、KCl、NaHCO 3 、Na 2 SO 4 And NaCl, and the anolyte is KHCO 3 、K 2 SO 4 、KCl、NaHCO 3 、Na 2 SO 4 And NaCl or a combination thereof.
For example, the concentration of the catholyte and the concentration of the anolyte are both 0.1-5M, such as 0.1M, 0.5M, 1M, 2M, 3M, 4M, 5M, and the like.
Preferably, the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 。
Specifically, the potential is-0.25 to-4.0V vs. RHE, such as-0.25V vs. RHE, -0.5V vs. RHE, -1.0V vs. RHE, -2.0V vs. RHE, -3.0V vs. RHE, -4.0V vs. RHE, and the current is-0.01 to-5A/cm 2 For example, -0.01A/cm 2 、-0.1A/cm 2 、-1A/cm 2 、-2A/cm 2 、-3A/cm 2 、-4A/cm 2 、-5A/cm 2 And the like.
Preferably, the potential has a voltage of-0.25 to-3.0V vs. RHE, such as-0.25V vs. RHE, -0.5V vs. RHE, -1.0V vs. RHE, -2.0V vs. RHE, -3.0V vs. RHE, and the like.
In order to further illustrate the silver hollow fiber electrode, the preparation method and the application of the present invention, the following specific examples are further illustrated.
Example 1
The embodiment provides a silver hollow fiber electrode, and the preparation method specifically comprises the following steps:
s1, mixing spherical silver powder with the particle size of 200nm, N-methyl-2-pyrrolidone and polyethyleneimine respectively according to the proportion of 43wt%, 46wt% and 11wt% at room temperature, ball-milling for 24 hours at the rotating speed of 300r/min to obtain uniform slurry, and standing the slurry in a vacuum drying oven to degas for 5 hours;
s2, extruding the degassed slurry through a core liquid and a phi 1.0 multiplied by 0.3mm spinning head at the flow rate of 5mL/min, forming initial fibers along with the core liquid, and allowing the initial fibers to enter a solidification liquid for phase conversion after passing through an air bath to obtain hollow fiber soft bodies; wherein the core liquid is ultrapure water, the flow rate of the core liquid is 5mL/min, the solidification liquid is tap water, and the air distance between the spinning head and the liquid level of the solidification liquid is 1 cm;
s3, washing the hollow fiber soft body with a large amount of tap water to remove the organic solvent, and shaping to obtain a hollow fiber green body;
s4, heating the hollow fiber blank to 600 ℃ at a heating rate of 1 ℃/min under an air atmosphere with a flow rate of 100mL/min, roasting and oxidizing for 6h so as to remove polyethyleneimine in the hollow fiber blank and cause sintering of silver particles to obtain a first product;
s5, heating the first intermediate product to 300 ℃ at a heating rate of 1 ℃/min under the atmosphere of hydrogen/argon mixed gas (the volume percentage of hydrogen is 5%) at a flow rate of 100mL/min, and preserving heat for 4h to obtain a second product;
s6, the second product is 0.5M KHCO 3 The electrolyte is subjected to in-situ anodic oxidation for 4min, and then is subjected to cathodic reduction for 10min, wherein the anodic oxidation potential is 2.0V vs. Ag/AgCl, and the cathodic reduction potential is-0.5V vs. Ag/AgCl.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.8V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO and H 2 The total current density of the product is 1.26A/cm 2 The Faraday current efficiency of CO reaches 91.1%, the selectivity is good, and the conversion per pass exceeds 50%.
Example 2
This example provides a silver hollow fiber electrode, which is prepared by the following method different from that of example 1: the raw materials in the step S1 are spherical silver powder with the particle size of 10 mu m, N-methyl-2-pyrrolidone and polyethyleneimine which are respectively mixed according to the proportion of 60wt%, 30wt% and 10 wt%; the other methods and steps are the same as those in embodiment 1, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.8V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO and H 2 The total current density of the product is 1.24A/cm 2 The Faraday current efficiency of CO reaches 88.3%, the selectivity is good, and the conversion per pass exceeds 50%.
Example 3
This example provides a silver hollow fiber electrode, which is prepared by the following method different from that of example 1: the raw materials in the step S1 are spherical silver powder with the particle size of 50nm, N-methyl-2-pyrrolidone and polyethyleneimine which are respectively mixed according to the proportion of 40wt%, 48wt% and 12 wt%; the slurry degassed in step S2 was extruded at a flow rate of 5mL/min through a core liquid and a spinneret of phi 1.5X 0.3 mm; the other methods and steps are the same as those in embodiment 1, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.8V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO and H 2 The total current density of the product was 1.43A/cm 2 The Faraday current efficiency of CO reaches 93.5%, the selectivity is good, and the conversion per pass exceeds 50%.
Example 4
This example provides a silver hollow fiber electrode, which is prepared by the following method different from that of example 1: the raw materials in the step S1 are spherical silver powder with the particle size of 50nm, N-methyl-2-pyrrolidone and polyethyleneimine which are respectively mixed according to the proportion of 40wt%, 48wt% and 12 wt%; the degassed slurry in step S2 was extruded through a core liquid and a spinneret of 1.5X 0.5mm in diameter at a flow rate of 5 mL/min; the other methods and steps are the same as embodiment 1, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.8V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO and H 2 The total current density of the product is 1.35A/cm 2 The Faraday current efficiency of CO reaches 93.2%, the selectivity is good, and the conversion per pass exceeds 50%.
Example 5
This example provides a silver hollow fiber electrode, which is prepared by the following method different from that of example 1: the raw materials in the step S1 are spherical silver powder with the particle size of 50nm, N-methyl-2-pyrrolidone and polyethyleneimine which are respectively mixed according to the proportion of 40wt%, 48wt% and 12 wt%; the degassed slurry in step S2 was extruded through a core liquid and a spinneret of phi 2.0X 1.0mm at a flow rate of 5 mL/min; the other methods and steps are the same as those in embodiment 1, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.8V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO, H 2 The total current density of the product was 1.33A/cm 2 The Faraday current efficiency of CO reaches 92.7%, the selectivity is good, and the conversion per pass exceeds 50%.
Example 6
This example provides a silver hollow fiber electrode, which is prepared by a method different from that of example 1 in that: the raw materials in the step S1 are spherical silver powder with the particle size of 50nm, N-methyl-2-pyrrolidone and polyethyleneimine which are respectively mixed according to the proportion of 40wt%, 48wt% and 12 wt%; the other methods and steps are the same as those in embodiment 1, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.25V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.7 percent, and has good selectivity.
Example 7
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.2V vs. RHE, the reaction time is 1h, and the catholyte is 1.5M KHCO 3 The anolyte is 1.5M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 92.9 percent, and has good selectivity.
Example 8
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.3V vs. RHE, the reaction time is 1h, and the catholyte is 2.0M KHCO 3 The anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.5 percent, and has good selectivity.
Example 9
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-1.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.8 percent, and has good selectivity.
Example 10
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-2.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 97.8 percent, and has good selectivity.
Example 11
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-3.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 92.8 percent, and has good selectivity.
Example 12
This example provides a silver hollow fiber electrode, which is prepared by a method different from that of example 6 in that the second product is 0.5M KHCO at step S6 3 In the electrolyte, an Ag/AgCl electrode with the voltage of-0.5-1.2V vs, and scanning for 50 circles by cyclic voltammetry at the scanning speed of 20 mV/s; other methods and steps are the same as those in embodiment 6, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-0.3V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.6 percent, and has good selectivity.
Example 13
This example provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in example 12, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode reduces CO by a constant potential method 2 The applied voltage is-1.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO, H 2 The Faraday current efficiency of the product, CO, reaches 98.8 percent, and has good selectivity.
Example 14
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 12, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode reduces CO by a constant potential method 2 The applied voltage is-2.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 96.3 percent, and has good selectivity.
Example 15
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 12, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-2.5V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 92.3 percent, and has good selectivity.
Example 16
This example provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in example 12, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-3.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 82.1 percent, and has good selectivity.
Example 17
The present embodiment provides a silver hollow fiber electrode, and the preparation method thereof is different from that in embodiment 6, in step S6, the second product is scanned for 50 cycles in cyclic voltammetry at a sweep rate of 20mV/S in 0.2M KOH electrolyte and 0-2.4V vs. Ag/AgCl electrode; other methods and steps are the same as those in embodiment 6, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode reduces CO by a constant potential method 2 The applied voltage is-0.3V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.1 percent, and has good selectivity.
Example 18
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 17, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode reduces CO by a constant potential method 2 The applied voltage is-1.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.4 percent, and has good selectivity.
Example 19
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 17, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-2.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 93.4 percent, and has good selectivity.
Example 20
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 17, and are not repeated herein.
The silver hollow prepared by the preparation methodThe embodiment also provides an application of the silver hollow fiber electrode, and the silver hollow fiber electrode reduces CO by a potentiostatic method 2 The applied voltage is-3.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 93.4 percent, and has good selectivity.
Example 21
The present embodiment provides a silver hollow fiber electrode, and the preparation method thereof is different from that in embodiment 6, in step S6, the second product is scanned for 50 cycles in cyclic voltammetry at a sweep rate of 20mV/S in 0.5M KCl electrolyte and 0-1.5V vs. Ag/AgCl electrode; other methods and steps are the same as those in embodiment 6, and are not described herein again.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode reduces CO by a constant potential method 2 The applied voltage is-0.3V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.8 percent, and has good selectivity.
Example 22
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 21, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-1.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.3%, and the product has good selectivity.
Example 23
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 21, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the implementation is thatThe silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-2.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 95.2 percent, and has good selectivity.
Example 24
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 21, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by a potentiostatic method 2 The applied voltage is-3.0V vs. RHE, the reaction time is 1h, the catholyte is 2.0M KCl, and the anolyte is 2.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 90.8 percent, and has good selectivity.
Example 25
This example provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in example 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode reduces CO by using a constant current method 2 Applying constant current of-0.1A/cm 2 The reaction time is 1h, the catholyte is 3.0M KCl, and the anolyte is 3.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.9%, and the product has good selectivity.
Example 26
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by using a constant current method 2 Applying a constant current of-1A/cm 2 The reaction time is 1h, and the catholyte is3.0M KCl, anolyte 3.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 99.8 percent, and has good selectivity.
Example 27
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by using a constant current method 2 Applying a constant current of-2A/cm 2 The reaction time is 1h, the catholyte is 3.0M KCl, and the anolyte is 3.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 97.9 percent, and has good selectivity.
Example 28
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by using a constant current method 2 Applying constant current of-3A/cm 2 The reaction time is 1h, the catholyte is 3.0M KCl, and the anolyte is 3.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 94.7 percent, and has good selectivity.
Example 29
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by using a constant current method 2 The constant current is applied at-4A/cm 2 The reaction time is 1h, the catholyte is 3.0M KCl, and the anolyte is 3.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 87.9 percent, and has good selectivity.
Example 30
This embodiment provides a silver hollow fiber electrode, and the preparation method and steps thereof are the same as those in embodiment 6, and are not repeated herein.
The silver hollow fiber electrode is prepared by the preparation method, and the embodiment also provides application of the silver hollow fiber electrode, wherein the silver hollow fiber electrode is used for reducing CO by using a constant current method 2 Applying constant current of-5A/cm 2 The reaction time is 1h, the catholyte is 3.0M KCl, and the anolyte is 3.0M KHCO 3 To obtain CO and H 2 The Faraday current efficiency of the product, CO, reaches 80.5 percent, and has good selectivity.
In conclusion, the invention adopts a simple phase conversion method to prepare the hollow fiber green body, the hollow fiber green body is roasted in oxidizing atmosphere and reducing atmosphere in sequence to obtain a second product, and the silver hollow fiber electrode with the reconstructed outer surface is further obtained by electrochemical oxidation reduction and is used for electrocatalytic reduction of CO 2 The electrode has the advantages of easily available raw materials, low cost and simple preparation, the prepared electrode has controllable appearance, and the prepared silver hollow fiber electrode has good electro-catalytic activity, high selectivity, high current density and high stability; the silver hollow fiber electrode in the invention can be applied to CO 2 The method can be particularly applied to the reaction of generating CO by the electrocatalytic conversion of carbon dioxide in the electrocatalytic reduction, and can solve the problem of CO in the prior art 2 CO due to solution phase in the reaction of electrocatalytic conversion to CO 2 The problems of low total current density, low CO Faraday selectivity and short electrode service life caused by low solubility, slow mass transfer and other factors are solved 2 The CO is generated by electrocatalytic conversion, the Faraday current efficiency of the CO can reach 20-99.9% at normal temperature and normal pressure, and the CO is 2 The conversion rate of CO per pass is 1-90%, and the method has extremely high application prospect. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a silver hollow fiber electrode is characterized by comprising the following steps:
s1, ball-milling silver powder, N-methyl-2-pyrrolidone and polyethyleneimine according to a certain proportion at room temperature, uniformly mixing the silver powder, the N-methyl-2-pyrrolidone and the polyethyleneimine to obtain uniform slurry, and standing the slurry in a vacuum drying oven for degassing;
s2, extruding the degassed slurry through a core liquid and a spinning head at a certain flow rate to form initial fibers, and allowing the initial fibers to enter a coagulating liquid for phase conversion after passing through an air bath to obtain hollow fiber soft bodies;
s3, washing and shaping the hollow fiber soft body to obtain a hollow fiber green body;
s4, placing the hollow fiber blank in an oxidizing gas atmosphere, heating to a certain temperature at a certain heating rate, and roasting and oxidizing to obtain a first product;
s5, placing the first intermediate product in a reducing gas atmosphere, heating to a certain temperature at a certain heating rate, and carrying out heating reduction to obtain a second product;
and S6, carrying out electrochemical redox reaction on the second product to obtain the silver hollow fiber electrode.
2. The method for preparing a silver hollow fiber electrode according to claim 1, wherein step S1 includes any one or a combination of the following conditions:
in the slurry of step S1, the silver powder accounts for 30wt% to 80wt%, the N-methyl-2-pyrrolidone accounts for 5wt% to 65wt%, and the polyethyleneimine accounts for 5wt% to 15wt%, in terms of mass percentage;
the particle size of the silver powder particles is 20 nm-10 mu m;
the silver powder particles are in one or more of spherical, quasi-spherical, chain spherical, dendritic and irregular shapes;
the ball milling time is 10-30 h;
the degassing time is 2-12 h.
3. The method for preparing a silver hollow fiber electrode according to claim 1, characterized in that: step S2 includes any one or a combination of the following conditions:
extruding the slurry through a spinning head at a flow rate of 1-20 mL/min;
the size of the spinning head is one or the combination of phi 1.0 multiplied by 0.3mm, phi 1.5 multiplied by 0.5mm and phi 2.0 multiplied by 1.0 mm;
the flow rate of the core liquid is 1-20 mL/min;
and the air distance between the spinning head and the liquid level of the solidification liquid is 0.2-5 cm.
4. The method for preparing a silver hollow fiber electrode according to claim 1, characterized in that: step S4 includes any one or a combination of the following conditions:
the oxidizing gas is air or oxygen;
the flow rate of the oxidizing gas is 10-300 mL/min;
the heating rate is 1-20 ℃/min;
the roasting oxidation temperature is 500-1000 ℃;
the roasting oxidation time is 4-10 h;
the hollow fiber blank has an outer diameter of 0.5-5 mm and an inner diameter of 0.3-4.5 mm.
5. The method for preparing a silver hollow fiber electrode according to claim 1, characterized in that: step S5 includes any one or a combination of the following conditions:
the reducing gas is one of hydrogen, argon and hydrogen/argon mixed gas;
the flow rate of the reducing gas is 10-300 mL/min;
the heating rate is 1-20 ℃/min;
the temperature of the heating reduction is 300-800 ℃;
the heating reduction time is 2-10 h.
6. The method for preparing a silver hollow fiber electrode according to claim 1, characterized in that: the electrochemical redox reaction in step S6 specifically includes the following steps: the second product is anodically oxidized in situ in the electrolyte and subsequently cathodically reduced.
7. The method for preparing a silver hollow fiber electrode according to claim 6, characterized in that: step S6 includes any one or a combination of the following conditions:
the electrolyte is KHCO 3 、K 2 SO 4 、KOH、KCl、NaHCO 3 、Na 2 SO 4 And NaCl;
the concentration of the electrolyte is 0.1-3M;
the anodic oxidation potential is 0.1-10V vs. Ag/AgCl electrode, and the anodic oxidation time is 1-120 min;
the potential of the cathode reduction is-0.1 to-10V vs. Ag/AgCl electrode, and the time of the cathode reduction is 1 to 120 min;
the outer diameter of the obtained silver hollow fiber electrode is 0.2-4 mm, and the inner diameter is 0.15-3.5 mm.
8. The method for preparing a silver hollow fiber electrode according to claim 1, characterized in that: the electrochemical redox reaction in step S6 specifically includes the steps of: and scanning for 50 circles by adopting cyclic voltammetry at a scanning speed of 20mV/s and in a potential range of-0.5-2.4V vs.
9. A silver hollow fiber electrode prepared by the method for preparing the silver hollow fiber electrode according to any one of claims 1 to 8The polar application is characterized in that: the silver hollow fiber electrode is applied to CO 2 Electrocatalytic conversion of said CO 2 The electrocatalytic conversion comprises the following steps: introducing CO 2 Introducing the silver hollow fiber electrode into the electrolyte, placing the silver hollow fiber electrode into the electrolyte, and applying constant potential or constant current to carry out electrochemical reduction on CO 2 Introduction of CO into 2 Electrocatalytic conversion to CO.
10. Use of the silver hollow fiber electrode according to claim 9, characterized by comprising any one or a combination of the following conditions:
the electrolyte comprises catholyte and anolyte, and the catholyte is KHCO 3 、K 2 SO 4 、KCl、NaHCO 3 、Na 2 SO 4 And NaCl, and the anolyte is KHCO 3 、K 2 SO 4 、KCl、NaHCO 3 、Na 2 SO 4 One or a combination of NaCl;
the concentration of the catholyte and the concentration of the anolyte are both 0.1-5M;
the potential is-0.25 to-4.0V vs. RHE, and the current is-0.01 to-5A/cm 2 。
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