CN117779086A - Electrode with high-selectivity electrolytic carbonate and preparation method thereof - Google Patents
Electrode with high-selectivity electrolytic carbonate and preparation method thereof Download PDFInfo
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052709 silver Inorganic materials 0.000 claims abstract description 90
- 239000004332 silver Substances 0.000 claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000004744 fabric Substances 0.000 claims abstract description 48
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000006298 dechlorination reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000006872 improvement Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 239000013068 control sample Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Abstract
The invention discloses an electrode with high selectivity for electrolyzing carbonate, which comprises a silver mesh electrode with nano silver particles grown on the surface in situ, wherein carbon cloth with a microporous layer is further arranged on the silver mesh electrode with the nano silver particles grown on the surface in situ. The invention also discloses a preparation method of the electrode with high-selectivity electrolytic carbonate. The invention providesThe electrode prepared by carrying out electrochemical oxidation-reduction treatment on a commercial silver mesh electrode and then covering a layer of carbon cloth with a microporous layer on the surface of the silver mesh electrode remarkably improves the catalytic activity of the electrode on electrolytic bicarbonate and improves the catalytic selectivity, and the silver mesh electrode subjected to electrochemical oxidation-reduction is compared with an untreated silver mesh electrode at 50mA/cm 2 Under the condition of FE CO 296.02% improvement; and when the surface of the electrode is covered with a layer of carbon cloth with a microporous layer, FE CO Again by 196.75%, i.e. 492.8% compared to untreated silver mesh.
Description
Technical Field
The invention belongs to CO 2 The technical field of electrochemical reduction, in particular to a coupling alkali liquor method for trapping CO 2 And in situ reduced electrode preparation techniques.
Background
Along with rapid development of global industrialization for the 18 th century, global dependence on fossil energy continues to rise, global CO 2 The discharge amount is increasing drastically. By 2019, the total consumption of fossil energy reaches 138.65 hundred million tons of equivalent oil worldwide, and global CO is generated 2 The total discharge amount is up to 313 hundred million tons. Due to CO 2 The global temperature rise caused by excessive emission not only causes the greenhouse effect, so that the global natural weather disasters are obviously increased, but also the global biodiversity is obviously affected.
Facing due to excessive CO 2 Global climate problems caused by emissions in 2016, paris' agreement proposed that global temperature rise was limited to within 2 ℃ at the end of this century, which means that future carbon emissions worldwide would be greatly restricted. According to the prediction, about 10% of total consumption of fossil energy is still maintained in China in 2060. Therefore, to achieve the goal of "carbon neutralization", technical means must be employed to eliminate this portion of the CO generated by fossil energy consumption 2 。
Electrochemical reduction of CO 2 Technique (Electrochemical CO) 2 reaction reduction，CO 2 RR) has the advantages of mild reaction conditions, moderate reaction speed, small influence by environmental fluctuation factors and the like, and becomes a hot research direction in recent years. At the same time, CO 2 The RR technology can also be used as an energy storage technology, is combined with renewable energy sources such as solar energy, wind energy and water energy which are greatly influenced by environmental fluctuation, has complementary advantages, and can ensure that the renewable energy sources can continuously and stably work. In addition, CO 2 RR can also produce as HCOOH, CO, C 2 H 4 、CH 3 OH and other industrial organic matters can effectively relieve the requirement of human production on chemical raw materials. Therefore, develop high-efficiency and energy-saving CO capable of realizing large-scale production 2 RR technology is an important issue that needs to be addressed currently.
But most of the current COs 2 RR technology requires high purity gas phase CO 2 As a reactant supply. For CO 2 Reduction process, CO from the point of view of complete industrial flow 2 RR process flow generally involves the following five processes: (1) CO 2 Captured by the capture liquid; (2) CO 2 Desorbing from the capture liquid; (3) CO 2 Purifying and compressing; (4) High purity CO 2 Through CO 2 RR is converted to a high value-added chemical. (5) product gas separation. In this process, the CO is required to pass through an absorbent 2 Is to absorb CO 2 Desorption, CO 2 Pressurized storage and other series of energy-intensive processes can only obtain high-purity gas-phase CO 2 This results in a great energy consumption. Thus, CO is captured with lye 2 Bicarbonate is generated and then CO is treated by means of in-situ electrolytic reduction 2 Is receiving increasing attention from students. Compared with electrolytic pure gas phase CO 2 The method can save the cost of procedures such as purification, compression transportation and the like, and has more development potential. With KOH solution as CO 2 For example, each time 1t CO is produced, the gas phase CO is electrolyzed 2 The whole process flow needs to consume 34.24GJ energy, and the energy consumption of the electrolytic bicarbonate is only 20.75GJ, and the reaction path is to simplify the whole CO 2 Pricing chain, CO reduction 2 The overall energy requirement and cost of the utilization process provides a promising solution with great economic feasibilityAnd commercial application value.
At present, the existing electrode of the electrolytic bicarbonate system is mostly prepared by adopting a spray method, a catalyst is loaded on the surface of GDE (gas diffusion electrode) by using a binder such as Nafion, PTFE and the like, the preparation process is complicated, and the use of the binder usually brings about 1) covering a large number of active sites to inhibit the catalytic performance; 2) The conductivity is reduced, and the electron transfer resistance is increased; 3) In long-term use, the binder falls off, the system stability is reduced, and the study of a good electrode structure is lacking. In addition, due to electrolysis of bicarbonate cathode partial CO 2 The concentration is low, so that the prior research technology still has difficulty in obtaining higher Faraday efficiency under larger current density.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the main purpose of the invention is to provide an electrode with high selectivity for electrolyzing carbonate, which aims to solve the problems of covering active sites and low catalytic selectivity of the existing spray-type electrode. The application also provides a preparation method of the electrode with high-selectivity electrolytic carbonate.
The invention aims at realizing the following technical scheme:
in a first aspect, an electrode with high selectivity for electrolyzing carbonate comprises a silver mesh electrode with nano silver particles grown on the surface in situ, wherein carbon cloth with a microporous layer is further arranged on the silver mesh electrode with nano silver particles grown on the surface in situ.
In a second aspect, a method for preparing an electrode with high selectivity for electrolysis of carbonates according to the foregoing comprises the steps of:
1) Placing the silver net electrode subjected to impurity removal treatment in Cl - In the solution, positive potential is applied to enable the surface of the silver mesh electrode to generate oxidation reaction, so as to generate nano AgCl particles;
2) Placing the silver mesh electrode obtained in the step 1) in CO 2 Saturated HCO 3 - In the solution, negative potential is applied to generate dechlorination reduction reaction, so that nano AgCl particles on the surface of the silver mesh electrode in the step 1) are reduced into simple substance nano Ag particles;
3) And (3) tightly attaching the silver mesh electrode prepared in the step (2) with the carbon cloth with the microporous layer, so as to obtain the electrode with high-selectivity electrolytic carbonate.
In some specific embodiments, the impurity removal treatment in step 1) is to sequentially place the silver mesh electrode in absolute ethanol, dilute sulfuric acid and deionized water for ultrasonic oscillation cleaning for 10-30min.
In certain embodiments, the conditions for applying a positive potential in step 1) are: the positive potential is 0.3-1.4V vs. Ag/AgCl, and the oxidation time is 90-200s.
In certain embodiments, the conditions for applying a negative potential in step 2) are: the negative potential is-1 to-2V vs. Ag/AgCl, and the dechlorination time is 150-500s.
In certain embodiments, the Cl-solution has a concentration of 1.5-3mol/L.
Further, the Cl-containing solution is one or a mixture of a KCl solution and a NaCl solution.
In certain embodiments, the HCO 3 The concentration of the solution is 0.1 to 0.5mol/L.
Further, the HCO 3-containing solution is KHCO 3 、NaHCO 3 One or a mixture of several solutions; during use, in the HCO 3 - The solution is required to be blown with enough CO 2 Make HCO 3 - The solution was saturated.
In certain embodiments, the mesh number of the silver mesh electrode is 150-200 mesh.
In certain embodiments, the carbon cloth comprises a diffusion layer and a microporous layer, and one surface of the carbon cloth with the microporous layer is tightly combined with a silver mesh electrode; the other side of the electrode is tightly attached to the bipolar membrane.
In a third aspect, an electrode with high selectivity electrolytic carbonate according to the foregoing or an electrode with high selectivity electrolytic carbonate produced by the foregoing production method is used for a cathode for producing synthesis gas by electrolysis of bicarbonate.
Compared with the prior art, the invention has at least the following advantages:
1) The electrode with high selectivity electrolytic carbonate provided by the invention prepares an active electrode with high specific surface area by performing electrochemical oxidation-reduction treatment on a commercial silver mesh electrode; then covering the silver mesh electrode surface with a layer of carbon cloth with microporous layer to make partial CO inside the electrode 2 The concentration is improved, the catalytic activity of the electrode to the electrolytic bicarbonate is obviously improved, and the catalytic selectivity is improved. The electrochemical redox commercial silver mesh electrode provided herein was compared to untreated commercial silver mesh electrode at 50mA/cm 2 Under the condition of FE CO 296.02% improvement; and when the surface of the commercial silver mesh electrode subjected to electrochemical oxidation reduction is covered with a layer of carbon cloth with a microporous layer, FE CO Again, 196.75% improvement.
2) The preparation method of the electrode for high-selectivity electrolysis of bicarbonate provided by the invention has the advantages of simple process, strong repeatability and high-efficiency catalytic activity.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an electron microscopic scan of a commercial silver mesh electrode after oxidation-reduction provided in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the electric double layer capacitance of the commercial silver mesh electrode after oxidation reduction and the commercial silver mesh electrode according to example 1 of the present invention;
FIG. 3 is a combination of a double-layered silver mesh electrode and a carbon cloth with a microporous layer according to example 1 of the present invention;
FIG. 4 shows FE when the electrode for high-selectivity bicarbonate electrolysis provided in example 1 of the present invention is used for bicarbonate electrolysis CO 。
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings and examples which are given by way of illustration only and not by way of limitation, and are not intended to limit the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the following examples:
the silver mesh electrode used was purchased from Hebei super-invasive metal mesh Co., ltd, and was cut into 1X 1cm as used in the present application 2 Is a square of (2);
the carbon cloth with microporous layer used was purchased from taiwan carbon company (model: carbon energy CeTech W1S1010, material type: carbon fiber woven cloth, thickness: 410 μm), which was cut to 1×1cm at the time of use in the present application 2 Is a square of (2); as shown in fig. 3, the carbon cloth comprises a diffusion layer 21 and a microporous layer 22, one surface of the carbon cloth provided with the microporous layer 22 is tightly combined with the silver mesh electrode 1, and the other surface of the silver mesh electrode 1 is tightly combined with the bipolar membrane 3.
The composition contains Cl - The solution is one or a mixture of a plurality of KCl and NaCl solutions; wherein Cl - The concentration of the solution is 1.5-3mol/L;
the composition contains HCO 3 - The solution is KHCO 3 、NaHCO 3 One or a mixture of several solutions. Wherein HCO is 3 - The concentration of the solution is 0.1-0.5mol/L;
in the following examples, electrochemical workstation (PARSTAT MC, U.S.) equipment was used for electrode treatment and for electrolytic bicarbonate testing; the reduction products were tested using a gas chromatograph (Aglient 8890, USA) apparatus;
example 1
The electrode with high-selectivity electrolytic bicarbonate is prepared by the following preparation method:
1) Sequentially carrying out ultrasonic oscillation cleaning on a 180-mesh silver mesh electrode by adopting absolute ethyl alcohol, dilute sulfuric acid and deionized water for 15min so as to remove surface impurities;
2) And (3) oxidizing the silver mesh electrode subjected to impurity removal treatment in a three-electrode chamber by using a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode. Wherein the electrolyte solution is KCl solution of 3mol/L; applying a 1V vs. Ag/AgCl potential at the working electrode end, and oxidizing for 90s;
3) Washing the silver mesh electrode obtained in the step 2) by deionized water, and then using the silver mesh electrode as a working electrode, a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode to perform dechlorination treatment in a three-electrode chamber; wherein the electrolyte solution is KHCO of 0.5mol/L 3 Solution, in which CO is blown in a sufficient quantity 2 Make HCO 3 - The solution was saturated. And applying a potential of-2V vs. Ag/AgCl to the working electrode end, and dechlorinating for 300s.
4) Washing the silver mesh electrode obtained in the step 3) by deionized water, and drying in a vacuum drying oven; simultaneously, carrying out ultrasonic vibration cleaning on the carbon cloth with the microporous layer by adopting absolute ethyl alcohol and deionized water to remove impurities possibly existing on the surface, and then placing the carbon cloth in an oven for vacuum drying; and then covering a layer of carbon cloth with a microporous layer on the surface of the 2 layers of silver mesh electrode subjected to oxidation-reduction treatment, wherein one side of the carbon cloth with the microporous layer is tightly attached to the silver mesh electrode, and thus the electrode with high-selectivity electrolytic bicarbonate is obtained.
Example 2
The electrode with high-selectivity electrolytic bicarbonate is prepared by the following preparation method:
1) Sequentially carrying out ultrasonic oscillation cleaning on a 180-mesh silver mesh electrode by adopting absolute ethyl alcohol, dilute sulfuric acid and deionized water for 15min so as to remove surface impurities;
2) And (3) oxidizing the silver mesh electrode subjected to impurity removal treatment in a three-electrode chamber by using a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode. Wherein the electrolyte solution is KCl solution of 3mol/L; applying a potential of 1.1V vs. Ag/AgCl to the working electrode end, and oxidizing for 90s;
3) Washing the silver mesh electrode obtained in the step 2) by deionized water, and then using the silver mesh electrode as a working electrode, a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode to perform dechlorination treatment in a three-electrode chamber; wherein the electrolyte solution is KHCO of 0.5mol/L 3 Solution, in which CO is blown in a sufficient quantity 2 Make HCO 3 - The solution was saturated. Applied at the working electrode end-1.1v vs. ag/AgCl potential, dechlorination 300s.
4) Washing the silver mesh electrode obtained in the step 3) by deionized water, and drying in a vacuum drying oven; simultaneously, carrying out ultrasonic vibration cleaning on the carbon cloth with the microporous layer by adopting absolute ethyl alcohol and deionized water to remove impurities possibly existing on the surface, and then placing the carbon cloth in an oven for vacuum drying; and then covering a layer of carbon cloth with a microporous layer on the surface of the 2 layers of silver mesh electrode subjected to oxidation-reduction treatment, wherein one side of the carbon cloth with the microporous layer is tightly attached to the silver mesh electrode, and thus the electrode with high-selectivity electrolytic bicarbonate is obtained.
Example 3
The electrode with high-selectivity electrolytic bicarbonate is prepared by the following preparation method:
1) Sequentially carrying out ultrasonic oscillation cleaning on a 200-mesh silver mesh electrode by using absolute ethyl alcohol, dilute sulfuric acid and deionized water for 15min so as to remove surface impurities;
2) And (3) oxidizing the silver mesh electrode subjected to impurity removal treatment in a three-electrode chamber by using a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode. Wherein the electrolyte solution is KCl solution of 3mol/L; applying a potential of 1.2V vs. Ag/AgCl to the working electrode end, and oxidizing for 200s;
3) Washing the silver mesh electrode obtained in the step 2) by deionized water, and then using the silver mesh electrode as a working electrode, a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode to perform dechlorination treatment in a three-electrode chamber; wherein, the electrolyte solution is NaHCO of 0.1mol/L 3 Solution, in which CO is blown in a sufficient quantity 2 Make HCO 3 - The solution was saturated. And applying a potential of-2V vs. Ag/AgCl to the working electrode end, and dechlorinating for 300s.
4) Washing the silver mesh electrode obtained in the step 3) by deionized water, and drying in a vacuum drying oven; simultaneously, carrying out ultrasonic vibration cleaning on the carbon cloth with the microporous layer by adopting absolute ethyl alcohol and deionized water to remove impurities possibly existing on the surface, and then placing the carbon cloth in an oven for vacuum drying; and then covering a layer of carbon cloth with a microporous layer on the surface of the 3 layers of silver mesh electrode subjected to oxidation-reduction treatment, wherein one side of the carbon cloth with the microporous layer is tightly attached to the silver mesh electrode, and thus the electrode with high-selectivity electrolytic bicarbonate is obtained.
Comparative example 1
The preparation method of the electrode with high selectivity electrolytic carbonate provided in this comparative example is substantially the same as in example 1, steps 1), 2) and 3) are the same as in example 1, and step 4) replaces the carbon cloth with the microporous layer with the carbon cloth without the microporous layer, and others are the same.
Comparative example 2
The preparation method of the electrode with high-selectivity electrolytic carbonate provided in this comparative example is basically the same as example 1, except that steps 2) and 3) are not included, specifically:
1) Sequentially carrying out ultrasonic oscillation cleaning on a 180-mesh silver mesh electrode by adopting absolute ethyl alcohol, dilute sulfuric acid and deionized water for 15min so as to remove surface impurities;
4) Drying the silver mesh electrode in a vacuum drying oven; simultaneously, carrying out ultrasonic vibration cleaning on the carbon cloth with the microporous layer by adopting absolute ethyl alcohol and deionized water to remove impurities possibly existing on the surface, and then placing the carbon cloth in an oven for vacuum drying; and covering a layer of carbon cloth with a microporous layer on the surface of the silver mesh electrode, wherein one side of the carbon cloth with the microporous layer is tightly attached to the silver mesh electrode.
Comparative example 3
The preparation method of the electrode with high selectivity electrolytic carbonate provided in this comparative example is substantially the same as comparative example 2, except that the carbon cloth with the microporous layer is replaced with the carbon cloth without the microporous layer in step 2), and otherwise the same.
Performance test:
the performance index of the electrode for high-selectivity electrolysis of bicarbonate obtained in example 1 was tested in the present application:
(1) Morphology structure diagram
The result of electron microscopy scanning of the electrochemical redox silver mesh electrode prepared by the preparation method of the embodiment 1 is shown in fig. 1, wherein fig. 1 (a) (b) (c) and (d) are electron microscopy scanning diagrams of the silver mesh electrode before treatment, and fig. 1 (e) (f) (g) and (h) are redox silver mesh electrodes (specifically, the silver mesh electrode prepared in the step 3 of the embodiment 1); as can be seen from the figure, a plurality of silver nano particles are grown on the surface of the silver mesh in the electrochemical oxidation and chemical reduction modes, so that the specific surface area of the electrode is greatly increased while the structure of the electrode is maintained, and the number of active sites is increased. As shown in fig. 2, the electric double layer capacitance of the silver mesh electrode (2 b) treated by the oxidation-reduction method is increased by about 59 times compared with that of the silver mesh electrode (2 a) untreated, and the specific surface area is greatly improved.
(2) Electrical performance testing
1) Preparing KHCO 3 Solution: preparing a saturated potassium bicarbonate solution with the molar concentration of 3mol/L by using potassium bicarbonate particles with the purity of 99.5% and deionized water under the water bath condition of 35 ℃, and then adding a certain mass of ethylenediamine tetraacetic acid particles, wherein the molar concentration of the ethylenediamine tetraacetic acid is 0.01mol/L so as to chelate impurity ions possibly existing in the salt solution;
2) The electrodes with high selectivity for the electrolysis of bicarbonate prepared in example 1, comparative examples 1-3 were used for the electrolysis of bicarbonate solution: the test reactor was a commercial MEA reactor. On the anode side of the reactor, the working electrode had an area of 2.5X2.5 cm 2 And a 60sccm 1mol/L KOH solution was passed as a reactant. On the cathode side, the electrode with high selectivity for electrolytic bicarbonate prepared in example 1 was put into the saturated KHCO prepared in step 1 at a flow rate of 60sccm 3 A solution. Wherein the two chambers are made by Fumatech companyFBM bipolar membranes are separated. The test was performed under a two-electrode system with cathodic currents of-50, -100, -150, -200mA/cm, respectively 2 The electrochemical reduction reaction is carried out for 10min. The reaction product is composed of N 2 Purging into a gas-collecting bag, and then quantitatively analyzing the gas-collecting bag by using gas chromatography to calculate Faraday efficiency; the results are shown in FIG. 4.
In addition, under the same test conditions, commercial silver mesh electrode and silver mesh electrode without carbon cloth after redox treatment are introduced as a control sample, and the electrode performances of the commercial silver mesh electrode and the silver mesh electrode are tested, and the results are shown in fig. 4, wherein a is the electrolytic performance of the commercial silver mesh electrode, b is the electrolytic performance of the electrode prepared in comparative example 2, c is the electrolytic performance of the electrode prepared in comparative example 3, d is the electrolytic performance of the silver mesh electrode without carbon cloth after redox treatment in example 1, e is the electrolytic performance of the electrode prepared in comparative example 1, and f is the electrolytic performance of the electrode prepared in example 1.
As can be seen from FIG. 4, the electrochemically redox silver mesh electrode was compared with the untreated silver mesh electrode at 50mA/cm 2 Under the condition of FE CO 296.02% improvement; and when the surface of the electrode is covered with a layer of carbon cloth with a microporous layer, FE CO Again, 196.75% improvement. As is clear from the comparison of example 1 and comparative example 1, the electrode performance hardly improved when the electrode was covered with the carbon cloth without the microporous layer; as is clear from the comparison between the example 1 and the comparative example 2, the electrochemical treatment of the electrode is not performed, and the electrolysis performance of the electrode is not changed no matter the electrode is covered with the microporous carbon cloth or the microporous carbon cloth, namely, the purpose of improving the electrolysis performance of the electrode can not be achieved only by arranging the microporous carbon cloth on the common electrode; in conclusion, the electrochemical oxidation reduction is carried out on the silver mesh electrode, and the carbon cloth with micropores is arranged, so that excellent electrolysis performance is obtained under the synergistic effect.
No CO and H removal was found in the reaction product test of the present invention 2 Other products are added, and the total FE calculated by the product meets the actual condition.
According to the invention, the electrochemical oxidation-reduction mode is adopted to grow silver nano particles on the surface of the silver mesh electrode, so that the specific surface area of the electrode is greatly increased, and active sites are enriched. Has the advantages of simple operation, strong repeatability and the like. In addition, the surface of the silver mesh electrode is covered with a layer of carbon cloth with a microporous layer, so that the local CO of the electrode is increased 2 The concentration greatly improves the current density of the carbon products. The method has the following characteristics:
1) In the presence of Cl - By applying positive potential to the electrode to oxidize the electrode, on the surface of silver meshAgCl particles are formed and then in CO 2 HCO in atmosphere 3 - And (3) applying negative potential in the solution to dechlorinate the electrode, so that nano silver particles are successfully formed on the surface of the electrode. Wherein, can be controlled by Cl - The size and nanocrystallization degree of the silver nano-particles are regulated in the modes of concentration, oxidation voltage, oxidation time and the like.
2) Covering the surface of silver mesh electrode with carbon cloth with microporous layer to increase local CO of electrode 2 Localized CO inside the electrode 2 The concentration is equivalent to the increase of reactants, and the current density of the carbon products is improved, so that the catalytic performance is improved.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (10)
1. The electrode is characterized by comprising a silver mesh electrode with nano silver particles grown on the surface in situ, and carbon cloth with a microporous layer is further arranged on the silver mesh electrode with the nano silver particles grown on the surface in situ.
2. A method for producing an electrode with high selectivity for electrolytic carbonate according to claim 1, comprising the steps of:
1) Placing the silver net electrode subjected to impurity removal treatment in Cl - In the solution, positive potential is applied to enable the surface of the silver mesh electrode to generate oxidation reaction, so as to generate nano AgCl particles;
2) Placing the silver mesh electrode obtained in the step 1) in CO 2 Saturated HCO 3 - Dechlorination reduction occurs by applying negative potential in the solutionThe reaction is carried out, so that the nano AgCl particles on the surface of the silver mesh electrode in the step 1) are reduced into simple substance nano Ag particles;
3) And (3) tightly attaching the silver mesh electrode prepared in the step (2) with the carbon cloth with the microporous layer, so as to obtain the electrode with high-selectivity electrolytic carbonate.
3. The method for preparing an electrode with high selectivity for electrolytic carbonate according to claim 2, wherein the impurity removal treatment in step 1) is to sequentially place a silver mesh electrode in absolute ethanol, dilute sulfuric acid and deionized water for ultrasonic vibration cleaning for 10-30min.
4. The method for preparing an electrode with high selectivity for electrolysis of carbonate according to claim 2, wherein the conditions for applying the positive potential in step 1) are: the positive potential is 0.3-1.4V vs. Ag/AgCl, and the oxidation time is 90-200s.
5. The method for preparing an electrode with high selectivity for electrolysis of carbonate according to claim 2, wherein the conditions for applying negative potential in step 2) are: the negative potential is-1 to-2V vs. Ag/AgCl, and the dechlorination time is 150-500s.
6. The method for producing an electrode with high selectivity for electrolytic carbonate according to claim 2, wherein the Cl - The concentration of the solution is 1.5-3mol/L.
7. The method for producing an electrode with high selectivity for electrolysis of carbonate according to claim 2, wherein the HCO 3 - The concentration of the solution is 0.1-0.5 mol/L.
8. The method for producing an electrode with high selectivity for electrolytic carbonate according to claim 2, wherein the mesh number of the silver mesh electrode is 150 to 200 mesh.
9. The method for preparing an electrode with high selectivity for electrolytic carbonate according to claim 2, wherein the carbon cloth comprises a diffusion layer and a microporous layer, and one surface of the carbon cloth with the microporous layer is tightly combined with a silver mesh electrode.
10. A cathode for the electrolysis of bicarbonate to synthesis gas, according to the electrode with high selectivity for the electrolysis of carbonate according to claim 1 or the electrode with high selectivity for the electrolysis of carbonate produced by the production process according to any one of claims 2 to 9.
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