CN110860294B - Method for preparing formic acid by electrochemical reduction reaction of carbon dioxide by using copper-lead composite metal as electrode - Google Patents
Method for preparing formic acid by electrochemical reduction reaction of carbon dioxide by using copper-lead composite metal as electrode Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 74
- 239000001569 carbon dioxide Substances 0.000 title claims description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 37
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims description 25
- 238000006722 reduction reaction Methods 0.000 title claims description 23
- 235000019253 formic acid Nutrition 0.000 title claims description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 230000008021 deposition Effects 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 26
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000006260 foam Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- -1 1-butyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- YBOVOIIYARCCLH-UHFFFAOYSA-N [Br].NC(C)C1=NC=CN1C Chemical compound [Br].NC(C)C1=NC=CN1C YBOVOIIYARCCLH-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 2
- BQKHKRLJOPTILQ-UHFFFAOYSA-M 1-(3-methylimidazol-3-ium-1-yl)ethanamine;bromide Chemical compound [Br-].CC(N)[N+]=1C=CN(C)C=1 BQKHKRLJOPTILQ-UHFFFAOYSA-M 0.000 claims 3
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 29
- 239000002608 ionic liquid Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 7
- RUISNDKLNVFPBQ-UHFFFAOYSA-N CC(C1=NC=CN1C)N.Br Chemical compound CC(C1=NC=CN1C)N.Br RUISNDKLNVFPBQ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ARQKUPJDNMBTLN-UHFFFAOYSA-N [Br].CN1CN(C=C1)CCC Chemical compound [Br].CN1CN(C=C1)CCC ARQKUPJDNMBTLN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Abstract
The invention provides a preparation method of a copper-lead composite metal catalyst and application of the copper-lead composite metal catalyst. The preparation method of the copper-lead composite metal catalyst has the advantages of simple process, convenient operation, mild conditions and contribution to industrial production.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a copper-lead composite metal catalyst, and also relates to application of the copper-lead composite metal catalyst in an electrochemical reduction reaction of carbon dioxide.
Background
In the past, environmental problems caused by economic development have been intensified, among which emission of carbon dioxide, which is a main greenhouse gas, is one of the most significant problems, and global warming caused by carbon dioxide emission has become the most important environmental problem, which threatens not only national economy but also global environment, and thus needs to be solved urgently.
IEA made a report on global carbon dioxide emissions in 2019 and 3 months, which reported that the total amount of carbon dioxide emissions produced by the global energy consumption in 2018 increased by 1.7% (about 5.61 hundred million tons, which corresponds to the total amount of global international aviation emissions), reaching the highest emission in history. China is currently in the stage of high-speed and high-quality economic development, and although the country is strictly controlling the emission of carbon dioxide, the emission of carbon dioxide is still large due to the tendency of international situation.
In consideration of the economical efficiency and availability of carbon dioxide, carbon dioxide can be regarded as a carbon resource with higher cost performance, so how to effectively utilize carbon dioxide becomes an important link for solving the problem of global warming at the present stage, and by fully utilizing carbon dioxide, energy can be saved, carbon emission can be reduced, and economic value can be created for society.
Because the chemical property of the carbon dioxide is very stable, the reaction can only occur under specific conditions, thereby bringing certain difficulty to the utilization of the carbon dioxide, and the development of the electrochemical reduction technology provides a better idea for solving the problem. By means of an electrochemical reduction technology, the carbon dioxide can be converted into valuable chemicals and carbon-containing fuels such as methanol, formic acid and the like by means of electric energy provided by clean energy sources such as solar energy, wind energy and the like. Meanwhile, the reaction process is controllable, and the whole electrochemical reduction reaction can be regulated and controlled by changing the conditions of the type of the electrolyte solution, the type of the electrode, the application potential and the like so as to selectively generate a certain specific high-value product.
At present, in the utilization of the carbon dioxide electrochemical reduction technology, the research on the electrolyte is relatively deep, but in the aspect of electrodes, when a plurality of single metal electrodes are applied to the carbon dioxide electrochemical reduction, the overpotential required by the reaction is high, and the industrial production is not facilitated. Therefore, it is important to develop a novel carbon dioxide electrochemical reduction catalyst with high catalytic activity and stable performance.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing a copper-lead composite metal catalyst, so as to obtain a catalyst suitable for an electrochemical reduction reaction of carbon dioxide.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a copper-lead composite metal catalyst comprises the following steps:
s1, dissolving ionic liquid in deionized water to prepare an ionic liquid aqueous solution A;
s2, adjusting the pH value of the solution A to 1~6, adding lead nitrate into the solution A, and uniformly stirring to obtain a mixed solution B of ionic liquid and lead nitrate;
s3, introducing current to carry out constant current deposition reaction on the mixed solution B on the substrate, and after the reaction is finished, washing and drying a deposition sample to obtain the copper-lead composite metal catalyst;
wherein the ionic liquid is one of 1-propyl-3-methylimidazole bromine salt, 1-propyl-3-methylimidazole tetrafluoroborate and 1-aminoethyl-3-methylimidazole bromine salt.
Further, in the step s1, the concentration of the ionic liquid aqueous solution A is 0.005 to 0.05mol/L.
Further, in the step s1, the concentration of the ionic liquid aqueous solution A is 0.01 to 0.025 mol/L.
Further, in step s2, hydrochloric acid is added to the solution A under stirring to adjust the pH of the solution A.
Further, in step s2, the hydrochloric acid is concentrated hydrochloric acid.
Further, in step s2, the pH of solution a is adjusted to 1~3.
Further, in the step s2, the concentration of lead nitrate in the mixed solution B is 0.030 to 0.090 mol/L.
Further, in the step s2, the concentration of lead nitrate in the mixed solution B is 0.035 to 0.065 mol/L.
Furthermore, the current in the step s3 is between 5mA and 50mA, and the constant current deposition reaction time is between 5 and 50min.
Furthermore, the current in the step s3 is between 10mA and 30mA, and the constant current deposition reaction time is 10 to 30min.
Further, the substrate is foam copper.
Further, in the step s3, deionized water is adopted for washing to be neutral, and high-purity nitrogen is adopted for blow-drying.
Compared with the prior art, the invention has the following advantages:
the preparation method has the advantages of simple process, convenient operation, mild conditions and easy industrial production, and the generated formic acid can be used for producing other chemicals or used as a raw material of a formic acid fuel cell.
The invention also provides a preparation method of the copper-lead composite metal catalyst and application of the prepared copper-lead composite metal catalyst, and the copper-lead composite metal catalyst is used in the electrochemical reduction reaction of carbon dioxide.
The prepared copper-lead composite metal catalyst is used for carbon dioxide electroreduction, has good catalytic activity, can reduce the electroreduction potential of carbon dioxide and increase current density, and simultaneously, the obtained liquid product is formic acid, can be used for producing other chemicals or manufacturing formic acid fuel cells, and can obtain good application effect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a scanning electron micrograph (5.00 μm) of a Cu-Pb composite metal catalyst prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph (2.00 μm) of a Cu-Pb composite metal catalyst prepared in accordance with example 1 of the present invention;
FIG. 3 is a cyclic voltammogram of a copper foam electrode (f-Cu) of the present invention and a copper-lead composite metal catalyst electrode (Pb/f-Cu) prepared in example 1.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The embodiment relates to a preparation method of a copper-lead composite metal catalyst, which is to prepare a micron-sized copper-lead composite metal catalyst by adopting an electrochemical deposition method.
Specifically, the preparation method of this embodiment includes dissolving imidazole type ionic liquid in deionized water to obtain an ionic liquid aqueous solution a, adjusting the pH of solution a to 1~6, adding lead nitrate into solution a, and stirring uniformly to obtain a mixed solution B of ionic liquid and lead nitrate. And then, introducing current to carry out constant current deposition reaction on the mixed solution B on the substrate, and after the reaction is finished, washing and drying a deposition sample to obtain the copper-lead composite metal catalyst.
In the above preparation method, the ionic liquid is specifically one of 1-propyl-3-methylimidazole bromine salt, 1-propyl-3-methylimidazole tetrafluoroborate and 1-aminoethyl-3-methylimidazole bromine salt, and preferably the ionic liquid is 1-aminoethyl-3-methylimidazole bromine salt. Meanwhile, the concentration of the ionic liquid aqueous solution A is 0.005 to 0.050 mol/L, and preferably 0.01 to 0.025 mol/L.
In the above-mentioned production method, hydrochloric acid is added to the solution a under stirring to adjust the pH of the solution a, and specifically, concentrated hydrochloric acid is used as the hydrochloric acid, and it is preferable to adjust the pH of the solution a to 1~3, for example, to 1, 1.5, 2, 2.5, or 3. In addition, the concentrated hydrochloric acid is commercially available concentrated hydrochloric acid which is commonly adopted in the chemical field, namely concentrated hydrochloric acid with the concentration of 36-38%, and except the concentration interval, concentrated hydrochloric acid with other concentrations of which the mass fraction exceeds 20% is also feasible.
In the preparation method, the concentration of lead nitrate in the mixed solution B obtained by adding lead nitrate and uniformly stirring is 0.030 to 0.090 mol/L, and the concentration is preferably 0.035 to 0.065 mol/L. In addition, the substrate for the constant current deposition reaction can be specifically copper foam, so that the porosity of the copper foam is up to more than 95%, and the characteristics of good conductivity and ductility are utilized, thereby being beneficial to the effective reaction. Of course, in addition to copper foam, galvanostatic deposition reactions are also possible using nickel foam, although nickel foam is more expensive to produce than copper foam and is more conductive than copper foam.
In the constant current deposition reaction of the present embodiment, the current is specifically between 5ma and 50ma, and the time of the constant current deposition reaction is between 5 and 50min, preferably between 10ma and 30ma, and between 10 and 30min. Meanwhile, after the reaction is finished, specifically, deionized water is adopted to wash the deposition sample to be neutral, and high-purity nitrogen is adopted to blow dry to obtain the copper-lead composite metal catalyst, wherein the adopted high-purity nitrogen is nitrogen with the purity of 99.999% (O2 is less than or equal to 0.001%).
The copper-lead composite metal catalyst prepared by the embodiment can be particularly applied to the electrochemical reduction reaction of carbon dioxide, can effectively reduce the overpotential required by the electrochemical reduction reaction in the reaction, can increase the current density in the reaction, and can be used as a catalyst suitable for the electrochemical reduction reaction of carbon dioxide.
The preparation method of the copper-lead composite metal catalyst of the present embodiment will be further described below with several preparation examples.
Preparation of example 1
In the preparation of the copper-lead composite metal catalyst of the embodiment, 1-aminoethyl-3-methylimidazole bromine salt is dissolved in deionized water to prepare 0.01 mol/L1-aminoethyl-3-methylimidazole bromine salt solution A, the pH value is adjusted to 2 by concentrated hydrochloric acid, then lead nitrate is added into the obtained solution A, and the mixture is stirred uniformly to obtain a mixed solution B of the 1-aminoethyl-3-methylimidazole bromine salt and the lead nitrate, wherein the concentration of the lead nitrate is 0.05mol/L. And then, carrying out constant current deposition on the mixed solution B on a foam copper substrate under the current of 10mA for 20min, washing a deposition sample with deionized water for 3 times to be neutral after the reaction is finished, and drying with high-purity nitrogen to obtain the copper-lead composite metal catalyst.
The copper-lead composite metal catalyst prepared in the example 1 is used as a working electrode for carbon dioxide electrochemical reduction reaction, and in 40mg/mL 1-butyl-3-methylimidazolium tetrafluoroborate, the faradic efficiency of the obtained HCOOH is 29.36% under the electrolytic potential of-1.8V.
Preparation of example 2
In the preparation of the copper-lead composite metal catalyst of the embodiment, 1-aminoethyl-3-methylimidazole bromide is dissolved in deionized water to prepare 0.01 mol/L1-aminoethyl-3-methylimidazole bromide solution A, then concentrated hydrochloric acid is used for adjusting the pH value to 2, lead nitrate is added into the obtained solution A, and the mixture is stirred uniformly to obtain 0.05 mol/L1-aminoethyl-3-methylimidazole bromide and lead nitrate mixed solution B. And then, carrying out constant current deposition on the mixed solution B on a foam copper substrate under the current of 15 mA for 20min, washing the deposition sample with deionized water for 3 times until the deposition sample is neutral, and drying the deposition sample with high-purity nitrogen to obtain the copper-lead composite metal catalyst.
The copper-lead composite metal catalyst prepared in the example 2 was used as a working electrode in an electrochemical reduction reaction of carbon dioxide, and in 40mg/mL of 1-butyl-3-methylimidazolium tetrafluoroborate, and the electrolytic potential was-2.0V, the faradic efficiency of the obtained HCOOH was 21.40%.
Preparation of example 3
In the preparation of the copper-lead composite metal catalyst of the present example, 1-aminoethyl-3-methylimidazole bromide salt was dissolved in deionized water to prepare 0.02 mol/L1-aminoethyl-3-methylimidazole bromide salt solution a, concentrated hydrochloric acid was then used to adjust the pH to 1.5, and lead nitrate was added to the obtained solution a, and the mixture was stirred uniformly to obtain a mixed solution B of 1-aminoethyl-3-methylimidazole bromide salt and lead nitrate having a lead nitrate concentration of 0.04 mol/L. And then, carrying out constant current deposition on the mixed solution B on a foam copper substrate under the current of 30mA for 20min, washing the deposition sample with deionized water for 3 times until the deposition sample is neutral, and drying the deposition sample with high-purity nitrogen to obtain the copper-lead composite metal catalyst.
The copper-lead composite metal catalyst obtained in the example 3 was used as a working electrode in an electrochemical reduction reaction of carbon dioxide, and the faradic efficiency of the obtained HCOOH was 25.92% in 40mg/mL of 1-butyl-3-methylimidazolium tetrafluoroborate at an electrolytic potential of-2.1V.
Preparation of example 4
In the preparation of the copper-lead composite metal catalyst of the embodiment, 1-aminoethyl-3-methylimidazole bromide is dissolved in deionized water to prepare 0.02 mol/L1-aminoethyl-3-methylimidazole bromide solution A, the pH value is adjusted to 3 by concentrated hydrochloric acid, then lead nitrate is added into the obtained solution A, and the mixture is stirred uniformly to obtain 0.06 mol/L1-aminoethyl-3-methylimidazole bromide and lead nitrate mixed solution B. And then, carrying out constant current deposition on the mixed solution B on a foam copper substrate under the current of 25 mA for 10min, washing the deposition sample with deionized water for 3 times until the deposition sample is neutral, and drying the deposition sample with high-purity nitrogen to obtain the copper-lead composite metal catalyst.
The copper-lead composite metal catalyst prepared in the example 4 was applied to the electrochemical reduction reaction of carbon dioxide as a working electrode, and the faradic efficiency of the obtained HCOOH was 4.22% in 40mg/mL of 1-butyl-3-methylimidazolium tetrafluoroborate at an electrolytic potential of-2.2V.
Preparation of example 5
In the preparation of the copper-lead composite metal catalyst of the present example, 1-aminoethyl-3-methylimidazole bromide salt was dissolved in deionized water to prepare 0.01 mol/L1-aminoethyl-3-methylimidazole bromide salt solution a, then concentrated hydrochloric acid was used to adjust the pH to 3, and lead nitrate was added to the obtained solution and stirred uniformly to obtain a mixed solution B of 1-aminoethyl-3-methylimidazole bromide salt and lead nitrate having a lead nitrate concentration of 0.05mol/L. And then, carrying out constant current deposition on the mixed solution B on a foam copper substrate under the current of 30mA for 30min, washing a deposition sample with deionized water for 3 times until the deposition sample is neutral, and drying the deposition sample by using high-purity nitrogen to obtain the copper-lead composite metal catalyst.
The copper-lead composite metal catalyst prepared in this example 5 was applied to a carbon dioxide electrochemical reduction reaction as a working electrode, and the faradic efficiency of the obtained HCOOH was 4.61% in 40mg/mL of 1-butyl-3-methylimidazolium tetrafluoroborate at an electrolytic potential of-1.8V.
In the above preparation example, taking preparation example 1 as an example, the copper-lead composite metal catalyst prepared in example 1 is subjected to electron microscope scanning, and the obtained field emission scanning electron microscope images are shown in fig. 1 and fig. 2, wherein fig. 1 is 5.00 μm scale, fig. 2 is 2.00 μm scale, and as can be seen from fig. 1 and fig. 2, the copper-lead composite metal catalyst prepared in this example is micron-sized and has a "bulk" morphology.
In addition, the cyclic voltammograms of the copper-lead composite metal catalyst and the copper foam were tested using the Princeton electrochemical workstation, again taking the copper-lead composite metal catalyst obtained in example 1 as an example and the copper foam as a comparison. The method comprises the following steps of preparing a copper-lead composite metal catalyst, preparing a copper foam electrode, preparing a copper-lead composite metal catalyst electrode, preparing a copper foam electrode, preparing a platinum mesh, preparing a reaction solution, and carrying out cyclic voltammetry testing, wherein a three-electrode system is adopted in the testing, the prepared copper-lead composite metal catalyst and the prepared copper foam are respectively used as working electrodes, namely the working electrodes respectively adopt a copper-lead composite metal catalyst electrode (Pb/f-Cu) and a copper foam electrode (f-Cu), the platinum mesh is a counter electrode, ag/AgCl is a reference electrode, a closed H-type electrolytic cell is adopted, the reaction solution adopts 0.5mol/L potassium bicarbonate solution, the reaction is carried out at normal temperature and normal pressure in a carbon dioxide atmosphere, the working potential range of the cyclic voltammetry testing is 0.5 to-2.5V, and the scanning rate is 50mV/s.
Through tests, cyclic voltammetry curves of a foam copper electrode (f-Cu) and a copper-lead composite metal catalyst electrode (Pb/f-Cu) are shown in FIG. 3, and as can be seen from FIG. 3, compared with the f-Cu electrode, the Pb/f-Cu electrode has a smaller initial reduction potential of carbon dioxide, can effectively reduce the potential required by the reaction, and has a larger current density, so that the Pb/f-Cu electrode, namely the copper-lead composite metal catalyst prepared in the embodiment, is more beneficial to industrial production of electrochemical reduction of carbon dioxide.
In addition, the embodiment also relates to a preparation method of the copper-lead composite metal catalyst and application of the prepared copper-lead composite metal catalyst, and the copper-lead composite metal catalyst is specifically used in the electrochemical reduction reaction of carbon dioxide.
The copper-lead composite metal catalyst of the embodiment is used for carbon dioxide electroreduction, has good catalytic activity, can reduce the electroreduction potential of carbon dioxide, increases current density, and can obtain good application effect because the liquid product obtained by the reaction is formic acid which can be used for producing other chemicals or manufacturing formic acid fuel cells.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A method for preparing formic acid by using copper-lead composite metal as an electrode for electrochemical reduction reaction of carbon dioxide is characterized by comprising the following steps:
the electrolyte adopted by the method is a 1-butyl-3-methylimidazole tetrafluoroborate solution, and the preparation of the copper-lead composite metal comprises the following steps:
s1. dissolving 1-aminoethyl-3-methylimidazolium bromide in deionized water to obtain 1-aminoethyl-3-methylimidazolium bromide solution A;
s2, adjusting the pH value of the 1-aminoethyl-3-methylimidazole bromine salt solution A to 2, adding lead nitrate into the solution A, and uniformly stirring to obtain a mixed solution B of the 1-aminoethyl-3-methylimidazole bromine salt and the lead nitrate;
s3., introducing 10mA current to carry out constant current deposition reaction on the mixed solution B on the foam copper substrate for 20min, washing a deposition sample to be neutral by using deionized water after the reaction is finished, and drying by using high-purity nitrogen to obtain the copper-lead composite metal catalyst;
wherein in the step s2, concentrated hydrochloric acid is added into the 1-aminoethyl-3-methylimidazolium bromide solution A under stirring to adjust the pH value of the solution A;
the obtained copper-lead composite metal is micron-sized and has a 'blocky' shape.
2. The method of claim 1, wherein:
in the step s1, the concentration of the solution A is 0.005 to 0.05mol/L.
3. The method of claim 1, wherein:
in the step s2, the concentration of lead nitrate in the mixed solution B is 0.030 to 0.090 mol/L.
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