CN113471495B - Method for improving electric oxidation current efficiency of multi-carbon alcohol and reducing poisoning of electrocatalyst - Google Patents
Method for improving electric oxidation current efficiency of multi-carbon alcohol and reducing poisoning of electrocatalyst Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 14
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 14
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 135
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 107
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- 239000013067 intermediate product Substances 0.000 claims abstract description 37
- 231100000331 toxic Toxicity 0.000 claims abstract description 33
- 230000002588 toxic effect Effects 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000003411 electrode reaction Methods 0.000 claims abstract description 7
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 42
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 21
- 235000019253 formic acid Nutrition 0.000 claims description 21
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000002574 poison Substances 0.000 claims description 4
- 231100000614 poison Toxicity 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 229910052697 platinum Inorganic materials 0.000 description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 description 18
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 229960004063 propylene glycol Drugs 0.000 description 12
- 235000013772 propylene glycol Nutrition 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 9
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- 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
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
A method for improving the efficiency of the electric oxidation current of the multi-carbon alcohol and reducing the poisoning of an electrocatalyst relates to the field of direct alcohol fuel cells. Mixing the multi-carbon alcohols and the active fuel in proportion and dissolving the mixture in distilled water containing supporting electrolyte to obtain mixed fuel electrolyte for the liquid fuel cell; the mixed fuel electrolyte is applied to a three-electrode reaction system, and a constant potential is applied to a working electrode, so that fuel molecules generate an electrooxidation reaction on the surface of a catalyst, an improved electrooxidation current is obtained, and the toxicity of toxic intermediate products generated by electrooxidation of the multi-carbon alcohol to the catalyst is weakened. By means of mixing with active fuel to affect the electric adsorption and electric oxidation process of the multi-carbon alcohol, the multiple C-C bond fracture in the electric oxidation process of the multi-carbon alcohol is promoted, the complete oxidation of the multi-carbon alcohol is greatly promoted, the current efficiency of the multi-carbon alcohol is improved, and the poisoning of toxic intermediate products to electrode catalysts is weakened.
Description
Technical Field
The invention relates to the field of direct alcohol fuel cells, in particular to a method for promoting the breaking of multiple C-C bonds when a multi-carbon alcohol is used as a liquid fuel for electro-oxidation, converting more chemical energy into electric energy, improving the electro-oxidation current efficiency of the multi-carbon alcohol and reducing the poisoning of an electrocatalyst.
Background
The use of fuel cell power can continuously convert chemical energy stored within fuel molecules directly into electrical energy without the restriction of the carnot cycle. Compared with hydrogen, the liquid fuel has a series of advantages of convenient storage and transportation, wide source, renewability and the like. The core technology of power generation using a liquid fuel cell is to promote the liquid fuel to generate oxidation reaction on the surface of an electrode catalyst, release electrons, and convert chemical energy stored in fuel molecules into electric energy.
Compared with single-carbon liquid fuels (such as formic acid and methanol) and double-carbon liquid fuels (such as ethanol) which are widely researched at present, the multi-carbon liquid fuel has higher theoretical energy density and lower cell membrane permeation rate, thereby having wide application prospect in the field of fuel cell research. However, in the actual electrooxidation, multiple C — C bonds in the molecules of the polyols are difficult to break, which severely limits the conversion of most of the chemical energy stored therein to electrical energy, and reduces the electrooxidation current efficiency. For the reasons, the current efficiency of the multi-carbon liquid fuel generated in the electro-oxidation process is often low, and the application of the multi-carbon liquid fuel in the field of direct liquid fuel cells is limited.
Disclosure of Invention
The invention aims to overcome and solve the defects of the application of the multi-carbon alcohol as the liquid fuel in the power supply of the fuel cell, and provides a method for improving the electric oxidation current efficiency of the multi-carbon alcohol and reducing the poisoning of an electrocatalyst, so as to promote the breaking of multiple C-C bonds of the multi-carbon alcohol in the electric oxidation process.
The invention comprises the following steps:
1) mixing the multi-carbon alcohols and the active fuel in proportion and dissolving the mixture in distilled water containing supporting electrolyte to obtain mixed fuel electrolyte for the liquid fuel cell;
2) the mixed fuel electrolyte obtained in the step 1) is applied to a three-electrode reaction system, and a constant potential is applied to a working electrode, so that fuel molecules are subjected to an electro-oxidation reaction on the surface of a catalyst, an increased electro-oxidation current is obtained, and the toxicity of toxic intermediate products generated by the electro-oxidation of the multi-carbon alcohol to the catalyst is weakened.
In step 1), the multi-carbon alcohols include alcohols having a number of carbon atoms in a molecule of three or more; the active fuel category comprises liquid fuel with higher electrocatalytic activity, such as ethanol, formic acid and the like; the kind of the supporting electrolyte includes all electrolytes which can enhance the conductivity of the solution but do not participate in the electrode reaction by themselves; mixing the multi-carbon alcohol and the active fuel in proportion, namely mixing a single active fuel with the multi-carbon alcohol, or mixing two or more active fuels with the multi-carbon alcohol; the molar ratio of the multi-carbon alcohol to the active fuel is 1: 0-1; if the active fuel adopts X types, and X is a positive integer greater than 0, the molar ratio of the multi-carbon alcohol to the active fuel 1, the active fuel 2, … and the active fuel X is 1: 0-1, … (0-1).
In the step 2), the three-electrode reaction system is a three-electrode catalytic system of a working electrode, a counter electrode and a reference electrode of the surface modified electrode catalyst; applying a constant potential on the working electrode to carry out electrooxidation on the mixed fuel to obtain an improved electrooxidation current and weaken the poison of toxic intermediate products generated by electrooxidation of the multi-carbon alcohol on the catalyst; the electrode catalyst can be a noble metal catalyst, a non-noble metal catalyst and a noble metal-non-noble metal composite catalyst; the applied constant potential can be (0.1-1.2) V (v.s.Ag/AgCl), preferably (0.1-0.6) V (v.s.Ag/AgCl); the toxic intermediate products generated by the electric oxidation of the multi-carbon alcohol comprise CO and multi-carbon compounds generated by that only-OH is oxidized and C-C bonds are not broken.
The invention aims to improve the electrooxidation current efficiency of the multi-carbon alcohol and weaken the poisoning of the intermediate product generated by incomplete oxidation of the multi-carbon alcohol to the catalyst. The invention promotes the fracture of multiple C-C bonds of the multi-carbon alcohol in the electro-oxidation process and weakens the poisoning of the intermediate product of incomplete oxidation of the multi-carbon alcohol to the catalyst by means of influencing the electro-adsorption and electro-oxidation processes of the multi-carbon alcohol by mixing with the active fuel.
Compared with the prior art, the invention has the following advantages and remarkable effects:
(1) the method does not need to synthesize a new catalyst or modify the catalyst, thereby avoiding complex treatment process and saving time cost and money cost.
(2) Obviously promoting the breakage of multiple C-C bonds of the multi-carbon alcohol in the electro-oxidation process and obtaining obviously improved current efficiency.
(3) Effectively reducing the poisoning of incomplete oxidation products generated in the electro-oxidation process of the multi-carbon alcohol to the catalyst.
Drawings
FIG. 1 is a comparison of current densities for the mixed system and the single-polyol system of example 1 of the present invention.
FIG. 2 is a comparison of current densities for the mixed system and the single multi-carbon alcohol system of example 2.
FIG. 3 is a comparison of current densities for the mixed system and the single multi-carbon alcohol system of example 3.
FIG. 4 is a graph of the CO and CO for a single multi-carbon alcohol system in examples 1,2, and 3 of the present invention 2 The generated in-situ Fourier transform infrared spectrum.
FIG. 5 shows the CO and CO contents of the mixed system of examples 1,2 and 3 of the present invention 2 And (3) generating an in-situ Fourier transform infrared spectrum.
FIG. 6 shows the CO and CO for the one-and-more-carbon alcohol systems in examples 22, 23 and 24 of the present invention 2 The generated in-situ Fourier transform infrared spectrum.
FIG. 7 shows the CO and CO contents of the mixed system in examples 22, 23 and 24 of the present invention 2 And (3) generating an in-situ Fourier transform infrared spectrum.
FIG. 8 is a desorption curve of an intermediate product CO generated in the electro-oxidation process of the mixed system and the single three-carbon alcohol system in the electrode surface in the example 2 of the invention.
Detailed Description
The invention is suitable for a direct alcohol fuel cell, and comprises the following steps: (1) selecting active fuel with high electrochemical activity to mix with the multi-carbon alcohol, and applying the mixed fuel to a three-electrode system half cell, wherein an electrode catalyst is modified on the surface of a working electrode; (2) applying a constant potential to the working electrode to oxidize the fuel, and comparing the obtained current efficiency of the mixed system with the current efficiency of the single multi-carbon alcohol system; (3) in-situ Fourier transform infrared spectroscopy is adopted to treat products (CO and CO) generated by multiple C-C bond breakage in the electrooxidation process 2 ) And (4) carrying out measurement.
The present invention will be described in further detail with reference to the following examples, but the embodiments of the present invention are not limited thereto. The invention mixes the multi-carbon alcohol with the active fuel to improve the current efficiency in the multi-carbon alcohol electro-oxidation process and weaken the poison of toxic intermediate products generated in the multi-carbon alcohol electro-oxidation process to the electrode catalyst.
Example 1:
in this example, 1, 2-propanediol containing three carbons in a molecule and formic acid, which is an active fuel, are mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial platinum on carbon is used as an electrode catalyst, and a potential of 0.4V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished. The current density for the mixed system of example 1 is compared to that for the single, multi-carbon alcohol system as shown in FIG. 1.
Example 2:
in this example, 1, 2-propanediol containing three carbons in a molecule and formic acid, which is an active fuel, are mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial platinum on carbon is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished. The current density for the mixed system versus the single multi-carbon alcohol system of example 2 is compared as shown in figure 2. The desorption curve of the intermediate product CO generated in the electro-oxidation process of the mixed system and the single three-carbon alcohol system in the example 2 on the electrode surface is shown in FIG. 8.
Example 3:
in this example, 1, 2-propanediol containing three carbons in the molecule and active fuel formic acid were mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon supported platinum was used as an electrode catalyst, and a potential of 0.6V was applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished. A comparison of the current densities corresponding to the mixed system and the single multi-carbon alcohol system of example 3 is shown in figure 3.
FIG. 4 shows the CO and CO for the one-and-more-carbon alcohol systems of examples 1,2 and 3 of the present invention 2 The generated in-situ Fourier transform infrared spectrum. FIG. 5 shows the CO and CO related mixed system in examples 1,2 and 3 of the present invention 2 The generated in-situ Fourier transform infrared spectrum.
Example 4:
in this example, 1, 2-propanediol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 1: 2 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.4V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 5:
in this example, 1, 2-propanediol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 1: 2 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 6:
in this example, 1, 2-propanediol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 1: 2 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.6V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 7:
in this example, 1, 2-propanediol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 2: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.4V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And after the electro-oxidation reaction is finished, measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst.
Example 8:
in this example, 1, 2-propanediol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 2: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And after the electro-oxidation reaction is finished, measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst.
Example 9:
in this example, 1, 2-propanediol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 2: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.6V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. Recording the current generated by fuel electrooxidation in real time during the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same conditions. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 10:
in this example, 1, 2-propanediol containing three carbons in a molecule and active fuel ethanol are mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.4V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. Recording the current generated by fuel electrooxidation in real time during the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same conditions. And after the electro-oxidation reaction is finished, measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst.
Example 11:
in this example, 1, 2-propanediol containing three carbons in the molecule and active fuel ethanol are mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 12:
in this example, 1, 2-propanediol containing three carbons in a molecule and active fuel ethanol are mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.6V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 13:
in this example, isopropanol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 1: 2 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.4V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 14:
in this example, isopropanol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 1: 2 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. Recording the current generated by fuel electrooxidation in real time during the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same conditions. And after the electro-oxidation reaction is finished, measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst.
Example 15:
in this example, isopropanol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 1: 2 and applied to a three-electrode system, commercial platinum on carbon is used as an electrode catalyst, and a potential of 0.6V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 16:
in this example, isopropanol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 2: 1 and applied to a three-electrode system, commercial platinum on carbon is used as an electrode catalyst, and a potential of 0.4V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 17:
in this example, isopropanol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 2: 1 and applied to a three-electrode system, commercial carbon-supported platinum is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 18:
in this example, isopropanol containing three carbons in the molecule, active fuel ethanol and formic acid are mixed at a molar ratio of 2: 1 and applied to a three-electrode system, commercial platinum on carbon is used as an electrode catalyst, and a potential of 0.6V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. Recording the current generated by fuel electrooxidation in real time during the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same conditions. And after the electro-oxidation reaction is finished, measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst.
Example 19:
in this example, isopropanol containing three carbons in the molecule and active fuel ethanol were mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum was used as an electrode catalyst, and a potential of 0.4V was applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 20:
in this example, isopropanol containing three carbons in a molecule and active fuel ethanol are mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon supported platinum is used as an electrode catalyst, and a potential of 0.5V is applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And after the electro-oxidation reaction is finished, measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst.
Example 21:
in this example, isopropanol containing three carbons in the molecule and active fuel ethanol were mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum was used as an electrode catalyst, and a potential of 0.6V was applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 22:
in this example, isopropanol containing three carbons in the molecule and active fuel formic acid were mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum was used as an electrode catalyst, and a potential of 0.4V was applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. Recording the current generated by fuel electrooxidation in real time during the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same conditions. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 23:
in this example, isopropanol containing three carbons in the molecule and active fuel formic acid were mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum was used as an electrode catalyst, and a potential of 0.5V was applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
Example 24:
in this example, isopropanol containing three carbons in the molecule and active fuel formic acid were mixed at a molar ratio of 1: 1 and applied to a three-electrode system, commercial carbon-supported platinum was used as an electrode catalyst, and a potential of 0.6V was applied to a working electrode to cause an electrooxidation reaction of the mixed fuel. And recording the current generated by the fuel electrooxidation in real time in the reaction process, dividing the obtained current value by the effective area of the catalyst to obtain the current density, and comparing the current density with the current density of the single multi-carbon alcohol obtained under the same condition. And (3) measuring the amount of the toxic intermediate product adsorbed on the surface of the catalyst after the electro-oxidation reaction is finished.
FIG. 6 shows the CO and CO for the one-and-more-carbon alcohol systems of examples 22, 23 and 24 of the present invention 2 The generated in-situ Fourier transform infrared spectrum. FIG. 7 shows the CO and CO related mixing systems of examples 22, 23 and 24 of the present invention 2 Generated in-situ FourierThe infrared spectrum is subjected to the Fourier transform.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, and all equivalent variations and modifications made within the scope of the present invention and the content of the description should be included in the scope of the present invention.
Claims (6)
1. The method for improving the electrooxidation current efficiency of the multi-carbon alcohol and reducing the poisoning of the electrocatalyst is characterized by comprising the following steps of:
1) mixing the multi-carbon alcohols and the active fuel in proportion and dissolving the mixture in distilled water containing supporting electrolyte to obtain mixed fuel electrolyte for the liquid fuel cell; the multi-carbon alcohols comprise alcohols with the number of carbon atoms contained in the molecules being more than or equal to three; the active fuel category comprises liquid fuel with higher electrocatalytic activity, and the liquid fuel with higher electrocatalytic activity is at least one of ethanol and formic acid;
2) applying the mixed fuel electrolyte obtained in the step 1) to a three-electrode reaction system, and applying a constant potential to a working electrode to enable fuel molecules to generate an electro-oxidation reaction on the surface of a catalyst, so as to obtain an improved electro-oxidation current and weaken the poison of toxic intermediate products generated by the electro-oxidation of the multi-carbon alcohol to the catalyst;
the three-electrode reaction system is a counter electrode, a reference electrode and a three-electrode catalytic system of a working electrode of a surface modified electrode catalyst; applying a constant potential on the working electrode to carry out electrooxidation on the mixed fuel to obtain an improved electrooxidation current and weaken the poison of toxic intermediate products generated by electrooxidation of the multi-carbon alcohol on the catalyst;
the applied constant potential is 0.1-1.2 V.s.Ag/AgCl.
2. The method for improving the efficiency of the current in the electro-oxidation of a polyhydric alcohol and alleviating the poisoning of an electrocatalyst as claimed in claim 1, wherein in step 1), the supporting electrolyte comprises an electrolyte that enhances the conductivity of the solution but does not participate in the electrode reaction itself.
3. The method for improving the efficiency of the electric oxidation current of the multi-carbon alcohol and reducing the poisoning of the electrocatalyst according to claim 1, wherein in the step 1), the multi-carbon alcohol and the active fuel are mixed in proportion, that is, a single active fuel is mixed with the multi-carbon alcohol, or at least two active fuels are mixed with the multi-carbon alcohol; the molar ratio of the multi-carbon alcohol to the active fuel is 1: y, 0<y is less than or equal to 1; if the active fuel is X, and X is a positive integer greater than 0, the molar ratio of the multi-carbon alcohol to the active fuel 1, the active fuel 2, … and the active fuel X is 1: y 1 ︰y 2 ︰…︰y X Wherein y is 1 、y 2 、…、y X Are all greater than 0 and not more than 1.
4. The method for improving the current efficiency of the electro-oxidation of a multi-carbon alcohol and reducing the poisoning of the electrocatalyst as claimed in claim 1, wherein in the step 2), the electrode catalyst is a noble metal catalyst, a non-noble metal catalyst, or a noble metal-non-noble metal composite catalyst.
5. The method for improving the efficiency of the current for the electro-oxidation of a polyhydric alcohol and reducing the poisoning of an electrocatalyst according to claim 1, wherein the constant potential applied in step 2) is 0.1 to 0.6 v.s.ag/AgCl.
6. The method as claimed in claim 1, wherein in step 2), the toxic intermediate products generated by the electro-oxidation of the multi-carbon alcohol include CO and multi-carbon compounds generated by oxidation of only-OH without breaking C-C bonds.
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