CN111229195A - Electro-reduction carbon dioxide catalytic material and preparation and application thereof - Google Patents
Electro-reduction carbon dioxide catalytic material and preparation and application thereof Download PDFInfo
- Publication number
- CN111229195A CN111229195A CN201811443486.0A CN201811443486A CN111229195A CN 111229195 A CN111229195 A CN 111229195A CN 201811443486 A CN201811443486 A CN 201811443486A CN 111229195 A CN111229195 A CN 111229195A
- Authority
- CN
- China
- Prior art keywords
- catalytic material
- electro
- reduction
- catalytic
- carbon dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 65
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 51
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000009792 diffusion process Methods 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001413 amino acids Chemical class 0.000 claims abstract description 9
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000001014 amino acid Nutrition 0.000 claims description 8
- 235000018417 cysteine Nutrition 0.000 claims description 7
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- -1 melamine-cysteine Chemical compound 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method and application of a carbon material. The carbon material is obtained by high-temperature carbonization synthesis, and the synthesis raw materials comprise melamine and amino acid. The material structure is nitrogen-doped graphene, and is applied to a carbon dioxide electrochemical reduction catalyst gas diffusion electrode. The invention obviously improves the CO pairing of the catalyst2The activity of electric reduction improves the catalytic stability, effectively inhibits the hydrogen evolution reaction and enhances the selectivity of the product CO.
Description
Technical Field
The invention relates to electrochemical reduction of CO2Especially relates to a high-efficiency CO catalyzing catalyst and a preparation method thereof2A preparation method and application of a carbon material catalyst for preparing CO belong to the field of electrochemistry.
Background
CO2As a greenhouse gas, the rise of the greenhouse gas causes a series of environmental problems such as rise of sea level, drought and flood, extreme climate and the like, and seriously threatens the sustainable development of the earth. Recently, it is aimed at how to reduce global CO2Scientists have developed about CO2Studies on capture, storage and transformation. As early as the 20 th century, people began to fight CO2The carbon dioxide is stable in chemical property and almost inert, and needs high temperature, high pressure or a catalyst to perform chemical reaction, so the development is slow.
Therefore, how to activate CO2Becomes the key of research work, and methods such as chemical catalysis, photocatalysis, electrocatalysis and the like are adopted at present. The electrochemical method can effectively avoid high temperature and high pressure, can realize large scale and effectively utilize renewable energy sources. Electrochemical CO2The products of the conversion are complex and include various species such as carbon monoxide, formic acid, methane, ethylene, and the like. Based on the existing industrial production model, CO2The high-efficiency electrochemical reduction and conversion into CO can solve the problem of the dependence on the technology of reforming methane to prepare synthesis gas at high temperature and high pressure. CO of greatest concern today2The catalysts for the electroreductive conversion to CO are gold, silver and related alloys. CN104846393A can generate nearly 90% of CO by using an Ag-containing electrode, but an ionic liquid needs to be added, so that the pollution is larger; CN104032324A takes polyoxometalate as catalyst, the catalyst preparation is difficult, and the product is complex. The whole catalyst has the problems of low activity, poor stability, high price and the like, so that the catalyst is difficult to apply to industrial production. In order to solve the above problems, it is necessary to develop a novel non-noble metal catalyst having high activity and stability. Reportedly, graphene materials, especially doped graphene materials, can effectively catalyze the electro-reduction of O2Similarly, the material pair CO is borrowed2Resulting in a better reaction. The catalyst can not only effectively inhibit hydrogen evolution reaction, but also selectively reduce CO2To CO.
In addition to the catalyst, CO2The working electrode for electroreduction is another important factor affecting the reaction. Gas diffusion electrode (GDL) not only can increase CO2Electrochemical reduction current can also increase reaction selectivity. GDL can not only convert CO into reaction raw material2Effectively transferred to the surface of the catalyst and can quickly generate COQuickly diffuse out of the electrode, increase the reaction rate and inhibit the hydrogen evolution reaction. Through optimization, the catalyst of the invention not only can efficiently and selectively reduce CO2Forming CO, the Faraday efficiency is more than 85 percent, and the catalyst has higher catalytic performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing an electroreduction method for CO2The invention relates to preparation and application of a catalytic material, in particular to a carbon material catalyst, which is synthesized by high-temperature carbonization to form a doped graphene structure, and remarkably improves electrochemical reduction of CO2And (4) activity.
The invention relates to an electroreduction method for CO2Catalytic material of said CO2The catalytic material is a doped graphene material.
The material is synthesized by high-temperature carbonization, wherein a synthesis precursor is a mixture of melamine and amino acid, wherein the ratio of melamine: the mass ratio of the amino acid is 1:1-8: 1.
The electroreduction of CO2The carbonization temperature of the catalytic material is 800-1200 ℃, and the carbonization time is 10min-10 h.
Electroreduction of CO according to the invention2A method of preparing a catalytic material comprising: putting melamine and amino acid into a ball milling tank according to a certain proportion for ball milling to obtain a uniformly mixed catalytic material precursor, then putting the precursor into a zirconia boat for high-temperature carbonization reaction for a certain time to obtain a carbon material, namely the electroreduction CO2A catalytic material.
The amino acid is cysteine, glycine, alanine, phenylalanine or tryptophan.
The reactor for high-temperature carbonization in inert atmosphere is a tubular furnace; the atmosphere is Ar gas, He gas or N2And (4) qi.
The invention relates to electro-reduction of CO2Use of catalytic materials for CO2Gas diffusion electrode of electro-reduction catalytic material, wherein carbon material CO is loaded on the gas diffusion electrode2Electro-reduction catalytic material, gas diffusion electrode size of 0.5cm-10cm, supported CO2The weight of the electro-reduction catalytic material is 0.1-10 mg/cm2(ii) a Wherein middle warmer energyThe bulk diffusion electrode is carbon paper, carbon felt, carbon cloth or carbon fiber.
The CO is2The preparation method of the gas diffusion electrode of the electro-reduction catalytic material comprises the following steps: dispersing a carbon material into a mixed solution of isopropanol and water, adding 1-10 wt% of perfluorinated sulfonic acid resin Nafion solution, stirring to obtain a mixed solution, coating the mixed solution on a gas diffusion electrode, and drying.
Isopropanol in the mixed solution of isopropanol and water: the water content is 1:5-5: 1.
The ratio of the carbon material to the mixed solution of isopropanol and water is 0.1-20 mg:1 mL.
The ratio of the 1-10 wt% perfluorinated sulfonic acid resin Nafion solution to the mixed solution of isopropanol and water is 1:100-1: 10.
The drying is vacuum drying at 60-120 ℃.
The invention is synthesized by a high-temperature carbonization method, changes the type and proportion of a synthesized precursor, changes the carbonization temperature and atmosphere, can regulate and control the parameters of doping degree, specific surface area and the like of a carbon material catalyst, and further changes the catalytic activity point position. Meanwhile, the catalyst is more suitable for industrial application due to the abundant raw materials, simple synthesis method and excellent catalytic effect.
The invention obviously improves the CO pairing of the catalyst2The activity of electric reduction improves the catalytic stability, effectively inhibits the hydrogen evolution reaction and enhances the selectivity of the product CO.
Drawings
FIG. 1 shows the Scanning Electron Microscope (SEM) scales of the materials of example 3, which are 2 μm each.
FIG. 2 is a Transmission Electron Micrograph (TEM) and a High Resolution Transmission Electron Micrograph (HRTEM) (inset) of example 3, with 20nm and 5nm respectively.
FIG. 3 shows the materials of example 3, in which Ar and CO are respectively introduced into the electrolyte2Cyclic voltammogram from bottom.
Figure 4 is a graph of the faradaic efficiency of the materials of examples 2, 3, 4 and 5 at different potentials.
FIG. 5 is a graph of the current density at different potentials for the materials of examples 2, 3, 4 and 5.
Figure 6 represents the stability experiment of the material in example 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the present invention, and such equivalents also fall within the scope of the appended claims.
Example 1
Preparing a carbon material catalyst precursor: putting 16g of melamine and 8g of cysteine into a ball milling tank, then carrying out ball milling on a ball mill at the ball milling rotation speed of 100rpm/min for 2h, and fully mixing to obtain a precursor of the catalytic material.
Example 2
Electro-reduction of CO2The catalytic material comprises a carbon material, the carbon material is synthesized by a high-temperature carbonization method, and the preparation method comprises the following steps: and (2) putting 16g of melamine and 16g of cysteine into a ball milling tank, then carrying out ball milling on a ball mill at the ball milling rotation speed of 100rpm/min for 2h, and fully mixing to obtain the precursor of the catalytic material. Transferring the precursor into a zirconia boat, then placing the zirconia boat in a tube furnace, introducing Ar gas at the flow rate of 25mL/min, heating to 300 ℃ at the speed of 5 ℃/min and keeping for 1h, then heating to 600 ℃ at the speed of 2.5 ℃/min and keeping for 2h, then heating to 1000 ℃ at the speed of 2 ℃/min and keeping for 2h, finally naturally cooling, and taking out to obtain the carbon material, namely the carbon material for the electro-reduction CO2Catalytic material, referred to as GM 1.
Example 3
Electro-reduction of CO2The catalytic material comprises a carbon material, the carbon material is synthesized by a high-temperature carbonization method, and the preparation method comprises the following steps: putting 16g of melamine and 8g of cysteine into a ball milling tank, then carrying out ball milling on a ball mill at the ball milling rotation speed of 100rpm/min for 2h, and fully mixing to obtain the melamine-cysteine-containing aqueous solutionA catalytic material precursor. Transferring the precursor into a zirconia boat, then placing the zirconia boat in a tube furnace, introducing Ar gas at the flow rate of 25mL/min, heating to 300 ℃ at the speed of 5 ℃/min and keeping for 1h, then heating to 600 ℃ at the speed of 2.5 ℃/min and keeping for 2h, then heating to 1000 ℃ at the speed of 2 ℃/min and keeping for 2h, finally naturally cooling, and taking out to obtain the carbon material, namely the carbon material for the electro-reduction CO2Catalytic material, referred to as GM 2.
Example 4
Electro-reduction of CO2The catalytic material comprises a carbon material, the carbon material is synthesized by a high-temperature carbonization method, and the preparation method comprises the following steps: putting 16g of melamine and 4g of cysteine into a ball milling tank, then carrying out ball milling on a ball mill at the ball milling rotation speed of 100rpm/min for 2h, and fully mixing to obtain a precursor of the catalytic material. Transferring the precursor into a zirconia boat, then placing the zirconia boat in a tube furnace, introducing Ar gas at the flow rate of 25mL/min, heating to 300 ℃ at the speed of 5 ℃/min and keeping for 1h, then heating to 600 ℃ at the speed of 2.5 ℃/min and keeping for 2h, then heating to 1000 ℃ at the speed of 2 ℃/min and keeping for 2h, finally naturally cooling, and taking out to obtain the carbon material, namely the carbon material for the electro-reduction CO2Catalytic material, referred to as GM 4.
Example 5
Electro-reduction of CO2The catalytic material comprises a carbon material, the carbon material is synthesized by a high-temperature carbonization method, and the preparation method comprises the following steps: putting 16g of melamine and 2g of cysteine into a ball milling tank, then carrying out ball milling on a ball mill at the ball milling rotation speed of 100rpm/min for 2h, and fully mixing to obtain a precursor of the catalytic material. Transferring the precursor into a zirconia boat, then placing the zirconia boat in a tube furnace, introducing Ar gas at the flow rate of 25mL/min, heating to 300 ℃ at the speed of 5 ℃/min and keeping for 1h, then heating to 600 ℃ at the speed of 2.5 ℃/min and keeping for 2h, then heating to 1000 ℃ at the speed of 2 ℃/min and keeping for 2h, finally naturally cooling, and taking out to obtain the carbon material, namely the carbon material for the electro-reduction CO2Catalytic material, referred to as GM 8.
Example 6
10mg of the nitrogen-doped carbon material of example 3 was dispersed in 480. mu.L of ultrapure water, 480. mu.L of iso-carbonAdding 40 mu L of 5 wt% Nafion solution into the mixed solution of propanol, ultrasonically mixing, taking 120 mu L of the obtained mixed solution, coating the mixed solution on carbon paper, and drying in vacuum at 60 ℃ for 2h to obtain the load-type electroreduction CO2Carbon paper of catalytic material, wherein the carbon paper has a size of 1cm x 1cm and is loaded with electro-reduced CO2The weight of the catalytic material is 1mg, and the electro-reduction CO is prepared2Catalytic electrode
Example 7
10mg of the nitrogen-doped carbon material prepared in example 3 was dispersed in a mixed solution of 480. mu.L of ultrapure water and 480. mu.L of isopropyl alcohol, 40. mu.L of a 5 wt% Nafion solution was added thereto, and the mixture was ultrasonically mixed, 120. mu.L of the resulting mixed solution was applied to a carbon cloth, and vacuum-dried at 60 ℃ for 2 hours to obtain a carbon cloth loaded with electro-reduced CO2Carbon cloth of catalytic material, wherein the size of the carbon cloth is 1cm x 1cm, and electro-reduction CO is loaded on the carbon cloth2The weight of the catalytic material is 1mg, and the electro-reduction CO is prepared2A catalytic electrode.
Claims (10)
1. A preparation method of an electro-reduction carbon dioxide catalytic material is characterized by comprising the following steps:
1) uniformly mixing melamine and amino acid into a catalytic material precursor;
2) carbonizing the precursor of the catalytic material at high temperature of 800-1200 ℃ in an inert atmosphere to obtain the doped graphene material, namely, electrically reducing CO2A catalytic material.
2. A method of preparing a catalytic material for the electro-reduction of carbon dioxide as claimed in claim 1, wherein: melamine in the catalytic material precursor: the mass ratio of the amino acid is 1:1-8: 1; the amino acid is one or more of cysteine, glycine, alanine, phenylalanine or tryptophan.
3. The method of preparing an electroreductive carbon dioxide catalytic material as set forth in claim 1, wherein: the electroreduction of CO2The carbonization time of the catalytic material is 10min-10 h;
the reactor for high-temperature carbonization in inert atmosphere is a tubular furnace; the atmosphere is Ar gas, He gas or N2One or more of the following gases.
4. The method of preparing an electroreductive carbon dioxide catalytic material as set forth in claim 1, wherein: the high-temperature carbonization process comprises the steps of heating the precursor of the catalytic material from room temperature to 450 ℃ at the speed of 1-3 ℃/min in an inert atmosphere, keeping the temperature for 0.5-4h, heating to 450-650 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 0.5-4h, heating to 800-1200 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 0.5-5h, finishing high-temperature carbonization, naturally cooling to room temperature, taking out to obtain the electro-reduction CO2A catalytic material.
5. The method for preparing an electro-reductive carbon dioxide catalyst material as claimed in any one of claims 1 to 4, wherein: putting melamine and amino acid into a ball milling tank for ball milling to obtain a uniformly mixed catalytic material precursor, then putting the precursor into a zirconia boat for high-temperature carbonization reaction to obtain a doped graphene material, namely the electroreduction CO2A catalytic material.
6. An electro-reduction carbon dioxide catalytic material prepared by the preparation method of any one of claims 1 to 5.
7. Use of the catalytic material for the electro-reduction of carbon dioxide according to claim 6, wherein: the catalytic material can be used for electroreduction of CO2In the catalytic reaction of (1).
8. Use according to claim 7, characterized in that: application to electroreduction of CO2Loaded with CO for catalytic reactions2Gas diffusion electrode for the electroreduction of catalytic materials, wherein the gas diffusion electrode is loaded with CO2Electroreduction catalytic material, supported CO2The weight of the electro-reduction catalytic material is 0.1-10 mg/cm2(ii) a Wherein the gas diffusion electrode is carbon paper, carbon felt, carbon cloth or carbon fiber.
9. According to the claimsThe use of 8, characterized in that: the CO is2The preparation method of the gas diffusion electrode of the electro-reduction catalytic material comprises the following steps: dispersing doped graphene into a mixed solution of isopropanol and water, adding 1-10 wt% of perfluorinated sulfonic acid resin Nafion solution, stirring to obtain a mixed solution, coating the mixed solution on a gas diffusion electrode, and drying;
isopropanol in the mixed solution of isopropanol and water: the volume ratio of water is 1:5-5: 1;
the ratio of the carbon material to the mixed solution of isopropanol and water is 1 mg-20 mg:1 mL;
the volume ratio of the 1-10 wt% perfluorinated sulfonic acid resin Nafion solution to the mixed solution of isopropanol and water is 1:100-1: 10.
10. Use according to claim 9, characterized in that: the drying is vacuum drying at 60-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811443486.0A CN111229195A (en) | 2018-11-29 | 2018-11-29 | Electro-reduction carbon dioxide catalytic material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811443486.0A CN111229195A (en) | 2018-11-29 | 2018-11-29 | Electro-reduction carbon dioxide catalytic material and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111229195A true CN111229195A (en) | 2020-06-05 |
Family
ID=70861618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811443486.0A Pending CN111229195A (en) | 2018-11-29 | 2018-11-29 | Electro-reduction carbon dioxide catalytic material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111229195A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892038A (en) * | 2020-08-12 | 2020-11-06 | 河北科技大学 | Acidic carbon quantum dot and preparation method and application thereof |
| CN113289625A (en) * | 2021-05-31 | 2021-08-24 | 中国人民解放军空军勤务学院 | Catalyst for preparing liquid fuel from carbon dioxide based on reactant enrichment and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837821A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of carbon dioxide electroreduction electrode and its preparation and application |
| CN108654623A (en) * | 2018-04-26 | 2018-10-16 | 中国科学院长春应用化学研究所 | Carbon dioxide electrochemical reduction catalyst and preparation method thereof and the gas-diffusion electrode for loading the catalyst |
-
2018
- 2018-11-29 CN CN201811443486.0A patent/CN111229195A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837821A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of carbon dioxide electroreduction electrode and its preparation and application |
| CN108654623A (en) * | 2018-04-26 | 2018-10-16 | 中国科学院长春应用化学研究所 | Carbon dioxide electrochemical reduction catalyst and preparation method thereof and the gas-diffusion electrode for loading the catalyst |
Non-Patent Citations (1)
| Title |
|---|
| SONG LIU等: "Identifying Active Sites of Nitrogen-Doped Carbon Materials for the CO2 Reduction Reaction", 《ADV. FUNCT. MATER.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892038A (en) * | 2020-08-12 | 2020-11-06 | 河北科技大学 | Acidic carbon quantum dot and preparation method and application thereof |
| CN111892038B (en) * | 2020-08-12 | 2023-03-10 | 河北科技大学 | Acidic carbon quantum dot and preparation method and application thereof |
| CN113289625A (en) * | 2021-05-31 | 2021-08-24 | 中国人民解放军空军勤务学院 | Catalyst for preparing liquid fuel from carbon dioxide based on reactant enrichment and preparation method thereof |
| CN113289625B (en) * | 2021-05-31 | 2023-04-18 | 中国人民解放军空军勤务学院 | Catalyst for preparing liquid fuel from carbon dioxide based on reactant enrichment and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110295375B (en) | Electro-reduction of CO2Preparation of catalyst, catalyst and application | |
| Guo et al. | Lowering reaction temperature: Electrochemical ammonia synthesis by coupling various electrolytes and catalysts | |
| CN109569683B (en) | Preparation method and application of nitrogen-phosphorus-codoped porous carbon sheet/transition metal phosphide composite material | |
| CN107020075B (en) | Simple substance bismuth catalyst for electrochemical reduction of carbon dioxide and preparation and application thereof | |
| CN110560076B (en) | Preparation method and application of nano Cu-Bi alloy catalyst | |
| CN106180747B (en) | A kind of palladium copper binary alloy nano material, preparation method and its CO is restored as catalyst electro-catalysis2Application | |
| CN110743603B (en) | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN107597169A (en) | A kind of multi-functional composite catalyst of biomass-based N doping porous carbon, preparation method and applications | |
| Abbas et al. | Novel strongly coupled tungsten-carbon-nitrogen complex for efficient hydrogen evolution reaction | |
| CN112647095B (en) | Atomically dispersed bimetallic site anchored nitrogen-doped carbon material and preparation and application thereof | |
| CN111653792A (en) | Method for synchronously preparing hierarchical pore cobalt and nitrogen co-doped nanorod supported platinum-cobalt alloy nano oxygen reduction electrocatalyst | |
| Li et al. | Preparation of a Pb loaded gas diffusion electrode and its application to CO 2 electroreduction | |
| Liang et al. | Recent advances of bismuth-based electrocatalysts for CO2 reduction: Strategies, mechanism and applications | |
| CN114293200A (en) | Porous carbon loaded amorphous/crystalline ruthenium-based high-efficiency hydrogen evolution catalyst and preparation and application thereof | |
| CN114657592B (en) | Nickel-based catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof | |
| CN113136597A (en) | Copper-tin composite material and preparation method and application thereof | |
| Chen et al. | Carbon monoxide-resistant copper-cobalt nanocrystal@ nitrogen-doped carbon electrocatalysts for methanol oxidation reaction | |
| CN110350213B (en) | High-efficiency PtRu/C bifunctional fuel cell anode catalyst and preparation method thereof | |
| CN111841598A (en) | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof | |
| CN111229195A (en) | Electro-reduction carbon dioxide catalytic material and preparation and application thereof | |
| CN110560094B (en) | Preparation method of 3D porous cobalt-tin-molybdenum trimetal catalyst | |
| CN110052281B (en) | Oxygen vacancy enriched nitrogen doped tin oxide and preparation method and application thereof | |
| Du et al. | Catalysts and electrolyzers for the electrochemical CO 2 reduction reaction: from laboratory to industrial applications | |
| CN114388819B (en) | Preparation method of sub-nano-scale platinum catalyst with high CO tolerance and application of sub-nano-scale platinum catalyst in fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |
|
| RJ01 | Rejection of invention patent application after publication |