CN111790410A - Halogen-doped basic copper chloride compound and preparation method and application thereof - Google Patents
Halogen-doped basic copper chloride compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN111790410A CN111790410A CN202010514857.0A CN202010514857A CN111790410A CN 111790410 A CN111790410 A CN 111790410A CN 202010514857 A CN202010514857 A CN 202010514857A CN 111790410 A CN111790410 A CN 111790410A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- halogen
- copper chloride
- basic copper
- 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
- 238000001994 activation Methods 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000006262 metallic foam Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 239000005752 Copper oxychloride Substances 0.000 description 10
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- CZZBXGOYISFHRY-UHFFFAOYSA-N copper;hydroiodide Chemical compound [Cu].I CZZBXGOYISFHRY-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 150000002496 iodine Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006690 co-activation Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
Abstract
The invention belongs to the technical field of electrocatalytic carbon dioxide reduction, and particularly relates to a catalyst precursor halogen-doped basic copper chloride compound for electrocatalytic carbon dioxide reduction reaction, and a preparation method and application thereof. The halogen-doped basic copper chloride compound is prepared by a sol-gel method, wherein the halogen is bromine or iodine, and the content of the halogen is 1-20%. The halogen-doped basic copper chloride prepared by the invention can be used as a precursor of a catalyst for electrocatalytic carbon dioxide reduction reaction to prepare an electrode of the catalyst for electrocatalytic carbon dioxide reduction reaction; the halogen doping can promote the formation of the specific surface micro-morphology and structure of the catalyst precursor in the catalyst activation process, and regulate and control the catalyst structure, so as to regulate and control the catalytic reaction path and change the catalyst selectivity. The sol-gel method has simple process, can realize the high-selectivity electrocatalysis of carbon dioxide to reduce to generate methane or ethylene, and has good application prospect in the field of electrocatalysis of carbon dioxide reduction.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis carbon dioxide reduction catalysts, and particularly relates to a halogen-doped basic copper chloride catalyst precursor, and a preparation method and application thereof.
Background
The electrocatalytic carbon dioxide reduction has the potential of simultaneously solving the problems of clean energy development, greenhouse gas emission reduction, industrial raw material preparation and the like, so the electrocatalytic carbon dioxide reduction has important research value. Due to the rich d-electron structure of the copper element, the copper catalyst realizes various modes and strength adsorption of a primary product CO of carbon dioxide reduction, and can realize different CO activation modes and different reaction paths, so that the copper catalyst can realize the preparation of various reduction products. However, since the electrocatalytic carbon dioxide reduction reaction path is complicated and competing products are numerous, it is extremely difficult to achieve high selectivity of a single product. In the carbon dioxide reduction, the transition state CO can determine a catalytic reaction path and a product type, and the adsorption and activation of the CO on the surface of the catalyst are influenced by a series of factors, including catalyst factors such as a local structure of the catalyst, a particle size of the catalyst, a crystal boundary and a crystal face, and catalytic reaction condition factors such as an applied potential, an electrolyte type, a local pH value and an electrolyte concentration. Wherein the under-coordinated copper catalyst favors the hydrogenation of CO to CHO, thereby promoting CH4And (4) generating. But localized Cu0/Cu+The microstructure is favorable for promoting the coupling reaction to generate C2H4. By introducing different halogen doping into the catalyst precursor, the microstructure of the catalyst can be regulated, so that the intermediate state adsorption property can be regulated, and the catalytic reaction path and the catalytic product can be regulated.
Disclosure of Invention
The invention aims to provide a method for preparing p-CH with high catalytic activity for electrocatalytic carbon dioxide reduction reaction4A catalyst precursor halogen-doped basic copper chloride compound with high selectivity, a preparation method and application thereof.
The catalyst precursor halogen-doped basic copper chloride compound for the electrocatalytic carbon dioxide reduction reaction is prepared by a sol-gel method, wherein the halogen is one of bromine or iodine and accounts for 1% -20%.
The preparation method of the halogen-doped basic copper chloride compound provided by the invention specifically adopts an epoxy propane auxiliary hydrolysis method; the method comprises the following specific steps:
first, ethanol and isopropanol were mixed in a vessel, and CuCl was added2And KBr or KI, stirring until the KBr or the KI is dissolved; adding deionized water into the solution, and then slowly dropwise adding propylene oxide; standing for 12-36 hours, adding acetone into the container, transferring the container into a centrifuge tube, and continuously standing for 80-120 hours; and finally, centrifuging for 5-8 times by using a high-speed centrifuge and acetone as a solvent, drying the product, grinding and collecting to obtain a catalyst precursor bromine or iodine doped basic copper chloride.
The halogen-doped basic copper chloride prepared by the invention can be used as a precursor of a catalyst for electrocatalytic carbon dioxide reduction reaction to prepare an electrode of the catalyst for electrocatalytic carbon dioxide reduction reaction, and the preparation method comprises the following specific steps:
firstly, preparing catalyst precursor slurry: dispersing 5-10 mg of catalyst in 0.8-1.2 ml of deionized water, isopropanol and 5wt% of Nafion mixed solution, and performing ultrasonic dispersion for 25-35 minutes to obtain slurry; then:
and (II) preparing a catalyst electrode. There may be two types:
(1) preparing a glassy carbon working electrode loaded with a catalyst film by a dropping method: dropping 4-6. mu.l of the slurry onto a surface area of 0.07 cm2Naturally drying the glassy carbon electrode to obtain a working electrode; then, applying a constant potential by using an electrochemical workstation for activation; the resulting catalyst pair CH4Has high selectivity, and the activated catalyst is named as CH4-a Cu catalyst;
(2) dispersing halogen-doped basic copper chloride and a binder in a mixed solvent of ethanol and water, and after ultrasonic dispersion, dropwise coating catalyst slurry on a catalyst carrier; drying to obtain a catalyst electrode;
wherein the binder is a 5% perfluorosulfonic acid polymer solution, and the specific gravity of the binder in the catalyst slurry is 5-10%.
Wherein, the catalyst carrier can be carbon paper, carbon cloth, carbon felt, metal foam or metal foil, etc., and the loading capacity of the catalyst is 2-20 mg/cm2。
Wherein, carbon black, carbon nano tube, graphene and other conductive agents with the specific gravity of 10-30% can also be added.
In the invention, halogen doping can promote the formation of the specific surface micro-morphology and structure of the basic copper chloride catalyst precursor in the catalyst activation process, and regulate and control the catalyst structure, further regulate and control the catalytic reaction path, and change the catalyst selectivity. The sol-gel method has simple process, can realize the high-selectivity electrocatalysis of carbon dioxide to reduce to generate methane or ethylene, the bromine-doped basic copper chloride catalyst has the methane Faraday efficiency of 59 percent and the carbon selectivity of 83 percent; the iodine-doped basic copper chloride has the advantages that the Faraday efficiency of ethylene reaches 71%, the carbon selectivity reaches 93%, and the iodine-doped basic copper chloride has a good application prospect in the field of electrocatalysis of carbon dioxide reduction.
Drawings
FIG. 1 is a scanning electron microscope image of bromine-doped copper oxychloride and iodine-doped copper oxychloride. Wherein, (a) and (b) are SEM images of bromine-doped basic copper chloride precursors under different times; (c) and (d) SEM images of the iodine-doped copper oxychloride precursor under different times.
FIG. 2 shows XPS results of bromine-doped basic copper chloride and iodine-doped basic copper chloride after activation. Wherein, (a), (b) and (c) are bromine-doped basic copper chloride Cu 2PXPS spectrograms, Cl 2PXPS, Br 3dXPS spectrograms; (d) and (e) and (f) are iodine doped copper oxychloride Cu 2PXPS spectrogram, Cl 2PXPS, I3 dXPS spectrogram.
FIG. 3 is a scanning electron microscope and a transmission electron microscope image of bromine-doped copper oxychloride and iodine-doped copper oxychloride after activation. Wherein, (a) is a bromine-doped copper oxychloride SEM image after activation; (b) TEM image of bromine-doped basic copper chloride after activation; (c) SEM image of bromine-doped basic copper chloride after activation; (d) TEM image of iodine doped basic copper chloride after activation.
FIG. 4 is a schematic diagram of a difference electron microscope showing the spheres of bromine-doped copper oxychloride and iodine-doped copper oxychloride after activation. Wherein, (a) is bromine-doped basic copper chloride after activation; (b) doping basic copper chloride for activated iodine.
FIG. 5 shows the carbon dioxide reduction results of bromine-doped basic copper chloride and iodine-doped basic copper chloride after activation. Wherein the potential is-1.71 Vvs. RHE, and the electrolyte is 0.05 MKHCO3. (a) The faradaic efficiency distribution of bromine-doped basic copper chloride after activation; (b) the faradaic efficiency distribution of the activated iodine doped basic copper chloride is shown.
Detailed Description
Example 1
(1) Preparing a bromine-doped basic copper chloride compound by a sol-gel method: 0.3g of copper dichloride (CuCl) is weighed out2) And 0.03 g of potassium bromide (K-bromine) dissolved in a mixed solvent of 4 mL of ethanol and 0.5 mL of deionized water. Then, 1 mL of propylene oxide was added dropwise to the solution and mixed well by shaking. After the solution was allowed to stand for 1 day, 30 mL of acetone was added, standing was continued for 5 days, and the precipitated product was washed with acetone. After the product is dried, the bromine-doped basic copper chloride shown in figures 1a and b, 2a and b and 3a and c can be obtained by grinding.
(2) Preparing a bromine-doped basic copper chloride compound electrode: 10 mg of the compound material was dispersed in a mixed solvent of 1 mL of ethanol and water (volume ratio: 1/4), and 80. mu.L of a 5% perfluorosulfonic acid type polymer solution was added, and after 30 minutes of sonication, the catalyst slurry was drop-coated on a glassy carbon electrode. And naturally drying to obtain the carbon dioxide reduction reaction catalyst electrode. The electrode was used for electrocatalytic carbon dioxide reduction, and the activated catalyst had a Cu-Cu coordination number of 7 (FIG. 4 a) and gave 59% CH4Faradaic efficiency with 83% carbon selectivity (figure 5 a).
Example 2
(1) Preparing iodine-doped basic copper chloride by a sol-gel method: 0.3g of copper dichloride (CuCl) is weighed out2) And 0.03 g of potassium iodide (KI) dissolved in a mixed solvent of 4 mL of ethanol and 0.5 mL of deionized water. Then, 1 mL of propylene oxide was added dropwise to the solution and mixed well by shaking. After the solution is kept stand for 1 day, 30 mL of acetone is added, and the solution is kept stand for 5 daysAnd washing the precipitated product with acetone. After the product is dried, grinding can obtain iodine doped copper oxychloride as shown in figures 1c and d, figures 2d, e and f and figures 3b and d.
(2) Preparing an iodine-doped basic copper chloride compound electrode: 10 mg of the compound material was dispersed in a mixed solvent of 1 mL of ethanol and water (volume ratio: 1/4), and 80. mu.L of a 5% perfluorosulfonic acid type polymer solution was added, and after 30 minutes of sonication, the catalyst slurry was drop-coated on a glassy carbon electrode. And naturally drying to obtain the carbon dioxide reduction reaction catalyst electrode. The electrode is used for electrocatalytic carbon dioxide reduction, and the activated catalyst has a large amount of local Cu+/Cu0Microstructure (FIG. 4 b), and 71% C was obtained2H4Faradaic efficiency with 93% carbon selectivity (figure 5 b).
Claims (7)
1. A catalyst precursor halogen-doped basic copper chloride compound for electrocatalytic carbon dioxide reduction reaction is characterized by being prepared by a sol-gel method, wherein halogen is one of bromine or iodine and accounts for 1% -20%.
2. A process for the preparation of a halogen-doped basic copper chloride compound according to claim 1, wherein propylene oxide-assisted hydrolysis is employed; the method comprises the following specific steps:
first, ethanol and isopropanol were mixed in a vessel, and CuCl was added2And KBr or KI, stirring until the KBr or the KI is dissolved; adding deionized water into the solution, and then slowly dropwise adding propylene oxide; standing for 12-36 hours, adding acetone into the container, transferring the container into a centrifuge tube, and continuously standing for 80-120 hours; and finally, centrifuging for 5-8 times by using a high-speed centrifuge and acetone as a solvent, drying the product, grinding and collecting to obtain a catalyst precursor bromine or iodine doped basic copper chloride.
3. Use of a halogen-doped basic copper chloride compound as defined in claim 1 as a precursor for a catalyst for electrocatalytic carbon dioxide reduction for the preparation of an electrode for the electrocatalytic carbon dioxide reduction catalyst.
4. The application of claim 3, which comprises the following steps:
firstly, preparing catalyst precursor slurry: dispersing 5-10 mg of catalyst in 0.8-1.2 ml of deionized water, isopropanol and 5wt% of Nafion mixed solution, and performing ultrasonic dispersion for 25-35 minutes to obtain slurry; then:
(II) preparing catalyst electrodes, wherein the catalyst electrodes comprise two types:
(1) preparing a glassy carbon working electrode loaded with a catalyst film by a dropping method: dropping 4-6 microliters of slurry on a glassy carbon electrode with the surface area of 0.07 square centimeter, and naturally drying to obtain a working electrode; then, applying a constant potential by using an electrochemical workstation for activation; the resulting catalyst pair CH4Has high selectivity, and the activated catalyst is named as CH4-a Cu catalyst;
(2) dispersing halogen-doped basic copper chloride and a binder in a mixed solvent of ethanol and water, and after ultrasonic dispersion, dropwise coating catalyst slurry on a catalyst carrier; and drying to obtain the catalyst electrode.
5. The use according to claim 4, wherein the binder is a 5% perfluorosulphonic polymer solution and the specific gravity of the binder in the catalyst slurry is 5-10%.
6. The use of claim 5, wherein the catalyst carrier is carbon paper, carbon cloth, carbon felt, metal foam or metal foil, and the loading of the catalyst is 2-20 mg/cm2。
7. The use of claim 6, wherein the conductive agent such as carbon black, carbon nanotube, graphene, etc. with a specific gravity of 10-30% can be added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010514857.0A CN111790410A (en) | 2020-06-08 | 2020-06-08 | Halogen-doped basic copper chloride compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010514857.0A CN111790410A (en) | 2020-06-08 | 2020-06-08 | Halogen-doped basic copper chloride compound and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111790410A true CN111790410A (en) | 2020-10-20 |
Family
ID=72804062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010514857.0A Pending CN111790410A (en) | 2020-06-08 | 2020-06-08 | Halogen-doped basic copper chloride compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111790410A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113020614A (en) * | 2021-02-26 | 2021-06-25 | 中国科学技术大学 | Copper-based monatomic alloy catalyst, preparation method and application thereof, and membrane electrode electrolyte battery for preparing formic acid through carbon dioxide electroreduction |
| CN113774423A (en) * | 2021-08-31 | 2021-12-10 | 北京大学深圳研究生院 | Copper-based composite nano material and preparation method and application thereof |
| CN115821321A (en) * | 2023-02-15 | 2023-03-21 | 天津大学 | Phosphorus-doped catalyst with Cu (100) -rich crystal face exposure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004176129A (en) * | 2002-11-27 | 2004-06-24 | Kotaro Ogura | Method for manufacturing ethylene selectively from carbon dioxide |
| CN105316701A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院大连化学物理研究所 | CO2 electrochemical reduction electrode, preparation and application thereof |
| CN109536991A (en) * | 2018-12-14 | 2019-03-29 | 天津大学 | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide |
| CN111229261A (en) * | 2020-03-06 | 2020-06-05 | 厦门大学 | Catalyst for preparing multi-carbon product by electro-reduction of carbon dioxide and carbon monoxide, preparation method and application thereof |
-
2020
- 2020-06-08 CN CN202010514857.0A patent/CN111790410A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004176129A (en) * | 2002-11-27 | 2004-06-24 | Kotaro Ogura | Method for manufacturing ethylene selectively from carbon dioxide |
| CN105316701A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院大连化学物理研究所 | CO2 electrochemical reduction electrode, preparation and application thereof |
| CN109536991A (en) * | 2018-12-14 | 2019-03-29 | 天津大学 | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide |
| CN111229261A (en) * | 2020-03-06 | 2020-06-05 | 厦门大学 | Catalyst for preparing multi-carbon product by electro-reduction of carbon dioxide and carbon monoxide, preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| ANA SOFIA VARELA ET AL.: ""Tuning the Catalytic Activity and Selectivity of Cu for CO2 Electroreduction in the Presence of Halides"", 《ACS CATALYSIS》 * |
| DUNFENG GAO ET AL.: ""Improved CO2 Electroreduction Performance on Plasma-Activated Cu Catalysts via Electrolyte Design: Halide Effect"", 《ACS CATALYSIS》 * |
| KARTHISH MANTHIRAM ET AL.: ""Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| PHIL DE LUNA ET AL.: ""Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction"", 《NATURE CATALYSIS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113020614A (en) * | 2021-02-26 | 2021-06-25 | 中国科学技术大学 | Copper-based monatomic alloy catalyst, preparation method and application thereof, and membrane electrode electrolyte battery for preparing formic acid through carbon dioxide electroreduction |
| CN113774423A (en) * | 2021-08-31 | 2021-12-10 | 北京大学深圳研究生院 | Copper-based composite nano material and preparation method and application thereof |
| CN113774423B (en) * | 2021-08-31 | 2022-09-27 | 北京大学深圳研究生院 | Copper-based composite nano material and preparation method and application thereof |
| CN115821321A (en) * | 2023-02-15 | 2023-03-21 | 天津大学 | Phosphorus-doped catalyst with Cu (100) -rich crystal face exposure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea | |
| CN110038634B (en) | Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof | |
| CN111790410A (en) | Halogen-doped basic copper chloride compound and preparation method and application thereof | |
| Zhang et al. | Highly active and durable Pt/MXene nanocatalysts for ORR in both alkaline and acidic conditions | |
| Sun et al. | Poor crystalline MoS2 with highly exposed active sites for the improved hydrogen evolution reaction performance | |
| CN104549242B (en) | Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst | |
| CN106960948B (en) | MoSxCarbon black nano composite material, preparation method and application thereof | |
| CN107010670A (en) | A kind of MoSxOy/ carbon nano-composite material, its preparation method and its application | |
| CN106252616A (en) | A kind of nickelous selenide/hollow carbon fiber composite and preparation method thereof | |
| CN107746051A (en) | A kind of nitrogen-doped graphene nanobelt nano-cobaltic-cobaltous oxide hybrid material and preparation method thereof | |
| CN107829107A (en) | A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application | |
| CN103480406A (en) | Nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper and preparation method thereof | |
| Shi et al. | Biomass-derived precious metal-free porous carbon: Ca-N, P-doped carbon materials and its electrocatalytic properties | |
| CN113718281A (en) | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof | |
| CN108232213A (en) | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof | |
| CN101607197A (en) | A kind of preparation method of fuel-cell catalyst | |
| CN109244484A (en) | A kind of preparation method of porous graphene/carbon nano tube flexible self-supported membrane material | |
| Dong et al. | MnO2 nanowires/CNTs composites as efficient non-precious metal catalyst for oxygen reduction reaction | |
| CN105977501A (en) | High-performance oxygen reduction MnO2-Mn3O4/carbon nanotube composite catalyst and preparation method and application thereof | |
| He et al. | Hydrophobic electrocatalyst for the enhanced activity of oxygen reduction reaction through controllable liquid/gas/solid interface | |
| CN109935840A (en) | A kind of preparation method of fuel cell Pt base catalyst | |
| Ding et al. | Modulating electronic structure of cobalt phosphide precatalysts via dual-metal incorporation for highly efficient overall water splitting | |
| CN104258848B (en) | Preparation method and application of Pt/3D (Three dimensional) graphene composite catalyst | |
| Wang et al. | Oxygen self-doping formicary-like electrocatalyst with ultrahigh specific surface area derived from waste pitaya peels for high-yield H2O2 electrosynthesis and efficient electro-Fenton degradation | |
| Miao et al. | A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201020 |