CN115138855A - Preparation method of bimetallic monatomic material and application of bimetallic monatomic material in new energy - Google Patents
Preparation method of bimetallic monatomic material and application of bimetallic monatomic material in new energy Download PDFInfo
- Publication number
- CN115138855A CN115138855A CN202210810339.2A CN202210810339A CN115138855A CN 115138855 A CN115138855 A CN 115138855A CN 202210810339 A CN202210810339 A CN 202210810339A CN 115138855 A CN115138855 A CN 115138855A
- Authority
- CN
- China
- Prior art keywords
- bimetallic monatomic
- bimetallic
- hours
- ball milling
- monatomic material
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000498 ball milling Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 33
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000001103 potassium chloride Substances 0.000 claims abstract description 23
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 23
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 239000012153 distilled water Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 11
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 11
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 19
- 229910002535 CuZn Inorganic materials 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 abstract description 11
- 239000010949 copper Substances 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a bimetallic monatomic material and application thereof in new energy, wherein potassium chloride is adopted as a template in the preparation method, the calcination temperature is low, and the migration and agglomeration of metal atoms are greatly limited, so that a bimetallic monatomic catalyst with atomically dispersed paired copper and zinc metal atoms loaded on microporous nitrogen-doped carbon is prepared; the preparation method only comprises the operations of ball milling, ultrasonic treatment, calcination, freeze drying and the like, and has simple processAnd the sample does not need to be subjected to acid treatment, so that the method is environment-friendly. The CuZn bimetallic monatomic material prepared by the preparation method has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday efficiency is as high as 84.7 percent, and the current density is-49.7 mA cm under-1.1V (vs. RHE) ‑2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Description
Technical Field
The invention belongs to the field of carbon dioxide reduction electrocatalysts, and particularly relates to a preparation method of a bimetallic monatomic material and application of the bimetallic monatomic material in new energy.
Technical Field
Introducing CO 2 Conversion to chemicals or fuels is one of the effective ways to achieve energy conversion, chemical energy storage, and "carbon neutralization". Methane (CH) 4 ) Is an important fuel and is also the main component of natural gas. CO 2 2 Conversion to CH 4 Is a very efficient solution and can achieve the purposes of energy conservation and emission reduction. In a plurality of CO 2 In the conversion process, electrochemical reduction of CO 2 The ERC has the advantages of simple operation, easy control of experimental conditions and the like. But due to CO 2 Are very stable and therefore require highly efficient catalysts to facilitate the ERC process.
Because of their high metal atom utilization and excellent performance, transition metal monatomic catalysts have been widely used in ERC. However, the limited single metal loading and insufficient activity results in a limited performance of the monatomic catalyst. The controllable synthesis of the bimetallic monatomic catalyst is difficult to realize, and particularly, the separation of metal atoms is ensured to form a large number of stable monatomic active sites. In addition, in the preparation process, metal atoms are easy to migrate and aggregate to form nanoclusters/particles, and often need to be removed by subsequent acid treatment, which is not environment-friendly. Therefore, the development of the environment-friendly and excellent-performance bimetallic monatomic ERC catalyst has great significance and value for solving the energy crisis and relieving the environmental problem.
Disclosure of Invention
Aiming at the defects in the preparation of the bimetallic monatomic ERC catalyst in the prior art, the invention provides a preparation method of a bimetallic monatomic material and application of the bimetallic monatomic material in new energy. The preparation method is simple in process, and the prepared CuZn bimetallic monatomic catalyst has excellent ERC performance.
The technical scheme for solving the technical problems is as follows: the preparation method of the bimetallic monatomic material is characterized by comprising the following steps of:
step 1: placing 0.1-0.2 mmol of hydrated copper acetate, 0.1-0.2 mmol of hydrated zinc acetate and 0.1-0.3 mmol of o-phenanthroline in a centrifuge tube, adding 1-3 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 20-40 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 100-300 mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of the ball mill to be 200-400rpm, the time to be 2-8 hours, and the ball-material ratio to be 4, wherein a primary mixture is obtained after the ball milling is finished;
and step 3: pouring 0.01-0.05mmol of leucine and 1-3 mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 10-40 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 200-400rpm, the time to be 1-5 hours, the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of the ball milling tank, and grinding the composite mixture into powder by using a mortar;
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 2-6 hours at 400-600 ℃, and naturally cooling to room temperature after the calcination is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material.
Further, the invention designs an application of the bimetallic monatomic material in new energy, which is characterized in that the bimetallic monatomic material is obtained by the preparation method, and the application process is as follows: firstly, accurately weighing 5.0mg of catalyst, 500 mu L of ethanol and 500 mu L of 0.5wt% Nafion solution, mixing the three, and carrying out ultrasonic treatment for 20min to disperse the three into a mixed solution; finally, 200. Mu.L of the mixed solution was added dropwise to 1X 1cm 2 And air-drying the carbon paper for 5 hours at room temperature to obtain the working electrode of the ERC.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method adopts potassium chloride as a template, has lower calcination temperature, and greatly limits the migration and agglomeration of metal atoms, thereby preparing the double-metal monatomic catalyst with the atomically dispersed paired metal atoms (Cu, zn) loaded on the microporous nitrogen-doped carbon;
(2) The preparation method only comprises the steps of ball milling, ultrasonic treatment, calcination, freeze drying and the like, is simple, does not need to carry out acid treatment on the sample, and is environment-friendly.
(3) The CuZn bimetallic monatomic material prepared by the method has excellent ERC (oxygen tolerance) performance and can be used for CO 2 Saturated 1M KHCO 3 In solution, the Faraday Efficiency (FE) is up to 84.7%, and the current density under-1.1V (vs. RHE) is-49.7 mA cm -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 Has high selectivity.
Drawings
FIG. 1 is an electrocatalytic CO of a CuZn-SAs/NC catalyst obtained in example 1, a Cu-SAs/NC catalyst obtained in comparative example 1, and a Zn-SAs/NC catalyst obtained in comparative example 2, which are the methods for preparing a bimetallic monatomic material according to the present invention 2 Reduction (ERC) performance versus plot (i.e., linear sweep voltammogram).
Fig. 2 (a) is a scanning electron microscope image of the CuZn SAs/NC catalyst obtained in example 1 of the method for preparing a bimetallic monatomic material according to the present invention; fig. 2 (b) is an aberration-corrected high-angle annular dark-field image (HAADF-STEM) of the CuZn SAs/NC catalyst obtained in example 1 of the method for preparing a bimetallic monatomic material according to the present invention, wherein bright spots circled in white are atomically dispersed Cu atoms and Zn atoms.
FIG. 3 shows that the CuZn-SAs/NC catalyst obtained in example 1, the Cu-SAs/NC catalyst obtained in comparative example 1 and the Zn-SAs/NC catalyst obtained in comparative example 2 are subjected to ERC to prepare CH under different overpotentials in the preparation method of the bimetallic monatomic material of the invention 4 Faradaic Efficiency (FE).
FIG. 4 shows that CuZn-SAs/NC catalyst obtained in example 1, cu-SAs/NC catalyst obtained in comparative example 1 and Zn-SAs/NC catalyst obtained in comparative example 2 catalyze ERC to prepare CH according to the preparation method of bimetallic monatomic material of the invention 4 Tafel plot of (1).
FIG. 5 is the FE values of all ERC products of CuZn-SAs/NC catalysts obtained in example 1 of a method for preparing a bimetallic monatomic material according to the invention at different overpotentials.
FIG. 6 is a graph showing the stability of the catalytic ERC of the CuZn-SAs/NC catalyst obtained in example 1 of the method for preparing a bimetallic monatomic material according to the present invention at an overpotential of-1.1V (vs. RHE) (after 45 hours, there is almost no change in current density and Faraday efficiency).
Detailed Description
The patent relates to a preparation method of a bimetallic monatomic material and application of the bimetallic monatomic material in new energy. The experimental contents will be fully and clearly described below in conjunction with the summary of the patent and the specific examples so as to enable the researchers in the field to better understand the invention.
The catalysts prepared in the following examples and comparative examples were applied and tested for performance by the following methods: the electrocatalytic carbon dioxide reduction reaction (ERC) was carried out in an H-cell with good gas tightness, the anode and cathode compartments being separated by a Nafion-117 proton exchange membrane. The test used a standard three-electrode system: the catalyst supported on carbon paper was used as a working electrode, and the platinum sheet and the reversible hydrogen electrode were used as a counter electrode and a reference electrode, respectively. All tests were performed at ambient temperature and pressure.
Preparation of a working electrode: firstly, accurately weighing 5.0mg of catalyst, 500 mu L of ethanol and 500 mu L of 0.5wt% Nafion solution, mixing the three, and carrying out ultrasonic treatment for 20min to disperse the three into a mixed solution; finally, 200. Mu.L of the mixed solution was added dropwise to 1X 1cm 2 And air-drying the carbon paper for 5 hours at room temperature to obtain the working electrode of the ERC.
ERC measurement process: measurements were performed using an electrochemical workstation (CHI 760E). Before measurement, high purity CO is added 2 Introducing the electrolyte for 30 minutes at the flow rate of 200sccm to ensure that CO in the electrolyte 2 The concentration reached a saturated state. During testing, the sample was first pre-activated by Cyclic Voltammetry (CV). Subsequently, at 10mV s -1 Linear Sweep Voltammograms (LSVs) were recorded between potentials of-1.2V to 0V (vs. rhe) to obtain key performance indicators of the catalyst, such as faraday efficiency, current density, etc.
The invention provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: placing 0.1-0.2 mmol of hydrated copper acetate, 0.1-0.2 mmol of hydrated zinc acetate and 0.1-0.3 mmol of o-phenanthroline in a centrifuge tube, adding 1-3 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 20-40 minutes to obtain a mixed solution;
and 2, step: dropwise adding the mixed solution obtained in the step 1 into 100-300 mmol of potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of the ball mill to be 200-400rpm, the time to be 2-8 hours, and the ball-material ratio to be 4, wherein a primary mixture is obtained after the ball milling is finished;
and 3, step 3: pouring 0.01-0.05mmol of leucine and 1-3 mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 10-40 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 200-400rpm, the time to be 1-5 hours, the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 2-6 hours at 400-600 ℃, and naturally cooling to room temperature after the calcination is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
Example 1
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after the ball milling is finished;
and step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotation speed of a ball mill to be 200rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, so that Zn atoms and Cu atoms are uniformly dispersed on a porous carbon substrate, and no nanocluster or particle is generated. The obtained CuZn bimetallic single-atom catalyst (CuZn SAs/NC) has excellent ERC performance in CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is as high as 84.7%, and the current density is-49.7 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 Has high selectivity.
Example 2
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.2mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after the ball milling is finished;
and step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotation speed of a ball mill to be 200rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of the ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (4) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetal monatomic material (CuZn SAs/NC catalyst for short, the same is applied below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is as high as 80.3%, and the current density is-39.8 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Example 3
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.2mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after ball milling;
and 3, step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotation speed of a ball mill to be 200rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst (CuZn SAs/NC) has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is up to 79.5%, and the current density is-44.3 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 Has high selectivity.
Example 4
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
and 2, step: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after the ball milling is finished;
and step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 3 hours, the ball-to-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 400 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (4) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetal monatomic material (CuZn SAs/NC catalyst for short, the same is applied below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is up to 70.4%, and the current density is-35.7 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Example 5
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
and 2, step: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after ball milling;
and 3, step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 400rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 600 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) was 75.1%, and the current density at-1.1V was-36.9 mA cm -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Comparative example 1
The present comparative example provides a method for preparing a copper monatomic ERC catalyst, comprising the steps of:
step 1: placing 0.1mmol of hydrated copper acetate and 0.3mmol of o-phenanthroline in a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol of potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotation speed to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4;
and step 3: pouring 0.03mmol of leucine and a certain amount of ethanol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution in the step 3 into the sample subjected to ball milling in the step 2, continuing ball milling, setting the rotation speed to be 200rpm, the duration to be 3 hours, and the ball-to-material ratio to be 4;
and 5: after the ball milling is finished, scraping the sample from the wall of the ball milling tank, and grinding the sample into powder by using a mortar;
step 6: calcining the powder sample obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling the sample to room temperature after the calcining is finished;
and 7: and (3) washing the sample obtained in the step (6) by using distilled water until the potassium chloride template is removed, transferring the obtained powder into 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper metal monoatomic ERC catalyst (Cu-SAs/NC catalyst for short).
The copper metal monatomic ERC catalyst obtained in the comparative example is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and CO is subjected to 2 Saturated 1M KHCO 3 In solution, the Tafel slope is 265Mv dec -1 And a current density of-13.1 mA cm at-1.1V -2 。
Comparative example 2
The comparative example provides a preparation method of a zinc monatomic ERC catalyst, which comprises the following steps:
step 1: placing 0.1mmol of hydrated zinc acetate and 0.3mmol of phenanthroline in a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol of potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotation speed to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4;
and step 3: pouring 0.03mmol of leucine and a certain amount of ethanol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution in the step 3 into the sample subjected to ball milling in the step 2, continuing ball milling, setting the rotation speed to be 200rpm, the duration to be 3 hours, and the ball-to-material ratio to be 4;
and 5: after the ball milling is finished, scraping the sample from the wall of the ball milling tank, and grinding the sample into powder by using a mortar;
step 6: calcining the sample obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling the sample to room temperature after the calcining is finished;
and 7: washing the sample obtained in the step 6 by using distilled water until a potassium chloride template is removed, transferring the obtained powder into 50mL of distilled water, and freeze-drying to obtain black powder, namely the zinc monoatomic ERC catalyst (Zn-SAs/NC catalyst for short);
the zinc metal single atom ERC catalyst obtained in the comparative example is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and CO is subjected to 2 Saturated 1M KHCO 3 In solution, the Tafel slope is 248Mv dec -1 And a current density of-12.2 mA cm at-1.1V -2 。
According to the test results of examples 1-5 and comparative examples 1-2, it can be seen that the copper-zinc bimetallic monatomic material obtained by the preparation method of the bimetallic monatomic material of the invention has excellent ERC performance in CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is 70.4-84.7%, and the current density under-1.1V (vs. RHE) is-35.7 mA cm -2 ~-49.7mA cm -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. The preparation method of the bimetallic monatomic material is characterized by comprising the following steps of:
step 1: placing 0.1-0.2 mmol of hydrated copper acetate, 0.1-0.2 mmol of hydrated zinc acetate and 0.1-0.3 mmol of o-phenanthroline in a centrifuge tube, adding 1-3 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 20-40 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 100-300 mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of the ball mill to be 200-400rpm, the time to be 2-8 hours, and the ball-material ratio to be 4, wherein a primary mixture is obtained after the ball milling is finished;
and step 3: pouring 0.01-0.05mmol of leucine and 1-3 mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 10-40 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 200-400rpm, the time to be 1-5 hours, the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of the ball milling tank, and grinding the composite mixture into powder by using a mortar;
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 2-6 hours at 400-600 ℃, and naturally cooling to room temperature after the calcination is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the bimetallic monatomic material.
2. The method for preparing the bimetallic monatomic material according to claim 1, wherein in step 1, 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate, and 0.3mmol of o-phenanthroline are used.
3. The method for preparing a bimetallic monatomic material according to claim 1, wherein in step 1, the amount of absolute ethyl alcohol is 1.5mL.
4. The method for preparing a bimetallic monatomic material as defined in claim 1, wherein in the step 2, the potassium chloride is 150mmol.
5. The method for preparing a bimetallic monatomic material according to claim 1, wherein in the step 2, the ball mill rotation speed is set to 300rpm for 5 hours.
6. The method of claim 1, wherein in step 3, the leucine content is 0.03mmol.
7. The method for preparing a bimetallic monatomic material according to claim 1, wherein in step 3, the absolute ethyl alcohol is 1.5mL, and the sonication time is 30 minutes.
8. The method for preparing a bimetallic monatomic material according to claim 1, wherein in step 4, the ball mill rotation speed is set at 200rpm for 3 hours.
9. The method of claim 1, wherein the calcination time in step 6 is 4 hours, and the calcination temperature is 500 ℃.
10. The application of the bimetallic monatomic material in new energy is characterized in that the bimetallic monatomic material is obtained by the preparation method according to any one of the claims 1 to 9 and the application process is as follows: firstly, accurately weighing 5.0mg of catalyst, 500 mu L of ethanol and 500 mu L of 0.5wt% Nafion solution, mixing the three, and carrying out ultrasonic treatment for 20min to disperse the three into a mixed solution; finally, 200. Mu.L of the mixed solution was added dropwise to 1X 1cm 2 And air-drying the carbon paper for 5 hours at room temperature to obtain the working electrode of the ERC.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210810339.2A CN115138855B (en) | 2022-07-11 | 2022-07-11 | CO2Conversion to CH4Preparation method of catalytic material and application of catalytic material in new energy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210810339.2A CN115138855B (en) | 2022-07-11 | 2022-07-11 | CO2Conversion to CH4Preparation method of catalytic material and application of catalytic material in new energy |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115138855A true CN115138855A (en) | 2022-10-04 |
CN115138855B CN115138855B (en) | 2024-06-11 |
Family
ID=83411606
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210810339.2A Active CN115138855B (en) | 2022-07-11 | 2022-07-11 | CO2Conversion to CH4Preparation method of catalytic material and application of catalytic material in new energy |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115138855B (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107841762A (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 electrochemical reduction elctro-catalyst and its preparation and application |
CN109888318A (en) * | 2019-02-13 | 2019-06-14 | 上海交通大学 | A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal- |
CN110433809A (en) * | 2019-07-30 | 2019-11-12 | 南开大学 | A kind of high dispersive transition-metal catalyst preparation method of carbon load |
CN111841601A (en) * | 2020-07-03 | 2020-10-30 | 江南大学 | CuZn double-monoatomic electrochemical catalysis CO2Reduced material and method for producing the same |
CN112853379A (en) * | 2021-02-08 | 2021-05-28 | 北京航空航天大学 | Preparation method and application of supported metal monatomic catalyst |
CN113549935A (en) * | 2021-05-20 | 2021-10-26 | 中国科学技术大学 | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof |
CN113611883A (en) * | 2021-07-27 | 2021-11-05 | 武汉大学 | Mesoporous nitrogen-doped carbon-supported transition metal monatomic material and preparation method and application thereof |
CN113680361A (en) * | 2021-08-09 | 2021-11-23 | 电子科技大学 | Cobalt-ruthenium bimetallic monatomic photocatalyst and preparation method and application thereof |
CN114672846A (en) * | 2022-05-06 | 2022-06-28 | 西南科技大学 | For electrocatalysis of CO2Preparation and application of reduced bimetallic catalytic material |
-
2022
- 2022-07-11 CN CN202210810339.2A patent/CN115138855B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107841762A (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 electrochemical reduction elctro-catalyst and its preparation and application |
CN109888318A (en) * | 2019-02-13 | 2019-06-14 | 上海交通大学 | A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal- |
CN110433809A (en) * | 2019-07-30 | 2019-11-12 | 南开大学 | A kind of high dispersive transition-metal catalyst preparation method of carbon load |
CN111841601A (en) * | 2020-07-03 | 2020-10-30 | 江南大学 | CuZn double-monoatomic electrochemical catalysis CO2Reduced material and method for producing the same |
CN112853379A (en) * | 2021-02-08 | 2021-05-28 | 北京航空航天大学 | Preparation method and application of supported metal monatomic catalyst |
CN113549935A (en) * | 2021-05-20 | 2021-10-26 | 中国科学技术大学 | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof |
CN113611883A (en) * | 2021-07-27 | 2021-11-05 | 武汉大学 | Mesoporous nitrogen-doped carbon-supported transition metal monatomic material and preparation method and application thereof |
CN113680361A (en) * | 2021-08-09 | 2021-11-23 | 电子科技大学 | Cobalt-ruthenium bimetallic monatomic photocatalyst and preparation method and application thereof |
CN114672846A (en) * | 2022-05-06 | 2022-06-28 | 西南科技大学 | For electrocatalysis of CO2Preparation and application of reduced bimetallic catalytic material |
Non-Patent Citations (4)
Title |
---|
刘卫涛;张桂伟;平丹;刘孟可;张金鸽;韩敬莉;樊凯奇;吴诗德;: "聚苯胺基ZnFe-N-C的制备及其电还原CO_2催化性能研究", 轻工学报, no. 01 * |
刘孟岩;王元双;邓雯;温珍海;: "铜基电催化剂还原CO_2", 化学进展, no. 04, 24 April 2018 (2018-04-24) * |
景维云;毛庆;石越;杜兆龙;肖宇;刘松;徐金铭;黄延强;: "CO_2电催化还原制烃类产物的研究进展", 化工进展, no. 06, 5 June 2017 (2017-06-05) * |
王路喜;杨芳麒;林欢欢;李响;王珺;邓曙光;: "Cu修饰的多孔碳材料高效电化学还原CO_2为CO", 化工进展, no. 09 * |
Also Published As
Publication number | Publication date |
---|---|
CN115138855B (en) | 2024-06-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11105009B2 (en) | Graphene material inlaid with single metal atoms and preparing method and application thereof | |
CN105107536B (en) | A kind of preparation method of polyhedron shape phosphatization cobalt water electrolysis hydrogen production catalyst | |
Billy et al. | Reducing the onset potential of CO2 electroreduction on CuRu bimetallic particles | |
CN113270595B (en) | Nitrogen-doped carbon-supported non-noble metal nano catalyst prepared based on MOF | |
Gavidia et al. | Carbon-supported Pt-free catalysts with high specificity and activity toward the oxygen reduction reaction in acidic medium | |
CN109174157B (en) | Preparation method of cobalt-nitrogen co-doped biomass carbon oxidation reduction catalyst | |
CN101814607A (en) | Preparation method of platinum/graphen catalyst for proton exchange membrane fuel cell | |
CN107020075B (en) | Simple substance bismuth catalyst for electrochemical reduction of carbon dioxide and preparation and application thereof | |
Xue et al. | Pt-based bimetallic catalysts for SO2-depolarized electrolysis reaction in the hybrid sulfur process | |
CN109546157B (en) | Preparation method of copper, cobalt nitride and carbon in-situ composite electrode | |
CN113067000A (en) | Oxygen vacancy-containing TiO2Upper load Pd-Co nano alloy catalyst and preparation method and application thereof | |
CN111957336A (en) | Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst | |
CN111755705A (en) | Three-atom-level dispersed metal cluster loaded nitrogen-doped nano carbon fuel cell catalyst | |
CN109731599B (en) | 2D oxygen reduction catalyst Fe3O4Preparation method of @ FeNC nanosheet | |
CN113943949B (en) | Platinum edge-modified nickel-based nano material and preparation method and application thereof | |
CN112680745B (en) | Tungsten nitride nano porous film integrated electrode with ruthenium nanocluster loaded in limited domain and preparation method and application thereof | |
Belmesov et al. | Anodic Electrocatalysts for Fuel Cells Based on Pt/Ti 1–x Ru x O 2 | |
CN115863679A (en) | Microporous carbon-coated platinum nanoparticle electrocatalyst and preparation method thereof | |
CN115138855B (en) | CO2Conversion to CH4Preparation method of catalytic material and application of catalytic material in new energy | |
CN108682874B (en) | Preparation method of efficient and stable Pt/GC catalyst | |
CN114959772B (en) | Long-life noble metal oxide oxygen evolution reaction electrocatalyst, preparation method and application | |
CN114855180B (en) | Preparation method of polyacid-derived low-platinum-load hydrogen evolution electrocatalyst | |
CN114899430B (en) | Fuel cell CCM with high durability and anti-counter pole and preparation method thereof | |
CN114045516B (en) | Electrocatalytic reduction of CO 2 Catalyst for preparing formic acid, and preparation method and application thereof | |
CN112510217B (en) | Carbon-supported platinum yttrium catalyst and preparation method and application thereof |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |