CN114990584B - Preparation method of copper-based catalyst for electrochemical reduction of carbon dioxide - Google Patents
Preparation method of copper-based catalyst for electrochemical reduction of carbon dioxide Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000010949 copper Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 18
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 37
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 24
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000011701 zinc Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide, which comprises the following steps: s1: synthesis of Zns nanoparticles, S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, and the mixture is subjected to ultrasonic treatment for 30 minutes and then poured into a crystallization kettle for crystallization for 18 hours; s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles; s1.3: washing with ethanol and deionized water alternately. In the ion exchange process, a method of dropwise adding a copper ion-containing aqueous solution is adopted, so that the efficient replacement of zinc ions by copper ions is ensured, the copper-zinc ratio in a target catalyst is ensured to be closer to the feed ratio, and meanwhile, the copper ion-containing aqueous solution is dropwise added at normal temperature by taking ZnS as a matrix, so that the preparation process is simple and the conditions are mild.
Description
Technical Field
The invention relates to the technical field of electrochemical reduction reaction for converting carbon dioxide into a C2+ product, in particular to a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide.
Background
Under the large background of a double-carbon target, carbon dioxide electrochemical reduction (CO 2 RR) is ethylene, ethanol and C2+ liquid fuel, so that carbon emission can be reduced, renewable energy sources can be stored, and the method is an important chemical technology integrating carbon capture, utilization and storage. Cu is recognized as the most efficient catalyst for converting CO2 into multi-carbon products, but its low efficiency and poor stability are the core problems to be solved. In CO2RR, the coupling of two CO to form OCCO is a key step in the formation of C2+ products. To increase CO concentration around Cu active sites, jouny and Li et al introduced CO separately into the CO2RR reaction system. The introduction of a second active component (Au, ag, zn) during the preparation of the copper catalyst has also been learned to obtain a tandem catalyst. Different research teams respectively adopt an atomic layer deposition method, a reverse micelle encapsulation method and an ion exchange method to successively develop a plurality of CO2RR high-efficiency series catalysts.
With respect to copper catalysts, attention has been given previously mainly to copper oxide, bimetallic copper, cu (N) -coated carbon materials. Recent research on copper-based catalytic materials has made new progress, and mainly focuses on modulation of copper coordination environment and structure. The university of compound denier Zheng Gengfeng team synthesized a copper catalyst with a ladder structure in a CO atmosphere with current density and faradaic efficiency of C2+ alcohols of 100mA/cm2 and 70%, respectively. A Grubbs team of California's institute of technology prepares a copper electrode modified by three organic components by an open-loop disproportionation method, the porosity and the hydrophobic property of the copper electrode are improved, the capture of CO2 and the mass transfer of the CO2 on the surface of the electrode are enhanced, the copper electrode is protected, the stability of the copper electrode is improved, and the Faraday efficiencies of ethylene and C2+ respectively reach 55% and 77%. The Gongwei Wang team of Wuhan university covers a thin layer of NxC on the surface of a copper catalyst, and enriches and activates CO2 in the form of N-CO2 bonds around the copper, wherein the total Faraday efficiency of ethylene and ethanol is as high as 72 percent. At the same time, the stability of the copper catalyst is improved due to the protection of NxC. The team Huang Yu of los angeles university of california, which prepares copper nanowires with surfaces rich in steps, the selectivity and the stability of ethylene are remarkably improved, and the faradaic efficiency of the ethylene is not lower than 70% in 200 hours.
The existing copper-based catalyst, including single (double) metal catalyst, has complex preparation process and harsh conditions. As the active sites, copper is distributed in both bulk phase and surface, and the chemical utilization rate is not high.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide comprises the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, and the mixture is subjected to ultrasonic treatment for 30 minutes and then poured into a crystallization kettle for crystallization for 18 hours;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing with ethanol and deionized water alternately;
s2: ion exchange method from ZnS → CuxZnyS
S2.1: weighing 0.017-0.151 g of copper chloride dihydrate, and dissolving in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then dispersing 0.1 g of the obtained ZnS solid powder in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the step S2.4 into a crystallization kettle, and crystallizing for 10 hours;
s2.6: washing the product in S2.5 with 10 ml ethanol and 10 ml deionized water respectively;
s2.7: performing centrifugal separation on the product in the S2.6, then pouring out supernatant liquor, and naturally airing to obtain a sample;
s3: oxidized CuxZnyS → CuxZnyO
S3.1: the sample obtained in S2.7 was raised from room temperature to 700 ℃ and held for 240 minutes;
s3.2: and cooling to obtain a catalyst sample.
Preferably, the temperature increase rate in S3.1 is 2 ℃/min.
Preferably, the cooling in S3.2 is natural cooling.
Preferably, the number of washes in S2.6 is three.
Preferably, the number of washes in S1.3 is three.
Preferably, the dropping speed in S2.3 is 2-3 drops/min.
Preferably, the crystallization temperature in S1.1 is 180 ℃.
Preferably, the crystallization temperature in S2.5 is 140 ℃.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide, which has the following beneficial effects:
1. according to the preparation method of the copper-based catalyst for electrochemical reduction of carbon dioxide, a method of dropwise adding the aqueous solution containing copper ions is adopted in the ion exchange process, so that efficient replacement of zinc ions by the copper ions is guaranteed, the copper-zinc ratio in the target catalyst is closer to the batch charging ratio, meanwhile, the ZnS is used as a matrix, the aqueous solution containing copper ions is dropwise added at normal temperature, the preparation process is simple, and the conditions are mild.
2. According to the preparation method of the copper-based catalyst for electrochemical reduction of carbon dioxide, the catalyst structure obtained by an ion exchange method is controllable. The copper-based catalyst with a core-shell structure can be obtained by using ZnS as a matrix and replacing zinc ions with copper ions, wherein more monoatomic copper is dispersed on the surface of the copper-based catalyst, and more zinc is contained in the copper-based catalyst.
3. The preparation method of the copper-based catalyst for electrochemical reduction of carbon dioxide has the advantage that the composition of the catalyst obtained by an ion exchange method is controllable. The ratio of copper to zinc in the catalyst can be adjusted according to the reaction requirement.
Drawings
FIG. 1 is a diagram illustrating the steps of the present invention;
FIG. 2 is a CO2RR performance graph of a copper-based catalyst of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The first embodiment is as follows:
a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide comprises the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, ultrasonic treatment is carried out for 30 minutes, and then the solution is poured into a crystallization kettle for crystallization for 18 hours, wherein the crystallization temperature is 180 ℃;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing the mixture by using ethanol and deionized water alternately for later use, wherein the washing times are three times;
s2: ion exchange method from ZnS → CuxZnyS
S2.1: weighing 0.017 g of copper chloride dihydrate and dissolving in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then, 0.1 g of the obtained ZnS solid powder is dispersed in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid at 2-3 drops/min;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the step S2.4 into a crystallization kettle, and crystallizing for 10 hours at the crystallization temperature of 140 ℃;
s2.6: washing the product in S2.5 with 10 ml of ethanol and 10 ml of deionized water respectively for three times;
s2.7: performing centrifugal separation on the product in the S2.6, pouring out supernatant, and naturally drying to obtain a sample Cu 1 Zn 9 S；
S3: oxidized CuxZnyS → CuxZnyO
S3.1: heating the sample obtained in the step S2.7 from room temperature to 700 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 240 minutes;
s3.2: and naturally cooling to obtain a catalyst sample.
Example two:
a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide comprises the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, ultrasonic treatment is carried out for 30 minutes, and then the solution is poured into a crystallization kettle for crystallization for 18 hours, wherein the crystallization temperature is 180 ℃;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing with ethanol and deionized water alternately for later use, wherein the washing times are three times;
s2: ion exchange method from ZnS → CuxZnyS
S2.1: weighing 0.0513 g of copper chloride dihydrate to be dissolved in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then, 0.1 g of the obtained ZnS solid powder is dispersed in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid at 2-3 drops/min;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the S2.4 into a crystallization kettle, and crystallizing for 10 hours at the crystallization temperature of 140 ℃;
s2.6: washing the product in S2.5 with 10 ml of ethanol and 10 ml of deionized water respectively for three times;
s2.7: performing centrifugal separation on the product in the S2.6, then pouring out supernatant liquid, and naturally airing to obtain a sample;
s3: oxidized CuxZnyS → CuxZnyO
S3.1: heating the sample obtained in the step S2.7 from room temperature to 700 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 240 minutes;
s3.2: naturally cooling to obtain a catalyst sample Cu 3 Zn 7 S。
Example three:
a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide comprises the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, ultrasonic treatment is carried out for 30 minutes, and then the solution is poured into a crystallization kettle for crystallization for 18 hours, wherein the crystallization temperature is 180 ℃;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing with ethanol and deionized water alternately for later use, wherein the washing times are three times;
s2: ion exchange method from ZnS → CuxZnyS
S2.1: weighing 0.08 g of copper chloride dihydrate, and dissolving in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then dispersing 0.1 g of the obtained ZnS solid powder in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid at 2-3 drops/min;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the S2.4 into a crystallization kettle, and crystallizing for 10 hours at the crystallization temperature of 140 ℃;
s2.6: washing the product in S2.5 with 10 ml of ethanol and 10 ml of deionized water respectively for three times;
s2.7: performing centrifugal separation on the product in the S2.6, then pouring out supernatant, naturally airing to obtain a sample Cu 5 Zn 5 S；
S3: oxidized CuxZnyS → CuxZnyO
S3.1: heating the sample obtained in the step S2.7 from room temperature to 700 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 240 minutes;
s3.2: and naturally cooling to obtain a catalyst sample.
Example four:
a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide comprises the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, ultrasonic treatment is carried out for 30 minutes, and then the solution is poured into a crystallization kettle for crystallization for 18 hours, wherein the crystallization temperature is 180 ℃;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing with ethanol and deionized water alternately for later use, wherein the washing times are three times;
s2: ion exchange method from ZnS → CuxZnyS
S2.1: weighing 0.107 g of copper chloride dihydrate and dissolving in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then dispersing 0.1 g of the obtained ZnS solid powder in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid at 2-3 drops/min;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the step S2.4 into a crystallization kettle, and crystallizing for 10 hours at the crystallization temperature of 140 ℃;
s2.6: washing the product in S2.5 with 10 ml of ethanol and 10 ml of deionized water respectively for three times;
s2.7: performing centrifugal separation on the product in the S2.6, then pouring out supernatant liquor, and naturally airing to obtain a sample Cu 7 Zn 3 S；
S3: oxidized CuxZnyS → CuxZnyO
S3.1: heating the sample obtained in the step S2.7 from room temperature to 700 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 240 minutes;
s3.2: and naturally cooling to obtain a catalyst sample.
Example five:
a preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide comprises the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, ultrasonic treatment is carried out for 30 minutes, and then the obtained solution is poured into a crystallization kettle for crystallization for 18 hours, wherein the crystallization temperature is 180 ℃;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing the mixture by using ethanol and deionized water alternately for later use, wherein the washing times are three times;
s2: ion exchange method from ZnS → CuxZnyS
S2.1: weighing 0.151 g of copper chloride dihydrate to be dissolved in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then dispersing 0.1 g of the obtained ZnS solid powder in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid at 2-3 drops/min;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the step S2.4 into a crystallization kettle, and crystallizing for 10 hours at the crystallization temperature of 140 ℃;
s2.6: washing the product in S2.5 with 10 ml of ethanol and 10 ml of deionized water respectively for three times;
s2.7: performing centrifugal separation on the product in the S2.6, then pouring out supernatant liquid, and naturally airing to obtain a sample;
s3: oxidized CuxZnyS → CuxZnyO
S3.1: heating the sample obtained in the step S2.7 from room temperature to 700 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 240 minutes;
s3.2: naturally cooling to obtain a catalyst sample Cu 9 Zn 1 S。
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a reference structure" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Claims (1)
1. A preparation method of a copper-based catalyst for electrochemical reduction of carbon dioxide is characterized by comprising the following steps:
s1: synthesis of Zns nanoparticles
S1.1: 2.44 g of zinc nitrate hexahydrate and 1.27 g of thiourea are dissolved in 25 ml of deionized water, and the mixture is subjected to ultrasonic treatment for 30 minutes and then poured into a crystallization kettle for crystallization for 18 hours;
s1.2: cooling the crystallized substance in the S1.2 to room temperature, performing centrifugal separation, and drying at 100 ℃ to obtain ZnS nano particles;
s1.3: washing with ethanol and deionized water alternately;
s2: the ion exchange method is represented by ZnS → CuxZnyS
S2.1: weighing 0.017 to 0.151 g of copper chloride dihydrate, and dissolving the copper chloride dihydrate in 10 ml of deionized water to prepare a copper chloride aqueous solution;
s2.2: then dispersing 0.1 g of the obtained ZnS solid powder in 5 ml of deionized water;
s2.3: dropwise adding the copper chloride aqueous solution prepared in the step S2.1 into the ZnS dispersion liquid;
s2.4: carrying out ultrasonic treatment on the S2.3 for 30 minutes;
s2.5: putting the product obtained after the ultrasonic treatment in the step S2.4 into a crystallization kettle, and crystallizing for 10 hours;
s2.6: washing the product in S2.5 with 10 ml ethanol and 10 ml deionized water respectively;
s2.7: performing centrifugal separation on the product in the S2.6, then pouring out supernatant liquor, and naturally airing to obtain a sample;
s3: oxidized CuxZnyS → CuxZnyO
S3.1: the sample obtained in S2.7 is heated from room temperature to 700 ℃ and kept for 240 minutes;
s3.2: cooling to obtain a catalyst sample;
the heating rate in the S3.1 is 2 ℃/min;
the cooling in the S3.2 is natural cooling;
the washing times in S2.6 are three times;
the number of washing times in the S1.3 is three;
the dripping speed in the S2.3 is 2-3 drops/min;
the crystallization temperature in the S1.1 is 180 ℃;
the crystallization temperature in S2.5 is 140 ℃.
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Denomination of invention: Preparation method of copper based catalyst for electrochemical reduction of carbon dioxide Granted publication date: 20230404 Pledgee: Postal Savings Bank of China Co.,Ltd. Pingxiang Xiangdong District Sub branch Pledgor: JIANGXI BALIUSAN INDUSTRIAL CO.,LTD. Registration number: Y2024980006778 |