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 PDF

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CN114990584B
CN114990584B CN202210715063.XA CN202210715063A CN114990584B CN 114990584 B CN114990584 B CN 114990584B CN 202210715063 A CN202210715063 A CN 202210715063A CN 114990584 B CN114990584 B CN 114990584B
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copper
zns
deionized water
crystallization
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CN114990584A (en
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陈彦霖
陈远兴
陈亚琴
俞曦
张斌
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Jiangxi Baliusan Industrial Co ltd
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    • C25B3/26Reduction of carbon dioxide
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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

Preparation method of copper-based catalyst for electrochemical reduction of carbon dioxide
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

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