CN112642434A - For electrochemical reduction of CO2Cu of (2)2O-supported ZnO catalyst - Google Patents
For electrochemical reduction of CO2Cu of (2)2O-supported ZnO catalyst Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 claims abstract 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012716 precipitator Substances 0.000 claims abstract 2
- 239000001509 sodium citrate Substances 0.000 claims abstract 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract 2
- 238000004729 solvothermal method Methods 0.000 claims abstract 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 20
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 12
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- 239000000203 mixture Substances 0.000 claims description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
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- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
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- 239000000446 fuel Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 39
- 229910002091 carbon monoxide Inorganic materials 0.000 description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
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- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
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- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention discloses a flower cluster Cu2Preparation method of O-supported ZnO catalyst and application of catalyst in electrocatalytic reduction of CO2High selectivity for CO fuel production. The catalyst takes nitric acid hexahydrate as a raw material, sodium hydroxide as a precipitator and sodium citrate as a surfactant, and a flower-like ZnO carrier is synthesized by a solvothermal method; then, copper sulfate pentahydrate is used as a raw material, hydrazine hydrate is used as a reducing agent, and a rapid thermal reduction method is adopted to synthesize different Cu2Cu of O content2And O loads ZnO nano material. The catalyst is a flower cluster-shaped Cu catalyst formed by combining ZnO carrier particles and sheets2O is loaded on the surface of ZnO and is uniformly dispersed, and the catalyst can be used for electrocatalytic reduction of CO2The application research for preparing CO is novel. The preparation method and the process of the catalyst are simple and easy to implement, and the raw materials are low in priceGood electrochemical performance, CO2The selectivity of CO generated by electrochemical reduction is high, and the Faraday efficiency can reach 86.9%.
Description
Technical Field
The invention relates to a method for electrocatalytic reduction of CO2Cu for producing CO2O-supported ZnO bimetallic oxide catalyst, in particular to Cu-supported ZnO bimetallic oxide catalyst2Flower cluster formed by O-loaded ZnO nanosheet and nanoparticlesStructure of CO2High efficiency to CO.
Background
The large development and consumption of fossil energy continuously increase the carbon dioxide content in the environment and break through the natural carbon balance cycle, so that the global warming is caused by the greenhouse effect, and further ecological environment problems such as melting of glaciers in the north and south, rising of sea level, abnormal climate and the like are caused. The international commission on climate change predicts that by 2100 the carbon dioxide content in the environment will increase from 350 ppm to 590 ppm and the global average temperature will rise by 1.9 ℃. Thus, mitigating the continuing increase in atmospheric carbon dioxide concentration is an important issue that is currently urgently needed to be solved worldwide. The carbon dioxide reduction technology can not only reduce the content of carbon dioxide in the environment and relieve the greenhouse effect, but also can generate carbon-containing chemicals and industrial raw materials with high added values, thereby realizing carbon cycle. Wherein CO is reduced by electrocatalytic reduction2The conversion to a variety of high value-added chemicals and fuels is a technology that is of great interest. Due to CO2The reaction path of electrocatalytic reduction is too many, resulting in low product selectivity, while high selectivity catalysts often require expensive noble metals. Therefore, the key problem of this technology is to find a low cost, high selectivity catalyst for CO2Conversion to a single species.
Electrocatalytic reduction of CO2Can be used for preparing carbon monoxide (CO) and methane (CH)4) Formic acid (HCOOH), ethylene (C)2H4) Methanol (CH)3OH) and the like, and has important significance in the aspects of environment and energy. CO is used as one of raw materials for Fischer-Tropsch synthesis and is CO2One of the important products of electroreduction. Due to CO2The complexity of electrocatalytic reduction products, and few catalysts are currently reported to efficiently produce CO. Despite this, the vigorous development of inexpensive metal catalysts rich in hulls instead of noble metal catalysts has received a high degree of attention in the relevant field of catalytic research. To date, catalysts meeting these conditions have been found to be highly scalable, and most catalysts can convert only CO under the corresponding catalytic conditions2Reduction to CO and HCOOH and other carbon-oxygen mixtures, how to efficiently convert CO2The further conversion with high selectivity into CO with a high calorific value deserves intensive research.
Disclosure of Invention
The invention aims to provide a method for electrocatalytic reduction of CO2Flower-like Cu for CO production2The O-supported ZnO catalyst has the advantages of relatively low raw material price, simple and easy preparation process, and higher CO selectivity and Faraday efficiency.
The invention mainly comprises the flower cluster Cu2O-loaded ZnO catalyst for electrocatalytic reduction of CO2Preparation of CO by adjusting Cu2The amount of O component improves the CO Faraday efficiency. The technical scheme provided by the invention is as follows: for electrocatalytic reduction of CO2Flower-like Cu for CO production2O-supported ZnO catalyst, said catalyst Cu2The O loading was 3wt.%, 5wt.%, 10 wt.%.
Furthermore, the ZnO carrier in the catalyst is a 2-micron flower cluster.
The following are the operational steps and a schematic illustration of the present invention:
1) weighing 5.96g Zn (NO)3)2·6H2Dissolving O in 45 mL of deionized water, ultrasonically dissolving, and stirring at normal temperature for 15 min to form a uniform colorless transparent solution:
2) weighing 2.4g of NaOH, and ultrasonically dissolving the NaOH in 15 mL of deionized water for later use;
3) adding the solution 2) into the solution 1) dropwise, heating to 85 ℃ under continuous stirring, keeping for 3 hours, naturally cooling to room temperature, collecting the product, washing with deionized water and ethanol for several times, and drying in a drying oven at 70 ℃ for 12 hours. Obtaining a flower cluster-shaped ZnO carrier for later use;
4) weigh 0.0277g CuSO4·5H2Dissolving O in 50 mL of deionized water by ultrasonic, and magnetically stirring for 10 min at room temperature to form a uniform transparent blue solution for later use;
5) measuring 4.85 ml of N with the mass fraction of 50% by using a measuring cylinder2H4·H2O, adding the mixture into a volumetric flask to make the volume of the mixture to be 100 ml, and preparing 0.5 mol/L N2H4·H2O, standby;
6) weighing 0.3g of ZnO obtained in the steps 1) -3), dissolving in the solution 4), stirring with a magnetic stirrer for 10 min, and performing ultrasonic treatment for 15 min to obtain Cu2O is loaded on the surface of ZnO;
7) raising the temperature to 70 ℃ and keeping the temperature for 20 min while stirring the solution of 5);
8) stirring, slowly adding 5) solution dropwise into 6) solution, maintaining for 60 min, naturally cooling to room temperature, collecting product, washing with deionized water and ethanol for several times, and drying in vacuum drying oven at 60 deg.C for 8 hr to obtain 3wt.% Cu2O-loaded ZnO flower-like catalyst;
9) 0.461g and 0.922g of copper sulfate pentahydrate are respectively weighed according to the step 5) and put into a 100 mL beaker, 30 mL of deionized water is added, and the mixture is stirred for 20 min by a magnetic stirrer. Repeat steps 5), 6), 7), 8) to 5wt.% Cu2O loaded ZnO and 10wt.% Cu2O supports ZnO flower-like catalyst.
By adopting the technical scheme, the invention has the technical effects that:
1. the invention has relatively low raw material price, simple and easy preparation process, and can realize the modulation of the activity by changing the preparation conditions (load capacity and the like).
2. The flower-like Cu prepared by the invention2The O-loaded ZnO catalyst has better CO-producing Faraday efficiency which can reach 86.9 percent.
Drawings
FIG. 1 is a floral 5wt.% Cu2O-loaded ZnO Scanning Electron Microscopy (SEM) images;
FIG. 2 is a floral 5wt.% Cu2EDS energy spectrum of O loaded ZnO;
FIG. 3 shows flower-like Cu with different loading2Electrocatalytic reduction of CO by O-loaded ZnO catalyst2Schematic representation of the faradaic efficiency of CO.
FIG. 4 shows Cu loading at different contents2Electrocatalytic reduction of CO by O-loaded ZnO catalyst2Is a schematic current density diagram of CO.
Detailed Description
The following examples are provided to further illustrate the invention and are not intended to be limiting.
The method comprises the following specific steps:
1) weighing 5.96g Zn (NO)3)2·6H2Dissolving O in 45 mL of deionized water, ultrasonically dissolving, and stirring at normal temperature for 15 min to form a uniform colorless transparent solution:
2) weighing 2.4g of NaOH, and ultrasonically dissolving the NaOH in 15 mL of deionized water for later use;
3) adding the solution 2) into the solution 1) dropwise, heating to 85 ℃ under continuous stirring, keeping for 3 hours, naturally cooling to room temperature, collecting the product, washing with deionized water and ethanol for several times, and drying in a drying oven at 70 ℃ for 12 hours. Obtaining a flower cluster-shaped ZnO carrier for later use;
example 1
4) 0.0461g of CuSO were weighed out4·5H2Dissolving O in 50 mL of deionized water by ultrasonic, and magnetically stirring for 10 min at room temperature to form a uniform transparent blue solution for later use;
5) measuring 4.85 ml of N with the mass fraction of 50% by using a measuring cylinder2H4·H2O, the volume is 100 mL in a volumetric flask, and 0.5 mol/L N is prepared2H4·H2O, standby;
6) weighing 0.3g of ZnO obtained in the steps 1) -3), dissolving in the solution 4), stirring with a magnetic stirrer for 10 min, and performing ultrasonic treatment for 15 min to obtain Cu2O is loaded on the surface of ZnO;
7) raising the temperature to 70 ℃ and keeping the temperature for 20 min while stirring the solution of 5);
8) stirring, slowly adding 5) solution dropwise into 6) solution, maintaining for 60 min, naturally cooling to room temperature, collecting product, washing with deionized water and ethanol for several times, and drying in vacuum drying oven at 60 deg.C for 8 hr to obtain 5wt.% Cu2O-loaded ZnO flower-like catalyst;
example 2
4) 0.0922g of CuSO was weighed out4·5H2Dissolving O in 50 mL deionized water by ultrasonic, and magnetically stirring at room temperature for 10 min to form uniform transparent solutionBlue solution for later use;
5) measuring 4.85 ml of N with the mass fraction of 50% by using a measuring cylinder2H4·H2O, adding the mixture into a volumetric flask to make the volume of the mixture to be 100 ml, and preparing 0.5 mol/L N2H4·H2O, standby;
6) weighing 0.3g of ZnO obtained in the steps 1) -3), dissolving in the solution 4), stirring with a magnetic stirrer for 10 min, and performing ultrasonic treatment for 15 min to obtain Cu2O is loaded on the surface of ZnO;
7) raising the temperature to 70 ℃ and keeping the temperature for 20 min while stirring the solution of 5);
8) stirring, slowly adding 5) solution dropwise into 6) solution, maintaining for 60 min, naturally cooling to room temperature, collecting product, washing with deionized water and ethanol for several times, and drying in vacuum drying oven at 60 deg.C for 8 hr to obtain 10wt.% Cu2O-loaded ZnO flower-like catalyst;
example 3
4) Weigh 0.0277g CuSO4·5H2Dissolving O in 50 mL of deionized water by ultrasonic, and magnetically stirring for 10 min at room temperature to form a uniform transparent blue solution for later use;
5) measuring 4.85 ml of N with the mass fraction of 50% by using a measuring cylinder2H4·H2O, the volume is 100 mL in a volumetric flask, and 0.5 mol/L N is prepared2H4·H2O, standby;
6) weighing 0.3g of ZnO obtained in the steps 1) -3), dissolving in the solution 4), stirring with a magnetic stirrer for 10 min, and performing ultrasonic treatment for 15 min to obtain Cu2O is loaded on the surface of ZnO;
7) raising the temperature to 70 ℃ and keeping the temperature for 20 min while stirring the solution of 5);
8) stirring, slowly adding 5) solution dropwise into 6) solution, maintaining for 60 min, naturally cooling to room temperature, collecting product, washing with deionized water and ethanol for several times, and drying in vacuum drying oven at 60 deg.C for 8 hr to obtain 5wt.% Cu2O-loaded ZnO flower-like catalyst;
the catalyst prepared by the method is used for electrocatalytic reduction of CO2Performance measurementTest:
1) 5mg of catalyst was weighed into 0.9 mL of absolute ethanol, and 0.1 mL of 5wt.% nafion solution was added, and sonicated for 20 min to form a uniformly dispersed solution.
2) Taking 1X 1.5cm2Polishing the carbon paper to be smooth, putting the carbon paper in a diluted sulfuric acid solution overnight to remove impurity oxides, and ultrasonically cleaning the carbon paper by using deionized water and absolute ethyl alcohol. And (3) coating 0.2 mL of the solution obtained in the step 1) on the surface of the carbon paper, and drying at normal temperature for later use.
3) The reaction gas is 99% CO2The gas chromatography on-line analysis uses a 5A molecular sieve column to separate CO and CO2And H2The carrier gas is high-purity nitrogen, and the flow rate is 20 mL/min-1. The electrochemical workstation was CHI760 e.
Flower cluster shaped Cu2O-loaded ZnO catalyst for electrocatalytic reduction of CO2Preparing CO performance test results:
test results for example 1:
the Faraday efficiency of CO is 53.8 percent at-1.4V
The faradaic efficiency of CO is 68.8 percent at-1.5V
The faradaic efficiency of CO is 68.4 percent when the voltage is minus 1.6V
The faradaic efficiency of CO is 73.7 percent when the voltage is-1.7V
The faradaic efficiency of CO is 71.2 percent when the voltage is-1.8V
The faradaic efficiency of CO is 66.6 percent when the voltage is-1.9V
Test results for example 2:
the faradaic efficiency of CO is 61.2 percent at-1.4V
The faradaic efficiency of CO is 71.9 percent when the voltage is minus 1.5V
The Faraday efficiency of CO is 85.8 percent at minus 1.6V
The faradaic efficiency of CO is 86.9 percent when the voltage is minus 1.7V
The faradaic efficiency of CO is 84.2 percent when the voltage is minus 1.8V
The faradaic efficiency of CO is 86.1 percent when the voltage is minus 1.9V
Test results for example 3:
the faradaic efficiency of CO is 58.1 percent at-1.4V
The faradaic efficiency of CO is 67.2 percent when the voltage is-1.5V
The faradaic efficiency of CO is 78.6 percent when the voltage is-1.6V
The faradaic efficiency of CO is 80.1 percent when the voltage is-1.7V
The Faraday efficiency of CO is 79.4 percent at minus 1.8V
The Faraday efficiency of CO is 77.0 percent at minus 1.9V
As can be seen from the above tests, 5wt.% Cu was obtained from example 22The O-loaded ZnO catalyst is the best implementation mode, the CO selectivity is high, and the Faraday efficiency can reach 86.9%.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered by the claims of the present invention.
Claims (10)
1. For electrocatalytic reduction of CO2Preparation of CO nanosheet and nanoparticle combined flower-like Cu2An O-supported ZnO catalyst, characterized in that: the method is used for electrochemical reduction of CO2Cu of (2)2The O-loaded ZnO catalyst is in a flower cluster shape, ZnO is a copolymer formed by combining nano particles and nano sheets, and Cu2O is highly dispersed on the surface of ZnO.
2. The method of claim 1 for electrocatalytic reduction of CO2Flower-like Cu for CO production2An O-supported ZnO catalyst, characterized in that: the ZnO carrier of the catalyst is in a 5-micron cluster shape.
3. The method of claim 1 for electrocatalytic reduction of CO2Flower-like ZnO loaded Cu for preparing CO2An O catalyst characterized by: the catalyst Cu2The O loading was 3wt.%, 5wt.%, 10 wt.%.
4. For electrocatalytic reduction of CO2Flower-like Cu for CO production2An O-supported ZnO catalyst, characterized in that: it comprises the following steps:
1) weighing 5.96g Zn (NO)3)2·6H2Dissolving O in 45 mL of deionized water, ultrasonically dissolving, and stirring at normal temperature for 15 min to form a uniform colorless transparent solution:
2) weighing 2.4g of NaOH, and ultrasonically dissolving the NaOH in 15 mL of deionized water for later use;
3) dropwise adding the solution 2) into the solution 1), heating to 85 ℃ under continuous stirring, keeping for 3 hours, naturally cooling to room temperature, collecting the product, washing with deionized water and ethanol for several times, and keeping at 70 ℃ in a drying oven for drying for 12 hours to obtain a flower cluster-shaped ZnO carrier for later use;
4) weigh 0.0277g CuSO4·5H2Dissolving O in 50 mL of deionized water by ultrasonic, and magnetically stirring for 10 min at room temperature to form a uniform transparent blue solution for later use;
5) measuring 4.85 ml of N with the mass fraction of 50% by using a measuring cylinder2H4·H2O, the volume is 100 mL in a volumetric flask, and 0.5 mol/L N is prepared2H4·H2O, standby;
6) weighing 0.3g of ZnO obtained in the steps 1) -3), dissolving in the solution 4), stirring with a magnetic stirrer for 10 min, and performing ultrasonic treatment for 15 min to obtain Cu2O is loaded on the surface of ZnO;
7) raising the temperature to 70 ℃ and keeping the temperature for 20 min while stirring the solution of 5);
8) stirring, slowly adding 5) solution dropwise into 50 mL solution in 6) solution, maintaining for 60 min, naturally cooling to room temperature, collecting product, washing with deionized water and ethanol for several times, and drying in vacuum drying oven at 60 deg.C for 8 hr to obtain 5wt.% Cu2O-loaded ZnO flower-like catalyst;
8) weighing 0.461g and 0.922g of blue vitriol according to the step 5) respectively, putting the blue vitriol into a 100 mL beaker, adding 30 mL of deionized water, stirring for 20 min by a magnetic stirrer, and repeating the steps 5), 6), 7) and 8) to obtain 5wt.% of Cu2O loaded ZnO and 10wt.% Cu2O supports ZnO flower-like catalyst.
5. The method of claim 4 for electrocatalytic reduction of CO2Flower-like ZnO loaded Cu for preparing CO2The preparation method of the novel O catalyst is characterized by comprising the following steps: the structure and composition of the catalyst are synthesized by combining a solvothermal method with a thermochemical reduction method by taking NaOH as a precipitator and sodium citrate as a surfactant.
6. The catalyst is used for electrocatalytic reduction of CO2Flower-like Cu for CO production2The preparation method of the O-loaded ZnO novel catalyst is characterized by comprising the following steps: in the step 1), Zn (NO)3)2·6H2O is dissolved in water to form a solution.
7. The catalyst is used for electrocatalytic reduction of CO2Flower-like Cu for CO production2The preparation method of the O-loaded ZnO novel catalyst is characterized by comprising the following steps: in the step 2), NaOH solution is slowly added, which is beneficial to the polymerization of ZnO particles to form flower clusters.
8. The catalyst is used for electrocatalytic reduction of CO2Flower-like Cu for CO production2The preparation method of the O-loaded ZnO novel catalyst is characterized by comprising the following steps: in the step 3), ZnO is favorable for forming stable flower clusters under the heating condition of 85 ℃.
9. The catalyst is used for electrocatalytic reduction of CO2Flower-like Cu for CO production2The preparation method of the O-loaded ZnO novel catalyst is characterized by comprising the following steps: in the step 4), CuSO is regulated and controlled4·5H2O and Zn (NO)3)2·6H2The O feeding ratio is favorable for controlling Cu2The amount of O supported.
10. The catalyst is used for electrocatalytic reduction of CO2Flower-like Cu for CO production2The preparation method of the O-loaded ZnO novel catalyst is characterized by comprising the following steps: in the step 8), the addition amount of the reducing agent hydrazine hydrate is controlled, which is beneficial to controlling Cu2O particles are formed and loaded on the surface of ZnO, the cluster Cu2The novel O-supported ZnO catalyst is characterized in that: synthesizing a flower-like ZnO carrier and then loading small-particle Cu2O preparation of Cu2Load of ONovel ZnO catalyst for electrocatalytic reduction of CO2And preparing CO.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114108029A (en) * | 2021-10-22 | 2022-03-01 | 北京科技大学 | Bimetal series catalytic efficient reduction CO2Process for preparing a polycarbonic product |
| CN114836778A (en) * | 2022-03-16 | 2022-08-02 | 杭州师范大学 | TiO supported by PdCu alloy particles 2 Preparation method of metal nanosheet material electrocatalyst |
| CN115852417A (en) * | 2022-12-07 | 2023-03-28 | 南昌大学 | Spherical Cu 2 O nanoparticle catalyst and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407123A (en) * | 2011-09-30 | 2012-04-11 | 内蒙古大学 | CuO loaded CeO2 catalyst for CO preferential oxidation |
| CN102716743A (en) * | 2012-06-14 | 2012-10-10 | 东华大学 | Method for preparing aqueous dispersion nano-cuprous oxide/graphene composite powder |
| CN104959135A (en) * | 2015-06-29 | 2015-10-07 | 华中师范大学 | Nanometer zinc catalyst and method for reducing CO2 to CO by efficiently catalyzing CO2 through nanometer zinc catalyst |
| CN106732617A (en) * | 2016-12-05 | 2017-05-31 | 安徽理工大学 | A kind of ZnO/Cu2O hetero-junctions novel photocatalysis materials and preparation method thereof |
| US20180119296A1 (en) * | 2016-11-01 | 2018-05-03 | King Fahd University Of Petroleum And Minerals | Method for electrochemical reduction of carbon dioxide |
| CN108043410A (en) * | 2017-11-07 | 2018-05-18 | 国家纳米科学中心 | Cu is modified on top2ZnO nanorod hetero-junctions of O and preparation method and application |
| CN108543530A (en) * | 2018-03-15 | 2018-09-18 | 中国科学技术大学先进技术研究院 | A kind of Zinc oxide nano sheet in oxygen-enriched vacancy, preparation method and applications |
| US20190202762A1 (en) * | 2017-12-29 | 2019-07-04 | Uchicago Argonne, Llc | Photocatalytic reduction of carbon dioxide to methanol or carbon monoxide using cuprous oxide |
| CN110479289A (en) * | 2019-08-29 | 2019-11-22 | 陕西科技大学 | A kind of composite nano cuprous oxide/zinc oxide material and its preparation method and application with photocatalysis performance |
| WO2020056507A1 (en) * | 2018-09-18 | 2020-03-26 | The Governing Council Of The University Of Toronto | Metal nanoparticle electrocatlysts with confinement cavity morphology for improved selectivity |
| CN111621850A (en) * | 2019-02-28 | 2020-09-04 | 本田技研工业株式会社 | For electrochemical reduction of CO2Of (2) polycrystalline surface of Cu2Synergistic effect of O nanocrystals |
-
2021
- 2021-01-07 CN CN202110015717.3A patent/CN112642434A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407123A (en) * | 2011-09-30 | 2012-04-11 | 内蒙古大学 | CuO loaded CeO2 catalyst for CO preferential oxidation |
| CN102716743A (en) * | 2012-06-14 | 2012-10-10 | 东华大学 | Method for preparing aqueous dispersion nano-cuprous oxide/graphene composite powder |
| CN104959135A (en) * | 2015-06-29 | 2015-10-07 | 华中师范大学 | Nanometer zinc catalyst and method for reducing CO2 to CO by efficiently catalyzing CO2 through nanometer zinc catalyst |
| US20180119296A1 (en) * | 2016-11-01 | 2018-05-03 | King Fahd University Of Petroleum And Minerals | Method for electrochemical reduction of carbon dioxide |
| CN106732617A (en) * | 2016-12-05 | 2017-05-31 | 安徽理工大学 | A kind of ZnO/Cu2O hetero-junctions novel photocatalysis materials and preparation method thereof |
| CN108043410A (en) * | 2017-11-07 | 2018-05-18 | 国家纳米科学中心 | Cu is modified on top2ZnO nanorod hetero-junctions of O and preparation method and application |
| US20190202762A1 (en) * | 2017-12-29 | 2019-07-04 | Uchicago Argonne, Llc | Photocatalytic reduction of carbon dioxide to methanol or carbon monoxide using cuprous oxide |
| CN108543530A (en) * | 2018-03-15 | 2018-09-18 | 中国科学技术大学先进技术研究院 | A kind of Zinc oxide nano sheet in oxygen-enriched vacancy, preparation method and applications |
| WO2020056507A1 (en) * | 2018-09-18 | 2020-03-26 | The Governing Council Of The University Of Toronto | Metal nanoparticle electrocatlysts with confinement cavity morphology for improved selectivity |
| CN111621850A (en) * | 2019-02-28 | 2020-09-04 | 本田技研工业株式会社 | For electrochemical reduction of CO2Of (2) polycrystalline surface of Cu2Synergistic effect of O nanocrystals |
| CN110479289A (en) * | 2019-08-29 | 2019-11-22 | 陕西科技大学 | A kind of composite nano cuprous oxide/zinc oxide material and its preparation method and application with photocatalysis performance |
Non-Patent Citations (2)
| Title |
|---|
| JONATHAN ALBO ET AL.: "Production of methanol from CO2electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 柴晴雯等: "Cu2O@ZnO 复合光催化剂对难生物降解有机物的光降解", 《中国环境科学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114108029A (en) * | 2021-10-22 | 2022-03-01 | 北京科技大学 | Bimetal series catalytic efficient reduction CO2Process for preparing a polycarbonic product |
| CN114836778A (en) * | 2022-03-16 | 2022-08-02 | 杭州师范大学 | TiO supported by PdCu alloy particles 2 Preparation method of metal nanosheet material electrocatalyst |
| CN115852417A (en) * | 2022-12-07 | 2023-03-28 | 南昌大学 | Spherical Cu 2 O nanoparticle catalyst and preparation method and application thereof |
| CN115852417B (en) * | 2022-12-07 | 2023-10-03 | 南昌大学 | Spherical Cu 2 O nanoparticle catalyst and preparation method and application thereof |
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