CN111408372B - Copper-based CO with hollow nanosphere morphology 2 Preparation process of electro-reduction catalyst - Google Patents
Copper-based CO with hollow nanosphere morphology 2 Preparation process of electro-reduction catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 15
- 239000010949 copper Substances 0.000 title claims abstract description 15
- 239000002077 nanosphere Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000000499 gel Substances 0.000 description 12
- 239000013213 metal-organic polyhedra Substances 0.000 description 11
- 238000012011 method of payment Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 102100025912 Melanopsin Human genes 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XTEXMYNJEMCTNI-UHFFFAOYSA-N ethene;methane Chemical group C.C=C XTEXMYNJEMCTNI-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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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
- B01J23/72—Copper
-
- B01J35/33—
-
- B01J35/51—
-
- 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
-
- 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
Abstract
Copper-based CO with hollow nanosphere morphology 2 The invention relates to a preparation process of an electro-reduction catalyst, which relates to the technical field of environmental protection, and is characterized in that newly synthesized Cu-MOP and a high molecular polymer are dissolved in ethanol according to the mass ratio of 10:1 in a beaker to obtain a mixed solution, then the mixed solution is stirred for 30min at room temperature, a blue gel is formed after the mixed solution is fully dissolved, then the gel is kept stand for 3 days, and is carbonized for 5h at 400 ℃ after the gel is gradually hardened, and a solid product is obtained after the gel is naturally cooled to the room temperature. The preparation and synthesis process is simple and feasible, the obtained catalyst has adjustable morphology, and the method has the advantages of simple process, convenience in operation, suitability for large-scale production and the like.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to copper-based CO with a shape of a hollow nanosphere 2 A preparation process of an electro-reduction catalyst.
Background
With the development of industry and the rapid increase of world population, the amount of carbon dioxide emission is constantly innovative around the world, which not only brings about various serious environmental problems (such as global warming), but also has great influence on our lives. Over the past few decades, much effort has been expended to control carbon dioxide emissions and reduce their environmental impact. However, since human beings have a very high dependence on fossil fuels in terms of power generation, transportation, industrial development, and the like, carbon dioxide emissions have not been reasonably controlled. It was reported that 362 million metric tons of carbon dioxide was emitted into the atmosphere for human reasons in 2015, and the corresponding global average air temperature increased by about 0.1 ℃ since 2015. The damage to global agricultural productivity, human health, property loss and energy system is calculated as carbon consumption at 201The total amount can be as high as $ 1.5 trillion over a period of 5 years to 2050 years. Therefore, how to effectively reduce CO in the atmosphere 2 Concentration has become an extremely serious problem. The conversion of CO which is now common 2 The method of (1) includes chemical modification, photochemical method, electrochemical method and the like.
Electrochemical CO 2 Reduction reaction (CO) 2 RR) as a green technical approach can provide a method for synthesizing CO 2 And the method is converted into a sustainable solution of high-value energy products or chemicals, so that the aim of effectively relieving the environmental problem is gradually fulfilled. CO is introduced into 2 Converted into carbon-based fuel, not only partially meets the energy demand of human beings, but also can reduce CO in the atmosphere 2 In an amount to mitigate the effect of the "greenhouse effect", copper-based catalysts, as an electrocatalyst widely discussed, show a very potential application and excellent performance in the field of carbon dioxide electroreduction reactions, and can be used to produce a range of products, such as CH 4 、C 2 H 4 、C 2 H 5 OH、CH 3 COOH, etc., and CH 4 And C 2 H 4 Because of the high energy density and wide applicability of such multi-electron transfer products, copper-based catalysts are the most promising electrocatalysts for producing multi-carbon products by multi-electron transfer based on the current literature reports, which makes the research on copper-based catalysts more and more important. Firstly, the catalysts are relatively weak in material design, so that the products are relatively complex and low in selectivity, various types of products such as methane and the like can be produced while carbon monoxide is produced, and a large amount of hydrogen can be separated out in the general reaction process, so that the difficulty of producing a single product by the catalysts on the basis of inhibiting hydrogen production is caused. In addition, a large number of known copper-based electrocatalysts exist in powder form and are easy to agglomerate, and the morphology of the catalyst is difficult to control. In view of this, some hollow or porous structures suitable for mass transfer have attracted interest to researchers. To our knowledge, it is an object how to adjust the electrocatalyst to promote mass transfer and expose more specific surface area to favor the electrocatalytic processThe difficult problem that needs to be solved by the copper-based electrocatalyst.
Disclosure of Invention
The invention aims to provide a copper-based CO with a hollow nanosphere shape and reasonable design aiming at the defects and the defects of the prior art 2 The preparation process of the electro-reduction catalyst adopts a simple and feasible preparation and synthesis process, the obtained catalyst has adjustable morphology, and the preparation process has the advantages of simple process, convenience in operation, suitability for large-scale production and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: the method comprises the following steps:
1. 365mg of 5-hydroxyisophthalic acid ligand is dissolved in 10mL of methanol, 400mg of copper acetate metal salt is dissolved in 30mL of methanol, then the two are mixed in a glass bottle and fully stirred for 30 minutes, 10mL of N, N-Dimethylacetamide (DMA) is added into the mixture, and the mixture is transferred into a high-temperature high-pressure reaction kettle and kept at 85 ℃ for 24 hours; after the mixture is cooled to room temperature, repeatedly washing unreacted materials by using DMA and dichloromethane, and then drying in vacuum to obtain newly synthesized Cu-MOP;
2. dissolving newly synthesized Cu-MOP and a high molecular polymer in ethanol according to a mass ratio of 10:1 in a beaker to obtain a mixed solution, then stirring the mixed solution at room temperature for 30min, fully dissolving to form blue gel, standing the gel for 3 days, gradually hardening the gel, carbonizing the gel at 400 ℃ for 5h, and naturally cooling the gel to room temperature to obtain a solid product.
Further, the carbonization steps are as follows: raising the temperature from 5 ℃ per minute to 400 ℃ at room temperature, keeping the temperature for 5 hours, naturally reducing the temperature to room temperature, and collecting the product after complete cooling.
Further, said CO 2 The loading capacity of the electro-reduction catalyst is 1mg cm -2 。
After the process is adopted, the invention has the beneficial effects that: the invention provides copper-based CO with the shape of a hollow nanosphere 2 The preparation process of the electro-reduction catalyst comprises the steps of self-assembling soluble MOP and a polymer into gel and further carbonizing the gel to prepare a hollow nanosphere material, and further applying the hollow nanosphere material to CO 2 RR to get highA grade product; compared with the traditional preparation method, the preparation method adopts a simple and feasible preparation synthesis process, the obtained catalyst has adjustable morphology, and the preparation method has the advantages of simple process, convenience in operation, suitability for large-scale production and the like.
Description of the drawings:
FIG. 1 is a PXRD graph comparing HSAC (Hydrogel self-assembly and carbonisation) series materials synthesized in the examples, such as HSAC-10 and HSAC-5.
FIG. 2 is a comparative infrared image of HSAC family materials synthesized in the examples (HSAC-10 and HSAC-5 are examples).
FIG. 3 is SEM and TEM images of HSAC series synthesized in example (a, b are SEM and TEM images of HSAC-10, respectively; c, d are SEM and TEM images of HSAC-5, respectively).
FIG. 4 is a LSV graph of an embodiment tested on HSAC-10.
FIG. 5 is a graph of LSV of an embodiment tested on HSAC-5.
FIG. 6 is a FE graph of an example tested on HSAC-10.
FIG. 7 is a FE chart of the HSAC-5 test of the embodiment.
The specific implementation mode is as follows:
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. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The technical scheme adopted by the specific implementation mode (embodiment) is as follows: the preparation method comprises the following steps:
step one, 365mg of 5-hydroxyisophthalic acid ligand was dissolved in 10mL of methanol, 400mg of copper acetate metal salt was dissolved in 30mL of methanol, and then both were mixed in a glass bottle and sufficiently stirred for 30 minutes, 10mL of N, N-Dimethylacetamide (DMA) was added thereto, and the mixture was transferred to a high temperature and high pressure reaction vessel and maintained at 85 ℃ for 24 hours. After the mixture is cooled to room temperature, repeatedly washing unreacted materials by using DMA and dichloromethane, and then drying in vacuum to obtain newly synthesized Cu-MOP;
step two, taking HSAC-10 as an example, referring to triblock high molecular polymer F127 (EO) in the precursor solution 106 PO 70 EO 106 ) The mass ratio of the two substances to newly synthesized Cu-MOP is 10:1, the two substances are respectively dissolved in ethanol and then mixed in a beaker, the mixed solution is stirred for 30min at room temperature, blue gel is formed after full dissolution, then the gel is kept stand for 3-5 days, the gel is carbonized for 5h at 400 ℃ after being gradually hardened, and a solid product HSAC-10 is obtained after the gel is naturally cooled to room temperature;
and step three, obtaining a solid product HSAC-5 by adopting the step two (the mass ratio of the HSAC-5, namely the macromolecule to the MOP is 5: 1).
Examples testing:
the resulting products (HSAC10 and HSAC-5) were analyzed by powder X-Ray diffraction (PXRD) and infrared, and the results are shown in FIGS. 1 and 2, and the morphology of the products was further characterized by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) (grinding treatment was required before characterization), the SEM images show that HSAC-10 is a sphere with a diameter of about 340nm, TEM shows that the interior is a hollow structure, and HSAC-5 is a hollow sphere with a diameter of about 480nm, and the characterization is shown in FIG. 3.
CO of HSAC-10 and HSAC-5 2 In the RR test (which uses a three-electrode system, a gas diffusion electrode as a working electrode, a platinum electrode as an auxiliary electrode, a silver/silver chloride electrode as a reference electrode, and an electrolyte of 1M KOH, and different working voltages are applied at room temperature for the test), the LSV curve in fig. 4 and the FE in fig. 5 both show that the catalyst has excellent performance when used as a carbon dioxide electro-reduction catalyst. The LSV curves in FIGS. 4 and 5 show that at the same potential during catalysis, the current density is lower in an argon atmosphere than in a carbon dioxide atmosphere, and the catalyst is on CO compared to HER 2 RR has a higher selectivity. The FE plots in FIGS. 6 and 7 show that HSAC-10 has methane as the main product at a potential of-0.7V, and as the potential increases, the FE of methane increases to a maximum of 55.78% at-0.9V, while the FE of ethylene also reaches 22.25%. Whereas ethylene has been made it electrocatalytic for CO at a potential of-0.7V compared to HSAC-5 2 Major products of RR withThe increase of the potential, the FE of ethylene is continuously enhanced, and the FE is in the potential range of-0.8 to-1.0V C2H4 The content of the catalyst is about 60%, and the catalyst is proved to have excellent performance on generating multi-electron transfer and generating methane ethylene high-grade products in the process of carrying out carbon dioxide electro-reduction test.
The working principle of the specific implementation mode is as follows: metal Organic Polyhedra (MOPs) are a class of discrete molecular structures constructed from metal ions and organic ligands. MOPs have received extensive attention over the past decade due to their interesting structure, relevance to bio-self-assembled systems, and various potential applications (e.g., in sensing and catalysis). And the self-assembly of the selected soluble MOP and the triblock polymer can lead hydrophilic groups to interact, further form hollow appearance and be beneficial to electron transfer in the catalytic reaction process.
After the process is adopted, the beneficial effects of the specific embodiment are as follows: the invention provides copper-based CO with a hollow nanosphere shape 2 The preparation process of the electro-reduction catalyst is characterized in that the soluble MOP and the polymer are self-assembled into gel and further carbonized to prepare the hollow nanosphere material, and the nano hollow nanosphere material is further applied to CO 2 RR to obtain a higher product; compared with the traditional preparation method, the preparation method adopts a simple and feasible preparation synthesis process, the obtained catalyst has adjustable morphology, and the preparation method has the advantages of simple process, convenience in operation, suitability for large-scale production and the like.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (3)
1. Copper-based CO with hollow nanosphere morphology 2 The preparation process of the electro-reduction catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) 365mg of 5-hydroxyisophthalic acid ligand is dissolved in 10mL of methanol, 400mg of copper acetate metal salt is dissolved in 30mL of methanol, then the two are mixed in a glass bottle and fully stirred for 30 minutes, 10mL of N, N-dimethylacetamide is added into the mixture, and the mixture is transferred into a high-temperature high-pressure reaction kettle and kept at 85 ℃ for 24 hours; after the mixture is cooled to room temperature, repeatedly washing unreacted materials by using DMA and dichloromethane, and then drying in vacuum to obtain newly synthesized Cu-MOP;
(2) dissolving newly synthesized Cu-MOP and a high molecular polymer in ethanol according to the mass ratio of 10:1 in a beaker to obtain a mixed solution, then stirring the mixed solution at room temperature for 30min, fully dissolving to form blue gel, standing the gel for 3 days, gradually hardening the gel, carbonizing the gel at 400 ℃ for 5h, and naturally cooling the gel to room temperature to obtain a solid product.
2. Copper-based CO with hollow nanosphere morphology according to claim 1 2 The preparation process of the electro-reduction catalyst is characterized by comprising the following steps: the carbonization steps are as follows: raising the temperature from 5 ℃ per minute to 400 ℃ at room temperature, keeping the temperature for 5 hours, naturally reducing the temperature to room temperature, and collecting the product after complete cooling.
3. Copper-based CO with hollow nanosphere morphology according to claim 1 2 The preparation process of the electro-reduction catalyst is characterized by comprising the following steps: said CO 2 The loading of the electro-reduction catalyst is 1mg cm -2 。
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| JP2017078190A (en) * | 2015-10-19 | 2017-04-27 | 富士通株式会社 | Electrode for carbon dioxide reduction, container, and carbon dioxide reduction device |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN108816258A (en) * | 2018-06-13 | 2018-11-16 | 吉林大学 | A kind of hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen in situ for adulterating hollow phosphatization cobalt nanoparticle |
| CN109728311A (en) * | 2019-01-09 | 2019-05-07 | 长江大学 | The metal organic framework compound hollow microsphere of load iron cobalt sulfide |
| CN110586150A (en) * | 2019-06-04 | 2019-12-20 | 东南大学 | Hollow structure catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method of catalyst |
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|---|---|---|---|---|
| JP2017078190A (en) * | 2015-10-19 | 2017-04-27 | 富士通株式会社 | Electrode for carbon dioxide reduction, container, and carbon dioxide reduction device |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN108816258A (en) * | 2018-06-13 | 2018-11-16 | 吉林大学 | A kind of hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen in situ for adulterating hollow phosphatization cobalt nanoparticle |
| CN109728311A (en) * | 2019-01-09 | 2019-05-07 | 长江大学 | The metal organic framework compound hollow microsphere of load iron cobalt sulfide |
| CN110586150A (en) * | 2019-06-04 | 2019-12-20 | 东南大学 | Hollow structure catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method of catalyst |
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