CN116876009A - Metal-supported carbon-based fiber structure catalyst, preparation method and application - Google Patents
Metal-supported carbon-based fiber structure catalyst, preparation method and application Download PDFInfo
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- CN116876009A CN116876009A CN202310740977.6A CN202310740977A CN116876009A CN 116876009 A CN116876009 A CN 116876009A CN 202310740977 A CN202310740977 A CN 202310740977A CN 116876009 A CN116876009 A CN 116876009A
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- 239000000835 fiber Substances 0.000 title claims abstract description 141
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 188
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 94
- 239000001569 carbon dioxide Substances 0.000 claims description 88
- 238000010438 heat treatment Methods 0.000 claims description 74
- 238000009987 spinning Methods 0.000 claims description 46
- 239000012298 atmosphere Substances 0.000 claims description 44
- 239000010949 copper Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000011065 in-situ storage Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 30
- 239000002105 nanoparticle Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000033228 biological regulation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000005303 weighing Methods 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 125000004151 quinonyl group Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of catalyst preparation, and in particular relates to electrocatalytic reduction of CO 2 The invention relates to a metal-loaded carbon-based fiber structure catalyst and a preparation method thereof, and the preparation method of the metal-loaded carbon-based fiber structure catalyst comprises the following steps: uniformly mixing polyacrylonitrile and divalent soluble metal salt in a solvent so as to obtain electrostatic spinning solution; placing the electrostatic spinning solution into an electrostatic spinning device for electrostatic spinning, and collecting to obtain electrostatic spinning fibers; calcining the electrospun fibers to obtain the metal-supported carbon-based fiber structured catalyst.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a metal-loaded carbon-based fiber structure catalyst in the carbon dioxide capturing and converting process, a preparation method and application thereof.
Background
Carbon dioxide (CO) 2 ) Electrocatalytic reduction is used as a carbon negative technology with great development potential, and renewable electric power is used as energy to convert CO 2 Electrochemical conversion into high value-added fuels and chemicals is an effective way to achieve carbon recycling. However, CO 2 The molecule has symmetrical carbon-oxygen double bond structure and extremely stable thermodynamicsAnd the metal surface has weak interaction with the metal surface, the adsorption and activation are difficult, the products are various, and the product selectivity is difficult to regulate and control.
Patent CN202110872599.8 takes Cu with stable performance as base metal, and utilizes small molecular organic solvent with the functions of solvent and organic ligand to uniformly disperse transition metal in a single atom form in Cu nano crystal lattice to form a single atom alloy structure with double metal active sites, which is more beneficial to electrocatalytic CO 2 Cleavage of the c=c double bond during reduction increases the rate of CO formation, but due to the difficulty of adsorption of CO2 molecules, it is responsible for the electrocatalytic CO 2 The selectivity for the production of CO is significantly inadequate, resulting in lower catalytic efficiency. Thus, CO is increased 2 The molecules are adsorbed on the metal surface, which is more beneficial to the subsequent CO2 activation and conversion.
Integrated CO 2 Capturing and converting technologies are being developed vigorously as a promising, cost-effective carbon neutralization technology. However, the lack of long-sought molecular consensus for the synergistic effect between adsorption and in situ catalytic reactions has hindered its development. Therefore, how to construct a high CO 2 The catalyst which has the capability of capturing and in-situ conversion and can cooperatively promote the energy utilization efficiency of the system is CO 2 The problem to be solved in the field of transformation is urgent.
Disclosure of Invention
The invention aims to solve the technical problems that the prior catalyst does not support CO 2 The molecules have better adsorption capacity on the metal surface, and the catalytic efficiency is lower, thereby leading to CO 2 There is a need to provide a catalyst with a high CO content due to its poor capture and in situ conversion capabilities 2 A catalyst that captures and converts capacity in situ.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the metal-supported carbon-based fiber structure catalyst comprises the following steps:
(1) Uniformly mixing polyacrylonitrile and divalent soluble metal salt in a solvent so as to obtain electrostatic spinning solution;
(2) Placing the electrostatic spinning solution into an electrostatic spinning device for electrostatic spinning, and collecting to obtain electrostatic spinning fibers;
(3) Calcining the electrospun fibers to obtain the metal-supported carbon-based fiber structured catalyst.
Optionally, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the divalent soluble metal salt is at least one selected from soluble copper salt, cobalt salt, nickel salt and zinc salt;
optionally, the divalent soluble metal salt is selected from at least one of the chlorides, nitrates, sulphates or acetates of copper, cobalt, nickel and/or zinc;
optionally, the weight percentage of metal nanoparticles formed from the divalent soluble metal salt in a metal supported carbon based fiber structure catalyst is 5% -20%.
Optionally, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the mass concentration of the polyacrylonitrile in the electrostatic spinning solution is 8-15 wt%;
optionally, the solvent is N, N-dimethylformamide.
Optionally, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the condition of electrostatic spinning is that the temperature is 20-40 ℃, the humidity is 15-35%, the propulsion rate is 0.2-2ml/min, and the spinning voltage is 10-20V.
Optionally, the preparation method of the metal-supported carbon-based fiber structure catalyst further comprises the following steps: and collecting the electrostatic spinning fiber by adopting aluminum foil paper at a fixed receiving distance of 12-20cm, and drying the collected electrostatic spinning fiber at room temperature for 24-72h.
Optionally, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the temperature rising rate of the calcination is 2 ℃/min-10 ℃/min, the temperature is 700-1000 ℃, and the calcination time is 0.1-5h;
optionally, the calcined atmosphere is one or a mixture of two of carbon dioxide and argon.
Optionally, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the calcination is to heat up to 600 ℃ at a heating rate of 10 ℃/min for 1-2h, heat up to 700 ℃ at a heating rate of 5 ℃/min for 0.5-1h, and finally heat up to 700-1000 ℃ at a heating rate of 2 ℃/min for 5-10min.
Optionally, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the calcination is that the temperature is firstly increased to 600 ℃ in argon atmosphere at a heating rate of 10 ℃/min, and then the temperature is kept for 1-2h, and then the temperature is increased to CO at a heating rate of 5 ℃/min 2 Heating to 700 ℃ in the atmosphere, preserving heat for 0.5-1h, and finally heating at a heating rate of 2 ℃/min in CO 2 Calcining at 700-1000 deg.C for 5-10min.
The invention also provides a metal-supported carbon-based fiber structure catalyst, which is prepared by adopting any one of the methods.
The invention also provides the electrochemical CO of the metal-loaded carbon-based fiber structure catalyst 2 Use of the metal-supported carbon-based fiber structured catalyst in synergy of capture and in situ conversion, optionally, for CO realization by electrocatalysis 2 Capturing and in situ conversion.
The scheme of the invention at least comprises the following beneficial effects:
(1) The preparation method of the metal-supported carbon-based fiber structure catalyst provided by the embodiment of the invention has high universality, is suitable for various metals, has high repeatability and is beneficial to large-scale production;
(2) According to the preparation method of the metal-supported carbon-based fiber structure catalyst, provided by the embodiment of the invention, when the metal-supported carbon-based fiber structure is prepared, the surface of the carbon-based fiber can be modified with oxygen-containing groups, so that the preparation and modification can be completed in one step, and the complex process of subsequent modification is avoided.
(3) The metal-supported carbon-based fiber structure catalyst provided by the embodiment of the invention can realize electrochemical CO 2 Synergistic capture and in situ conversion with CO 2 Capturing and converting, wherein the high-activity C=O quinone structure of the carbon-based fiber structure has excellent carbon capturing capability, and can optimize CO 2 Is beneficial to CO capture by adsorption 2 Remarkably strengthen CO 2 Also increases the residence time of the CO intermediate on the Cu surface, promotes C-C couplingFor electrochemical CO 2 Capturing and in situ conversion to produce ethylene products exhibits excellent properties.
Drawings
Fig. 1 is a TEM image of cu@c=o prepared in example 1 of the present invention;
fig. 2 is a TEM image of co@c=o prepared in example 2 of the present invention.
Fig. 3 is a TEM image of ni@c=o obtained in example 3 of the present invention.
Fig. 4 is a CO 2-adsorption drawing of cu@c=o, cu@c, c=o and C prepared in example 1 and comparative example 1, comparative example 2 and comparative example 3 according to the present invention.
FIG. 5 shows the Cu@C=O electrochemical CO obtained in example 1 of the present invention 2 Conversion different product faraday efficiency profiles of c2+ and ethylene obtained at different current densities.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The embodiment of the invention provides a preparation method of a metal-supported carbon-based fiber structure catalyst, which comprises the following steps:
(1) Uniformly mixing Polyacrylonitrile (PAN) and divalent soluble metal salt in a solvent so as to obtain an electrostatic spinning solution;
(2) Placing the electrostatic spinning solution into an electrostatic spinning device for electrostatic spinning, and collecting to obtain electrostatic spinning fibers;
(3) Calcining the electrospun fibers to obtain the metal-supported carbon-based fiber structured catalyst.
In this example, in step (1), the polyacrylonitrile and the divalent soluble metal salt are uniformly mixed in a solvent, wherein the solvent can be selected from N, N-Dimethylformamide (DMF), and specifically, PAN is added into a sealed bottle filled with the solvent, stirred at room temperature for 24 hours for complete dissolution, and then the divalent soluble metal salt is added into the above mixed solution, and stirred at room temperature for 24 hours to obtain the electrostatic spinning solution.
In an alternative embodiment, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the divalent soluble metal salt is at least one selected from soluble copper salt, cobalt salt, nickel salt and zinc salt;
optionally, the divalent soluble metal salt is selected from at least one of the chlorides, nitrates, sulphates or acetates of copper, cobalt, nickel and/or zinc;
optionally, the weight percentage of metal nanoparticles formed from the divalent soluble metal salt in a metal supported carbon based fiber structure catalyst is 5% -20%.
In the selected example, the bivalent soluble metal salt is preferably copper salt, the Cu nano-crystallite structure in the transition metal material has higher grain boundary density and defect potential energy to optimize the binding energy of reaction intermediates such as CO and the like, and the chemical stability of the Cu crystallite structure is stronger and is often used as a base metal for stabilizing single atoms of the transition metal.
In an alternative embodiment, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the mass concentration of the polyacrylonitrile in the electrostatic spinning solution is 8wt% -15 wt%;
optionally, the solvent is N, N-dimethylformamide.
In this embodiment of the present invention, the process is performed,
in an alternative embodiment, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the condition of electrostatic spinning is that the temperature is 20-40 ℃, the humidity is 15-35%, the advancing rate is 0.2-2ml/min, and the spinning voltage is 10-20V.
In the embodiment, the electrostatic spinning device can adopt a common spinning device, in the embodiment, a 10m injector with a 20G needle is adopted for spinning, the advancing rate of the spinning solution is 0.5mL/h, and the spinning voltage is 20kV.
In an alternative embodiment, a method for preparing a metal supported carbon-based fiber structure catalyst further comprises: and collecting the electrostatic spinning fiber by adopting aluminum foil paper at a fixed receiving distance of 12-20cm, and drying the collected electrostatic spinning fiber at room temperature for 24-72h.
In this example, the collection of the electrospun fibers is not limited to aluminum foil, so long as the collection of the electrospun fibers is facilitated, the collection conditions may be determined according to specific needs, the receiving distance in this embodiment is 18cm, the ambient temperature is 25 ℃, and the humidity is 25±5%. The collected electrospun fibers are air dried at room temperature for 24-72 hours, preferably air dried at 40 ℃ for 24 hours.
In an alternative embodiment, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the temperature rising rate of the calcination is 2 ℃/min-10 ℃/min, the temperature is 700-1000 ℃, and the calcination time is 0.1-5h;
optionally, the calcined atmosphere is one or a mixture of two of carbon dioxide and argon.
In an alternative embodiment, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the calcination is to heat up to 600 ℃ at a heating rate of 10 ℃/min for 1-2h, heat up to 700 ℃ at a heating rate of 5 ℃/min for 0.5-1h, and heat up to 700-1000 ℃ at a heating rate of 2 ℃/min for 5-10min.
In an alternative embodiment, in the preparation method of the metal-supported carbon-based fiber structure catalyst, the calcination is that the temperature is firstly increased to 600 ℃ in argon atmosphere at a heating rate of 10 ℃/min, and then is kept for 1-2 hours, and then is carried out in CO at a heating rate of 5 ℃/min 2 Heating to 700 ℃ in the atmosphere, preserving heat for 0.5-1h, and finally heating at a heating rate of 2 ℃/min in CO 2 Calcining at 700-1000 deg.C for 5-10min.
In this embodiment, the electrospun fiber may be calcined in a tube furnace using staged atmosphere control, and the metal nanoparticles formed during the calcination process of the divalent soluble metal salt are uniformly dispersed in the carbon-based fiber structure. In this example, the specific calcination conditions were first warmed up to 600℃in Ar atmosphere at a warming up rate of 10℃per minute for 2 hours, and then warmed up to CO at a warming up rate of 5℃per minute 2 Heating from 600 ℃ to 700 ℃ in the atmosphere for 0.5h, and finally heating at the rate of 2 ℃/min in CO 2 Heating from 700 ℃ to 900 ℃ in the atmosphere, preserving heat for 10min, and keeping Ar and CO 2 The flow rate of (2) was 30sccm.
The invention also provides a metal-supported carbon-based fiber structure catalyst, which is prepared by adopting any one of the methods.
In this embodiment, when the divalent soluble metal salt is a soluble copper salt, the metal-supported carbon-based fiber structure catalyst includes Cu nanoparticles and a carbon-based fiber structure, and when the metal-supported carbon-based fiber structure is prepared, an oxygen-containing group can be modified on the surface of the carbon-based fiber, so that the preparation and modification are completed in one step, and a complex process of subsequent modification is avoided.
The invention also provides the electrochemical CO of the metal-loaded carbon-based fiber structure catalyst 2 Use of the metal-supported carbon-based fiber structured catalyst in synergy of capture and in situ conversion, optionally, for CO realization by electrocatalysis 2 Capturing and in situ conversion.
In the embodiment, the metal-supported carbon-based fiber structure catalyst is applied to the electrochemical mode to realize CO2 capture and in-situ conversion, and the specific operation is that the metal-supported carbon-based fiber structure catalyst is coated on a gas diffusion electrode at normal temperature to serve as a working electrode, mercury-oxidized mercury serves as a reference electrode, a platinum sheet serves as a counter electrode, and potassium hydroxide solution serves as electrolyte to carry out electrochemical CO in a flowing electrolytic cell 2 In situ capture and transformation studies.
In this example, the metal supported carbon-based fiber structured catalyst has CO 2 Capturing and converting, wherein the high-activity C=O quinone structure of the carbon-based fiber structure has excellent carbon capturing capability, and can optimize CO 2 Is beneficial to CO capture by adsorption 2 Remarkably strengthen CO 2 Also increases the formation of CO intermediates, promotes C-C coupling, for electrochemical CO 2 Capturing and in situ conversion to produce ethylene products exhibits excellent properties.
The preparation method of the metal-supported carbon-based fiber structure catalyst provided by the invention is further explained by specific preparation examples and comparative examples.
Examples
Comparative example
Example 1
As shown in fig. 1, the present embodiment provides a metal-supported carbon-based fiber structural catalyst, which is prepared by a preparation method comprising the following specific steps:
(1) 1.0g of PAN was weighed into a 50ml sealed bottle containing 10g of DMF and stirred at room temperature for 24 hours to dissolve it sufficiently, and then 1.0g of Cu (CO 2 CH 3 )2·H 2 Adding O into the spinning solution, and continuing stirring at room temperature for 24 hours to obtain electrostatic spinning solution;
(2) Injecting the electrostatic spinning solution into a 10ml injector and preparing a 20G needle head for electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the advancing rate of the spinning solution is 0.5mL/h, the spinning voltage is 20kV, the receiving distance is 18cm, the electrostatic spinning fiber is collected by aluminum foil paper, the ambient temperature is 25 ℃, and the humidity is 25+/-5%;
(3) Drying the spinning fiber in a blast drying oven at 40 ℃ for 24 hours, weighing 250mg of the spinning fiber, placing the spinning fiber in a high-temperature area of a tube furnace, and calcining in a sectional heating atmosphere regulation mode, namely: heating to 600 ℃ in Ar atmosphere at a heating rate of 10 ℃/min, preserving heat for 2 hours, and then heating to CO at a heating rate of 5 ℃/min 2 Heating from 600 ℃ to 700 ℃ in the atmosphere for 0.5h, and finally heating at the rate of 2 ℃/min in CO 2 Calcining for 10min from 700 ℃ to 900 ℃ in the atmosphere, and maintaining Ar and CO in the step (3) 2 The flow rate of (2) was 30sccm; and then cooling the system to room temperature to obtain the metal-supported carbon-based fiber structure catalyst, which is marked as Cu@C=O.
In this embodiment, fig. 1 is a cu@c=o TEM transmission electron micrograph, and the carbon-based fiber structure has a unique porosityThe structure is that Cu nano particles are uniformly limited in the carbon-based fiber structure. The thickness of the graphene-like shell layer on the surface of the Cu nano particle is about 4-5 nm. The metal-supported carbon-based fiber structure catalyst obtained by adopting the preparation method comprises Cu nano particles and a carbon-based fiber structure, and the Cu nano particles are uniformly dispersed in the carbon-based fiber structure to form the metal-supported carbon-based fiber structure catalyst with stable structure, and the catalyst has the advantages of high repeatability, high loading efficiency, good size controllability and contribution to improving the CO content of the catalyst 2 Catalytic performance during capture and conversion.
Example 2
As shown in fig. 2, the present embodiment provides a composite metal oxide catalyst, which is prepared by a preparation method comprising the following specific steps:
(1) 1.0g PAN was weighed into a 50ml sealed bottle containing 10g DMF and stirred at room temperature for 24 hours to dissolve thoroughly, and then 1.0g Co (CO 2 CH 3) 2.4H2O is added into the spinning solution, and stirring is continued at room temperature for 24 hours to obtain electrostatic spinning solution;
(2) Injecting the spinning solution into a 10ml injector and preparing a 20G needle head for electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the advancing rate of the spinning solution is 0.5mL/h, the spinning voltage is 20kV, the receiving distance is 18cm, the electrostatic spinning fiber is collected by aluminum foil paper, the ambient temperature is 25 ℃, and the humidity is 25+/-5%;
(3) Drying the spinning fiber in a blast drying oven at 40 ℃ for 24 hours, weighing 250mg of the spinning fiber, placing the spinning fiber in a high-temperature area of a tube furnace, and calcining in a sectional heating atmosphere regulation mode, namely: heating to 600 ℃ in Ar atmosphere at a heating rate of 10 ℃/min, preserving heat for 2 hours, and then heating to CO at a heating rate of 5 ℃/min 2 Heating from 600 ℃ to 700 ℃ in the atmosphere for 0.5h, and finally heating at the rate of 2 ℃/min in CO 2 Calcining for 10min from 700 ℃ to 900 ℃ in the atmosphere, and maintaining Ar and CO in the step (3) 2 The flow rate of (2) was 30sccm; and then cooling the system to room temperature to obtain the metal-supported carbon-based fiber structure catalyst, which is denoted as Co@C=O.
In this embodiment, fig. 2 is a co@c=o transmission electron microscope image, and it can be seen from the image that the carbon-based fiber structure has a unique porous structure, and the Co nanoparticles are uniformly confined in the carbon-based fiber structure, and the thickness of the graphene-like shell layer on the surface of the Co nanoparticles is about 4-5 nm. The metal-supported carbon-based fiber structure catalyst obtained by adopting the preparation method comprises Co nano particles and a carbon-based fiber structure, the Co nano particles are uniformly dispersed in the carbon-based fiber structure to form the metal-supported carbon-based fiber structure catalyst with stable structure, the loading efficiency is high, the size controllability is good, the catalytic performance is improved, and the catalyst with better stability can be obtained by adopting the metal salt of Co as the bivalent soluble metal salt in the embodiment.
Example 3
As shown in fig. 3, the present embodiment provides a composite metal oxide catalyst, which is prepared by a preparation method comprising the following specific steps:
(1) 1.0g of PAN is weighed and added into a 50ml sealed bottle filled with 10g of DMF, stirring is carried out at room temperature for 24 hours to fully dissolve the PAN, then 1.0g of Ni (OCOCOCH 3) 2.4H2O is added into the spinning solution, and stirring is carried out at room temperature for 24 hours to obtain electrostatic spinning solution;
(2) Injecting the spinning solution into a 10ml injector and preparing a 20G needle head for electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the advancing rate of the spinning solution is 0.5mL/h, the spinning voltage is 20kV, the receiving distance is 18cm, the electrostatic spinning fiber is collected by aluminum foil paper, the ambient temperature is 25 ℃, and the humidity is 25+/-5%;
(3) Drying the spinning fiber in a blast drying oven at 40 ℃ for 24 hours, weighing 250mg of the spinning fiber, placing the spinning fiber in a high-temperature area of a tube furnace, and calcining in a sectional heating atmosphere regulation mode, namely: heating to 600 ℃ in Ar atmosphere at a heating rate of 10 ℃/min, preserving heat for 2 hours, and then heating to CO at a heating rate of 5 ℃/min 2 Heating from 600 ℃ to 700 ℃ in the atmosphere for 0.5h, and finally heating at the rate of 2 ℃/min in CO 2 Calcining for 10min from 700 ℃ to 900 ℃ in the atmosphere, and maintaining Ar and CO in the step (3) 2 The flow rate of (2) was 30sccm; then cooling the system to room temperature to obtain the metalThe supported carbon-based fiber structure catalyst was noted as ni@c=o.
In this embodiment, as shown in fig. 3, a transmission electron microscope image of ni@c=o is shown, and it can be obtained from the image that the carbon-based fiber structure has a unique porous structure, and the Ni nanoparticles are uniformly confined in the carbon-based fiber structure, and the thickness of the graphene-like shell layer on the surface of the Ni nanoparticles is about 4-5 nm. Namely, the metal-supported carbon-based fiber structure catalyst obtained by adopting the preparation method comprises Co nano particles and a carbon-based fiber structure, ni nano particles are uniformly dispersed in the carbon-based fiber structure to form the metal-supported carbon-based fiber structure catalyst with stable structure, the loading efficiency is high, the size controllability is good, the catalyst with better stability can be obtained by adopting the metal salt of Ni as the bivalent soluble metal salt in the embodiment, namely, the preparation method of the metal-supported carbon-based fiber structure catalyst has good universality, is suitable for Cu, co, ni and other metals, namely, the preparation method of the metal-supported carbon-based fiber structure catalyst has high universality, is suitable for various metals, has high repeatability, and is beneficial to large-scale production
Comparative example 1
The comparative example provides a metal-supported carbon-based fiber structure catalyst, which is prepared by a preparation method comprising the following specific steps:
(1) 1.0g PAN was weighed into a 50ml sealed bottle containing 10g DMF and stirred at room temperature for 24 hours to dissolve it sufficiently, and then 1.0g Cu (CO) 2 CH3)2·H 2 Adding O into the spinning solution, and continuing stirring at room temperature for 24 hours to obtain electrostatic spinning solution;
(2) Injecting the spinning solution into a 10ml injector and preparing a 20G needle head for electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the advancing rate of the spinning solution is 0.5mL/h, the spinning voltage is 20kV, the receiving distance is 18cm, the electrostatic spinning fiber is collected by aluminum foil paper, the ambient temperature is 25 ℃, and the humidity is 25+/-5%;
(3) Drying the spinning fiber in a blast drying oven at 40 ℃ for 24 hours, weighing 250mg of the spinning fiber, placing the spinning fiber in a high-temperature area of a tube furnace, and calcining in a sectional heating atmosphere regulation mode, namely: heating to 600 ℃ in Ar atmosphere at a heating rate of 10 ℃/min for 2 hours, heating to 700 ℃ from 600 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 0.5 hours, and calcining for 10 minutes from 900 ℃ to 700 ℃ in Ar atmosphere at a heating rate of 2 ℃/min, wherein in the step (3), the flow rate of Ar is kept at 30sccm; and then cooling the system to room temperature to obtain the metal-supported carbon-based fiber structure catalyst, which is marked as Cu@C.
Comparative example 1 is different from example 1 in that in the calcination process in the sectional temperature-raising atmosphere control manner, the three-stage calcination atmosphere in the comparative example is Ar gas, the obtained catalyst is Cu@C, the first-stage temperature-raising atmosphere in example 1 is Ar, and the two-stage and three-stage temperature-raising atmospheres are CO 2 The catalyst obtained was cu@c=o, i.e. CO was demonstrated 2 The atmosphere regulation can form a C=O high-activity oxygen-containing functional group structure on the surface of the carbon-based fiber structure, the C=O structure is not affected after metal loading, and the simple Ar atmosphere is unfavorable for the formation of the C=O high-activity oxygen-containing functional group structure.
Comparative example 2
The comparative example provides a metal-supported carbon-based fiber structure catalyst, which is prepared by a preparation method comprising the following specific steps:
(1) 1.0g PAN was weighed into a 50ml sealed bottle containing 10g DMF and stirred at room temperature for 24h to be fully dissolved;
(2) Injecting the spinning solution into a 10ml injector and preparing a 20G needle head for electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the advancing rate of the spinning solution is 0.5mL/h, the spinning voltage is 20kV, the receiving distance is 18cm, the electrostatic spinning fiber is collected by aluminum foil paper, the ambient temperature is 25 ℃, and the humidity is 25+/-5%;
(3) Drying the spinning fiber in a blast drying oven at 40 ℃ for 24 hours, weighing 250mg of the spinning fiber, placing the spinning fiber in a high-temperature area of a tube furnace, and calcining in a sectional heating atmosphere regulation mode, namely: heating to 600 ℃ in Ar atmosphere at a heating rate of 10 ℃/min, preserving heat for 2 hours, and then heating to CO at a heating rate of 5 ℃/min 2 Heating from 600 ℃ to 700 ℃ in the atmosphere for 0.5h, and finally heating at the rate of 2 ℃/min in CO 2 Calcining for 10min from 700 ℃ to 900 ℃ in the atmosphere, in the step (3),maintaining CO 2 And Ar has a flow rate of 30sccm; and then cooling the system to room temperature to obtain the metal-supported carbon-based fiber structure catalyst, which is marked as C=O.
Comparative example 2 in comparison with example 1, comparative example 1 did not participate in the soluble metal salt and thus did not form a metal-supported carbon-based fiber structure, and the catalyst obtained was c=o.
Comparative example 3
The comparative example provides a metal-supported carbon-based fiber structure catalyst, which is prepared by a preparation method comprising the following specific steps:
(1) 1.0g PAN was weighed into a 50ml sealed bottle containing 10g DMF and stirred at room temperature for 24h to be fully dissolved;
(2) Injecting the spinning solution into a 10ml injector and preparing a 20G needle head for electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the advancing rate of the spinning solution is 0.5mL/h, the spinning voltage is 20kV, the receiving distance is 18cm, the electrostatic spinning fiber is collected by aluminum foil paper, the ambient temperature is 25 ℃, and the humidity is 25+/-5%;
(3) Drying the spinning fiber in a blast drying oven at 40 ℃ for 24 hours, weighing 250mg of the spinning fiber, placing the spinning fiber in a high-temperature area of a tube furnace, and calcining in a sectional heating atmosphere regulation mode, namely: heating to 600 ℃ in Ar atmosphere at a heating rate of 10 ℃/min, preserving heat for 2 hours, and then heating to CO at a heating rate of 5 ℃/min 2 Heating from 600 ℃ to 700 ℃ in the atmosphere, preserving heat for 0.5h, and finally heating from 700 ℃ to 900 ℃ in Ar atmosphere at a heating rate of 2 ℃/min for calcination for 10min, wherein in the step (3), the flow rate of Ar is kept at 30sccm; and then cooling the system to room temperature to obtain the metal-supported carbon-based fiber structure catalyst, which is marked as C.
Comparative example 3 compared with comparative example 2, the first two stages of the calcination and the temperature increase process were the same as those of comparative example 2, the catalyst obtained in the Ar atmosphere of comparative example 3 in the third stage was C, the catalyst obtained in the CO2 atmosphere of comparative example 2 was c=o, and CO was again demonstrated 2 Atmosphere control can form a structure with C=O high-activity oxygen-containing functional groups on the surface of the carbon-based fiber structure.
In summary, in the examples and comparative examples, we performed CV scansIt was found that only example 1 and comparative example 2 showed redox peaks at 0.41V and 0.49V (compared to reversible hydrogen electrode) to demonstrate CO 2 The atmosphere induction can introduce high-activity oxygen-containing functional groups (C=O quinone structures) on the surface of the carbon fiber.
In the examples and comparative examples, the c=o quinone structure vs. CO is demonstrated by fig. 4 2 Has capturing capability.
CO shown in FIG. 4 2 Adsorption of CO by respective Cu@C=O, cu@C, C=O and C catalysts 2 Physical adsorption tests show that under the same condition, the carbon fiber catalyst CO with the C=O quinone structure is constructed 2 The adsorption capacity is obviously increased, which indicates that C=O quinone structural carbon fiber and CO 2 The molecules have stronger interaction, namely, the C=O quinone structure can effectively capture and activate CO2 molecules, and reduce the reaction energy barrier of the molecules.
Application example
Cu@c=o provided in example 1 and comparative examples 1, 2 and 3 were used for electrochemical CO 2 The test is carried out by taking the capturing and in-situ conversion of ethylene as an example, and electrochemical CO 2 The capture and in situ conversion process is carried out in a flow cell with an anion exchange membrane as a membrane, the specific steps are as follows:
coating the metal-supported carbon-based fiber structure catalyst on a gas diffusion electrode to serve as a working electrode, wherein a platinum sheet electrode is used as an anode, a mercury-mercury oxide electrode is used as a reference electrode, and potassium hydroxide solution is used as cathode/anode chamber electrolyte to carry out electrochemical CO in a flowing electrolytic cell 2 In situ capture and transformation studies.
Then constant current of 100-500mA cm < -2 > and whole CO 2 The flow rate was 50sccm, the catholyte circulation flow rate was 10sccm, the anolyte circulation flow rate was 200sccm, and the reaction was carried out at 25℃for 1 hour. After 1h of reaction, detection of electrochemical products was performed.
In this application example, the specific preparation method of the working electrode is as follows: mixing 5mg of the catalyst with 470 isopropanol, respectively, and subjecting the obtained mixed solution to ultrasonic treatment at room temperature for 35min to form uniform solutions, and adding the uniform solutions20 mu L of 5wt% Nafion solution is dripped, and the ultrasonic treatment is continued for 40min, so as to obtain catalyst slurry. Then 100 mu L of catalyst slurry is dripped on the gas diffusion electrode by using a pipetting gun, and the catalyst slurry is dried under an infrared baking lamp to finish the manufacture of the working electrode. The effective area of the working electrode (cathode) is 1cm 2 In the working electrode, the loading of the catalyst was 1mg cm-2.
In this example, the KOH electrolyte was a 1M solution having a volume of 30 mL.
In this application example, the faraday efficiency of the product obtained by the cu@c=o catalyst prepared in example 1 at different current densities is shown in fig. 5, from which it can be seen that the faraday efficiency of the multi-carbon product (c2+) is significantly improved with increasing current density, and at a current density of 400mA cm -2 When the total faradaic efficiency of the carbon two product is greater than 73%, the faradaic efficiency of ethylene is as high as 63%.
For the Cu@C catalyst prepared in comparative example 1, after 1 hour of reaction, the total Faraday efficiency of C2+ was less than 30% at a current density of 400mA cm-2, with methane having a Faraday efficiency as high as 55%.
For the c=o catalyst prepared in comparative example 2, after 1 hour of reaction, at a current density of 400mA cm "2, some CO was generated, and the faraday efficiency of CO was more than 30%.
For the catalyst C prepared in comparative example 3, only a trace amount of CO and H were produced at a current density of 400mA cm-2 after 1 hour of reaction 2 The faraday efficiency of (2) is greater than 80%.
Faraday efficiency
As can be seen from the above table, the catalyst obtained by the preparation method of the metal-supported carbon-based fiber structure catalyst in example 1 is Cu@C=O, the divalent soluble metal salt of Cu is added into the mixed reagent of PAN and DMF, and the second section and the third section are placed in CO during the three-section calcination 2 Faraday catalyst obtained by calcination in atmosphereThe efficiency is highest. Next, comparative example 1, in which all of them were placed in Ar, the Faraday efficiency was slightly weak because of CO 2 Atmosphere regulation can form a C=O high-activity oxygen-containing functional group structure on the surface of the carbon-based fiber structure, which is unfavorable for forming the C=O structure, and can optimize CO 2 Is beneficial to CO capture by adsorption 2 Increase the formation of CO intermediate, which is beneficial to electrochemical CO 2 Captured and transformed in situ. Compared with comparative example 2, in comparative example 3, the carbon capturing capability is too weak due to the fact that the C=O high-activity oxygen-containing functional group structure is not provided, the CO Faraday efficiency is extremely low, the metal catalyst is loaded on the carbon-based fiber structure, and the intermediate CO is enriched on the surface of the metal Cu due to the excellent CO2 capturing capability, so that the concentration of local CO is improved, and the C-C coupling is promoted to improve the C2 Faraday efficiency.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the metal-supported carbon-based fiber structure catalyst is characterized by comprising the following steps of:
(1) Uniformly mixing polyacrylonitrile and divalent soluble metal salt in a solvent so as to obtain electrostatic spinning solution;
(2) Placing the electrostatic spinning solution into an electrostatic spinning device for electrostatic spinning, and collecting to obtain electrostatic spinning fibers;
(3) Calcining the electrospun fibers to obtain the metal-supported carbon-based fiber structured catalyst.
2. The method for preparing the metal-supported carbon-based fiber structure catalyst according to claim 1, wherein the divalent soluble metal salt is at least one selected from soluble copper salt, cobalt salt and nickel salt;
optionally, the divalent soluble metal salt is selected from at least one of copper, cobalt, nickel and/or zinc chloride, nitrate, sulfate or acetate;
optionally, the metal-supported carbon-based fiber structure catalyst comprises 5-20% by weight of metal nanoparticles formed from the divalent soluble metal salt.
3. The method for preparing a metal-supported carbon-based fiber structure catalyst according to claim 1, wherein the mass concentration of the polyacrylonitrile in the electrostatic spinning solution is 8wt% -15 wt%;
optionally, the solvent is N, N-dimethylformamide.
4. The method for preparing the metal-supported carbon-based fiber structure catalyst according to claim 1, wherein the condition of electrostatic spinning is that the temperature is 20-40 ℃, the humidity is 15-35%, the advancing rate is 0.2-2ml/min, and the spinning voltage is 10-20V.
5. The method for preparing a metal-supported carbon-based fiber structure catalyst according to claim 4, further comprising: and collecting the electrostatic spinning fiber by adopting aluminum foil paper at a fixed receiving distance of 12-20cm, and drying the collected electrostatic spinning fiber at room temperature for 24-72h.
6. The method for preparing a metal-supported carbon-based fiber structure catalyst according to claim 1, wherein the temperature rise rate of the calcination is 2 ℃/min-10 ℃/min, the temperature is 700-1000 ℃, and the calcination time is 0.1-5h;
optionally, the calcined atmosphere is one or a mixture of two of carbon dioxide and argon.
7. The method for preparing the metal-supported carbon-based fiber structure catalyst according to claim 1, wherein the calcination is performed by heating to 600 ℃ at a heating rate of 10 ℃/min for 1-2 hours, heating to 700 ℃ at a heating rate of 5 ℃/min for 0.5-1 hour, and heating to 700-1000 ℃ at a heating rate of 2 ℃/min for 5-10 minutes.
8. The method for preparing a metal-supported carbon-based fiber structure catalyst according to claim 1, wherein the calcination is performed by heating to 600 ℃ in an argon atmosphere at a heating rate of 10 ℃/min for 1-2 hours, and heating to CO at a heating rate of 5 ℃/min 2 Heating to 700 ℃ in the atmosphere, preserving heat for 0.5-1h, and finally heating at a heating rate of 2 ℃/min in CO 2 Calcining at 700-1000 deg.C for 5-10min.
9. A metal-supported carbon-based fiber structured catalyst, characterized in that the metal-supported carbon-based fiber structured catalyst is prepared by the method of any one of claims 1 to 8.
10. A metal-supported carbon-based fiber structured catalyst as claimed in claim 9 in electrochemical CO 2 The use of capture in conjunction with in situ conversion, characterized in that,
optionally, the metal-supported carbon-based fiber structure catalyst may be used to achieve CO by electrocatalysis 2 Capturing and in situ conversion.
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