CN111215146B - Group-modified noble metal-based carbon dioxide electro-reduction catalyst and preparation method and application thereof - Google Patents
Group-modified noble metal-based carbon dioxide electro-reduction catalyst and preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 97
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005977 Ethylene Substances 0.000 claims abstract description 37
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 8
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- 238000000576 coating method Methods 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims description 27
- 229920000767 polyaniline Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 12
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 12
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- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010931 gold Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 9
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- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
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- 230000004048 modification Effects 0.000 description 16
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- 238000005868 electrolysis reaction Methods 0.000 description 9
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- -1 amino, hydroxyl Chemical group 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
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- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C25B3/25—Reduction
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Abstract
The invention discloses a group-modified noble metal-based carbon dioxide electro-reduction catalyst, and a preparation method and application thereof. The group-modified noble metal-based carbon dioxide electro-reduction catalyst is formed by coating a noble metal substrate with a conductive polymer. The group-modified noble metal-based carbon dioxide electro-reduction catalyst is applied to electro-catalysis of CO2Reduction process, can catalyze CO2Reducing to ethylene, thereby changing the characteristic that noble metal catalysts (e.g., silver-based catalysts) can only catalyze carbon dioxide to produce CO.
Description
Technical Field
The invention relates to a catalyst for electrocatalytic reduction of carbon dioxide, in particular to a conductive polymer modified noble metal-based carbon dioxide electroreduction catalyst, a method for preparing the conductive polymer modified noble metal-based carbon dioxide electroreduction catalyst by in-situ polymerization, and the conductive polymer modified noble metal-based carbon dioxide electroreduction catalyst used as the catalyst for electrocatalytic reduction of carbon dioxide to reduce CO2A method for synthesizing ethylene with high selectivity, belonging to the greenhouse gas emission reduction and resource utilizationAnd the synthesis and application fields of electrocatalytic materials.
Background
Fossil fuels have become a major source of human energy since the industrial revolution in the sixties of the eighteenth century. Fossil fuels in nature may be exhausted by humans in their entirety for hundreds of years. Meanwhile, the environmental impact of the products of fossil fuel combustion, greenhouse gases represented by carbon dioxide, is also becoming more and more significant. The world weather organization (WMO) global atmospheric monitoring system collects observation data showing the present atmospheric CO2The concentration was 145% of the pre-industrial level. The greenhouse effect will have a series of disastrous consequences, such as: glacier melting and sea level rising; exacerbation of the early effects, frequent extreme weather; plant diseases and insect pests, reduced yield of grains, global drought and the like.
Compared with other greenhouse gas treatment means, the electrocatalytic reduction of carbon dioxide has many advantages: firstly, the existing carbon dioxide can be used as a raw material, the carbon dioxide does not need to be prepared again, and the energy problem and the environmental problem are solved; secondly, the reaction condition is mild and controllable; thirdly, the variety of the reduction product can be artificially controlled to obtain the required product.
The catalyst for carbon dioxide electroreduction also presents specificity due to the difference of adsorption strength of the catalyst to CO intermediate and H intermediate. Such as: a metal catalyst represented by tin, lead, bismuth, cobalt, mercury, and indium tends to reduce carbon dioxide to formic acid; noble metals such as gold, silver, palladium, etc. tend to reduce carbon dioxide to carbon monoxide. The reduction of carbon dioxide to hydrocarbons with higher value and energy density (e.g., ethylene) is more valuable than formic acid and carbon monoxide. Copper is currently the only metal electrocatalyst capable of reducing carbon dioxide to hydrocarbons due to its unique binding energy with reaction intermediates.
Although hydrocarbons have a higher industrial added value than other reduction products, the synthesis of hydrocarbons involves multiple electron transfer and is more difficult to achieve. Thus, carbon dioxide is reduced to ethylene (2 CO)2+12H++12e-→C2H4+4H2O) is a research with wide prospect, and the research can realize the emission reduction of greenhouse gases and the conversion of high value-added chemical products. The catalyst capable of generating ethylene by electrocatalysis of carbon dioxide has fewer types, and the current catalyst with ethylene selectivity is mainly concentrated on a copper catalyst. For other metals, CO is catalyzed2Reduction to ethylene still lacks effective means. Therefore, it is of practical significance to develop a catalyst capable of reducing carbon dioxide to ethylene and to broaden the selection range of the catalyst.
Disclosure of Invention
According to the problem that only carbon monoxide can be specifically generated when noble metals represented by silver are used as carbon dioxide electro-catalytic reduction catalysts in the prior art, the first purpose of the invention is to provide a carbon dioxide electro-reduction catalyst which can selectively and electrically reduce carbon dioxide into ethylene products with more values than formic acid, carbon monoxide and the like, the catalyst thoroughly solves the technical problem that the existing silver-based noble metal catalysts can only electrically reduce carbon dioxide to generate carbon monoxide but cannot generate hydrocarbons with high added values, and the carbon dioxide electro-reduction catalyst shows the characteristics of stable performance and controllable product types in the catalytic conversion process of carbon dioxide and has higher application value.
The second purpose of the invention is to develop a method for preparing the group-modified noble metal-based carbon dioxide electro-reduction catalyst, which has the advantages of simple synthesis, low cost and mild reaction conditions.
The third purpose of the invention is to provide the application of the group-modified noble metal-based carbon dioxide electro-catalytic reduction catalyst in the electro-catalytic reduction of carbon dioxide, which can carry out the electro-catalytic reduction of carbon dioxide into ethylene with high selectivity.
In order to achieve the technical purpose, the invention provides a group-modified noble metal-based carbon dioxide electro-reduction catalyst which is formed by coating a noble metal substrate with a conductive polymer.
The present invention is directed to modifying an existing noble metal catalyst with a conductive polymer comprisingVarious functional groups, such as imidazole, amino, hydroxyl and the like, which can form coordinate bonds with the transition metal, so that the conductive polymer can be stably coated on the surface of the noble metal catalyst, and the stability of the noble metal catalyst is improved; in addition, a large number of experiments find that the groups are favorable for stabilizing intermediates such as carbon monoxide generated in the reduction process of the carbon dioxide, can promote the further hydrogenation of the carbon monoxide intermediates to form ethylene, has a remarkable adjusting effect on the catalytic selectivity of the noble metal catalyst, and can obviously improve the reduction of the carbon dioxide (CO)2RR) the selectivity of ethylene in the product changes the current situation that the noble metal catalyst can only carry out specific electrocatalytic reduction on carbon dioxide to generate carbon monoxide.
In a preferred embodiment, the noble metal substrate is nano silver or nano gold. The noble metal matrix is a common carbon dioxide electro-reduction catalyst type in the prior art, such as silver nanowires and the like. These noble metal catalysts are carbon dioxide electro-reduction catalysts that can electro-reduce carbon dioxide to carbon monoxide, which are common in the art.
In a preferred embodiment, the conductive polymer includes at least one functional group selected from imidazole, benzene ring, amino group, and hydroxyl group.
In a preferred embodiment, the conductive polymer is at least one of PIL (imidazole ring-containing ionic liquid polymer), PPL (polyphenol), and PANI (polyaniline).
Preferably, the mass ratio of the conductive polymer to the noble metal matrix is 1:100 to 40: 100. Within the preferred ratio range, it is ensured that the conductive polymer forms a relatively stable coating layer of a suitable thickness on the surface of the noble metal catalyst.
The invention also provides a preparation method of the group-modified noble metal-based carbon dioxide electro-reduction catalyst, which is characterized in that a conductive polymer monomer is generated by an in-situ polymerization method and is coated on the surface of the noble metal substrate. The in-situ polymerization method of conductive polymers such as PIL, PPL, PANI, etc. is a common polymerization method in the prior art, for example, a noble metal matrix is dispersed into a solution containing a conductive polymer monomer for oxidative polymerization, or the conductive polymer monomer and the noble metal matrix are mixed and then heated for polymerization, etc., so that the noble metal matrix wrapped by the PIL, the PPL, the PANI, etc. can be obtained.
The invention also provides an application of the group-modified noble metal-based carbon dioxide electro-reduction catalyst in electrocatalysis of CO2Reduction to produce ethylene.
Preferably, an electrode of the noble metal-based carbon dioxide electro-reduction catalyst modified by a supported group is used as a working electrode, a Pt sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, a potassium bicarbonate solution is used as an electrolyte, a proton exchange membrane is used for separating a cathode chamber and an anode chamber, and the cathode chamber is continuously exposed to CO2Gas, CO reduction at constant potential2. The electrolytic cell is an H-shaped electrolytic cell. The proton exchange membrane is a Nafion N117 membrane.
In the preferable scheme, the loading amount of the group-modified noble metal-based carbon dioxide electro-reduction catalyst in an electrode is 0.25-2.5 mg/cm2. The electrode may be a glassy carbon electrode or a carbon paper.
In a preferred embodiment, the reduction of CO by potentiostatic reduction2In the process, the potential control range is-1.0 to-2.2V, vs Ag/AgCl.
In a preferable scheme, the concentration of the potassium bicarbonate solution is 0.1-0.7 mol/L.
The group-modified noble metal-based carbon dioxide electro-reduction catalyst is applied to electro-catalysis of CO2The reaction mechanism for the reduction to ethylene:
first, carbon dioxide is reduced to carbon monoxide intermediates at the silver nanowire surface:
CO2(g)+H++2e-→COOH-；COOH-+H+→CO(adsorption state)+H2O；
If the carbon monoxide intermediate can not be stably adsorbed on the surface of the catalyst at this time, the carbon monoxide can be released in the form of gas products, which is the reason that the silver nanowires before modification can only generate carbon monoxide:
CO(adsorption state)→CO；
When a conductive polymer containing different groups is presentDuring the process, the polymer on the surface of the silver nanowire can stabilize a carbon monoxide intermediate and conduct protons, so that carbon monoxide has an opportunity to be coupled and hydrogenated, and the catalyst which can only generate carbon monoxide originally has the ability of generating ethylene: 2CO +8H+→C2H4+2H2O; the reaction process is schematically shown in FIG. 7.
The noble metal matrix of the invention is preferably silver nanowires (AgNWs), and compared with noble metal materials such as gold, palladium and the like, silver is relatively low in cost and easy to prepare. The invention takes the synthesis method of the silver nanowires as an example for explanation: mixing 40mL of ethylene glycol and 10mL of diethylene glycol, adding 0.66g of polyvinylpyrrolidone, adding 0.2mL of sodium chloride solution and sodium bromide solution after the solution is clarified, adding 0.54g of silver nitrate, heating the solution to 145 ℃, maintaining the temperature for 4 hours, and finally obtaining the silver nanowires through centrifugal separation.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) the invention adopts the group-modified noble metal-based carbon dioxide electro-reduction catalyst, can utilize imidazole, amino, hydroxyl and other groups on polymers such as PIL, PPL, PANI and the like to improve the catalytic selectivity of noble metal materials, and can effectively improve the selectivity of ethylene in carbon dioxide reduction products (under the same potential, the noble metal catalytic materials which do not produce ethylene originally can have the ability of producing ethylene).
2) According to the invention, the precious metal catalyst is wrapped and modified by the PIL, the PPL and the PANI, so that the chemical stability and the morphological stability of the precious metal material can be obviously improved, and the failure of the precious metal catalyst is prevented.
3) The preparation method of the group-modified noble metal-based carbon dioxide electro-reduction catalyst is easy to operate and low in cost.
Drawings
FIG. 1 shows XRD patterns of the noble metal-based carbon dioxide electro-reduction catalyst before radical modification (AgNWs) and after radical modification (AgNWs @ PIL) synthesized in example 1.
FIG. 2 is a TEM image of the noble metal-based carbon dioxide electro-reduction catalyst before (a) and after (b) the group modification synthesized in example 1.
FIG. 3 shows Raman spectra of the noble metal-based carbon dioxide electro-reduction catalyst synthesized in example 1 before the modification of the group (AgNWs) and after the modification of the group (AgNWs @ PIL).
FIG. 4 shows the shapes of noble metal-based carbon dioxide electroreduction catalysts before radical modification (AgNWs) and after radical modification (AgNWs @ PIL) synthesized in example 1.
FIG. 5 shows the ethylene selectivity (a) and the product concentration (b) at different potentials for the noble metal-based carbon dioxide electroreduction catalysts synthesized in example 1 before (AgNWs) and after (AgNWs @ PIL) group modification, and the ethylene selectivity (c) at a potential of-1.8V (vs Ag/AgCl) for the noble metal modified by the conductive polymer containing different groups.
FIG. 6 is a comparison of current densities of carbon dioxide electroreduction at-1.8V (vs Ag/AgCl) for noble metal-based catalysts synthesized in example 1 before radical modification (AgNWs) and after radical modification (AgNWs @ PIL).
Fig. 7 is a schematic diagram of a reaction process of reducing carbon dioxide into ethylene by using a noble metal carbon dioxide electro-reduction catalyst after group modification.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it. The invention also provides a method for controlling the operation of the device, and the device is suitable for the operation of the device.
Example 1
Preparing a PIL modified silver nanowire (AgNWs @ PIL) electrode and performing a carbon dioxide electro-catalytic reduction experiment.
1) Preparation of a PIL modified silver nanowire (AgNWs @ PIL) electrode:
the silver nanowire can be prepared by the following method: mixing 40mL of ethylene glycol and 10mL of diethylene glycol, adding 0.66g of polyvinylpyrrolidone, adding 0.2mL of sodium chloride solution and sodium bromide solution after the solution is clarified, adding 0.54g of silver nitrate, heating the solution to 145 ℃, maintaining the temperature for 4 hours, and finally obtaining the silver nanowires through centrifugal separation.
Adding 5g of styrene, 3g of 4-chloromethyl styrene and 0.08g of azobisisobutyronitrile into 7mL of chlorobenzene, reacting at 60 ℃ for 12h, adding methanol for precipitation, and drying the precipitate in vacuum. Putting the precipitate into 1-methylimidazole ionic liquid according to a certain mass ratio (the precipitate is that 1-methylimidazole is 2:1), adding the prepared silver nanowire into the 1-methylimidazole silver nanowire (the mass ratio of the 1-methylimidazole to the silver nanowire is 10:100), dissolving the mixture into N, N-dimethylformamide, and reacting at 115 ℃ for 24 hours to obtain AgNWs @ PIL.
5mg of the synthesized AgNWs @ PIL was taken. Adding 1mLN, N-dimethylformamide, adding 40ul Nafion solution, vibrating, and ultrasonically dispersing to obtain the dispersion of the AgNWs @ PIL. Then uniformly dripping more than 60uL of dispersion liquid on a round glassy carbon electrode with the diameter of 1cm (the loading amount is 0.25 mg/cm)2) And drying in vacuum at 60 ℃ to prepare the AgNWs @ PIL working electrode.
Combining the results of fig. 1 and fig. 2, the silver substrate was not oxidized before and after wrapping the PIL, and the nanowire structure was also intact, indicating that the preparation process of the material did not damage the substrate. By combining the results of fig. 2 and fig. 3, the apparent wrapping layer appears on the silver nanowire transmission electron microscope modified by the PIL, and the Raman spectrum of the silver nanowire modified by the PIL appears three distinct carbon peaks, which indicates that the surface of the silver nanowire is wrapped by the PIL.
Combining the results of fig. 4, silver nanowires can be intertwined, deformed, and agglomerated, which affects stability. The silver nanowire after the group modification has stable appearance.
And (3) electrolyzing and reducing the carbon dioxide under the condition of constant potential. The flow rate of carbon dioxide was controlled to 30mL/min using a mass flow meter. For obtaining higher selectivity of carbon dioxide reduction product, CO is reduced by constant potential2The potential of (b) is controlled to be-1.6V, -1.8V, -2.0V (vs Ag/AgCl), and the preferable concentration of the electrolyte potassium bicarbonate is 0.5 mol/L.
During electrolysis, the catalytic current on the electrodes was recorded by an electrochemical workstation and the carbon dioxide reduction gas phase product was measured on-line using gas chromatography. After 1h of electrolysis, the gaseous products were detected according to gas chromatography. AgNWs @ PIL electrode CO2And (3) electroreduction test:
the method for converting carbon dioxide into ethylene by using the AgNWs @ PIL electrode provided by the invention in an electrocatalytic manner is as follows: the AgNWs @ PIL electrode in example 1 was used as a working electrode, a 2X 2cm Pt electrode was used as a counter electrode, an Ag/AgCl electrode was used as a reference electrode, an H-type electrolytic cell was used to form a three-electrode system, a potassium bicarbonate solution was used as an electrolyte, a Nafion N117 membrane was used to separate a cathode chamber and an anode chamber, carbon dioxide gas was continuously introduced into the cathode chamber, and the Faraday efficiency of each gas-phase product was obtained at a constant concentration of the electrolyte and the amount of electricity consumed by electrolysis. Combining the results of fig. 5(a) and 5(b), the selectivity of AgNWs @ PIL to ethylene is improved, and can be effectively controlled according to the potential. Under the potentials of-1.6V, -1.8V and-2.0V, the Faraday efficiencies of AgNWs to ethylene are respectively as follows: 0%, 0.62%; the faradaic efficiencies of AgNWs @ PIL for ethylene were 2.50%, 14.05%, 6.28%, respectively, and the product concentrations of AgNWs ethylene were: 0ppm, 4.7 ppm; the product concentrations of AgNWs @ PIL ethylene were 3.60ppm, 71.19ppm, 36.61ppm, respectively; the results in conjunction with fig. 6 demonstrate that the AgNWs @ PIL electrode has a higher current density for electrocatalytic reduction of carbon dioxide, meaning that it has a higher catalytic activity, compared to typical silver-based catalytic materials.
In conclusion, the conductive polymer modification with the nitrogen-containing group can effectively improve the ability of the noble metal to catalyze the reduction of carbon dioxide to ethylene.
Example 2
Preparation of PPL (polypropylene random) modified silver nanowire (AgNWs @ PPL) electrode and carbon dioxide electro-catalytic reduction experiment
1) Preparation of PPL modified silver nanowire (AgNWs @ PPL) electrode
Silver nanowires used for polyphenol-wrapped silver nanowires (AgNWs @ PPL) can be prepared by the method described in example 1.
The PPL modified silver nanowire (AgNWs @ PPL) electrode working electrode is prepared by electrochemical oxidation. Sodium bicarbonate solution is adopted as electrolyte, aniline monomer is added into the electrolyte (the mass ratio of the monomer to silver is 10:100), and an electrode formed by dripping silver nanowires on the surface of glassy carbon or carbon paper and naturally drying is used as a positive electrode (the AgNWs loading is 0.25 mg/cm)2) Pt electrode as negative electrode at 2.0VAnd (3) performing constant potential electrochemical oxidation to directly obtain the silver nanowire working electrode wrapped by the PPL.
2) AgNWs @ PPL electrode CO2And (3) electroreduction test:
the AgNWs @ PPL electrode prepared above was used as a catalyst, and a carbon dioxide electrocatalytic reduction experiment was performed at a potential of-1.8V (vs Ag/AgCl) using the apparatus and experimental method of example 1. During electrolysis, the catalytic current on the electrodes was recorded by an electrochemical workstation and the carbon dioxide reduction gas phase product was measured on-line using gas chromatography. After 1h of electrolysis, the concentration of the gas product and the power consumption of the electrolysis are actually measured according to the gas chromatography, and the Faraday efficiency of each gas product is obtained. In conjunction with FIG. 5(c), the selectivity of AgNWs @ PPL to ethylene was increased (0.93% for the Faraday efficiency of AgNWs to ethylene and 5.56% for the Faraday efficiency of AgNWs @ PPL to ethylene at a voltage of-1.8V (vs Ag/AgCl)).
In conclusion, the conductive polymer modification containing benzene and hydroxyl can effectively improve the ability of noble metal to catalyze the reduction of carbon dioxide into ethylene.
Example 3
Preparation of PANI modified silver nanowire (AgNWs @ PANI) electrode and carbon dioxide electrocatalytic reduction experiment
2) Preparation of PANI modified silver nanowire (AgNWs @ PANI) electrode
Silver nanowires used for polyaniline-wrapped silver nanowires (AgNWs @ PANI) can be prepared by the method described in example 1.
The PANI modified silver nanowire (AgNWs @ PANI) electrode working electrode is prepared through electrochemical oxidation. Sodium bicarbonate solution is adopted as electrolyte, aniline monomer is added into the electrolyte (the mass ratio of the monomer to silver is 10:100), and an electrode formed by dripping silver nanowires on the surface of glassy carbon or carbon paper and naturally drying is used as a positive electrode (the AgNWs loading is 0.25 mg/cm)2) And the Pt electrode is used as a negative electrode to carry out constant potential electrochemical oxidation at the potential of 2.0V, so that the silver nanowire working electrode wrapped by the PANI can be directly obtained.
2) AgNWs @ PANI electrode CO2And (3) electroreduction test:
the AgNWs @ PANI electrode prepared above was used as a catalyst, and carbon dioxide electrocatalytic reduction experiments were performed at a potential of-1.8V (vs Ag/AgCl) using the apparatus and experimental method of example 1. During electrolysis, the catalytic current on the electrodes was recorded by an electrochemical workstation and the carbon dioxide reduction gas phase product was measured on-line using gas chromatography. After 1h of electrolysis, the concentration of the gas product and the power consumption of the electrolysis are actually measured according to the gas chromatography, and the Faraday efficiency of each gas product is obtained. In conjunction with FIG. 5(c), the selectivity of AgNWs @ PANI for ethylene was increased (0.93% for the Faraday efficiency of AgNWs for ethylene and 7.48% for the Faraday efficiency of AgNWs @ PANI for ethylene at a voltage of-1.8V (vs Ag/AgCl)).
In conclusion, the conductive polymer modification containing benzene and amino can effectively improve the ability of noble metal to catalyze the reduction of carbon dioxide into ethylene.
Claims (8)
1. The application of the group-modified noble metal-based carbon dioxide electro-reduction catalyst is characterized in that: application to electrocatalysis of CO2Reducing to generate ethylene; the group-modified noble metal-based carbon dioxide electro-reduction catalyst is formed by coating a noble metal substrate with a conductive polymer; the conductive polymer comprises at least one functional group of imidazole ring, benzene ring, amino and hydroxyl.
2. The use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 1, wherein: the noble metal substrate is nano silver or nano gold.
3. Use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 1 or 2, characterized in that: the conductive polymer is at least one of ionic liquid polymer PIL, polyphenol PPL and polyaniline PANI containing imidazole rings.
4. Use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 1 or 2, characterized in that: the mass ratio of the conductive polymer to the noble metal matrix is 1: 100-40: 100.
5. The use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 1, wherein: taking an electrode of a noble metal-based carbon dioxide electro-reduction catalyst modified by a load group as a working electrode, a Pt sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to form a three-electrode system, taking a potassium bicarbonate solution as an electrolyte, separating a cathode chamber and an anode chamber by using a proton exchange membrane, and continuously exposing CO into the cathode chamber2Gas, CO reduction at constant potential2。
6. The use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 5, wherein: the loading capacity of the group-modified noble metal-based carbon dioxide electro-reduction catalyst in an electrode is 0.25-2.5 mg/cm2。
7. The use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 5, wherein: the reduction of CO at constant potential2In the process, the potential control range is-1.0 to-2.2V, and vs. Ag/AgCl.
8. The use of a group-modified noble metal-based carbon dioxide electro-reduction catalyst according to claim 5, wherein: the concentration of the potassium bicarbonate solution is 0.1-0.7 mol/L.
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