CN115896848A - Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof - Google Patents
Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst, which comprises the following steps: dissolving zinc salt in a solvent, and adding a 2-methylimidazole solution to obtain a zinc-based metal organic framework precursor; then dispersing the precursor in a solvent containing 5-amino-1,2,3-thiadiazole to obtain a sulfur-doped zinc-based metal organic framework precursor; calcining to obtain nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atoms; sputtering a copper target to a polytetrafluoroethylene film to obtain a polytetrafluoroethylene film loaded copper nanoparticle substrate; spraying the dispersion liquid of nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms to the polytetrafluoroethylene film loaded with copper nanoparticlesAnd (3) obtaining the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper tandem catalyst on the surface of the particle substrate. The invention also discloses the catalyst prepared by the preparation method and the application of the catalyst as a working electrode in electrocatalysis of CO 2 The application in the reaction for preparing ethylene by reduction shows excellent electrochemical activity and selectivity.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and a preparation method and application thereof.
Background
The mass combustion of fossil fuels results in atmospheric carbon dioxide (CO) 2 ) Excessive accumulation of exhaust gas. CO reduction by electroreduction driven by the use of renewable clean electrical energy 2 The conversion to valuable chemicals is a promising process that not only reduces the build-up of atmospheric CO 2 And chemicals with high added value can also be produced. To date, researchers have been directed to electroreduction of CO 2 The preparation of catalysts for the production of C1 and C2 products has made a great deal of effort. CO, as a C1 product involving only two electron transfers, has the advantages of: (1) The reaction path is relatively simple, the thermodynamic potential of the reaction is low, and high-selectivity conversion is easy to realize; (2) Can be directly extracted from CO as a gaseous product 2 The electrolyte is separated from the aqueous electrolyte of the electroreduction system, so that the subsequent separation cost is reduced; (3) The separated CO gas can be directly used as a synthesis gas raw material, and C2 chemicals are produced through a Fischer-Tropsch synthesis process.
Electrocatalytic reduction of CO 2 The key to the preparation of CO products is the development of inexpensive, efficient and highly stable electrocatalysts. Noble metal-based catalysts have been demonstrated for the electroreduction of CO 2 The preparation of CO products has good selectivity and reactivity, but the high cost of noble metal-based catalysts limits their large-scale application. The research results show that the nitrogen-doped carbon-supported metal single-atom catalyst can be used as a substitute material of a noble metal-based catalyst and is used for high energy efficiencyCatalytic reduction of CO 2 And preparing CO. For example, chinese patent publication No. CN109652821A discloses a Ni-N-C electrocatalyst, which is prepared by pyrolyzing a nickel-doped zinc-based metal organic framework precursor and has high activity and selectivity, and is used for reducing CO 2 Preparing CO, wherein the Faraday efficiency of CO is more than 92% in a wider applied voltage range, and the highest CO partial current density reaches 71.5mA cm -2 . For example, chinese patent document with publication number CN113118451A discloses a preparation method of Mg monatomic catalyst and application thereof in electrocatalysis of CO 2 Excellent performance of reducing to prepare CO, and calcining mixture of dicyandiamide, potassium chloride and sodium chloride to obtain C 3 N 4 Nanosheets, and mixing C 3 N 4 Calcining a mixture consisting of the nanosheets, the magnesium salt and the carbon nanotubes to obtain the Mg monatomic catalyst.
Copper-based catalysts are widely used for electrochemical reduction of CO 2 C2 products were prepared. For example, chinese patent document with publication number CN110548509A discloses a copper-based CO 2 The catalytic material and the preparation method thereof are characterized in that an oxidant solution and an organic ligand solution are mixed to prepare a mixed solution; putting metal copper into the mixed solution, so that the organic ligand is adsorbed on part of specific crystal faces of the metal copper, and oxidation reaction is carried out on crystal faces of the metal copper which are not adsorbed by the organic ligand; cleaning the metal copper after the oxidation reaction to remove the organic ligand adsorbed on the crystal face of the metal copper, and performing electrochemical reduction to obtain the OD-Cu catalytic material with more specific crystal faces; the catalyst exhibited 40% electrocatalytic reduction of CO 2 Faradaic efficiency for ethylene production. For example, chinese patent publication No. CN111636074A discloses electrochemical reduction of CO 2 The preparation and application of copper electrode for preparing ethylene are characterized by that it utilizes chemical oxidation reaction to grow copper oxide with nano wire structure on the base, then utilizes hydrothermal reaction to grow thin-layer nano granules on its surface, and introduces surfactant and reducing agent in the course of hydrothermal reaction, and utilizes the directional adsorption of surfactant on the metal surface of base to regulate and control growth orientation of metal oxide, and utilizes hydrothermal reaction deposition to introduceAnd the reducing agent is used for partially reducing the copper nanowires of the substrate layer to form hole copper, and depositing nano copper particles with high specific surface area on the surface of the hole copper, so that the active specific surface area of the copper electrode is increased, and the proportion of edge and corner active sites is increased.
Although the development of nitrogen-doped carbon-supported metal monatomic electrocatalyst has made a certain progress, the reaction kinetics of the proton-coupled electron transfer process involved in the reaction path is slow, and the electrocatalysis of CO is limited 2 The performance of the conversion; in addition, the reduction of CO by a single metal monoatomic active site is difficult to achieve 2 To the C2 product. Therefore, the nitrogen/sulfur CO-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst is prepared, and the reduction of CO by carbon material loaded zinc monoatomic 2 The performance of preparing CO is realized, and the CO prepared by the method is further reduced into a C2 product, which is very significant.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen/sulfur CO-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst, the catalyst obtained by the preparation method and a working electrode for electrocatalysis of CO 2 The application in the reaction for preparing ethylene by reduction shows excellent electrochemical activity and selectivity.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst comprises the following steps:
(1) Dissolving zinc salt in a solvent, adding a 2-methylimidazole solution, stirring, mixing, centrifuging and drying to obtain a zinc-based metal organic framework precursor;
(2) Dispersing the precursor prepared in the step (1) in a methanol solution containing 5-amino-1,2,3-thiadiazole, stirring, mixing, centrifuging and drying to obtain a sulfur-doped zinc-based metal organic framework precursor;
(3) Calcining the sulfur-doped zinc-based metal organic framework precursor prepared in the step (2) to obtain the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atom;
(4) Sputtering a high-purity copper target to a polytetrafluoroethylene film with the aperture of 100nm by using a magnetron sputtering instrument to obtain a polytetrafluoroethylene film loaded copper nanoparticle substrate;
(5) And (4) dispersing the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atom prepared in the step (3) in an ethanol solution, and then spraying the dispersion liquid on the surface of a polytetrafluoroethylene film loaded copper nanoparticle substrate to obtain the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atom/metallic copper serial catalyst.
In the invention, 2-methylimidazole is used as an organic ligand and forms a zinc-based metal organic framework compound with divalent zinc ions through self-assembly. And dispersing the zinc-based metal organic framework compound in a methanol solution containing 5-amino-1,2,3-thiadiazole, and replacing a 2-methylimidazole ligand part in the zinc-based metal organic framework compound with 5-amino-1,2,3-thiadiazole through a ligand exchange process to form the sulfur-containing zinc-based metal organic framework compound. And then carbonizing the sulfur-doped zinc-based metal organic framework compound through a high-temperature pyrolysis process to obtain the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atom. Wherein, the additionally introduced sulfur atom is used as an auxiliary site to accelerate the dissociation of bicarbonate radical to provide proton, thereby accelerating CO 2 High efficiency conversion at the zinc-nitrogen active site.
In step (1), the zinc salt is a soluble salt, preferably, the zinc salt is zinc nitrate hexahydrate.
In the step (1), the zinc salt and the 2-methylimidazole are respectively dissolved in a solvent, the reaction temperature is room temperature, the solvent is methanol, and the reaction time is 0.5 to 1 hour, preferably 1 hour.
In the step (1), the mass ratio of the zinc salt to the 2-methylimidazole is 1. By changing the using amount of the solvent, zinc-based metal organic framework precursors with different sizes are prepared. The higher the molar concentration of zinc salt and 2-methylimidazole, the larger the size of the obtained zinc-based metal organic framework precursor.
In the step (1), the mass concentration of the dissolved zinc salt is 7.3-95.2 g/L, and the mass concentration of the dissolved 2-methylimidazole is 16.4-210.4 g/L.
Preferably, the mass concentration of the zinc salt is 7.3g/L, and the mass concentration of the 2-methylimidazole is 16.4g/L.
Dispersing a zinc-based metal organic framework precursor in a solvent, and then adding a 5-amino-1,2,3-thiadiazole solution, wherein the reaction temperature is room temperature, and the solvent is methanol.
In the step (2), the mass ratio of the zinc-based metal organic framework precursor to the 5-amino-1,2,3-thiadiazole is 1:2-3, and the reaction time is 0.5-48 h. The higher the concentration of the 5-amino-1,2,3-thiadiazole ligand is, or the longer the ligand exchange time is, the higher the sulfur content in the obtained sulfur-doped zinc-based metal organic framework is. When the sulfur doping amount is too low, the nitrogen/sulfur CO-doped porous carbon loaded with zinc monoatomic catalyst is used for reducing CO 2 The improvement in performance is not significant; and when the sulfur doping amount is too high, the activity of the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atom on the competitive electrolytic water hydrogen evolution reaction is obviously improved.
Preferably, the mass ratio of the zinc-based metal organic framework precursor to the 5-amino-1,2,3-thiadiazole is 1:2, the reaction time is 48h, and the optimal sulfur doping content is obtained.
In the step (3), the calcining temperature of the sulfur-doped zinc-based metal organic framework precursor is 800-1100 ℃, and the calcining time is 2h. The higher the calcination temperature is, the better the conductivity of the obtained nitrogen/sulfur-codoped porous carbon loaded zinc monoatomic atom is. Preferably, the calcination temperature is 1100 ℃, so that the nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms with best conductivity is obtained.
In the step (4), the magnetron sputtering time is 0.5-1.5 h. Preferably, the magnetron sputtering time is 1h, resulting in an optimal copper nanoparticle layer thickness.
In the step (5), the loading capacity of nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic atoms on the copper nanoparticle substrate loaded by the polytetrafluoroethylene film is 0.5-1 mg cm -2 . Preferably, the loading is 0.5mg cm -2 。
The invention also provides a nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper tandem catalyst obtained by the preparation method, wherein zinc and nitrogen atoms in the catalyst are coordinately anchored in a nitrogen/sulfur co-doped fine granular nano porous carbon structure in a single atom form, zinc in the catalyst is anchored in a nitrogen/sulfur co-doped porous nano carbon skeleton in a monoatomic form, and the mass percent of sulfur atoms is 1.7-7.5 wt.%. Preferably, the mass fraction of zinc atoms is 0.2wt%, the mass fraction of sulfur atoms is 4.5wt%, and the thickness of the metallic copper nanoparticle layer is 300nm.
The invention also provides the application of the nitrogen/sulfur CO-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst in electrocatalysis of CO 2 The catalyst has excellent electrochemical activity and selectivity.
The invention aims at reducing CO by using nitrogen-doped carbon substrate supported single metal atom catalyst in the prior art 2 Slow reaction kinetics and difficulty in reducing CO 2 To the problem of C2 products, a preparation method of a nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst is provided; CO reduction in process of improving carbon material loaded with zinc monatomic material 2 The prepared CO can be further reduced into a C2 product while the performance of the prepared CO is realized. The single nitrogen/sulfur CO-doped porous carbon loaded with zinc monoatomic atom has ultrahigh CO 2 To CO conversion frequency, there is close to 100% CO selectivity at commercial grade current density. The nitrogen/sulfur CO-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst has excellent CO reduction performance 2 To ethylene catalytic performance at a commercial current density (440 mA cm) -2 ) A higher ethylene selectivity (43%) was achieved and exhibited 250mA cm -2 The ethylene partial current density is 1.7 times of that of a pure copper nano-particle catalyst, and the CO is obviously improved 2 Conversion to ethylene.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method firstly obtains the nitrogen/sulfur co-doped porous carbon loaded zinc monatomic material by combining a solvent-assisted ligand exchange method with a high-temperature carbonization treatment method, wherein the material has a fine granular porous nano carbon structure with uniform grain size, and has high specific surface area, uniformly dispersed monatomic zinc-nitrogen coordination active sites and proper sulfur doping amount; nitrogen/sulfur co-doped porous carbon loaded zincApplication of monatomic material to electrocatalysis of CO 2 During the reduction reaction, the reaction temperature is 0.5M KHCO 3 In the electrolyte, excellent electrocatalytic performance is shown, wherein the sulfur atom is used as an auxiliary site for accelerating the dissociation of bicarbonate radical to accelerate the transfer of protons, so that the kinetics of the proton-coupled electron transfer process on the zinc-nitrogen active site is improved, and the CO is accelerated 2 Rapid conversion at the zinc-nitrogen active site.
(2) The nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst is obtained by utilizing magnetron sputtering and spraying methods, and the thickness of a copper nanoparticle layer in the catalyst is 300nm. CO 2 2 The carbon dioxide is reduced to CO on the nitrogen/sulfur-codoped porous carbon-loaded zinc monoatomic atom, so that the local concentration and the retention time of the CO on the nitrogen/sulfur-codoped porous carbon-loaded zinc monoatomic atom/metal copper interface are improved, the CO is further reduced to ethylene on the copper nanoparticle layer, and the integral CO is improved 2 Reduction to ethylene conversion.
Drawings
Fig. 1 is a transmission electron microscope image of a nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms prepared in example 1.
Fig. 2 is a transmission electron microscope image of spherical aberration correction-high-angle annular dark field scanning of the nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic ions prepared in example 1.
FIG. 3 shows that nitrogen (sulfur) -codoped porous carbon loaded with zinc and prepared in example 1, example 2 and comparative example 1 are used for single-atom electrocatalytic reduction of CO 2 Yield of CO produced.
FIG. 4 shows that the nitrogen/sulfur CO-doped porous carbon loaded with zinc monoatomic/metallic copper tandem catalyst prepared in example 3 reduces CO 2 The properties of ethylene are prepared.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention. The raw materials used in the following embodiments are all commercially available.
Example 1
(1) 13.14g of 2-methylimidazole was dissolved in 400mL of methanol with stirring, and then 400mL of a methanol solution in which 5.80g of zinc nitrate hexahydrate was dissolved was added, and the above mixed solution was stirred at room temperature for 1 hour, followed by centrifugal separation, and dried in a vacuum oven at 60 ℃ for 12 hours to obtain a zinc-based metal organic framework precursor.
(2) Dispersing 150mg of the zinc-based metal organic framework precursor obtained in the step (1) in 60mL of methanol, then adding 300mg of 5-amino-1,2,3-thiadiazole, continuously stirring for 48h, then performing centrifugal separation, washing for more than 3 times by using a methanol solution to remove residual organic ligands, and finally drying for 12h in a vacuum drying oven at 60 ℃ to obtain the sulfur-doped zinc-based metal organic framework precursor.
(3) Placing the sulfur-doped zinc-based metal organic framework precursor obtained in the step (2) into a tube furnace, calcining for 2h at 1100 ℃ in the atmosphere of argon protective gas, and raising the temperature for 5 min -1 And collecting a product, namely the nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms. Wherein the mass fraction of sulfur is 4.5wt%.
The obtained nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic morphology was observed by a transmission electron microscope, and the result is shown in fig. 1. It can be seen from fig. 1 that the material has the appearance of stacked fine carbon particles, and the surface of the material is free from the stacking of metal particles and compounds thereof.
FIG. 2 is a transmission electron microscope image of spherical aberration correction-high-angle annular dark field scanning of nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms, and it can be clearly seen that zinc is uniformly dispersed on a carbon carrier in a monoatomic form.
Example 2
According to the preparation process of the example 1, the mass of the 5-amino-1,2,3-thiadiazole in the step (2) is adjusted to 450mg, so that nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms is obtained, wherein the mass fraction of sulfur is 7.6wt%.
Example 3
(1) Sputtering a high-purity copper target to a polytetrafluoroethylene film with the aperture of 100nm by magnetron sputtering for 1h to obtain a polytetrafluoroethylene film loaded copper nanoparticle substrate;
(2) The nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atom obtained in example 1 is sprayed on the surface of a polytetrafluoroethylene film loaded with copper nanoparticle substrate, and the loading amount is 0.5mg cm -2 And obtaining the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper tandem catalyst.
Comparative example 1
According to the preparation process of the embodiment 1, the step (2) is not executed, the zinc-based metal organic framework precursor obtained in the step (1) is directly carbonized, and the nitrogen-doped porous nanocarbon-supported zinc monoatomic atom without sulfur is obtained.
FIG. 3 shows that nitrogen/sulfur CO-doped porous carbon loaded with zinc monoatomic atoms prepared in example 1 and example 2 and sulfur-free nitrogen-doped porous nanocarbon loaded with zinc monoatomic atoms prepared in comparative example 1 electrocatalytic reduction of CO 2 Comparison of the yield of the prepared CO shows that the additional introduction of a proper amount of sulfur atoms has great influence on the overall catalytic performance of the nitrogen/sulfur CO-doped porous carbon loaded with zinc monoatomic atoms from FIG. 3.
Comparative example 2
Sputtering a high-purity copper target to a polytetrafluoroethylene film with the aperture of 100nm by magnetron sputtering for 1h to obtain a polytetrafluoroethylene film loaded copper nanoparticle substrate, and directly applying the polytetrafluoroethylene film loaded copper nanoparticle substrate to electrocatalytic reduction of CO 2 To ethylene testing.
Application of the catalyst to the electrochemical reduction of CO 2 Preparation of ethylene
The method comprises the following specific steps: firstly, 5mg of nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic solution is dispersed in 500 mu L of ethanol/Nafion dispersion liquid with the volume ratio of 9:1, and then 50 mu L of dispersion liquid is sprayed to 1 x 1cm 2 The polytetrafluoroethylene membrane loaded copper nanoparticle substrate is placed in a liquid flow cell as a working electrode after being naturally dried, and electrochemical performance determination is carried out by utilizing a three-electrode system, wherein the counter electrode is nickel foam, the reference electrode is a silver/silver chloride electrode, and the electrolyte is 0.5M KHCO 3 And (3) solution.
Cyclic Voltammetric (CV) activation: using electrochemical workstation of CHI 760E, adopting CV program, the test interval is 0-1.2V vs. RHE, and the sweep speed is 50mV s -1 And after 40 circles of cyclic scanning, the electrode reaches a stable state.
Linear Sweep Voltammetry (LSV) test: after CV activation, switching the program to an LSV program, wherein the test interval is 0 to-1.2V vs.RHE, and the sweep rate is 5mV s -1 。
Faraday Efficiency (FE) test: the switching program was a galvanostatic voltage-time test during which the FE of the product was calculated using gas chromatography to determine the product concentration.
The result is shown in fig. 4, the nitrogen/sulfur CO-doped porous carbon supported zinc monatomic/metallic copper tandem catalyst prepared in example 3 shows excellent electrocatalytic CO 2 Reduction to ethylene Performance, exhibiting 250mA cm -2 The ethylene current density is 1.7 times of that of the pure copper nano-particle catalyst prepared in the comparative example 2, and the CO is obviously improved 2 Conversion to ethylene.
Claims (10)
1. The preparation method of the nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst is characterized by comprising the following steps:
(1) Dissolving zinc salt in a solvent, adding a 2-methylimidazole solution, stirring, mixing, centrifuging and drying to obtain a zinc-based metal organic framework precursor;
(2) Dispersing the precursor prepared in the step (1) in a solvent containing 5-amino-1,2,3-thiadiazole, stirring, mixing, centrifuging and drying to obtain a sulfur-doped zinc-based metal organic framework precursor;
(3) Calcining the sulfur-doped zinc-based metal organic framework precursor prepared in the step (2) to obtain nitrogen/sulfur-codoped porous carbon loaded zinc monoatomic atoms;
(4) Sputtering a copper target to a polytetrafluoroethylene film to obtain a polytetrafluoroethylene film loaded copper nanoparticle substrate;
(5) And (4) dispersing the nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms prepared in the step (3) in an ethanol solution to form dispersion liquid, and spraying the dispersion liquid on the surface of a polytetrafluoroethylene film loaded copper nanoparticle substrate to obtain the nitrogen/sulfur co-doped porous carbon loaded with zinc monoatomic atoms/metallic copper serial catalyst.
2. The preparation method of nitrogen/sulfur-codoped porous carbon-supported zinc monatomic according to claim 1, wherein in the step (1), the mass ratio of the zinc salt to the 2-methylimidazole is 1.
3. The preparation method of the nitrogen/sulfur-codoped porous carbon-loaded zinc monoatomic atom according to claim 1, wherein the stirring time in the step (1) is 0.5 to 1 hour.
4. The preparation method of the nitrogen/sulfur-codoped porous carbon-loaded zinc monatomic according to claim 1, wherein in step (2), the mass ratio of the zinc-based metal organic framework precursor to 5-amino-1,2,3-thiadiazole is 1:2-3.
5. The preparation method of the nitrogen/sulfur-codoped porous carbon-loaded zinc monoatomic atom according to claim 1, wherein the stirring time in the step (2) is 0.5 to 48 hours.
6. The preparation method of the nitrogen/sulfur-codoped porous carbon-loaded zinc monoatomic atom according to claim 1, wherein the calcination temperature in the step (3) is 800-1100 ℃, and the calcination time is 1-2 h.
7. The method for preparing a substrate with copper nanoparticles loaded on a polytetrafluoroethylene film according to claim 1, wherein the magnetron sputtering time in the step (4) is 0.5-1.5 h.
8. The preparation method of the nitrogen/sulfur-codoped porous carbon-loaded zinc monatomic/metallic copper series catalyst according to claim 1, wherein in the step (5), the nitrogen/sulfur-codoped porous carbon-loaded zinc monatomic loaded porous carbon-loaded copper nanoparticle substrate on the polytetrafluoroethylene film is subjected to the step (5)The amount is 0.5-1 mg cm -2 。
9. The nitrogen/sulfur-codoped porous carbon-supported zinc monatomic/metallic copper tandem catalyst obtained by the preparation method according to any one of claims 1 to 8, wherein zinc in the catalyst is anchored in a nitrogen/sulfur-codoped porous nanocarbon skeleton in the form of a metal monatomic, the mass percent of sulfur atoms is 1.7 to 7.5wt.%, and the thickness of the copper nanoparticle layer on the polytetrafluoroethylene film is 150 to 450nm.
10. The nitrogen/sulfur CO-doped porous carbon-supported zinc monatomic/metallic copper series catalyst as claimed in claim 9, used as a working electrode for electrocatalysis of CO 2 Application in the reaction for preparing ethylene by reduction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116459857A (en) * | 2023-04-24 | 2023-07-21 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
| CN117286533A (en) * | 2023-11-27 | 2023-12-26 | 北京理工大学 | Preparation method of sulfur-nitrogen coordinated zinc-manganese diatomic catalyst loaded on eggshell structure carbon-based carrier |
| CN116459857B (en) * | 2023-04-24 | 2024-04-19 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116459857A (en) * | 2023-04-24 | 2023-07-21 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
| CN116459857B (en) * | 2023-04-24 | 2024-04-19 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
| CN117286533A (en) * | 2023-11-27 | 2023-12-26 | 北京理工大学 | Preparation method of sulfur-nitrogen coordinated zinc-manganese diatomic catalyst loaded on eggshell structure carbon-based carrier |
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