CN116219469A - Electrocatalytic nitrogen reduction catalyst and preparation method thereof - Google Patents

Electrocatalytic nitrogen reduction catalyst and preparation method thereof Download PDF

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Publication number
CN116219469A
CN116219469A CN202211515443.5A CN202211515443A CN116219469A CN 116219469 A CN116219469 A CN 116219469A CN 202211515443 A CN202211515443 A CN 202211515443A CN 116219469 A CN116219469 A CN 116219469A
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nitrogen reduction
coupling agent
doped graphene
catalyst
preparing
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周凤玲
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Dongguan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/27—Ammonia
    • 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
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses an electrocatalytic nitrogen reduction catalyst, which belongs to the technical field of electrochemical synthesis, wherein the catalyst takes boron doped graphene as a substrate, a fluorine-containing silane coupling agent is used for modifying fluoroalkyl on the surface of the substrate, and strong N is constructed on the surface of the catalyst 2 The interaction layer dynamically improves the catalytic performance of nitrogen reduction to prepare the catalyst capable of catalyzing NRR with high efficiency, the Faraday current efficiency reaches 9.8%, and the yield of nitrogen reduction synthetic ammonia reaches 2.04 multiplied by 10 ‑ 10 mol·s ‑1 ·cm ‑2 。

Description

Electrocatalytic nitrogen reduction catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical synthesis, in particular to an electrocatalytic nitrogen reduction catalyst and a preparation method thereof.
Background
The electrocatalytic nitrogen reduction (nitrogen reduction reaction, NRR) Process for synthesizing ammonia has received attention in recent years, which has several advantages over the traditional "Haber Process" (HBP) Process: 1) Thermodynamically, the energy utilization rate is 20% higher than that of the HBP method; 2) Using H 2 O replaces H 2 As a raw material, the method can effectively solve the dependence of the synthetic ammonia industry on fossil energy; 3) Can be realized under the mild condition of normal temperature and normal pressure, and greatly reduces the requirements on equipment. However, electrocatalytic NRR has problems in that: 1) N (N) 2 The N (identical to) N bond is very stable under normal temperature and normal pressure, the activation is very difficult, and the reduction reaction is driven by higher negative potential; 2) NRR is generally carried out in aqueous solution, in the presence of a counter-currentHydrogen Evolution Reactions (HER) tend to dominate under conditions where a negative voltage is applied to the pole. This results in a very inefficient electrocatalytic NRR synthesis of ammonia (current efficiency Faradic efficiency, FE)<1%). Therefore, research is conducted on the aspects of catalyst design and synthesis and electrolyte regulation, so that the efficiency of the electrocatalytic NRR is required to be effectively improved.
One important reason for the inefficiency of electrocatalytic NRR is due to N 2 Solubility in aqueous solutions was very low (0.017 mg/g), resulting in a catalyst surface N 2 The concentration is low, so that the NRR reaction kinetics process is slower, and the improvement of the electrocatalytic NRR efficiency is limited. Therefore, the regulation and control of the electrolyte are carried out, and the hydrogen evolution can be restrained from the aspect of reaction dynamics and the NRR efficiency can be improved. The prior art introduces a solution with N by optimizing the electrolyte 2 High solubility hydrophobic ionic liquids [ P ] 6,6,6,14 ][eFAP]And [ C ] 4 mpyr][eFAP](the solubility of nitrogen is 0.29mg/g and 0.20mg/g respectively), and simultaneously the water content in the electrolyte is regulated and controlled, thereby effectively inhibiting HER reaction and greatly improving N 2 Current efficiency of reduction. However, ionic liquids have some problems in practical use in NRR processes: due to the considerable viscosity of the ionic liquids used (e.g. [ P ] 6,6,6,14 ][eFAP]The room temperature viscosity is as high as 400 mPa.s), the mass transfer efficiency is low, the catalytic reaction rate is low, and the synthetic ammonia rate in the ionic liquid is low (about 10) -11 mol·s -1 ·cm -2 ). Although the viscosity of the system can be reduced and the mass transfer efficiency can be improved by a mode of compounding ionic liquid/solvent, the problems of high price and difficult recycling of the ionic liquid still exist.
Disclosure of Invention
Aiming at low performance of an electrocatalytic nitrogen reduction ammonia synthesis catalyst, N in an aqueous solution 2 The invention provides an electrocatalytic nitrogen reduction catalyst and a preparation method thereof, which are used for solving the problem of slower NRR reaction kinetics process caused by low solubility.
The aim of the invention is realized by adopting the following technical scheme:
an electrocatalytic nitrogen reduction catalyst is boron doped graphene with a fluorosilane modified surface.
Another object of the present invention is to provide a method for preparing the catalyst, comprising the steps of:
(1) Preparing boron doped graphene;
(2) And carrying out surface modification on the boron doped graphene by using a fluorosilane coupling agent.
Preferably, the preparation method of the boron doped graphene in the step (1) includes the following steps:
s1, dispersing graphene oxide in water to obtain a suspension, adding boric acid solution, stirring for reaction, and freeze-drying and dehydrating after the reaction is completed to obtain a dehydrated product;
s2, carrying out heat treatment on the dehydration product in an argon or hydrogen atmosphere, sequentially carrying out acid washing and water washing on the heat treatment product, dispersing insoluble matters obtained after washing in deionized water again, and carrying out freeze-drying dehydration to obtain the boron doped graphene.
Preferably, the temperature of the heat treatment is 600-900 ℃, and the heat treatment time is 1-5h.
Preferably, the surface modification in step (2) includes the steps of:
dispersing the boron-doped graphene in isopropanol to obtain a dispersion liquid; dissolving the fluorosilane coupling agent in isopropanol to obtain fluorosilane coupling agent solution, mixing the dispersion liquid and the fluorosilane coupling agent solution, adding glacial acetic acid, stirring at 50-90 ℃ for reaction for 2-18h, washing the precipitate with isopropanol, absolute ethyl alcohol and deionized water in sequence after the reaction is completed, dispersing the washed precipitate in deionized water again, and freeze-drying and dehydrating to obtain the fluorosilane coupling agent.
Preferably, the fluorosilane coupling agent is tridecyl octyl trimethyl/ethoxy silane, trifluoro propyl trimethyl/ethoxy silane, heptadecyl trimethyl/ethoxy silane, pentafluoroethyl trimethyl/ethyl silane, heptafluoro propyl trimethyl silane or nonafluoro hexyl trimethyl/ethoxy silane.
The beneficial effects of the invention are as follows:
the invention takes boron doped graphene as a substrate, uses fluorine-containing silane coupling agent to modify fluoroalkyl on the surface of the substrate, and constructs strong N on the surface of a catalyst 2 Interaction with each otherThe layer is used for improving the catalytic performance of nitrogen reduction in dynamics, the catalyst capable of catalyzing NRR with high efficiency is prepared, the Faraday current efficiency reaches 9.8%, and the yield of nitrogen reduction synthetic ammonia reaches 2.04 multiplied by 10 -10 mol·s -1 ·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, graphene is used as a carrier material, and the sp2 structure on the surface of the graphene can be opened to react with organic molecules, so that a large number of active groups such as hydroxyl, carboxyl and epoxy bonds exist on the surface of the graphene oxide, and the graphene oxide is conveniently modified by chemical covalent bonds to be functionalized; boron atom doping is beneficial to improving interaction with nitrogen, improving adsorption of nitrogen on the surface of the catalyst and reducing reaction potential barrier; the fluorosilane modification increases the nitrogen concentration on the surface layer of the catalyst and increases the kinetics of nitrogen reduction reaction, and preliminary researches show that functional groups with promotion effect on NRR are related to the hydrophobic structures of fluoroalkyl groups, and the hydrophobic fluoroalkyl structures are related to N 2 Has stronger interaction, the invention utilizes the structural pairs N of fluoroalkyl 2 Functional groups with strong interaction, and research on chemically modified graphene is developed to realize effective capture of N in aqueous solution 2 Molecular and catalyst surface enrichment of N 2 Further, the NRR efficiency is improved from the aspect of reaction kinetics; meanwhile, the catalyst provided by the invention has the advantages of simple preparation method and stable catalytic performance.
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The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a schematic illustration of an electrocatalytic nitrogen reduction process for a catalyst according to the present invention;
FIG. 2 is a scanning electron microscope image of the catalyst described in example 1, (a) graphene oxide, (b) boron doped graphene, (c) perfluorooctyl trimethylsilane modified boron doped graphene;
FIG. 3 is an EDS spectrum of the catalyst described in example 1;
FIG. 4 is a graph of the ammonia synthesis performance of the reduced nitrogen of the catalyst described in example 1;
FIG. 5 is a graph of the cycle performance of the catalyst described in example 1.
Detailed Description
The invention will be further described with reference to the following examples.
Example 1
The embodiment relates to an electrocatalytic nitrogen reduction catalyst, and the preparation method comprises the following steps:
(1) 200mg of Graphene Oxide (GO) is weighed and added into 150mL of deionized water, and graphene suspension is obtained after alternating ultrasonic and stirring for 12 hours; adding 1g of boric acid into 50mL of water for dissolution to obtain a boric acid solution, adding the boric acid solution into the graphene suspension, stirring for 24 hours at normal temperature, and freeze-drying the stirred suspension for 48 hours to obtain a graphene oxide boric acid mixture;
(2) Weighing 500mg of the graphene oxide boric acid mixture prepared in the step (1), carrying out heat treatment at 900 ℃ for 2 hours in an argon atmosphere, washing a heat treatment product with 0.05mol/L dilute sulfuric acid to remove boron oxide impurities, repeatedly washing with deionized water, filtering to remove soluble impurities, dispersing the insoluble matters obtained by the last filtering in 50mL of deionized water again, carrying out ultrasonic dispersion, and carrying out freeze drying to remove water to obtain boron doped graphene (B-rGO);
(3) Weighing 20mg of boron-doped graphene prepared in the step (2) and dispersing the boron-doped graphene in 40mL of isopropanol, and alternately carrying out ultrasonic treatment and stirring for 12 hours to obtain a dispersion; dissolving 0.5mmol of perfluorooctyl trimethyl silane coupling agent in 5mL of isopropanol to obtain a coupling agent solution, adding 3.2mL of the coupling agent solution into the dispersion liquid, dropwise adding 1.6mL of glacial acetic acid, carrying out heat preservation reaction on the mixed system at 50 ℃ for 10 hours, respectively washing with isopropanol, absolute ethyl alcohol and deionized water after the reaction is finished, filtering, dispersing insoluble matters obtained by the last filtering in 20mL of deionized water again, and freeze-drying for 12 hours to obtain perfluorooctyl trimethyl silane modified boron doped graphene (POTS-B-rGO).
Example 2
The embodiment relates to an electrocatalytic nitrogen reduction catalyst, and the preparation method comprises the following steps:
(1) 200mg of graphene oxide is weighed and added into 150mL of deionized water, and graphene suspension is obtained after alternating ultrasonic and stirring for 12 hours; adding 1g of boric acid into 50mL of water for dissolution to obtain a boric acid solution, adding the boric acid solution into the graphene suspension, stirring for 24 hours at normal temperature, and freeze-drying the stirred suspension for 48 hours to obtain a graphene oxide boric acid mixture;
(2) Weighing 500mg of the graphene oxide boric acid mixture prepared in the step (1), carrying out heat treatment at 800 ℃ for 2 hours in an argon atmosphere, washing a heat treatment product with 0.05mol/L dilute sulfuric acid to remove boron oxide impurities, repeatedly washing with deionized water, filtering to remove soluble impurities, dispersing the insoluble matters obtained by the last filtering in 50mL of deionized water again, carrying out ultrasonic dispersion, and carrying out freeze drying to remove water to obtain boron doped graphene;
(3) Weighing 20mg of boron-doped graphene prepared in the step (2) and dispersing the boron-doped graphene in 40mL of isopropanol, and alternately carrying out ultrasonic treatment and stirring for 12 hours to obtain a dispersion; dissolving 0.5mmol of heptadecafluorodecyl trimethoxy silane coupling agent in 5mL of isopropanol to obtain a coupling agent solution, adding 3.2mL of the coupling agent solution into the dispersion liquid, dropwise adding 1.6mL of glacial acetic acid, carrying out heat preservation reaction on the mixed system at 70 ℃ for 2h, respectively washing with isopropanol, absolute ethyl alcohol and deionized water after the reaction is finished, filtering, dispersing insoluble matters obtained by the last filtering in 20mL of deionized water again, and freeze-drying for 12h to obtain the perfluorooctyl trimethyl silane modified boron doped graphene.
The scanning electron microscope image of the perfluorooctyl trimethylsilane modified boron doped graphene described in example 1 is shown in fig. 2, and the folds on the surface of the graphene are increased due to the modification of the fluorosilane on the surface of the graphene.
The EDS spectrum of perfluorooctyl trimethylsilane modified boron doped graphene described in example 1 is shown in fig. 3, and from fig. 3 it can be seen that the fluorosilane coupling agent has been successfully grafted to the surface of the boron doped graphene.
As can be seen from FIG. 4, the ammonia reduction synthesis of perfluorooctyl trimethylsilane modified boron doped graphene of example 1, and the nitrogen reduction synthesis of the catalyst of example 1, compared with graphene and boron doped graphene, is shown in FIG. 4The Faraday current efficiency of ammonia is improved from 0.5% to 2.2% to 9.8%, and the yield of ammonia synthesized by nitrogen reduction reaches 2.04 multiplied by 10 at-1.6V vs Ag/AgCl -10 mol·s -1 ·cm -2 。
The cycling catalytic performance of the perfluorooctyl trimethylsilane modified boron doped graphene described in example 1 is shown in fig. 5, and as can be seen from fig. 5, the catalyst described in example 1 is continuously used four times, and the current efficiency of nitrogen reduction synthesis ammonia is respectively 3.7%, 3.4%, 3.8% and 3.6% at-1.3V vs Ag/AgCl, so that the catalyst has excellent stability.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. An electrocatalytic nitrogen reduction catalyst is characterized in that the catalyst is boron doped graphene with a fluorosilane modified surface.
2. The method for preparing the electrocatalytic nitrogen reduction catalyst as claimed in claim 1, comprising the following steps:
(1) Preparing boron doped graphene;
(2) And carrying out surface modification on the boron doped graphene by using a fluorosilane coupling agent.
3. The method for preparing the electrocatalytic nitrogen reduction catalyst as claimed in claim 2, wherein the method for preparing the boron doped graphene in the step (1) comprises the following steps:
s1, dispersing graphene oxide in water to obtain a suspension, adding boric acid solution, stirring for reaction, and freeze-drying and dehydrating after the reaction is completed to obtain a dehydrated product;
s2, carrying out heat treatment on the dehydration product in an argon or hydrogen atmosphere, sequentially carrying out acid washing and water washing on the heat treatment product, dispersing insoluble matters obtained after washing in deionized water again, and carrying out freeze-drying dehydration to obtain the boron doped graphene.
4. A method for preparing an electrocatalytic nitrogen reduction catalyst as claimed in claim 3, wherein the heat treatment temperature is 600-900 ℃ and the heat treatment time is 1-5h.
5. The method for preparing an electrocatalytic nitrogen reduction catalyst as claimed in claim 2, wherein the surface modification in step (2) comprises the steps of:
dispersing the boron-doped graphene in isopropanol to obtain a dispersion liquid; dissolving the fluorosilane coupling agent in isopropanol to obtain fluorosilane coupling agent solution, mixing the dispersion liquid and the fluorosilane coupling agent solution, adding glacial acetic acid, stirring at 50-90 ℃ for reaction for 2-18h, washing the precipitate with isopropanol, absolute ethyl alcohol and deionized water in sequence after the reaction is completed, dispersing the washed precipitate in deionized water again, and freeze-drying and dehydrating to obtain the fluorosilane coupling agent.
6. The method for preparing an electrocatalytic nitrogen reduction catalyst as claimed in claim 2, wherein the fluorosilane coupling agent is tridecafluorooctyl trimethyl/ethoxy silane, trifluoropropyl trimethyl/ethoxy silane, heptadecafluorodecyl trimethyl/ethoxy silane, pentafluoroethyl trimethyl/ethyl silane, heptafluoropropyl trimethyl silane or nonafluorohexyl trimethyl/ethoxy silane.
CN202211515443.5A 2023-05-06 2023-05-06 Electrocatalytic nitrogen reduction catalyst and preparation method thereof Pending CN116219469A (en)

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Citations (7)

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WO2016177951A1 (en) * 2015-05-06 2016-11-10 Commissariat A L'energie Atomique Et Aux Energies Alternatives Catalyst supported by carbon nanotubes and by graphene, and method for preparing same
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WO2020169848A1 (en) * 2019-02-22 2020-08-27 Katholieke Universiteit Leuven Electrocatalytic reduction of nitrogen to ammonia
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WO2016177951A1 (en) * 2015-05-06 2016-11-10 Commissariat A L'energie Atomique Et Aux Energies Alternatives Catalyst supported by carbon nanotubes and by graphene, and method for preparing same
WO2020169848A1 (en) * 2019-02-22 2020-08-27 Katholieke Universiteit Leuven Electrocatalytic reduction of nitrogen to ammonia
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CN111646459A (en) * 2020-06-12 2020-09-11 北京航空航天大学 Preparation method and application of boron-doped graphene material
CN114836782A (en) * 2022-03-31 2022-08-02 福州大学 Preparation method and application of hydrophobic zirconium-supported electrocatalyst
CN115418658A (en) * 2022-07-21 2022-12-02 山东科技大学 Surface hydrophobic modified MXene electrocatalyst and preparation method thereof

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Title
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