CN111229310B - Preparation method and application of ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material - Google Patents
Preparation method and application of ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011593 sulfur Substances 0.000 title claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 27
- 150000002829 nitrogen Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
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- 238000013329 compounding Methods 0.000 claims description 4
- IPKOOFMMRKTNNW-UHFFFAOYSA-N Br.NC(CC)C1=NC=CN1C Chemical compound Br.NC(CC)C1=NC=CN1C IPKOOFMMRKTNNW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- 239000001301 oxygen Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
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- 238000006722 reduction reaction Methods 0.000 description 19
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- 239000000047 product Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 7
- 239000000446 fuel Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 101100202556 Arabidopsis thaliana SCPL8 gene Proteins 0.000 description 4
- 101100149742 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SNG1 gene Proteins 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
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- 101100476844 Arabidopsis thaliana SCPL19 gene Proteins 0.000 description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- RTOHRHYCOSVZQZ-UHFFFAOYSA-M 1-(3-methylimidazol-3-ium-1-yl)propan-1-amine;bromide Chemical compound [Br-].CCC(N)[N+]=1C=CN(C)C=1 RTOHRHYCOSVZQZ-UHFFFAOYSA-M 0.000 description 2
- PQIYSSSTRHVOBW-UHFFFAOYSA-N 3-bromopropan-1-amine;hydron;bromide Chemical compound Br.NCCCBr PQIYSSSTRHVOBW-UHFFFAOYSA-N 0.000 description 2
- MNSSXOZNQBWEPR-UHFFFAOYSA-N [Br].NC(CC)C1=NC=CN1C Chemical compound [Br].NC(CC)C1=NC=CN1C MNSSXOZNQBWEPR-UHFFFAOYSA-N 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- VHMNTEGEQDQFCT-UHFFFAOYSA-M 1-(3-ethenylimidazol-1-ium-1-yl)propan-1-amine bromide Chemical compound [Br-].NC(CC)[N+]1=CN(C=C1)C=C VHMNTEGEQDQFCT-UHFFFAOYSA-M 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 101100149737 Caenorhabditis elegans sng-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J35/33—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- 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
Abstract
The invention relates to a preparation method of an ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material. The method comprises the following steps: preparing dispersion liquid from graphene oxide and deionized water, mixing the 1-aminopropyl-3-alkyl imidazole bromide, potassium hydroxide and the graphene oxide dispersion liquid, and reacting to obtain a composite product of the 1-aminopropyl-3-alkyl imidazole bromide and the graphene oxide; then mixing the mixture with thiourea, adding a solvent to dissolve the mixture, and reacting at the temperature of 160-200 ℃ to obtain the composite material. The composite material of the invention is loaded on a cathode electrode as a catalyst. The material obtained by the invention has good oxygen reduction catalytic activity and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of graphene oxide composite materials, particularly relates to an ionic liquid modified graphene oxide composite material, and more particularly relates to a preparation method of an ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material and application of the ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material as an oxygen reduction catalyst.
Background
The fuel cell adopts an efficient energy conversion mode to directly convert chemical energy into electric energy, and the reaction process has no pollutants, so that the fuel cell is regarded as one of the most promising new energy sources in the 21 st century. However, the operating efficiency of the fuel cell depends greatly on the oxygen reduction reaction rate on the cathode, and the current catalyst for catalyzing the reaction needs a large amount of rare noble metal Pt, and the high price of the catalyst can not promote the use of the fuel cell. Therefore, it is necessary to develop a high-efficiency non-metal catalyst.
With the recent intensive research on carbon materials (such as graphene oxide, carbon nanotubes, etc.), their effects in electrocatalytic oxygen reduction reactions are more prominent, and carbon materials are considered as oxygen reduction catalysts that may be applied on a large scale in the future because they have the advantages of low price, large storage capacity, high stability, etc. In particular, graphene Oxide (GO) has the characteristics of large specific surface area, excellent thermal conductivity and mechanical properties and the like, and is a 2D layered structure, each layer of graphene oxide nanosheet has a large number of oxygen-containing groups (such as hydroxyl, carboxyl, carbonyl, epoxy group and the like), and the oxygen-containing groups can react with carboxyl, amino and other groups to realize surface modification of GO, and serve as a carrier of a nano material, so that GO has good dispersibility in water due to extremely strong hydrophilicity, and is favorable for synthesis of graphene oxide-based composite materials, so that GO has large specific surface area and strong stability, and is suitable for being used as an electrode modification material. In recent years, non-metal heteroatom-doped graphene oxide has been developed and researched as an electrocatalyst, and a large amount of data indicates that the doped graphene also has significant oxygen reduction catalytic activity.
The ionic liquid has incombustibility, low toxicity, strong ionic conductivity, good chemical stability and structure controllability, and can be subjected to covalent reaction with oxygen-containing groups on the surface of graphene oxide to prepare a composite material, so that the conductivity of the graphene oxide is improved.
Therefore, the ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material having the above advantages is drawing attention and widely applied to various electrochemical studies, and the application of the composite material as an oxygen reduction catalyst in a fuel cell will become an important issue.
Disclosure of Invention
The invention aims to provide a preparation method of an ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material and application of the ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material as an oxygen reduction catalyst aiming at the defects in the prior art. The method comprises the steps of firstly synthesizing novel amino functionalized ionic liquid, connecting the ionic liquid to the surface of graphene oxide by a chemical bonding method to form an amide group, and then carrying out nitrogen-sulfur doping by a hydrothermal method to prepare the oxygen reduction catalytic material with better catalytic performance. The material obtained by the invention has good oxygen reduction catalytic activity and wide application prospect.
The invention provides the following specific technical scheme:
a preparation method of an ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material comprises the following steps:
step one, compounding 1-aminopropyl-3-alkyl imidazole bromide with graphene oxide by adopting a chemical bonding method:
preparing dispersion liquid from graphene oxide and deionized water, mixing 1-aminopropyl-3-alkyl imidazole bromide, potassium hydroxide and the dispersion liquid of the graphene oxide, ultrasonically dispersing for 1-2 hours, carrying out reflux reaction at the temperature of 40-80 ℃ for 12-36 hours, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain a composite product (IL-GO-1) of the 1-aminopropyl-3-alkyl imidazole bromide and the graphene oxide;
wherein, 100-200 mL of deionized water is added into every 0.05-0.1 g of graphene oxide; adding 0.1-0.2 g of 1-aminopropyl-3-hydroxyimidazole bromide and 0.2-0.4 g of potassium hydroxide into every 100-200 mL of graphene oxide dispersion liquid;
the 1-aminopropyl-3-alkyl imidazole bromide salt is specifically 1-aminopropyl-3-methyl imidazole bromide salt or 1-aminopropyl-3-vinyl imidazole bromide salt;
secondly, carrying out atom doping on the composite material by using thiourea as a nitrogen source and a sulfur source by adopting a hydrothermal method:
mixing the product obtained in the first step with thiourea, adding a solvent to dissolve the thiourea, magnetically stirring for 0.5-1 hour, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 160-200 ℃ for 3-6 hours, cooling to room temperature, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain the composite material;
wherein, the mass ratio of the product obtained in the first step is: thiourea =0.05 to 0.1:1.5 to 3.0; the solvent is deionized water; 1.5 to 3.0g of thiourea is added into every 50 to 100ml of solvent;
the application of the ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material is that the composite material is loaded on a cathode electrode to be used as a catalyst.
The invention has the substantive characteristics that:
compared with the known preparation method of the nitrogen-sulfur co-doped graphene oxide composite material, the preparation method disclosed by the invention has the advantages that the ionic liquid is connected to the surface of the graphene oxide through a chemical bonding method, and then nitrogen-sulfur doping is carried out. After the ionic liquid is connected to the graphene oxide, amide groups can be formed on the surface of the graphene oxide. The amide group can provide electrons, and the electron transfer process of the reaction is accelerated. Meanwhile, hydrogen on the amide group is easy to form a hydrogen bond, which is beneficial to the smooth proceeding of the oxygen reduction reaction.
The invention has the beneficial effects that:
according to the invention, the ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material is prepared by chemical bonding and a hydrothermal method, compared with a metal catalyst, the non-metal catalyst has the advantages of reduced cost, low price, easy obtainment and mild synthesis conditions; meanwhile, due to the doping of nitrogen and sulfur elements, the charge density and spin density distribution of carbon atoms around the graphene oxide are effectively changed, a unique electronic structure is formed, the electronic performance and chemical activity of the graphene are improved, catalytic active sites are increased, good oxygen reduction catalytic activity is achieved, the limiting current density of the SNG1 connected with the ionic liquid is improved by 29.4% compared with that of the SNG not connected with the ionic liquid, and the application prospect is very wide.
Drawings
Fig. 1 is an SEM image of graphene oxide;
fig. 2 is an SEM image of nitrogen and sulfur co-doped graphene oxide;
fig. 3 is an SEM image of the synthesized composite SNG1 in example 1;
fig. 4 is an SEM image of the synthesized composite SNG2 in example 2;
FIG. 5 is a LSV curve of electrochemical testing of two composites synthesized as oxygen reduction catalysts in examples 1-2;
Detailed Description
The preparation method of the composite material of the ionic liquid modified nitrogen and sulfur co-doped graphene oxide and the application of the composite material as an oxygen reduction catalyst are further described by specific examples below.
The ionic liquid 1-aminopropyl-3-methylimidazolium bromide and 1-aminopropyl-3-vinylimidazolium bromide are well-known materials, and the specific synthetic route is as follows:
example 1
1. Synthesis of ionic liquids
Mixing N-methylimidazole 0.05mol (4.1 g) and 3-bromopropylamine hydrobromide 0.04mol (8.76 g) in a reactor, adding 100ml of absolute ethyl alcohol solvent to dissolve the mixture in N 2 Under protection, the mixture is placed in an oil bath pot to be heated to 78 ℃, and stirred and refluxed for 24 hours to obtain a light yellow solution. Purifying the obtained crude product with rotary evaporator to obtain viscous liquid, adding water to dissolve the evaporated substances, adjusting pH to 11 with KOH to reduce protected amino group, distilling under reduced pressure, and vacuum drying the washed productAnd (2) heating to 80 ℃ in a drying box, drying for 4h, drying in vacuum to constant weight, taking out the mixture to be light yellow viscous paste after drying is finished, adding 50mL of a mixture of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran =4: 1), stirring for dissolving, extracting the product by reduced pressure distillation, drying the obtained product in a vacuum drying box at 80 ℃ for 24h, and drying in vacuum to obtain the ionic liquid 1-aminopropyl-3-methylimidazolium bromide.
2. Preparation of ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material
The method comprises the following steps of firstly, compounding 1-aminopropyl-3-methylimidazole bromine salt with graphene oxide by adopting a chemical bonding method, wherein the specific steps are as follows:
firstly, according to the mass volume ratio (g/mL) of 0.0005:1.0 graphene oxide and deionized water are prepared into 200mL of dispersion liquid, then 1-aminopropyl-3-methylimidazole bromine salt, potassium hydroxide and the graphene oxide dispersion liquid are mixed according to the mass volume ratio (g/g/mL) of 0.2.
Secondly, carrying out atom doping on the composite material by using thiourea as a nitrogen source and a sulfur source by adopting a hydrothermal method, and specifically comprising the following steps:
mixing the product obtained in the first step with thiourea according to a mass ratio (g/g) of 0.1, adding 100ml of deionized water to dissolve the thiourea, magnetically stirring for 1 hour, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 5 hours at the temperature of 180 ℃, cooling to room temperature, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain the composite ionic liquid modified nitrogen-sulfur co-doped graphene oxide (SNG 1). FIG. 3 shows that the synthesized composite material SNG1 is in a multilayer porous shape, and the material is large in specific surface area, has more active sites, improves the activity of the catalyst and is beneficial to smooth oxygen reduction reaction.
Example 2
1. Synthesis of ionic liquids
Taking 0.0 part of 1-vinyl imidazole5mol (4.1 g) and 0.04mol (8.76 g) of 3-bromopropylamine hydrobromide were mixed in a reactor, dissolved in 100ml of an anhydrous ethanol solvent, and dissolved in N 2 Under protection, the mixture is placed in an oil bath pot to be heated to 78 ℃, and stirred and refluxed for 24 hours to obtain a light yellow solution. Purifying the obtained crude product by a rotary evaporator to obtain viscous liquid, adding water to completely dissolve the substances subjected to rotary evaporation, adjusting the pH value to 11 by using KOH to reduce the protected amino, carrying out reduced pressure distillation, putting the washed product in a vacuum drying oven, heating to 80 ℃, drying for 4h, carrying out vacuum drying to constant weight, taking out the product to be light yellow viscous paste after drying, adding 50mL of a mixture of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 4.
2. Preparation of composite material of ionic liquid modified nitrogen and sulfur co-doped graphene oxide
The method comprises the following steps of firstly, compounding 1-aminopropyl-3-vinyl imidazole bromide with graphene oxide by adopting a chemical bonding method, and specifically:
firstly, according to the mass volume ratio (g/mL) of 0.0005:1.0, preparing 200mL of dispersion liquid by graphene oxide and deionized water, then mixing 1-aminopropyl-3-vinyl imidazole bromide, potassium hydroxide and the graphene oxide dispersion liquid according to a mass volume ratio (g/g/mL) of 0.4.
Secondly, carrying out atom doping on the composite material by using thiourea as a nitrogen source and a sulfur source by adopting a hydrothermal method, and specifically comprising the following steps:
mixing the product obtained in the first step with thiourea according to a mass ratio (g/g) of 0.1, adding 100ml of deionized water to dissolve the thiourea, magnetically stirring for 1 hour, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 5 hours at the temperature of 180 ℃, cooling to room temperature, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain the composite ionic liquid modified nitrogen-sulfur co-doped graphene oxide (SNG 2). Fig. 4 shows that the synthesized composite material SNG2 has a multilayer porous shape, which indicates that the material has a large specific surface area and many active sites, improves the activity of the catalyst, and is beneficial to the smooth progress of the oxygen reduction reaction.
Comparative example 1
1. Preparation of nitrogen and sulfur co-doped graphene oxide material not connected with ionic liquid
Carrying out atom doping on graphene oxide by using thiourea as a nitrogen source and a sulfur source by adopting a hydrothermal method, and specifically comprising the following steps:
mixing graphene oxide and thiourea according to a mass ratio (g/g) of 0.1, adding 100ml of deionized water to dissolve the graphene oxide and the thiourea, magnetically stirring for 1 hour, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 5 hours at the temperature of 180 ℃, cooling to room temperature, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain the nitrogen-sulfur co-doped graphene oxide material (SNG) which is not connected with the ionic liquid.
Application examples
The synthesized nitrogen-sulfur co-doped graphene oxide composite material modified by the two ionic liquids is used as an oxygen reduction catalyst for application in oxygen reduction reaction for testing.
The test was carried out on an electrochemical workstation, using a three-electrode system (working electrode is a glassy carbon electrode; auxiliary electrode is a platinum electrode; reference electrode is a platinum electrode) in an oxygen-saturated 0.1M KOH solution at 1600rpm for the LSV test (as catalyst, the catalyzed reaction is O) 2 +2H 2 O+4e - →4OH - (i.e., oxygen reduction reaction)), each experiment was repeated 3 times to ensure the reliability of the experimental data.
As shown in fig. 5, two synthesized ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite materials were subjected to electrochemical tests by linear voltammetry (LSV). Under the condition of the rotating speed of 1600rpm, the limiting current density of the SNG1 and the SNG2 is-4.862 mA/cm 2 And-4.433 mA/cm 2 Average ratio Graphene Oxide (GO) -2.307mA/cm 2 Has the advantages of large liftAnd (5) rising. Meanwhile, compared with pure nitrogen and sulfur co-doped graphene oxide (SNG) -3.758mA/cm 2 The composite material has higher limiting current density, which indicates that the synthesized two ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite materials have excellent oxygen reduction catalytic activity.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, while the invention has been described in detail with reference to the above-mentioned embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
The invention is not the best known technology.
Claims (2)
1. A preparation method of an ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material is characterized by comprising the following steps:
step one, compounding 1-aminopropyl-3-alkyl imidazole bromide with graphene oxide by adopting a chemical bonding method:
preparing dispersion liquid from graphene oxide and deionized water, mixing 1-aminopropyl-3-alkyl imidazole bromide, potassium hydroxide and the dispersion liquid of the graphene oxide, ultrasonically dispersing for 1-2 hours, carrying out reflux reaction at the temperature of 40-80 ℃ for 12-36 hours, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain a composite product (IL-GO-1) of the 1-aminopropyl-3-alkyl imidazole bromide and the graphene oxide;
wherein, 100-200 mL of deionized water is added into every 0.05-0.1 g of graphene oxide; adding 0.1-0.2 g of 1-aminopropyl-3-hydroxyimidazole bromide and 0.2-0.4 g of potassium hydroxide into every 100-200 mL of graphene oxide dispersion liquid;
the 1-aminopropyl-3-alkyl imidazole bromide salt is specifically 1-aminopropyl-3-methyl imidazole bromide salt or 1-aminopropyl-3-vinyl imidazole bromide salt;
secondly, carrying out atom doping on the composite material by using thiourea as a nitrogen source and a sulfur source by adopting a hydrothermal method:
mixing the product obtained in the first step with thiourea, adding a solvent to dissolve the thiourea, magnetically stirring for 0.5-1 hour, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 3-6 hours at 160-200 ℃, cooling to room temperature, filtering the obtained solid, washing with ethanol and water respectively, and drying to obtain the composite material;
wherein, the mass ratio of the product obtained in the first step is: thiourea =0.05 to 0.1:1.5 to 3.0; 1.5 to 3.0g of thiourea is added into every 50 to 100ml of solvent;
the solvent is deionized water.
2. The application of the ionic liquid modified nitrogen and sulfur co-doped graphene oxide composite material as claimed in claim 1, wherein the composite material is loaded on a cathode electrode as a catalyst.
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