CN109402664B - Preparation and application of graphene/polyion liquid-based carbon material - Google Patents
Preparation and application of graphene/polyion liquid-based carbon material Download PDFInfo
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- CN109402664B CN109402664B CN201811520799.1A CN201811520799A CN109402664B CN 109402664 B CN109402664 B CN 109402664B CN 201811520799 A CN201811520799 A CN 201811520799A CN 109402664 B CN109402664 B CN 109402664B
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Abstract
The invention discloses a preparation method of a graphene oxide/polyion liquid composite carbon material, which comprises the steps of taking polyion liquid as a nitrogen source and a sulfur source, compounding the polyion liquid with graphene oxide, deprotonating to obtain an electrostatic cross-linked precursor material, and further carbonizing to obtain an N, S co-doped porous GCs carbon material. The composite carbon material is found to have very high specific surface area up to 723.61 m through the characteristic tests of TEM, XRD, XPS, BET, Raman and the like2g‑1Is a mesoporous material. Electrochemical tests show that the obtained carbon material shows excellent catalytic activity in both hydrogen evolution reaction and oxygen evolution reaction, so that the carbon material has good application prospects in the hydrogen evolution reaction and the oxygen evolution reaction.
Description
Technical Field
The invention relates to preparation of a composite carbon material, in particular to a method for preparing a graphene/polyion liquid composite carbon material by taking polyion liquid (PCMVImTf 2N) and Graphene Oxide (GO) as raw materials, which is mainly used as a catalyst for hydrogen production reaction by water electrolysis.
Background
Hydrogen is a clean fuel that is abundant, renewable, and environmentally friendly, and is considered an ideal substitute for today's fossil fuels. Among many hydrogen production methods, hydrogen production by electrolysis of water is receiving attention from a large number of researchers because of low cost, simple operation equipment and high purity of the produced hydrogen. It is well known that Pt is a highly efficient electrocatalyst for hydrogen evolution reactions. However, Pt-based catalysts are not widely used at present because of their small storage capacity and high price. Therefore, the development of a hydrogen evolution reaction catalyst that is inexpensive and can be mass-produced is one of the hot directions of current new energy research. Currently, molybdenum-based sulfides, nitrides, carbides and selenides (such as: MoS2, Mo2C, Ni-Mo-N, MoSe 2), cobalt/nickel-based metal sulfides, selenides, phosphides (such as: CoS2, CoSe2, CoP, Ni12P 5) and other metal sulfides (TiS 2, TaS 2) all show better catalytic activity in hydrogen evolution reaction. However, based on the consideration of energy sustainability and environmental friendliness, it is a more ideal strategy to develop a non-metal catalyst which is efficient, cheap and capable of being produced in a large scale.
Graphene has many advantages of large specific surface area, high mechanical strength, good conductivity and the like, and is an ideal electrochemical reaction electrode material. However, current research shows that graphene has very low catalytic activity in electrochemical processes such as Oxygen Reduction Reaction (ORR), Oxygen Evolution Reaction (OER), and Hydrogen Evolution Reaction (HER), and in order to reduce the electrode overpotential of these reactions, graphene and different materials are often required to be compounded. Recent research shows that boron/nitrogen, nitrogen/sulfur, nitrogen/phosphorus and other heteroatom co-doped graphene and graphene carbon materials can significantly improve the catalytic activity of graphene in hydrogen evolution reaction and oxygen evolution reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide/polyion liquid composite carbon material;
another object of the present invention is to study the catalytic activity of the above graphene oxide/polyion liquid composite carbon material as a catalyst for hydrogen evolution reaction.
Preparation of graphene/polyion liquid composite carbon material
Ultrasonically dispersing graphene oxide GO and polyion liquid PCMVImTf2N in DMSO to form a uniform solution; transferring the solution into a culture dish, drying at 70-80 ℃ for 3-4 h under normal pressure, and volatilizing to remove a solvent DMSO; soaking the obtained solid compound in an ammonia water solution with the mass concentration of 0.2-1% for 1-2 h to obtain an electrostatic crosslinking precursor material; and then placing the precursor material in a tube furnace, and carrying out high-temperature carbonization under the protection of inert gas (argon) to obtain the graphene/polyion liquid composite carbon material, wherein the label is GCs. For ease of study, labeled GC-X, X represents the mass ratio of pcmvmimtf 2N to GO.
The mass ratio of the graphene oxide GO to the polyion liquid PCMVImTf2N is 1: 5-1: 9, and preferably 1: 7.
The carbonization temperature of the precursor material is 800-1000 ℃, and the carbonization time is 5-7 h:
in order to regulate and control the pore structure of the composite carbon material and obtain a better appearance, a sectional heating mode is adopted: firstly, heating from room temperature to 300 ℃ and keeping for 0.5-1 h, wherein the heating rate is 3 ℃/min; then raising the temperature from 300 ℃ to 1000 ℃ and keeping the temperature for 0.5-1 h, wherein the temperature raising speed is 3 ℃/min; and finally, naturally cooling to room temperature.
Structure of graphene/polyion liquid composite carbon material
1. SEM and TEM analysis
As shown in fig. 1 (a), which is a scanning SEM image of the composite carbon material, it can be seen that the morphology of the composite carbon material is a layered structure. The polyion liquid and the graphene are successfully compounded together. A TEM image of FIG. 1 (b). The figure shows that the morphology of the composite carbon material has wrinkles attached to the carbon, which further illustrates that graphene and the carbon material are better compounded together. The wrinkles also indicate that the composite carbon material has a pore structure and irregular structure defects in the carbonization process, so that the electrical properties of the composite carbon material can be effectively improved.
2. XRD analysis of graphene/polyion liquid composite carbon material
As shown in fig. 2, the crystal structure of the GCs carbon material was further confirmed using wide-angle X-ray diffraction (XRD). Carbon materials GC-6 and GC-7 are prepared according to different proportions of graphene oxide and polyion liquid, and two diffraction peaks appear in 2 theta =25 degrees and 43.8 degrees in GC-8, and are respectively corresponding to a 002 crystal face and a 100 crystal face, which shows that GCs are amorphous carbon structures, and the graphene oxide and the polyion liquid PCMVImTf2N form strong interaction, so that the GCs carbon material has low crystallinity and graphitization degree.
3. Raman analysis of GCs materials
FIG. 3 is a Raman spectrum of the composite carbon material, which is shown at 1350 cm-1And 1585 cm-1There are characteristic peaks corresponding to the D peak and the G peak. The D peak represents the defect structure of the disordered graphitic carbon. The G peak represents sp2 hybridization of the graphitized carbon. The ratio of ID/IG generally represents the defect density degree of graphene, and the larger the ratio is, the larger the defect degree is, and the more favorable the transmission of electrons is. The ID/IG of GC-6, GC-7 and GC-8 are 1.03, 1.06 and 1.04 respectively, wherein the ID/IG ratio of GC-7 is 1.06, which indicates that the structural defects of GC-7 graphitized disordered graphite carbon are more obvious, and the result is consistent with XRD.
4. Nitrogen adsorption desorption curve analysis of GCs material
FIG. 4 shows a nitrogen adsorption/desorption curve (a) and a pore size distribution curve (b) of a carbon material for GCs. As can be seen from fig. 4 (a), the isotherm of the GCs carbon material is type iv while the retention ring is type H2, indicating that the GCs carbon material is a porous material mainly having mesopores. The surface area of GC-7 was 723.61 m2g-1The total pore volume was 0.637 cm3 g-1Comparison with the specific surface area 588.43 m2g of GC-6-1And a specific surface area of 695.12 m2g of GC-8-1The in-situ compounding of the graphene oxide and the polyionic liquid in the mass ratio of 1:7 is demonstrated to have a higher specific surface area. FIG. 4 (b) shows that the obtained GC-7 is mainly mesoporous, and simultaneously has a small amount of macropores, and the pore structure is favorable for electron transmission and electrochemical performance.
Third, electrochemical performance analysis of graphene/polyion liquid composite carbon material
The catalytic activity of the carbon material hydrogen evolution performance was tested in a three-electrode system with an electrolyte of 0.5M H2SO4 using CHI 600e electrochemical workstation with a suitable amount of catalyst dropped on a glassy carbon electrode as the working electrode. FIG. 5 (a) is a polarization curve diagram of GCs catalyst obtained by doping and carbonizing graphene oxide and polyion liquid at different ratios at a sweep rate of 5 mV/s. As can be seen, the LSV curves of GC-5 and GC-6 deviate far from the baseline and show poor hydrogen evolution performance. GC-7, GC-8 and GC-9 show better catalytic performance, and the overpotentials are 112 mV, 363 mV and 170 mV respectively at the current density of 10 mA cm < -2 >. In addition, the Tafel slopes corresponding to the polarization curves can be calculated by the formula η = b log + a (j is the current density, b is the Tafel slope), and the Tafel slopes corresponding to GC-7, GC-8 and GC-9 are 52 mV/dec, 95 mV/dec and 101 mV/dec, respectively (FIG. 5 b). GC-7 showed excellent hydrogen evolution catalytic performance compared to the overpotential (27 mV) and the tafel slope (41 mV/dec) of Pt/C.
To further explore the electrochemical properties of GCs, we examined the OER catalytic activity of GCs carbon materials in 1 MKOH solution by polarization curves. As shown in FIG. 6, it can be seen that GC-8 has better oxygen evolution performance than GC-6 and GC-7, with an overpotential of 430 mV at a current density of 10 mA cm-2, which corresponds to a tafel slope of 301 mV.
In conclusion, the polyion liquid is used as a nitrogen source and a sulfur source, and is compounded with graphene oxide, and then deprotonation is carried out to obtain an electrostatically crosslinked precursor material, and further carbonization is carried out to obtain the N and S co-doped porous GCs carbon material. The composite carbon material is found to have high specific surface area and to be a mesoporous material through the characteristic tests of TEM, XRD, XPS, BET, Raman and the like. Electrochemical tests show that the obtained carbon material shows excellent catalytic activity in both hydrogen evolution reaction and oxygen evolution reaction, so that the carbon material has good application prospect in electro-catalytic hydrogen evolution reaction and oxygen evolution reaction.
Drawings
Fig. 1 is SEM and TEM images of the composite carbon material.
Fig. 2 is an XRD pattern of the composite carbon material.
FIG. 3 is a Raman spectrum of a carbon material for GCs.
Fig. 4 is a graph (a) of nitrogen adsorption-desorption and a corresponding graph (b) of pore size distribution of the composite carbon material.
Fig. 5 shows the electrocatalytic performance of different catalysts under acidic conditions. Wherein (a) the polarization curves of the different catalysts in 0.5 MH2SO 4; (b) corresponds to the Tafel curve of graph (a).
FIG. 6 (a) is a plot of the polarization of different catalysts in 1M KOH; (b) corresponds to the Tafel curve of graph (a).
Detailed Description
The preparation and properties of the composite carbon material of the present invention are further illustrated by the following specific examples.
Example 1 preparation of GC-6
Dissolving PCMVImTf2N and GO in a proper amount of DMSO according to the mass ratio of 6:1, and performing ultrasonic treatment for 30 min to form a uniform solution; transferring the solution into a culture dish, drying at 80 ℃ for 4 h under normal pressure, and volatilizing to remove a solvent DMSO to obtain a solid compound; soaking the dried solid compound in an ammonia water solution with the mass concentration of 0.2% for 2 h, taking out the solution, and naturally airing to obtain a precursor material; then placing the precursor material in a tube furnace, taking argon as inert gas, heating from room temperature to 300 ℃ for 1h, wherein the heating rate is 3 ℃/min, then heating from 300 ℃ to 1000 ℃ for 1h, and the heating rate is 3 ℃/min; and finally, naturally cooling to room temperature to obtain the composite carbon material GC-6.
Specific surface area 588.43 m2g of GC-6-1. At a current density of 10 mA cm-2When the voltage is higher than the threshold voltage, the overpotential is 327mV respectively. In addition, the Tafel slope for the polarization curve was 78 mV/dec.
Example 2 preparation of GC-7
Dissolving PCMVImTf2N and GO in a proper amount of DMSO according to the mass ratio of 7:1, and performing ultrasonic treatment for 30 min to form a uniform solution; transferring the solution into a culture dish, drying at 80 ℃ for 4 h under normal pressure, and volatilizing to remove a solvent DMSO to obtain a solid compound; soaking the dried solid compound in an ammonia water solution with the mass concentration of 0.2% for 2 h, taking out the solution, and naturally airing to obtain a precursor material; then placing the precursor material in a tube furnace, taking argon as inert gas, heating from room temperature to 300 ℃ for 1h, wherein the heating rate is 3 ℃/min, then heating from 300 ℃ to 1000 ℃ for 1h, and the heating rate is 3 ℃/min; and finally, naturally cooling to room temperature to obtain the composite carbon material GC-7.
The surface area of GC-7 was 723.61 m2g-1. At a current density of 10 mA cm-2When the voltage is higher than the threshold voltage, the overpotential is 112 mV. In addition, the Tafel slope corresponding to the polarization curve is 52 mV/dec.
Example 3 preparation of GC-8
Dissolving PCMVImTf2N and GO in a proper amount of DMSO according to the mass ratio of 8:1, and performing ultrasonic treatment for 30 min to form a uniform solution; transferring the solution into a culture dish, drying at 80 ℃ for 4 h under normal pressure, and volatilizing to remove a solvent DMSO to obtain a solid compound; soaking the dried solid compound in an ammonia water solution with the mass concentration of 0.2% for 2 h, taking out the solution, and naturally airing to obtain a precursor material; then placing the precursor material in a tube furnace, taking argon as inert gas, heating from room temperature to 300 ℃ for 1h, wherein the heating rate is 3 ℃/min, then heating from 300 ℃ to 1000 ℃ for 1h, and the heating rate is 3 ℃/min; and finally, naturally cooling to room temperature to obtain the composite carbon material GC-8.
GCSpecific surface area 695.12 m2g of-8-1. At a current density of 10 mA cm-2When the voltage is higher than the threshold voltage, the overpotential is 363 mV. In addition, the Tafel slope for the polarization curve was 95 mV/dec.
In each of the above examples, the polyionic liquid PCMVImTf2Preparation of N: preparation of polyion liquid PCMVImTf by three-step reaction2And N is added. Firstly, preparing 1-vinyl-3-cyanomethylimidazole bromine (CMVImBr) by quaternizing N-vinylimidazole and bromoacetonitrile, then preparing poly (1-vinyl-3-cyanomethylimidazole bromine) (PCMVImBr) by performing free radical polymerization of CMVImBr by using dimethyl sulfoxide (DMSO) as a solvent and Azobisisobutyronitrile (AIBN) as an initiator, and finally preparing a polyion liquid PCMVImTf by anion exchange2And N is added. For specific preparation see the following documents:
1：J. Yuan, C. Giordano, M. Antonietti, Ionic Liquid Monomers andPolymers as Precursors of Highly Conductive, Mesoporous, Graphitic CarbonNanostructures.Polym. Chem., 2010,225003-5012；
2：H. Wang, S. Min, C. Ma, Z. Liu, W. Zhang, Q. Wang, D. Li, Y. Li, S.Turner, Y. Han, H. Zhu, E. Abou-hamad, M. N. Hedhili, J. Pan, W. Yu, K. W.Huang, L. J. Li, J. Yuan, M. Antonietti, T. Wu, Synthesis of single-crystal-like nanoporous carbon membranes and their application in overall watersplitting,Nat. Commun., 2017,8, 13592.]。
PCMVImTf2N（n = 200~2000）
preparing graphene oxide: prepared by the Hummers method as follows: 2g NaNO3Adding into 96 mL concentrated sulfuric acid, ultrasonic dispersing for 10 min until NaNO3After dissolving, 2g of flake graphite is added, and then stirred for 30 min in an ice-water bath. The temperature of the reaction system was kept at 0 ℃ and 12 g of KMnO was added in three portions4After stirring for 90 min, the temperature is raised to 35 ℃, after 2 h, the water bath is removed, and 80 mL of water is added. Reacting at 90 ℃ for 2 h, and adding 200 mL of waterAnd (5) stopping the reaction, and finally adding 12 mL of hydrogen peroxide to obtain GO colloid. And adding the prepared HCl solution into the prepared graphene oxide colloid, stirring for 1h, and standing overnight. And pouring out the supernatant, centrifuging and washing the lower layer until the pH value of the upper layer is more than 6, and finally freeze-drying to obtain the graphene oxide.
Claims (4)
1. The preparation method of the graphene/polyion liquid composite carbon material comprises the steps of mixing graphene oxide and polyion liquid PCMVImTf2N is ultrasonically dispersed in DMSO to form a uniform solution; transferring the solution into a culture dish, drying at 70-80 ℃ under normal pressure for 3-4 h, volatilizing to remove a solvent DMSO, and soaking the obtained solid compound in an ammonia water solution to remove protonation to obtain an electrostatic crosslinking precursor material; then placing the precursor material in a tubular furnace, and carrying out high-temperature carbonization under the protection of inert gas to obtain the graphene/polyion liquid composite carbon material;
graphene oxide and polyion liquid PCMVImTf2The mass ratio of N is 1: 5-1: 9;
the carbonization temperature of the precursor material is 800-1000 ℃, and the carbonization time is 5-7 h.
2. The method for producing a graphene/polyion liquid composite carbon material according to claim 1, wherein: the mass concentration of the ammonia water solution is 0.2-1%, and the deprotonation soaking time is 1-2 h.
3. The method for producing a graphene/polyion liquid composite carbon material according to claim 1, wherein: a heating mode: firstly, heating from room temperature to 300 ℃ for 0.5-1 h, wherein the heating rate is 3 ℃/min; then raising the temperature from 300 ℃ to 1000 ℃ and keeping the temperature for 0.5-1 h, wherein the temperature raising speed is 3 ℃/min; and finally, naturally cooling to room temperature.
4. The graphene/polyion liquid composite carbon material prepared by the method of claim 1 is used as a catalyst in hydrogen evolution reaction and oxygen evolution reaction.
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