CN112349921B - Nitrogen-doped graphene hollow sphere catalyst, preparation method and application - Google Patents
Nitrogen-doped graphene hollow sphere catalyst, preparation method and application Download PDFInfo
- Publication number
- CN112349921B CN112349921B CN202011285508.2A CN202011285508A CN112349921B CN 112349921 B CN112349921 B CN 112349921B CN 202011285508 A CN202011285508 A CN 202011285508A CN 112349921 B CN112349921 B CN 112349921B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped graphene
- hollow sphere
- graphene hollow
- nghs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
Abstract
A nitrogen-doped graphene hollow sphere catalyst, a preparation method and applications thereof, wherein the nitrogen-doped graphene hollow sphere catalyst is a nitrogen-doped graphene hollow sphere (CN) modified by carbon nitride used as a carrierx-NGHS) and nitrogen-doped graphene hollow sphere (CN) modified by carbon nitride and loaded by transition metal and transition metal oxidex-NGHS) surface composition; the preparation method comprises the following steps: preparing the carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS); growing transition metal/oxide nanoparticles on CNxCN made on the surface of-NGHSxThe application of the nitrogen-doped graphene hollow sphere negative catalyst in Oxygen Reduction Reaction (ORR) and Oxygen Evolution (OER) reactions of the catalytic chargeable zinc-air battery can obviously enhance O2The molecular adsorption efficiency is improved, the stability and the electric conductivity are improved, and the overpotential in ORR and OER reactions is low, so that the requirements of commercial application can be met.
Description
Technical Field
The invention belongs to the technical field of air electrode bifunctional catalysts of rechargeable zinc-air batteries, and particularly relates to a nitrogen-doped graphene hollow sphere catalyst, a preparation method and application.
Background
Nowadays, fossil fuel-dominated energy sources are the main driving force for promoting the development of the well-off socioeconomic development. However, with the excessive consumption and exhaustion of traditional fossil fuels, not only global greenhouse effect and environmental pollution are aggravated, but also a severe energy crisis is brought. This not only hinders the establishment of a good well-being society, but also affects the national living environment. Therefore, the efficient and reasonable utilization of green and sustainable new energy has become a research hotspot in the energy field at home and abroad nowadays.
A metal-air battery has two important reaction units, an air electrode and a metal electrode. Among them, the air electrode (cathode) is the core unit of the metal-air battery, and the oxygen utilization rate of the air electrode is a major factor affecting the discharge efficiency, life and actual specific energy of the battery. The other electrode is a metal electrode, the active material of the metal electrode (anode) is metal, and the metal is continuously consumed in the discharge process, so the energy density of the battery is influenced by the metal material. I.e., the greater the energy density of the metal material, the greater the energy density of the battery, and the discharge reaction of the anode depends mainly on the activity of the metal used, the type of electrolyte, and the progress of the discharge reaction. The two units are core reaction units of renewable energy technology, and the application relates to a plurality of fields of metal-air batteries, fuel cells, water hydrogen production and the like. The metal-air battery may be classified into a zinc-air battery, a magnesium-air battery, a lithium-air battery, an aluminum-air battery, and the like according to the difference of metal electrodes. In the metal-air battery, oxygen or pure oxygen in air is used as an active material of a cathode, and active metals of zinc, aluminum, magnesium, lithium or an alloy thereof are used as active materials of an anode. The zinc-air battery is an ideal energy battery in metal-air batteries and has wide commercial application prospect due to the advantages of rich zinc reserves, low price, no pollution of raw materials and products and the like.
Zinc-air fuel cells have many advantages such as green safety, zero pollution, high energy conversion, high power, low cost, and renewable materials. Compared with a lithium ion battery, the zinc-air battery has the advantages of high theoretical energy density, low preparation cost, simple equipment structure and the like. Therefore, the zinc-air battery gradually receives wide attention of researchers and becomes a research hotspot for developing green energy, but how to improve the slow dynamic characteristics of the air electrode of the zinc-air battery is still one of the challenges of the current research. The electrochemical reaction process of the air electrode is complex in mechanism, involves mass transfer among multiple phases and multiple interfaces, and has inherent delayed reaction kinetics including Oxygen Reduction Reaction (ORR) in a discharging process and Oxygen Evolution Reaction (OER) in a charging process, which are main reasons for high polarization and low reversibility of the zinc-air battery. Catalysts prepared from precious metals used at present have various problems, for example, Pt and its alloys have excellent oxygen reduction performance, but their OER activity is low; ir and RuO2The oxygen evolution performance of (2) is high, however, the oxygen reduction performance is not good. In addition, the use of noble metal catalysts in electrochemistry is greatly limited due to the factors of scarce reserves, high price, poor stability and the like. Therefore, the development of a highly efficient, low cost bifunctional electrocatalyst with high activity and excellent durability for both ORR and OER is crucial to improve the popularity and commercialization of zinc-air batteries.
Nowadays, there are mainly transition metal oxide catalysts, transition metal sulfide catalysts, metal nitride and metal carbide catalysts, and the like. These catalysts have been widely developed as ORR/OER bifunctional catalysts, and exhibit excellent electrochemical activity, but when they are directly used as catalysts, they are subject to certain restrictions, resulting in poor electrical conductivity. The introduction of conductive agents such as nanocarbon or doped carbon-based materials is the key to solving this problem. The nitrogen-doped graphene hollow sphere (NGHS) has a unique elastic three-dimensional hollow structure, so that the prepared catalyst can be effectively prevented from deforming and collapsing in the charging and discharging processes. The nitrogen-doped graphene hollow sphere (NGHS) also has physicochemical properties of excellent electronic conductivity, high mechanical strength, higher specific surface area, good chemical stability and the like. However, the surface of the nitrogen-doped graphene hollow spheres (NGHS) which are not modified or surface-treated is inert and hydrophobic, and is difficult to disperse in most organic or inorganic solvents, so that active metal or metal oxide nanoparticles with small size are not easy to uniformly deposit on the surface. Therefore, modifying the surface of the nitrogen-doped graphene hollow sphere to construct a carbon nitride modified nitrogen-doped graphene hollow sphere with sufficient support strength and good conductivity, and then loading transition metal and oxide thereof with small size on the carbon nitride modified nitrogen-doped graphene hollow sphere are key factors for exploring the application of the high-efficiency bifunctional catalyst to the rechargeable zinc-air battery. Therefore, the invention provides the bifunctional electrocatalyst with good catalysis effect on the oxygen reduction reaction and the oxygen precipitation reaction, which is used for improving the charge and discharge performance of the rechargeable zinc-air battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nitrogen-doped graphene hollow sphere catalyst, a preparation method and application.
The purpose of the invention is realized by the following technical scheme on one hand:
a preparation method of a nitrogen-doped graphene hollow sphere catalyst comprises the following steps:
the method comprises the following steps: mixing the Graphene Oxide (GO) with negative charges dispersed in the aqueous solution with the Polystyrene Spheres (PS) with positive charges dispersed in the acid solution, stirring at room temperature for 10-15h, and wrapping the Graphene Oxide (GO) on the surfaces of the Polystyrene Spheres (PS) through electrostatic interaction in the process; then adding aniline monomer and dropwise adding ammonium persulfate solution, initiating aniline monomer oxidative polymerization reaction for 12-24h at-5-2 ℃, adding urea and hydrazine hydrate, further heating to 100-150 ℃ and reacting for 12-24 h; freeze drying to obtain the product;
step two: dispersing the product obtained after freeze drying in the step one in an aqueous solution dissolved with melamine, stirring for 6-24h at room temperature, collecting the suspension generated by the step one, drying the suspension, and then carrying out inert atmosphere 400-500 DEG CCalcining for 1-3h, and then calcining and reacting for 1-3h at the temperature of 700-x-NGHS)；
Step three: adding ammonia water, transition metal salt solution, ethanol and carbon nitride modified nitrogen-doped graphene hollow spheres (CN) into a hydrothermal reaction kettlex-NGHS), stirring for 0.5-1h at room temperature, heating to 160-.
Further, in the first step, the mass-to-volume ratio of the graphene oxide, the polystyrene spheres, the acid solution, the ammonium persulfate, the aniline monomer, the urea and the hydrazine hydrate is as follows: 50-150 mg: 1-3 g; 50-150mL, 5-10g, 3-7mL, 0.2-0.4mol, 0.05-2 mL.
Further, the mass ratio of the product obtained after freeze drying in the second step to melamine is as follows: 2-10g and 1-5 g.
Further, in the third step, the mass-to-volume ratio of the ammonia water, the transition metal salt, the ethanol and the carbon nitride modified nitrogen-doped graphene hollow sphere is as follows: 2-8mL, 0.4-1.6mmol, 2-20mL, 20-100 mg.
Further, the acid solution in the first step is 0.1-2mol L-1Hydrochloric acid or sulfuric acid.
Further, the inert gas in the second step and the third step is high-purity N2Or high purity Ar.
Further, the transition metal salt in step three is one or any combination of transition metal salts of iron, cobalt and nickel, wherein the cobalt transition metal salt comprises Co (NO)3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、CoCl2、CoSO4·7H2O、CoSO4·H2O, nickel transition metal salts including Ni (NO)3)2·6H2O、NiCl2·6H2O、Ni(CH3COO)2、NiSO4·6H2O, Fe transition metal salts including FeCl3、Fe2(SO4)3、Fe(NO3)3。
The other aim of the invention is realized by the following technical scheme:
the nitrogen-doped graphene hollow sphere catalyst is prepared by modifying nitrogen-doped graphene hollow spheres (CN) by using carbon nitride as a carrierx-NGHS) and transition metal oxide nanoparticles loaded on the carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS) surface, wherein the carbon nitride modified nitrogen doped graphene hollow spheres have a three-dimensional and porous structure.
The other aspect of the object of the invention is realized by the following technical scheme:
the application of the nitrogen-doped graphene hollow sphere catalyst is characterized in that the nitrogen-doped graphene hollow sphere catalyst is used for catalyzing an Oxygen Reduction Reaction (ORR)/Oxygen Evolution Reaction (OER) of a rechargeable zinc-air battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon nitride modified nitrogen-doped graphene hollow sphere is a preferential carrier compared with a common carbon-based support material due to the three-dimensional and porous structure. By doping nitrogen and other heteroatoms, the conductivity of the graphene can be further enhanced, and the electron transfer capacity of the graphene can be improved by adjusting the electron orbital energy of carbon; and the stability of the elastic three-dimensional hollow structure is also obviously optimized, so that the elastic three-dimensional hollow structure is not easy to deform and collapse in the repeated charging and discharging process.
(2) The Polyaniline (PANI) material coated on the outer surface of the hollow sphere further forms nitrogen-doped Carbide (CN) in the calcining processx) Thereby effectively improving the anchoring of the metal/oxide while avoiding collapse of the spheres during metal/oxide deposition.
(3) The combination of the carbon nitride and the nitrogen-doped graphene hollow sphere is beneficial to the nucleation and growth of the loaded metal/oxide nanoparticles, and the interaction between the metal/oxide nanoparticles and the carbon nitride modified nitrogen-doped graphene hollow sphere is promoted, so that the electrochemical catalytic activity is greatly improved.
Description of the figures
Fig. 1 is a microscopic topography of the nitrogen-doped graphene hollow sphere catalyst prepared in example 2 under a scanning electron microscope.
Figure 2 is a plot of the linear sweep voltammetry measurements for the oxygen reduction reactions of the prepared catalysts of example 2, example 3, example 4, example 5, example 6 and a commercial 20 wt.% Pt/C catalyst.
FIG. 3 shows the preparation of catalyst and commercial RuO in example 2, example 3, example 4, example 5, example 62Linear sweep voltammetric plots of the oxygen evolution reaction of the catalyst.
Fig. 4 polarization and power density profiles of assembled zinc air cells prepared with nitrogen doped graphene hollow sphere catalyst and commercial 10 wt% Pt/C catalyst of example 2.
Detailed Description
In order to make the purpose, technical scheme and beneficial technical effects of the present invention clearer, the following describes in detail a preparation method of a bifunctional catalyst of a carbon nitride modified nitrogen-doped graphene hollow sphere loaded transition metal and an oxide nanoparticle thereof, with reference to the accompanying drawings and specific embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and the parameters, proportions and the like of the embodiments may be suitably selected without materially affecting the results.
Example 1;
the nitrogen-doped graphene hollow sphere catalyst is prepared by modifying nitrogen-doped graphene hollow spheres (CN) by using carbon nitride as a carrierx-NGHS) and transition metal oxide nanoparticles loaded on the carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS) surface, wherein carbon nitride modified nitrogen doped graphene hollow spheres are preferential carriers compared to common carbon based support materials due to their three-dimensional and porous structure. By hetero atoms, e.g. nitrogenThe doping of the particles can further enhance the conductivity of the graphene, and the electron transfer capacity of the graphene is improved by adjusting the electron orbital energy of carbon; and the stability of the elastic three-dimensional hollow structure is also obviously optimized, so that the elastic three-dimensional hollow structure is not easy to deform and collapse in the repeated charging and discharging process.
Example 2;
the preparation method of the nitrogen-doped graphene hollow sphere catalyst comprises the following steps of taking a carbon nitride modified nitrogen-doped graphene hollow sphere as a carrier, and loading cobalt transition metal salt (Co) and cobalt transition metal salt oxide (CoO) nanoparticles on the surface of the carbon nitride modified nitrogen-doped graphene hollow sphere:
step one, dispersing 100mg of Graphene Oxide (GO) in an aqueous solution, then mixing with 2g of positively charged Polystyrene Spheres (PS) dispersed in 100mL of hydrochloric acid (0.5M) solution, stirring at 25 ℃ for 12h, then adding 5mL of aniline monomer, simultaneously dropwise adding an aqueous solution containing 7.5g of ammonium persulfate, stirring the reaction mixture at 0 ℃ for 24h, then adding 0.25mol of urea and 0.1mL of hydrazine hydrate, further heating to 110 ℃, keeping for 24h, and freeze-drying to obtain a product;
step two, 5g of the product obtained in step one are immersed in 100mL of H containing 3g of melamine2Magnetically stirring the mixture in O solution at room temperature for 12 hours, collecting the suspension, calcining the suspension at 420 ℃ for 2 hours in a nitrogen atmosphere, and calcining the suspension at 750 ℃ for 1 hour in a nitrogen atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS)。
Step three, adding 4mL of ammonia water into a 50mL polytetrafluoroethylene reaction vessel, and simultaneously adding 800 muL of 1.0M Co (NO) into the 50mL polytetrafluoroethylene reaction vessel3)2Adding 8mL of ethanol into the solution, and adding 66.8mg of carbon nitride modified nitrogen-doped graphene hollow spheres (CN) into a containerx-NGHS) and reacted for 30 min. The mixture was then transferred to a sealed autoclave and reacted at 180 ℃ for 24 h. Then, filtering the obtained mixture by using a vacuum filter, drying the mixture in a vacuum drying oven at 70 ℃ to obtain powder, and calcining the powder for 2 hours at 800 ℃ in a nitrogen atmosphere to obtain carbon nitride modified nitrogen-doped graphene hollow sphere loaded Co and CoO nanoparticle bifunctional catalyst (Co @ CoO/CN)x-NGHS), i.e. nitrogen doped graphene hollow sphere catalyst.
As shown in fig. 1, a sample is subjected to morphological analysis by using a scanning electron microscope, and it is known that the prepared nitrogen-doped graphene hollow sphere catalyst is composed of cobalt transition metal salt (Co) and cobalt transition metal salt oxide (CoO) nanoparticles loaded on the surface of a hollow graphene sphere, and not only the conductivity of graphene is improved by doping N atoms, but also the prepared catalyst is prevented from deforming and collapsing in the charge and discharge processes due to the elastic three-dimensional hollow structure.
Carbon nitride modified nitrogen-doped graphene hollow sphere loaded Co and CoO nanoparticle dual-functional catalyst (Co @ CoO/CN)x-NGHS) is catalyzed in oxygen reduction reaction ORR/oxygen evolution reaction OER of rechargeable zinc-air battery as follows:
in the testing process, a standard three-electrode electrochemical testing system is adopted and respectively consists of a Saturated Calomel Electrode (SCE) (reference electrode), a platinum wire electrode (counter electrode) and a glassy carbon electrode/disc electrode (working electrode) coated with various catalysts.
The experimental procedure was carried out in KOH (0.1M) solution at room temperature. 4.0mg of the experimentally synthesized catalyst was mixed with 13. mu.L Nafion solution (5.0 wt%), 705. mu.L DI water and 282. mu.L isopropanol. The mixture was sonicated for at least 1h to form a homogeneous mixed solution. Then, 10. mu.L of the prepared solution was dropped on a glassy carbon electrode having a diameter of 5 mm. The mass density of the working electrode was about 2.04mg cm-2. The electrode potential in the experiment is controlled by ERHE＝ESCEThe +0.2415+0.059pH translates to the reversible hydrogen electrode scale (RHE).
Co @ CoO/CN test Using a Rotating Disk Electrode (RDE)xNGHS sample with commercial 20 wt.% Pt/C catalyst at saturation O2The LSV curve at 1600rpm for the 0.1M KOH solution of (2) is shown in FIG. 2, curves # 1 and # 6. Co @ CoO/CNxThe NGHS samples exhibited very high ORR electrocatalytic activity, with an onset potential and half-wave potential of 1.144 and 0.836V vs. rhe, respectively, which was close to that of the commercial Pt/C catalysts tested under the same conditions (onset potential and half-wave potential of 0.997 and 0.848V vs. rhe, respectively). Electric powerAt a bit of less than 0.8V, Co @ CoO/CNxThe NGHS sample exhibits a high limiting current density, very close to the commercial Pt/C catalyst, indicating that the material has faster reaction kinetics in the ORR electrocatalytic process.
Testing of Co @ CoO/CN Using a Rotating Disk Electrode (RDE)xNGHS sample at O2OER catalytic Activity in saturated 0.1M KOH electrolyte, commercial RuO2The catalysts were tested under the same conditions as a comparative reference. FIG. 3, curve 1# is Co @ CoO/CNxLSV curve of OER catalytic Performance of-NGHS sample, Co @ CoO/CNxSamples of-NGHS at a current density of 10mA cm-2The OER overpotential is only 334 mV. Specific commercial RuO under the same test conditions2The overpotential for the catalyst (curve 6#) was 95mV lower, indicating Co @ CoO/CNxThe NGHS samples had excellent OER electrocatalytic activity.
Preparing a zinc-air battery working electrode: preparing the synthesized catalyst into catalyst slurry, spraying the catalyst slurry on carbon paper to prepare an air electrode, and drying the air electrode at room temperature for 24 hours (the catalyst loading is 2.0mg cm)-2) And a polished zinc plate with the thickness of 0.2mm is adopted for preparing the anode. Using a catalyst containing 0.2M ZnCl2The 6M KOH solution of (1) was used as an electrolyte for a rechargeable zinc-air cell.
With Co/CoO/CN under the same test conditionsxMaximum power density of 117mW cm for the-NGHS catalyst-assembled zinc-air cell-2As shown in FIG. 4, curve 1#, higher than commercial 10% Pt/C (95mW cm)-2) Power density (curve 2#), which indicates Co/CoO/CNxthe-NGHS catalysts have excellent bifunctional electrocatalytic properties.
Example 3;
the preparation method of the nitrogen-doped graphene hollow sphere catalyst comprises the following steps of taking a carbon nitride modified nitrogen-doped graphene hollow sphere as a carrier, and loading nickel transition metal salt (Ni) and nickel transition metal salt oxide (NiO) nanoparticles on the surface of the carbon nitride modified nitrogen-doped graphene hollow sphere:
step one, dispersing 100mg of Graphene Oxide (GO) in an aqueous solution, then mixing with 2g of positively charged Polystyrene Spheres (PS) dispersed in 100mL of hydrochloric acid (0.5M) solution, stirring at 25 ℃ for 12h, then adding 5mL of aniline monomer, simultaneously dropwise adding an aqueous solution containing 7.5g of ammonium persulfate, stirring the reaction mixture at 0 ℃ for 24h, then adding 0.25mol of urea and 0.1mL of hydrazine hydrate, further heating to 110 ℃, keeping for 24h, and freeze-drying the obtained product.
Step two, 5g of the product obtained in step one are immersed in 100mL of H containing 3g of melamine2Magnetically stirring the mixture in O solution at room temperature for 12 hours, collecting the suspension, calcining the suspension at 420 ℃ for 2 hours in a nitrogen atmosphere, and calcining the suspension at 750 ℃ for 1 hour in a nitrogen atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS)。
Step three, adding 4mL of ammonia water into a 50mL polytetrafluoroethylene reaction vessel, and simultaneously adding 800 μ L of 1.0M Ni (NO) into the reaction vessel3)2Adding 8mL of ethanol into the solution, and adding 66.8mg of carbon nitride modified nitrogen-doped graphene hollow spheres (CN) into a containerx-NGHS) and reacted for 30min, after which the mixture was transferred to a sealed autoclave and reacted at 180 ℃ for 24 h. Then, filtering the obtained mixture by using a vacuum filter, drying the mixture in a vacuum drying oven at 70 ℃ to obtain powder, calcining the obtained powder for 2 hours at 800 ℃ in a nitrogen atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow sphere loaded Ni and NiO nanoparticle dual-function catalyst (Ni @ NiO/CN)x-NGHS)。
Carbon nitride modified nitrogen-doped graphene hollow sphere loaded Ni and NiO nanoparticle dual-function catalyst (Ni @ NiO/CN)x-NGHS) is catalyzed in oxygen reduction reaction ORR/oxygen evolution reaction OER of rechargeable zinc-air battery as follows: carbon nitride modified nitrogen-doped graphene hollow sphere loaded Ni and NiO nanoparticle dual-function catalyst (Ni @ NiO/CN)xNGHS) using a Rotating Disk Electrode (RDE) test, a Rotating Disk Electrode (RDE) test Ni @ NiO/CNxNGHS samples in saturated O2The LSV curve at 1600rpm in 0.1M KOH solution, the result is shown in FIG. 2 as curve # 2. Ni @ NiO/CNxNGHS samples exhibited very high ORR electrocatalytic activity, with an onset potential and half-wave potential of 1.112 and 0.815V vs. RHE, respectively, close to that of the commercial Pt/C catalyst tested under the same conditionsAgent (initial potential and half-wave potential 0.997 and 0.848V vs. rhe, respectively). When the potential is lower than 0.8V, Ni @ NiO/CNxThe NGHS sample exhibits a high limiting current density, very close to the commercial Pt/C catalyst, indicating that the material has faster reaction kinetics in the ORR electrocatalytic process.
Carbon nitride modified nitrogen-doped graphene hollow sphere loaded Ni and NiO nanoparticle dual-function catalyst (Ni @ NiO/CN)xNGHS) using a Rotating Disk Electrode (RDE) test, a Rotating Disk Electrode (RDE) test Ni @ NiO/CNxNGHS sample at O2OER catalytic activity in saturated 0.1M KOH electrolyte. FIG. 3, curve 2# is Ni @ NiO/CNxLSV curve of OER catalytic Performance of-NGHS samples, Ni @ NiO/CNxSamples of-NGHS at a current density of 10mA cm-2The OER overpotential is only 366 mV. Specific commercial RuO under the same test conditions2The overpotential of the catalyst is low by 63mV, which shows that Ni @ NiO/CNxThe NGHS samples had excellent OER electrocatalytic activity.
Example 4;
the preparation method of the nitrogen-doped graphene hollow sphere catalyst comprises the following steps of taking a carbon nitride modified nitrogen-doped graphene hollow sphere as a carrier, and loading nickel transition metal salt (NiCo) and nickel transition metal salt oxide (NiO-CoO) nanoparticles on the surface of the carbon nitride modified nitrogen-doped graphene hollow sphere, wherein the carbon nitride modified nitrogen-doped graphene hollow sphere catalyst is prepared by the following steps:
step one, dispersing 100mg of Graphene Oxide (GO) in an aqueous solution, then mixing with 2g of positively charged Polystyrene Spheres (PS) dispersed in 100mL of hydrochloric acid (0.5M) solution, stirring at 25 ℃ for 12h, then adding 5mL of aniline monomer, simultaneously dropwise adding an aqueous solution containing 7.5g of ammonium persulfate, stirring the reaction mixture at 0 ℃ for 24h, then adding 0.25mol of urea and 0.1mL of hydrazine hydrate, further heating to 110 ℃, keeping for 24h, and freeze-drying to obtain a product;
step two, 5g of the product obtained in step one are immersed in 100mL of H containing 3g of melamine2O solution, after 12h of magnetic stirring at room temperature, the resulting suspension was collected. Then calcining for 2 hours at the temperature of 420 ℃ in a nitrogen atmosphere, and then calcining for 1 hour at the temperature of 750 ℃ in a nitrogen atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow coreBall (CN)x-NGHS)。
Step three, adding 4mL of ammonia water into a 50mL polytetrafluoroethylene reaction vessel, and simultaneously adding 400 μ L of 1.0M Ni (NO) into the reaction vessel3)2And 400. mu.L of 1.0M Co (NO)3)2An additional 8mL of ethanol was added, and then 66.8mg of CN was added to the vesselxNGHS and reaction for 30 min. The mixture was then transferred to a sealed autoclave and reacted at 180 ℃ for 24 h. Then, filtering the obtained mixture by using a vacuum filter, drying the mixture in a vacuum drying oven at 70 ℃ to obtain powder, calcining the obtained powder for 2 hours at 800 ℃ in a nitrogen atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow sphere loaded NiCo and NiO-CoO nanoparticle dual-function catalyst (NiCo @ NiO-CoO/CN)x-NGHS)。
The carbon nitride modified nitrogen-doped graphene hollow sphere loaded NiCo and NiO-CoO nanoparticle bifunctional catalyst (NiCo @ NiO-CoO/CNx-NGHS) is catalyzed in an oxygen reduction reaction ORR/oxygen evolution reaction OER of a rechargeable zinc-air battery as follows:
the carbon nitride modified nitrogen-doped graphene hollow sphere loaded NiCo and NiO-CoO nanoparticle bifunctional catalyst (NiCo @ NiO-CoO/CNx-NGHS) adopts a Rotating Disk Electrode (RDE) to test an LSV curve with the rotating speed of 1600rpm of a NiCo @ NiO-CoO/CNx-NGHS sample in a 0.1M KOH solution of saturated O2, and the result is shown as a curve 3# in FIG. 2. Samples of NiCo @ NiO-CoO/CNx-NGHS exhibited very high ORR electrocatalytic activity at 1.104 and 0.829V vs. RHE for the onset and half-wave potentials, respectively, which was close to that of the commercial Pt/C catalyst tested under the same conditions (0.997 and 0.848V vs. RHE for the onset and half-wave potentials, respectively). At potentials below 0.8V, the NiCo @ NiO-CoO/CNx-NGHS samples exhibited high limiting current densities, very close to commercial Pt/C catalysts, indicating that the material had faster reaction kinetics during ORR electrocatalysis.
The carbon nitride modified nitrogen-doped graphene hollow sphere loaded NiCo and NiO-CoO nanoparticle bifunctional catalyst (NiCo @ NiO-CoO/CNx-NGHS) adopts a Rotating Disk Electrode (RDE) to test the OER catalytic activity of a NiCo @ NiO-CoO/CNx-NGHS sample in O2 saturated 0.1M KOH electrolyte. As shown in FIG. 3, curve # 3 is the LSV curve for OER catalytic performance for NiCo @ NiO-CoO/CNx-NGHS samples, and at a current density of 10mA cm-2, the OER overpotential for NiCo @ NiO-CoO/CNx-NGHS samples is only 335 mV. The overpotential was 94mV lower than that of the commercial RuO2 catalyst under the same test conditions, indicating that the NiCo @ NiO-CoO/CNx-NGHS sample had excellent OER electrocatalytic activity.
Example 5;
the preparation of the Co and CoO nano-particle bifunctional catalyst (Co @ CoO) comprises the following steps:
to a 50mL polytetrafluoroethylene reaction vessel, 4mL of aqueous ammonia was added, and simultaneously to the above reaction vessel, 800. mu.L of a 1.0M Co (NO3)2 solution and 8mL of ethanol were added and reacted for 30min, after which the mixture was transferred to a sealed autoclave and reacted at 180 ℃ for 24 h. Subsequently, the resulting mixture was filtered with a vacuum filter and dried in a vacuum oven at 70 ℃ to give a powder, and the resulting powder was calcined at 800 ℃ for 2h in a nitrogen atmosphere to give a Co and CoO nanoparticle bifunctional catalyst (Co @ CoO).
The bifunctional catalyst (Co @ CoO) of Co and CoO nano particles and the oxygen reduction reaction ORR/oxygen evolution reaction OER of the chargeable zinc-air battery are catalyzed as follows:
co and CoO nanoparticle bifunctional catalysts (Co @ CoO) the LSV curve of a Co @ CoO sample in a 0.1M KOH solution of saturated O2 at 1600rpm was tested using a Rotating Disk Electrode (RDE) and the results are shown in FIG. 2 as curve # 4. The Co @ CoO sample exhibited poor ORR electrocatalytic activity with an onset potential and a half-wave potential of 0.674 and 0.598V vs.
Co and CoO nanoparticle bifunctional catalysts (Co @ CoO) the OER catalytic activity of the Co @ CoO samples was tested in a 0.1M KOH electrolyte saturated with O2 using a Rotating Disk Electrode (RDE). As shown in FIG. 3, curve # 4 is the LSV curve for OER catalytic performance of the Co @ CoO sample, which has an OER overpotential of 397mV at a current density of 10mA cm-2.
Example 6;
the preparation method of the carbon nitride modified nitrogen-doped graphene hollow sphere comprises the following steps:
step one, dispersing 100mg of Graphene Oxide (GO) in an aqueous solution, then mixing with 2g of positively charged Polystyrene Spheres (PS) dispersed in 100mL of hydrochloric acid (0.5M) solution, stirring at 25 ℃ for 12h, then adding 5mL of aniline monomer, simultaneously dropwise adding an aqueous solution containing 7.5g of ammonium persulfate, stirring the reaction mixture at 0 ℃ for 24h, then adding 0.25mol of urea and 0.1mL of hydrazine hydrate, further heating to 110 ℃, keeping for 24h, and freeze-drying to obtain a product;
step two, 5g of the product obtained in step one are immersed in 100mL of H containing 3g of melamine2O solution, after 12h of magnetic stirring at room temperature, the resulting suspension was collected. Calcining for 2h at 420 ℃ in a nitrogen atmosphere, and then calcining for 1h at 750 ℃ in a nitrogen atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS)。
Carbon nitride modified nitrogen-doped graphene hollow sphere (CN)x-NGHS) is catalyzed in oxygen reduction reaction ORR/oxygen evolution reaction OER of rechargeable zinc-air battery as follows:
carbon nitride modified nitrogen-doped graphene hollow sphere (CN)xNGHS) CN was tested using a Rotating Disk Electrode (RDE)xNGHS samples in saturated O2The LSV curve at 1600rpm in 0.1M KOH solution, the result is shown in FIG. 2 as curve # 5. CNxNGHS samples exhibited relatively poor ORR electrocatalytic activity, with onset and half-wave potentials of 1.039 and 0.769V vs.
Carbon nitride modified nitrogen-doped graphene hollow sphere (CN)xNGHS) CN was tested using a Rotating Disk Electrode (RDE)xNGHS sample at O2OER catalytic activity in saturated 0.1M KOH electrolyte. CN at curve 5# in FIG. 3xLSV curve, CN, of OER catalytic Performance of NGHS samplesxSamples of-NGHS at a current density of 10mA cm-2The OER overpotential is 512 mV.
Example 7;
the application of the nitrogen-doped graphene hollow sphere catalyst is characterized in that the nitrogen-doped graphene hollow sphere catalyst is adopted to be catalyzed in Oxygen Reduction Reaction (ORR)/Oxygen Evolution Reaction (OER) of a rechargeable zinc-air battery, the synthesized catalyst is prepared into catalyst slurry and sprayed on carbon paper to prepare an air electrode, and the air electrode is dried at room temperature for 24 hours (the catalyst loading amount is equal to that of the catalyst)2.0mg cm-2) And a polished zinc plate with the thickness of 0.2mm is adopted for preparing the anode. Using a catalyst containing 0.2M ZnCl2The 6M KOH solution of (1) was used as an electrolyte for a rechargeable zinc-air cell.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A preparation method of a nitrogen-doped graphene hollow sphere catalyst is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: mixing the Graphene Oxide (GO) with negative charges dispersed in the aqueous solution with the Polystyrene Spheres (PS) with positive charges dispersed in the acid solution, stirring at room temperature for 10-15h, and wrapping the Graphene Oxide (GO) on the surfaces of the Polystyrene Spheres (PS) through electrostatic interaction in the process; then adding an aniline monomer and dropwise adding an ammonium persulfate solution, initiating an aniline monomer oxidative polymerization reaction for 12-24h under the condition of-5-2 ℃, then adding urea and hydrazine hydrate, further heating to 100-; freeze drying to obtain the product;
step two: dispersing the product obtained after freeze drying in the step one in an aqueous solution dissolved with melamine, stirring at room temperature for 6-24h, collecting the suspension generated by the step one, drying the suspension, calcining at 500 ℃ in an inert atmosphere of 400-x-NGHS)；
Step three: adding ammonia water, transition metal salt solution, ethanol and carbon nitride modified nitrogen-doped graphene hollow spheres (CN) into a hydrothermal reaction kettlex-NGHS), stirring for 0.5-1h at room temperature, heating to 160-800 ℃ for 12-24h to obtain powder, and calcining the powder at 600-800 ℃ for 1-3h in an inert atmosphere to obtain the carbon nitride modified nitrogen-doped graphene hollow sphere loaded transition metal and oxide nanoparticle thereofAnd a catalyst, namely a nitrogen-doped graphene hollow sphere catalyst.
2. The preparation method of the nitrogen-doped graphene hollow sphere catalyst according to claim 1, which is characterized by comprising the following steps: in the first step, the mass-to-volume ratio of the graphene oxide, the polystyrene spheres, the acid solution, the ammonium persulfate, the aniline monomer, the urea and the hydrazine hydrate is as follows: 50-150 mg: 1-3 g: 50-150mL, 5-10g, 3-7mL, 0.2-0.4mol, 0.05-2 mL.
3. The preparation method of the nitrogen-doped graphene hollow sphere catalyst according to claim 1, wherein the mass ratio of the product obtained after freeze drying in the second step to melamine is as follows: 2-10g and 1-5 g.
4. The preparation method of the nitrogen-doped graphene hollow sphere catalyst according to claim 1, wherein the mass-to-volume ratio of the ammonia water, the transition metal salt, the ethanol and the carbon nitride modified nitrogen-doped graphene hollow sphere in the third step is as follows: 2-8mL, 0.4-1.6mmol, 2-20mL, 20-100 mg.
5. The preparation method of the nitrogen-doped graphene hollow sphere catalyst according to claim 1, wherein the acid solution in the first step is hydrochloric acid or sulfuric acid, and the concentration of the acid solution is 0.1-2mol L-1。
6. The method for preparing the nitrogen-doped graphene hollow sphere catalyst according to claim 1, wherein the transition metal salt in the third step is one or any combination of transition metal salts of iron, cobalt and nickel, wherein the transition metal salt of cobalt comprises Co (NO)3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、CoCl2、CoSO4·7H2O、CoSO4·H2O, nickel transition metal salts including Ni (NO)3)2·6H2O、NiCl2·6H2O、Ni(CH3COO)2、NiSO4·6H2O, Fe transition metal salts including FeCl3、Fe2(SO4)3、Fe(NO3)3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011285508.2A CN112349921B (en) | 2020-11-17 | 2020-11-17 | Nitrogen-doped graphene hollow sphere catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011285508.2A CN112349921B (en) | 2020-11-17 | 2020-11-17 | Nitrogen-doped graphene hollow sphere catalyst, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112349921A CN112349921A (en) | 2021-02-09 |
| CN112349921B true CN112349921B (en) | 2021-09-24 |
Family
ID=74363995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011285508.2A Active CN112349921B (en) | 2020-11-17 | 2020-11-17 | Nitrogen-doped graphene hollow sphere catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112349921B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120883B (en) * | 2021-04-21 | 2023-08-18 | 湖南理工学院 | Doped porous carbon nano-roll electrode material and preparation method thereof |
| CN114540868B (en) * | 2022-01-19 | 2022-11-08 | 苏州大学 | Preparation method and application of Co, N and S Co-doped carbon nano candida composite material |
| CN114695908A (en) * | 2022-04-21 | 2022-07-01 | 浙江理工大学 | Preparation and application of composite hollow graphene ball-loaded platinum-nickel nanoparticles |
| CN114976067B (en) * | 2022-06-09 | 2023-04-07 | 中南大学 | Metal-oxygen compound heterogeneous combination single-site catalyst and preparation method thereof |
| CN115224293B (en) * | 2022-08-17 | 2024-01-16 | 郑州大学 | ORR and OER dual-function catalyst and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210042A (en) * | 2008-09-08 | 2011-10-05 | 新加坡南洋理工大学 | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
| CN103985875A (en) * | 2014-05-21 | 2014-08-13 | 南京理工大学 | Application of graphene-carbon nitride composite material |
| CN105236399A (en) * | 2015-10-14 | 2016-01-13 | 上海大学 | Nitrogen-doped graphene hollow microsphere (NGHM) preparation method |
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| KR101640545B1 (en) * | 2015-03-27 | 2016-07-18 | 부산대학교 산학협력단 | Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same |
| CN106475081A (en) * | 2015-08-18 | 2017-03-08 | 华为技术有限公司 | A kind of C2N Graphene composite noble metal nanocatalyst and preparation method thereof |
| CN108615905A (en) * | 2018-05-09 | 2018-10-02 | 武汉理工大学 | A kind of nitrogen-doped graphene load cobalt atom and its preparation method and application |
| CN109300703A (en) * | 2018-12-04 | 2019-02-01 | 浙江理工大学 | Cobalt nickel bimetal hydroxide nano piece/nitridation carbon coating N doping hollow graphite alkene ball composite material and preparation method and application |
| CN111554941A (en) * | 2020-04-01 | 2020-08-18 | 南方科技大学 | Bifunctional catalyst, preparation method thereof and metal-air battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016086234A1 (en) * | 2014-11-30 | 2016-06-02 | The Texas A&M University System | Non-noble element catalysts and methods for making |
-
2020
- 2020-11-17 CN CN202011285508.2A patent/CN112349921B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210042A (en) * | 2008-09-08 | 2011-10-05 | 新加坡南洋理工大学 | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
| CN103985875A (en) * | 2014-05-21 | 2014-08-13 | 南京理工大学 | Application of graphene-carbon nitride composite material |
| KR101640545B1 (en) * | 2015-03-27 | 2016-07-18 | 부산대학교 산학협력단 | Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same |
| CN106475081A (en) * | 2015-08-18 | 2017-03-08 | 华为技术有限公司 | A kind of C2N Graphene composite noble metal nanocatalyst and preparation method thereof |
| CN105236399A (en) * | 2015-10-14 | 2016-01-13 | 上海大学 | Nitrogen-doped graphene hollow microsphere (NGHM) preparation method |
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN108615905A (en) * | 2018-05-09 | 2018-10-02 | 武汉理工大学 | A kind of nitrogen-doped graphene load cobalt atom and its preparation method and application |
| CN109300703A (en) * | 2018-12-04 | 2019-02-01 | 浙江理工大学 | Cobalt nickel bimetal hydroxide nano piece/nitridation carbon coating N doping hollow graphite alkene ball composite material and preparation method and application |
| CN111554941A (en) * | 2020-04-01 | 2020-08-18 | 南方科技大学 | Bifunctional catalyst, preparation method thereof and metal-air battery |
Non-Patent Citations (2)
| Title |
|---|
| "Nitrogen-Doped Graphene with a Three-Dimensional Architecture Assisted by Carbon Nitride Tetrapods as an Efficient Metal-Free Electrocatalyst for Hydrogen Evolution";Pranav K. Gangadharan et al.;《ChemElectroChem》;20170723;第4卷(第10期);第2643-2652页 * |
| "Reduction of the oxygen reduction reaction overpotential of nitrogen-doped graphene by designing it to a microspherical hollow shape";Zhong-Jie Jiang et al.;《Journal of Materials Chemistry A》;20140702;第2卷(第34期);第14071-14081页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112349921A (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112349921B (en) | Nitrogen-doped graphene hollow sphere catalyst, preparation method and application | |
| Deng et al. | NiCo-doped CN nano-composites for cathodic catalysts of Zn-air batteries in neutral media | |
| Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
| CN111001427B (en) | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof | |
| Jiang et al. | Enhanced electrochemical performance by nickel-iron layered double hydroxides (LDH) coated on Fe3O4 as a cathode catalyst for single-chamber microbial fuel cells | |
| CN110838588B (en) | Rechargeable zinc-air battery bifunctional catalyst and preparation method and application thereof | |
| CN108565478B (en) | Amino carbon nanotube loaded nickel cobaltate composite electrocatalytic material and preparation and application thereof | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
| CN111933961B (en) | Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof | |
| CN111682223A (en) | Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst | |
| Zhang et al. | Isolated transition metal nanoparticles anchored on N-doped carbon nanotubes as scalable bifunctional electrocatalysts for efficient Zn–air batteries | |
| CN112886029B (en) | Preparation and application of bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier | |
| CN113611881B (en) | Atomic-level dispersed Fe/nitrogen-doped mesoporous carbon spheres and preparation method and application thereof | |
| CN110732331A (en) | method for preparing amorphous iron-nickel-phosphorus compound composite carbon electrocatalytic material | |
| CN112968184A (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN112652778B (en) | Graphene-loaded nitrogen-doped carbon nanotube composite material and preparation and application thereof | |
| CN111744522A (en) | Universal preparation and application of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on sol-gel method | |
| Salarizadeh et al. | Comparison of methanol oxidation reaction process for NiCo2O4/X (X= rGO, MWCNTs, HCNs) nanocatalyst | |
| CN114921796B (en) | Dual-function self-supporting electrolyzed water catalytic material and preparation method and application thereof | |
| CN109546170A (en) | A kind of preparation method of combination electrode catalyst and its application in metal-air battery | |
| CN114400340A (en) | Nitrogen-sulfur co-doped carbon nanotube composite material and preparation method and application thereof | |
| CN113410472A (en) | Alcohol fuel cell anode catalyst and preparation method thereof | |
| CN113394411A (en) | Preparation and application of perovskite nanofiber electrocatalyst for rechargeable zinc-air battery | |
| CN112054217A (en) | CoSe2/C composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |