CN111477892B - V, N co-doped graphene Pt-supported catalyst and preparation method and application thereof - Google Patents
V, N co-doped graphene Pt-supported catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an V, N co-doped graphene Pt-loaded catalyst and a preparation method and application thereof, wherein the method comprises the steps of synthesizing a V, N co-doped graphene material in one step by taking vanadium phthalocyanine as a precursor, and preparing a V, N co-doped graphene Pt-loaded catalyst by taking a V, N co-doped graphene material as a catalytic particle carrier. The method is simple and effective, the operation condition is mild and controllable, the prepared catalyst can enhance the electrocatalytic activity, the electrochemical stability and the CO poisoning resistance to methanol oxidation, and has good application prospect in the direct methanol fuel cell anode reaction application.
Description
Technical Field
The invention relates to the field of electrocatalysis and fuel cells, in particular to an V, N co-doped graphene Pt-supported catalyst and a preparation method and application thereof.
Namely preparation of a novel high-performance V, N co-doped graphene Pt-loaded electrocatalyst and application thereof in the anode reaction process of a direct methanol fuel cell.
Background
The Direct Methanol Fuel Cell (DMFC) has the advantages of high energy conversion efficiency, abundant fuel sources, environmental protection, convenient storage and transportation, and the like, and is gradually a research hotspot in recent years. But its further commercial application is limited due to the disadvantages of high cost and low activity of its electrocatalyst. Therefore, how to improve the electrochemical activity of the anode electrocatalyst while reducing the cost becomes a hot issue of research in the field related to DMFC. Nowadays, the anode electrocatalyst of the DMFC is still mainly made of Pt-based materials, but the high cost and poor stability and poisoning resistance of Pt are a great obstacle to the development of the anode electrocatalyst, which prompts people to continuously search for high cost performance Pt-based materials with higher electrocatalytic performance, stronger stability and poisoning resistance.
The morphology, size, performance and utilization efficiency of Pt nanoparticles in the catalyst are greatly affected by the catalyst support used and its surface properties. As a typical carbon nano material, graphene has the advantages of high conductivity, low resistivity, large specific surface area, outstanding mechanical properties and the like, is an ideal carrier material of a noble metal Pt-based catalyst, and has attracted extensive attention in the construction field of fuel cell electrocatalysts. However, the surface of the original graphene is in an inert state, and lacks enough active sites, which affects the dispersion and stability of the original graphene in common solvents (such as water and the like) and is difficult to meet the requirement of being used as a Pt catalytic particle carrier. Therefore, how to activate the surface of graphene conveniently and effectively to fully exert the excellent characteristics thereof is a difficult problem to be solved urgently in the field of graphene-based catalysts at present.
Recent researches show that the band structure and the surface activity of graphene can be effectively optimized by doping heterogeneous atoms in the graphene nanosheets, so that the electrochemical performance of the graphene is improved. Meanwhile, the electrocatalytic activity of the metal nanoparticles loaded on the surface of the metal nanoparticles is greatly improved. Therefore, research on controllable preparation and performance control of doped graphene has gradually become the leading edge and hot spot in the field of material science nowadays. Currently, singly-doped graphene occupies the mainstream of doped graphene materials, and nitrogen-doped graphene is the most widely studied singly-doped graphene. In order to further improve the synergistic catalytic effect among doping atoms in the doped graphene-based catalyst, people try to introduce a second heterogeneous doping atom on the basis of nitrogen-doped graphene, wherein the introduction of transition metal active sites such as Fe, Co, Ni, Cu and the like and the structural design are widely concerned. At present, among doped carbon nanomaterials containing transition metal active sites, there is very little research on V-doped carbon nanomaterials, and only the following several literature reports are involved: (1) an Applied Surface Science report in 2016 (VO)3H7)3The V-doped graphene prepared by thermal annealing and other methods for the precursor can effectively reduce the sheet resistance of the graphene film and keep good optical performance of the graphene film, and is contained in the transparent conductive film of the solar cellGood application prospect; (2) 2018, Inorganic Chemistry Frontiers reports Na2MoO4·2H2O，Na3VO4·12H2V, N double-doped MoS prepared by taking O and dicyandiamide as precursors through solvothermal method and the like2the/RGO nano-sheet shows excellent hydrogen evolution electro-catalysis performance; (3) in 2019, ChemCatchem reports a V-N double-doped carbon nanosheet prepared by using melamine, glucose and vanadyl acetylacetonate as precursors through methods such as thermal annealing and the like, and the performance of the V-N double-doped carbon nanosheet in the catalytic oxidation of lactic acid into pyruvic acid is researched. However, no literature or patent report exists on the research of constructing V, N co-doped graphene nanocomposite material by taking vanadium phthalocyanine as a precursor in one step and using the nanocomposite material as a DMFC anode electrocatalyst carrier.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an V, N co-doped graphene supported Pt catalyst, a preparation method thereof and application thereof in the anode reaction process of a direct methanol fuel cell. The method is simple and effective, the operation condition is mild and controllable, the prepared catalyst can enhance the electrocatalytic activity, the electrochemical stability and the CO poisoning resistance to methanol oxidation, and has good application prospect in the direct methanol fuel cell anode reaction application.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the V, N co-doped graphene supported Pt catalyst is different from the prior art in that the preparation method comprises the following steps:
1) weighing 20 mg of graphene and 15-50 mg of vanadium phthalocyanine, uniformly mixing the graphene and the vanadium phthalocyanine in a reaction kettle filled with 20 mL of tertiary distilled water, carrying out hydrothermal treatment at 80-120 ℃ for 10 h, standing for 0.5 h to naturally cool the mixture to room temperature, washing a product with absolute ethyl alcohol, centrifuging, and carrying out vacuum drying at 60 ℃ for 18 h to obtain the vanadium phthalocyanine functionalized graphene composite material;
2) uniformly paving 40 mg of vanadium phthalocyanine functionalized graphene in a combustion boat, and placing the combustion boat in a quartz tube furnace to perform heat treatment for 4 hours at 500-1000 ℃ in a nitrogen atmosphere to obtain V, N co-doped graphene carrier;
3) weighing V, N co-doped graphene carrier 5-20 mg, adding into 20 mL of ethylene glycol, ultrasonically dispersing for 2H until the two are uniformly mixed, and slowly dropwise adding 0.667 mL of 0.0193M H into the dispersion liquid2PtCl6And continuously carrying out ultrasonic treatment on the solution for 1 h, then moving the solution into a 30 mL reaction kettle, reacting for 24 h at the temperature of 190 ℃ and washing, centrifuging and vacuum drying the obtained product to obtain the V, N co-doped graphene Pt-loaded catalyst.
The V, N co-doped graphene supported Pt catalyst prepared by the preparation method is used.
The V, N co-doped graphene Pt-loaded catalyst prepared by the preparation method is applied to the anode reaction process of a direct methanol fuel cell.
The catalyst support used in the fuel cell electrocatalyst and its surface properties have a significant impact on the morphology, size, performance, and utilization efficiency of its supported Pt nanoparticles.
According to the technical scheme, the vanadium phthalocyanine is used as a precursor to synthesize V, N codoped graphene materials in one step, the vanadium phthalocyanine is used as a catalytic particle carrier to prepare the V, N codoped graphene supported Pt catalyst, V, N codoped atoms which are uniformly distributed obviously improve the microscopic morphology and structure of the supported Pt nanoparticles, the electrochemical activity surface area and the utilization efficiency of noble metal Pt are further improved, meanwhile, the strong coupling effect between the V, N atoms and the Pt nanoparticles doped in the prepared catalyst changes the electronic structure of Pt, and therefore the electrocatalytic activity, the electrochemical stability and the CO poisoning resistance of the catalyst to methanol oxidation are greatly enhanced.
The method is simple and effective, the operation condition is mild and controllable, the prepared catalyst can enhance the electrocatalytic activity, the electrochemical stability and the CO poisoning resistance to methanol oxidation, and has good application prospect in the direct methanol fuel cell anode reaction application.
Description of the drawings:
fig. 1 is a schematic flow chart of V, N co-doped graphene supported Pt catalyst prepared in example;
fig. 2 is a TEM image of V, N co-doped graphene supported Pt catalyst prepared in example;
FIG. 3 shows the Pt/V-N-GR, Pt/N-GR, Pt/GR and commercial Pt/C catalysts prepared in the examples at 0.5M CH3OH + 0.5 M H2SO4Cyclic voltammograms in solution;
FIG. 4 shows the Pt/V-N-GR, Pt/N-GR, Pt/GR and commercial Pt/C catalysts prepared in the examples at 0.5M CH3OH + 0.5 M H2SO4Chronoamperometric profile in solution;
FIG. 5 shows that the Pt/V-N-GR, Pt/N-GR, Pt/GR and commercial Pt/C catalysts prepared in the examples are at 0.5M H2SO4CO stripping voltammogram in solution.
Detailed Description
The invention will be further elucidated with reference to the drawings and examples, without however being limited thereto.
Example (b):
a preparation method of V, N co-doped graphene supported Pt catalyst comprises the following steps:
referring to fig. 1, 1) weighing 20 mg of graphene and 15-50 mg of vanadium phthalocyanine, uniformly mixing the graphene and the vanadium phthalocyanine in a reaction kettle filled with 20 mL of tertiary distilled water, carrying out hydrothermal treatment at 80-120 ℃ for 10 h, standing for 0.5 h to naturally cool the mixture to room temperature, washing a product with absolute ethyl alcohol, centrifuging, and carrying out vacuum drying at 60 ℃ for 18 h to obtain the vanadium phthalocyanine functionalized graphene composite material;
2) uniformly paving 40 mg of vanadium phthalocyanine functionalized graphene in a combustion boat, and placing the combustion boat in a quartz tube furnace to perform heat treatment for 4 hours at 500-1000 ℃ in a nitrogen atmosphere to obtain V, N co-doped graphene carrier (V-N-GR);
3) weighing V, N co-doped graphene carrier 5-20 mg, adding into 20 mL of ethylene glycol, ultrasonically dispersing for 2H until the two are uniformly mixed, and slowly dropwise adding 0.667 mL of 0.0193M H into the dispersion liquid2PtCl6And (3) continuing carrying out ultrasonic treatment on the solution for 1 h, moving the solution into a 30 mL reaction kettle, reacting for 24 h at 190 ℃ under 120, and washing, centrifuging and vacuum drying the obtained product to obtain the V, N co-doped graphene Pt-loaded catalyst (Pt/V-N-GR).
The V, N co-doped graphene supported Pt catalyst prepared by the preparation method is used.
The V, N co-doped graphene Pt-loaded catalyst prepared by the preparation method is applied to the anode reaction process of a direct methanol fuel cell.
TEM test results show that the Pt nanoparticles are uniformly and stably deposited on the surface of the V-N-GR support, and the average particle size of the Pt nanoparticles is measured to be about 3.02 nm, which is probably due to the strong coupling effect between Pt and co-doped V, N atoms, so that the deposition and dispersion of the Pt nanoparticles on the surface of the V-N-GR are facilitated, as shown in FIG. 2, and a TEM image of the prepared Pt/V-N-GR catalyst is given in FIG. 2.
The electrocatalytic activity and electrochemical stability of Pt/V-N-GR, Pt/GR and commercial Pt/C catalysts for methanol oxidation were compared by electrochemical cyclic voltammetry and chronoamperometry, as shown in FIGS. 3 and 4, indicating that the Pt/V-N-GR catalyst prepared in this example has the highest electrocatalytic activity for methanol oxidation and has a forward scan peak current density of 1063.8 mA mgPt −1Pt/N-GR (229 mA mg), respectivelyPt −1）、Pt/GR（197.7 mA mgPt −1) And commercial Pt/C (292.2 mA mg)Pt −1) 4.65, 5.38 and 3.64 times of the catalyst, and in addition, the Pt/V-N-GR catalyst also shows excellent electrochemical stability for methanol oxidation.
The CO poisoning resistance of Pt/V-N-GR, Pt/GR and commercial Pt/C catalysts were compared by electrochemical CO stripping voltammetry and the results of the tests showed that, as shown in FIG. 5: the initial oxidation potential of CO on Pt/V-N-GR was 0.43V, which was shifted negatively by 60, 120 and 110 mV compared to Pt/N-GR (0.49V), Pt/GR (0.55V) and commercial Pt/C (0.54V) catalysts, respectively, indicating that the Pt/V-N-GR catalysts have superior resistance to CO poisoning.
Claims (3)
1. The preparation method of the V, N codoped graphene supported Pt catalyst is characterized by comprising the following steps:
1) weighing 20 mg of graphene and 15-50 mg of vanadium phthalocyanine, uniformly mixing the graphene and the vanadium phthalocyanine in a reaction kettle filled with 20 mL of tertiary distilled water, carrying out hydrothermal treatment at 80-120 ℃ for 10 h, standing for 0.5 h to naturally cool the mixture to room temperature, washing a product with absolute ethyl alcohol, centrifuging, and carrying out vacuum drying at 60 ℃ for 18 h to obtain the vanadium phthalocyanine functionalized graphene composite material;
2) uniformly paving 40 mg of vanadium phthalocyanine functionalized graphene in a combustion boat, and placing the combustion boat in a quartz tube furnace to perform heat treatment for 4 hours at 500-1000 ℃ in a nitrogen atmosphere to obtain V, N co-doped graphene carrier;
3) weighing V, N co-doped graphene carrier 5-20 mg, adding into 20 mL of ethylene glycol, ultrasonically dispersing for 2H until the two are uniformly mixed, and slowly dropwise adding 0.667 mL of 0.0193M H into the dispersion liquid2PtCl6And continuously carrying out ultrasonic treatment on the solution for 1 h, then moving the solution into a 30 mL reaction kettle, reacting for 24 h at the temperature of 190 ℃ and washing, centrifuging and vacuum drying the obtained product to obtain the V, N co-doped graphene Pt-loaded catalyst.
2. V, N co-doped graphene Pt-supported catalyst prepared by the preparation method of claim 1.
3. The application of the V, N co-doped graphene supported Pt catalyst in the anode reaction process of a direct methanol fuel cell.
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