CN115020718A - Non-noble metal nano catalyst for methanol oxidation reaction and preparation method thereof - Google Patents

Non-noble metal nano catalyst for methanol oxidation reaction and preparation method thereof Download PDF

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CN115020718A
CN115020718A CN202210664263.7A CN202210664263A CN115020718A CN 115020718 A CN115020718 A CN 115020718A CN 202210664263 A CN202210664263 A CN 202210664263A CN 115020718 A CN115020718 A CN 115020718A
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mwcnt
catalyst
noble metal
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metal nano
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CN115020718B (en
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左志军
王文静
李瑞敏
傅林
高志华
黄伟
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Taiyuan University of Technology
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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
    • H01M4/90—Selection of catalytic material
    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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

The invention provides a non-noble metal nano electro-catalyst for methanol oxidation reaction and a preparation method thereof, wherein the catalyst is marked as follows: TM-Mo 2 C/MWCNT; the preparation method comprises the following steps: s1: dispersing MWCNT in a mixed solution of sulfuric acid and nitric acid, performing ultrasonic treatment, standing, washing with distilled water to be neutral, and drying to obtain acid-treated MWCNT; s2: dispersing the MWCNT, the ammonium molybdate and the metal nitrate obtained in the step S1 into absolute ethyl alcohol, placing the mixed solution into a microwave reactor, heating, centrifugally collecting precipitates after the solution is cooled to room temperature, washing the precipitates with deionized water and ethyl alcohol for three times respectively, and drying to obtain a solid mixture; s3: placing the solid mixture obtained in the step S2 in a tube furnace, rapidly heating in Ar atmosphere, and calcining at constant temperature to obtain TM-Mo 2 The preparation method of the C/MWCNT is simple, the cost is obviously reduced, the MWCNT is adopted as the carrier, the dispersibility of the nano-particles is improved, andthe conductivity and activity of the catalyst are improved, and the catalyst has excellent activity and stability for electrocatalytic oxidation of methanol under alkaline conditions.

Description

Non-noble metal nano catalyst for methanol oxidation reaction and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cell electrocatalysts, and particularly relates to a non-noble metal nano catalyst for methanol oxidation reaction and a preparation method thereof.
Background
Direct Methanol Fuel Cells (DMFCs) are an attractive and promising power source for future energy demand, and have attracted extensive research interest due to the advantages of easy storage and transportation of fuels, high energy density, freedom from carnot cycle, low emissions, and simple operation; the performance and output of DMFCs is largely dependent on the efficiency of the methanol oxidation reaction, which involves a six-electron transfer process, is slow in kinetics, and requires the use of a catalyst to accelerate its reaction rate.
At present, noble metal-based materials (such as Pt and Pd) are still recognized as high-efficiency catalysts for methanol oxidation, however, scarcity and high cost limit the large-scale application of these materials as functional methanol oxidation catalysts.
Disclosure of Invention
The invention aims to provide a non-noble metal nano catalyst for methanol oxidation reaction and a preparation method thereof, the preparation method of the electrocatalyst is simple, energy-saving and environment-friendly, the cost of the non-noble metal is low, and meanwhile, MWCNT is used as a carrier, so that the dispersibility of nano particles can be improved, and the conductivity of the nano particles can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a non-noble metal nano-catalyst for the oxidizing reaction of methanol features that multi-wall carbon nanotubes (MWCNT) are used as carrier and the transition metal doped molybdenum carbide as active center (TM-Mo) 2 C/MWCNT; in the catalyst, TM-Mo 2 The C nanoparticles grow uniformly and are anchored on the MWCNT tube walls.
The preparation method of the non-noble metal nano catalyst for the methanol oxidation reaction comprises the following steps:
s1: dispersing MWCNT in a mixed solution of sulfuric acid and nitric acid with a certain concentration, firstly performing ultrasonic treatment for 30 min, then standing for 24 h, finally washing with distilled water to be neutral, and drying to obtain the acid-treated MWCNT;
s2: dispersing the acid-treated MWCNT obtained in the step S1, ammonium molybdate and metal nitrate into absolute ethyl alcohol, performing ultrasonic treatment for 30 min to completely disperse, then filling the mixed solution into a round-bottom flask, placing the round-bottom flask into a microwave reactor, performing microwave heating for 0-2 h under the power of 300W, collecting precipitates by centrifugation after the solution is cooled to room temperature, washing the precipitates with deionized water and ethanol for three times respectively, and then drying the precipitates for 12 h at the temperature of 80 ℃ to obtain a solid mixture;
s3: the solid mixture obtained in step S2 was placed in a tube furnace under Ar atmosphere at 5 ℃ C. min -1 The temperature rising rate is increased from 25 ℃ to 800 ℃, and the constant temperature calcination is carried out for 2 hours to obtain the TM-Mo 2 C/MWCNT。
Further, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the step S1 is 3: 1.
Further, in the step S2, the metal nitrate is one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and copper nitrate trihydrate.
Further, the total mass ratio of the MWCNT to the ammonium molybdate and the metal nitrate in the step S2 is 0 to 2.
Further, in the step S2, TM in metal nitrate and ammonium molybdate: the molar ratio of Mo is 0-0.5.
The application of the non-noble metal nano catalyst is used for oxidizing methanol and is used as an electrocatalyst for the methanol oxidation reaction of the anode of a methanol fuel cell, and the application comprises the following specific steps:
preparation of a working electrode: weighing 4 mg of the catalyst prepared by the invention, sequentially adding 400 mu L of isopropanol and 20 mu L of Nafion solution (0.5 wt%), ultrasonically treating the slurry for 30 min, transferring 15 mu L of the slurry to a pretreated glassy carbon electrode, and drying at room temperature after finishing the dropwise coating to obtain the working electrode.
The electrochemical performance tests are carried out on a Princeton electrochemical workstation (PMC 1000), the test temperature is 25 +/-1 ℃, the test system is a standard three-electrode system, wherein Hg/HgO electrodes and Pt sheet electrodes are used as referenceThe electrode and the counter electrode, the glassy carbon electrode coated with the catalyst are used as working electrodes, and 30 min of high-purity N is introduced into a three-electrode system before methanol electrooxidation test 2 To exclude dissolved oxygen from the medium.
Cyclic voltammetry test (CV): the test scan voltage range is 0-0.7V (vs. Hg/HgO), and the scan speed is 50 mV.s -1 。
Chronoamperometric test (i-t): the parameters of the test were set to a constant potential of 0.6V (vs. Hg/HgO) and the test time was 10 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the microwave hydrothermal method and the one-step heat treatment method are combined to obtain the TM-Mo with high dispersion and uniform particle size distribution on the MWCNT 2 The preparation method of the C nano-particles is simple and efficient, has low requirements on equipment, is easy to implement and has important industrial application value;
(2) the nano electro-catalyst prepared by the invention is firstly applied to the anode methanol oxidation reaction of a direct methanol fuel cell, is used as a catalyst and also serves as an electrode, and shows excellent electro-catalytic activity (278 mA-cm) -2 @ 0.7V vs. Hg/HgO) and good methanol durability, the invention provides a new idea for a non-noble metal catalyst for electrocatalytic methanol oxidation;
(3) the doping can not only form an additional energy level near the Fermi level, but also change the d-band position of the active center, thereby influencing the adsorption energy and reaction energy barrier of reactant molecules at the active center, and the VIII group transition metal (TMs, such as Ni, Co, Cu and the like) has more abundant electrons than Mo, so that Mo can be adjusted 2 The intrinsic electronic structure of C can provide more electronic orbitals through hybridization with non-metallic three-dimensional orbitals, thereby improving the electrocatalytic activity of C.
Drawings
Figure 1 is an XRD pattern of the electrocatalysts of example 1, example 2, example 3 and comparative example 1;
FIG. 2 is a cyclic voltammogram of the electrocatalysts of example 1, example 2, example 3 and comparative example 1, measured in a 1M KOH electrolyte at a sweep rate of 50 mV/s at room temperature;
FIG. 3 shows electrocatalysts of example 1, example 2, example 3 and comparative example 1 at 1M KOH + 1M CH 3 In OH electrolyte, sweeping the cyclic voltammogram measured at room temperature at 50 mV/s;
FIG. 4 is a plot of the chronoamperometric current of the electrocatalyst for 10 h in example 1 for a methanol oxidation reaction.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
Ni-Mo 2 The preparation process of the C/MWCNT catalyst is as follows:
s1: 0.5 g of MWCNT is dispersed in a mixed solution containing 4.5 mL of concentrated sulfuric acid, 1.5 mL of concentrated nitric acid and 14 mL of distilled water, sonicated for 30 min, left to stand for 24 h, finally washed to neutrality with distilled water, and dried at 80 ℃ for 24 h to obtain the acid-treated MWCNT.
S2: dispersing the acid-treated MWCNT obtained in the step S1, ammonium molybdate and nickel nitrate hexahydrate (the total mass ratio of the MWCNT to the ammonium molybdate to the nickel nitrate hexahydrate is 1: 1; and the molar ratio of Ni to Mo in the ammonium molybdate to the nickel nitrate hexahydrate is 0.2: 1) into absolute ethyl alcohol, carrying out ultrasonic treatment for 30 min to complete dispersion, then filling the mixed solution into a round-bottom flask, placing the round-bottom flask into a microwave reactor, and carrying out microwave heating for 30 min under the power of 300W. After the solution was cooled to room temperature, the precipitate was collected by centrifugation and washed three times with deionized water and ethanol, respectively, and then dried at 80 ℃ for 12 hours to obtain a solid mixture.
S3: the solid mixture obtained in step S2 was placed in a tube furnace under Ar atmosphere at 5 ℃ C. min -1 The temperature rise rate is increased from 25 ℃ to 800 ℃, and the mixture is calcined for 2 hours at constant temperature to obtain Ni-Mo 2 C/MWCNT。
Example 2
Co-Mo 2 The preparation process of the C/MWCNT catalyst is as follows:
the procedure was repeated as in example 1 except that the metal nitrate in step S2 was cobalt nitrate hexahydrate.
Example 3
Cu-Mo 2 The preparation process of the C/MWCNT catalyst is as follows:
the procedure was repeated as in example 1 except that the metal nitrate in step S2 was copper nitrate trihydrate.
Comparative example 1
Mo 2 The preparation process of the C/MWCNT catalyst is as follows:
s1: 0.5 g of MWCNT is dispersed in a mixed solution containing 4.5 mL of concentrated sulfuric acid, 1.5 mL of concentrated nitric acid and 14 mL of distilled water, sonicated for 30 min, left to stand for 24 h, finally washed to neutrality with distilled water, and dried at 80 ℃ for 24 h to obtain the acid-treated MWCNT.
S2: dispersing the acid-treated MWCNT and ammonium molybdate obtained in the step S1 (the mass ratio of the MWCNT to the ammonium molybdate is 1: 1) into absolute ethyl alcohol, performing ultrasonic treatment for 30 min until the solution is completely dispersed, then filling the mixed solution into a round-bottom flask, placing the round-bottom flask into a microwave reactor, and performing microwave heating for 30 min under the power of 300W. After the solution was cooled to room temperature, the precipitate was collected by centrifugation and washed three times with deionized water and ethanol, respectively, and then dried at 80 ℃ for 12 hours to obtain a solid mixture.
S3: the solid mixture obtained in step S2 was placed in a tube furnace under Ar atmosphere at 5 ℃ C. min -1 The temperature rising rate is increased from 25 ℃ to 800 ℃, and the Mo is obtained after the constant temperature calcination for 2 hours 2 C/MWCNT。
The catalyst prepared by the invention is subjected to structural characterization
FIG. 1 is an XRD pattern of electrocatalysts of example 1, example 2, example 3 and comparative example 1, and it can be seen from FIG. 1 that Mo is excluded from the three example catalysts 2 Both the characteristic diffraction peaks of C and MWCNT have new diffraction peaks, and Co-Mo is known from (JCPDS number 04-0850), (JCPDS number 15-0806), (JCPDS number 48-1719) and (JCPDS number 04-0836) 2 C/MWCNT、Cu-Mo 2 C/MWCNT and Ni-Mo 2 In the three catalysts of the C/MWCNT, the main existing forms of Co, Cu and Ni are metal Co and CoO, metal Cu and metal Ni respectively.
The performance test of the electrocatalytic oxidation methanol is carried out on the catalyst prepared by the invention
Preparation of a working electrode: weighing 4 mg of the catalyst prepared by the invention, sequentially adding 400 mu L of isopropanol and 20 mu L of Nafion solution (0.5 wt%), carrying out ultrasonic treatment on the slurry for 30 min, then transferring 15 mu L of the slurry to be coated on a pretreated glassy carbon electrode in a dripping way, and drying at room temperature after finishing the dripping to obtain the working electrode.
The electrochemical performance tests are carried out on a Princeton electrochemical workstation (PMC 1000), the test temperature is 25 +/-1 ℃, the test system is a standard three-electrode system, Hg/HgO electrodes and Pt sheet electrodes are used as reference electrodes and counter electrodes, glassy carbon electrodes coated with catalysts are used as working electrodes, and 30 min of high-purity N is introduced into the three-electrode system before methanol electrooxidation test is carried out 2 To exclude dissolved oxygen from the medium.
Cyclic voltammetry test (CV): the test scan voltage range is 0-0.7V (vs. Hg/HgO), and the scan speed is 50 mV.s -1 。
Chronoamperometric test (i-t): the parameters of the test were set to a constant potential of 0.6V (vs. Hg/HgO) and the test time was 10 h.
FIGS. 2 and 3 are the results of example 1, example 2, example 3 and comparative example 1 at 1M KOH and 1M KOH + 1M CH, respectively 3 CV curve in OH electrolyte. As can be seen from FIGS. 2 and 3, 1M CH was introduced into 1M KOH electrolyte 3 After OH, the current density of the electrode rises sharply, indicating that the four electrocatalysts have an electrochemical response to methanol oxidation. Under the voltage of 0.7V (vs. Hg/HgO), Ni-Mo 2 C/MWCNT、Co-Mo 2 C/MWCNT and Cu-Mo 2 The current densities of the C/MWCNT electrocatalytic oxidation of methanol are 278, 261 and 204 mA-cm respectively -2 Comparative Mo 2 C/MWCNT catalyst (185 mA cm) -2 ），TM-Mo 2 The catalytic performance of the C/MWCNT is obviously improved; thus, the addition of the second elements Ni, Co and Cu can increase Mo 2 Activity of C/MWCNT catalyst.
FIG. 4 shows the results of example 1 in 1M KOH + 1M CH 3 The catalyst retained 85.61% of the initial catalytic activity after 10 h on the chronoamperometric curve at 0.6V (vs. hg/HgO) in OH electrolyte, indicating good methanol durability.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (8)

1. A non-noble metal nano electro-catalyst for methanol oxidation reaction is characterized in that a multi-wall carbon nano tube (MWCNT) is taken as a carrier, and transition metal doped molybdenum carbide is taken as an active center, which is represented as TM-Mo 2 C/MWCNT; in the catalyst, TM-Mo 2 The C nanoparticles grow uniformly and are anchored on the MWCNT tube walls.
2. The method for preparing the non-noble metal nano electrocatalyst, as recited in claim 1, is characterized by the following specific steps:
s1: dispersing MWCNT in a mixed solution of sulfuric acid and nitric acid with a certain concentration, firstly performing ultrasonic treatment for 30 min, then standing for 24 h, finally washing with distilled water to be neutral, and drying to obtain the acid-treated MWCNT;
s2: dispersing the acid-treated MWCNT obtained in the step S1, ammonium molybdate and metal nitrate into absolute ethyl alcohol, performing ultrasonic treatment for 30 min to completely disperse, then filling the mixed solution into a round-bottom flask, placing the round-bottom flask into a microwave reactor, performing microwave heating for 0-2 h under the power of 300W, collecting precipitates by centrifugation after the solution is cooled to room temperature, washing the precipitates with deionized water and ethanol for three times respectively, and then drying the precipitates for 12 h at the temperature of 80 ℃ to obtain a solid mixture;
s3: the solid mixture obtained in step S2 was placed in a tube furnace under Ar atmosphere at 5 ℃ C. min -1 The temperature rising rate is increased from 25 ℃ to 800 ℃, and the constant temperature calcination is carried out for 2 hours to obtain the TM-Mo 2 C/MWCNT。
3. The method for preparing a non-noble metal nano electrocatalyst according to claim 2, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in step S1 is 3: 1.
4. The method for preparing a non-noble metal nano electrocatalyst according to claim 2, wherein the metal nitrate in step S2 is one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate.
5. The method of claim 2, wherein the total mass ratio of MWCNT to ammonium molybdate and metal nitrate in the step S2 is 0-2.
6. The method for preparing a non-noble metal nano electrocatalyst according to claim 2, characterized in that in step S2 TM: the molar ratio of Mo is 0-0.5.
7. Use of the non-noble metal nano-electrocatalyst according to any one of claims 1-6, as an electrocatalyst for the anodic methanol oxidation reaction in methanol fuel cells.
8. The use of a non-noble metal nano electrocatalyst according to claim 7, characterised in that the method steps are as follows: (1) preparation of a working electrode: weighing 4 mg of the catalyst prepared by the invention, sequentially adding 400 mu L of isopropanol and 20 mu L of Nafion solution (0.5 wt%), ultrasonically treating the slurry for 30 min, transferring 15 mu L of the slurry to a pretreated glassy carbon electrode in a dropwise manner, and drying at room temperature after dropwise coating to obtain a working electrode;
(2) the electrochemical performance tests are carried out on a Princeton electrochemical workstation (PMC 1000), the test temperature is 25 +/-1 ℃, the test system is a standard three-electrode system, Hg/HgO electrodes and Pt sheet electrodes are used as reference electrodes and counter electrodes, glassy carbon electrodes coated with catalysts are used as working electrodes, and 30 min of high-purity N is introduced into the three-electrode system before methanol electrooxidation test is carried out 2 To exclude dissolved oxygen from the medium;
(3) cyclic voltammetry test (CV): the test scan voltage range is 0-0.7V (vs. Hg/HgO), and the scan speed is 50 mV.s -1 (ii) a Chronoamperometric test (i-t): the parameters of the test were set to a constant potential of 0.6V (vs. Hg/HgO) and the test time was 10 h.
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