CN115020718B - 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 PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 13
- 239000011943 nanocatalyst Substances 0.000 title description 8
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 14
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 14
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 14
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 14
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000008247 solid mixture Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000010306 acid treatment Methods 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000012360 testing method Methods 0.000 claims description 19
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- 102000020897 Formins Human genes 0.000 claims description 4
- 108091022623 Formins Proteins 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000011056 performance test Methods 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 238000006056 electrooxidation reaction Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910003296 Ni-Mo Inorganic materials 0.000 description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
- H01M4/90—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 a reaction of methanol oxidation and a preparation method thereof, wherein the catalyst is recorded as: TM-Mo 2 C/MWCNT; the preparation method comprises the following steps: s1: dispersing MWCNT in a sulfuric acid and nitric acid mixed solution, carrying out ultrasonic treatment, standing, washing with distilled water to be neutral, and drying to obtain the MWCNT subjected to acid treatment; s2: dispersing the MWCNT, ammonium molybdate and metal nitrate obtained in the step S1 into absolute ethyl alcohol, placing the mixed solution into a microwave reactor, heating, centrifugally collecting precipitate after the solution is cooled to room temperature, washing with deionized water and ethanol for three times respectively, and drying to obtain a solid mixture; s3: placing the solid mixture obtained in the step S2 into a tube furnace, rapidly heating up 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 a carrier, the dispersibility of the nano particles is improved, the conductivity and the activity of the nano particles are improved, and the nano particles have excellent electrocatalytic oxidation methanol activity and stability under alkaline conditions.
Description
Technical Field
The invention belongs to the technical field of fuel cell electrocatalysts, and particularly relates to a non-noble metal nano catalyst for a methanol oxidation reaction and a preparation method thereof.
Background
Direct Methanol Fuel Cells (DMFCs) are attractive and promising power sources for future energy demands, and have attracted extensive research interest due to their advantages of easy storage and transportation of fuel, high energy density, no carnot cycle limitations, 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, which is slow in kinetics and requires a catalyst to accelerate its reaction rate.
Noble metal-based materials (such as Pt and Pd) are currently still recognized efficient catalysts for methanol oxidation reactions. However, scarcity and high cost limit its large-scale application as a functional methanol oxidation catalyst.
Disclosure of Invention
The invention aims to provide a non-noble metal nano catalyst for methanol oxidation reaction and a preparation method thereof, wherein the preparation method of the electrocatalyst is simple, energy-saving and environment-friendly, the cost of non-noble metal is low, and MWCNT is taken 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 above purpose, the invention adopts the following technical scheme:
a non-noble metal nano-catalyst for methanol oxidation reaction is prepared from multi-wall carbon nanotubes (MWCNT) as carrier, transition metal doped Mo carbide as active center, and is expressed as TM-Mo 2 C/MWCNT; TM-Mo in the catalyst 2 The C nanoparticles uniformly grow and anchor on the MWCNT 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 sulfuric acid and nitric acid mixed solution with a certain concentration, carrying out ultrasonic treatment for 30 min, standing for 24 and h, washing with distilled water to be neutral, and drying to obtain the MWCNT after acid treatment;
s2: dispersing the MWCNT, ammonium molybdate and transition metal nitrate which are treated by acid and obtained in the step S1 into absolute ethyl alcohol, carrying out ultrasonic treatment for 30 min until the MWCNT, ammonium molybdate and transition metal nitrate are completely dispersed, then filling the mixed solution into a round-bottom flask, placing the round-bottom flask into a microwave reactor, carrying out microwave heating for 0-2 h under the power of 300W, cooling the solution to room temperature, collecting precipitate through centrifugation, washing with deionized water and ethanol for three times respectively, and then drying 12-h at 80 ℃ to obtain a solid mixture;
s3: placing the solid mixture obtained in the step S2 in a tube furnace, and in Ar atmosphere, heating at 5 ℃ for min -1 The temperature rising rate of (2) is increased from 25 ℃ to 800 ℃, and the TM-Mo is obtained by constant-temperature calcination of 2 h 2 C/MWCNT。
Further, in the step S1, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
Further, the transition metal nitrate in the step S2 is one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate.
Further, in the step S2, the total mass ratio of the MWCNT to the ammonium molybdate and the transition metal nitrate is 0-2.
Further, in the step S2, TM of transition 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 the non-noble metal nano catalyst is used as an electrocatalyst for the anodic methanol oxidation reaction of a methanol fuel cell, and comprises the following specific steps:
preparation of working electrode: the catalyst prepared by the invention is weighed 4 mg, 400 mu L of isopropanol and 20 mu L of Nafion solution (0.5 wt%) are sequentially added, the slurry is ultrasonically treated for 30 min, 15 mu L of the slurry is removed and dripped on a pretreated glassy carbon electrode, and the working electrode is obtained after the dripping is finished and is dried at room temperature.
The electrochemical performance test is carried out on a Prlington electrochemical workstation PMC1000, the test temperature is 25+/-1 ℃, the test system is a standard three-electrode system, wherein an Hg/HgO electrode and a Pt sheet electrode are used as a reference electrode and a counter electrode, a glassy carbon electrode coated with a catalyst is used as a working electrode, and before the methanol electrooxidation test is carried out, the three-electrode system is introduced with high purity for 30 minN 2 To exclude dissolved oxygen from the medium.
Cyclic Voltammetry (CV): the test scanning voltage range is 0-0.7V (vs. Hg/HgO), and the scanning speed is mV.s -1 。
Chronoamperometric test (i-t): the parameters tested were set to constant potential 0.6V (vs. Hg/HgO) for a test time of 10 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) Combining a microwave hydrothermal method and a one-step heat treatment method 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 electrocatalyst prepared by the invention is firstly applied to the direct methanol fuel cell anode methanol oxidation reaction, is used as an electrode while being used as a catalyst, and shows excellent electrocatalytic activity (278 mA cm) -2 @0.7V vs. Hg/HgO) and good methanol durability, the invention provides a new idea for electrocatalytic methanol oxidation of non-noble metal catalysts.
Drawings
FIG. 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 at room temperature in 1M KOH electrolyte at a sweep rate of 50 mV/s;
FIG. 3 shows the electrocatalysts of example 1, example 2, example 3 and comparative example 1 at 1M KOH+1M CH 3 Cyclic voltammograms measured at room temperature at a sweeping speed of 50 mV/s in an OH electrolyte;
FIG. 4 is a graph of the chronoamperometric current of the electrocatalyst of example 1 for 10 h methanol oxidation reactions.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
Example 1
Ni-Mo 2 The preparation process of the C/MWCNT catalyst is as follows:
s1: dispersing 0.5 g MWCNT in a mixed solution containing 4.5 mL concentrated sulfuric acid, 1.5 mL concentrated nitric acid and 14 mL distilled water, carrying out ultrasonic treatment for 30 min, standing for 24 h, washing with distilled water to neutrality, and drying at 80 ℃ for 24 h to obtain the acid-treated MWCNT.
S2: dispersing the acid-treated MWCNT, ammonium molybdate and nickel nitrate hexahydrate obtained in the step S1 (the total mass ratio of the MWCNT to the ammonium molybdate and the nickel nitrate hexahydrate is 1:1, and the molar ratio of Ni to Mo in the ammonium molybdate and 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 h to give a solid mixture.
S3: placing the solid mixture obtained in the step S2 in a tube furnace, and in Ar atmosphere, heating at 5 ℃ for min -1 The heating rate of (2) is increased from 25 ℃ to 800 ℃ and the constant temperature calcination is carried out for 2 h, thus obtaining the Ni-Mo 2 C/MWCNT。
Example 2
Co-Mo 2 The preparation process of the C/MWCNT catalyst is as follows:
the remainder was the same as in example 1 except that the transition 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 remainder was the same as in example 1 except that the transition 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: dispersing 0.5 g MWCNT in a mixed solution containing 4.5 mL concentrated sulfuric acid, 1.5 mL concentrated nitric acid and 14 mL distilled water, carrying out ultrasonic treatment for 30 min, standing for 24 h, washing with distilled water to neutrality, and drying at 80 ℃ for 24 h to obtain the acid-treated MWCNT.
S2: dispersing the acid-treated MWCNT and ammonium molybdate (the mass ratio of the MWCNT to the ammonium molybdate is 1:1) obtained in the step S1 into absolute ethyl alcohol, carrying out ultrasonic treatment for 30 min till the MWCNT and the ammonium molybdate are completely dispersed, 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 h to give a solid mixture.
S3: placing the solid mixture obtained in the step S2 in a tube furnace, and in Ar atmosphere, heating at 5 ℃ for min -1 The temperature rising rate of (2) is increased from 25 ℃ to 800 ℃, and the Mo is obtained by constant-temperature calcination of 2 h 2 C/MWCNT。
Structural characterization of the catalyst prepared according to the invention
FIG. 1 is an XRD pattern of the electrocatalysts of example 1, example 2, example 3 and comparative example 1. As can be seen from FIG. 1, mo is removed in the catalysts of the three examples 2 The characteristic diffraction peaks of both C and MWCNT appear as new diffraction peaks, and Co-Mo is known from (JCPDS No. 04-0850), (JCPDS No. 15-0806), (JCPDS No. 48-1719) and (JCPDS No. 04-0836) 2 C/MWCNT、Cu-Mo 2 C/MWCNT and Ni-Mo 2 In the three catalysts of the C/MWCNT, the main existence forms of Co, cu and Ni are metallic Co and CoO, metallic Cu and metallic Ni respectively.
The performance test of electrocatalytic oxidation of methanol is carried out on the catalyst prepared by the invention
Preparation of working electrode: the catalyst prepared by the invention is weighed 4 mg, 400 mu L of isopropanol and 20 mu L of Nafion solution (0.5 wt%) are sequentially added, the slurry is ultrasonically treated for 30 min, 15 mu L of the slurry is removed and dripped on a pretreated glassy carbon electrode, and the working electrode is obtained after the dripping is finished and is dried at room temperature.
The electrochemical performance test is carried out on a Prlington 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 reference electrodes and counter electrodes, a glassy carbon electrode coated with a catalyst is used as a working electrode, and before the methanol electrooxidation test is carried out, 30 min of high-purity N is introduced into the three-electrode system 2 To exclude dissolution in the mediumOxygen.
Cyclic Voltammetry (CV): the test scanning voltage range is 0-0.7V (vs. Hg/HgO), and the scanning speed is mV.s -1 。
Chronoamperometric test (i-t): the parameters tested were set to constant potential 0.6V (vs. Hg/HgO) for a test time of 10 h.
FIGS. 2 and 3 are examples 1, 2, 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 is introduced into 1M KOH electrolyte 3 After OH, the current density of the electrode increased dramatically, indicating that the four electrocatalysts had an electrochemical response to methanol oxidation. Ni-Mo at 0.7V (vs. Hg/HgO) voltage 2 C/MWCNT、Co-Mo 2 C/MWCNT and Cu-Mo 2 The current densities of the electrocatalytic oxidation of methanol by the C/MWCNT are 278, 261 and 204 mA cm respectively -2 Compared with Mo 2 C/MWCNT catalyst (185 mA cm) -2 ），TM-Mo 2 The catalytic performance of the C/MWCNT is obviously improved; therefore, the addition of the second elements Ni, co and Cu can improve Mo 2 Activity of the C/MWCNT catalyst.
FIG. 4 is a graph of example 1 at 1M KOH+1M CH 3 In the OH electrolyte, the catalyst retained 85.61% of its initial catalytic activity after 10 h, indicating good methanol durability, as measured by a chronoamperometric curve at a voltage of 0.6V (vs. Hg/HgO).
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (1)
1. The application of the non-noble metal nano electrocatalyst in the anodic methanol oxidation reaction of the methanol fuel cell is characterized in that the catalyst preparation comprises the following specific steps:
s1: dispersing MWCNT in a mixed solution of sulfuric acid and nitric acid with a certain concentration, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, performing ultrasonic treatment for 30 min, standing for 24 h, washing with distilled water to be neutral, and drying to obtain the MWCNT subjected to acid treatment;
s2: dispersing the MWCNT, ammonium molybdate and transition metal nitrate which are obtained in the step S1 and are subjected to acid treatment into absolute ethyl alcohol, wherein the transition metal nitrate is one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate, the total mass ratio of the MWCNT to the ammonium molybdate to the transition metal nitrate is 1-2, and the TM in the transition metal nitrate and the ammonium molybdate is as follows: the molar ratio of Mo is 0.2-0.5, ultrasound is carried out for 30 min till the Mo is completely dispersed, then the mixed solution is filled into a round bottom flask and placed into a microwave reactor, microwave heating is carried out for 0.5-2 h under the power of 300W, the precipitate is collected through centrifugation after the solution is cooled to room temperature, deionized water and ethanol are used for three times respectively, and then the solid mixture is obtained by drying 12 h at 80 ℃;
s3: placing the solid mixture obtained in the step S2 in a tube furnace, and in Ar atmosphere, heating at 5 ℃ for min -1 The temperature rising rate of (2) is increased from 25 ℃ to 800 ℃, and the TM-Mo is obtained by constant-temperature calcination of 2 h 2 C/MWCNT；
The application method comprises the following steps:
(1) Preparation of working electrode: weighing 4-mg of the prepared catalyst, sequentially adding 400-L isopropanol and 20-L Nafion solution with mass fraction of 0.5%, carrying out ultrasonic treatment on the slurry for 30 min, transferring 15-L of the slurry, dripping the slurry on a pretreated glassy carbon electrode, and drying at room temperature after the dripping is finished to obtain a working electrode;
(2) The electrochemical performance test is carried out on a Prlington electrochemical workstation PMC1000, the test temperature is 25+/-1 ℃, the test system is a standard three-electrode system, wherein an Hg/HgO electrode and a Pt sheet electrode are used as a reference electrode and a counter electrode, a glassy carbon electrode coated with a catalyst is used as a working electrode, and high-purity N is introduced into the three-electrode system for 30 min before the methanol electrooxidation test is carried out 2 To exclude dissolved oxygen in the medium;
(3) Cyclic voltammetry test: the test scan voltage range is 0-0.7V, and the scan speed is mV.s -1 The method comprises the steps of carrying out a first treatment on the surface of the Timing current test: the parameters tested were set to constant potential 0.6V for a test time of 10 h.
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| JPS5887767A (en) * | 1981-11-20 | 1983-05-25 | Hitachi Ltd | Activating treatment of electrode catalyst |
| JPS58128661A (en) * | 1982-01-27 | 1983-08-01 | Hitachi Ltd | Activation treatment of electrode catalyst |
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