CN111063902A - Preparation method of nano metal intercalated hydrotalcite material electrode catalyst - Google Patents

Preparation method of nano metal intercalated hydrotalcite material electrode catalyst Download PDF

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CN111063902A
CN111063902A CN201911218566.0A CN201911218566A CN111063902A CN 111063902 A CN111063902 A CN 111063902A CN 201911218566 A CN201911218566 A CN 201911218566A CN 111063902 A CN111063902 A CN 111063902A
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ldh
catalyst
electrode
hydrotalcite
mgal
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李亮
杨涯
黄远星
杨俊豪
胡守训
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University of Shanghai for Science and 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
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a preparation method of a nano metal intercalated hydrotalcite material electrode catalyst, belonging to the technical field of electrocatalysis and energy; the catalyst is a nano metal intercalation hydrotalcite material, and the preparation process comprises the following steps: impregnating soluble metal complex anions (PtCl)4 2‑) Intercalated into the interlayer of hydrotalcite-like materials (such as magnesium aluminum hydrotalcite, nickel iron hydrotalcite and the like), and the anion of the metal complex is reduced by an electrochemical method, so as to successfully prepare the nano metal intercalated hydrotalcite-like catalyst (Pt/MgAl-LDH, Pt/NiFe-LDH). Further adding PtCl in different proportions4 2‑And AuCl4 ‑Simultaneously intercalated into the interlayer of the hydrotalcite-like material, and the PtCl between the interlayers is reduced by an electrochemical reduction method4 2‑And AuCl4 ‑Reduction is carried out to successfully prepare PtxAuyMgAl-LDHs. The invention has the advantages of simple and easy preparation process, lower catalyst cost, uniform distribution of nano metal among hydrotalcite layers, higher catalytic activity and anti-poisoning performance and excellent electro-catalytic performance in alkaline methanol fuel cells.

Description

Preparation method of nano metal intercalated hydrotalcite material electrode catalyst
Technical Field
The invention belongs to the field of preparation of electrode catalysts, and particularly relates to a preparation method of a nano metal intercalated hydrotalcite material electrode catalyst.
Background
Direct Methanol Fuel Cells (DMFC) are Proton Exchange Membrane Fuel Cells (PEMFC) using Methanol as Fuel, and have a wide application prospect in the fields of automobiles, electronic devices, aerospace, and the like. Methanol has the characteristics of simple molecular structure, high energy density, low oxidation potential, rich sources and the like, and is often used as a fuel of PEMFC. Platinum (Pt) is an elemental metal catalyst which is found to have high activity at present, but is expensive and easily poisoned by intermediate products such as CO, and the catalytic activity of the electrode is sharply reduced. Therefore, finding and designing an anode catalyst material with high catalytic activity, stability and strong resistance to CO poisoning is one of the important research tasks for realizing the commercial development of the DMFC.
At present, most anode catalysts of DMFC use Pt as a main catalyst, and in order to improve the catalytic activity of the Pt catalyst, Pt nanoparticles are generally dispersed on a carrier with a large specific surface area. Or a second transition metal is introduced to form the Pt-based composite catalyst, wherein the Pt and Au bimetal composite material has good catalytic activity and CO poisoning resistance. The hydrotalcite has anion exchange property and larger specific surface area, can be used as an electrocatalyst carrier, can effectively improve the electrochemical performance of the catalyst and reduce the consumption of Pt. The invention takes magnesium-aluminum hydrotalcite and nickel-iron hydrotalcite as carriers, and utilizes an impregnation method and an electrochemical reduction method to intercalate a certain amount of Pt and Au nano metal particles to prepare the novel anode catalyst material with excellent catalytic performance and anti-poisoning performance.
Disclosure of Invention
The invention aims to provide a preparation method of a nano metal intercalated hydrotalcite material electrode catalyst, which is simple to operate and convenient for preparing various motor catalysts.
In order to achieve the aim, the invention provides a preparation method of a nano metal intercalated hydrotalcite material electrode catalyst, which takes a hydrotalcite-like material (LDH) as a carrier and adopts an impregnation method to intercalate metal complex anions into hydrotalcite layers; and manufacturing a drop-coated electrode, and reducing the metal complex anions between the hydrotalcite layers into nano metal particles under a specific voltage by using an electrochemical reduction method to prepare the nano metal intercalated hydrotalcite composite electrode material.
Preferably, the nano metal intercalated hydrotalcite composite electrode material is a Pt/MgAl-LDH catalyst;
the preparation method of the Pt/MgAl-LDH catalyst comprises the following steps:
step 1: preparing a Pt/MgAl-LDH catalyst precursor: adding 0.5g of magnesium-aluminum/nickel-iron hydrotalcite into 10ml of 0.01mol/LK2PtCl4 aqueous solution, uniformly stirring for 5 hours at 80 ℃, keeping the temperature constant during stirring, washing for 3-5 times by using deionized water, and drying for 8-10 hours at 60 ℃ to obtain a Pt/MgAl-LDH catalyst precursor PtCl4 2-/MgAl-LDH；
Step 2: preparation of anode catalyst:
step 2.1: weighing the PtCl4 2-Mixing the/MgAl-LDH, carbon black, absolute ethyl alcohol and nafion solution, carrying out ultrasonic treatment on the mixed solution for 45-60 min to obtain a uniform dispersion solution, dropwise coating 10 mu L of the dispersion solution on the surface of a glassy carbon electrode for five times, and naturally drying;
step 2.2: and (3) forming a three-electrode system by the electrode prepared in the step (2.1), a platinum wire and a double-salt bridge saturated calomel electrode, and carrying out constant potential electrolysis in a 0.5mol/L sodium sulfate solution to obtain the Pt/MgAl-LDH catalyst.
Preferably, the nano metal intercalated hydrotalcite composite electrode material is a Pt/NiFe-LDH catalyst;
the preparation method of the Pt/NiFe-LDH catalyst comprises the following steps:
step 1: preparing a Pt/NiFe-LDH catalyst precursor: adding 0.5g of magnesium-aluminum/nickel-iron hydrotalcite into 10ml of 0.01mol/LK2PtCl4 aqueous solution, uniformly stirring for 5 hours at 80 ℃, keeping the temperature constant in the stirring process, washing for 3-5 times by using deionized water, and drying for 8-10 hours at 60 ℃ to obtain PPrecursor PtCl of t/NiFe-LDH catalyst4 2-/NiFe-LDH；
Step 2: preparation of anode catalyst:
step 2.1: weighing the PtCl4 2-Mixing NiFe-LDH, carbon black, absolute ethyl alcohol and nafion solution, carrying out ultrasonic treatment on the mixed solution for 45-60 min to obtain uniform dispersed solution, dropwise coating 10 mu L of the dispersed solution on the surface of a glassy carbon electrode for five times, and naturally drying;
step 2.2: and (3) forming a three-electrode system by the electrode prepared in the step (2.1), a platinum wire and a double-salt bridge saturated calomel electrode, and carrying out constant potential electrolysis in a 0.5mol/L sodium sulfate solution to obtain the Pt/NiFe-LDH catalyst.
Preferably, the nano metal intercalated hydrotalcite composite electrode material is PtxAuya/MgAl-LDH catalyst;
the PtxAuyThe preparation method of the/MgAl-LDH catalyst comprises the following steps:
step 1: preparing a Pt/NiFe-LDH catalyst precursor: 0.5g of magnesium aluminum hydrotalcite is added with K of different molar ratios of 10ml each2PtCl4And KAuCl4Uniformly stirring the mixed solution at 80 ℃ for 5 hours, keeping the temperature constant in the stirring process, washing the mixed solution with deionized water for 3-5 times, and drying the mixed solution at 60 ℃ for 8-10 hours to obtain Pt/MgAl-LDH and Pt/NiFe-LDH catalyst precursors;
step 2: preparation of anode catalyst:
step 2.1: weighing the Pt/MgAl-LDH catalyst precursor, the Pt/NiFe-LDH catalyst precursor, carbon black, absolute ethyl alcohol and nafion solution, mixing, carrying out ultrasonic treatment on the mixed solution for 45-60 min to obtain a uniform dispersion solution, taking 10 mu L of the dispersion solution, dropwise coating the dispersion solution on the surface of a glassy carbon electrode for five times, and naturally drying;
step 2.2: forming the electrode prepared in the step 2.1, a platinum wire and a double-salt bridge saturated calomel electrode into a three-electrode system, and carrying out constant potential electrolysis in a 0.5mol/L sodium sulfate solution to obtain the PtxAuyA MgAl-LDH catalyst.
Preferably, 5mg of each catalyst precursor, 2mg of the carbon black, 1mL of the absolute ethyl alcohol and 100 μ L of the nafion solution are weighed respectively.
Preferably, in step 2.2, the three-electrode system is electrocatalytically reduced for 2000S in a 0.5mol/L sodium sulfate solution at a voltage of-1.5V.
Compared with the prior art, the invention has the advantages that:
(1) the Pt/MgAl-LDH catalyst prepared by the invention has high current density, high catalytic activity and good CO poisoning resistance, and is a good anode catalyst for direct methanol fuel cells.
(2) The Pt/NiFe-LDH catalyst prepared by the method has obviously improved catalytic activity.
(3) Pt prepared by the inventionxAuythe/MgAl-LDH composite catalyst has obviously improved CO poisoning resistance.
The preparation method has the advantages of simple preparation process, easy operation, reduced Pt consumption and low production cost.
Drawings
FIG. 1 is an EDS spectrum of the Pt/MgAl-LDH catalyst prepared in example 1.
FIG. 2 is an EDS map of the Pt/NiFe-LDH catalyst prepared in example 2.
FIG. 3 is a graph of current density of Pt/MgAl-LDH and Pt/NiFe-LDH prepared in examples 1 and 2 compared to commercial Pt/C catalysts.
FIG. 4 is a graph of the catalytic activity of Pt/MgAl-LDH and Pt/NiFe-LDH prepared in examples 1 and 2 compared to commercial Pt/C catalysts.
FIG. 5 shows Pt prepared in example 3xAuyEDS pattern of MgAl-LDH catalyst.
FIG. 6 shows different ratios of Pt prepared in example 3xAuyComparative current density plot of/MgAl-LDH.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described below.
Example 1: preparation of Pt/MgAl-LDH
Step 1: preparation of Pt/MgAl-LDH: 0.0415g of potassium chloroplatinite is weighed and dissolved in 10ml of ultrapure water, 0.5g of magnesium-aluminum hydrotalcite is weighed and placed in a beaker, the potassium chloroplatinite solution is added into the beaker, and the mixture is stirred in a constant-temperature water bath kettle.
Step 2: stirring for 5h at the constant temperature of 80 ℃, washing for 3-5 times by using deionized water, filtering, and drying for 8-10h at the temperature of 60 ℃ to obtain the catalyst PtCl4 2-/MgAl-LDH。
As shown in FIG. 1, it can be seen that Mg, Al, O and other elements exist in the EDS energy spectrum of the prepared catalyst, the catalyst carrier in example 1 is magnesium aluminum hydrotalcite, and in addition, the existence of Pt element can be observed, which indicates that PtCl is generated by an impregnation method4 2-Is successfully intercalated into the magnesium aluminum hydrotalcite layers.
And step 3: weighing the PtCl obtained in the step 24 2-5mg of/MgAl-LDH catalyst, 2mg of carbon black, 1mL of absolute ethyl alcohol and 100 mu L of nafion solution are prepared into a mixed solution, and ultrasonic treatment is carried out for 45-60 min to obtain a uniform dispersion solution 1.
And 4, step 4: the working electrode surface modification method comprises the following steps: and polishing the glassy carbon electrode on polishing cloth by using alumina with the particle size of 1.0 micron and 0.3 micron in sequence to form a mirror surface, washing the mirror surface by using absolute ethyl alcohol and ultrapure water, and airing for later use. 10 μ L of solution 1 was dropped dropwise onto the polished glassy carbon electrode by a microsyringe and dried at room temperature.
And 5: and (4) forming a three-electrode system by the working electrode, the platinum wire and the double-salt bridge saturated calomel electrode in the step (4), and electrolyzing 2000S at a constant potential under the voltage of-1.5V in 0.5mol/L sodium sulfate solution to obtain the Pt/MgAl-LDH.
Example 2: preparation of Pt/NiFe-LDH
Step 1: preparing nickel-iron hydrotalcite: 13.073g of nickel nitrate and 6.047g of ferric nitrate are weighed and added into a 100mL volumetric flask to prepare a salt solution, 6.4g of sodium hydroxide and 5.3g of anhydrous sodium carbonate are weighed to prepare an alkali solution, and the salt solution and the alkali solution are simultaneously dripped into a glass beaker containing 200mL of ultrapure water while vigorously stirring on a water bath constant-temperature magnetic stirrer at the temperature of 80 ℃, so that the pH value of the aqueous solution of the system is kept between 9.0 and 11.0. And after the dropwise addition is finished, continuously stirring for 0.5h, aging for 1h at the temperature of 80 ℃, repeatedly washing the precipitated product by ultrapure water until the solution is neutral, and drying in a drying oven at the temperature of 60 ℃ to obtain the nickel-iron hydrotalcite.
Step 2: 0.0415g of potassium chloroplatinite is weighed and dissolved in 10ml of ultrapure water, 0.5g of nickel-iron hydrotalcite is weighed and put in a beaker, the potassium chloroplatinite solution is added in the beaker, and the mixture is stirred in a constant-temperature water bath kettle.
And step 3: stirring for 5h at the constant temperature of 80 ℃, washing for 3-5 times by using deionized water, filtering, and drying for 8-10h at the temperature of 60 ℃ to obtain the catalyst PtCl4 2-/NiFe-LDH。
As shown in FIG. 2, it can be seen that Ni, Fe, O and other elements exist in the EDS energy spectrum of the prepared catalyst, which indicates that the catalyst carrier in example 2 is nickel-iron hydrotalcite, and in addition, the existence of Pt element can be observed, which indicates that PtCl is generated by the impregnation method4 2-Is successfully intercalated into the nickel iron hydrotalcite interlayer.
And 4, step 4: weighing the PtCl obtained in the step 34 2-5mg of NiFel-LDH catalyst, 2mg of carbon black, 1mL of absolute ethanol and 100 mu L of nafion solution are prepared into a mixed solution, and ultrasonic treatment is carried out for 45-60 min to obtain a uniform dispersion solution 1.
And 5: the working electrode surface modification method comprises the following steps: and polishing the glassy carbon electrode on polishing cloth by using alumina with the particle size of 1.0 micron and 0.3 micron in sequence to form a mirror surface, washing the mirror surface by using absolute ethyl alcohol and ultrapure water, and airing for later use. 10 μ L of solution 1 was dropped dropwise onto the polished glassy carbon electrode by a microsyringe and dried at room temperature.
Step 6: and (5) forming a three-electrode system by the working electrode, the platinum wire and the double-salt bridge saturated calomel electrode in the step (5), and electrolyzing 2000S at a constant potential under the voltage of-1.5V in 0.5mol/L sodium sulfate solution to obtain Pt/NiFe-LDH.
The catalysts obtained in example 1 and example 2 were electrochemically characterized using cyclic voltammetry.
As shown in FIG. 3, it can be seen that both Pt/MgAl-LDH and Pt/NiFe-LDH have significantly higher current densities for the electrocatalytic oxidation of methanol than the commercial Pt/C catalyst, where the current density of Pt/MgAl-LDH is about 2.7 times that of the commercial Pt/C catalyst and the current density of Pt/NiFe-LDH is about 4.6 times that of the commercial Pt/C catalyst. The nano metal Pt intercalated hydrotalcite material can improve the catalytic activity of Pt. Is usually represented byf/IbThe peak current (I) of the Pt/MgAl-LDH forward scanning is used for judging the CO poisoning resistance of the catalystf) Peak current (I) with reverse scanb) The ratio of 8.24 is more than 5.03 of Pt/NiFe-LDH, which indicates that the Pt/MgAl-LDH has good CO poisoning resistance. As shown in FIG. 4, it can be seen that the catalytic activity per unit mass of Pt in both Pt/MgAl-LDH and Pt/NiFe-LDH is significantly greater than that of commercial Pt/C catalyst, wherein the catalytic activity of Pt/MgAl-LDH is 10 times that of commercial Pt/C catalyst, and the catalytic activity of Pt/NiFe-LDH is about 2.5 times that of Pt/MgAl-LDH, indicating that the nickel iron hydrotalcite as the catalyst carrier can significantly improve the mass catalytic activity of Pt.
Example 3: ptxAuyPreparation of/MgAl-LDH composite catalyst
Step 1: ptxAuyPreparation of a/MgAl-LDH composite catalyst: 0.0415g of potassium chloroplatinite is added into deionized water to prepare 10mL of solution A, 0.0756g of potassium chloroaurate is added into deionized water to prepare 10mL of solution B, the solution A and the solution B are simultaneously added into a beaker weighed with 0.5g of magnesium-aluminum hydrotalcite, the mixture is stirred for 5 hours in a constant-temperature water bath kettle at 80 ℃, the mixture is washed for 3-5 times by deionized water, filtered and dried for 8-10 hours at 60 ℃, and the catalyst 1 is obtained.
Step 2: 0.0415g of potassium chloroplatinite is added into deionized water to prepare 10mL of solution C, 0.0378g of potassium chloroaurate is added into deionized water to prepare 10mL of solution D, the solution C and the solution D are simultaneously added into a beaker weighed with 0.5g of magnesium-aluminum hydrotalcite, the mixture is stirred for 5 hours in a constant-temperature water bath kettle at 80 ℃, the mixture is washed for 3-5 times by deionized water, filtered and dried for 8-10 hours at 60 ℃, and the catalyst 2 is obtained.
And step 3: 0.0415g of potassium chloroplatinite is added into deionized water to prepare 10mL of solution E, 0.0189g of potassium chloroaurate is added into deionized water to prepare 10mL of solution F, the solution E and the solution F are simultaneously added into a beaker weighed with 0.5g of magnesium-aluminum hydrotalcite, the mixture is stirred for 5 hours in a constant-temperature water bath kettle at 80 ℃, the mixture is washed for 3-5 times by deionized water, filtered and dried for 8-10 hours at 60 ℃, and the catalyst 3 is obtained.
And 4, step 4: 0.0415G of potassium chloroplatinite is added into deionized water to prepare 10mL of solution G, 0.0125G of potassium chloroaurate is added into deionized water to prepare 10mL of solution H, the solution G and the solution H are simultaneously added into a beaker weighed with 0.5G of magnesium-aluminum hydrotalcite, the mixture is stirred for 5 hours in a constant-temperature water bath kettle at 80 ℃, the mixture is washed for 3-5 times by deionized water, filtered and dried for 8-10 hours at 60 ℃, and the catalyst 4 is obtained.
As shown in FIG. 5, with Pt2Au1the/MgAl-LDH catalyst is taken as an example, and the EDS energy spectrum chart of the prepared catalyst can be seen that elements such as Pt and Au can be observed besides elements such as Mg, Al, O and the like, which indicates that PtCl is shown4 2-And AuCl4 -The anions are successfully intercalated into the magnesium-aluminum hydrotalcite layers.
And 5: weighing 5mg of each of the catalyst 1, the catalyst 2, the catalyst 3 and the catalyst 4 obtained in the previous step, preparing a mixed solution with 2mg of carbon black, 1mL of absolute ethyl alcohol and 100 mu L of nafion solution, and performing ultrasonic treatment for 45-60 min to obtain uniform dispersion solution 1, solution 2, solution 3 and solution 4.
Step 6: the working electrode surface modification method comprises the following steps: and polishing the glassy carbon electrode on polishing cloth by using alumina with the particle size of 1.0 micron and 0.3 micron in sequence to form a mirror surface, washing the mirror surface by using absolute ethyl alcohol and ultrapure water, and airing for later use. And (3) dropwise adding 10 mu L of each of the dispersion solution 1, the solution 2, the solution 3 and the solution 4 obtained in the step (5) to the polished glassy carbon electrode by using a microsyringe, and drying at room temperature to obtain a working electrode a, a working electrode b, a working electrode c and a working electrode d.
And 7: and (3) forming a three-electrode system by the working electrode a, the working electrode b, the working electrode c and the working electrode d in the step (6) and a platinum wire and a double-salt bridge saturated calomel electrode, and respectively carrying out constant potential electrolysis for 2000S in 0.5mol/L sodium sulfate solution at the voltage of-1.5V to obtain PtxAuy/MgAl-LDH。
The catalyst obtained in example 3 was electrochemically characterized using cyclic voltammetry.
As shown in FIG. 6, it can be seen that when Pt is usedxAuyPt in the/MgAl-LDH composite catalyst: au 2: current density for electrocatalytic oxidation of methanol is maximum at 1 hour, and Pt0.5Au1I of/MgAl-LDHf/IbRatio of 20.59, Pt1Au124.04 parts of/MgAl-LDH, Pt2Au121.38 of/MgAl-LDH, Pt3Au1the/MgAl-LDH content is 13.38, which is obviously higher than the poisoning resistance of Pt/MgAl-LDH by 8.24, which shows that the CO poisoning resistance of the pure nano Pt intercalation magnalium hydrotalcite catalyst is obviously improved by introducing the Au element. Considering the catalytic activity and CO poisoning resistance of the catalyst, the preferred catalyst is Pt2Au1a/MgAl-LDH composite catalyst.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. A preparation method of a nano-metal intercalated hydrotalcite material electrode catalyst is characterized in that a hydrotalcite-like material (LDH) is used as a carrier, and a metal complex anion is intercalated between hydrotalcite layers by adopting an impregnation method; and manufacturing a drop-coated electrode, and reducing the metal complex anions between the hydrotalcite layers into nano metal particles under a specific voltage by using an electrochemical reduction method to prepare the nano metal intercalated hydrotalcite composite electrode material.
2. The method for preparing the electrode catalyst of the nano metal intercalated hydrotalcite material according to claim 1, wherein the nano metal intercalated hydrotalcite composite electrode material is a Pt/MgAl-LDH catalyst;
the preparation method of the Pt/MgAl-LDH catalyst comprises the following steps:
step 1: preparing a Pt/MgAl-LDH catalyst precursor: adding 0.5g of magnesium-aluminum/nickel-iron hydrotalcite into 10ml of 0.01mol/LK2PtCl4 aqueous solution, uniformly stirring for 5 hours at 80 ℃, keeping the temperature constant during stirring, washing for 3-5 times by using deionized water, and drying for 8-10 hours at 60 ℃ to obtain a Pt/MgAl-LDH catalyst precursor PtCl4 2-/MgAl-LDH；
Step 2: preparation of anode catalyst:
step 2.1: weighing the PtCl4 2-Mixing the/MgAl-LDH, carbon black, absolute ethyl alcohol and nafion solution, carrying out ultrasonic treatment on the mixed solution for 45-60 min to obtain a uniform dispersion solution, dropwise coating 10 mu L of the dispersion solution on the surface of a glassy carbon electrode for five times, and naturally drying;
step 2.2: and (3) forming a three-electrode system by the electrode prepared in the step (2.1), a platinum wire and a double-salt bridge saturated calomel electrode, and carrying out constant potential electrolysis in a 0.5mol/L sodium sulfate solution to obtain the Pt/MgAl-LDH catalyst.
3. The method for preparing the electrode catalyst of the nano metal intercalated hydrotalcite material according to claim 1, wherein the nano metal intercalated hydrotalcite composite electrode material is a Pt/NiFe-LDH catalyst;
the preparation method of the Pt/NiFe-LDH catalyst comprises the following steps:
step 1: preparing a Pt/NiFe-LDH catalyst precursor: adding 0.5g of magnesium-aluminum/nickel-iron hydrotalcite into 10ml of 0.01mol/LK2PtCl4 aqueous solution, uniformly stirring for 5 hours at 80 ℃, keeping the temperature constant during stirring, washing for 3-5 times by using deionized water, and drying for 8-10 hours at 60 ℃ to obtain a Pt/NiFe-LDH catalyst precursor PtCl4 2-/NiFe-LDH；
Step 2: preparation of anode catalyst:
step 2.1: weighing the PtCl4 2-Mixing NiFe-LDH, carbon black, absolute ethyl alcohol and nafion solution, carrying out ultrasonic treatment on the mixed solution for 45-60 min to obtain uniform dispersed solution, dropwise coating 10 mu L of the dispersed solution on the surface of a glassy carbon electrode for five times, and naturally drying;
step 2.2: and (3) forming a three-electrode system by the electrode prepared in the step (2.1), a platinum wire and a double-salt bridge saturated calomel electrode, and carrying out constant potential electrolysis in a 0.5mol/L sodium sulfate solution to obtain the Pt/NiFe-LDH catalyst.
4. The method of claim 1The preparation method of the electrode catalyst of the nano metal intercalated hydrotalcite material is characterized in that the nano metal intercalated hydrotalcite composite electrode material is PtxAuya/MgAl-LDH catalyst;
the PtxAuyThe preparation method of the/MgAl-LDH catalyst comprises the following steps:
step 1: preparing a Pt/NiFe-LDH catalyst precursor: 0.5g of magnesium aluminum hydrotalcite is added with K of different molar ratios of 10ml each2PtCl4And KAuCl4Uniformly stirring the mixed solution at 80 ℃ for 5 hours, keeping the temperature constant in the stirring process, washing the mixed solution with deionized water for 3-5 times, and drying the mixed solution at 60 ℃ for 8-10 hours to obtain Pt/MgAl-LDH and Pt/NiFe-LDH catalyst precursors;
step 2: preparation of anode catalyst:
step 2.1: weighing the Pt/MgAl-LDH catalyst precursor, the Pt/NiFe-LDH catalyst precursor, carbon black, absolute ethyl alcohol and nafion solution, mixing, carrying out ultrasonic treatment on the mixed solution for 45-60 min to obtain a uniform dispersion solution, taking 10 mu L of the dispersion solution, dropwise coating the dispersion solution on the surface of a glassy carbon electrode for five times, and naturally drying;
step 2.2: forming the electrode prepared in the step 2.1, a platinum wire and a double-salt bridge saturated calomel electrode into a three-electrode system, and carrying out constant potential electrolysis in a 0.5mol/L sodium sulfate solution to obtain the PtxAuyA MgAl-LDH catalyst.
5. The method for preparing the electrode catalyst of the nano metal intercalated hydrotalcite material according to any one of the claims 2, 3 and 4, wherein 5mg of each catalyst precursor, 2mg of the carbon black, 1mL of the absolute ethyl alcohol and 100 μ L of the nafion solution are weighed respectively.
6. The method for preparing the nanometal intercalated hydrotalcite material electrode catalyst according to any one of the claims 2, 3 and 4, wherein in step 2.2 the trimetallic system is electrocatalytically reduced for 2000S in a 0.5mol/L sodium sulfate solution at a voltage of-1.5V.
CN201911218566.0A 2019-12-03 2019-12-03 Preparation method of nano metal intercalated hydrotalcite material electrode catalyst Pending CN111063902A (en)

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Application publication date: 20200424