CN107799779B - Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof - Google Patents

Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof Download PDF

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CN107799779B
CN107799779B CN201710994086.8A CN201710994086A CN107799779B CN 107799779 B CN107799779 B CN 107799779B CN 201710994086 A CN201710994086 A CN 201710994086A CN 107799779 B CN107799779 B CN 107799779B
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iridium
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methanol solution
metal compound
formic acid
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CN107799779A (en
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李亚栋
陈远均
李治
冀淑方
王定胜
彭卿
陈晨
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Tsinghua University
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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
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/923—Compounds thereof with non-metallic elements
    • 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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

An iridium single atom catalyst for a direct formic acid fuel cell and a preparation method thereof are disclosed, wherein the catalyst is prepared by coordinating a zinc metal compound with an imidazole organic ligand in a methanol solution of an iridium metal compound to form a metal organic framework composite material wrapping the iridium metal compound, calcining at high temperature in an inert gas atmosphere, forming a porous carbon carrier doped with non-metal heteroatom nitrogen by the imidazole organic ligand, and loading the porous carbon carrier with the iridium atom interacting with the surrounding non-metal heteroatom nitrogen in a form of coordinating 4 nitrogen atoms with a single iridium atom (Ir-N4). The iridium monoatomic catalyst can be prepared by preparing the composite material of the iridium metal compound and the metal organic framework material in a simple mixing mode and then performing high-temperature pyrolysis. The method is simple and easy to implement, and the catalyst is suitable for the anode reaction of a direct formic acid fuel cell and has the characteristics of high atom utilization rate, excellent catalytic performance and good stability.

Description

Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof
Technical Field
The invention particularly relates to an iridium monatomic catalyst for an anode of a direct formic acid fuel cell and a preparation method thereof, belonging to the technical field of direct formic acid fuel cells.
Background
With the development of human society, the global energy consumption and climate change have attracted people's attention, and therefore, the search for alternative clean energy is urgent. At present, new energy sources under development include solar energy, wind energy, fuel cells, and the like. Among them, the direct formic acid fuel cell is a device that directly converts chemical energy into electric energy by generating carbon dioxide and water through an electrode reaction of formic acid and air, does not require charging, does not generate exhaust gas, receives attention from people due to superiorities such as high energy conversion efficiency and environmental friendliness, and is considered to be one of the preferred clean energy power generation technologies in the 21 st century. Fuel cells are particularly suitable for use as a power source for automobiles, and fuel cells have been regarded as one of the ultimate solutions for automobile business, and are superior to electric automobiles, and in fact, fuel cell automobiles produced in the first lot have been commercially sold in japan. However, anode formic acid oxidation kinetics of the direct formic acid fuel cell are slow, the catalyst is easy to deactivate, and the expensive anode catalyst is a large factor for limiting the commercialization process of the fuel cell. At present, palladium carbon and platinum carbon are the most widely used catalysts in commerce, but due to the high price, low activity per unit mass and easy attenuation and inactivation in the using process of the palladium carbon and the platinum carbon, the problems which need to be solved urgently for realizing large-scale commercialization of the direct formic acid fuel cell are all solved. The solution so far is to use palladium-based alloy or platinum-based alloy catalyst instead of single-component palladium-carbon or platinum-carbon catalyst, although the method can improve the activity and stability of the catalyst to some extent, compared with the requirement of commercial application, there is still a great gap. It is noteworthy that the currently reported electrocatalysts have a gradual decline in activity during cycling tests, because carbon monoxide, an intermediate product in the formic acid electrocatalysis process, poisons the catalyst material, which is an important factor limiting the stability of the electrocatalysts. The development of high-activity, high-stability and carbon monoxide poisoning-resistant electrocatalyst for direct formic acid fuel cell to replace the existing catalyst is an effective way to solve the problems, and will greatly promote the progress of the commercialization of the direct formic acid fuel cell.
Disclosure of Invention
The invention aims to provide an iridium monatomic catalyst for a direct formic acid fuel cell and a preparation method thereof, so that the preparation method is simple, and the prepared catalyst has good thermal stability, high yield and low price.
In order to achieve the purpose, the invention adopts the following technical scheme:
an iridium single-atom catalyst for a direct formic acid fuel cell anode is characterized in that an iridium metal compound is encapsulated in a zinc metal compound in a limited domain mode and coordinated with an imidazole organic ligand to form a metal organic framework material, then the imidazole organic ligand forms a non-metal heteroatom nitrogen-doped carbon carrier through high-temperature pyrolysis reaction in an inert gas atmosphere, iridium atoms interact with surrounding non-metal heteroatom nitrogen, and form Ir-N4 coordination with 4 surrounding nitrogen atoms in a single-atom mode and are loaded on a porous carbon carrier.
The iridium in the catalyst is a metal iridium element of a sixth period, and the organic ligand is 2-methylimidazole.
The non-metal heteroatom is N.
A preparation method of iridium monatomic catalyst of a direct formic acid fuel cell anode comprises the following steps:
step 1, adding an iridium metal compound methanol solution and a zinc metal compound methanol solution into an imidazole organic ligand methanol solution, dissolving, and then standing the mixed solution for 12-36 hours; the molar concentration of the iridium metal compound methanol solution is 0.024-0.027 mol/L, the molar concentration of the zinc metal compound methanol solution is 0.24-0.27 mol/L, and the volume ratio of a methanol solution of the iridium metal compound, the methanol solution of the zinc metal compound and the methanol solution of the imidazole organic ligand is 1:1:0.5 to 2.
Step 2, washing the suspension obtained in the step 1 with methanol, and drying overnight to obtain solid powder;
and 3, putting the solid powder obtained in the step 2 into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 800-1000 ℃ under inert atmosphere, calcining for 2-4 h, naturally cooling to room temperature, and taking out a black solid material to obtain the required catalyst.
The iridium metal compound required for synthesizing the metal organic framework material is iridium acetylacetone salt, and the zinc metal compound is nitrate, sulfate or chloride salt thereof.
The inert gas is N2Or Ar.
The invention has the following advantages and prominent technical effects: the iridium monatomic catalyst provided by the invention is prepared by taking an iridium metal compound and a metal organic framework composite material as precursors and only needing a high-temperature pyrolysis method, is simple and easy to prepare, and can also be used for preparing other various monatomics, wherein iridium atoms in the catalyst prepared by the invention exist in a form of single atom uniform dispersion and are loaded on a porous carbon material, and form Ir-N4 coordination with peripheral nitrogen atoms; ② the iridium monatomic catalyst provided by the invention has unprecedented high activity in an acid environment. At 0.5mol/L H2SO4And a specific mass activity measured in the mixed electrolyte of 0.5mol/LHCOOH was 11.1A/mgIrThe catalyst is the highest value reported by the literature materials in the related fields at present, and is 20 times of that of commercial palladium carbon and 44 times of that of commercial platinum carbon. The iridium monatomic catalyst had a maximum output power density of 557mW/mg during testing for assembly into a direct formic acid fuel cellIr9 times that of commercial palladium on carbon. More importantly, the iridium monatomic catalyst has unprecedented carbon monoxide poisoning resistance, and the electrocatalytic performance is hardly influenced even if a large amount of carbon monoxide is introduced in the formic acid electrooxidation process. Therefore, the iridium monatomic catalyst prepared by the method is suitable for the anode reaction of the direct formic acid fuel cell, has high atom utilization rate, excellent performance and good stability, and can promote the development of the fuel cell.
Drawings
FIGS. 1a and 1b are images of prepared iridium monatomic catalyst under a phase-difference corrected high-angle annular dark-field scanning transmission electron microscope. FIG. 2 shows that the prepared iridium monatomic catalyst is at 0.5mol/L H2SO4And 0.5mol/L HCOOH, wherein Ir-ISAS is an Ir monatomic catalyst; Pd/C is commercial palladium on carbon; Pt/C is commercial platinum carbon.
Fig. 3a, fig. 3b and fig. 3c are polarization curves of the prepared iridium monatomic catalyst in a direct formic acid fuel cell, respectively, wherein fig. 3a is an output power curve, fig. 3b is a stability curve, and fig. 3c is a carbon monoxide poisoning resistance curve.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
The invention provides an iridium monatomic catalyst for a direct formic acid fuel cell, which has the structure that iridium monatomic is coordinated with 4 nitrogen atoms around the iridium monatomic to form Ir-N4, and is loaded on a porous carbon carrier; the catalyst is structurally characterized in that a zinc metal compound and an imidazole organic ligand are coordinated in a methanol solution of an iridium metal compound to form a metal organic framework composite material wrapping the iridium metal compound, and then the metal organic framework composite material is calcined at high temperature in an inert gas atmosphere to enable the imidazole organic ligand to form a non-metal heteroatom nitrogen-doped porous carbon carrier. See fig. 1a and 1 b. The imidazole organic ligand is 2-methylimidazole, and the iridium metal compound is iridium acetylacetone salt; the zinc metal compound is nitrate, sulfate or chloride of zinc.
The invention provides a preparation method of an iridium monatomic catalyst for a direct formic acid fuel cell, which specifically comprises the following steps:
1) adding an iridium metal compound methanol solution and a zinc metal compound methanol solution into an imidazole organic ligand methanol solution, and reacting at room temperature for 12-36 hours to obtain a suspension; and washing the suspension with methanol and drying to obtain solid powder. The molar concentration of the iridium metal compound methanol solution is 0.024-0.027 mol/L, the molar concentration of the zinc metal compound methanol solution is 0.24-0.27 mol/L, and the molar concentration of the imidazole organic ligand methanol solution is 0.53-1.42 mol/L; wherein the volume ratio of the iridium metal compound methanol solution to the zinc metal compound methanol solution to the imidazole organic ligand methanol solution is 1:1:0.5 to 2;
2) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 800-1000 ℃ under inert atmosphere, calcining for 2-4 h, naturally cooling to room temperature, and taking out a black solid material to obtain the required catalyst. The inert gas is N2Or Ar.
Firstly, preparing an iridium monatomic catalyst:
example 1
(1) Preparing 0.024mol/L acetylacetone iridium methanol solution, 0.240mol/L zinc nitrate methanol solution and 1.42 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:1.5, and then stirring the mixed solution at room temperature for 24 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 900 ℃ under inert atmosphere, calcining for 3h, naturally cooling to room temperature, taking out a black solid material to obtain the required monatomic catalyst, and observing that iridium monatomic is uniformly dispersed on the nitrogen-doped porous carbon material under an electron microscope as shown in figure 1.
Example 2
(1) Preparing 0.024mol/L acetylacetone iridium methanol solution, 0.270mol/L zinc nitrate methanol solution and 1.42 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:1.5, and then stirring the mixed solution at room temperature for 12 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 800 ℃ under the inert atmosphere, calcining for 4 hours, naturally cooling to room temperature, and taking out a black solid material to obtain the needed monatomic catalyst.
Example 3
(1) Preparing 0.027mol/L acetylacetone iridium methanol solution, 0.270mol/L zinc nitrate methanol solution and 1.42 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:1.5, and then stirring the mixed solution at room temperature for 36 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 1000 ℃ under the inert atmosphere, calcining for 2h, naturally cooling to room temperature, and taking out a black solid material to obtain the required monatomic catalyst.
Example 4
(1) Preparing 0.027mol/L acetylacetone iridium methanol solution, 0.270mol/L zinc nitrate methanol solution and 0.53 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:1.5, and then stirring the mixed solution at room temperature for 18 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 800 ℃ under the inert atmosphere, calcining for 2 hours, naturally cooling to room temperature, and taking out a black solid material to obtain the needed monatomic catalyst.
Example 5
(1) Preparing 0.024mol/L acetylacetone iridium methanol solution, 0.240mol/L zinc nitrate methanol solution and 0.53 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:0.5, and then stirring the mixed solution at room temperature for 36 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 1000 ℃ under the inert atmosphere, calcining for 3h, naturally cooling to room temperature, and taking out a black solid material to obtain the required monatomic catalyst.
Example 6
(1) Preparing 0.024mol/L acetylacetone iridium methanol solution, 0.240mol/L zinc nitrate methanol solution and 0.53 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:2, and then stirring the mixed solution at room temperature for 12 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 800 ℃ under the inert atmosphere, calcining for 4 hours, naturally cooling to room temperature, and taking out a black solid material to obtain the needed monatomic catalyst.
Example 7
(1) Preparing 0.024mol/L acetylacetone iridium methanol solution, 0.240mol/L zinc nitrate methanol solution and 1.42 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:2, and then stirring the mixed solution at room temperature for 20 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 950 ℃ under the inert atmosphere, calcining for 3h, naturally cooling to room temperature, and taking out a black solid material to obtain the required monatomic catalyst.
Example 8
(1) Preparing 0.027mol/L acetylacetone iridium methanol solution, 0.270mol/L zinc nitrate methanol solution and 0.53 mol/L2-methylimidazole methanol solution; then uniformly mixing the acetylacetone iridium methanol solution, the zinc nitrate methanol solution and the 2-methylimidazole methanol solution in a volume ratio of 1:1:2, and then stirring the mixed solution at room temperature for 18 hours;
(2) centrifugally washing the obtained suspension with methanol, and drying to obtain solid powder;
(3) and putting the obtained solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 850 ℃ under the inert atmosphere, calcining for 4 hours, naturally cooling to room temperature, and taking out a black solid material to obtain the needed monatomic catalyst.
II, evaluating the formic acid electrooxidation activity of the iridium monatomic catalyst: (as shown in FIG. 2)
Example 1
To a solution containing 495. mu.L of an anhydrous ethanol solution, 495. mu.L of water and 10. mu.L of Nafion solution having a mass concentration of 5%, 5mg of the iridium monatomic catalyst prepared in the above example was added, and ultrasonic dispersion was carried out for 30min to obtain a dispersed catalyst solution. Then at 0.5mol/L H2SO4And 0.5mol/L HCOOH. The reaction conditions are as follows: at 0.5mol/L H2SO4And 0.5mol/L HCOOH mixed electrolyte, introducing nitrogen for saturation, dripping 5 mu L of the prepared dispersed catalyst solution on a glassy carbon electrode for drying, and obtaining a sweep voltammetry curve at room temperature under 50 mV/s.
Comparative example 1
Adding 5mg of commercial Pt/C (Pt content is 20%) catalyst into 495 mu L of absolute ethyl alcohol solution, 495 mu L of water and 10 mu L of Nafion solution with the mass concentration of 5%, and performing ultrasonic dispersion for 30min to obtain a solution; then commercial Pt/C catalyst was used at 0.5mol/L H2SO4And 0.5mol/L HCOOH.
Comparative example 2
Adding 5mg of commercial Pd/C (Pd content is 20%) catalyst into 495 mu L of absolute ethanol solution, 495 mu L of water and 10 mu L of Nafion solution with mass concentration of 5%, and performing ultrasonic dispersion for 30min to obtain a solution; then commercial Pd/C catalyst was used at 0.5mol/L H2SO4And 0.5mol/L HCOOH.
Dripping 5 mu L of the solution on a rotating disc electrode, and airing at room temperature to obtain a film electrode; and a three-electrode system with a saturated calomel electrode as a reference electrode and a Pt wire as a counter electrode. 0.5mol/L H saturated with nitrogen2SO4And 0.5mol/L HCOOH in the mixed electrolyteThe scanning speed is 50mV/s in an ampere test.
Thirdly, evaluating the activity of the iridium monatomic catalyst direct formic acid fuel cell: (as shown in FIG. 3 a)
Example 1
To a solution containing 495. mu.L of an anhydrous ethanol solution, 495. mu.L of water and 10. mu.L of Nafion solution having a mass concentration of 30% was added 20mg of the iridium monatomic catalyst prepared in the above example, and the mixture was ultrasonically dispersed for 30min to obtain a dispersed catalyst solution. Then spraying the catalyst solution on 5 cm-5 cm carbon paper, and hot-pressing with proton exchange membrane to obtain catalyst loading (including carbon carrier) of 4.0mg/cm2The anode of the direct formic acid fuel cell of (1). The platinum-carbon (commercial platinum-carbon with 20 percent of content) loading capacity is 4mg/cm2The anode of the direct formic acid fuel cell of (1). A3M formic acid solution was fed to the anode at a flow rate of 5.0mL/min, and humidified air was fed to the cathode at a flow rate of 750mL/min, and the measurements were carried out at room temperature, 60 ℃ and 90 ℃ respectively.
Comparative example 1
A direct formic acid fuel cell was prepared in the same manner as in example 1 with a palladium on carbon (10% commercial Pt on carbon) loading of 4.0mg/cm in the cathode2The anode platinum-carbon (commercial platinum-carbon with 20 percent content) loading is 4.0mg/cm2. A3M formic acid solution was fed to the anode at a flow rate of 5.0mL/min, and humidified air was fed to the cathode at a flow rate of 750mL/min, and the measurements were carried out at room temperature, 60 ℃ and 90 ℃ respectively.
Fourthly, evaluating the formic acid electrooxidation stability of the iridium monatomic catalyst: (as shown in FIG. 3 b)
Example 1
To a solution containing 495. mu.L of an anhydrous ethanol solution and 495. mu.L of water, and 10. mu.L of Nafion solution having a mass concentration of 5%, 5mg of the iridium monatomic catalyst prepared in the above example was added, and ultrasonic dispersion was carried out for 30min to obtain a dispersed catalyst solution. Then at 0.5mol/L H2SO4And 0.5mol/L HCOOH. The reaction conditions are as follows: at 0.5mol/L H2SO4And 0.5mol/L HCOOH mixed electrolyte, introducing nitrogen gas for saturation, dripping 5 mu L of the prepared dispersed catalyst solution on a glassy carbon electrode for drying, and placing in a roomAt room temperature, the scanning speed was 50mV/s, the peak current was recorded every 200 cycles (cycle) for a total of 1000 cycles, and the corresponding peak current was compared to the initial peak current.
Comparative example 1
Adding 5mg of commercial Pd/C (Pd content is 20%) catalyst into 495 mu L of absolute ethanol solution, 495 mu L of water and 10 mu L of Nafion solution with mass concentration of 5%, and performing ultrasonic dispersion for 30min to obtain a solution; then commercial Pt/C catalyst was used at 0.5mol/L H2SO4And 0.5mol/L HCOOH.
Comparative example 2
Adding 5mg of commercial Pd/C (Pd content is 20%) catalyst into 495 mu L of absolute ethanol solution, 495 mu L of water and 10 mu L of Nafion solution with mass concentration of 5%, and performing ultrasonic dispersion for 30min to obtain a solution; then commercial Pd/C catalyst was used at 0.5mol/L H2SO4And 0.5mol/L HCOOH.
Dripping 5 mu L of the solution on a rotating disc electrode, and airing at room temperature to obtain a film electrode; and a three-electrode system with a saturated calomel electrode as a reference electrode and a Pt wire as a counter electrode. 0.5mol/L H saturated with nitrogen2SO4And 0.5mol/L HCOOH, the sweep rate was 50mV/s, the peak current was recorded every 200 cycles (cycles), for a total of 1000 cycles, and the corresponding peak current was compared to the initial peak current. As a result, as shown in FIG. 3b, the performance of the iridium monatomic catalyst was not substantially changed after 1000 cycles, while the performance of the commercial Pd/C was reduced by half.
Fifthly, evaluating carbon monoxide poisoning resistance of the iridium monatomic catalyst: (as shown in FIG. 3 c)
Example 1
To a solution containing 495. mu.L of an anhydrous ethanol solution and 495. mu.L of water, and 10. mu.L of Nafion solution having a mass concentration of 5%, 5mg of the iridium monatomic catalyst prepared in the above example was added, and ultrasonic dispersion was carried out for 30min to obtain a dispersed catalyst solution. Then at 0.5mol/L H2SO4And 0.5mol/L HCOOH. Inverse directionThe conditions are as follows: at 0.5mol/L H2SO4And 0.5mol/L HCOOH mixed electrolyte, introducing nitrogen for saturation, dripping 5 mu L of the prepared dispersed catalyst solution on a glassy carbon electrode for drying, and making an electrochemical current-time curve at room temperature, wherein the set voltage is 0.48V and the set time is 2000 s. At 300s, the nitrogen was turned off and a large amount of carbon monoxide (CO) gas was bubbled in. When the time reaches 600s, the carbon monoxide gas is stopped passing through, and the nitrogen gas is introduced instead.
Comparative example 1
Adding 5mg of commercial Pt/C (Pt content is 20%) catalyst into 495 mu L of absolute ethyl alcohol solution, 495 mu L of water and 10 mu L of Nafion solution with the mass concentration of 5%, and performing ultrasonic dispersion for 30min to obtain a solution; then commercial Pt/C catalyst was used at 0.5mol/L H2SO4And 0.5mol/LHCOOH in the mixed electrolyte.
Comparative example 2
Adding 5mg of commercial Pd/C (Pd content is 20%) catalyst into 495 mu L of absolute ethanol solution, 495 mu L of water and 10 mu L of Nafion solution with mass concentration of 5%, and performing ultrasonic dispersion for 30min to obtain a solution; then commercial Pd/C catalyst was used at 0.5mol/L H2SO4And 0.5mol/L HCOOH.
Dripping 5 mu L of the solution on a rotating disc electrode, and airing at room temperature to obtain a film electrode; and a three-electrode system with a saturated calomel electrode as a reference electrode and a Pt wire as a counter electrode. 0.5mol/L H saturated with nitrogen2SO4And 0.5mol/L HCOOH, setting the voltage to be 0.48V and the time to be 2000 s. At 300s, the nitrogen was turned off and a large amount of carbon monoxide (CO) gas was bubbled in. When the time reaches 600s, the carbon monoxide gas is stopped passing through, and the nitrogen gas is introduced instead. As a result, as shown in FIG. 3C, the performance of iridium monatomic was not substantially affected by carbon monoxide, whereas commercial Pd/C and commercial Pt/C were deactivated shortly after carbon monoxide was introduced, and had no activity even after carbon monoxide was removed.

Claims (4)

1. An iridium monatomic catalyst for a direct formic acid fuel cell, characterized in that the catalyst has a structure in which an iridium monatomic is coordinated with 4 nitrogen atoms around it to form Ir-N4, and is supported on a porous carbon support; the catalyst is structurally characterized in that a zinc metal compound and an imidazole organic ligand are coordinated in a methanol solution of an iridium metal compound to form a metal organic framework composite material wrapping the iridium metal compound, and then the metal organic framework composite material is calcined at high temperature in an inert gas atmosphere to enable the imidazole organic ligand to form a non-metal heteroatom nitrogen-doped porous carbon carrier; the catalyst was prepared by the following method:
1) adding an iridium metal compound methanol solution and a zinc metal compound methanol solution into an imidazole organic ligand methanol solution, reacting at room temperature for 12-36 h to obtain a suspension after reaction; the molar concentration of the iridium metal compound methanol solution is 0.024-0.027 mol/L, the molar concentration of the zinc metal compound methanol solution is 0.24-0.27 mol/L, and the molar concentration of the imidazole organic ligand methanol solution is 0.53-1.42 mol/L; wherein the volume ratio of the iridium metal compound methanol solution to the zinc metal compound methanol solution to the imidazole organic ligand methanol solution is 1:1:0.5 to 2;
2) washing the suspension obtained in the step 1) with methanol, and drying to obtain solid powder;
3) putting the solid powder obtained in the step 2) into a porcelain boat, putting the porcelain boat into a tubular furnace, sealing, introducing inert gas, heating to 800-1000 ℃ under inert atmosphere, calcining for 2-4 h, naturally cooling to room temperature, and taking out a black solid material to obtain the required catalyst.
2. The iridium monatomic catalyst for a direct formic acid fuel cell according to claim 1, wherein said imidazole-based organic ligand is 2-methylimidazole.
3. The iridium monatomic catalyst for a direct formic acid fuel cell as defined in claim 1, wherein the iridium metal compound is an iridium acetylacetonate; the zinc metal compound is nitrate, sulfate or chloride of zinc.
4. The iridium monatomic catalyst for a direct formic acid fuel cell as defined in claim 1, wherein the inert gas in the step 3) is N2Or Ar.
CN201710994086.8A 2017-10-23 2017-10-23 Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof Active CN107799779B (en)

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CN111326745B (en) * 2020-02-12 2021-07-27 北京化工大学 Two-dimensional zinc monoatomic/carbon nitrogen composite material and preparation method and application thereof
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