CN111020624B - Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst - Google Patents

Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst Download PDF

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CN111020624B
CN111020624B CN201911203568.2A CN201911203568A CN111020624B CN 111020624 B CN111020624 B CN 111020624B CN 201911203568 A CN201911203568 A CN 201911203568A CN 111020624 B CN111020624 B CN 111020624B
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frequency vibration
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亓钧雷
闫耀天
钟正祥
曹健
冯吉才
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Harbin Institute of Technology
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Abstract

The invention discloses a preparation method of a self-supporting electrocatalyst with high-frequency vibration corrosion, and relates to a preparation method of a self-supporting electrocatalyst. The invention aims to solve the problems that the existing electrocatalysis electrode material with a three-dimensional nano structure is complex in synthesis process, long in production period and high in energy consumption of total water decomposition of the existing industrially applied catalyst. The method comprises the following steps: firstly, washing a precursor by using protective gas; secondly, activating the surface of the precursor; and thirdly, carrying out high-frequency vibration corrosion on the electrode material, namely completing the preparation of the self-supporting electrocatalyst with high-frequency vibration corrosion.

Description

Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst
Technical Field
The present invention relates to a method for preparing a self-supporting electrocatalyst.
Background
Electrochemical cracking reactions, including oxygen-producing half reactions (OERs) and hydrogen-producing half reactions (HERs), are recognized as important pathways for sustainable production of hydrogen energy in water. In order to overcome the problem of slow kinetic process of OER and HER at low overpotential and increase reaction rate, the development of efficient electrocatalyst is a challenging and important issue.
Currently, the mainstream electrocatalysts for OER and HER are noble metal catalysts comprising Ir/Ru-based oxides and Pt. Such noble metal catalysts possess high catalytic activity, but their application is greatly limited by the high cost and scarce reserves of noble metals. Therefore, the development of transition metal-based electrocatalysts with low cost, high efficiency and abundant reserves has great practical significance. Although transition group metal-based electrocatalysts such as transition group metal oxides, phosphides, sulfides and selenides have been widely developed and used for water decomposition research, the intrinsic activity and electrochemical properties of these electrocatalysts still cannot meet the requirements of industrial production and commercial popularization, and further optimization of the components and structures is still needed.
Considering that electrochemical reactions generally first occur at the surface or interface of a material, starting from morphological engineering and constructing active sites is an effective means for improving the electrocatalytic performance, wherein a strategy favored by researchers is to increase the specific surface area by constructing a three-dimensional nanostructure, promote the electron transfer and ion diffusion processes and further improve the electrocatalytic activity. In recent years, researchers develop a solvothermal method to grow nanostructures in situ on a conductive substrate to prepare a so-called self-supporting system electrode material, so that the use of an organic binder can be avoided, the contact resistance is reduced, more active sites are provided, and the structural stability is improved. In addition, the total water decomposition potential of the existing industrial application catalyst is about 1.8V-2.0V in most cases, and the energy consumption needs to be further reduced.
Disclosure of Invention
The invention provides a preparation method of a high-frequency vibration corrosion self-supporting electrocatalyst, aiming at solving the problems that the existing three-dimensional nanostructure electrocatalysis electrode material is complex in synthesis process, long in production period and high in energy consumption of full-water decomposition of the existing industrially applied catalyst.
A preparation method of a self-supporting electrocatalyst with high-frequency vibration corrosion is completed by the following steps:
firstly, washing a precursor by using a protective gas:
firstly, placing the pretreated precursor in a quartz tube, and then placing the quartz tube filled with the precursor in a tube furnace;
secondly, closing the air inlet valve, opening the air outlet valve, pumping the air pressure in the quartz tube to 0.1-10 torr by using an air pump, and then closing the air outlet valve;
thirdly, opening an air inlet valve, introducing protective gas into the quartz tube with the gas flow of 10 sccm-100 sccm, controlling the air pressure to rise to 100 torr-700 torr, and closing the air inlet valve;
fourthly, repeating the steps from the first step to the third step for 3 to 4 times;
secondly, activating the surface of the precursor:
placing an activating agent in the direction of an air inlet of a quartz tube and at a position 1-5 cm away from a precursor, introducing protective gas into the quartz tube at a gas flow rate of 10-100 sccm, heating the quartz tube to 200-600 ℃ at a heating rate of 10-20 ℃/min, preserving the heat for 10-2 h at the temperature of 200-600 ℃, and finally reducing the temperature to below 100 ℃ at a cooling rate of 10-20 ℃/min under the condition of continuously introducing the protective gas to obtain a precursor with the surface activated;
thirdly, carrying out high-frequency vibration corrosion on the electrode material:
and dipping the precursor with the activated surface in an active medium, placing the active medium dipped with the precursor in a high-frequency current transducer, oscillating for 5-600 s under the condition that the frequency is 0.01-40 kHz, and taking out and cleaning after the oscillation is finished to obtain the self-supporting electrocatalyst corroded by high-frequency vibration.
The invention has the beneficial effects that:
1. the preparation method of the high-frequency vibration corrosion self-supporting electrocatalyst provided by the invention simplifies the production process to a certain extent, and simultaneously has adjustable and controllable components, namely, the activation of different anion components can be carried out on the substrate according to the actual production requirement.
2. The preparation method can rapidly generate the three-dimensional cross-linked flaky nano structure at low cost, optimize the charge conduction path, obviously increase the number of active sites, and further improve the catalytic activity of the electrode material, soThe prepared self-supporting electrocatalyst is used as a working electrode, and the total hydrolysis reaction reaches 10mA/cm under the condition of a double-electrode test system which takes KOH solution with the concentration of 1mol/L as electrolyte2Only 1.67V of operating voltage is required for the current density of (2). Compared with the 1.8V-2.0V full-water decomposition voltage required under most of the existing conditions, the energy consumption is greatly reduced.
3. The invention provides a preparation method of a high-frequency vibration corrosion self-supporting electrocatalyst, which can greatly shorten the production period to be within 3h on the premise of ensuring the advantages of self-supporting system electrode materials, and can obviously improve the production efficiency compared with the preparation period of tens of hours to tens of hours under most conditions. The self-supporting electrode plate with the size of about 20cm multiplied by 20cm can be conveniently prepared according to the requirement, compared with the electrode size of a plurality of square centimeters in most cases, the preparation size of the electrode material is greatly expanded, and the production safety is improved.
Drawings
FIG. 1 is a scanning electron micrograph of a high frequency shock corroded self-supporting electrocatalyst prepared according to example one.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the self-supporting electrocatalyst with high-frequency vibration corrosion, which is provided by the embodiment, is completed according to the following steps:
firstly, washing a precursor by using a protective gas:
firstly, placing the pretreated precursor in a quartz tube, and then placing the quartz tube filled with the precursor in a tube furnace;
secondly, closing the air inlet valve, opening the air outlet valve, pumping the air pressure in the quartz tube to 0.1-10 torr by using an air pump, and then closing the air outlet valve;
thirdly, opening an air inlet valve, introducing protective gas into the quartz tube with the gas flow of 10 sccm-100 sccm, controlling the air pressure to rise to 100 torr-700 torr, and closing the air inlet valve;
fourthly, repeating the steps from the first step to the third step for 3 to 4 times;
secondly, activating the surface of the precursor:
placing an activating agent in the direction of an air inlet of a quartz tube and at a position 1-5 cm away from a precursor, introducing protective gas into the quartz tube at a gas flow rate of 10-100 sccm, heating the quartz tube to 200-600 ℃ at a heating rate of 10-20 ℃/min, preserving the heat for 10-2 h at the temperature of 200-600 ℃, and finally reducing the temperature to below 100 ℃ at a cooling rate of 10-20 ℃/min under the condition of continuously introducing the protective gas to obtain a precursor with the surface activated;
thirdly, carrying out high-frequency vibration corrosion on the electrode material:
and dipping the precursor with the activated surface in an active medium, placing the active medium dipped with the precursor in a high-frequency current transducer, oscillating for 5-600 s under the condition that the frequency is 0.01-40 kHz, and taking out and cleaning after the oscillation is finished to obtain the self-supporting electrocatalyst corroded by high-frequency vibration.
The beneficial effects of the embodiment are as follows:
1. the preparation method of the high-frequency vibration corrosion self-supporting electrocatalyst provided by the embodiment simplifies the production process to a certain extent, and meanwhile, the components can be regulated and controlled, namely, the activation of different anion components can be carried out on the substrate according to the actual production requirement.
2. The preparation method of the embodiment can generate the three-dimensional cross-linked flaky nano structure rapidly at low cost, optimizes the charge conduction path, can obviously increase the number of active sites, and further improves the catalytic activity of the electrode material, and the total hydrolysis reaction reaches 10mA/cm under the condition of a double-electrode test system which takes the prepared self-supporting electrocatalyst as a working electrode and takes KOH solution with the concentration of 1mol/L as electrolyte2Only 1.67V of operating voltage is required for the current density of (2). Compared with the 1.8V-2.0V full-water decomposition voltage required under most of the existing conditions, the energy consumption is greatly reduced.
3. The embodiment provides a preparation method of a high-frequency vibration corrosion self-supporting electrocatalyst, which can greatly shorten the production period to within 3h on the premise of ensuring the advantages of self-supporting system electrode materials, and can obviously improve the production efficiency compared with the preparation period of tens of hours to tens of hours under most conditions. The self-supporting electrode plate with the size of about 20cm multiplied by 20cm can be conveniently prepared according to the requirement in the embodiment, compared with the electrode size of a plurality of square centimeters in most cases, the preparation size of the electrode material is greatly expanded, and the production safety is improved.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the pretreated precursor in the first step is prepared according to the following steps: and sequentially washing the precursor by using HCl solution with the concentration of 0.1-5 mol/L, deionized water and absolute ethyl alcohol for 0.5-5 min respectively. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the precursor is foam iron, foam nickel, foam cobalt, foam copper, foam NiFe, iron foil, cobalt foil, NiFe foil or NiTi foil. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the protective gas in the step one is one or two of argon and nitrogen, or a mixed gas of argon and hydrogen; the volume percentage of hydrogen in the mixed gas of argon and hydrogen is 2-10%. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and in the second step, protective gas is introduced into the quartz tube with the gas flow rate of 10 sccm. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and the activating agent in the second step is one or a mixture of more of Se powder, S powder, sodium hypophosphite and sodium tellurite. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the mass ratio of the activating agent in the second step to the area of the precursor working surface is (0.01-2) g:10cm2. The others are the same as the first to sixth embodiments.
Since the resulting self-supporting electrocatalyst from the precursor can be used directly as the working electrode, the working surface of the precursor, i.e. the working surface of the working electrode, can be said.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the protective gas in the second step is one or a mixture of argon and nitrogen, or a mixture of argon and hydrogen; the volume percentage of hydrogen in the mixed gas of argon and hydrogen is 2-10%. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the active medium in the third step is one or a mixture of more of hydrochloric acid with the mass percent of 0.1-30%, nitric acid with the mass percent of 0.1-30%, oxalic acid with the mass percent of 0.1-30%, ammonium fluoride solution with the mass percent of 0.1-30%, ammonium chloride solution with the mass percent of 0.1-30%, ferric chloride solution with the mass percent of 0.1-30%, hydrogen peroxide water solution with the mass percent of 0.1-30% and sodium hypochlorite solution with the mass percent of 0.1-10%. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: in the third step, the vibration is carried out for 5 s-1 min under the condition that the frequency is 0.01 kHz-40 kHz. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of a self-supporting electrocatalyst with high-frequency vibration corrosion is completed by the following steps:
firstly, washing a precursor by using a protective gas:
firstly, placing the pretreated precursor in a quartz tube, and then placing the quartz tube filled with the precursor in a tube furnace;
closing the air inlet valve, opening the air outlet valve, pumping the air pressure in the quartz tube to 10torr by using an air pump, and then closing the air outlet valve;
thirdly, opening an air inlet valve, introducing protective gas into the quartz tube with the gas flow of 10sccm, controlling the air pressure to rise to 700torr, and closing the air inlet valve;
thirdly, repeating the steps from the first step to the third step for 4 times;
secondly, activating the surface of the precursor:
placing 1g of activating agent in the direction of an air inlet of a quartz tube and at a position 5cm away from a precursor, introducing protective gas into the quartz tube at a gas flow rate of 10sccm, heating the quartz tube to 400 ℃ at a heating rate of 20 ℃/min, preserving the temperature for 10min at the temperature of 400 ℃, and finally reducing the temperature to 90 ℃ at a cooling rate of 20 ℃/min under the condition of continuously introducing the protective gas to obtain a precursor with an activated surface;
thirdly, carrying out high-frequency vibration corrosion on the electrode material:
dipping the precursor with the activated surface in an active medium, placing the active medium dipped with the precursor in a high-frequency current transducer, oscillating for 5s under the condition that the frequency is 10kHz, taking out and cleaning with deionized water and ethanol after the oscillation is finished, and obtaining the self-supporting electrocatalyst corroded by high-frequency vibration;
the pretreated precursor in the first step is prepared according to the following steps: sequentially washing the precursor with the size of 10cm multiplied by 10cm for 5min by using HCl solution with the concentration of 5mol/L, deionized water and absolute ethyl alcohol respectively;
the precursor is foam iron, and the thickness of the precursor is 2 mm;
the protective gas in the step one is argon;
the activating agent in the second step is S powder;
the protective gas in the second step is argon;
the active medium in the third step is a hydrogen peroxide aqueous solution with the mass percent of 0.1%;
FIG. 1 is a scanning electron micrograph of the HF-vibrationally-corroded self-supported electrocatalyst prepared in example one, and it can be seen that the HF-vibrationally-corroded self-supported electrocatalyst has a uniform three-dimensional cross-linked lamellar nanostructure on its surface.
The preparation period in this embodiment is about 0.5h, which significantly improves the production efficiency compared to the preparation period of tens of hours to tens of hours in most cases.
The size of the precursor is 10cm multiplied by 10cm, namely the area of the working surface is 100cm2Compared with the electrode size of a plurality of square centimeters in most of the prior cases, the preparation size of the electrode material is greatly expanded.
Under the condition of a double-electrode test system which takes the prepared high-frequency vibration corrosion self-supporting electrocatalyst as a working electrode and takes KOH solution with the concentration of 1mol/L as electrolyte, the total hydrolysis reaction reaches 10mA/cm2Only 1.67V of operating voltage is required for the current density of (2). Compared with the 1.8V-2.0V full-water decomposition voltage required under most of the existing conditions, the energy consumption is greatly reduced.

Claims (6)

1. A preparation method of a self-supporting electrocatalyst with high-frequency vibration corrosion is characterized by comprising the following steps:
firstly, washing a precursor by using a protective gas:
firstly, placing the pretreated precursor in a quartz tube, and then placing the quartz tube filled with the precursor in a tube furnace;
the pretreated precursor is prepared according to the following steps: sequentially washing the precursor with HCl solution with the concentration of 5mol/L, deionized water and absolute ethyl alcohol for 5min respectively; the precursor is foam iron;
secondly, closing the air inlet valve, opening the air outlet valve, pumping the air pressure in the quartz tube to 0.1-10 torr by using an air pump, and then closing the air outlet valve;
thirdly, opening an air inlet valve, introducing protective gas into the quartz tube with the gas flow of 10 sccm-100 sccm, controlling the air pressure to rise to 100 torr-700 torr, and closing the air inlet valve;
fourthly, repeating the steps from the first step to the third step for 3 to 4 times;
secondly, activating the surface of the precursor:
placing an activating agent in the direction of an air inlet of a quartz tube and at a position 1-5 cm away from a precursor, introducing protective gas into the quartz tube at a gas flow rate of 10-100 sccm, heating the quartz tube to 200-600 ℃ at a heating rate of 10-20 ℃/min, preserving the temperature for 10min at the temperature of 200-600 ℃, and finally reducing the temperature to below 100 ℃ at a cooling rate of 10-20 ℃/min under the condition of continuously introducing the protective gas to obtain a precursor with the surface activated;
the mass ratio of the activating agent to the area of the precursor working surface is (0.01-2) g:10cm2；
Thirdly, carrying out high-frequency vibration corrosion on the electrode material:
dipping the precursor with the activated surface in an active medium, placing the active medium dipped with the precursor in a high-frequency current transducer, oscillating for 5-600 s under the condition that the frequency is 0.01-40 kHz, and taking out and cleaning after the oscillation is finished to obtain the self-supporting electrocatalyst corroded by high-frequency vibration;
the active medium is 0.1 percent of aqueous hydrogen peroxide solution by mass percent.
2. The method for preparing the high-frequency vibration corrosion self-supporting electrocatalyst according to claim 1, wherein: the protective gas in the step one is one or two of argon and nitrogen, or a mixed gas of argon and hydrogen; the volume percentage of hydrogen in the mixed gas of argon and hydrogen is 2-10%.
3. The method for preparing the high-frequency vibration corrosion self-supporting electrocatalyst according to claim 1, wherein: and in the second step, protective gas is introduced into the quartz tube with the gas flow rate of 10 sccm.
4. The method for preparing the high-frequency vibration corrosion self-supporting electrocatalyst according to claim 1, wherein: and the activating agent in the second step is one or a mixture of more of Se powder, S powder, sodium hypophosphite and sodium tellurite.
5. The method for preparing the high-frequency vibration corrosion self-supporting electrocatalyst according to claim 1, wherein: the protective gas in the second step is one or a mixture of argon and nitrogen, or a mixture of argon and hydrogen; the volume percentage of hydrogen in the mixed gas of argon and hydrogen is 2-10%.
6. The method for preparing the high-frequency vibration corrosion self-supporting electrocatalyst according to claim 1, wherein: in the third step, the vibration is carried out for 5 s-1 min under the condition that the frequency is 0.01 kHz-40 kHz.
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