CN115948768A - Preparation method and application of graphene-activated metal oxygen evolution electrocatalyst - Google Patents

Preparation method and application of graphene-activated metal oxygen evolution electrocatalyst Download PDF

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CN115948768A
CN115948768A CN202310078694.XA CN202310078694A CN115948768A CN 115948768 A CN115948768 A CN 115948768A CN 202310078694 A CN202310078694 A CN 202310078694A CN 115948768 A CN115948768 A CN 115948768A
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graphene
electrode
oxygen evolution
electrocatalyst
metal oxygen
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刘志斌
侯阳
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention belongs to the technical field of electrocatalysis, and relates to a preparation method and application of a graphene activated metal oxygen evolution electrocatalyst, wherein in a two-electrode system, a graphite-based material is used as an electrode, a solution containing sulfate ions is used as an electrolyte, a voltage of +10V is applied to an anode, the obtained stripped graphene is washed with water, then freeze-dried, dispersed in ethanol and then dripped on the metal electrode, and naturally dried at room temperature to obtain the graphene activated metal oxygen evolution electrocatalyst, the active component of the graphene activated metal electrode in the catalytic oxygen evolution reaction is gamma-phase metal oxyhydroxide, the catalytic performance is higher than that of beta-phase metal oxyhydroxide of the unactivated metal electrode, and the conductivity and the catalytic performance are both obviously improved; the adopted raw materials are commercialized, are simple and easily obtained, have simple preparation process, low energy consumption and low cost, and can be used for producing the corresponding electrocatalyst in a large scale.

Description

Preparation method and application of graphene-activated metal oxygen evolution electrocatalyst
Technical Field
The invention belongs to the technical field of electrocatalysis, and relates to a preparation method and application of a graphene-activated metal oxygen evolution electrocatalyst.
Background
The water electrolysis hydrogen production technology is a simple preparation method of clean and high-purity hydrogen, and comprises an anode oxygen evolution reaction and a cathode hydrogen evolution reaction process. The oxygen evolution reaction is a four-electron transmission process, and the reaction kinetics is slower. In order to improve the reaction kinetics, the alkaline solution is selected as the electrolyte, so that the multistep adsorption, desorption and transmission processes of the hydroxyl can be accelerated. In addition, the alkaline-resistant electrocatalyst is adopted, so that the kinetics of the anodic oxygen evolution reaction of alkaline electrolyzed water can be obviously improved. Metals such as nickel, cobalt, iron and the like are known alkaline oxygen evolution reaction electro-catalysts with excellent performance, but the catalytic performance of the metals is poor, the true active components are oxides and hydroxides formed by converting the metals in an alkaline catalytic environment, and the conductivity of the correspondingly formed metal oxides and hydroxides is obviously reduced, so that the electron transmission of the three-phase interface of the electro-catalyst-electrolyte-oxygen evolution is hindered. Therefore, how to activate the metal electrocatalyst into efficient metal oxides and hydroxides and strengthen the electron transfer process of a three-phase interface is a problem that the application of the metal electrocatalyst to the alkaline electrolysis water anode oxygen evolution reaction needs to be solved urgently.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to design and provide a preparation method and application of a graphene-activated metal oxygen evolution electrocatalyst.
In order to achieve the purpose, the specific preparation process of the graphene-activated metal oxygen evolution electrocatalyst comprises the following steps:
(1) In a two-electrode system, taking a graphite-based material as an electrode, taking a solution containing sulfate ions as an electrolyte, and applying a voltage of +10V to an anode to obtain stripped graphene;
(2) Washing the stripped graphene with water, freeze-drying, and dispersing in ethanol to obtain graphene dispersion liquid with the concentration of 4 mg/mL;
(3) And (3) dripping the graphene dispersion liquid on a metal electrode, and naturally drying at room temperature for 12 hours to obtain the graphene activated metal oxygen evolution electrocatalyst.
As a further technical scheme of the invention, the graphite-based material in the step (1) is a stone grinding rod, graphite paper or pencil core, and the solution containing sulfate ions is 0.1mol/L of ammonium sulfate, sulfuric acid, potassium sulfate or sodium sulfate aqueous solution.
As a further technical scheme of the invention, the metal electrode in the step (3) is foamed nickel, a nickel sheet, a cobalt sheet or an iron sheet.
The method comprises the steps of taking a graphene activated metal oxygen evolution electrocatalyst as a working electrode, immersing KOH electrolyte with the concentration of 1M, taking a platinum sheet as a counter electrode, taking a silver/silver chloride electrode as a reference electrode, carrying out oxygen evolution reaction by using a salt bridge filled with 3mol/L potassium chloride solution as the reference electrode, testing the oxygen evolution electrocatalytic performance of the working electrode by using a linear voltammetry method, wherein the sweep rate is 5mV/s, automatically carrying out 95% compensation resistance correction on a linear voltammetry curve by using EC-Lab 11.36 software, testing the conductivity of the working electrode by using an electrochemical impedance technology, wherein the frequency range is 100kHz-0.1Hz, the voltage disturbance is 5mV, the voltage value is 1.6V vs RHE, testing the structural change of the working electrode under different voltages in situ by using an electrochemical-Raman combined technology, setting the voltage to be 1.0-1.50V vs RHE, and increasing the voltage value by 0.05V.
According to the method, graphene with oxygen-rich defects is prepared by an electrochemical stripping method, the surface of a metal electrode is oxidized into oxides and hydroxides by utilizing the oxidability of the graphene, and the graphene is coated on the surfaces of the metal oxides and hydroxides, so that the conductivity and the catalytic performance are improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The metal electrocatalyst activated by the graphene is prepared by a simple dropping coating method, so that the graphene with excellent conductivity can be coated on the metal surface, namely oxide and hydroxide;
(2) The active component of the graphene-activated metal electrode in the catalytic oxygen evolution reaction is gamma-phase metal oxyhydroxide, the catalytic performance of the graphene-activated metal electrode is higher than that of beta-phase metal oxyhydroxide of an unactivated metal electrode, and the conductivity and the catalytic performance of the graphene-activated metal electrode are both obviously improved;
(3) The adopted raw materials are commercialized, are simple and easily obtained, have simple preparation process, low energy consumption and low cost, and can be used for producing the corresponding electrocatalyst in a large scale.
Drawings
Fig. 1 is a topographic map of a graphene-coated nickel foam electrode prepared in example 1 of the present invention.
Fig. 2 is a linear voltammetry graph of a graphene-coated nickel foam electrode prepared in example 1 of the present invention.
Fig. 3 is an electrochemical impedance spectrum of the graphene-coated nickel foam electrode prepared in example 1 of the present invention.
Fig. 4 is an in-situ electrochemical-raman spectrum of the graphene-coated nickel foam electrode prepared in example 1 of the present invention.
Fig. 5 is a linear voltammetry graph of a graphene drop-coated nickel plate electrode prepared in example 2 of the present invention.
Fig. 6 is an electrochemical impedance spectrum of a nickel plate electrode after dropping coating of graphene prepared in example 2 of the present invention.
Fig. 7 is a linear voltammetry graph of a cobalt plate electrode after graphene drop coating prepared in example 3 of the present invention.
FIG. 8 is a topographical view of a nickel foam electrode according to comparative example 1 of the present invention.
FIG. 9 is a plot of the linear voltammetry of the foamed nickel electrode of comparative example 1 of the present invention.
Fig. 10 is an electrochemical impedance spectrum of the nickel foam electrode of comparative example 1 of the present invention.
Fig. 11 is an in situ electrochemical-raman spectrum of a nickel foam electrode according to comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1:
in the embodiment, in a two-electrode system, a graphite rod is used as an electrode, 0.1mol/L ammonium sulfate is used as an electrolyte, a voltage of +10V is applied to an anode to obtain exfoliated graphene, the exfoliated graphene is washed, freeze-dried and dispersed in ethanol to obtain a graphene dispersion liquid with a concentration of 4mg/mL, then the graphene dispersion liquid is dropwise coated on a foam nickel electrode, and natural drying is performed at room temperature for 12 hours to obtain the foam nickel electrode with the morphology shown in fig. 1 and the surface coated with flaky graphene.
In the embodiment, the obtained graphene-coated nickel foam electrode is used as a working electrode, the electrode is immersed in KOH electrolyte with the concentration of 1M, a platinum sheet is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, a Rujin capillary tube filled with 3mol/L potassium chloride solution is used as a salt bridge of the reference electrode, the oxygen evolution electrocatalytic performance of the working electrode is tested by a linear voltammetry method, the sweep rate is 5mV/s, 95% compensation resistance correction is automatically carried out on a linear voltammetry curve by using software, the conductivity of the working electrode is tested by an electrochemical impedance technology, the frequency range is 100kHz-0.1Hz, the voltage disturbance is 5mV, and the voltage value is 1.6V vs RHE; the linear voltammetry curve of the electrocatalyst is shown in FIG. 2 at 10mA/cm 2 Over-potential of 336mV; the electrochemical impedance spectrogram is shown in fig. 3, wherein the solution resistance is 3.5 ohms, and the electron transmission resistance is 5.7 ohms; the in-situ electrochemical-raman spectrum result of the electrocatalyst is shown in fig. 4, and a characteristic peak of gamma-phase nickel oxyhydroxide appears at 1.35V vs RHE.
Example 2:
in the embodiment, in a two-electrode system, graphite paper is used as an electrode, 0.1mol/L sulfuric acid is used as an electrolyte, a voltage of +10V is applied to an anode to obtain exfoliated graphene, the exfoliated graphene is washed, freeze-dried and dispersed in ethanol to obtain a graphene dispersion solution with a concentration of 4mg/mL, then the graphene dispersion solution is dropwise coated on a nickel sheet electrode, and natural drying is carried out at room temperature for 12 hours to obtain the graphene dropwise coated nickel sheet electrode.
In the embodiment, a nickel sheet electrode on which graphene is dripped is used as a working electrode, the working electrode is immersed in KOH electrolyte with the concentration of 1M, a platinum sheet is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, a Rujin capillary tube filled with 3mol/L potassium chloride solution is used as a salt bridge of the reference electrode, the oxygen evolution electrocatalytic performance of the working electrode is tested by a linear voltammetry method, the sweep rate is 5mV/s, and the linear voltammetry curve is automatically corrected by 95% of compensation resistance by software; testing the conductivity of the working electrode by an electrochemical impedance technology, wherein the frequency range is 100kHz-0.1Hz, the voltage disturbance is 5mV, and the voltage value is 1.6V vs RHE; the linear voltammetry curve of the electrocatalyst is shown in FIG. 5 at 10mA/cm 2 The overpotential of (1) is 351mV; the electrochemical impedance spectrum is shown in fig. 6, and the solution resistance is 4.0 ohm, and the electron transfer resistance is 6.4 ohm.
Example 3:
in the embodiment, in a two-electrode system, a pencil lead is used as an electrode, 0.1mol/L potassium sulfate is used as an electrolyte, a voltage of +10V is applied to an anode to obtain peeled graphene, the peeled graphene is washed by water, then is freeze-dried and is dispersed in ethanol to obtain graphene dispersion liquid with the concentration of 4 mg/mL; and then, dropwise coating the graphene dispersion liquid on a cobalt sheet electrode, and naturally drying at room temperature for 12 hours to obtain the graphene dropwise coated cobalt sheet electrode.
In this embodiment, a cobalt sheet electrode with graphene drop-coated is used as a working electrode, the working electrode is immersed in KOH electrolyte with a concentration of 1M, a platinum sheet is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, a luggin capillary tube filled with 3mol/L potassium chloride solution is used as a salt bridge of the reference electrode, the oxygen evolution electrocatalytic performance of the working electrode is tested by linear voltammetry, the sweep rate is 5mV/s, 95% compensation resistance correction is automatically performed on a linear voltammetry curve by using software, the linear voltammetry curve of the electrocatalyst is shown in fig. 7, and the linear voltammetry curve is measured at 10mA/cm 2 The overpotential of (2) is 355mV.
Example 4:
in the embodiment, in a two-electrode system, a graphite grinding rod is used as an electrode, 0.1mol/L sodium sulfate is used as an electrolyte, a voltage of +10V is applied to an anode to obtain stripped graphene, the stripped graphene is washed, freeze-dried and dispersed in ethanol to obtain graphene dispersion liquid with a concentration of 4mg/mL, then the graphene dispersion liquid is dropwise coated on an iron sheet electrode, and the iron sheet electrode coated with the graphene is obtained after natural drying for 12 hours at room temperature.
In this embodiment, an iron sheet electrode on which graphene is dripped is used as a working electrode, the working electrode is immersed in KOH electrolyte with a concentration of 1M, a platinum sheet is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, a luggin capillary tube filled with 3mol/L potassium chloride solution is used as a salt bridge of the reference electrode, the oxygen evolution electrocatalytic performance of the working electrode is tested by a linear voltammetry method, the sweep rate is 5mV/s, 95% compensation resistance correction is automatically performed on a linear voltammetry curve by software, and the correction is performed at 10mA/cm 2 Is 442mV.
Comparative example 1:
in the comparative example, the foamed nickel electrode is used as the working electrode, the appearance is shown in FIG. 8, and the surface is smooth; immersing a foamed nickel electrode into 1MKOH electrolyte, taking a platinum sheet as a counter electrode, taking a silver/silver chloride electrode as a reference electrode, taking a Rujin capillary tube filled with 3mol/L potassium chloride solution as a salt bridge of the reference electrode, testing the oxygen evolution electrocatalysis performance of a working electrode by a linear voltammetry, wherein the sweep rate is 5mV/s, and automatically carrying out 95% compensation resistance correction on a linear voltammetry curve by using software; the linear voltammetry curve for the electrocatalyst is shown in FIG. 9 at 10mA/cm 2 Has an overpotential of 387mV; the electrochemical impedance spectrogram is shown in fig. 10, wherein the solution resistance is 4.5 ohms, and the electron transmission resistance is 12.3 ohms; the in-situ electrochemical-raman spectrogram result of the electrocatalyst is shown in fig. 11, a characteristic peak of beta-phase nickel oxyhydroxide appears at 1.35V vs RHE, and the catalytic activity of the electrocatalyst is lower than that of gamma-phase nickel oxyhydroxide.
The previous description of the disclosed embodiments is provided to aid those skilled in the art in understanding and practicing the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (4)

1. A preparation method of a metal oxygen evolution electrocatalyst activated by graphene is characterized by comprising the following specific preparation processes:
(1) In a two-electrode system, taking a graphite-based material as an electrode, taking a solution containing sulfate ions as an electrolyte, and applying a voltage of +10V to an anode to obtain stripped graphene;
(2) Washing the stripped graphene, freeze-drying, and dispersing in ethanol to obtain graphene dispersion liquid with the concentration of 4 mg/mL;
(3) And (3) dripping the graphene dispersion liquid on a metal electrode, and naturally drying at room temperature for 12 hours to obtain the graphene activated metal oxygen evolution electrocatalyst.
2. The preparation method of the graphene-activated metal oxygen evolution electrocatalyst according to claim 1, wherein the graphite-based material in step (1) is a graphite rod, a graphite paper or a pencil lead, and the sulfate ion-containing solution is 0.1mol/L ammonium sulfate, sulfuric acid, potassium sulfate or sodium sulfate aqueous solution.
3. The method for preparing the graphene-activated metal oxygen evolution electrocatalyst according to claim 1, wherein the metal electrode in step (3) is foamed nickel, nickel sheet, cobalt sheet or iron sheet.
4. The application of the graphene-activated metal oxygen evolution electrocatalyst prepared by the method according to claim 1 is characterized in that the application process comprises the following steps: the method comprises the steps of taking a graphene activated metal oxygen evolution electrocatalyst as a working electrode, immersing the metal oxygen evolution electrocatalyst into KOH electrolyte with the concentration of 1M, taking a platinum sheet as a counter electrode, taking a silver/silver chloride electrode as a reference electrode, carrying out oxygen evolution reaction by using a Rujin capillary tube filled with 3mol/L potassium chloride solution as a salt bridge of the reference electrode, testing the oxygen evolution electrocatalytic performance of the working electrode by using a linear voltammetry method, wherein the sweep rate is 5mV/s, automatically carrying out 95% compensation resistance correction on a linear voltammetry curve by using EC-Lab 11.36 software, testing the conductivity of the working electrode by using an electrochemical impedance technology, wherein the frequency range is 100kHz-0.1Hz, the voltage disturbance is 5mV, and the voltage value is 1.6V vs RHE, in-situ testing the structural change of the working electrode under different voltages by using an electrochemical-Raman coupling technology, setting the voltage to be 1.0-1.50V vs RHE, and increasing the voltage value by 0.05V step speed.
CN202310078694.XA 2023-02-08 2023-02-08 Preparation method and application of graphene-activated metal oxygen evolution electrocatalyst Pending CN115948768A (en)

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