CN114921808B - Vanadium-doped iridium dioxide electrocatalyst, and preparation method and application thereof - Google Patents
Vanadium-doped iridium dioxide electrocatalyst, and preparation method and application thereof Download PDFInfo
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- CN114921808B CN114921808B CN202210288328.2A CN202210288328A CN114921808B CN 114921808 B CN114921808 B CN 114921808B CN 202210288328 A CN202210288328 A CN 202210288328A CN 114921808 B CN114921808 B CN 114921808B
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- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
Abstract
The invention discloses a preparation method of a vanadium doped iridium dioxide electrocatalyst, which adopts the technical scheme that an iridium compound and a vanadium compound are prepared into the vanadium doped iridium dioxide electrocatalyst by a sol-gel method, and the molar ratio of the iridium compound to the vanadium compound is 1-10. Vanadium doped IrO prepared by sol-gel pyrolysis method 2 The nano composite material has uniform morphology and controllable particle size (realized by adjusting the content of doped vanadium (V) and the pyrolysis temperature), and finally the nano amorphous doped vanadium iridium dioxide has higher activity by adjusting the crystallinity of the catalyst. The obtained vanadium-doped iridium dioxide has high-efficiency catalytic activity in electrocatalytic hydrogen and oxygen evolution, and can be used as a good difunctional electrolyzed water catalyst.
Description
Technical Field
The invention relates to the field of inorganic functional materials, in particular to a vanadium doped iridium dioxide electrocatalyst, a preparation method and application thereof.
Background
The hydrogen production by water electrolysis meets the requirement of green energy development, and the development of hydrogen energy is important under the large background of energy environment friendliness. The hydrogen energy is a clean secondary energy source, has the advantages of high energy density, zero pollution, zero carbon emission and the like, and is known as a final energy source for human beings. Currently the main means of electrolysis of water are Alkaline Electrolysers (AEM) and proton exchange membrane electrolysers (PEM). Alkaline (AWE) electrolyzers are the most mature, lowest cost, most commercially available water electrolysis devices for use in current technology. In a typical AEM electrolytic cell, the electrolyte is 10-30% sodium hydroxide or potassium hydroxide solution, the operating temperature of the electrolytic cell is 70-90 ℃, the gas pressure is less than 0.3 atmosphere, the working electrode is nickel alloy, the main component of the diaphragm is asbestos, and the gas generated by two poles can be separated. The disadvantages of alkaline cells are: low current density, low conversion efficiency and working pressure, low gas purity, high maintenance cost and potential safety hazard. PEM cells solve the above problems well compared to AEM cells, but at present they are not available on a large scale, the main reason limiting their application is the high price of proton exchange membranes and of the available electrocatalysts (iridium, platinum, etc.), which makes the cell cost too high.
In order to enable the electrolyzed water to continuously produce hydrogen and oxygen, the commercial IrO is used at present 2 Both anode catalysts and Pt/C cathode catalysts, which contain noble metal catalysts, are costly, resource scarce, limiting their widespread use in commerce. In addition, irO 2 Dissolution occurs easily in OER process, and is unstable under acidic condition, and the main reason for dissolution is IrO with increase of potential in reaction process 2 Dissolution to form IrO 2 OH. IrO is to be made into 2 The dissolution process is broken down into three steps, the first step being IrO after application of a voltage 2 The cleavage of the Ir-O bond of (2) is easy to cause the Ir of the intermediate structure to form a new bond with the nearest structural oxygen atom; the second step is that the dissolved Ir is easily dissolved by H in the solution 2 O attack, irO formation on surface 2 OH; the third step is that the bond between the dissolved Ir and the surface oxygen atom is broken, resulting in IrO 2 OH is stripped to solution. IrO (IrO) 2 Stability of (C)The problem is to limit it to become one of the main reasons for the anode catalyst of the proton exchange membrane water electrolyzer, so how to solve IrO under acidic conditions 2 And at the same time, improving activity becomes a very important issue.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings of the prior art and provides a vanadium doped iridium dioxide electrocatalyst, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is that the vanadium doped iridium oxide electrocatalyst is prepared from an iridium compound and a vanadium compound by a sol-gel method, wherein the molar ratio of the iridium compound to the vanadium compound is 1-10.
Further provided that the iridium compound is iridium trichloride hydrate, H 2 IrCl 6 、K 2 IrCl 6 、(NH 4 ) 3 IrCl 6 、(NH 4 ) 2 IrCl 6 Or Ir 4 (CO) 12 。
Further provided is that the vanadium compound adopts vanadium trichloride hydrate and a precursor vanadium oxide thereof.
The sol-gel method is characterized in that: the iridium compound and the vanadium compound are heated, stirred and dissolved in deionized water, then citric acid and glycol are added, stirred to gel microbubbles in a heating state, and then high-temperature pyrolysis is carried out.
Further provided that the molar ratio of the amount of citric acid added to the iridium compound is 0.3 to 40, and the molar ratio of the amount of ethylene glycol to citric acid is 2 to 1.
The stirring temperature in the heating state is 100-150 ℃, and the stirring rotating speed range is 100-600 r/min.
The pyrolysis temperature is 300-700 ℃, and the heating rate is 1.5-10 ℃/min.
In a second aspect, the invention provides a vanadium doped iridium dioxide electrocatalyst prepared by the method.
In addition, the invention also provides application of the vanadium-doped iridium dioxide electrocatalyst serving as a dual-function electrocatalyst for electrolytic water oxygen evolution and hydrogen evolution reaction.
The application method comprises the following steps:
a. the prepared vanadium doped iridium dioxide electrocatalyst (marked as V/IrO) 2 Catalyst) for further preparation of V/IrO 2 The catalyst-supported test electrode served as the working electrode. Firstly, weighing 1-8 mg of catalyst, ultrasonically dispersing for 0.5-2 h, adding 0.5-2 mL of dispersing agent (adding water, methanol, ethanol, nafion aqueous solution and the like), dripping 10uL of catalyst suspension on a glassy carbon electrode and carbon paper, and naturally airing in an incubator.
b. The electrochemical performance of the catalyst was measured using an electrochemical workstation. Using the electrode obtained in (a) as a working electrode, a platinum wire as a counter electrode, calomel as a reference electrode and electrolyte of 0.5M H 2 SO 4 The electrocatalyst was placed in a three electrode system and its OER, HER and electrochemical performance of full water splitting were evaluated. The OER test electrochemical window is 0.9-1.6V (vs SCE), and the sweeping speed is 0.005-0.1V/s; the electrochemical window of the HER test is-0.8 to-0.2V (vs SCE), and the sweeping speed is 0.005 to 0.1V/s; the full water electrolysis electrochemical window is 0.8-2.0V (vs SCE), and the sweeping speed is 0.005-0.1V/s.
The vanadium doped iridium dioxide electrocatalyst prepared by the method of the invention has the characteristics that: the composite material has small particle diameter, more edge active sites and high activity, and has great advantages in oxygen evolution, thereby greatly improving IrO 2 Activity in alkaline and acidic media and advantage in acidic large scale applications.
Vanadium doped IrO prepared by sol-gel pyrolysis method 2 The nano composite material has uniform morphology and controllable particle size (realized by adjusting the content of doped V and the pyrolysis temperature), and finally shows that the amorphous doped vanadium iridium dioxide has higher activity by adjusting the crystallinity of the catalyst. The obtained vanadium-doped iridium dioxide has high-efficiency catalytic activity in electrocatalytic hydrogen and oxygen evolution. Can be used as a good difunctional water electrolysis catalyst.
The innovation mechanism of the invention is as follows:
vanadium doping prepared by the inventionThe hetero iridium dioxide has high catalytic activity and good electrochemical performance, and is compared with common IrO 2 Vanadium-doped IrO 2 The OER performance is obviously improved in alkaline and acidic media. The catalyst has the characteristics of controllable morphology, controllable particle size, adjustable crystallinity and the like. The catalyst prepared by the invention has simple preparation method, practical operation and good application prospect in the aspect of oxygen evolution of electrolyzed water and the application of electrocatalytic materials. The method provides a thinking for the design thought and the research method of the catalyst and lays a solid foundation for the synthesis and preparation of materials.
In addition, according to the inventors, from experimental and analytical studies, it is considered that: vanadium and iridium have synergistic effect, and vanadium has multivalent state and is beneficial to regulating and controlling IrO 2 So that IrO is provided 2 The octahedral structure undergoes an odd change, optimizing catalyst performance. By doping IrO 2 The method can greatly reduce the use amount of noble metal iridium (the best performance when the mole ratio of doped vanadium is 25% -30%), thereby reducing the cost of the catalyst. The doped catalyst not only can keep good stability (the test potential under the acidic condition can be kept to be constant for more than 200 hours), but also has obviously improved activity (the overpotential of the acidic common iridium dioxide is about 320mV, and the optimized performance can reach 264 mV). The particle size and crystallinity of the catalyst are closely related to the performance by a transmission electron microscope analysis, and the amorphous vanadium-doped iridium dioxide nano-scale particles are obtained by the different contents (25%) of doped vanadium and the regulation and control of temperature (350 ℃) to show the optimal electrochemical performance on oxygen evolution reaction. The invention solves the problem of IrO by reducing the iridium content of noble metal 2 The activity and stability are maintained, and precious experience is provided for the research of amorphous materials, so that a feasible strategy is provided for the synthesis and structural design of electrochemical catalytic materials.
The benefits of the invention are as follows:
(1) The prepared catalyst doped with vanadium can effectively reduce the content of noble metal Ir, and the preparation method is simple and convenient, so that the cost of the catalyst is reduced;
(2) The appearance, the particle size and the crystallinity of the prepared vanadium doped iridium dioxide catalyst are controllable;
(3) The prepared doping material has more edge active sites; has excellent durability of more than 200 hours
(4) The prepared material has small resistance, is favorable for efficient transmission of electrons, improves the synergistic effect between materials, and better plays an active role.
In conclusion, according to the research method for the vanadium doped iridium dioxide used for the electrocatalyst, on one hand, the preparation is simple and convenient, the practicability is strong, the reaction condition is mild, the reaction yield is high, the large-scale production is easy, and the environment is not polluted, so that the environment-friendly sustainable chemical production is met; on the other hand, by proper condition control, vanadium can be doped into iridium dioxide, and the electronic structure of iridium dioxide can be regulated by doping vanadium into iridium dioxide, and the activity of the catalyst can be increased by adding disordered structure and amorphous layer of iridium dioxide. The prepared doped material has better electrochemical performance in catalyzing electrolyzed water, shows better performance than commercial iridium dioxide in oxygen evolution reaction, and has lower overpotential; also shows good electrochemical performance in terms of hydrogen evolution; the materials used also exhibit a lower decomposition voltage when applied to electrolyzed water.
The specific effects are shown in experimental data of examples.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIGS. 1 (a), (b) are IrO at 350℃before doping with vanadium 2 (c) and (d) are V after doping at 350 DEG C 0.25 IrO 2 As can be seen from fig. 1, under the same synthesis condition by TEM image analysis, the contrast of particles after doping vanadium and before undoped is observed to be smaller, and the crystallinity is obviously reduced; indicating that doping changes IrO 2 And further optimize the structure to improve the vanadium-doped IrO 2 Catalytic properties of (a);
FIG. 2 over XRD patterns of vanadium doped Ir dioxide catalytic materials prepared at different doping levels and different temperature conditions, as can be seen from FIG. 2, the successful doping of vanadium into IrO can be demonstrated by XRD pattern analysis 2 Lattice deviation occurs when vanadium with different contents is doped in the lattice, and the crystallinity also changes when different temperatures are regulated and controlled;
the electrochemical performance diagram of the vanadium doped iridium dioxide electrocatalytic material prepared in FIG. 3; as can be seen from fig. 3, the regulation of the different contents of doped vanadium proves that the optimum OER activity is achieved when the molar ratio of doped vanadium is 25%; the regulation of different temperatures shows that the optimum OER activity is achieved at 350 ℃, the minimum overpotential of the doped vanadium is 25% at 350 ℃ in alkaline and acidic media, and d) e) shows that the vanadium-doped IrO 2 The composite material has significant advantages in application of hydrogen evolution and water electrolysis due to the fact that the content of noble metal iridium is greatly reduced. (f) The graph is an electrochemical impedance spectrum chart, which shows that the vanadium-doped IrO2 composite material catalyst and the IrO2 have very small impedance and good conductivity;
fig. 4: stability test chart, vanadium doped IrO by acid test 2 The durability test of the steel sheet is more than 200 hours.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1: synthetic vanadium doped iridium dioxide catalytic material and electrochemical performance characterization
(1) A vanadium doped iridium dioxide catalyst for synthesis: irCl is added to 3 .xH 2 O and VCl 3 .xH 2 Adding deionized water, citric acid and glycol into O according to a molar ratio of 3:1, stirring, heating, mixing uniformly, reacting, and stirring to gel. And then transferring to a muffle furnace for pyrolysis, and obtaining the powdery vanadium-doped catalyst. The reactant IrCl 3. xH 2 O and VCl 3. xH 2 O is not limited thereto, and also includes iridium compound H 2 IrCl 6 、K 2 IrCl 6 、(NH 4 ) 3 IrCl 6 、(NH 4 ) 2 IrCl6、Ir 4 (CO) 12 And the like, and the molar ratio of the iridium compound to the vanadium compound is 1-10;
(2) Preparation of working electrode: weighing 4.0mg of the vanadium-doped iridium dioxide catalyst, performing ultrasonic treatment at 40KHz for 1h to form a suspension, dripping a certain volume of the suspension on carbon paper (or a glassy carbon electrode) with the size of 0.5X5 cm by using a pipetting gun, airing at room temperature after dripping, dripping a layer of 0.2% nafion solution, standing and airing to obtain the working electrode modified by the vanadium-doped iridium dioxide catalyst.
(3) Electrolyte preparation: 13.3mL of concentrated sulfuric acid is added into 500mL of deionized water, stirred evenly and cooled to room temperature to obtain 0.5. 0.5M H 2 SO 4 Is used as an electrolyte.
(4) Electrochemical testing: oxygen evolution electrochemical performance was tested in a three electrode system and electrolytic hydroelectric electrochemical performance was tested in a two electrode system. In a three electrode system, at 0.5. 0.5M H 2 SO 4 In the electrolyte, a platinum net is used as a counter electrode, calomel is used as a reference electrode, and a self-contained catalyst is used as a working electrode. The above system was connected to an electrochemical workstation to test its linear voltammogram (LSV) for its electrochemical performance. In the two-electrode system, the reference electrode and the counter electrode are replaced by the same electrode, namely the self-provided working electrode, and the electrolysis water decomposition voltage is tested by linear volt-ampere scanning in the system.
Example 2: vanadium doped IrO 2 Electrochemical performance control of different contents
The electrochemical properties of the vanadium compounds in alkaline and acidic media are regulated by different molar ratios of the vanadium compounds. For the synthesis of different vanadium doping levels (mainly IrO) based on the synthesis conditions of example 1 and the test 2 5%, 15%, 25%, 30%) of the electrochemical performance.
Example 3: regulation and control of different temperatures
On the basis of example 2, the synthesis temperature was controlled to the content (25%) with the best performance, and the electrochemical performance of the catalyst was tested.
The experiment shows that the doped vanadium has 25% and the best oxygen evolution catalytic activity at the synthetic pyrolysis temperature of 350 ℃ through the description of the drawing.
Example 4: compounding vanadium-doped oxide with IrO 2 Application of material in hydrogen evolution and water electrolysis
And carrying out hydrogen evolution and electrolysis waterline voltammetry scanning test on the Vx/IrO2 composite material.
Example 5: morphology and object image characterization of vanadium-doped iridium dioxide material
Transmission Electron Microscope (TEM) analysis and X-ray diffraction (XRD) analysis tests are carried out on the doped Vx/IrO 2.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. A preparation method of a vanadium-doped iridium dioxide electrocatalyst is characterized by comprising the following steps of:
preparing a vanadium doped iridium dioxide electrocatalyst from an iridium compound and a vanadium compound by a sol-gel method, wherein the molar ratio of the iridium compound to the vanadium compound is 1-10;
heating and stirring an iridium compound and a vanadium compound to dissolve in deionized water, then adding citric acid and ethylene glycol, stirring to gel microbubbles in a heating state, and then performing high-temperature pyrolysis;
the molar ratio of the added citric acid to the iridium compound is 0.3-40, and the molar ratio of the glycol to the citric acid is 2-1;
the stirring temperature in the heating state is 100-150 ℃, and the stirring rotating speed range is 100-600 r/min.
2. The method for preparing the vanadium-doped iridium dioxide electrocatalyst according to claim 1, wherein the method comprises the following steps: the iridium compound is iridium trichloride hydrate, H 2 IrCl 6 、K 2 IrCl 6 、(NH 4 ) 3 IrCl 6 、(NH 4 ) 2 IrCl 6 Or Ir 4 (CO) 12 。
3. The method for preparing the vanadium-doped iridium dioxide electrocatalyst according to claim 1, wherein the method comprises the following steps: the vanadium compound adopts vanadium trichloride hydrate.
4. The method for preparing the vanadium-doped iridium dioxide electrocatalyst according to claim 1, wherein the method comprises the following steps: the pyrolysis temperature is 300-700 ℃, and the heating rate is 1.5-10 ℃/min.
5. A vanadium doped iridium dioxide electrocatalyst obtainable by a process according to any one of claims 1 to 4.
6. Use of the vanadium doped iridium dioxide electrocatalyst according to claim 5 as a catalyst for the electrolytic water oxygen and hydrogen evolution reactions.
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| US4382846A (en) * | 1979-08-09 | 1983-05-10 | Engelhard Corporation | Simultaneous production of hydrogen and oxygen from water |
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| CN101565835A (en) * | 2009-06-11 | 2009-10-28 | 浙江大学 | Silica doped modified insoluble iridium oxide anode and preparation method thereof |
| KR102569084B1 (en) * | 2016-10-28 | 2023-08-22 | 바스프 에스이 | An electrocatalyst composition comprising a noble metal oxide supported on tin oxide |
| US10450201B2 (en) * | 2017-10-04 | 2019-10-22 | King Fahd University Of Petroleum And Minerals | Method for the synthesis of nanoparticles of heterometallic nanocomposite materials |
| CN111266110B (en) * | 2020-02-24 | 2023-02-03 | 中国科学院广州能源研究所 | Anode catalyst for water electrolysis hydrogen production by using transition metal doped titanium oxide as carrier and preparation method thereof |
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| US4382846A (en) * | 1979-08-09 | 1983-05-10 | Engelhard Corporation | Simultaneous production of hydrogen and oxygen from water |
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| IrO_2纳米棒的制备及电化学性能;汪广进;徐甜;程凤;余意;梁聪;潘牧;;中国有色金属学报(07);203-207 * |
| Rhenium Suppresses Iridium (IV) Oxide Crystallization and Enables Efficient, Stable Electrochemical Water Oxidation;Wenjing Huo et al.;small;1-9 * |
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