CN113046784B - Oxygen-rich defect IrO2-TiO2Solid solution material, its preparation method and application - Google Patents

Oxygen-rich defect IrO2-TiO2Solid solution material, its preparation method and application Download PDF

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CN113046784B
CN113046784B CN202110288242.5A CN202110288242A CN113046784B CN 113046784 B CN113046784 B CN 113046784B CN 202110288242 A CN202110288242 A CN 202110288242A CN 113046784 B CN113046784 B CN 113046784B
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oxygen
iro
tio
solid solution
defect
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CN113046784A (en
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陈亮
武斌
林贻超
李涛
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Hangzhou Bay Research Institute Of Ningbo Institute Of Materials
Ningbo Institute of Material Technology and Engineering of CAS
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Hangzhou Bay Research Institute Of Ningbo Institute Of Materials
Ningbo Institute of Material Technology and Engineering of CAS
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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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 an oxygen-enriched defect IrO2‑TiO2Solid solution material, its preparation method and application. The oxygen-rich defect IrO2‑TiO2The solid solution material has a rutile structure, and the unit cell parameter of the solid solution material is between that of rutile IrO2And rutile TiO2And, said oxygen-rich defect IrO2‑TiO2The surface of the solid solution material is rich in oxygen defects. The preparation method comprises the following steps: dissolving Ir-containing metal salt in an organic solvent, adding the activated Ti-based metal-organic framework material, uniformly mixing to obtain the Ir-adsorbed Ti-based metal-organic framework material, and then annealing to obtain oxygen-enriched defect IrO2‑TiO2A solid solution material. Oxygen-enriched defect IrO of the invention2‑TiO2The solid solution material has good electrochemical oxygen evolution performance and excellent stability, can be applied to an anode catalyst in acidic electrolyzed water, and is an Ir-based acid oxygen evolution catalyst with great prospect.

Description

Oxygen-rich defect IrO2-TiO2Solid solution material, its preparation method and application
Technical Field
The invention belongs to the field of nano material preparation and electrochemical catalysis, relates to a preparation method based on Ir-based material, and particularly relates to oxygen-enriched defect IrO2-TiO2Solid solution material, a preparation method thereof and application thereof in electrocatalysis of oxygen evolution reaction in an acid medium.
Background
Converting intermittent energy sources such as wind energy, solar energy, tidal energy and the like into hydrogen energy through an electrolytic water technology is one of the most promising ways to relieve the world energy crisis in the future. Hydrogen production by electrolysis of water involves two simultaneous half-reactions, namely a Hydrogen Evolution Reaction (HER) at the cathode and an Oxygen Evolution Reaction (OER) at the anode. OER is kinetically slower with 4 electron transfer compared to HER, which has only 2 electron transfer, and requires an efficient oxygen evolution electrocatalyst to lower the reaction energy barrier and accelerate OER. Over decades of effort, a number of basic OER electrocatalysts have been developed that are highly efficient and stable, but have been less effective in the development of acidic OER electrocatalysts because most OER electrocatalysts are not stable in harsh acidic environments. However, the advantages of lower ohmic loss, higher mass transfer rate and product purity, more compact system design and faster system response of the related acid Proton Exchange Membrane (PEM) electrolytic cell compared with the alkaline electrolytic cell are also more widely favored. The lack of high activity and stable acidic OER electrocatalysts currently limits the further development of this electrocatalytic energy conversion technology. Therefore, the development of the high-efficiency acidic OER electrocatalyst has very important significance.
Over decades of effort, a great deal of efficiency has been developedAnd stable basic OER electrocatalysts such as transition metal oxides, layered structure materials, spinel structure materials, etc., have little effect on the development of acidic OER electrocatalysts. The more efficient acidic OER electrocatalytic materials found at present are mainly classified into two categories, namely Ru-based electrocatalytic materials and Ir-based electrocatalytic materials. Of these, Ir-based electrocatalytic materials have been relatively extensively studied, mainly due to their excellent stability in acidic electrochemical environments, such as the representative IrO2. In order to develop a high-activity Ir-based electrocatalytic material, a great deal of research is carried out on the aspects of changing the surface electronic state, the shape and the size and the like. However, currently commercial IrO2And perovskite-type and pyrochlore-type iridium-based materials reported in recent years are not only expensive but also insufficient in catalytic activity. Therefore, the development of an Ir-based acid-based oxygen evolution catalyst with low cost, high activity and high stability is urgently needed.
Disclosure of Invention
In view of the above technical situation, the main object of the present invention is to provide an oxygen-rich defect IrO2-TiO2Solid solution material and a preparation method thereof, thereby overcoming the defects in the prior art.
It is another object of the present invention to provide said oxygen-rich defect IrO2-TiO2The application of the solid solution material in electrocatalysis of oxygen evolution reaction in an acidic medium.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides oxygen-enriched defect IrO2-TiO2Solid solution material having rutile structure with unit cell parameter between rutile IrO2And rutile TiO2And, said oxygen-rich defect IrO2-TiO2The surface of the solid solution material is rich in oxygen defects.
The embodiment of the invention also provides oxygen-enriched defect IrO2-TiO2A method of preparing a solid solution material, comprising:
dissolving Ir-containing metal salt in an organic solvent, adding the activated Ti-based metal-organic framework material, and uniformly mixing to obtain the Ir-adsorbed Ti-based metal-organic framework material;
annealing the Ir-adsorbed Ti-based metal-organic framework material to obtain oxygen-enriched defect IrO2-TiO2A solid solution material.
In some embodiments, the Ir-containing metal salt includes any one or a combination of two or more of chloroiridic acid, iridium trichloride hydrate, iridium tetrachloride, and iridium acetylacetonate.
In some embodiments, the temperature of the annealing treatment is 300-600 ℃, and the time of the annealing treatment is 1-6 h.
The embodiment of the invention also provides oxygen-enriched defect IrO prepared by the method2-TiO2A solid solution material.
The embodiment of the invention also provides the oxygen-enriched defect IrO2-TiO2The application of the solid solution material in the electrocatalytic material for the oxygen evolution reaction in the acidic medium.
Correspondingly, the embodiment of the invention also provides an Ir-based acid oxygen evolution catalyst, which comprises the oxygen enrichment defect IrO2- TiO2A solid solution material.
Compared with the prior art, the invention has at least the following beneficial effects:
1) relative to commercial IrO2The oxygen-enriched defect IrO provided by the invention2-TiO2The solid solution material has the characteristics of low cost, high catalytic activity and high stability, and is an Ir-based acid oxygen evolution catalyst with a very good prospect;
2) in acid condition, the oxygen-enriched defect IrO provided by the invention2-TiO2The solid solution material has good electrochemical oxygen evolution performance and excellent stability, can be applied to an anode catalyst in acidic electrolyzed water, and has oxygen-rich defects on the surface before and after electrochemical life test through X-ray photoelectron spectroscopy (XPS) analysis, wherein lattice oxygen on the surface disappears completely after 100 hours, the content of the defect oxygen is increased, and the catalytic performance is further improved;
3) when used as an acidic oxygen evolution electrocatalyst, the concentration is 10mA cm-2Current density ofUnder certain degree, the oxygen-rich defect IrO2-TiO2The overpotential of the solid solution material is 296mV at the lowest, and can be stabilized for more than 100 hours, and the overpotential (overpotential) is reduced to 276 mV.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows IrO obtained in example 1 of the present invention2-TiO2A powder XRD pattern of the solid solution material;
FIG. 2 shows IrO obtained in example 1 of the present invention2-TiO2A microscopic topography of the solid solution material;
FIG. 3 shows IrO obtained in example 2 of the present invention2-TiO2A microscopic topography of the solid solution material;
FIG. 4 shows IrO obtained in example 3 of the present invention2-TiO2A microscopic topography of the solid solution material;
FIG. 5 shows IrO obtained in examples 1, 2 and 3 of the present invention2-TiO2A powder XRD pattern of the solid solution material;
FIG. 6 shows IrO prepared in examples 1, 2 and 3 of the present invention2-TiO2Linear Sweep Voltammetry (LSV) profile of solid solution material;
FIG. 7 shows IrO obtained in example 1 of the present invention2-TiO2Solid solution material and commercial IrO2At 10mA cm-2Electrochemical life test pattern of;
FIG. 8 shows IrO obtained in example 1 of the present invention2-TiO2Solid solution materials and commercial IrO2Linear Sweep Voltammetry (LSV) profiles of the electrochemical lifetime test of (1) before and after 100 hours;
FIG. 9 shows IrO obtained in example 1 of the present invention2-TiO2An iridium 4fXPS energy spectrum in the solid solution material;
FIG. 10 shows IrO obtained in example 1 of the present invention2-TiO2An XPS energy spectrum of 1s oxygen in the solid solution material;
FIG. 11 shows IrO obtained in example 4 of the present invention2-TiO2A powder XRD pattern of the solid solution material;
FIG. 12 shows IrO obtained in example 4 of the present invention2-TiO2Linear Sweep Voltammetry (LSV) profile of solid solution material;
FIG. 13 shows IrO obtained in example 5 of the present invention2-TiO2A powder XRD pattern of the solid solution material;
FIG. 14 shows IrO obtained in example 5 of the present invention2-TiO2Linear Sweep Voltammetry (LSV) profile of solid solution material.
Detailed Description
As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose a technical solution of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In particular, as one aspect of the technical scheme of the invention, the invention relates to oxygen-enriched defect IrO2-TiO2A solid solution material having a rutile structure with a unit cell parameter between rutile IrO2And rutile TiO2And, said oxygen-rich defect IrO2-TiO2The surface of the solid solution material is rich in oxygen defects.
Further, the oxygen-rich defect IrO2-TiO2The concentration ratio of the defect oxygen and the lattice oxygen contained in the solid solution material is 1: 1-6: 1.
Wherein, the oxygen-rich defect IrO of the invention2-TiO2Oxygen defects in solid solution materials can be known by characterization means such as X-ray photoelectron spectroscopy (XPS).
Relative to commercial IrO2Oxygen-rich defect IrO of the invention2-TiO2The solid solution material has lower cost, high catalytic activity and high stabilityIs characterized by being an Ir-based acid oxygen evolution catalyst with great prospect.
As another aspect of the technical scheme of the invention, the invention relates to oxygen-rich defect IrO2-TiO2A method of preparing a solid solution material, comprising:
dissolving Ir-containing metal salt in an organic solvent, adding the activated Ti-based metal-organic framework material, and uniformly mixing to obtain the Ir-adsorbed Ti-based metal-organic framework material;
annealing the Ir-adsorbed Ti-based metal-organic framework material to obtain oxygen-enriched defect IrO2-TiO2A solid solution material.
In some embodiments of the invention, the oxygen-rich defect, IrO2-TiO2The preparation method of the solid solution material comprises the following steps: dissolving a certain amount of metal salt containing Ir in an organic solvent, adding a Ti-based metal organic framework material, stirring and dispersing, centrifugally washing, drying and annealing at a certain temperature to obtain oxygen-enriched defect IrO2-TiO2A solid solution material.
In some embodiments, the Ir-containing metal salt includes, but is not limited to, chloroiridic acid (H)2IrCl6·6H2O), Iridium trichloride hydrate (IrCl)3·xH2O), Iridium tetrachloride (IrCl)4) Iridium acetylacetonate (C)15H21IrO6) And the like, or a combination of two or more thereof.
In some embodiments, the mass ratio of the Ir-containing metal salt to the activated Ti-based metal-organic framework material is in the range of x:1, wherein 0 < x.ltoreq.2, preferably 0 < x.ltoreq.1.
In some embodiments, the Ti-based metal-organic framework material includes, but is not limited to, NH2-MIL-125。
Further, the Ti-based metal-organic framework material comprises Ti4+And terephthalic acid or diaminoterephthalic acid ligands, and the like, but are not limited thereto.
In some embodiments, the method of making comprises: and activating the Ti-based metal-organic framework material to obtain the activated Ti-based metal-organic framework material.
Further, the activation treatment specifically includes: and under a vacuum environment, heating the Ti-based metal organic framework material to remove solvent molecules and coordinated water molecules in the pore channels of the Ti-based metal organic framework material.
Further, the heating may be performed under a vacuum environment.
In some embodiments, the temperature of the activation treatment is 100 to 200 ℃, preferably 120 to 180 ℃, and more preferably 120 to 160 ℃, and the time of the activation treatment is 1 to 10 hours.
In some embodiments, the temperature of the annealing treatment is 300-600 ℃, preferably 350-450 ℃, and the time of the annealing treatment is 1-6 h.
In some preferred embodiments, the oxygen-rich deficient IrO of the present invention2-TiO2The preparation method of the solid solution material comprises the following steps:
dissolving a certain amount of metal salt containing Ir in an organic solvent, dispersing the activated Ti-based metal organic framework material into the metal salt solution containing Ir, stirring for a certain time, then obtaining the Ti-based metal organic framework material adsorbed with Ir ions by centrifugal separation, washing, drying and annealing to obtain the oxygen-enriched defect IrO2-TiO2The oxygen defect concentration of the solid solution material can be controlled by adjusting the annealing temperature.
Further, in the preparation process, the oxygen-enriched defect IrO with different crystallinity can be obtained by changing the annealing temperature2- TiO2A solid solution material.
Further, the organic solvent includes, but is not limited to, any one or a combination of two or more of methanol, ethanol, tetrahydrofuran, acetone, and the like.
Further, the stirring time is 1 to 18 hours, preferably 5 to 12 hours.
Further, the stirring temperature is 10-30 ℃.
Further, the preparation method further comprises the following steps: and washing the Ti-based metal organic framework material adsorbing Ir by using an organic solvent, drying, and then carrying out annealing treatment.
As another aspect of the technical scheme of the invention, the invention relates to oxygen-enriched defect IrO prepared by the method2-TiO2A solid solution material.
Another aspect of the embodiments of the present invention also provides the oxygen-rich defect IrO mentioned above2-TiO2The solid solution material is applied as an acidic medium oxygen evolution reaction electrocatalytic material.
Further, the oxygen-rich defect IrO2-TiO2Application of solid solution material as acidic oxygen evolution electrocatalyst at 10mA cm-2At a current density of (1), the oxygen-rich defect IrO2-TiO2The overpotential of the solid solution material is 296mV at the lowest, and can be stabilized for more than 100 hours, and the overpotential (overpotential) is reduced to 276 mV.
Accordingly, another aspect of the embodiments of the present invention also provides an Ir-based acid based oxygen evolution catalyst, which comprises the oxygen-rich deficient IrO described above2-TiO2A solid solution material.
Further, in acidic conditions, the oxygen-rich defect IrO2-TiO2The solid solution material has good electrochemical oxygen evolution performance and excellent stability, and can be applied to an anode catalyst in acidic electrolyzed water. Through X-ray photoelectron spectroscopy (XPS) analysis, oxygen-rich defects on the surface of the material before and after electrochemical life test completely disappear after 100 hours, the oxygen content of the defects is increased, and the catalytic performance is further improved.
In conclusion, the oxygen-rich defect IrO of the invention2-TiO2The solid solution material has good electrochemical oxygen evolution performance and excellent stability, can be applied to an anode catalyst in acidic electrolyzed water, and is an Ir-based acid oxygen evolution catalyst with great prospect.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
Oxygen-rich defect IrO in this example2-TiO2-350 the preparation steps of the solid solution material are as follows:
0.12g of IrCl3·xH2Dissolving O in 20mL methanol solvent, stirring to dissolve completely, adding 0.12g NH activated by vacuum at 160 deg.C for 10 hr2MIL-125 powder and stirring at room temperature (25 ℃) is continued for 10 hours, and the resulting brown suspension is centrifuged and washed 3 times with methanol to obtain the product. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Placing the powder in a muffle furnace, annealing at 350 deg.C for 4 hr to obtain black powder, and obtaining oxygen-rich defect IrO by powder XRD2-TiO2Solid solution material with XRD peak position just at standard R-TiO2And IrO2As shown in fig. 1. The oxygen-rich defect IrO2-TiO2The microscopic morphology of the solid solution material is shown in fig. 2, and nanoparticles smaller than 50nm exist on the surface of the material.
The prepared oxygen-enriched defect IrO2-TiO2-350 the solid solution material is applied to an acid medium oxygen evolution reaction for electrochemical performance evaluation, and the specific method is as follows:
(1) preparation of anode material:
4mg of oxygen-rich defect IrO2-TiO2The solid solution material is ultrasonically dispersed into a mixed solution (the mixed solution comprises 750mL of deionized water, 220mL of absolute ethyl alcohol and 30 muL of Nafion 117 solution), 250 muL of the solution is transferred onto carbon paper with the thickness of 1 square centimeter and is dried for standby.
(2) And (3) electrochemical performance testing:
in the electrolytic cell, 0.5mol/L H is used2SO4The solution is used as electrolyte and contains mercury/mercurous sulfate (Hg/Hg)2SO4) As a reference electrode, a platinum wire is used as a counter electrode, and an anode material is used as a working electrode. Firstly, Cyclic Voltammetry (CV) test is carried out, the voltage range is 1.0V-1.6V (vs. RHE), and the sweep rate is 50mVs-1Performing 50 circles; then Linear Sweep Voltammetry (LSV) test is carried out, and the sweep rate is 5mV-1. After the test is finished, the impedance test is carried out under the condition of 100kHz to 0.1 Hz; then at a current density of 10mA cm-2Electrochemical life tests were performed.
The test results are shown in fig. 7 and 8, from which it can be seen that: at 10mA cm-2The overpotential under the current density is only 296mV, the stability can reach more than 100 hours, and the overpotential is reduced to 276mV after the stability test is finished, which shows that the oxygen-enriched defect IrO is generated at the temperature2-TiO2The solid solution material has high efficiency and stability under an acidic medium.
XPS characterization technology can detect the chemical composition and valence state of material surface. From FIG. 9, Ir taken before and after the electrochemical lifetime test4+/Ir3+There was little change. While the material in fig. 10 was oxygen-deficient on the surface before and after the electrochemical lifetime test and after 100 hours the surface was completely converted to species with deficient oxygen.
Example 2
Oxygen-rich defect IrO in this example2-TiO2The preparation steps of the solid solution material of-450 are as follows:
0.12g of IrCl3·xH2Dissolving O in 20mL methanol solvent, stirring to dissolve completely, adding 0.12g NH activated by vacuum at 160 deg.C for 10 hr2MIL-125 powder and stirring at room temperature for a further 10 hours, the resulting brown suspension being centrifuged and washed 3 times with methanol to give the product. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Putting the powder into a muffle furnace and annealing for 4 hours at the temperature of 450 ℃ to obtain oxygen-enriched defect IrO2-TiO2A solid solution material is prepared by the following steps of,the peak position of XRD is just positioned in standard R-TiO2And IrO2Between XRD (fig. 5). The oxygen-rich defect IrO2-TiO2The microscopic morphology of the solid solution material is shown in fig. 3, and nanoparticles smaller than 50nm exist on the surface of the material.
The prepared oxygen-enriched defect IrO2-TiO2The solid solution material is applied to an acidic medium oxygen evolution reaction for electrochemical performance evaluation, and the specific method comprises the following steps:
(1) preparation of anode material:
4mg of oxygen-rich defect IrO2-TiO2The solid solution material is ultrasonically dispersed into a mixed solution (the mixed solution comprises 750mL of deionized water, 220mL of absolute ethyl alcohol and 30 muL of Nafion 117 solution), 250 muL of the solution is transferred onto carbon paper with the thickness of 1 square centimeter and is dried for standby.
(2) And (3) electrochemical performance testing:
in the electrolytic cell, 0.5mol/L H is used2SO4The solution is used as electrolyte and contains mercury/mercurous sulfate (Hg/Hg)2SO4) As a reference electrode, a platinum wire is used as a counter electrode, and an anode material is used as a working electrode. Firstly, Cyclic Voltammetry (CV) test is carried out, the voltage range is 1.0V-1.6V (vs. RHE), and the sweep rate is 50mVs-1Performing 50 circles; then Linear Sweep Voltammetry (LSV) test is carried out, and the sweep rate is 5mV-1. After the test is finished, the impedance test is carried out under the condition of 100kHz to 0.1 Hz; then at a current density of 10mA cm-2Electrochemical life tests were performed.
The test results are shown in fig. 6, from which it can be seen that: at 10mA cm-2The overpotential under the current density is higher than the oxygen-rich defect IrO prepared in example 12-TiO2A solid solution material.
Example 3
Oxygen-rich defect IrO in this example2-TiO2The preparation steps of the-550 solid solution material are as follows:
0.12g of IRCl3·xH2Dissolving O in 20mL methanol solvent, stirring to dissolve completely, adding 0.12g NH activated by vacuum at 160 deg.C for 10 hr2MIL-125 powder and continued at room temperatureAfter stirring for 10 hours, the resulting brown suspension is centrifuged and washed 3 times with methanol to give the product. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Placing the powder in a muffle furnace and annealing at 550 ℃ for 4 hours to obtain IrO2-TiO2Solid solution material with XRD peak position just at standard R-TiO2And IrO2Between XRD (fig. 5). The oxygen-rich defect IrO2-TiO2The microscopic morphology of the solid solution material is shown in fig. 4, and nanoparticles smaller than 50nm exist on the surface of the material.
The prepared oxygen-enriched defect IrO2-TiO2The solid solution material is applied to oxygen evolution reaction under an acidic medium for electrochemical performance evaluation, and the specific method comprises the following steps:
(1) preparation of anode material:
4mg of oxygen-rich defect IrO2-TiO2The solid solution material is ultrasonically dispersed into a mixed solution (the mixed solution comprises 750mL of deionized water, 220mL of absolute ethyl alcohol and 30 muL of Nafion 117 solution), 250 muL of the solution is transferred onto carbon paper with the thickness of 1 square centimeter and is dried for standby.
(2) And (3) electrochemical performance testing:
in the electrolytic cell, 0.5mol/L H is used2SO4The solution is used as electrolyte and contains mercury/mercurous sulfate (Hg/Hg)2SO4) As a reference electrode, a platinum wire is used as a counter electrode, and an anode material is used as a working electrode. Firstly, Cyclic Voltammetry (CV) test is carried out, the voltage range is 1.0V-1.6V (vs. RHE), and the sweep rate is 50mVs-1Performing 50 circles; then Linear Sweep Voltammetry (LSV) test is carried out, and the sweep rate is 5mV-1. After the test is finished, the impedance test is carried out under the condition of 100kHz to 0.1 Hz; then at a current density of 10mA cm-2Electrochemical life tests were performed.
The test results are shown in fig. 6, from which it can be seen that: at 10mA cm-2Oxygen-enriched defect IrO obtained at the annealing temperature of which the overpotential under the current density is far higher than 350 DEG C2-TiO2A solid solution material.
Example 4
Dissolving 0.12g of chloroiridic acid in 20mL of methanol solvent, stirring until the chloroiridic acid is completely dissolved, adding 0.12g of NH activated in vacuum at 120 ℃ for 10 hours2-MIL-125 powder and stirring is continued at room temperature for 5 hours, and the product is obtained after centrifuging the resulting brown suspension and washing 3 times with tetrahydrofuran. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Putting the powder into a muffle furnace and annealing for 4 hours at 350 ℃ to obtain IrO2-TiO2Solid solution material with XRD peak position just at standard R-TiO2And IrO2As shown in figure 11.
The test results are shown in fig. 12, from which it can be seen that: at 10mA cm-2The overpotential under the current density is higher than the oxygen-rich defect IrO prepared in example 12-TiO2A solid solution material.
Example 5
0.12g of IrCl3·xH2Dissolving O in 20mL tetrahydrofuran, stirring to dissolve completely, adding 0.12g NH vacuum-activated at 180 deg.C for 5 hr2MIL-125 powder and stirring at room temperature is continued for 12 hours, and the product is obtained after centrifugation of the resulting brown suspension and washing 3 times with tetrahydrofuran. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Putting the powder into a muffle furnace and annealing for 4 hours at 350 ℃ to obtain IrO2-TiO2Solid solution material with XRD peak position just at standard R-TiO2And IrO2As shown in figure 13.
The test results are shown in fig. 14, from which it can be seen that: at 10mA cm-2The overpotential under the current density is higher than the oxygen-rich defect IrO prepared in example 12-TiO2A solid solution material.
Example 6
Dissolving 0.24g of iridium tetrachloride in 30mL of ethanol solvent, stirring until the iridium tetrachloride is completely dissolved, adding 0.12g of NH which is activated for 10 hours in vacuum at 100 DEG C2-MIL-125 powder and continuing stirring at 10 ℃ for 18 hours, andthe resulting brown suspension was centrifuged and washed 3 times with tetrahydrofuran to give the product. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Putting the powder into a muffle furnace and annealing for 6 hours at 300 ℃ to obtain IrO2-TiO2A solid solution material.
Example 7
0.18g of iridium acetylacetonate was dissolved in 30mL of acetone solvent, stirred until completely dissolved, and 0.12g of NH activated under vacuum at 200 ℃ for 1 hour was added2MIL-125 powder and stirring at 30 ℃ for 1 hour, the product being obtained after centrifuging the brown suspension and washing 3 times with tetrahydrofuran. The product is put into a vacuum oven at 60 ℃ for drying to obtain brown NH2-MIL-125 precursor powder. Placing the powder in a muffle furnace and annealing at 600 ℃ for 1 hour to obtain IrO2-TiO2A solid solution material.
Comparative example 1
(1) Using commercial IrO2As an anode material;
(2) the electrochemical performance test procedure was the same as in example 1.
The test results are shown in fig. 7 and 8, from which it can be seen that: at 10mA cm-2The overpotential at the current density was 360mV, which is far inferior to the oxygen evolution reaction performance of example 1, and the electrocatalytic activity was decreased by 106 hours of electrochemical life test.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (12)

1. Oxygen enrichment defect IrO2-TiO2The preparation method of the solid solution material is characterized by comprising the following steps:
dissolving a metal salt containing Ir in an organic solvent, adding the activated Ti-based metal organic framework material, and uniformly mixing to obtain the Ir-adsorbed Ti-based metal organic framework material, wherein the Ir-containing metal salt is selected from one or the combination of more than two of chloroiridic acid, iridium trichloride hydrate, iridium tetrachloride and iridium acetylacetonate, and the Ti-based metal organic framework material contains Ti4 +And terephthalic acid or diamino terephthalic acid ligand, wherein the mass ratio of the Ir-containing metal salt to the activated Ti-based metal organic framework material is x:1, wherein x is more than 0 and less than or equal to 2;
annealing the Ir-adsorbed Ti-based metal-organic framework material to obtain oxygen-enriched defect IrO2-TiO2A solid solution material; the annealing treatmentThe temperature of the annealing furnace is 350-450 ℃, and the time of the annealing treatment is 1-6 h;
the oxygen-rich defect IrO2-TiO2The solid solution material has a rutile structure, and the unit cell parameter of the material is between rutile IrO2And rutile TiO2And, said oxygen-rich defect IrO2-TiO2The surface of the solid solution material is rich in oxygen defects; the oxygen-rich defect IrO2-TiO2The concentration ratio of the defect oxygen to the lattice oxygen contained in the solid solution material is 1:1 to 6: 1.
2. The method of claim 1, wherein: the value of x is more than 0 and less than or equal to 1.
3. The production method according to claim 1, characterized by comprising: activating the Ti-based metal-organic framework material to obtain an activated Ti-based metal-organic framework material; the activation treatment specifically includes: and heating the Ti-based metal organic framework material in a vacuum environment to remove solvent molecules and coordinated water molecules in the pore channels of the Ti-based metal organic framework material.
4. The production method according to claim 3, characterized in that: the temperature of the activation treatment is 120-180 ℃, and the time of the activation treatment is 1-10 h.
5. The method of claim 4, wherein: the temperature of the activation treatment is 120-160 ℃.
6. The method according to claim 1, comprising: dissolving Ir-containing metal salt in an organic solvent, adding the activated Ti-based metal-organic framework material, stirring, and then centrifugally separating to obtain the Ir-adsorbed Ti-based metal-organic framework material.
7. The method of claim 6, wherein: the organic solvent is selected from any one or combination of more than two of methanol, ethanol, tetrahydrofuran and acetone.
8. The method of claim 6, wherein: the stirring time is 1-18 h, and the stirring temperature is 10-30 ℃.
9. The method of claim 8, wherein: the stirring time is 5-12 h.
10. The method of claim 6, further comprising: and washing the Ti-based metal organic framework material adsorbing Ir by using an organic solvent, drying, and then carrying out annealing treatment.
11. Oxygen-rich defect IrO obtained by the production method according to any one of claims 1 to 102-TiO2The application of the solid solution material in the electrocatalytic material for the oxygen evolution reaction in the acidic medium.
12. An Ir-based acidic oxygen evolution catalyst, characterized by comprising the oxygen-rich defective IrO prepared by the preparation method of any one of claims 1 to 102-TiO2A solid solution material.
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