阅读说明：本技术 一种辐照改性羟基氧化铁的制备方法及其应用 (Preparation method and application of irradiation modified iron oxyhydroxide ) 是由 王建强 张林娟 胡义甜 于 2021-11-11 设计创作，主要内容包括：本发明涉及一种辐照改性羟基氧化铁的制备方法,其包括如下步骤：制备羟基氧化铁；对羟基氧化铁进行干燥得到干燥羟基氧化铁；将干燥羟基氧化铁平铺在电子加速器的辐照区内进行辐照改性,辐照接受剂量为2.28×10～(5)～1.37×10～(6)KGy,得到辐照改性羟基氧化铁。本发明还提供一种辐照改性羟基氧化铁作为阳极催化剂在电解水中的应用。根据本发明的辐照改性羟基氧化铁的制备方法,在电子流的作用下,羟基氧化铁表面形成了许多局部的团簇缺陷,缺陷有利于提升材料的催化活性；在电解水应用中,与常规方法制备的羟基氧化铁相比,辐照改性羟基氧化铁的缺陷促进催化剂的重构和相的转变,进而促进电解水的活性,产氧的质量活性明显提升。(The invention relates to a preparation method of irradiation modified iron oxyhydroxide, which comprises the following steps: preparing iron oxyhydroxide; drying the iron oxyhydroxide to obtain dry iron oxyhydroxide; spreading dry iron oxyhydroxide in the irradiation area of electron accelerator for irradiation modification with irradiation acceptance dose of 2.28 × 10 5 ～1.37×10 6 KGy, obtaining the irradiation modified iron oxyhydroxide. The invention also provides application of the irradiation modified iron oxyhydroxide serving as an anode catalyst in electrolytic water. According to the preparation method of the irradiation modified iron oxyhydroxide, under the action of electron current, a plurality of local cluster defects are formed on the surface of the iron oxyhydroxide, and the defects are favorable for improving the catalytic activity of the material; irradiation modification of hydroxyl groups in electrolyzed water applications, as compared to conventionally prepared iron oxyhydroxidesThe defects of the iron oxide promote the reconstruction of the catalyst and the phase transformation, further promote the activity of the electrolyzed water, and obviously improve the quality activity of the generated oxygen.)

1. A preparation method of irradiation modified iron oxyhydroxide is characterized by comprising the following steps:

s1, preparing iron oxyhydroxide;

s2, drying the iron oxyhydroxide to obtain dry iron oxyhydroxide;

s3, spreading the dry hydroxyl ferric oxide in the irradiation area of an electron accelerator for irradiation modification, wherein the irradiation receiving dose is 2.28 multiplied by 10⁵～1.37×10⁶KGy, obtaining the irradiation modified iron oxyhydroxide.

2. The method according to claim 1, wherein in step S1, iron oxyhydroxide is prepared by a conventional method.

3. The method of claim 1, wherein step S2 is performed in an oven.

4. The method according to claim 3, wherein the drying temperature is 50 ° to 80 ° in step S2.

5. The production method according to claim 1, wherein in step S3, the radiation-receiving dose is 6.85 x 10⁵～1.14×10⁶KGy。

6. The production method according to claim 5, wherein the radiation-receiving dose is 9.14X 10⁵KGy。

7. An application of irradiation modified iron oxyhydroxide as an anode catalyst in electrolytic water.

8. Use according to claim 7, wherein the electrochemical activation system of the use is a three-electrode system, a working electrode, a counter electrode and a reference electrode.

9. The use of claim 8, wherein the working electrode comprises radiation modified iron oxyhydroxide supported on carbon paper.

10. The use according to claim 9, wherein the loading is 0.196 milligrams per square centimeter.

Technical Field

The invention relates to iron oxyhydroxide, in particular to a preparation method and application of irradiation modified iron oxyhydroxide.

Background

The iron oxyhydroxide is an iron-containing inorganic compound with a molecular formula of FeOOH and a molecular weight of 88.9326. Iron oxyhydroxide is known to be applicable as an anode catalyst for electrolysis of water, but the oxygen production quality activity is not high.

Disclosure of Invention

In order to solve the problem of low activity of the catalyst in the prior art, the invention provides a preparation method and application of irradiation modified iron oxyhydroxide.

According to one aspect of the present invention, there is provided a method for preparing irradiation modified iron oxyhydroxide, comprising the steps of: s1, preparing iron oxyhydroxide; s2, drying the iron oxyhydroxide to obtain dry iron oxyhydroxide; s3, spreading the dry hydroxyl ferric oxide in the irradiation area of an electron accelerator for irradiation modification, wherein the irradiation receiving dose is 2.28 multiplied by 10⁵～1.37×10⁶KGy, obtaining the irradiation modified iron oxyhydroxide.

Preferably, in step S1, iron oxyhydroxide is prepared using a conventional method.

Preferably, step S2 is performed in an oven.

Preferably, in step S2, the drying temperature is 50 ° to 80 °, more preferably, the drying time is 24 h.

Preferably, in step S3, the radiation acceptance dose is 6.85 × 10⁵～1.14×10⁶KGy。

Preferably, the radiation-receiving dose is 9.14X 10⁵KGy。

According to another aspect of the present invention there is provided the use of a radiation modified iron oxyhydroxide as an anode catalyst in the electrolysis of water.

Preferably, the electrochemical activation system for this application is a three-electrode system, working, counter and reference electrodes respectively.

Preferably, the working electrode comprises radiation modified iron oxyhydroxide supported on carbon paper.

Preferably, the loading is 0.196 milligrams per square centimeter.

According to the preparation method of the irradiation modified iron oxyhydroxide, under the action of electron current, a plurality of local cluster defects are formed on the surface of the iron oxyhydroxide, and the defects are favorable for improving the catalytic activity of the material; in the application of the electrolyzed water, compared with the hydroxyl ferric oxide prepared by the conventional method, the defects of the irradiation modified hydroxyl ferric oxide promote the reconstruction of the catalyst and the phase transformation, so that the activity of the electrolyzed water is promoted, and the quality activity of the generated oxygen is obviously improved.

Drawings

FIG. 1 is a graph comparing the X-ray diffraction patterns of FeOOH of the comparative example and the radiation modified FeOOH of example 3;

FIG. 2A is a transmission electron micrograph of FeOOH of a comparative example;

FIG. 2B is a comparative transmission electron micrograph of irradiation modified FeOOH of example 3;

FIG. 3 is a graph comparing the performance of FeOOH of the comparative example and the radiation modified FeOOH of example 1;

FIG. 4 is a graph comparing the performance of FeOOH of the comparative example and the radiation modified FeOOH of example 2;

FIG. 5 is a graph comparing the performance of FeOOH of the comparative example and the radiation modified FeOOH of example 3.

Detailed Description

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

Comparative example: preparing FeOOH by a conventional method

525mg of Fe (NO) are weighed out separately₃)₃·9H₂O，100mg NH₄F and 400mg urea reactant;

dissolving the reactants in 54ml of deionized water, and magnetically stirring until a uniform solution is formed;

transferring the solution into a high-pressure reaction kettle, heating to 120 ℃, and keeping the temperature for 6 hours;

after reaction, naturally cooling the mixture to room temperature, repeatedly washing the mixture with deionized water for many times, and finally collecting the solid by a centrifugal method;

and transferring the solid collected above to an oven at 80 ℃ for drying for 12h to finally obtain FeOOH. The X-ray diffraction pattern is shown in figure 1, which is compared with a standard card to show that the iron oxyhydroxide is successfully synthesized and prepared. The transmission electron micrograph of the nanoparticle is shown in fig. 2A, and a rod-like nanoparticle was synthesized.

Example 1

Preparing FeOOH by adopting the same method as the comparative example, and transferring the prepared FeOOH to an oven for drying for 24 hours at 80 ℃;

spreading the dried FeOOH in the irradiation region of the electron accelerator for irradiation modification, wherein the irradiation acceptance measurement of the material is 2.28 × 10⁵KGy, obtaining irradiation modified FeOOH.

Example 2

Preparing FeOOH by adopting the same method as the comparative example, and transferring the prepared FeOOH to an oven for drying for 24 hours at 50 ℃;

spreading the dried FeOOH in the irradiation region of the electron accelerator for irradiation modification, wherein the irradiation acceptance measurement of the material is 1.37 × 10⁶KGy, obtaining irradiation modified FeOOH.

Example 3

Preparing FeOOH by adopting the same method as the comparative example, and transferring the prepared FeOOH to an oven for drying for 24 hours at 60 ℃;

spreading the dried FeOOH in the irradiation region of the electron accelerator for irradiation modification, wherein the irradiation acceptance measurement of the material is 9.14 × 10⁵KGy, obtaining irradiation modified FeOOH. The X-ray diffraction pattern is shown in figure 1, which is compared to a standard card to show that successfully synthesized iron oxyhydroxide does not change its phase after irradiation. The transmission electron micrograph of the nanoparticle is shown in fig. 2B, and a rod-like nanoparticle was synthesized.

Application example

Weighing 5mg of FeOOH in the comparative example, mixing with 5mg of carbon powder, dissolving in a mixed solution containing 750 mu l of deionized water, 250 mu l of isopropanol and 40 mu l of naphthylene, and roll-grinding for 12 h; 40 μ l of the above solution was drawn and uniformly coated on a carbon paper to be used as a working electrode to be tested.

Weighing 5mg of the irradiation modified FeOOH obtained in the embodiments 1 to 3, mixing the weighed 5mg with 5mg of carbon powder, dissolving the mixture in a mixed solution containing 750 mu l of deionized water, 250 mu l of isopropanol and 40 mu l of naphthylene, and rolling and grinding for 12 hours; 40 μ l of the above solution was drawn and uniformly coated on a carbon paper to be used as a working electrode to be tested.

Activating the catalyst: electric powerThe chemical activation system is a three-electrode system, which comprises a working electrode, a counter electrode and a reference electrode, and the neutralization constant current density in 1M KOH is 10mA cm²The activation of the catalyst is continued until the activity is finally stabilized.

FIG. 3 is a graph comparing the properties of the irradiation modified FeOOH of comparative example and example 1, and it is evident that the modified iron oxyhydroxide properties are superior to those of the unmodified one.

FIG. 4 is a graph comparing the properties of the irradiation modified FeOOH of comparative example and example 2, and it is evident that the modified iron oxyhydroxide properties are superior to the unmodified one.

FIG. 5 is a graph comparing the properties of the irradiation modified FeOOH of comparative example and example 3, and it is evident that the modified iron oxyhydroxide properties are superior to those of the unmodified one. Under the standard electrolytic water test, the oxygen production quality activity is improved to 8 times compared with the unirradiated FeOOH, and the oxygen production quality activity is improved to 10mA cm²The overpotential at (c) was reduced by 65mV, see fig. 5.

The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.