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CN-119549145-B - Iridium ruthenium tin composite catalyst and preparation method and application thereof

CN119549145BCN 119549145 BCN119549145 BCN 119549145BCN-119549145-B

Abstract

The invention relates to an iridium ruthenium tin composite catalyst, a preparation method and application thereof, wherein the iridium ruthenium tin composite catalyst comprises iridium element, ruthenium element and tin element, and an XRD spectrum of the iridium ruthenium tin composite catalyst only has an amorphous peak package within 25-40 degrees. The iridium ruthenium tin composite catalyst has higher catalytic activity than that of a commercial iridium oxide catalyst, the noble metal dosage is obviously reduced, the cost is reduced, and the iridium ruthenium tin composite catalyst has higher use value.

Inventors

  • GU FANGWEI
  • YANG XUE
  • LIN WEI
  • WAN NIANFANG
  • Cheng Binlv
  • WANG CHENG

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20230830

Claims (16)

  1. 1. The iridium ruthenium tin composite catalyst is characterized by comprising iridium element, ruthenium element and tin element, wherein an XRD spectrum of the iridium ruthenium tin composite catalyst only shows amorphous peak packets at 25-40 degrees; The O1s characteristic peak of the XPS spectrum of the iridium ruthenium tin composite catalyst comprises an M-O characteristic peak and an M-OH characteristic peak, and B 0 defined by the following formula (1) is any numerical value between 0.4 and 0.5; B 0 =B 1 /(B 1 +B 2 ) formula (1); wherein B 1 is the peak area of the M-OH characteristic peak of the XPS spectrum of the iridium ruthenium tin composite catalyst, and B 2 is the peak area of the M-O characteristic peak of the XPS spectrum of the iridium ruthenium tin composite catalyst; the chemical composition of the iridium ruthenium tin composite catalyst is Ir x Ru y Sn 1-x-y O 2 , wherein x is any value between 0.4 and 0.6, and y is any value between 0.1 and 0.2.
  2. 2. The iridium ruthenium tin composite catalyst according to claim 1, wherein the BET specific surface area of the iridium ruthenium tin composite catalyst is 60-80 m 2 /g, and the particle size is 3-8 nm.
  3. 3. The iridium ruthenium tin composite catalyst according to claim 1, wherein the XRD spectrum of the iridium ruthenium tin composite catalyst has no crystal plane diffraction peaks of IrO 2 、RuO 2 and SnO 2 .
  4. 4. A method for preparing the iridium ruthenium tin composite catalyst as claimed in any one of claims 1 to 3, wherein the method comprises the following steps: S1, mixing an iridium source, a ruthenium source, a tin source, a complexing agent and water, and reacting the obtained mixed material to obtain a first material, wherein the pH value of the mixed material is 5-9, and the complexing agent is selected from C4-C8 organic polyacid and soluble salts of the C4-C8 organic polyacid; S2, separating water in the first material to obtain an iridium ruthenium tin composite catalyst precursor; S3, roasting the iridium ruthenium tin composite catalyst precursor in an oxygen-containing atmosphere; wherein in the step S1, the molar ratio of the iridium source calculated by iridium to the tin source calculated by tin to the ruthenium source calculated by ruthenium is (2-6): (1-5): 1; in the step S3, the roasting treatment conditions comprise a roasting temperature of 300-380 ℃ and a roasting time of 1-3 h.
  5. 5. The method of claim 4, wherein step S1 comprises the steps of: s1-1, carrying out first mixing on the iridium source, the first complexing agent and water, and regulating pH to 5-9 to obtain a first mixture; s1-2, carrying out second mixing on the ruthenium source, the second complexing agent and water, and regulating the pH value to be 5-9 to obtain a second mixture; S1-3, carrying out third mixing on the tin source, the third complexing agent and water, and regulating the pH value to be 5-9 to obtain a third mixture; s1-4, mixing the first mixture, the second mixture and the third mixture to obtain the mixed material.
  6. 6. The method of claim 5, wherein step S1 comprises the steps of: S1-1, carrying out first mixing on the iridium source, the first complexing agent and water, and regulating pH to 7-8 to obtain a first mixture; s1-2, carrying out second mixing on the ruthenium source, the second complexing agent and water, and regulating the pH value to 7-8 to obtain a second mixture; s1-3, carrying out third mixing on the tin source, the third complexing agent and water, and regulating the pH value to 7-8 to obtain a third mixture; s1-4, mixing the first mixture, the second mixture and the third mixture to obtain the mixed material.
  7. 7. The method according to claim 4, wherein the iridium source is selected from one or more of chloroiridic acid and chloroiridic acid alkali metal salt; The ruthenium source is a soluble salt of ruthenium; the tin source is a soluble salt of tin and/or a soluble alkali metal stannate.
  8. 8. The method according to claim 7, wherein the alkali metal chloroiridate is selected from one or both of potassium chloroiridate and sodium chloroiridate; The ruthenium source is one or two of ruthenium trichloride and ruthenium acetate; The tin source is one or two of tin tetrachloride or sodium stannate.
  9. 9. The method of claim 5, wherein the first complexing agent, the second complexing agent, and the third complexing agent are the same or different and are each independently selected from one or more of citric acid, tartaric acid, malic acid, succinic acid, sodium citrate, sodium tartrate, sodium malate, sodium succinate; the molar ratio of the first complexing agent to the iridium source calculated by iridium is 1.5-2.5:1; The molar ratio of the second complexing agent to the ruthenium source calculated by ruthenium is 1-2:1; the mole ratio of the third complexing agent to the tin source calculated by tin is 2-3:1.
  10. 10. The method of claim 9, wherein a molar ratio of the first complexing agent to the iridium source calculated as iridium is 1.8-2.2:1; the molar ratio of the second complexing agent to the ruthenium source calculated by ruthenium is 1.5-1.8:1; the mole ratio of the third complexing agent to the tin source calculated by tin is 2.2-2.7:1.
  11. 11. The method according to claim 4, wherein in the step S1, the reaction condition comprises a temperature of 50-80 ℃ and a reaction time of 0.5-4 h; in the step S1, the pH value of the mixed material is 7-8; and adding a pH regulator to regulate the pH of the mixed material, wherein the pH regulator is one or more selected from sodium carbonate, sodium bicarbonate, sodium hydroxide and ammonia water.
  12. 12. The method according to claim 4, wherein in the step S1, the reaction condition comprises a temperature of 60-70 ℃ and a reaction time of 1-2 hours.
  13. 13. The method according to claim 4, wherein in the step S3, the condition of the baking treatment comprises a baking temperature of 340-370 ℃.
  14. 14. The method according to claim 4, further comprising the step of washing a product obtained by the roasting treatment, wherein a solvent adopted by the washing treatment is a mixed solution of alcohol and water, and the alcohol accounts for 10-95% by weight of the mixed solution; The alcohol is one or more selected from methanol, ethanol, n-propanol and isopropanol.
  15. 15. The method of claim 14, wherein the alcohol comprises 30-60 wt% of the mixed solution.
  16. 16. Use of the iridium ruthenium tin composite catalyst according to any one of claims 1 to 3 in hydrogen production by water electrolysis.

Description

Iridium ruthenium tin composite catalyst and preparation method and application thereof Technical Field The present disclosure relates to the field of hydrogen energy and chemical industry, and in particular, to an iridium ruthenium tin composite catalyst, a preparation method and applications thereof. Background Compared with the alkaline water electrolysis technology, the proton exchange membrane water electrolysis hydrogen production technology has the advantages of high response speed, high current density, wide work load range, high hydrogen purity and the like, and particularly has incomparable advantages in the field of generating electricity by using renewable energy sources and further producing hydrogen by water electrolysis, and is a main mode for obtaining green hydrogen in the future. The anode catalyst is one of key materials for producing hydrogen by water electrolysis of a proton exchange membrane, and is a main speed control step for producing hydrogen by water electrolysis of PEM. At present, the commercial PEM water electrolysis device basically uses iridium oxide or iridium black catalyst, the noble metal iridium is expensive (1000 yuan/g), and the dosage reaches 1-2mg/cm 2, so that the reduction of the dosage of anode iridium is one of important break-through openings for large-scale application of PEM water electrolysis. There are two strategies to reduce the amount of iridium, one is to increase the electrochemical intrinsic activity of the catalyst, and only a small amount of catalyst is needed to achieve the same performance, and the other is to increase the utilization rate of the active components. Disclosure of Invention The iridium ruthenium tin composite catalyst has higher catalytic activity than a commercial iridium oxide catalyst, the noble metal consumption is obviously reduced, the cost is reduced, and the iridium ruthenium tin composite catalyst has a larger use value. In order to achieve the above object, a first aspect of the present disclosure provides an iridium ruthenium tin composite catalyst, which includes iridium element, ruthenium element and tin element, wherein an XRD spectrum of the iridium ruthenium tin composite catalyst only has an amorphous peak packet between 25 ° and 40 °. Optionally, the O1s characteristic peak of the XPS spectrum of the iridium ruthenium tin composite catalyst comprises an M-O characteristic peak and an M-OH characteristic peak, and B 0 defined by the following formula (1) is any numerical value between 0.4 and 0.5; B 0＝B1/(B1+B2) formula (1); Wherein B 1 is the peak area of the M-OH characteristic peak of the XPS spectrum of the iridium-ruthenium-tin composite catalyst, and B 2 is the peak area of the M-O characteristic peak of the XPS spectrum of the iridium-ruthenium-tin composite catalyst. Optionally, the BET specific surface area of the iridium-ruthenium-tin composite catalyst is 60-80 m 2/g, and the particle size is 3-8 nm. Optionally, the chemical composition of the iridium ruthenium tin composite catalyst is Ir xRuySn1-x-yO2, wherein x is any value between 0.4 and 0.6, and y is any value between 0.1 and 0.2. Alternatively, the XRD patterns of the iridium ruthenium tin composite catalyst are free of crystal plane diffraction peaks of IrO 2、RuO2 and SnO 2. A second aspect of the present disclosure provides a method of preparing an iridium ruthenium tin composite catalyst, the method comprising the steps of: S1, mixing an iridium source, a ruthenium source, a tin source, a complexing agent and water, and reacting the obtained mixed material to obtain a first material, wherein the pH value of the mixed material is 5-9, and the complexing agent is selected from C4-C8 organic polyacid and soluble salts of the C4-C8 organic polyacid; S2, separating water in the first material to obtain an iridium ruthenium tin composite catalyst precursor; and S3, roasting the iridium ruthenium tin composite catalyst precursor in an oxygen-containing atmosphere. Optionally, step S1 includes the steps of: s1-1, carrying out first mixing on the iridium source, the first complexing agent and water, and adjusting the pH to 5-9, preferably 7-8, so as to obtain a first mixture; s1-2, carrying out second mixing on the ruthenium source, the second complexing agent and water, and adjusting the pH to 5-9, preferably 7-8, so as to obtain a second mixture; S1-3, carrying out third mixing on the tin source, the third complexing agent and water, and adjusting the pH to 5-9, preferably 7-8, so as to obtain a third mixture; S1-4, mixing the first mixture, the second mixture and the third mixture to obtain the mixed material. Optionally, the iridium source is selected from one or more of chloroiridic acid and chloroiridic acid alkali metal salt, preferably, the chloroiridic acid alkali metal salt is selected from one or two of chloroiridic acid potassium and chloroiridic acid sodium; The ruthenium source is a soluble salt of ruthenium, preferably one or two of ruthen