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CN-119500178-B - Noble metal supported amorphous metal oxide catalytic material and preparation method and application thereof

CN119500178BCN 119500178 BCN119500178 BCN 119500178BCN-119500178-B

Abstract

The invention relates to the field of photocatalytic conversion, and discloses a noble metal loaded amorphous metal oxide catalytic material, and a preparation method and application thereof. The catalytic material comprises amorphous metal oxide of VIII family and ruthenium, wherein the amorphous metal oxide of VIII family is selected from at least one of amorphous nickel oxide, amorphous cobalt oxide and amorphous iron oxide, and the content of ruthenium is 0.1-6.5 mass% based on the total amount of the catalytic material and calculated on the element. The catalytic material provided by the invention contains noble metal and amorphous metal oxide at the same time, and is rich in coordination unsaturated structure, so that surface reaction active sites can be provided, and the reaction efficiency is improved.

Inventors

  • SUN SHANGCONG
  • PENG BO
  • CAO TIANTIAN
  • Jiang Qiuqiao
  • GAO DI

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
20260508
Application Date
20230817

Claims (20)

  1. 1. The catalytic material is characterized by comprising amorphous metal oxide of a VIII group and ruthenium, wherein the amorphous metal oxide of the VIII group is amorphous nickel oxide, amorphous cobalt oxide and amorphous iron oxide, and the content of the ruthenium is 2-5% by mass based on the total amount of the catalytic material and calculated by elements; Wherein the mass ratio of the amorphous cobalt oxide to the sum of the amorphous nickel oxide and the amorphous iron oxide is 1.2-3:1; wherein the content of amorphous cobalt oxide is 50 to 80 mass percent, the content of amorphous nickel oxide is 7.5 to 25 mass percent, and the content of amorphous iron oxide is 7.5 to 25 mass percent based on the total amount of amorphous metal oxides of group VIII; wherein the catalytic material contains oxygen defects, and the content of the oxygen defects in the catalytic material is 2-10%; the preparation method of the catalytic material comprises the following steps: s1, carrying out contact reaction on a dispersion liquid A containing a VIII family metal precursor and first alcohol and a precipitator to obtain a solid reaction product; S2, carrying out reduction reaction on the dispersion liquid B containing the solid reaction product and the second alcohol in the step S1 and a ruthenium precursor in the presence of a reducing agent, and then drying to obtain a noble metal supported amorphous metal oxide catalytic material; the contact reaction conditions in the step S1 comprise the temperature of 5-40 ℃ and the time of 0.5-24h; in the step S2, the conditions of the reduction reaction comprise the temperature of 0-30 ℃ and the time of 1-8h.
  2. 2. Catalytic material according to claim 1, wherein the catalytic material has a specific surface area of 200-800cm 2 /g.
  3. 3. Catalytic material according to claim 2, wherein the catalytic material has a specific surface area of 600-800cm 2 /g.
  4. 4. The catalytic material of claim 1, wherein the catalytic material exhibits no characteristic diffraction peak at 10-90 ° in an X-ray diffraction pattern and the catalytic material exhibits an amorphous packet characteristic diffraction peak at 30-40 ° in an X-ray diffraction pattern.
  5. 5. Catalytic material according to claim 1, wherein the content of oxygen defects in the catalytic material is 4-6%.
  6. 6. A preparation method of a noble metal supported amorphous metal oxide catalytic material for photocatalytic ammonia decomposition hydrogen production reaction comprises the following steps: s1, carrying out contact reaction on a dispersion liquid A containing a VIII family metal precursor and first alcohol and a precipitator to obtain a solid reaction product; S2, carrying out reduction reaction on the dispersion liquid B containing the solid reaction product and the second alcohol in the step S1 and a ruthenium precursor in the presence of a reducing agent, and then drying to obtain a noble metal supported amorphous metal oxide catalytic material; The VIII group metal is iron, cobalt and nickel; the ruthenium precursor is used in an amount such that the content of ruthenium in the prepared noble metal-supported amorphous metal oxide catalytic material is 2 to 5 mass% in terms of elements based on the total amount of the catalytic material, The contact reaction conditions in the step S1 comprise the temperature of 5-40 ℃ and the time of 0.5-24h; The mass ratio of the cobalt precursor calculated as oxide to the sum of the nickel precursor calculated as oxide and the iron precursor calculated as oxide is 1.2-3:1; Wherein, based on the total amount of the amorphous metal oxide of the VIII group, the content of the amorphous cobalt oxide is 50 to 80 mass percent, the content of the amorphous nickel oxide is 7.5 to 25 mass percent, and the content of the amorphous iron oxide is 7.5 to 25 mass percent; wherein the catalytic material contains oxygen defects, and the content of the oxygen defects in the catalytic material is 2-10%; in the step S2, the conditions of the reduction reaction comprise the temperature of 0-30 ℃ and the time of 1-8h.
  7. 7. The method of claim 6, wherein in step S1, the group VIII metal precursor is selected from soluble compounds of the respective metals.
  8. 8. The method of claim 7, wherein in step S1, the group VIII metal precursor is selected from at least one of the nitrates, chlorides, and sulfates of the respective metals.
  9. 9. The method according to claim 6, wherein in step S1, the first alcohol is a monohydric alcohol and/or a polyhydric alcohol.
  10. 10. The method of claim 9, wherein in step S1, the first alcohol is at least one of methanol, ethanol, and ethylene glycol.
  11. 11. The method of claim 6, wherein in step S1, the mass ratio of the group VIII metal precursor to the first alcohol is 1:1-10.
  12. 12. The method of claim 11, wherein in step S1, the mass ratio of the group VIII metal precursor to the first alcohol is 1:1-5.
  13. 13. The method according to any one of claims 6-12, wherein in step S1, the precipitant is carbonate and/or bicarbonate.
  14. 14. The method of claim 13, wherein in step S1, the precipitant is at least one of potassium carbonate, sodium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate.
  15. 15. The method according to any one of claims 6 to 12, wherein step S1 comprises adding the precipitant-containing dispersion C to the dispersion A containing the group VIII metal precursor and the first alcohol under stirring to effect a contact reaction.
  16. 16. The method of claim 15, wherein the precipitant-containing dispersion C is prepared by dispersing a precipitant in a solvent.
  17. 17. The method of claim 15, wherein the precipitant-containing dispersion C is added at a rate of 0.5-2.5mL/min relative to 10mL of the group VIII metal precursor and first alcohol-containing dispersion a.
  18. 18. The method according to any one of claims 6 to 12, wherein in step S1, the mass ratio of the group VIII metal precursor to the precipitant is 1:0.5-3.
  19. 19. The process according to any one of claims 6 to 12, wherein in step S1, the conditions of the contact reaction comprise a temperature of 20 to 40 ℃ for a time of 0.5 to 10 hours.
  20. 20. The process according to any one of claims 6 to 12, wherein in step S2, the dispersion B comprising the solid reaction product of step S1 and the second alcohol is prepared by dispersing the solid reaction product of step S1 in the second alcohol.

Description

Noble metal supported amorphous metal oxide catalytic material and preparation method and application thereof Technical Field The invention relates to the field of photocatalytic conversion, in particular to a noble metal loaded amorphous metal oxide catalytic material, and a preparation method and application thereof. Background Long-distance transportation research of hydrogen is carried out at home and abroad. At present, the most widely studied hydrogen long-distance transportation mainly comprises three modes, namely pipeline hydrogen transportation, liquid hydrogen storage and transportation and chemical storage and transportation, wherein the medium for chemical storage and transportation of hydrogen mainly comprises organic liquid, ammonia, methanol and the like. According to the international energy agency report, ammonia is utilized as a hydrogen storage medium, and the comprehensive cost is obviously lower than that of liquid hydrogen and an organic liquid hydrogen carrier. In the ammonia storage and transportation industry chain, ammonia synthesis and transportation technology are mature, so developing a high-efficiency ammonia decomposition technology is a key for realizing hydrogen storage and transportation of hydrogen. The thermodynamic calculation result shows that the equilibrium conversion rate of ammonia decomposition can reach 99% under normal pressure and 400 ℃, but the ammonia decomposition has higher activation energy and slow dynamics, so that the practical application is limited, and the development of the high-efficiency ammonia decomposition catalyst is the core for realizing the industrialization of hydrogen production by ammonia decomposition. The catalytic conversion paths commonly used at present mainly comprise thermocatalysis, photocatalysis, electrocatalytic and the like. The traditional thermocatalysis method has higher energy consumption and is unfavorable for large-scale application. The solar energy is utilized to assist the catalytic process to realize hydrogen production, and the dependence on fossil fuel is expected to be reduced. However, conventional semiconductor materials can only use ultraviolet light and a small portion of visible light, and have limited solar energy utilization efficiency. The amorphous semiconductor material can effectively capture near infrared sunlight due to the unique tail state absorption, and meanwhile, the amorphous semiconductor material is rich in coordination unsaturated structures to provide surface reaction active sites, so that the reaction efficiency is further improved. Disclosure of Invention The invention aims to solve the problem of low ammonia decomposition conversion rate in the prior art, and provides a noble metal loaded amorphous metal oxide catalytic material, a preparation method and application thereof. In order to achieve the above object, a first aspect of the present invention provides a noble metal-supported amorphous metal oxide catalytic material, wherein the catalytic material comprises a group VIII amorphous metal oxide and ruthenium, the group VIII amorphous metal oxide is selected from at least one of amorphous nickel oxide, amorphous cobalt oxide and amorphous iron oxide, and the ruthenium is contained in an amount of 0.1 to 6.5 mass% on an elemental basis based on the total amount of the catalytic material. Preferably, the mass ratio of the amorphous cobalt oxide to the sum of the amorphous nickel oxide and the amorphous iron oxide is 1-5:1, more preferably 1.2-3:1. Preferably, the catalytic material contains oxygen defects. Preferably, the content of oxygen defects in the catalytic material is 2 to 10%, more preferably 4 to 6%. The second aspect of the present invention provides a method for preparing a noble metal-supported amorphous metal oxide catalytic material, wherein the method comprises the steps of: S1, carrying out contact reaction on an alcohol solution A containing a VIII family metal precursor and a carbonate solution B to obtain a reaction product; s2, in the presence of a reducing agent, carrying out a reduction reaction on the alcohol solution C containing the reaction product of the step S1 and a ruthenium precursor, and then drying to obtain a noble metal catalytic material; the group VIII metal is selected from at least one of iron, cobalt, and nickel; the dosage of the ruthenium precursor is such that the content of ruthenium is 0.1-6.5 mass% based on the total amount of the catalytic material and calculated as element in the preparation of the noble metal catalytic material; the conditions of the step S1 contact reaction and the step S2 reduction reaction each independently comprise a temperature of 5-40 ℃ and a time of 0.5-24h. In a third aspect, the present invention provides a noble metal-supported amorphous metal oxide catalytic material prepared by the preparation method described in the second aspect. According to a fourth aspect of the invention, there is provided the use of