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CN-122006738-A - Solar-driven cyclohexane hydrogen production catalyst, preparation method and application thereof

CN122006738ACN 122006738 ACN122006738 ACN 122006738ACN-122006738-A

Abstract

The invention belongs to the technical field of catalyst preparation, and particularly relates to a solar-driven cyclohexane hydrogen production catalyst, a preparation method and application thereof, wherein the catalyst is high-entropy metal oxide and contains Ti, zr, al, W and Ni elements. The invention aims at the preparation process of the catalyst, has simple preparation process, uses non-noble metal salt as raw materials, uses solar energy as only input energy, efficiently converts cyclohexane into hydrogen under mild conditions, and has good industrial application prospect.

Inventors

  • PAN HU
  • JI MIMI
  • QIN SHENGXU

Assignees

  • 嘉兴大学

Dates

Publication Date
20260512
Application Date
20260327

Claims (9)

  1. 1. A solar-driven cyclohexane hydrogen production catalyst is characterized in that the catalyst is a high-entropy metal oxide and comprises Ti, zr, al, W and Ni elements, and the molar ratio of active component elements Ti to Zr to Al to W to Ni in the catalyst is 0.5-2.0:0.5-2.0:0.5-2.0:0.5-2.0:0.5-2.0.
  2. 2. The solar-driven cyclohexane hydrogen production catalyst according to claim 1, wherein the molar ratio of active component element Ti to Zr to Al to W to Ni in the catalyst is 0.8-1.2 to 0.8-1.2.
  3. 3. The solar-driven cyclohexane hydrogen production catalyst according to claim 1, wherein the molar ratio of active component elements Ti to Zr to Al to W to Ni in the catalyst is 1:1:1:1:1.
  4. 4. A method for preparing a solar-driven cyclohexane hydrogen production catalyst according to claim 1, characterized in that the method comprises the following steps: Dissolving the calculated organic weak acid in an organic solvent, and fully stirring at room temperature until the organic weak acid is completely dissolved; Dissolving Ti source, zr source, al source, W source and Ni source in the calculated amount into the solution obtained in the first step, and stirring the mixture fully at room temperature until the Ti source, the Zr source, the Al source, the W source and the Ni source are completely dissolved, wherein the addition amount of each metal source meets the metal element mole ratio of any one of claims 1-3; step three, dissolving the calculated amount of surfactant in the mixed solution obtained in the step two, and fully stirring at room temperature until the surfactant is completely dissolved; Step four, heating the mixed solution obtained in the step three at 120 ℃ to 3 h to prepare xerogel; placing the xerogel prepared in the step four in a tube furnace, calcining for 30min at 500 ℃ and heating up to 2 ℃ per minute to prepare precursor solid powder; and step six, placing the precursor solid powder prepared in the step five into a muffle furnace, calcining at 600 ℃ for 10 h ℃ and heating at a rate of5 ℃ per minute, and preparing the solar-driven cyclohexane hydrogen production catalyst.
  5. 5. The method of claim 4, wherein the Ti source is tetrabutyl titanate, the Zr source is zirconium chloride, the Al source is aluminum chloride, the W source is tungsten hexachloride, the Ni source is nickel chloride, the weak organic acid is citric acid, the organic solvent is ethanol, and the surfactant is polyethylene glycol.
  6. 6. The method according to claim 4, wherein the total molar ratio of the Ti source, zr source, al source, W source, ni source to the organic weak acid is 1 (2-4), and the mass ratio of the organic solvent to the surfactant is 6-10:1.
  7. 7. Use of the solar-driven cyclohexane hydrogen production catalyst of claim 1 in solar-driven cyclohexane hydrogen production.
  8. 8. The method of claim 7, wherein the sunlight is simulated by a 300W power xenon lamp as the light source in the reaction.
  9. 9. The method according to claim 7, wherein the reaction conditions are a reaction light intensity of 3.5-6.5W/cm 2 and an Ar atmosphere.

Description

Solar-driven cyclohexane hydrogen production catalyst, preparation method and application thereof Technical Field The invention belongs to the technical field of catalyst preparation, and particularly relates to a solar-driven cyclohexane hydrogen production catalyst, a preparation method and application thereof. Background With the active advancement of the worldwide carbon neutralization targets, hydrogen energy is regarded as a key energy carrier for replacing fossil fuel by virtue of zero carbon emission and no harmful byproducts, has potential to solve the global environmental problem and the energy crisis of the 21 st century, and is widely used in building, industry, traffic and power industries. However, the hydrogen has small mass density, is difficult to compress, is inflammable and explosive, has great storage, transportation and distribution difficulty, and is difficult to meet the huge requirement of the future low-carbon society on clean hydrogen energy. The traditional hydrogen storage and transportation mode mainly adopts a high-pressure gas state or low-temperature liquid state form, and the two methods have the remarkable defects that the high-pressure storage and transportation is high in energy consumption and has the safety risks of leakage and explosion, and the low-temperature liquefaction is high in cost and difficult to realize large-scale popularization. Under the background, the storage and transportation technology based on the Liquid Organic Hydrogen Carrier (LOHC) has the advantages that the hydrogen storage amount is ① units, the ② organic hydrogen carrier is liquid at normal temperature and normal pressure and is non-corrosive, the transportation is safe and convenient, the ③ hydrogen carrier is stable in property and low in volatility, the ④ hydrogen carrier can be recycled, the cost is reduced, and ⑤ can be well combined with the existing gasoline and diesel oil transportation technology, and the infrastructure does not need to be improved in a large range. Wherein cyclohexane is used as a representative liquid organic hydrogen carrier, and the hydrogen storage density in the dehydrogenation process is 56 g/L (7.2 wt%), which is far greater than the hydrogen storage amount of metal hydride (less than 3 wt%). Meanwhile, the product benzene is a chemical raw material for synthesizing styrene, phenol, maleic anhydride, alkylbenzene and the like. In addition, the main reaction of cyclohexane dehydrogenation is reversible, reactants and products can be recovered, and the method has the advantages of convenience in transportation, no carbon emission in the hydrogen production process, no carbon monoxide in the generated hydrogen and the like, is beneficial to the utilization of proton exchange membrane fuel cells, and has important application prospects. Although cyclohexane dehydrogenation is thermodynamically feasible, its reaction process faces a serious kinetic barrier. Since cyclohexane molecules contain a large amount of inert sp 3 C-H bonds, the activation energy barrier is extremely high, and the traditional industrial process is often required to be carried out under high temperature (573-673-K) and high pressure conditions, which not only causes huge energy consumption, but also easily causes the problems of deactivation of catalyst carbon deposit, increased side reactions and the like. Therefore, how to gently and efficiently break the inertness of the C-H bond, inhibit side reactions and improve the purity of hydrogen production at the same time becomes a core scientific problem to be solved in the field. In recent years, the advent of photocatalytic technology has provided a new solution to the above-mentioned problems. The light energy is used as a green reagent, so that inert C-H bonds can be directly activated under mild conditions, and the problem of high energy consumption in the traditional thermocatalysis process is avoided. Disclosure of Invention The invention aims to provide a solar-driven cyclohexane hydrogen production catalyst, which has the advantages of simple preparation method and low cost and easy acquisition of raw materials, and the prepared catalyst shows high hydrogen production activity under the irradiation reaction of simulated sunlight. The technical scheme adopted for solving the technical problems is as follows: The solar-driven cyclohexane hydrogen production catalyst is a high-entropy metal oxide and comprises Ti, zr, al, W and Ni elements, wherein the molar ratio of active component elements Ti to Zr to Al to W to Ni in the catalyst is 0.5-2.0:0.5-2.0:0.5-2.0:0.5-2.0:0.5-2.0. The invention develops a non-noble metal catalyst with high activity and stability, takes solar energy as the only input energy, efficiently converts cyclohexane into hydrogen under mild conditions, and shows high hydrogen yield and good catalyst reusability. Preferably, in the catalyst, the molar ratio of the active component element Ti to Zr to Al to W to Ni is 0