CN-122013226-A - High-entropy alloy catalyst for producing formic acid based on biomass, and preparation method and application thereof

Abstract

The invention discloses a high-entropy alloy catalyst for producing formic acid based on biomass, a preparation method and application thereof, and belongs to the technical field of catalytic materials, wherein the high-entropy alloy catalyst has a general formula MnFeCoNiCu and a face-centered cubic crystal structure. The preparation method of the high-entropy alloy catalyst comprises the following steps of loading thiourea solution on a substrate, drying and then carrying out first Joule heating treatment, loading mixed solution containing manganese salt, ferric salt, cobalt salt, nickel salt and copper salt on the substrate after the first Joule heating treatment, drying and then carrying out second Joule heating treatment, and thus the high-entropy alloy catalyst is obtained. The high-entropy alloy catalyst has high catalytic activity and formic acid selectivity on various biomass sugars such as glucose, arabinose, xylose and fructose, has excellent catalytic performance on waste straw hydrolysate, and can efficiently promote formic acid generation.

Inventors

• SHEN FENG
• LI FAN
• LI FUKUAN

Assignees

• 农业农村部环境保护科研监测所

Dates

Publication Date

20260512

Application Date

20260414

Claims (10)

1. 1. The high-entropy alloy catalyst for producing formic acid based on biomass is characterized by having a general formula MnFeCoNiCu and a face-centered cubic crystal structure.
2. 2. A method for preparing the high-entropy alloy catalyst for producing formic acid based on biomass as claimed in claim 1, comprising the following steps: Loading thiourea solution on a substrate, drying and performing first Joule heating treatment; And loading a mixed solution containing manganese salt, ferric salt, cobalt salt, nickel salt and copper salt on the substrate subjected to the first Joule heating treatment, and drying and then carrying out the second Joule heating treatment to obtain the high-entropy alloy catalyst.
3. 3. The method for preparing a high-entropy alloy catalyst for producing formic acid by biomass according to claim 2, wherein the substrate is pretreated carbon cloth.
4. 4. The method for preparing the high-entropy alloy catalyst for producing formic acid by biomass as claimed in claim 3, wherein the pretreatment method of the carbon cloth is that the carbon cloth is soaked in acetone and washed by ultrapure water.
5. 5. The method for preparing the high-entropy alloy catalyst based on biomass formic acid according to claim 2, wherein the thiourea solution is prepared by dissolving thiourea in absolute ethanol, and the concentration of thiourea is 0.05-0.15mol/L.
6. 6. The preparation method of the high-entropy alloy catalyst for producing formic acid by biomass according to claim 2, wherein the first joule heating treatment method is that heating is carried out to 1400-1600K under a vacuum environment, and the temperature is kept for 0.3-0.8s.
7. 7. The method for preparing the high-entropy alloy catalyst based on biomass formic acid production according to claim 2, wherein manganese salt, iron salt, cobalt salt, nickel salt and copper salt are all chloride salts, and molar concentrations are equal.
8. 8. The preparation method of the high-entropy alloy catalyst for producing formic acid by biomass according to claim 2, wherein the second joule heating treatment method is that heating is carried out to 900-1500K in a vacuum environment, and the temperature is kept for 0.0-1.0s.
9. 9. Use of the high-entropy alloy catalyst for biomass-based formic acid production according to claim 1 for the preparation of formic acid by electrocatalytic biomass conversion.
10. 10. The use according to claim 9, wherein the biomass comprises straw waste and biomass sugars, including glucose, arabinose, xylose and fructose.

Description

High-entropy alloy catalyst for producing formic acid based on biomass, and preparation method and application thereof Technical Field The invention relates to the technical field of catalytic materials, in particular to a high-entropy alloy catalyst for producing formic acid based on biomass, a preparation method and application thereof. Background Continuous consumption of fossil fuels has raised serious environmental challenges and energy crisis. In this context, biomass is a very abundant "zero carbon" resource reserve as the fourth world energy source following coal, oil and gas. The biomass-derived platform compound can be efficiently converted into various high-added-value products through catalytic conversion. Among them, formic acid is a non-corrosive and non-toxic chemical reagent, has high versatility and can be widely used in the fields of chemistry and energy. As a convenient source of carbon monoxide or hydrogen, formic acid can be used as a hydrogen donor to realize in-situ hydrogen production by virtue of strong reducibility. Furthermore, formic acid contains only C, H, O elements, which is advantageous over inorganic acids in terms of pretreatment of biomass, since it does not produce inorganic residues. Meanwhile, formic acid is also a key platform chemical for products such as synthetic textiles, medicines, leather, elastomers and the like. However, efficient conversion of biomass to formic acid typically involves selective cleavage of multiple c—c bonds, a complex reaction path, resulting in lower formic acid yields. Single or bimetallic catalysts suffer from high cost, single active sites, poor selectivity and stability, and the like. Therefore, the development of a catalyst having a combination of low cost, high activity, high selectivity and excellent durability is a core challenge in achieving high-value utilization of biomass resources. In recent years, the high-entropy catalyst shows excellent catalytic performance due to the unique high-entropy effect, lattice distortion effect, slow diffusion effect and cocktail synergistic effect, and provides a new opportunity for biomass high-value utilization of formic acid production. Therefore, the utilization of the high-entropy alloy catalyst to promote the high-value utilization of biomass to produce formic acid is a promising strategy. Disclosure of Invention The invention aims to provide a high-entropy alloy catalyst for producing formic acid based on biomass, and a preparation method and application thereof, so as to solve the problems in the background art. In order to achieve the above purpose, the present invention provides the following technical solutions: a high-entropy alloy catalyst for producing formic acid based on biomass has a general formula MnFeCoNiCu and a face-centered cubic crystal structure. The invention also aims to provide a preparation method of the high-entropy alloy catalyst for producing formic acid based on biomass, which comprises the following steps: Loading thiourea solution on a substrate, drying and performing first Joule heating treatment; And loading a mixed solution containing manganese salt, ferric salt, cobalt salt, nickel salt and copper salt on the substrate subjected to the first Joule heating treatment, and drying and then carrying out the second Joule heating treatment to obtain the high-entropy alloy catalyst. Further, the substrate is pretreated carbon cloth. Further, the pretreatment method of the carbon cloth comprises the steps of immersing the carbon cloth in acetone and washing with ultrapure water. Further, the thiourea solution is prepared by dissolving thiourea in absolute ethanol, and the concentration of thiourea is 0.05-0.15mol/L. Further, the first Joule heating treatment method comprises heating to 1400-1600K under vacuum environment, and maintaining the temperature for 0.3-0.8s. Further, the manganese salt, the ferric salt, the cobalt salt, the nickel salt and the copper salt are all chloride salts, and the molar concentrations are equal. Further, the second Joule heating treatment method comprises heating to 900-1500K under vacuum environment, and maintaining the temperature for 0.0-1.0s. The invention also aims to provide the application of the high-entropy alloy catalyst based on biomass formic acid production in preparing formic acid by electrocatalytic biomass conversion. Further, the biomass comprises straw waste and biomass sugar, wherein the biomass sugar comprises glucose, arabinose, xylose and fructose. The high-entropy alloy catalyst for producing formic acid based on biomass provided by the invention has high catalytic activity and formic acid selectivity on various biomass sugars such as glucose, arabinose, xylose and fructose, and has excellent catalytic performance on waste straw hydrolysate, so that formic acid can be efficiently promoted. Research shows that the preparation of formic acid by pushing biomass resources through high-value conversion by using the hi