CN113104833A - Biochar-based hard foam carbon, preparation method thereof and application thereof in electrocatalysis - Google Patents
Biochar-based hard foam carbon, preparation method thereof and application thereof in electrocatalysis Download PDFInfo
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Abstract
The invention provides biochar-based hard carbon foam, a preparation method thereof and application thereof in electrocatalysis, wherein the preparation method of the carbon foam comprises the following steps: s1, providing chitosan aerogel; s2, compounding the chitosan aerogel with phenolic resin, and then performing pyrolysis in an inert gas atmosphere to obtain biochar-based rigid foam carbon containing glassy carbon. The hard foam carbon prepared by the method has large specific surface area, higher mechanical strength and low synthesis cost, and is favorable for being used as an electrode material to realize high-efficiency selective catalytic oxidation of 5-hydroxymethylfurfural. The preferred layered double hydroxide catalyst shows excellent electrocatalytic oxidation performance on 5-hydroxymethylfurfural, and can quickly and selectively complete the oxidation of a target product. The catalyst synthesized by the embodiment of the invention has mild reaction conditions for electrocatalytic oxidation of 5-hydroxymethylfurfural, and can complete selective oxidation of 5-hydroxymethylfurfural in a short time under the mild conditions of normal temperature and normal pressure.
Description
Technical Field
The invention belongs to the technical field of chemical materials and the technical field of energy environmental protection, and particularly relates to biochar-based hard foam carbon, a preparation method thereof and application thereof in electrocatalysis, such as a method for preparing 2,5-furandicarboxylic acid by forming a layered double hydroxide catalyst by loading and carrying out electrocatalytic oxidation on 5-hydroxy furfural.
Background
With the excessive exploitation of traditional fossil energy, the reserves of fossil energy are continuously tightened, and the energy crisis and environmental problems are getting more severe in the world today. Therefore, the strategy of researching sustainable and renewable novel energy sources to replace traditional non-renewable energy sources is urgent for human beings. As a renewable non-fossil fuel carbon source, biomass is a very valuable alternative to fossil energy, and has been increasingly regarded as a biomass energy source.
5-Hydroxymethylfurfural (5-hydroxymethyfurfurfurral) is an important platform compound and can be used as a biomass carbohydrate to replace one of intermediate monomers of organic compounds in the petroleum industry; after hydrogenation or oxidation, the bio-fuel oil and a series of derivative chemical products can be generated, and the derivative chemical products can be used as partial substitutes of petrochemical products which are consumed in large quantity at present. For example, the oxidation product of 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid (2, 5-furyldicarbonyl carboxylic acid), is one of twelve important biomass platform compounds listed in the U.S. department of energy, can be used as a monomer to prepare various biomass-based polymers, and has application prospects in organic synthesis and biopharmaceutical fields.
At present, in the traditional method for preparing 2,5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, the mainly used catalyst is a noble metal catalyst such as platinum (Pt), palladium (Pd) and gold (Au); there is also the catalytic production of 2,5-furandicarboxylic acid by means of carbon electrode materials. The existing methods have certain limitations, which are mainly reflected in that the cost of the noble metal catalyst is high or the reaction needs high temperature and high pressure; and the traditional carbon paper carbon felt and other porous carbon electrode materials have low mechanical strength and short cycle service life, while the traditional graphite and glassy carbon electrode materials have small specific surface area and high manufacturing cost. Therefore, a new catalytic oxidation technology needs to be developed to overcome the problems of high catalytic cost and the like in the catalytic oxidation of 5-hydroxymethylfurfural.
Disclosure of Invention
In view of the above, the invention provides a biochar-based hard foam carbon, a preparation method thereof and application thereof in electrocatalysis, and the hard foam carbon prepared by the invention has the advantages of large specific surface area, higher mechanical strength and low synthesis cost, is favorable for being used as an electrode material to realize high-efficiency selective catalytic oxidation of 5-hydroxymethylfurfural, and reduces the catalytic cost.
The invention provides a preparation method of biochar-based hard carbon foam, which comprises the following steps:
s1, providing chitosan aerogel;
s2, compounding the chitosan aerogel with phenolic resin, and then performing pyrolysis in an inert gas atmosphere to obtain biochar-based rigid foam carbon containing glassy carbon.
In the embodiment of the invention, the chitosan aerogel is prepared by performing sol-gel and freeze drying on chitosan;
the chitosan aerogel and phenolic resin composite concrete comprises: dissolving phenols, formaldehyde and an alkaline catalyst in water to obtain a solution containing phenolic resin, and enabling the solution to permeate the chitosan aerogel; heating the soaked chitosan aerogel at a temperature below 100 ℃.
Preferably, after the heating is finished, the composite precursor substance is heated in an inert gas atmosphere at 900-1000 ℃ for pyrolysis to obtain the biochar-based rigid foamy carbon containing glassy carbon.
The invention provides biochar-based rigid foam carbon prepared by the preparation method, wherein the surface carbon material of the biochar-based rigid foam carbon comprises a glassy carbon form.
In the method for preparing the hard foam carbon, the biological carbon-based foam carbon is synthesized by taking chitosan aerogel and phenolic resin as precursors, and belongs to porous carbon substrate materials and porous carbon electrode materials. The biochar-based foam carbon substrate synthesized by the embodiment of the invention has large specific surface area, more catalytic load sites and good electron transfer efficiency and conductivity; meanwhile, the synthesized biochar-based foam carbon substrate is reinforced by the resin glassy carbon, and compared with carbon felt and carbon paper materials, the mechanical strength and durability of the carbon substrate are improved. In addition, the raw material for synthesizing the biochar-based foam carbon substrate is chitosan, and the raw material is environment-friendly, renewable and low in cost. According to the invention, the electrode substrate is prepared by taking the biochar as a raw material, so that not only can the utilization of waste biomass resources be realized, but also the synthesized foam carbon substrate has stronger mechanical property and practicability compared with carbon paper and carbon felt materials. The method is simple and easy to implement, low in synthesis cost and beneficial to application in electrocatalysis.
The embodiment of the invention provides a catalyst, which takes the biochar-based hard foam carbon as a substrate, wherein non-noble metal catalytic active components are loaded on the substrate.
In an embodiment of the invention, the non-noble metal catalytically active component is a layered double hydroxide composition; the metal element in the layered double hydroxide is preferably any two combinations of Ni, Co, Cu, Fe, Al and Ga.
Preferably, the layered double hydroxide component is directly and orderly grown on the biochar-based hard foam carbon substrate through hydrothermal treatment and has a regular layered structure.
The embodiment of the invention provides application of the catalyst in preparing 2,5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural.
Preferably, the preparation of the 2,5-furandicarboxylic acid from the 5-hydroxymethylfurfural is carried out under the conditions of normal temperature and normal pressure.
In the embodiment of the invention, in the preparation of 2,5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural, the catalyst is used as a working electrode; the concentration of the 5-hydroxymethylfurfural is preferably 5mM to 50 mM.
In the embodiment of the invention, the layered double hydroxide material is preferably loaded on the foamed carbon substrate through hydrothermal reaction, and the obtained catalyst can be called a biochar-based hard foamed carbon substrate loaded hydrotalcite-based catalyst, which is called an "LDH @ CF electrode" for short. Furthermore, in the embodiment of the invention, the prepared catalyst is used as a working electrode of electrocatalytic reaction, and a three-electrode system is used for carrying out electrocatalytic oxidation on 5-hydroxymethylfurfural to synthesize 2,5-furandicarboxylic acid.
The hydrotalcite-based catalyst loaded on the biochar-based hard foam carbon substrate provided by the embodiment of the invention has the characteristics that the active component is non-noble metal, and the catalyst is cheap and easy to obtain and has wide natural reserve. In the embodiment of the invention, the preferable layered double-metal hydroxide hydrotalcite component uniformly and orderly grows on the prepared biochar-based foam carbon substrate, and has a regular layered structure, a larger specific surface area and more reaction catalytic sites. The biocarbon-based hard foam carbon substrate-supported hydrotalcite-based catalyst synthesized by the embodiment of the invention has the advantages of high OER activity, high current density, low overpotential and good cycle stability. In addition, the embodiment of the invention uses a hydrothermal coprecipitation method to load the layered double hydroxide catalytic active component, and the synthesis method is simple and easy to implement and consumes less energy.
In a preferred embodiment of the invention, the layered double hydroxide shows excellent electrocatalytic oxidation performance on 5-hydroxymethylfurfural, and can rapidly and selectively complete the oxidation of a target product. The catalyst synthesized by the embodiment of the invention has mild reaction conditions for electrocatalytic oxidation of 5-hydroxymethylfurfural, can complete selective oxidation of 5-hydroxymethylfurfural in a short time under the mild conditions of normal temperature and normal pressure, and shows excellent electrochemical oxygen production performance and selective oxidation performance of 5-hydroxymethylfurfural. Experiments show that the product of the catalyst synthesized in the embodiment of the invention for electrocatalytic oxidation of 5-hydroxymethylfurfural is 2,5-furandicarboxylic acid, the conversion rate of reactants is above 97%, the selectivity of a target product is above 99.5%, and the purity of the product is above 99%, so that a proper method and a proper thought are provided for further conversion of biomass compound resources.
Drawings
FIG. 1 is the XRD result of scraping debris from the surface of the synthetic charcoal-based rigid foam carbon substrate in example 1;
FIG. 2 shows the Raman spectrum of the scraped debris on the surface of the biochar-based rigid foam carbon substrate synthesized in example 1;
FIG. 3 is an SEM photomicrograph of scraped debris from the surface of the synthetic biochar-based rigid foam carbon substrate of example 1;
fig. 4 is a photograph showing the results of an experiment of water contact angle measurement of the prepared substrate 3;
FIG. 5 is a photograph showing the results of a water contact angle test experiment on plain carbon paper;
FIG. 6 is a partial SEM photograph of a NiFe catalytic electrode of example 2;
FIG. 7 is a partial SEM micrograph of a NiFe catalytic electrode prepared in example 2;
FIG. 8 shows the results of the electrocatalytic oxidation of 5-hydroxymethylfurfural by the NiFe catalytic electrode in example 5 as a function of time;
FIG. 9 is a low magnification SEM of a NiFe catalytic electrode of example 2;
fig. 10 is a low magnification SEM photograph of electrode 1 in example 8.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of biochar-based hard carbon foam, which comprises the following steps:
s1, providing chitosan aerogel;
s2, compounding the chitosan aerogel with phenolic resin, and then performing pyrolysis in an inert gas atmosphere to obtain biochar-based rigid foam carbon containing glassy carbon.
The hard foam carbon prepared by the method has the advantages of large specific surface area, higher mechanical strength, long cycle service life and good practicability, can be used for preparing electrode materials, and meets the requirements of low cost, easiness in preparation, high efficiency and the like.
The preparation method comprises the steps of firstly preparing the chitosan aerogel, wherein the chitosan aerogel is used as a raw material, and preparing the porous light solid material through sol-gel and freeze drying. Chitosan (chitosan) is a product of chitin N-deacetylation, and is derived from the carapace of marine arthropods such as shrimps and crabs, the carapace of insects, the cell membranes of fungi and algae, the carapace and skeleton of mollusks, and the cell walls of higher plants. Chitin is widely distributed in the natural world, the reserve is only behind cellulose, and is the second largest natural polymer, the amount of chitin biosynthesis is about 100 hundred million tons every year, and the chitin is a recyclable renewable resource. Chitosan is a renewable natural polymer, and does not need artificial polymer materials as a framework.
According to the biochar-based rigid foam carbon substrate disclosed by the embodiment of the invention, the precursor raw materials are wide in source and renewable in nature, and the biochar-based rigid foam carbon substrate has the advantages of low carbon, environmental friendliness, low price and easiness in obtaining; the utilization of chitosan is also a way for utilizing solid biomass waste.
In the specific embodiment of the invention, 2g to 5g of chitosan powder can be dispersed in 50mL of water, and a small amount of acetic acid is dripped while stirring to dissolve the chitosan; freeze-drying the obtained chitosan gel in a vacuum freeze-drying machine at the temperature of-80 ℃ for 96-168 h; the obtained light chitosan aerogel is cut into blocks of 5cm multiplied by 1cm, or the obtained light chitosan aerogel is cut into blocks of 2cm multiplied by 1 cm.
Generally, the chitosan aerogels herein have a density of from 0.05 to 0.12g/cm3Preferably, the standard is that no ice crystal exists in the aerogel after freeze drying; the chitosan aerogel porosity is not particularly limited by the present application.
In addition, the phenolic resin is used as a precursor, and can be pyrolyzed into glassy carbon (which can be referred to as glassy carbon and glassy carbon for short, and amorphous carbon with a glassy shape) subsequently, so that the foamed carbon has a reinforcing and stabilizing effect; the glassy carbon is simultaneously beneficial to improving the catalytic loading sites, the conductivity and the like of the carbon foam substrate.
The embodiment of the invention compounds the chitosan aerogel with phenolic resin: specifically, phenols, formaldehyde and an alkaline catalyst can be dissolved in water to obtain a solution containing phenolic resin, and the solution is soaked in the chitosan aerogel; heating the soaked chitosan aerogel at a temperature below 100 ℃.
Among them, the phenols such as phenol and resorcinol, preferably resorcinol (also called rasol, English: Resorcin), are more preferable in general use. The alkaline catalyst is preferably sodium carbonate; the mass ratio of phenols to formaldehyde (calculated by 35% aqueous solution) is strictly proportioned according to 1:1.36, additional water is added to be controlled within one volume of the original formaldehyde solution, and the alkali catalyst is controlled to be about 1-3 per thousand of the mass of the added phenols. Preferably, 2.2g of rasol, 3g of formaldehyde solution and 5mg of sodium carbonate are dissolved in 1 mL-3 mL of water and ultrasonically mixed for 10min to obtain a resin precursor solution.
In the embodiment of the invention, the prepared solution is dripped on the prepared chitosan aerogel block, so that the chitosan aerogel block is completely soaked by the solution, and redundant resin solution flows out along with the self weight; placing the soaked chitosan block in a sealed environment, preferably heating at 60-90 ℃ for 36-48 h, wherein sealing and drying are carried out to enable phenolic resin molecules to be crosslinked and cured; then the material is transferred to an air-ventilated environment and is heated for 12 hours at 60-90 ℃ to remove the moisture in the material. Preferably, the process requires strict control of the seal drying time, and too short or too long seal heating time can cause incomplete curing or water softening of the material.
In a preferred embodiment of the present invention, after the heating is completed, the scraps on the chitosan block can be scraped off, and the composite precursor substance is heated at 900 to 1000 ℃ in an inert gas atmosphere for pyrolysis, so as to obtain the biochar-based rigid carbon foam containing glassy carbon. The inert gas atmosphere is mainly nitrogen atmosphere; the pyrolysis temperature is preferably 930-960 ℃, and more preferably 950 ℃; the temperature rise rate can be 1-5 ℃/min. Further preferably, the obtained composite precursor substance is heated for 6h at 950 ℃ in a nitrogen atmosphere, and the programmed heating rate is 2.5 ℃/min, so that the pyrolyzed chitosan carbon block is obtained. According to the embodiment of the invention, the pyrolyzed chitosan carbon block can be subjected to ultrasonic treatment in deionized water for 30min to remove surface debris, so that the prepared charcoal-based hard foam carbon substrate is obtained.
The embodiment of the invention provides biochar-based rigid foam carbon which can be prepared by the preparation method, and the surface carbon material of the biochar-based rigid foam carbon comprises a glassy carbon form.
Carbon foam (also called carbon foam) is a material composed of amorphous carbon or graphite and having characteristics of high porosity, high specific surface area and the like; the biochar-based hard carbon foam has a loose and porous structure, and is biochar carbon foam taking chitosan biomass as a raw material. The porous carbon substrate synthesized by the method takes chitosan which is a renewable resource as a raw material, and the synthesis cost is low. In addition, the biochar foam carbon substrate reinforced by the Raynaud phenolic resin in the embodiment of the invention has a large specific surface area equivalent to that of a carbon felt, but the mechanical strength and the cycle service life of the biochar foam carbon substrate are far better than those of carbon paper, carbon felt and other materials.
In some embodiments of the present invention, the biochar-based rigid foam carbon substrate surface highly exhibits a low graphitization degree and a high atomic disorder, i.e. the surface carbon material is in the form of glassy carbon; the foam carbon has good conductivity, and has good mechanical strength and repeated use stability. In addition, the biochar-based rigid foam carbon substrate has much higher hydrophilicity than carbon paper (for example, the carbon substrate has an average water contact angle below 30 degrees), and has extremely high catalyst loading capacity.
The embodiment of the invention provides a catalyst, which takes the biochar-based hard foam carbon as a substrate, wherein non-noble metal catalytic active components are loaded on the substrate. In an embodiment of the invention, the non-noble metal catalytically active component is a layered double hydroxide composition.
The layered double-metal hydroxide hydrotalcite catalyst has the advantages of easily regulated active components, good conductivity of a layered ion structure, simple, safe and environment-friendly material synthesis and the like, and can be prepared by a solvent dispersion method, a coprecipitation method, a micelle hydrothermal assembly method, an ion exchange method and the like. The primary active role in the layered double hydroxide catalyst is the variable valence pair of trivalent cations (e.g., Fe)2+/Fe3+) Another metal element (e.g. Ni)2+) The hydrotalcite skeleton is formed, and the shape of the catalyst is maintained. The preparation method of the catalyst used in the embodiment of the invention is mature, the operation is simple and convenient, the prepared electrode material meets the requirements of low cost, easy preparation and high efficiency, and the high-efficiency selective catalytic oxidation of the 5-hydroxymethylfurfural can be realized under the conditions of normal temperature and normal pressure.
The embodiment of the invention relates to a preparation method of a hydrotalcite-based catalyst loaded with layered double hydroxide on a charcoal-based hard foam carbon substrate, which comprises the following specific steps:
(1) respectively preparing a certain proportion of catalytic active component (Fe)2+、Ni2+、Co2+Etc.) such as a nitrate solution, while adding 90mg of triethanolamine and 0.36g of urea, and stirring them uniformly;
(2) placing the biochar-based rigid foam carbon substrate prepared as before in a 50mL stainless steel hydrothermal reaction kettle
Then slowly moving the mixed solution in the step (1) into a kettle, and placing the kettle in a blast oven at 120 ℃ for hydrothermal treatment for 12 hours;
(3) after the hydrothermal treatment is finished, taking out the reaction kettle, and slowly cooling the reaction kettle to room temperature in the air;
(4) taking out the biochar-based hard foamy carbon material in the reaction kettle, washing the sediment attached to the surface of the biochar-based hard foamy carbon material with deionized water for three times, and washing for 10s each time;
(5) and drying the washed charcoal-based hard foamed carbon material in the shade to obtain the prepared charcoal-based hard foamed carbon substrate supported hydrotalcite-based catalyst (LDH @ CF electrode for short).
The layered double metal hydroxide catalyst (LDH catalyst) has the advantages of being rich in natural reserves, low in cost and easy to obtain, and active ingredients of the layered double metal hydroxide catalyst are non-noble metals. The metal element in the layered double hydroxide is preferably any two combinations of nickel (Ni), cobalt (Co), copper (Cu), iron (Fe), aluminum (Al), and gallium (Ga), for example, NiFe, NiCo, NiCu, NiAl, CuAl, CoAl, and the like.
Namely, the hydrotalcite-based catalyst material suitable for the invention comprises various layered double hydroxide catalysts such as NiFe-LDH, NiCo-LDH, NiAl-LDH, NiGa-LDH, CoFe-LDH, CoAl-LDH, CoGa-LDH, CuFe-LDH, CuAl-LDH and CuGa-LDH.
The loading method of the layered double-metal hydroxide catalyst mainly loads the layered double-metal hydroxide material on the foam carbon substrate through the hydrothermal reaction to be used as the working electrode, and is suitable for the catalytic electrode of the layered double-metal hydroxide catalyst loaded on the charcoal-based electrode, such as NiCo-LDH, NiAl-LDH, NiGa-LDH, CoFe-LDH, CoAl-LDH, CoGa-LDH, CuFe-LDH, CuAl-LDH, CuGa-LDH and the like, but is not limited to the above.
The layered double hydroxide components directly and orderly grow on the charcoal-based hard foam carbon substrate by a hydrothermal coprecipitation method; the synthesis method of the layered double-metal hydroxide catalyst is simple and easy to implement, and the finally prepared catalyst has a self-assembled layered structure, more catalytic active sites, extremely high catalytic site utilization rate and larger specific surface area.
The catalyst is applied to the oxidation reaction of 5-hydroxymethylfurfural, so that the 5-hydroxymethylfurfural is rapidly oxidized. The embodiment of the invention provides application of the catalyst in preparing 2,5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural.
The embodiment of the invention provides a method for preparing 2,5-furandicarboxylic acid by performing electrocatalytic oxidation on 5-hydroxymethylfurfural by an LDH @ CF electrode, wherein the electrochemical test at least comprises the following steps:
(1) the prepared catalyst is used as a working electrode of electrocatalytic reaction, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the electrocatalytic oxygen production performance of the LDH @ CF electrode is tested by using an alkaline solution (0.1MKOH, 0.1MNaOH, 0.05MK2CO3 and the like);
(2) using the electrocatalytic system described in (1), 5-hydroxymethylfurfural (5 mM-50 mM) was added to the electrolyte, testing the LDH @ CF electrode for its selective electrocatalytic oxidation performance;
(3) the time of the electrocatalytic oxidation reaction, the reaction potential, the electrode size, the electrolyte solute and the concentration of 5-hydroxymethylfurfural are changed, and the influence of the factors on the performance of the LDH @ CF electrode electrocatalytic oxidation of 5-hydroxymethylfurfural is tested.
In some embodiments of the invention, the concentration of 5-hydroxymethylfurfural is preferably 5mM to 50mM, and more preferably 5mM to 20 mM. The LDH @ CF electrode prepared by the embodiment of the invention can complete the high-selectivity oxidation of 5-hydroxymethylfurfural under the mild conditions of normal temperature and normal pressure, and the oxidation product is 2,5-furandicarboxylic acid.
The isolation of the 2,5-furandicarboxylic acid product described in the examples of the present invention comprises at least the following steps:
(1) converting the 5-hydroxymethylfurfural solution into 2,5-furandicarboxylic acid by using the electrochemical system, transferring the electrolyte into a beaker, and adjusting the pH of the solution to 5-7 by using hydrochloric acid;
(2) removing water, volatile organic impurities and hydrogen chloride from the solution after the pH adjustment in a heating evaporation mode until the solution is completely evaporated to dryness to obtain light yellow powder;
(3) adding deionized water with the volume of 5-7.5% of the original electrolyte into the beaker, and uniformly stirring to dissolve the electrolyte in the product;
(4) and filtering the product solution, and washing the yellow filter residue with deionized water for three times to obtain the prepared crude product of the 2,5-furandicarboxylic acid. The separation method of the 2,5-furandicarboxylic acid is simple and easy to implement, and the product purity is high.
The biochar-based hard foam carbon substrate-supported hydrotalcite-based catalyst disclosed by the embodiment of the invention shows excellent OER performance, and the product of electrocatalytic oxidation of 5-hydroxymethylfurfural at normal temperature and normal pressure is 2,5-furandicarboxylic acid. The biocarbon-based hard foam carbon substrate-supported hydrotalcite-based catalyst can quickly and selectively complete the oxidation of a target product, the conversion rate of the catalyst to 20mM 5-hydroxymethylfurfural can reach more than 97.5 percent within 12 hours, the selectivity of the target product 2,5-furandicarboxylic acid is more than 99.5 percent (up to 99.7 percent), and the purity of the product is more than 99 percent.
For further understanding of the present application, the biochar-based rigid carbon foam provided herein, its preparation method and its application in electrocatalysis are specifically described below with reference to examples. The raw materials used in the following examples of the present invention are all commercially available products; chitosan powder, Shanghai test, national medicine, Biochemical Reagent (BR).
Example 1
Synthesizing a chitosan-rasol phenolic resin pyrolytic foam carbon substrate:
3.3g of chitosan powder was dispersed in 50mL of water, and a small amount of acetic acid was added dropwise with stirring to dissolve the chitosan. Freeze-drying the obtained chitosan gel in a vacuum freeze-drying machine at the temperature of-80 ℃ for 96 hours, and cutting the obtained light chitosan aerogel into blocks of 2cm multiplied by 1 cm. 2.2g of rasol, 3g of formaldehyde solution and 5mg of sodium carbonate were dissolved in 2mL of water and ultrasonically mixed for 10min and added dropwise to the chitosan aerogel cake so that it was completely soaked with the solution. The soaked chitosan block is placed in a sealed environment and heated at 70 ℃ for 36h, and then transferred to a ventilated environment and continuously dried and heated at 70 ℃ for 12 h. Then heating the mixture to 950 ℃ at the temperature of 2.5 ℃/min in the nitrogen atmosphere, and maintaining the temperature for 6 hours; and (3) performing ultrasonic treatment on the pyrolyzed chitosan carbon block in deionized water for 30min to obtain the prepared charcoal-based hard foam carbon substrate (substrate 1 for short).
Comparative example 1
Synthesis of a chitosan pyrolytic foam carbon substrate:
3.3g of chitosan powder was dispersed in 50mL of water, and a small amount of acetic acid was added dropwise with stirring to dissolve the chitosan. Freeze-drying the obtained chitosan gel in a vacuum freeze-drying machine at the temperature of-80 ℃ for 96 hours, and cutting the obtained light chitosan aerogel into blocks of 2cm multiplied by 1 cm. The dried chitosan cake was heated at 70 ℃ for 36h in a sealed environment, after which it was transferred to a ventilated environment and further heated at 70 ℃ for 12 h. And then heating the substrate to 950 ℃ at the temperature of 2.5 ℃/min in the nitrogen atmosphere, maintaining for 6 hours, and cooling to obtain the prepared chitosan pyrolytic foam carbon substrate (substrate 2 for short).
Comparative example 2
2.2g of rasol, 3g of formaldehyde solution and 5mg of sodium carbonate are dissolved in 2mL of water and ultrasonically mixed for 10min, and transferred to a mold. The mold filled with the resin solution is placed in a sealed environment and heated at 70 ℃ for 36h, and then the mold is transferred to a ventilated environment and dried and heated at 70 ℃ for 12 h. And then heating the cured resin to 950 ℃ at the temperature of 2.5 ℃/min in the nitrogen atmosphere, maintaining for 6 hours, and cooling to obtain the prepared glassy carbon substrate (substrate 3 for short).
Substrate 1, substrate 2, substrate 3 and a carbon felt cut to 2cm × 2cm × 0.6cm were soaked in 50mL beakers containing 1m koh solution, respectively, and placed in a large ultrasonic cleaner (model AS20500A) for 24h by pulse sonication.
After the ultrasonic treatment is finished, the substrate 1 in the beaker is not obviously cracked and dropped, and partial black suspended matters exist in the solution; more than half of the material of the substrate 2 is broken off; the substrate 3 is broken into two pieces according to an irregular crack, and simultaneously, a large amount of black suspended matters exist in the solution; a large amount of carbon fibers are separated from the surface of the carbon felt, particularly the shearing surface, and a part of flocculent precipitates are generated. From the results of the ultrasonic treatment, the substrate 1 has the best resistance to external mechanical damage and the best mechanical stability with respect to the comparative example.
FIGS. 1 and 2 are XRD and Raman spectrum characterization results of scraping debris on the surface of a synthetic biochar-based rigid foam carbon substrate in example 1; which highly exhibits a low degree of graphitization and a high degree of atomic disorder. FIG. 3 is an SEM micrograph of chips with very smooth fractured surfaces. These properties are well consistent with those of glassy carbon, indicating that the carbon material is present in the form of glassy carbon on the surface of the charcoal-based rigid foam carbon substrate.
Fig. 4 and 5 are photographs showing experimental results of water contact angle tests of the prepared substrate 3 and a plain carbon paper, respectively; it can be seen that the substrate 3, which is also glassy carbon, has a much higher hydrophilicity than the carbon paper, and the average water contact angles of the carbon substrates are all below 30 °. Because the subsequent hydrotalcite material is loaded by hydrothermal assembly, and the high hydrophilicity means that the subsequent hydrotalcite material has stronger affinity and catalytic assembly capacity to the catalyst, the biochar-based rigid foam carbon substrate prepared by the invention has great catalyst loading capacity.
Example 2
Loading of hydrotalcite-based catalytically active component:
60mg of FeCl was taken2·5H2O、262mg Ni(NO3)2·6H2O is dissolved in 30mL of deionized water, and 90mg of triethanolamine and 0.36g of urea are added simultaneously and stirred uniformly. The charcoal-based rigid carbon foam substrate prepared in the previous example 1 was placed in a 50mL stainless steel hydrothermal reaction vessel
And (3) slowly moving the mixed solution into the kettle in the inner lining, and performing hydrothermal treatment in a blast oven at 120 ℃ for 12 hours. After the water is heated, the reaction kettle is taken out and placed in the air to be slowly cooled to the room temperature. And after cooling, taking out the biochar-based hard foam carbon electrode in the reaction kettle, and washing the sediment attached to the surface of the biochar-based hard foam carbon electrode for three times by using deionized water, wherein each time of washing is 10 seconds. And drying the obtained product in the shade after washing to obtain the prepared biochar-based hard foam carbon substrate-supported hydrotalcite-based catalyst electrode (NiFe catalytic electrode).
FIG. 6 is a partial Scanning Electron Microscope (SEM) photograph of a NiFe catalytic electrode of example 2; the needle-shaped hydrotalcite nanosheets longitudinally grow on the surface of the charcoal-based foamy carbon material and are tightly overlapped to form a compact catalytic layer. In the figure, white granular objects are aggregated nanoflowers formed by a small amount of overflowing hydrotalcite nanosheets, and have no influence on the performance of the material.
FIG. 7 is a partial SEM micrograph of a NiFe catalytic electrode prepared in example 2; hydrotalcite nano-sheets growing on the biochar foam carbon substrate are longitudinally and densely arranged, and the loading capacity of the catalyst is far higher than that of common carbon paper.
And (3) testing the performance of producing oxygen by electrocatalysis water decomposition:
to investigate the OER performance of the catalyst material, tests were performed with a three-electrode system using a CHI-660C electrochemical workstation. The synthesized charcoal-based hard foam carbon substrate-supported hydrotalcite-based catalyst is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the electrolyte is 0.1MKOH solution.
To facilitate the comparison of OER catalytic performance, the reference potential measured was converted to the reversible hydrogen electrode potential, E, according to the following formulaRHE＝EHg/HgO+0.059*pH+E0 Hg/HgO. Before testing the electrocatalytic oxygen production performance, 20 cycles of cyclic voltammetry scanning pretreatment are carried out, so that the electrode reaches a stable state, and the scanning speed is 25 mV/s. After stabilization, the electrode was scanned polarographically at a scan rate of 1mV/s over a scan range of 0 to 1.0V (vs. Hg/HgO reference electrode). It was found that example 2 had a current density of 10mA/cm2The electrocatalytic oxygen generation over-potential is about 370mV, the Tafel slope is about 46.3mV/dec, and the charge transfer resistance is 4.13 Ω. (generally, the lower the charge transfer resistance, the better the effect of loading the active component)
Example 3:
the NiFe catalytic electrode manufactured in example 2 was used.
And 5-testing the electrochemical performance of the electrocatalytic oxidation of the hydroxymethylfurfural:
to investigate the OER performance of the catalyst material, tests were performed with a three-electrode system using a CHI-660C electrochemical workstation. The synthesized biochar-based hard foam carbon substrate-supported hydrotalcite-based catalyst is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the used electrolyte is a mixed solution of 0.1MKOH and 10mM 5-hydroxymethylfurfural.
In order to compare the OER catalytic performance conveniently, the reference potential of the test is converted into the potential of the reversible hydrogen electrode. Before testing the electrocatalytic oxygen production performance, 20 cycles of cyclic voltammetric sweep pretreatment were performed at a sweep rate of 25 mV/s. After stabilization, the electrode was scanned polarographically at a scan rate of 1mV/s over a scan range of 0 to 1.0V (vs. Hg/HgO reference electrode). It was found that example 2 had a current density of 10mA/cm2The electrocatalytic oxygen generation over-potential is about 390mV, the Tafel slope is about 75.3mV/dec, and the charge transfer resistance is 4.34 Ω.
10mM 5-hydroxymethylfurfural electrocatalytic oxidation performance test:
the test was performed by a three-electrode system using the CHI-660C electrochemical workstation. The synthesized biochar-based hard foam carbon substrate-supported hydrotalcite-based catalyst is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the used electrolyte is a mixed solution of 0.1MKOH and 10mM 5-hydroxymethylfurfural.
The potentiostatic reaction potential was set at 0.85V (relative to the Hg/HgO reference electrode) and the reaction duration was accumulated at 0 point of the reaction at this time. Finally, analysis of the sample using HPLC gave a conversion of 5-hydroxymethylfurfural and a yield of 2,5-furandicarboxylic acid. The conversion rate of 5-hydroxymethylfurfural and 2,5-furandicarboxylic acid is continuously increased along with the increase of time, when the reaction is carried out for 3 hours, the conversion rate of 5-hydroxymethylfurfural is 75 percent, and the yield of 2,5-furandicarboxylic acid is 62 percent; when the reaction is carried out for 6 hours, the conversion rate of 5-hydroxymethylfurfural is 95 percent, and the yield of 2,5-furandicarboxylic acid is 70 percent.
In addition, the application compares the electrocatalytic oxidation performance of the NiFe catalytic electrode of example 2 with other types of hydrotalcite-based catalysts on 5-hydroxymethylfurfural. Wherein the concentration of the 5-hydroxymethylfurfural is 10 mM; the same surface area of the foamed carbon substrate is used for loading the binary LDH material with different components, and the electrocatalytic oxidation is carried out on 5-hydroxymethylfurfural with the concentration of 10mM under the same reaction condition and voltage. Different catalysts were prepared by using a carbon foam electrode substrate having the same size as that of example 2, and synthesizing hydrotalcite-based catalysts having different compositions (e.g., NiCo, NiCu, etc.) by changing the metal salt composition added in the hydrothermal treatment in example 2. Other properties, except for the difference in the supported active ingredient, were consistent with the catalytic electrode in example 2.
The concentrations of 5-hydroxymethylfurfural and product 2,5-furandicarboxylic acid in the solution after three hours of reaction were selected and the resulting yield of 5-hydroxymethylfurfural (HMF conversion/%) and 2,5-furandicarboxylic acid selectivity (FDCA selectivity/%) were calculated.
See table 1 for results; among them, the LDH with the NiFe binary component has the best 5-hydroxymethylfurfural yield and 2,5-furandicarboxylic acid selectivity, so the nickel-iron binary LDH material is preferred in the application.
TABLE 1 Performance of different LDH catalysts
Example 4:
electrocatalytic oxidation of 20mM 5-hydroxymethylfurfural was performed using the NiFe catalytic electrode prepared in example 2.
The test was performed by a three-electrode system using the CHI-660C electrochemical workstation. The synthesized charcoal-based hard foam carbon substrate-supported hydrotalcite-based catalyst is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the used electrolyte is a mixed solution of 0.1MKOH and 20mM 5-hydroxymethylfurfural.
The potentiostatic reaction potential was set at 0.85V (relative to the Hg/HgO reference electrode) and the reaction duration was accumulated at 0 point of the reaction at this time. Finally, analysis of the sample using HPLC gave a conversion of 5-hydroxymethylfurfural and a yield of 2,5-furandicarboxylic acid. The conversion of 5-hydroxymethylfurfural and 2,5-furandicarboxylic acid increased continuously with time, and when the reaction proceeded for up to 12 hours, the conversion of 5-hydroxymethylfurfural was 90% and the yield of 2,5-furandicarboxylic acid was 50%.
Wherein, the concentration of the 5-hydroxy furfural is improved by 2 times, and the total reaction time is also improved. Therefore, the synthesized biochar-based carbon foam catalytic electrode has good durability and stability.
Example 5:
synthesizing a chitosan-rasol phenolic resin pyrolytic foam carbon substrate:
3.3g of chitosan powder was dispersed in 50mL of water, and a small amount of acetic acid was added dropwise with stirring to dissolve the chitosan. Freeze-drying the obtained chitosan gel in a vacuum freeze-drying machine at the temperature of-80 ℃ for 96 hours, and cutting the obtained light chitosan aerogel into blocks of 5cm multiplied by 1 cm. 2.2g of rasol, 3g of formaldehyde solution and 5mg of sodium carbonate were dissolved in 2mL of water and ultrasonically mixed for 10min and added dropwise to the chitosan aerogel cake so that it was completely soaked with the solution. The soaked chitosan block is placed in a sealed environment and heated at 70 ℃ for 36h, and then transferred to a ventilated environment and continuously dried and heated at 70 ℃ for 12 h. Then heating the mixture to 950 ℃ at the temperature of 2.5 ℃/min in the nitrogen atmosphere, and maintaining the temperature for 6 hours; and (3) carrying out ultrasonic treatment on the pyrolyzed chitosan carbon block in deionized water for 30min to obtain the prepared charcoal-based hard foam carbon substrate.
The sizes of the synthesized biochar foam carbon electrode substrates are different, and the electrode substrates have good adjustability and practical application capability.
Loading of hydrotalcite-based catalyst:
60mg of FeCl was taken2·5H2O、262mg Ni(NO3)2·6H2O is dissolved in 30mL of deionized water, and 90mg of triethanolamine and 0.36g of urea are added simultaneously and stirred uniformly. Placing the biochar-based rigid foam carbon substrate prepared in the previous step in a 50mL stainless steel hydrothermal reaction kettle
And (3) slowly moving the mixed solution into the kettle in the inner lining, and performing hydrothermal treatment in a blast oven at 120 ℃ for 12 hours. After the water is heated, the reaction kettle is taken out and placed in the air to be slowly cooled to the room temperature. And after cooling, taking out the biochar-based hard foam carbon electrode in the reaction kettle, and washing the sediment attached to the surface of the biochar-based hard foam carbon electrode for three times by using deionized water, wherein each time of washing is 10 seconds. And drying the obtained product in the shade after washing to obtain the prepared biochar-based hard foam carbon substrate-supported hydrotalcite-based catalyst electrode (NiFe catalytic electrode).
20mM 5-hydroxymethylfurfural electrocatalytic oxidation performance test:
the test was performed by a three-electrode system using the CHI-660C electrochemical workstation. The synthesized charcoal-based hard foam carbon substrate-supported hydrotalcite-based catalyst is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the used electrolyte is a mixed solution of 0.1MKOH and 20mM 5-hydroxymethylfurfural.
The potentiostatic reaction potential was set at 0.85V (relative to the Hg/HgO reference electrode) and the reaction duration was accumulated at 0 point of the reaction at this time. Finally, analysis of the sample using HPLC gave a conversion of 5-hydroxymethylfurfural and a yield of 2,5-furandicarboxylic acid. The conversion of 5-hydroxymethylfurfural and 2,5-furandicarboxylic acid increased continuously with time, and when the reaction proceeded for 12 hours, the conversion of 5-hydroxymethylfurfural was 99.9% and the yield of 2,5-furandicarboxylic acid was 97%.
FIG. 8 shows the Reaction time (Reaction time/h) of the NiFe catalytic electrode in example 5 with respect to the electrocatalytic oxidation of 5-hydroxymethylfurfural, and the Concentration of the reactants and the Concentration of the products (Concentration/mM) varied. Wherein the electrolyte is 20mM 5-hydroxymethylfurfural and 0.1 MKOH. As the reaction proceeds, 5-hydroxymethylfurfural in the solution is gradually converted into 2,5-furandicarboxylic acid while almost no side reaction occurs. Therefore, the biochar-based carbon foam catalytic electrode can effectively oxidize 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid with high efficiency and high selectivity.
Example 6:
using the NiFe catalytic electrode prepared in example 5, 50mM 5-hydroxymethylfurfural was electrocatalytically oxidized to 2,5-furandicarboxylic acid, and product isolation and purification were performed:
the test was performed by a three-electrode system using the CHI-660C electrochemical workstation. The synthesized biochar-based hard foam carbon substrate-supported hydrotalcite-based catalyst is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the used electrolyte is a mixed solution of 0.1MKOH and 50mM 5-hydroxymethylfurfural.
Setting 0.85V (relative to Hg/HgO reference electrode) as a potentiostatic reaction potential, and accumulating the reaction time length by taking the moment as a reaction 0 point for 24 hours in total. After the reaction, the electrolyte was transferred to a beaker and the pH of the solution was adjusted to 6 using hydrochloric acid. The solution was then freed of water, volatile organic impurities and hydrogen chloride using a rotary evaporator at 90 ℃ and a pressure of about-0.09 MPa until complete evaporation to dryness to give a pale yellow powder. 5mL of deionized water was added to the beaker and stirred to dissolve the electrolyte in the product. And filtering the solution, and washing the yellow filter residue with deionized water for three times to obtain the prepared crude product of the 2,5-furandicarboxylic acid. The purity of the 2,5-furandicarboxylic acid product was determined by NMR and HPLC to be about 99.5%.
Example 7:
the charcoal-based carbon foamy rigid substrate manufactured in example 1 was used.
And (3) testing the performance of producing oxygen by electrocatalysis water decomposition:
to compare the OER performance of the carbon foam substrate, tests were performed with a three-electrode system using a CHI-660C electrochemical workstation. The synthesized biochar-based hard foam carbon substrate is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the electrolyte is 0.1MKOH solution.
In order to compare the OER catalytic performance conveniently, the reference potential of the test is converted into the potential of the reversible hydrogen electrode. Before testing the electrocatalytic oxygen production performance, 20 cycles of cyclic voltammetry scanning pretreatment are carried out, so that the electrode reaches a stable state, and the scanning speed is 25 mV/s. After stabilization, the electrode was scanned polarographically at a scan rate of 1mV/s over a scan range of 0 to 1.0V (vs. Hg/HgO reference electrode). It was found that example 1 had a current density of 10mA/cm2The electrocatalytic oxygen generation over-potential is more than 500mV, the Tafel slope is about 246mV/dec, and the charge transfer resistance is 2.47 omega.
To compare the OER performance of the carbon foam substrate, tests were performed with a three-electrode system using a CHI-660C electrochemical workstation. The synthesized biochar-based hard foam carbon substrate is directly used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and the electrolyte is a mixed solution of 0.1MKOH and 10mM 5-hydroxymethylfurfural.
In order to compare the OER catalytic performance conveniently, the reference potential of the test is converted into the potential of the reversible hydrogen electrode. Before testing the electrocatalytic oxygen production performance, 20 cycles of cyclic voltammetry scanning pretreatment are carried out, so that the electrode reaches a stable state, and the scanning speed is 25 mV/s. After stabilization, the electrode was scanned polarographically at a scan rate of 1mV/s over a scan range of 0 to 1.0V (vs. Hg/HgO reference electrode). It was found that example 1 had a current density of 10mA/cm2The electrocatalytic oxygen generation over-potential is more than 500mV, the Tafel slope is about 297mV/dec, and the charge transfer resistance is 3.55 omega.
By comparing the data, the catalysis and promotion effects of the hydrotalcite base on the reaction can be embodied.
Example 8:
the substrate 2 prepared in comparative example 1 was loaded with a hydrotalcite-based catalyst in the same manner as in example 2 to obtain a glassy carbon catalytic electrode (electrode 1 for short). The experiment of the electrode 1 and the catalytic electrode prepared in example 2 (referred to simply as the electrode 2) was repeated in accordance with the experimental method of electrocatalytic oxidation of 5-hydroxymethylfurfural in example 2.
FIG. 9 is a Scanning Electron Microscope (SEM) micrograph of a NiFe-catalyzed electrode of example 2, and FIG. 10 is a Scanning Electron Microscope (SEM) micrograph of electrode 1 of example 8 (showing substantial exfoliation after multiple reactions). Compared with a smooth surface, the rough surface of the foam carbon can provide larger specific surface area, and the hydrotalcite catalyst layer on the foam carbon is in a shape of a curled fold, so that the specific surface area and the catalytic loading sites are further improved.
After five experiments, electrode 2 had no significant exfoliation compared to the original except for the yellow color of the surface hydrotalcite catalyst converted to the oxidized state (very little exfoliation could be observed under SEM micrographs). The catalyst layer on the electrode 1 was completely peeled off at the edge corner portion except for the catalyst layer at the center portion. This indicates that the excessively smooth glassy carbon material is not favorable for adhesion and stabilization of the surface hydrotalcite catalyst.
From the above examples, it can be seen that the hydrotalcite-based catalyst supported on the charcoal-based rigid foam carbon substrate according to the embodiment of the present invention has the characteristics of cheap and easily available active components and wide natural reserves, and the active components are non-noble metals. In the embodiment of the invention, the preferable layered double-metal hydroxide hydrotalcite component uniformly and orderly grows on the prepared biochar-based foam carbon substrate, and has a regular layered structure, a larger specific surface area and more reaction catalytic sites. The biocarbon-based hard foam carbon substrate-supported hydrotalcite-based catalyst synthesized by the embodiment of the invention has the advantages of high OER activity, high current density, low overpotential and good cycle stability. In addition, the embodiment of the invention uses a hydrothermal coprecipitation method to load the layered double hydroxide catalytic active component, and the synthesis method is simple and easy to implement and consumes less energy.
In a preferred embodiment of the invention, the layered double hydroxide shows excellent electrocatalytic oxidation performance on 5-hydroxymethylfurfural, and can rapidly and selectively complete the oxidation of a target product. The catalyst synthesized by the embodiment of the invention has mild reaction conditions for electrocatalytic oxidation of 5-hydroxymethylfurfural, can complete selective oxidation of 5-hydroxymethylfurfural in a short time under the mild conditions of normal temperature and normal pressure, and shows excellent electrochemical oxygen production performance and selective oxidation performance of 5-hydroxymethylfurfural. Experiments show that the product of the catalyst synthesized in the embodiment of the invention for electrocatalytic oxidation of 5-hydroxymethylfurfural is 2,5-furandicarboxylic acid, the conversion rate of reactants is above 97%, the selectivity of a target product is above 99.5%, and the purity of the product is above 99%, so that a proper method and a proper thought are provided for further conversion of biomass compound resources.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the biochar-based rigid carbon foam is characterized by comprising the following steps of:
s1, providing chitosan aerogel;
s2, compounding the chitosan aerogel with phenolic resin, and then performing pyrolysis in an inert gas atmosphere to obtain biochar-based rigid foam carbon containing glassy carbon.
2. The method for preparing the biochar-based rigid foam carbon according to claim 1, wherein the chitosan aerogel is prepared by performing sol-gel and freeze drying on chitosan;
the chitosan aerogel and phenolic resin composite concrete comprises: dissolving phenols, formaldehyde and an alkaline catalyst in water to obtain a solution containing phenolic resin, and enabling the solution to permeate the chitosan aerogel; heating the soaked chitosan aerogel at a temperature below 100 ℃.
3. The method for preparing biochar-based rigid foamy carbon according to claim 2, characterized in that after the heating is completed, the composite precursor substance is heated at 900-1000 ℃ in an inert gas atmosphere for pyrolysis to obtain biochar-based rigid foamy carbon containing glassy carbon.
4. A biochar-based rigid carbon foam prepared by the preparation method of any one of claims 1 to 3, wherein the surface carbon material comprises a glassy carbon form.
5. A catalyst, which takes the biochar-based rigid foam carbon as claimed in claim 4 as a substrate, and a non-noble metal catalytic active component is loaded on the substrate.
6. The catalyst of claim 5 wherein the non-noble metal catalytically active component is a layered double hydroxide composition; the metal element in the layered double hydroxide is preferably any two combinations of Ni, Co, Cu, Fe, Al and Ga.
7. The catalyst according to claim 6, wherein the layered double hydroxide component is directly and orderly grown on the biochar-based rigid foam carbon substrate through hydrothermal treatment and has a regular layered structure.
8. Use of a catalyst according to any one of claims 5 to 7 in the electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid.
9. The use according to claim 8, wherein the preparation of 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural is carried out under normal temperature and pressure conditions.
10. The use according to claim 9, wherein the electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid uses the catalyst as a working electrode; the concentration of the 5-hydroxymethylfurfural is preferably 5-50 mM.
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