CN116272942A - Method for functionalizing biomass tar derived carbon-based material - Google Patents
Method for functionalizing biomass tar derived carbon-based material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
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- 125000000524 functional group Chemical group 0.000 claims abstract description 28
- 238000011068 loading method Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
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- 239000000126 substance Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000007306 functionalization reaction Methods 0.000 claims description 18
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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Abstract
The invention discloses a method for functionalizing a biomass tar derived carbon-based material, which takes biomass tar derived carbon as a carbon-based material, selects a mild functionalizing agent which is non-corrosive and does not generate hazardous waste, and aims at the application of the biomass tar derived carbon-based material in the catalysis field, adopts different types and concentrations of the functionalizing agent to introduce and treat functional sites such as loading, grafting and the like, thereby realizing uniform high-loading and proportion regulation and control of specific functional sites such as metal, acid-base sites, functional groups and the like, and finishing modification of the biomass tar derived carbon-based material.
Description
Technical Field
The invention relates to the technical field of biomass tar utilization and carbon material preparation, in particular to a method for functionalizing a biomass tar derived carbon-based material, which is a method for loading metal and/or grafted functional groups on the biomass tar derived carbon material.
Background
During gasification of biomass, cellulose, hemicellulose and lignin in biomass can thermally decompose to produce biomass tar. Biomass tar is a complex compound composed of aromatic hydrocarbons and their derivatives and polycyclic aromatic hydrocarbons, and the analyzable components reach over 100, and many components are difficult to determine. The difficulty of biomass tar treatment is one of the decisive factors for restricting the commercialization development of biomass gasification technology. The biomass tar has the characteristics of being rich in carbon elements and aromatic groups, and can be used as a carbon source of various carbon nano materials to selectively synthesize the carbon materials with different morphologies and structures. The thinking of preparing carbon nanomaterial from biomass tar can be broadly divided into solid-solid and solid-gas-solid. The common methods include: pyrolysis, chemical Vapor Deposition (CVD), cyclic oxidation, mechanical activation, combustion, and the like. Aiming at the physicochemical properties of biomass tar, the biomass tar is converted into carbon materials with different morphology and properties, so that the method is not only a new high-added-value application way of biomass tar, but also a treatment method which is efficient, clean, economical, simple in process and capable of keeping the energy and properties of the tar is provided.
Carbon materials, particularly Porous Carbon (PC), carbon Nanotubes (CNT), carbon Nanofibers (CNF) and graphene, have excellent properties such as wide applicability, stable acid and alkali resistance, and excellent adsorption properties, and thus find important applications in the fields of energy, environment, catalysis, and the like. However, most of the raw materials for preparing the carbon nanomaterial are derived from non-renewable fossil fuels such as methane, ethylene, benzene, etc., which limits the sustainable development of the carbon nanomaterial to some extent and causes environmental and resource problems. Accordingly, researchers have focused their attention on obtaining high value carbon materials from renewable and widely available biomass energy sources. In recent years, a series of biomass-derived carbon materials, which take monosaccharides such as glucose, fructose and the like as carbon sources, lignin and cellulose materials, and real biomass and wastes thereof as carbon precursors and the like, are successfully substituted for fossil-based carbon materials in various fields.
Compared with other conventional carbon materials, the biomass tar derived carbon material has incomparable advantages of wide raw material sources, low price, controllable functions, structures and morphology, and the like, and has great development potential. However, the original carbon material has the defects of strong surface chemical inertia, poor wettability and the like, and cannot meet the application requirements generally, so that the further development of the original carbon material is limited. Functional modification or modification is needed to further improve the physical and chemical properties of the carbon material and widen the application range of the carbon material.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention aims to provide a method for functionalizing a biomass tar derived carbon-based material, which comprises the steps of loading metal particles and grafting functional groups on the carbon material. The biomass tar derived carbon is used as a carbon-based material, and different kinds and concentrations of functional reagents are adopted to carry out loading, grafting and other functional site introduction treatment aiming at different target reactions, so that the functionalization of the carbon material is realized. The method can obviously increase the active sites on the surface of the primary carbon material and regulate the acidity and alkalinity of the primary carbon material. Meanwhile, compared with concentrated sulfuric acid, fuming sulfuric acid and the like, the invention uses a mild acid-base functionalization reagent, and has the advantages of simple operation, no corrosiveness, high safety, no generation of hazardous waste and the like.
The aim of the invention is achieved by the following technical scheme:
a method for functionalizing biomass tar derived carbon-based materials, comprising metal loading and/or functional group grafting;
the method for loading metal comprises the following steps:
step (1): mixing a biomass tar derived carbon-based material with an activator, dropwise adding a carboxylic acid reagent to adjust the pH of the solution to be acidic, stirring uniformly, repeatedly filtering with deionized water until the filtrate is neutral, and vacuum drying the washed product; wherein the dosage ratio of the biomass tar derived carbon-based material to the activator is 1g: 30-60 ml;
step (2): under the condition of auxiliary reagent or no auxiliary reagent, mixing a metal compound or a metalloid compound capable of forming covalent bonds and/or ionic bonds with functional groups on the activated carbon-based material with the activated biomass tar derived carbon-based material in the step (1), continuously and uniformly stirring, filtering and washing; wherein the mass ratio of the biomass tar derived carbon-based material to the metal compound or metalloid compound is 1:0.01 to 0.3; if auxiliary reagents are used, the ratio of the metal compound or metalloid compound to the auxiliary reagent is 1g: 2-10 ml.
Step (3): transferring the solid washed in the step (2) into a quartz boat, placing the quartz boat into a tube furnace filled with hydrogen and/or nitrogen for calcination for 4-8 hours, cooling, taking out the dried solid substances, grinding and sieving, and placing the solid substances in a dryer for storage to obtain the biomass tar derived carbon-based material loaded with metal;
the method for grafting the functional group comprises the following steps:
step (1): mixing a biomass tar derived carbon-based material with an activator, slowly dropwise adding a carboxylic acid reagent to adjust the pH of the solution to be acidic, stirring uniformly, repeatedly filtering with deionized water until the filtrate is neutral, and vacuum drying the washed product; wherein the dosage ratio of the biomass tar derived carbon-based material to the activator is 1g: 30-60 ml;
step (2): uniformly mixing the product obtained in the step (1) with an acid-base functionalization reagent, and evaporating water to obtain viscous or colloidal liquid; wherein the dosage mass ratio of the product to the acid-base functionalization reagent is 1:5 to 15;
step (3): transferring the viscous or colloidal liquid obtained in the step (2) into a quartz boat, placing the quartz boat into a tube furnace protected by nitrogen for calcining for 2-6 hours, cooling, taking out the dried solid substance, grinding and sieving, and placing the solid substance into a dryer for storage to obtain the biomass tar-derived carbon-based material with the surface grafted with the functional groups.
The biomass tar derived carbon-based material in the metal loading method is one of biomass tar derived activated carbon, carbon black, carbon nanotubes, three-dimensional carbon molecular sieves, carbon spheres, two-dimensional ordered porous carbon and nitrogen doped carbon.
The biomass tar derived carbon-based material in the functional group grafting method is biomass tar derived activated carbon, carbon black, carbon nanotubes, three-dimensional carbon molecular sieves, carbon spheres, two-dimensional ordered porous carbon, nitrogen doped carbon and metal loaded biomass tar derived carbon-based material prepared in the metal loaded method.
The activating agent in the metal loading method and the functional group grafting method is one or more of hydrogen peroxide, potassium permanganate and sodium hypochlorite, and can enable the surface of the biomass tar derived carbon-based material to have more defect sites, so that more active groups are loaded, the connection stability of the biomass tar derived carbon-based material with hydroxyl and carboxyl is enhanced through polarity and electronegativity, and the service life of the material is prolonged.
The carboxylic acid in the metal loading method and the functional group grafting method is one or any combination of hydroxycarboxylic acid and dicarboxylic acid, and the carboxylic acid reagent is used for increasing oxygen-containing functional groups on the surface of the biomass tar-derived carbon-based material and providing oxygen anchor points for further functional group grafting.
The auxiliary reagent can dissociate H in aqueous solution + One or a combination of agents having a hydrolytic action.
The metal loading method is to form nano particles of one or a combination of metal, metal oxide, metalloid and metalloid oxide on a carbon material, wherein the metal is one or any combination of chemically active metals.
The acid-base functionalization reagent is a reagent capable of generating an acid-base functional group, and is specifically one of a sulfonation reagent, a phosphorylation reagent and a heteropolyacid; the acid-base functionalization reagent has the function of regulating and controlling physical or chemical properties of the surface of the material, so that the functionalization of the carbon material is realized; the product and the acid-base functionalization reagent are uniformly mixed in a mechanical mixing mode, an ultrasonic mixing mode or a constant-temperature water bath oscillating mode.
The evaporation of the water is carried out by heating at 80-90 c for a suitable time using a rotary evaporator or a drying oven.
The calcination in the metal loading method and the functional group grafting method is carried out at a temperature lower than the thermal decomposition temperature of the biomass tar derived carbon-based material, and the heating rate is 1-3 ℃/min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention takes cheap biomass tar derived carbon as a carbon-based material, and utilizes a chemical activation method, a metal impregnation method and a grafting functional group to combine, and introduces metal active sites on the surface of the inert biomass tar derived carbon material, thereby increasing the surface functionality and regulating the acidity and alkalinity of the material. The preparation process is simple, the cost is low, a novel method for high-value utilization is provided for the existing waste biomass tar by using a mild functionalization reagent which is non-corrosive and does not generate hazardous waste, such as p-toluenesulfonic acid, and a novel technology for further optimizing the chemical property of the carbon material is provided.
(2) According to the invention, biomass tar derived carbon is used as a carbon-based material, and functional agents with different types and concentrations are adopted to introduce and treat functional sites such as loading, grafting and the like aiming at the application of the biomass tar derived carbon material in the catalysis field, so that uniform high-loading and proportion regulation of specific functional sites such as metal, acid-base sites, functional groups and the like are realized, and the functionalization of the carbon material is completed.
Drawings
Fig. 1 and 2 are an XRD pattern and a scanning electron microscope pattern, respectively, of a functionalized biomass tar-derived carbon material prepared according to an embodiment of the present invention.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof.
Example 1
The embodiment relates to a method for functionalizing a biomass tar derived carbon material, which adopts a metal loading method and comprises the following steps:
(1) Slowly adding 1g of biomass tar derived porous carbon into 3 with stirring0ml H 2 O 2 (30 wt%) was then added dropwise to the solution to adjust the pH of the solution to 3, stirring was continued for 12h and then repeatedly rinsed with deionized water until the filtrate became neutral. The washed solid was placed in a drying oven and dried in vacuo at 80℃for 8h.
(2) The product obtained in the step (1) and the metalloid compound aluminum isopropoxide and tetraisopropyl titanate are respectively mixed according to the mass ratio of 1:0.1: 0.1: 0:0.1 and 1:0.06:0.04 is dissolved in 10ml deionized water, 0.2ml HCl is added to assist the hydrolysis of the metalloid compound, and after stirring for 12 hours, the mixture is repeatedly filtered with ethanol and deionized water.
(3) Transferring the solid washed in the step (2) into a quartz boat, and placing the quartz boat into a tube furnace filled with nitrogen to be calcined for 4 hours at 400 ℃, wherein the heating rate is 2 ℃/min. The metal oxide particles stabilized on the surface of the carbon material are acted on by the method. And naturally cooling to room temperature, taking out the dried solid substance, transferring the solid substance into a mortar, grinding, sieving, and storing in a dryer. The bio-tar derived carbon-based solid acid loaded with Al, ti and Al-Ti bimetallic can be obtained.
Fig. 1 is an XRD pattern of example 1, and from fig. 1, the type of metal oxide supported on a series of functionalized biomass tar-derived porous carbons prepared in accordance with the present invention can be clearly seen.
Example 2
The embodiment relates to a method for functionalizing a biomass tar derived carbon material, which adopts a method of grafting functional groups, and comprises the following steps:
(1) Slowly adding 1g of biomass tar derived porous carbon into 30ml of H under stirring 2 O 2 (30 wt%) was added dropwise to the solution, followed by adjusting the pH of the solution to 2 by malonic acid, stirring was continued for 12h and then repeated rinsing with deionized water until the filtrate became neutral. The washed solid was placed in a drying oven and dried in vacuo at 80℃for 8h.
(2) 1g of the solid obtained in the step (1) and 5g of acid-base functionalization reagent p-toluenesulfonic acid are dissolved in deionized water, and the mixture is placed in an ultrasonic mixer for ultrasonic treatment for 30min. The solution was transferred to a rotary evaporator and excess water was evaporated at 80 ℃ to give a viscous liquid.
(3) Transferring the liquid obtained in the step (3) into a quartz boat, placing the quartz boat into a tube furnace, and calcining the quartz boat for 4 hours at 250 ℃ under the nitrogen atmosphere, wherein the heating rate is 1 ℃/min. And naturally cooling to room temperature, taking out the dried solid substance, transferring the solid substance into a mortar, grinding, sieving, and storing in a dryer. The biomass tar carbon-based solid acid grafted by the benzenesulfonic acid group can be obtained.
Fig. 2 is a scanning electron microscope image of example 2, and it can be clearly seen from fig. 2 that p-toluenesulfonic acid sulfonated biomass tar derived porous carbon prepared by the present invention has a three-dimensional cross-linked pore morphology.
Example 3
The method for functionalizing the biomass tar derived carbon material comprises the following steps of:
(1) 1g of biomass tar derived porous carbon is slowly stirred into 60ml of potassium permanganate solution, acetic acid is added dropwise to adjust the pH of the solution to 3, stirring is continued for 12 hours, and deionized water is used for repeatedly flushing until the filtrate becomes neutral. The washed solid was placed in a drying oven and dried in vacuo at 80℃for 8h.
(2) Mixing the product obtained in the step (1) with a metalloid compound chloroplatinic acid hexahydrate according to the mass ratio of 1:0.06 was dissolved in 10ml of deionized water, stirred for 12h and then filtered repeatedly with ethanol and deionized water.
(3) Transferring the solid washed in the step (2) into a quartz boat, and placing the quartz boat into a tube furnace filled with hydrogen to be calcined for 4 hours at 350 ℃, wherein the heating rate is 2 ℃/min. The method is used for loading stable metal oxide particles on the surface of the carbon material.
(4) 1g of the solid obtained in the step (3) and 10g of acid-base functionalization reagent hypophosphorous acid are dissolved in deionized water, and are mechanically stirred for 2h. The solution was transferred to a rotary evaporator and excess water was evaporated at 80 ℃ to give a viscous liquid.
(5) Transferring the liquid obtained in the step (4) into a quartz boat, placing the quartz boat in a tube furnace, and calcining the quartz boat for 1.5 hours at 280 ℃ under the nitrogen atmosphere, wherein the heating rate is 1 ℃/min. And naturally cooling to room temperature, taking out the dried solid substance, transferring the solid substance into a mortar, grinding, sieving, and storing in a dryer. The phosphoric acid grafted Pt-supported bifunctional biomass tar-derived carbon-based solid acid can be obtained.
Example 4
The method for functionalizing the biomass tar derived carbon material comprises the following steps of:
(1) 1g of biomass tar derived porous carbon is slowly stirred into 30ml of sodium hypochlorite solution, oxalic acid is added dropwise to adjust the pH of the solution to 3, stirring is continued for 12 hours, and deionized water is used for repeatedly flushing until the filtrate becomes neutral. The washed solid was placed in a drying oven and dried in vacuo at 80℃for 8h.
(2) Mixing the product obtained in the step (1) with tetraisopropyl titanate serving as a metalloid compound according to a mass ratio of 1:0.04 is dissolved in 10ml deionized water, 0.2ml HCL is added to assist the hydrolysis of the precursor, and after stirring for 12 hours, the precursor is repeatedly filtered with ethanol and deionized water.
(3) Transferring the solid washed in the step (2) into a quartz boat, and placing the quartz boat into a tube furnace filled with nitrogen to be calcined for 4 hours at 400 ℃, wherein the heating rate is 2 ℃/min. The method is used for loading stable metal oxide particles on the surface of the carbon material.
(4) 1g of the solid obtained in the step (3) and 5g of acid-base functionalization reagent p-toluenesulfonic acid are dissolved in deionized water, and the mixture is oscillated in a constant temperature water bath for 30min. The solution was transferred to a drying oven and excess water was evaporated at 80 c to give a viscous liquid.
(5) Transferring the liquid obtained in the step (4) into a quartz boat, placing the quartz boat into a tube furnace, and calcining the quartz boat for 6 hours at 230 ℃ under the nitrogen atmosphere, wherein the heating rate is 1 ℃/min. And naturally cooling to room temperature, taking out the dried solid substance, transferring the solid substance into a mortar, grinding, sieving, and storing in a dryer. The Ti supported double-function carbon-based solid acid catalyst grafted by benzenesulfonic acid can be obtained.
Claims (10)
1. A method for functionalizing biomass tar derived carbon-based materials, which is characterized by comprising the following steps: including metal loading and/or functional group grafting;
the method for loading metal comprises the following steps:
step (1): mixing a biomass tar derived carbon-based material with an activator, dropwise adding a carboxylic acid reagent to adjust the pH of the solution to be acidic, stirring uniformly, repeatedly filtering with deionized water until the filtrate is neutral, and vacuum drying the washed product; wherein the dosage ratio of the biomass tar derived carbon-based material to the activator is 1g: 30-60 ml;
step (2): under the condition of auxiliary reagent or no auxiliary reagent, mixing a metal compound or a metalloid compound capable of forming covalent bonds and/or ionic bonds with functional groups on the activated carbon-based material with the activated biomass tar derived carbon-based material in the step (1), continuously and uniformly stirring, filtering and washing; wherein the mass ratio of the biomass tar derived carbon-based material to the metal compound or metalloid compound is 1:0.01 to 0.3; if auxiliary reagents are used, the ratio of the metal compound or metalloid compound to the auxiliary reagent is 1g: 2-10 ml.
Step (3): transferring the solid washed in the step (2) into a quartz boat, placing the quartz boat into a tube furnace filled with hydrogen and/or nitrogen for calcination for 4-8 hours, cooling, taking out the dried solid substances, grinding and sieving, and placing the solid substances in a dryer for storage to obtain the biomass tar derived carbon-based material loaded with metal;
the method for grafting the functional group comprises the following steps:
step (1): mixing a biomass tar derived carbon-based material with an activator, slowly dropwise adding a carboxylic acid reagent to adjust the pH of the solution to be acidic, stirring uniformly, repeatedly filtering with deionized water until the filtrate is neutral, and vacuum drying the washed product; wherein the dosage ratio of the biomass tar derived carbon-based material to the activator is 1g: 30-60 ml;
step (2): uniformly mixing the product obtained in the step (1) with an acid-base functionalization reagent, and evaporating water to obtain viscous or colloidal liquid; wherein the dosage mass ratio of the product to the acid-base functionalization reagent is 1:5 to 15;
step (3): transferring the viscous or colloidal liquid obtained in the step (2) into a quartz boat, placing the quartz boat into a tube furnace protected by nitrogen for calcining for 2-6 hours, cooling, taking out the dried solid substance, grinding and sieving, and placing the solid substance into a dryer for storage to obtain the biomass tar-derived carbon-based material with the surface grafted with the functional groups.
2. The method of claim 1, wherein the biomass tar-derived carbon-based material in the metal loading method is one of biomass tar-derived activated carbon, carbon black, carbon nanotubes, three-dimensional carbon molecular sieves, carbon spheres, two-dimensional ordered porous carbon, nitrogen doped carbon.
3. The method of claim 1, wherein the biomass tar-derived carbon-based material in the functional group grafting method is a metal-loaded biomass tar-derived carbon-based material prepared in a method of biomass tar-derived activated carbon, carbon black, carbon nanotubes, three-dimensional carbon molecular sieves, carbon spheres, two-dimensional ordered porous carbon, nitrogen-doped carbon, and metal loading.
4. The method according to claim 1, wherein the activating agent in the metal loading method and the functional group grafting method is one or more of hydrogen peroxide, potassium permanganate and sodium hypochlorite, and the activating agent can enable more defect sites to appear on the surface of the biomass tar derived carbon-based material, so that more active groups are favorably loaded, and meanwhile, the stability of connection between the biomass tar derived carbon-based material and hydroxyl and carboxyl groups is enhanced through polarity and electronegativity, and the service life of the material is prolonged.
5. The method of claim 1, wherein the carboxylic acid in the metal loading and functional group grafting methods is one or any combination of hydroxycarboxylic acids, dicarboxylic acids, and the carboxylic acid reagent acts to increase the oxygen-containing functional groups on the surface of the biomass tar-derived carbon-based material and to provide oxygen anchor points for further functional group grafting.
6. The method of claim 1, wherein the auxiliary agent is capable of dissociating H in aqueous solution + Is hydrolyzed by a reagent IA seed or a combination.
7. The method of claim 1, wherein the metal loading is by forming nanoparticles of one or a combination of a metal, a metal oxide, a metalloid, and a metalloid oxide on the carbon material, the metal being one or any combination of chemically active metals.
8. The method according to claim 1, wherein the acid-base functionalizing agent is an agent capable of generating an acid-base functional group, in particular one of a sulfonating agent, a phosphorylating agent, a heteropolyacid; the acid-base functionalization reagent has the function of regulating and controlling physical or chemical properties of the surface of the material, so that the functionalization of the carbon material is realized; the product and the acid-base functionalization reagent are uniformly mixed in a mechanical mixing mode, an ultrasonic mixing mode or a constant-temperature water bath oscillating mode.
9. The method according to claim 1, wherein the evaporation of water is achieved by heating at 80-90 ℃ for a suitable time using a rotary evaporator or a drying oven.
10. The method according to claim 1, wherein the calcination in the metal loading method and the functional group grafting method is performed at a temperature lower than the thermal decomposition temperature of the biomass tar-derived carbon-based material, and the heating rate is 1 to 3 ℃/min.
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