CN114196989B - Lignin-based trimetallic nitrogen-doped carbon material and preparation method and application thereof - Google Patents

Lignin-based trimetallic nitrogen-doped carbon material and preparation method and application thereof Download PDF

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CN114196989B
CN114196989B CN202111678942.1A CN202111678942A CN114196989B CN 114196989 B CN114196989 B CN 114196989B CN 202111678942 A CN202111678942 A CN 202111678942A CN 114196989 B CN114196989 B CN 114196989B
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lignin
carbon material
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doped carbon
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林绪亮
刘江淋
邱学青
秦延林
张文礼
俎喜红
陈理恒
仇中杰
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Guangdong University of Technology
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Abstract

The invention discloses a lignin-based tri-metal nitrogen doped carbon material and a preparation method and application thereof, wherein the method comprises the following steps: s1, preparing a mixed solution of carboxylated lignin, ferric salt, nickel salt and molybdenum salt, uniformly stirring, adjusting the pH value of the mixed solution to 4-8, performing hydrothermal treatment at 120-210 ℃ for 4-12 hours, and performing post-treatment to obtain a lignin-based trimetallic carbon material precursor; s2, mixing the lignin-based trimetallic carbon material precursor with a nitrogen source, and carbonizing in a reducing atmosphere to obtain the lignin-based trimetallic nitrogen-doped carbon material. The carbon material has higher electrolytic water HER and OER catalytic activity, and can be used as an electrolytic water HER and OER catalyst.

Description

Lignin-based trimetallic nitrogen-doped carbon material and preparation method and application thereof
Technical Field
The invention relates to the technical field of biomass materials and electrocatalytic materials, in particular to a lignin-based trimetallic nitrogen-doped carbon material, and a preparation method and application thereof.
Background
Electrolytic water hydrogen production is an ideal source of clean and renewable energy, but the large overpotential limits the efficiency of overall water decomposition. Therefore, the development of a highly efficient catalyst is of great importance for the electrocatalytic decomposition of water. Noble metals such as Pt, ir, ru and the like and oxides thereof are catalysts for producing hydrogen by water electrolysis with better performance at present, but Pt-based catalysts are easy to dissolve in electrolyte after long-time operation, and RuO 2 Or IrO 2 Can oxidize at high voltages, has poor stability, and the scarcity and high cost of noble metals limit their widespread use.
The carbon material has the advantages of various structures, abundant surface states, strong controllability, good conductivity, good corrosion resistance, easy coordination and combination with metal and the like, and is widely applied to synthetic catalysts and carriers of catalysts. The prior art discloses a high-performance transition metal-nitrogen doped carbon catalyst which is prepared by utilizing phenolic hydroxyl groups on lignin structural units to carry out coordination reaction with transition metal, wherein active sites of the high-performance transition metal-nitrogen doped carbon catalyst are uniformly distributed, and the catalyst has excellent catalytic activity of Oxygen Reduction Reaction (ORR), but has the problem of low activity of electrolytic water Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER).
Disclosure of Invention
The primary purpose of the invention is to overcome the problem of low activity of the existing carbon material used as a catalyst for water electrolysis, and provide a preparation method of the lignin-based trimetallic nitrogen-doped carbon material.
It is another object of the present invention to provide a lignin-based trimetallic nitrogen doped carbon material.
It is a further object of the present invention to provide the use of said lignin-based trimetallic nitrogen doped carbon material.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a lignin-based trimetallic nitrogen-doped carbon material comprises the following steps:
s1, preparing a mixed solution of carboxylated lignin, ferric salt, nickel salt and molybdenum salt, uniformly stirring, adjusting the pH value of the mixed solution to 4-8, performing hydrothermal treatment at 120-210 ℃ for 4-12 hours, and performing post-treatment to obtain a lignin-based trimetallic carbon material precursor;
s2, mixing the lignin-based trimetallic carbon material precursor with a nitrogen source, and carbonizing in a reducing atmosphere to obtain the lignin-based trimetallic nitrogen-doped carbon material.
The invention utilizes the characteristic that carboxylated lignin and transition metal ions have stronger coordination capability to mix the carboxylated lignin with ferric salt, nickel salt and molybdenum salt to obtain a mixed solution, and adjusts the pH value of the mixed solutionThe three metal ions of Fe, ni and Mo are in the most proper coordination environment, thus obtaining the metal-lignin-based supermolecule precursor, and NiO, feOOH, niOOH, moO (OH) is formed after further hydrothermal treatment 3 And (3) an oxide/oxyhydroxide intermediate such as NiFeOOH, and finally mixing the intermediate with a nitrogen source and carbonizing the mixture to obtain the N-doped carbon material.
In the invention, a core-shell structure is formed with C in situ after the non-metal element N is doped, metal active substances such as single metal and multi-metal carbide are coated, the active substances are prevented from agglomerating, the dispersibility of the metal is changed, fe and Ni in the three transition metals regulate the electronic structure of Mo, electrons are transferred from Fe and Ni to Mo, so that the bonding energy of Mo is reduced, the lower bonding energy enhances the electron donating ability due to the increase of d-electron occupation, and the HER and OER catalytic activities of electrolytic water are improved.
Preferably, the total molar amount of iron ions, nickel ions and molybdenum ions in the mixed solution containing 1g of carboxylated lignin is 6mmol or more.
More preferably, the total molar amount of iron ions, nickel ions and molybdenum ions per 1g of the mixed solution containing carboxylated lignin is 6 to 10mmol.
Preferably, the molar ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1: (1-8).
More preferably, the molar ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1: (2-6).
Further preferably, the molar ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1:4.
preferably, the carbonization temperature is 700-800 ℃, and the carbonization time is 2-3 h.
More preferably, the carbonization treatment temperature is 800 ℃, and the carbonization treatment time is 2 hours.
Preferably, the pH of the mixed solution is adjusted to 6.
Preferably, the mass ratio of the lignin-based tri-metal carbon material precursor to the nitrogen source is 1: (1-6).
Preferably, the hydrothermal treatment temperature is 150-180 ℃ and the hydrothermal treatment time is 6-10 h.
Iron, nickel and molybdenum salts, conventional in the art, are useful in the present invention.
Typically, the iron salt is selected from one or more of ferric chloride, ferric nitrate, ferric sulfate;
the nickel salt is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel oxalate;
the molybdenum salt is selected from one or more of ammonium molybdate, sodium molybdate and molybdenum chloride.
The reducing atmosphere of the invention is a conventional reducing atmosphere, and is generally a 5% hydrogen/argon atmosphere.
Nitrogen sources conventional in the art, typically selected from one or more of urea, dicyandiamide, melamine and chitosan, may be used in the present invention.
The invention also provides a preparation method of carboxylated lignin, which comprises the following steps: mixing sodium hydroxide aqueous solution dissolved with lignin and carboxylation reagent aqueous solution, reacting for 30-90 min in a constant-temperature water bath at 40-70 ℃, adjusting pH to 3-7, and post-treating to obtain carboxylated lignin.
The lignin is one or more selected from enzymatic lignin, alkali lignin, sulfite lignin and lignin sulfonate. Preferably, the lignin is Enzymatic Hydrolysis (EHL), and the molecular weight of the enzymatic hydrolysis lignin is 6000-12000.
The carboxylation reagent is one or more selected from monochloroacetic acid, monobromoacetic acid, monoiodoacetic acid, sodium monochloroacetate, sodium monobromoacetate, sodium monoiodoacetate, dichloroacetic acid, 2-chloropropionic acid and acrylic acid. Preference is given to monochloroacetic acid.
The post-treatment of the invention is specifically to sequentially carry out centrifugation, washing and drying.
A lignin-based trimetallic nitrogen-doped carbon material is prepared by the method.
The lignin-based trimetallic nitrogen-doped carbon material has higher catalytic activity when being used as a catalyst for electrolytic water oxygen evolution reaction, hydrogen evolution reaction and oxygen reduction reaction. Therefore, the application of the lignin-based trimetallic nitrogen-doped carbon material as an electrolytic water oxygen evolution reaction, a hydrogen evolution reaction and an oxygen reduction reaction catalyst is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of lignin-based trimetallic nitrogen-doped carbon material, the carbon material prepared by the method has higher electrolytic water HER and OER catalytic activity, and the current density is 10mA cm -2 When the HER overpotential is lower than 400mV and the OER overpotential is lower than 350mV, the catalyst can be used as an electrolytic water HER and OER catalyst.
Drawings
Fig. 1 is an XRD pattern of the carbon material prepared in example 1.
Fig. 2 is an SEM image of the carbon material prepared in example 1.
Fig. 3 is a TEM image of the carbon material produced in example 1.
Fig. 4 is a graph showing HER test results of the carbon materials obtained in examples 1 to 3 as catalysts.
FIG. 5 is a graph showing the OER test results of the carbon materials obtained in examples 1 to 3 as catalysts.
Fig. 6 is a graph showing the results of HER testing of the carbon materials obtained in example 1 and examples 4 to 6 as catalysts.
Fig. 7 is a graph showing the OER test results of the carbon materials obtained in example 1 and examples 4 to 6 as catalysts.
Fig. 8 is a graph showing the results of HER testing of the carbon materials obtained in example 1 and examples 7 to 9 as catalysts.
Fig. 9 is a graph showing the OER test results of the carbon materials obtained in example 1 and examples 7 to 9 as catalysts.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
The carboxylated lignin preparation method described in the examples and comparative examples is as follows: 10.0g of EHL was dissolved in 25g of 20wt% aqueous NaOH solution and poured into a reaction flask, followed by stirring at 30℃for 30 minutes; weighing 6.0g of monochloroacetic acid, dissolving in 10.0g of deionized water, dripping the monochloroacetic acid water solution into a reaction flask, reacting for 90min in a constant-temperature water bath at 70 ℃, cooling, measuring the pH value of the reaction solution, adjusting the pH value of the solution by 2mol/L hydrochloric acid to be=5.0+/-0.1, centrifuging at 8000rpm for 10min, washing, centrifuging, and drying the filtrate in an oven at 50 ℃ to obtain carboxylated lignin (EHL-COOH).
Example 1
A preparation method of a lignin-based trimetallic nitrogen-doped carbon material comprises the following steps:
s1, 1.0g of EHL-COOH is weighed and added into 50mL of pure water, and ferric chloride hexahydrate (FeCl) is additionally weighed 3 ·6H 2 O), nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) and ammonium molybdate tetrahydrate [ (NH) 4 ) 2 Mo 7 O 24 ·4H 2 O](total molar weight of iron ions, nickel ions and molybdenum ions is 8 mmol) is added into 50mL of pure water, magnetic stirring is carried out uniformly, the mixture is added into EHL-COOH aqueous solution dropwise, stirring is carried out for 10min to obtain mixed solution (molar ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1:4), pH value of the mixed solution is regulated to 6 by ammonia water and HCl, stirring is continued for 10min to obtain metal-lignin-based supermolecule precursor solution, then the metal-lignin-based supermolecule precursor solution is transferred into a 100mL Teflon-line stainless steel autoclave, the autoclave is sealed and kept at 150 ℃ for 8 h of hydrothermal treatment in a high-temperature oven, and the obtained sample is dried for 12h at 80 ℃ after centrifugation and washing, thus obtaining lignin-based trimetallic FeNiMo carbon material precursor;
s2, grinding and mixing 0.5g of the prepared lignin-based trimetallic FeNiMo carbon material precursor with 0.5g of urea uniformly, and mixing at 5%H 2 And (3) carrying out high-temperature charcoal burning to 800 ℃ in a heat stabilization procedure under Ar atmosphere, carbonizing at 800 ℃ for 2 hours, cooling the sample to room temperature, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the trimetallic N-doped lignin-based carbon material.
Example 2
The present example provides a method for preparing lignin-based trimetallic nitrogen-doped carbon material, unlike example 1, in which the molar ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1:1.
Example 3
The present example provides a method for preparing lignin-based trimetallic nitrogen-doped carbon material, unlike example 1, in which the molar ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1:8.
Example 4
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, differing from example 1 in the hydrothermal treatment temperature of 120 ℃.
Example 5
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, differing from example 1 in the hydrothermal treatment temperature of 180 ℃.
Example 6
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, differing from example 1 in the hydrothermal treatment temperature of 210 ℃.
Example 7
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, differing from example 1 in the carbonization temperature of 600 ℃.
Example 8
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, differing from example 1 in carbonization temperature of 700 ℃.
Example 9
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, differing from example 1 in carbonization temperature of 900 ℃.
Example 10
This example provides a method for preparing lignin-based trimetallic nitrogen-doped carbon materials, differing from example 1 in that the total molar amount of iron ions, nickel ions and molybdenum ions is 6mmol.
Example 11
This example provides a method for preparing lignin-based trimetallic nitrogen-doped carbon materials, differing from example 1 in that the total molar amount of iron ions, nickel ions and molybdenum ions is 10mmol.
Example 12
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, unlike example 1, in which the pH of the mixed solution is adjusted to 4 with ammonia and HCl.
Example 13
This example provides a method for preparing lignin-based tri-metal nitrogen doped carbon material, unlike example 1, in which the pH of the mixed solution is adjusted to 8 with ammonia and HCl.
Example 14
The present embodiment provides a method for preparing a lignin-based trimetallic nitrogen-doped carbon material, which is different from embodiment 1 in that the mass ratio of lignin-based trimetallic FeNiMo carbon material precursor to urea is 1:6.
Comparative example 1
The comparative example provides a preparation method of an iron-molybdenum bimetallic nitrogen-doped carbon material, which comprises the following steps:
1.0g of EHL-COOH was weighed into 50mL of pure water, and ferric chloride hexahydrate (FeCl) was additionally weighed 3 ·6H 2 O), ammonium molybdate tetrahydrate [ (NH) 4 ) 2 Mo 7 O 24 ·4H 2 O](the molar ratio of 2.6:5.4 is added into 50mL of pure water, the mixture is stirred uniformly by magnetic force, and is added into lignin aqueous solution dropwise, the mixture is stirred for 10min, the pH of the mixture is regulated by ammonia water and HCl, the mixture is stirred continuously for 10min to obtain a metal-lignin-based supermolecule precursor, then the metal-lignin-based supermolecule precursor solution is transferred into a 100mL Teflon-line stainless steel autoclave, the metal-lignin-based supermolecule precursor solution is sealed and kept in a high-temperature oven at 150 ℃ for 8 hours for hydrothermal reaction, and the obtained sample is dried at 80 ℃ for 12 hours after centrifugal washing to obtain a lignin-based bimetallic FeMo-based carbon material precursor;
grinding and mixing 0.5g of the prepared lignin-based bimetallic FeMo-based carbon material precursor and a certain amount of urea (the mass ratio is 1:1) uniformly, and adding the mixture into a mixture at 5%H 2 High temperature charcoal firing to 800 ℃ was performed in a heat stabilization procedure under an Ar atmosphere, andthe sample was kept at 800℃for 2h and cooled to room temperature. Washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the iron-molybdenum bimetal nitrogen doped carbon material.
The present comparative example differs from example 1 in that only iron salts and molybdenum salts were used in the present comparative example.
Comparative example 2
The comparative example provides a preparation method of an iron-nickel-cobalt trimetallic nitrogen doped carbon material, which comprises the following steps:
1.0g of EHL-COOH was weighed into 50mL of pure water, and ferric chloride hexahydrate (FeCl) was additionally weighed 3 ·6H 2 O), ammonium molybdate tetrahydrate [ (NH) 4 ) 2 Mo 7 O 24 ·4H 2 O]Cobalt nitrate hexahydrate [ Co (NO) 3 ) 2 ·6H 2 O]Adding 50mL of pure water (molar ratio of 1:1:4), magnetically stirring uniformly, dropwise adding into lignin aqueous solution, stirring for 10min, regulating the pH of the mixed solution with ammonia water and HCl, continuously stirring for 10min to obtain a metal-lignin-based supermolecule precursor, transferring the metal-lignin-based supermolecule precursor solution into a 100mL Teflon-line stainless steel autoclave, sealing and maintaining the metal-lignin-based supermolecule precursor solution in a high-temperature oven at 150 ℃ for 8 hours for hydrothermal reaction, centrifuging and washing the obtained sample, and drying the obtained sample at 80 ℃ for 12 hours to obtain a lignin-based trimetallic FeNiCo-based carbon material precursor;
grinding and mixing 0.5g of the prepared lignin-based trimetallic FeNiCo-based carbon material precursor and a certain amount of urea (the mass ratio is 1:1) uniformly, and adding the mixture into a mixture at 5%H 2 High temperature charcoal firing was performed to 800 ℃ in a heat stabilization procedure under Ar atmosphere and maintained at 800 ℃ for 2 hours, and the sample was cooled to room temperature. Washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 80 ℃ for 12 hours to obtain the Fe-Ni-Co trimetallic nitrogen doped carbon material.
The present comparative example differs from example 1 in that a cobalt salt was used instead of a nickel salt.
Test characterization
Fig. 1 is an XRD pattern of the carbon material prepared in example 1. As can be seen from FIG. 1, the phase composition of the trimetallic FeNiMo catalyst is Fe 3 Mo 3 C、Mo 2 C、(Fe 0.51 Mo 0.46 Ni 0.03 ) 6 And C and other single-metal and multi-metal carbides are active substances in HER and OER processes in the catalytic process.
Fig. 2 is an SEM image of the carbon material prepared in example 1. As can be seen from fig. 2, the prepared carbon material has a layered porous structure with a large number of macropores and mesopores, the porous structure can provide and expose more active sites, and the carbonized structure is easy to form metal bonds with different metal species, so that the conductivity is improved.
Fig. 3 is a TEM image of the carbon material produced in example 1. As can be seen from fig. 3, the prepared carbon material has a typical core-shell structure, and carbon is coated with metal active substances, so that agglomeration of metal is avoided, the active substances are uniformly dispersed, active sites are increased, and thus, the catalytic reaction performance is improved.
The carbon materials obtained in the examples and comparative examples were subjected to electrochemical performance tests performed on a Gamry Interface 1010 electrochemical workstation using a conventional three-electrode system with a spectrally pure graphite rod (99.999% purity) as a counter electrode and Hg/HgO as a reference electrode. The working electrode is prepared by a 'dripping method', namely, adding 4mg of carbon material powder into 200 mu L of 0.25% Nafion-ethanol solution, performing ultrasonic dispersion for 15min, sucking 50 mu L of sample dispersion liquid to drop on carbon paper (0.5X0.5 mm), respectively ultrasonically cleaning the carbon paper with acetone, ethanol and deionized water for 20min before dripping, boiling with concentrated nitric acid at 110 ℃ for 4h, washing to be neutral, and drying in a baking oven at 60 ℃. The loading of the obtained catalyst was 4.0mg cm -2 。
The electrochemical performance test is carried out in a KOH electrolyte solution of 1M, high-purity oxygen is continuously introduced during OER test, and the potentials are compensated by IR through the Thale software of the instrument. Measurement of polarization Curve by Linear sweep voltammetry, oxygen evolution reaction at 0V as initial potential, at 1 mV.s -1 Is scanned to 1V. The electrocatalytic activity of the catalyst was measured in a standard three electrode system, with the auxiliary electrode replaced by a spectrally pure graphite rod in order to exclude the potential gain effect of Pt on the catalyst.
Test results of examples please refer to fig. 4-9 and table 1, compareExample test results are shown in table 1. Fig. 4 is a graph showing HER test results of the carbon materials obtained in examples 1 to 3 as a catalyst, and fig. 5 is a graph showing OER test results of the carbon materials obtained in examples 1 to 3 as a catalyst. As can be seen from FIGS. 4 and 5, the current density was 10 mA.cm -2 The HER overpotential for example 1 was 128mV, the OER overpotential was 198mV, the HER overpotential for example 2 was 178mV, the OER overpotential was 294mV, the HER overpotential for example 3 was 231mv, and the OER overpotential was 301mV, indicating that the metal doping amount had an effect on the HER and OER catalytic properties of the carbon material according to the present invention, wherein the resulting carbon material of example 1 had the best electrolytic water HER and OER catalytic properties.
Fig. 6 is a graph showing HER test results of the carbon materials obtained in example 1 and examples 4 to 6 as catalysts, and fig. 7 is a graph showing OER test results of the carbon materials obtained in example 1 and examples 4 to 6 as catalysts. As can be seen from FIGS. 6 and 7, the current density was 10 mA.cm -2 The HER overpotential for example 1 was 128mV, the oer overpotential was 232mV, the HER overpotential for example 4 was 284 mV, the oer overpotential was 216mV, the HER overpotential for example 5 was 284 mV, the oer overpotential was 210mV, the HER overpotential for example 6 was 350mV, and the oer overpotential was 255mV, indicating that the hydrothermal treatment temperature had a large effect on the catalytic performance of the resulting carbon material, since the change in the hydrothermal temperature directly affected the production of its oxidation product intermediates, with 150 ℃ being the optimal hydrothermal treatment temperature.
FIG. 8 is a graph showing the results of HER test of the carbon materials obtained in example 1 and examples 7 to 9 as a catalyst, and FIG. 9 is a graph showing the results of OER test of the carbon materials obtained in example 1 and examples 7 to 9 as a catalyst, as can be seen from FIGS. 8 and 9, at a current density of 10 mA.cm -2 The HER overpotential for example 1 was 128mV, the oer overpotential was 198mV, the HER overpotential for example 7 was 178mV, the oer overpotential was 276mV, the HER overpotential for example 8 was 191mv, the oer overpotential was 247mV, the HER overpotential for example 9 was 378mV, and the oer overpotential was 255mV, i.e., the carbonization temperature had a large effect on the catalytic performance of the resulting carbon material because the graphitization degree of the material was different at different carbonization temperatures, wherein 800 ℃ was the optimal carbonization temperature.
TABLE 1 Current Density of 10mA cm -2 Time HER and OER overpotential
Figure BDA0003453380560000081
Figure BDA0003453380560000091
Comparative example 1 provides an iron-molybdenum bi-metallic nitrogen-doped carbon material, and comparative example 2 provides an iron-nickel-cobalt tri-metallic nitrogen-doped carbon material, as can be seen from Table 1, at a current density of 10mA cm -2 The HER overpotential of comparative example 1 was 450mV, the OER overpotential was 419mV, the OER overpotential of comparative example 2 was 394mV, and the OER overpotential of comparative example 2 was 450mV, which are inferior to the carbon materials obtained in the examples of the present invention because the carbon materials obtained in comparative example 1 and comparative example 2 do not contain the active material Fe 3 Mo 3 C、Mo 2 C、(Fe 0.51 Mo 0.46 Ni 0.03 ) 6 Single metal and multi-metal carbide such as C.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (9)

1. The preparation method of the lignin-based trimetallic nitrogen-doped carbon material is characterized by comprising the following steps of:
s1, preparing a mixed solution of carboxylated lignin, ferric salt, nickel salt and molybdenum salt, uniformly stirring, adjusting the pH value of the mixed solution to 4-8, performing hydrothermal treatment at 120-210 ℃ for 4-12 hours, and performing post-treatment to obtain a lignin-based trimetallic carbon material precursor;
s2, mixing the lignin-based trimetallic carbon material precursor with a nitrogen source, and carbonizing in a reducing atmosphere to obtain a lignin-based trimetallic nitrogen-doped carbon material;
the mole ratio of iron ions, nickel ions and molybdenum ions in the mixed solution is 1:1: (1-8).
2. The method for producing a lignin-based trimetallic nitrogen-doped carbon material according to claim 1, wherein the total molar amount of iron ions, nickel ions and molybdenum ions per 1g of the mixed solution containing carboxylated lignin is 6mmol or more.
3. The method for preparing lignin-based trimetallic nitrogen-doped carbon material according to claim 1, wherein the method for preparing carboxylated lignin comprises the steps of:
mixing a sodium hydroxide aqueous solution dissolved with lignin and a carboxylation reagent aqueous solution, reacting for 30-90 min at a constant temperature of 40-70 ℃ in a water bath, adjusting the pH value to 3-7, and performing post-treatment to obtain carboxylated lignin.
4. The method for preparing the lignin-based trimetallic nitrogen-doped carbon material according to claim 1, wherein the carbonization temperature is 700-800 ℃ and the carbonization time is 2-3 hours.
5. The method for preparing the lignin-based trimetallic nitrogen-doped carbon material according to claim 1, wherein the hydrothermal treatment temperature is 150-180 ℃.
6. The method for preparing the lignin-based trimetallic nitrogen-doped carbon material according to claim 1, wherein the mass ratio of the lignin-based trimetallic carbon material precursor to the nitrogen source is 1: (1-6).
7. The method for preparing the lignin-based trimetallic nitrogen-doped carbon material according to claim 1, wherein the iron salt is selected from one or more of ferric chloride, ferric nitrate, ferric sulfate; the nickel salt is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel oxalate; the molybdenum salt is selected from one or more of ammonium molybdate, sodium molybdate and molybdenum chloride.
8. A lignin-based trimetallic nitrogen-doped carbon material, characterized in that it is obtainable by the preparation method according to any one of claims 1 to 7.
9. The use of the lignin-based trimetallic nitrogen-doped carbon material of claim 8 as a catalyst for an electrolytic water oxygen evolution reaction and hydrogen evolution reaction.
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