CN117239156A - High-dispersion lignin derived Ru in-situ N-doped carbon material and preparation method and application thereof - Google Patents
High-dispersion lignin derived Ru in-situ N-doped carbon material and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 128
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 42
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 35
- 239000006185 dispersion Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 20
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- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 11
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method and application of a high-dispersion lignin derived Ru in-situ N-doped carbon material. According to the invention, the industrial lignin is subjected to ring opening modification through oxidative ammonolysis to access a functional group with strong coordination, so that the water solubility of the lignin is improved, the surface of the lignin is endowed with strong coordination capability, and the dispersibility of the microstructure of the lignin and the problem of the binding capability of the lignin with metal ions are effectively improved; then the precursor is coordinated and combined with Ru ions to form Ru-oxidative ammonolysis lignin precursor, and then the precursor is prepared after high-temperature carbon burning. The high-dispersion lignin derived Ru in-situ N-doped carbon material combines the advantages of biomass carbon materials and transition metal Ru, is a catalyst with relatively excellent performance, can be widely applied to the fields of zinc-air batteries, urea oxidation, glucose electrocatalytic conversion, furfural electrocatalytic oxidation and the like, and is stable, efficient, rich in resources and low in price; can also be used as an electrolyzed water catalyst for producing clean energy.
Description
Technical Field
The invention belongs to the technical field of biomass materials and electrocatalytic materials, and particularly relates to a high-dispersion lignin-derived Ru in-situ N-doped carbon material, and a preparation method and application thereof.
Background
With the widespread use of fossil fuels, non-renewable resources are gradually consumed, the environment is severely damaged, and renewable energy driven efficient clean energy technology (conversion and storage) is a great demand for sustainable development of human society. In order to solve the problems of energy shortage, environmental pollution and climate change, clean and sustainable energy must be developed to reduce fossil fuel consumption. Currently, a number of highly efficient advanced technologies, such as fuel cells, metal-air cells, small molecule to fuel conversion, etc., have been explored for efficient energy conversion devices. In general, in order to obtain a high-performance energy conversion device, it is necessary to manufacture an efficient electrocatalyst. The electrochemical reaction potential is reduced, and the reaction rate is improved. In general, electrocatalysts are often used to modify the electrodes to facilitate electron transfer between the electrodes and the reactants or intermediates.
Biomass carbon materials have a regulatable form and excellent electrical conductivity, and have been attracting attention in the catalytic field in recent years. Biomass carbon materials are widely used and exist as resources in nature, and ways and methods for researching efficient utilization of biomass carbon materials are increasing in recent years. Lignin is an important biomass next to cellulose in natural substances, and 60% of lignin is carbon element, so that lignin is an ideal carbon material precursor. Lignin is also an aromatic polymer with the most abundant sources, comprises three types of phenylpropane units of syringyl, guaiacyl and p-hydroxyphenylpropyl, is formed by combining carbon-carbon bonds and ether bonds, and can be converted into bioenergy, materials and chemicals by thermochemical, chemical, biocatalytic and other methods. The catalytic performance can be obviously improved by doping metal into lignin, wherein the metal Fe, co, ni, mn, cr, zn, cu, W, mo, pt, rh, ir and Ru have certain catalytic activity, and the noble metal can be gradually replaced in the catalytic field. The Ru-based material has excellent catalytic activity and higher electron transmission capacity than other single-metal catalysts.
In the process of forming the catalyst, the use of the activator often causes problems such as corrosion of instruments, gas pollution, inconvenient operation and the like. The biomass is modified, so that hetero atoms can be doped in situ, and the mutual binding force between metal and the catalyst can be improved, thereby being beneficial to forming an efficient catalyst. Therefore, the development of rich groups to enhance heteroatom doping capability and interaction with metals is particularly critical.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art, and provides a high-dispersion lignin-derived Ru in-situ N-doped carbon material, a preparation method and application thereof. The high-dispersion lignin derived Ru in-situ N-doped carbon material combines the advantages of biomass carbon materials and transition metal Ru, is a catalyst with relatively excellent performance, can be widely applied to the fields of zinc-air batteries, urea oxidation, glucose electrocatalytic conversion, furfural electrocatalytic oxidation and the like, and is stable, efficient, rich in resources and low in price; can also be used as an electrolyzed water catalyst for producing clean energy.
To achieve the above object, the present invention is achieved by the following means:
a preparation method of a high-dispersion lignin-derived Ru in-situ N-doped carbon material comprises the following steps:
(1) Placing lignin, an oxidant and an amination agent in a solvent, uniformly stirring to form a mixed solution, then carrying out hydrothermal reaction, and drying after the reaction is finished to obtain oxidized ammonolysis lignin;
(2) Placing the oxidized ammonolysis lignin obtained in the step (1) in a solvent, and uniformly stirring to obtain an oxidized ammonolysis lignin solution; placing Ru salt into a solvent, stirring and dispersing uniformly, adding the oxidative ammonolysis lignin solution, and fully stirring to form a mixed solution for coordination reaction to obtain Ru-lignin-based supermolecule precursor;
(3) And (3) placing the Ru-lignin-based supermolecule precursor obtained in the step (2) into a tube furnace for high-temperature charcoal burning, and then carrying out acid washing and drying to obtain the Ru-lignin-based supermolecule precursor.
Preferably, the lignin in the step (1) is selected from one or more of enzymatic lignin, alkali lignin, sulfite lignin and lignosulfonate; most preferably, the lignin is an alkali lignin.
Preferably, the oxidant in the step (1) is selected from one or more of hydrogen peroxide, ozone and 2, 6-tetramethyl piperidine oxide; most preferably, the oxidizing agent is selected from hydrogen peroxide.
Preferably, the amination agent in the step (1) is selected from one or more of ammonia water and ammonia gas; most preferably, the amination agent is selected from ammonia.
Preferably, the solvent in the step (1) is selected from one or more of ultrapure water, distilled water and deionized water; most preferably, the solvent is selected from ultrapure water.
Preferably, a base is optionally added to the solvent of step (1) to form an alkaline solution; the alkali is selected from one or more of potassium hydroxide, sodium hydroxide and ammonia water.
Preferably, the lignin concentration in the mixed solution of step (1) is 0.1-0.8g/mL.
Preferably, the concentration of the oxidizing agent in the mixed solution of step (1) is 0.02-0.2g/mL.
Preferably, the concentration of the amination agent in the mixed solution of step (1) is 0.01-0.1g/mL.
Preferably, the mass ratio of the oxidizing agent to the aminating agent in the step (1) is 1:1-3.
Preferably, the temperature of the hydrothermal reaction in step (1) is 90-200 ℃; most preferably, the temperature of the hydrothermal reaction is 120 ℃.
Preferably, the hydrothermal reaction in step (1) takes 1 to 3 hours; most preferably, the hydrothermal reaction time is 1.5h.
Preferably, the Ru salt in the step (2) is selected from one or more of ruthenium chloride hydrate, ruthenium acetate and ruthenium acetylacetonate; most preferably, the ruthenium salt is selected from ruthenium chloride hydrate.
Preferably, the concentration of the oxidized ammonolysis lignin in the mixed solution in the step (2) is 3-30g/L.
Preferably, the concentration of ruthenium element in the mixed solution of the step (2) is 0.01-0.15mmol/L.
Preferably, the time of the coordination reaction in step (2) is 2 to 24 hours; most preferably, the time of the coordination reaction is 12 hours.
Preferably, the temperature of the high-temperature charcoal in the step (3) is 800-1000 ℃, and the heating rate is 0.5-5 ℃/min; most preferably, the high temperature charcoal is burned at 900 ℃ and the heating rate is 5 ℃/min.
Preferably, the high temperature charcoal in step (3) is burned for a period of 1-4 hours; most preferably, the high temperature charcoal burns for a period of 2 hours.
Preferably, the acid washing in the step (3) is washing with hydrochloric acid solution and deionized water in sequence.
Preferably, the drying temperature in step (3) is 60 ℃ and the drying time is 12 hours.
Preferably, the high temperature charcoal firing in step (3) is optionally performed under a gas atmosphere selected from one or more of hydrogen, argon, nitrogen, inert gases.
The second aspect of the invention provides the high-dispersion lignin-derived Ru in-situ N-doped carbon material prepared by the preparation method.
The third aspect of the invention provides application of the high-dispersion lignin derived Ru in-situ N-doped carbon material prepared by the preparation method in zinc-air batteries, urea oxidation, glucose electrocatalytic conversion and furfural electrocatalytic oxidation.
According to the invention, an oxidative ammonolysis lignin ligand with a coordination function is synthesized by utilizing a lignin functional group structure to carry out amination, oxidation, modification and modification, and is precisely coordinated with metal ions Ru to form a Ru-oxidative ammonolysis lignin precursor, and Ru ions in lignin-based supermolecules are coordinated with amide groups. And then carrying out complexation precipitation self-assembly treatment on the Ru-ammoxidation lignin precursor, then placing the Ru-ammoxidation lignin precursor in a tube furnace for in-situ carbonization, and carrying out nitrogen doping through pyrolysis of amide groups to prepare the Ru-doped lignin-based carbon material, so that the electrochemical activity of the lignin/Ru composite is improved. In the carbonization process of the lignin/Ru compound precursor, ru ions and lignin molecules interact, so that in-situ pore forming can be performed on the lignin carbon material, and the metal doped modified lignin-based carbon material can be obtained through the synergistic catalysis between metals, wherein the doped part can be used as a catalytic active site, and the catalytic performance of the lignin-based carbon material is remarkably enhanced.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the functional group with strong coordination is accessed by ring opening modification of the industrial lignin, so that the water solubility of the lignin is improved, and the surface of the lignin is endowed with strong coordination capability, so that the lignin can be subjected to in-situ self-assembly with metal ions in a wide pH value range to form lignin/metal complexes with regular microstructures, and the problems of the dispersibility of the microstructure of the lignin and the binding capability of the lignin with the metal ions are effectively improved.
(2) According to the invention, the industrial lignin is subjected to oxidative ammonolysis modification, and part of amide groups are accessed, so that an oxygen source and a nitrogen source are introduced. Heteroatoms in the carbon skeleton can effectively modify the surface property of carbon, which is beneficial to the catalytic reaction.
(3) The invention directly utilizes the waste lignin extracted from the papermaking black liquor, and forms the high-efficiency electrocatalyst through modification, self-assembly and in-situ carbonization, thereby utilizing the industrial waste material in a high-value manner and effectively reducing the pollution to the environment caused by the papermaking waste liquid discharged in the industrial papermaking industry.
(4) The catalyst can be widely applied to the fields of zinc-air batteries, higher alcohol conversion, electrochemical oxidation of biomass micromolecules (such as benzyl alcohol, HMF, urea and the like) and the like, and has the advantages of stable and efficient property, rich preparation raw material resources and low price; meanwhile, the catalyst can be used as a catalyst for producing clean energy through electrolytic water hydrogen and oxygen evolution reaction, and has excellent catalytic performance.
Drawings
FIG. 1 is an electron micrograph of a single metal in situ N-doped oxidative ammonolysis lignin-based carbon material prepared by the method of example 1.
FIG. 2 is a graph showing the performance of a single metal in situ N-doped oxidative ammonolysis lignin-based carbon material catalyst prepared by the method of example 1 in a zinc-air battery.
FIG. 3 is a graph showing the oxidation performance of a single metal in situ N-doped oxidative ammonolysis lignin-based carbon material catalyst prepared by the method of example 1.
FIG. 4 is a graph showing the performance of the single metal in situ N-doped oxidative ammonolysis lignin-based carbon material catalyst prepared by the method of example 1 in electrocatalytic conversion of glucose.
FIG. 5 is a graph showing the electrooxidative performance of a single-metal in-situ N-doped oxidative ammonolysis lignin-based carbon material catalyst prepared by the method of example 1 for furfural.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods. The lignin used in the examples and comparative examples of the present invention was exemplified by Alkali Lignin (AL), and it should be understood that lignin was only used as a raw material for providing a carbon source, and its specific kind had no significant effect on the properties of the catalyst finished product, and when the catalyst preparation was carried out using other lignin kinds such as enzymatic lignin, lignin by sulfite method, lignin sulfonate, etc., the obtained catalyst properties were not significantly different from those of alkali lignin, and thus are not listed here.
Example 1
The preparation method of the high-dispersion lignin-derived Ru in-situ N-doped carbon material comprises the following steps:
(1) Dissolving 10g of alkali lignin in 5g of 3wt% ammonia solution, adding 10g of 30wt% hydrogen peroxide, stirring at room temperature for 10min, transferring to a polytetrafluoroethylene hydrothermal kettle, reacting at 120 ℃ for 90min, cooling to room temperature after the reaction is finished, steaming and drying, transferring to a 60 ℃ vacuum oven for drying, and grinding to obtain Oxidized Ammonolysis Lignin (OAL);
(2) Placing 1.0g of the oxidized aminolysis lignin obtained in the step (1) into 50mL of pure water, and uniformly stirring to obtain an oxidized aminolysis lignin solution; another 10mg of ruthenium chloride hydrate (RuCl) was taken 3 ·xH 2 O) placing the mixture in 50mL of pure water, and uniformly stirring the mixture by magnetic force to obtain a metal salt solution; dropwise adding the metal salt solution into the oxidative ammonolysis lignin solution, and stirring for 60min; then standing in a fume hood to allow metal ruthenium and oxidized ammonolysis lignin to precipitate for self-assembly coordination reaction for 12h; after the reaction is finished, placing the obtained sample in a plastic beaker, freezing the plastic beaker in a refrigerator, transferring the plastic beaker into a freeze dryer for drying, and grinding the obtained sample to obtain a ruthenium-lignin-based supermolecule precursor;
(3) Taking 1g of ruthenium-lignin-based supermolecule precursor prepared in the step (2), and adding the precursor into N 2 Carrying out high-temperature pyrolysis under the atmosphere by a thermal stabilization program, wherein the temperature of the high-temperature pyrolysis is 900 ℃, the heating rate is 5 ℃/min, and the time of the high-temperature pyrolysis is 2 hours; cooling the sample to after pyrolysis is completedWashing with 1mol/L hydrochloric acid solution and deionized water at room temperature, and drying at 60deg.C for 12 hr to obtain scanning electron micrograph shown in figure 1.
Further, different in-situ N-doped carbon materials of Ru derived from high-dispersion lignin are prepared by adjusting the mass ratio of ammonia water to hydrogen peroxide, the hydrothermal reaction temperature, the pyrolysis temperature, the dosage of ruthenium chloride hydrate and the like in the preparation process, and the specific details are shown in the following table 1.
Table 1A highly dispersed lignin-derived Ru in-situ N-doped carbon material prepared in examples 2-9
Comparative example 1
A lignin-based catalyst, the method of preparation comprising the steps of:
1g of AL and 10mg of ruthenium chloride hydrate are dispersed in 100mL of ultrapure water, stirred magnetically uniformly, stirred at 100 ℃ until the water is completely evaporated, and then dried in an oven, and named OAL-Ru. In N 2 Carrying out high-temperature pyrolysis under the atmosphere by a thermal stabilization program, wherein the temperature of the high-temperature pyrolysis is 900 ℃, the heating rate is 5 ℃/min, and the time of the high-temperature pyrolysis is 2 hours; and cooling the sample to room temperature after the pyrolysis is finished, washing the sample by using 1mol/L hydrochloric acid solution and deionized water respectively, and drying the sample at 60 ℃ for 12 hours to obtain the high-dispersion lignin-derived Ru in-situ N-doped carbon material Ru@OALC.
Comparative example 2
A lignin-based catalyst, the method of preparation comprising the steps of:
(1) 10.0g of alkali lignin is dissolved in 160g of a solution containing 3wt% NH 3 ·H 2 Pouring the aqueous solution of O serving as an ammoniating agent into a reaction flask, and stirring for 30min at 30 ℃; then transferring the mixture into a polytetrafluoroethylene hydrothermal kettle for reaction at the constant temperature of 120 ℃ for 90min, cooling and spin-drying after the reaction is finished, transferring the mixture into a 60 ℃ vacuum oven for drying, and grinding the mixture to obtain Oxidized Ammonolysis Lignin (OAL);
(2) 1.0g of the ammonia oxide obtained in step (1) was reacted withPlacing the lignin in 50mL of pure water, and uniformly stirring to obtain an oxidative ammonolysis lignin solution; another 10mg of ruthenium chloride hydrate (RuCl) was taken 3 ·xH 2 O) placing the mixture in 50mL of pure water, and uniformly stirring the mixture by magnetic force to obtain a metal salt solution; dropwise adding the metal salt solution into the oxidative ammonolysis lignin solution, and stirring for 60min; then standing in a fume hood to allow metal ruthenium and oxidized ammonolysis lignin to precipitate for self-assembly coordination reaction for 12h; after the reaction is finished, placing the obtained sample in a plastic beaker, freezing the plastic beaker in a refrigerator, transferring the plastic beaker into a freeze dryer for drying, and grinding the obtained sample to obtain the Ru-lignin-based supermolecule precursor;
(3) Taking 1g of Ru-lignin-based supermolecule precursor prepared in the step (2) and adding the precursor into N 2 Carrying out high-temperature pyrolysis under the atmosphere by a thermal stabilization program, wherein the temperature of the high-temperature pyrolysis is 900 ℃, the heating rate is 5 ℃/min, and the time of the high-temperature pyrolysis is 2 hours; and cooling the sample to room temperature after the pyrolysis is finished, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 60 ℃ for 12 hours to obtain the catalyst material.
Comparative example 3
A lignin-based catalyst, the method of preparation comprising the steps of:
(1) 10.0g of alkali lignin is dissolved in 10g of aqueous solution with 6wt% hydrogen peroxide as oxidant, and then poured into a reaction flask, and stirred for 30min at 30 ℃; then transferring the mixture into a polytetrafluoroethylene hydrothermal kettle for reaction at the constant temperature of 120 ℃ for 90min, cooling and spin-drying after the reaction is finished, transferring the mixture into a 60 ℃ vacuum oven for drying, and grinding the mixture to obtain Oxidized Ammonolysis Lignin (OAL);
(2) Placing 1.0g of the oxidized aminolysis lignin obtained in the step (1) into 50mL of pure water, and uniformly stirring to obtain an oxidized aminolysis lignin solution; another 10mg of ruthenium chloride hydrate (RuCl) was taken 3 ·xH 2 O) placing the mixture in 50mL of pure water, and uniformly stirring the mixture by magnetic force to obtain a metal salt solution; dropwise adding the metal salt solution into the oxidative ammonolysis lignin solution, and stirring for 60min; then standing in a fume hood to enable metal Ru and oxidized ammonolysis lignin to be precipitated for self-assembly coordination reaction for 12h; after the reaction is completed, the obtained sample is placed in a plastic beaker, and is put into a refrigerator for freezing and then is transferredTransferring to a freeze dryer for drying, and grinding the obtained sample to obtain Ru-lignin-based supermolecule precursor;
(3) Taking 1g of Ru-lignin-based supermolecule precursor prepared in the step (2) and adding the precursor into N 2 Carrying out high-temperature pyrolysis under the atmosphere by a thermal stabilization program, wherein the temperature of the high-temperature pyrolysis is 900 ℃, the heating rate is 5 ℃/min, and the time of the high-temperature pyrolysis is 2 hours; and cooling the sample to room temperature after the pyrolysis is finished, washing with 1mol/L hydrochloric acid solution and deionized water respectively, and drying at 60 ℃ for 12 hours to obtain the catalyst material.
Comparative example 4
The preparation method of the Ru-based catalyst supported by the lignin-based nanoflower porous carbon carrier comprises the following steps:
(1) 1g of alkali lignin is weighed, 0.5g of magnesium oxide is weighed and added into 20mL of water, and stirring is continued for 1h at a rotating speed of 300-500rpm, so that a uniform gray-yellow mixture is formed.
(2) The mixture was transferred to a microwave reactor and reacted at a temperature rising rate of 10 c/min to 200 c for 5min to obtain a pale yellow mixture.
(3) The pale yellow mixture was dried in a freeze-dryer at-50℃for 24 hours to obtain a lignin and magnesium oxide complex.
(4) Transferring the obtained compound into a tube furnace, and adding N 2 In the atmosphere of (2), the temperature is raised to 900 ℃ at a heating rate of 5 ℃/min for 2 hours to obtain black solid, the calcined product is respectively washed by 1mol/L hydrochloric acid solution and deionized water, and the lignin-based nanoflower porous carbon material is obtained after drying at 60 ℃ for 12 hours.
(5) And (3) taking the lignin-based nanoflower porous carbon material obtained in the step (2) as a carrier, and soaking the carrier in 0.2mg/mL ruthenium trichloride solution for 24 hours by using a soaking method to obtain the Ru-based catalyst supported by the lignin-based nanoflower porous carbon carrier.
Verification example 1
The high-dispersion lignin derived Ru in-situ N-doped carbon materials prepared in examples 1-9 were respectively subjected to electrochemical performance testing to investigate the zinc-air battery, urea oxidation, glucose electrocatalytic conversion and furfural electrocatalytic conversionCatalytic properties such as oxidation. The zinc-air battery is formed by sequentially assembling a zinc sheet (0.5 mm), a diaphragm, hydrophobic carbon cloth, foam nickel and a waterproof breathable layer. The exposed area of the air cathode was about 1.0cm 2 . The electrolyte was 6.0M KOH and 0.1M Zn (Ac) 2 A mixture of solutions. All battery tests were performed in natural air to reflect the performance of the battery in practical application scenarios. The circulation test adopts circulation constant current pulse, discharges for 10min, and then discharges at 10 mA.cm -2 Charging for 10min. 4mg of the catalyst was mixed with 784uL of ethanol and 16uL of Nafion (5%), and sonicated for 60min to obtain a slurry. The obtained slurry was uniformly coated on a 2X 2cm carbon cloth, followed by drying at 60℃for 12 hours to obtain a catalyst-supporting carbon cloth. The reaction area of the air cathode is 1cm 2 Open Circuit Voltage (OCV) and charge-discharge (LSV) curves were obtained with CHI760E (Shanghai C.H), and specific capacity and cyclic charge-discharge tests were performed with a new wei charge-discharge machine; electrochemical performance testing of electrocatalytic conversion was performed on a Gamry Interface 1010 electrochemical workstation using a conventional three electrode system with a spectrally pure graphite rod (99.999% purity) as the counter electrode and Hg/HgO as the reference electrode. The working electrode was prepared by "drop coating" in which 4mg of carbon material powder was added to 200. Mu.L of a 0.25% Nafion-ethanol solution and dispersed by ultrasound for 15min. 50. Mu.L of the sample dispersion was pipetted onto a carbon paper (0.5X0.5 mm). The loading of the obtained catalyst was 4.0mg cm -2 . OER and electrocatalytic conversion Performance tests were both carried out in 1M KOH electrolyte solution, polarization curve measurements by linear sweep voltammetry at 2 mV.s -1 Is scanned to 1V at a current density of 10mA cm -2 The time potential is a performance evaluation criterion. 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. The results of the measurements are shown in Table 2 below and in FIGS. 2-5.
Table 2 examples 1-9 catalyst zinc air cell and electrocatalytic conversion performance table
Wherein FIG. 2 is a graph of the charge-discharge voltage gap of example 1 applied to the zinc-air battery field, and the peak power density of the graph was 116 mW.cm by calculating the discharge curve -2 The electrolyte has good reversibility and stability in a rechargeable liquid zinc-air battery. FIG. 3 is an electrocatalytic oxidation of urea using the catalyst of example 1, providing an ultra-low potential of 1.43V (vs. RHE) for urea oxidation, achieving 10mA/cm 2 Is much lower than OER (1.56V versus RHE), indicating that urea oxidation on ru@oalc electrodes is more favourable than OER. FIG. 4 is an electrocatalytic oxidation of glucose using the catalyst of example 1, providing an ultra-low potential of 1.44V (vs. RHE) for urea oxidation, achieving 10mA/cm 2 A current density well below OER (1.56V versus RHE) indicates that glucose oxidation on the ru@oalc electrode is more favourable than OER. FIG. 5 is an electrocatalytic oxidation of furfural using the catalyst of example 1, providing an ultra-low potential of 1.40V (vs RHE) for urea oxidation, achieving 10mA/cm 2 Far lower than OER (1.56V versus RHE) indicates that furfural oxidation on ru@oalc electrodes is more advantageous than OER.
The result shows that the high-dispersion lignin-derived Ru in-situ N-doped carbon material has higher power density when used for zinc-air batteries, has better performance than OER (organic chemical engineering) process when used for electrochemical oxidation of urea, glucose and furfural, and has potential for replacing OER reaction to produce high-price chemicals. The dosage, the oxidative ammonolysis degree, the hydrothermal temperature, the high-temperature charcoal burning temperature and other conditions of Ru doped in the preparation process have obvious influence on the catalytic performance of the Ru in-situ N-doped carbon material derived from the high-dispersion lignin. In a comprehensive view, the high-dispersion lignin derived Ru in-situ N-doped carbon material prepared in the embodiment 1 has excellent comprehensive catalytic performance in zinc-air batteries, urea electrochemical oxidation, glucose electrocatalytic oxidation and furfural electrocatalytic oxidation.
Further, the materials prepared in example 1 and comparative examples 1 to 4 were each subjected to the above electrochemical performance test, and the results are shown in Table 3 below.
Table 3 example 1 and comparative examples 1-4 catalyst zinc-air cells and electrocatalytic conversion performance tables
In conclusion, the high-dispersion lignin derived Ru in-situ N-doped carbon material prepared by the method has obviously better catalytic performance in producing hydrogen and oxygen by electrolysis of water compared with catalysts prepared by other modified synthesis paths. Comparative example 1 when a high-dispersion lignin derived Ru in-situ N-doped carbon material is synthesized by an impregnation method, the zinc-air battery performance and the electrocatalytic conversion performance of the obtained catalyst are weaker than those of the in-situ complexation precipitation of example 1. In comparative example 2, only lignin is subjected to amination modification, in comparative example 3, only lignin is subjected to oxidation modification, and the properties of the obtained material are far lower than those of the oxidative ammonolysis modification strategy in example 1, so that the excellent metal complexing capability of amide groups is shown. Comparative example 4 is a preparation of lignin-derived Ru-based catalyst carbon material by a template method, and the zinc-air battery and the electrocatalytic conversion performance of the catalyst are weaker than those of example 1, and the advantage of in-situ complexing of metal by oxidative ammonolysis modified lignin is also proved.
The above detailed description describes the analysis method according to the present invention. It should be noted that the above description is only intended to help those skilled in the art to better understand the method and idea of the present invention, and is not intended to limit the related content. Those skilled in the art may make appropriate adjustments or modifications to the present invention without departing from the principle of the present invention, and such adjustments and modifications should also fall within the scope of the present invention.
Claims (10)
1. The preparation method of the high-dispersion lignin-derived Ru in-situ N-doped carbon material is characterized by comprising the following steps of:
(1) Placing lignin, an oxidant and an amination agent in a solvent, uniformly stirring to form a mixed solution, then carrying out hydrothermal reaction, and drying after the reaction is finished to obtain oxidized ammonolysis lignin;
(2) Placing the oxidized ammonolysis lignin obtained in the step (1) in a solvent, and uniformly stirring to obtain an oxidized ammonolysis lignin solution; placing Ru salt into a solvent, stirring and dispersing uniformly, adding the oxidative ammonolysis lignin solution, and fully stirring to form a mixed solution for coordination reaction to obtain Ru-lignin-based supermolecule precursor;
(3) And (3) placing the Ru-lignin-based supermolecule precursor obtained in the step (2) into a tube furnace for high-temperature charcoal burning, and then carrying out acid washing and drying to obtain the Ru-lignin-based supermolecule precursor.
2. The method according to claim 1, wherein the oxidizing agent in step (1) is one or more selected from the group consisting of hydrogen peroxide, ozone, 2, 6-tetramethylpiperidine oxide.
3. The method according to claim 1, wherein the amination agent in the step (1) is one or more selected from ammonia water and ammonia gas.
4. The method according to claim 1, wherein the mass ratio of the oxidizing agent to the aminating agent in the step (1) is 1:1-3.
5. The process according to claim 1, wherein the hydrothermal reaction in step (1) is carried out at a temperature of 90 to 200 ℃.
6. The method according to claim 1, wherein the Ru salt in step (2) is selected from one or more of ruthenium chloride hydrate, ruthenium acetate and ruthenium acetylacetonate.
7. The method according to claim 1, wherein the concentration of ruthenium element in the mixed solution in the step (2) is 0.01 to 0.15mmol/L.
8. The method according to claim 1, wherein the high-temperature charcoal in step (3) has a temperature of 800-1000 ℃ and a heating rate of 0.5-5 ℃/min.
9. The high-dispersion lignin-derived Ru in-situ N-doped carbon material prepared by the method of any one of claims 1-8.
10. The application of the high-dispersion lignin-derived Ru in-situ N-doped carbon material prepared by the preparation method according to any one of claims 1-8 in the fields of zinc-air batteries, urea oxidation, glucose electrocatalytic conversion, furfural electrocatalytic oxidation and the like.
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