CN109012590B - Lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof - Google Patents
Lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof Download PDFInfo
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- CN109012590B CN109012590B CN201810972735.9A CN201810972735A CN109012590B CN 109012590 B CN109012590 B CN 109012590B CN 201810972735 A CN201810972735 A CN 201810972735A CN 109012590 B CN109012590 B CN 109012590B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 88
- 229920005610 lignin Polymers 0.000 title claims abstract description 73
- 230000007704 transition Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- -1 transition metal salt Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 45
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 45
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 37
- 239000000203 mixture Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 238000009826 distribution Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000001075 voltammogram Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000003795 desorption Methods 0.000 description 9
- 238000010335 hydrothermal treatment Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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Abstract
The invention belongs to the technical field of carbon materials, and discloses a lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof. The method comprises the following steps: (1) uniformly mixing transition metal salt and lignin in water to obtain lignin/transition metal salt mixed solution; (2) carrying out hydrothermal pre-carbonization treatment on the lignin/transition metal salt mixed solution to obtain a hydrothermal pre-carbonization product; (3) and mixing the hydrothermal pre-carbonization product with a nitrogen source, carbonizing at high temperature in a protective atmosphere, and performing subsequent treatment to obtain the lignin-based transition metal-nitrogen doped carbon material. The lignin-based transition metal-nitrogen-doped carbon material has excellent electrochemical performance; the preparation process of the material is simple, the raw material source is wide, the price is low, and an effective way is provided for high-value utilization of biomass. The carbon material of the present invention is applied to the fields of fuel cells, supercapacitors, adsorbent materials and/or electrolyzed water.
Description
Technical Field
The invention belongs to the fields of material science and energy storage and conversion, and particularly relates to a lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof.
Background
With the exhaustion of fossil resources and the increasing prominence of environmental problems, research on novel energy conversion and storage devices with high energy efficiency and environmental protection has received wide attention. The fuel cell has the advantages of high energy conversion efficiency, no pollutant emission, high starting speed and the like, and has wide application prospect in the field of new energy. At present, the biggest challenge of fuel cells is the problems of high cost and poor durability due to the use of a large amount of platinum catalyst. Therefore, research and development of a non-platinum catalyst with abundant resources, low cost, and excellent catalytic activity and stability has become one of the most important research subjects in the fuel cell field. Among them, the transition metal-nitrogen doped carbon material has become one of the most important research subjects in the fuel cell field because of its characteristics of excellent oxygen reduction catalytic activity, wide sources, high stability, strong immunity against the influence of methanol permeation, and the like. The oxygen reduction activity of the transition metal nitrogen-doped carbon material is high, the oxygen reduction activity mainly comes from metal-nitrogen active sites, and how to prepare a high-performance carbon material with uniformly distributed active sites is one of the main research contents of the material at present. The common synthesis method prepares the transition metal-nitrogen doped carbon material by physically mixing and carbonizing metal, a carbon source and a nitrogen source, and easily forms agglomerated inactive metal particles to influence the improvement of the oxygen reduction performance of the transition metal-nitrogen doped carbon material.
If the carbon-based oxygen reduction catalyst is prepared by taking the biomass resource with rich and reproducible resources as the raw material, the limit of fossil resource crisis on the development of the carbon material can be overcome, and the high-value utilization of the biomass resource can be realized. As a renewable biological resource, the lignin has the characteristics of low cost, environmental friendliness, rich resources and the like. According to the invention, lignin is used as a raw material, and a high-performance transition metal-nitrogen doped carbon catalyst with uniformly distributed active sites (transition metal-nitrogen sites) is prepared by utilizing the coordination reaction of phenolic hydroxyl groups on lignin structural units and transition metals, so that the high-valued utilization of the lignin is realized, and the preparation cost of the carbon material is reduced. Meanwhile, the existence of the hetero atoms can improve the wettability of the carbon material, increase the hydrophilicity and the adsorption capacity to ions, thereby reducing the diffusion resistance of the ions and generating a certain pseudo capacitance, thereby further improving the specific capacitance of the carbon material. The heteroatom-doped carbon material of the invention can therefore also be used as electrode material, in particular for supercapacitors and/or fuel cells.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a lignin-based transition metal-nitrogen doped carbon material with excellent electrochemical properties and a preparation method thereof. The carbon material prepared by the method has the advantages of uniform distribution of active sites, low cost, large specific surface area, excellent electrochemical performance and the like.
The invention also aims to provide application of the lignin-based transition metal-nitrogen doped carbon material. The lignin-based transition metal-nitrogen-doped carbon material is applied to the fields of fuel cells, super capacitors, adsorbing materials, electrolytic water and the like, and is particularly used for preparing electrode materials of the fuel cells and/or the super capacitors.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a lignin-based transition metal-nitrogen doped carbon material with excellent electrochemical performance comprises the following steps:
(1) uniformly mixing transition metal salt and lignin in water to obtain lignin/transition metal salt mixed solution; the transition metal salt is a water-soluble salt;
(2) carrying out hydrothermal pre-carbonization treatment on the lignin/transition metal salt mixed solution to obtain a hydrothermal pre-carbonization product; the temperature of the hydrothermal pre-carbonization treatment is 120-300 ℃;
(3) and mixing the hydrothermal pre-carbonization product with a nitrogen source, carbonizing at high temperature in a protective atmosphere, and performing subsequent treatment to obtain the lignin-based transition metal-nitrogen doped carbon material.
In the step (1), the lignin is more than one of alkali lignin, lignosulfonic acid and organic solvent type lignin (lignin extracted by an organic solvent), and preferably lignosulfonic acid.
The concentration of the transition metal salt in the water in the step (1) is (0.05-0.5) g/mL, preferably 0.1 g/mL.
The mass ratio of the transition metal salt to the lignin in the step (1) is 1 (0.2-5), preferably 1: 0.5.
In the step (1), the transition metal salt is Fe3+Salt formed, Cu2+Salt formed, Co2+Salt formed, Ni2+Salt formed, Mn2+One or more of the salts formed; preferably, the metal salt is at least one of ferric chloride, cobalt chloride, nickel chloride, copper chloride, manganese chloride, cobalt chloride, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, manganese nitrate, cobalt nitrate, ferric sulfate, and copper sulfate, and more preferably ferric chloride.
The hydrothermal pre-carbonization treatment in the step (2) is carried out in a closed reaction kettle.
The time of the hydrothermal pre-carbonization treatment in the step (2) is 2-24 h.
Preferably, the temperature of the hydrothermal pre-carbonization treatment in the step (2) is 180 ℃ and the time is 4 h.
And (4) the protective atmosphere in the step (3) is nitrogen or argon atmosphere.
The temperature of the high-temperature carbonization in the step (3) is 600-1000 ℃, and the time of the high-temperature carbonization is 0.2-10 h.
The temperature rise rate of the high-temperature carbonization in the step (3) is 0.5-20 ℃/min.
Preferably, the high-temperature carbonization in the step (3) is carried out under the following conditions: the carbonization rate is 5 ℃/min, the carbonization temperature is 900 ℃, and the heat preservation time is 2 h.
In the step (3), the nitrogen source is more than one of melamine, urea, dicyandiamide, ethylenediamine, thiourea and diammonium hydrogen phosphate, and is preferably melamine.
The mass ratio of the hydrothermal pre-carbonization product to the nitrogen source in the step (3) is (0.1-5): 1. More preferably, the mass ratio is 0.25: 1.
And (3) performing subsequent treatment, namely carbonizing at high temperature, cooling to room temperature, washing with acid, washing with water to neutrality, and drying to obtain the lignin-based transition metal-nitrogen doped carbon material.
The acid is H with the concentration of 0.05-5M2SO4Or a solution of HCl.
A lignin-based transition metal-nitrogen-doped carbon material is prepared by the method.
The lignin-based transition metal-nitrogen-doped carbon material is applied to the fields of fuel cells, super capacitors, adsorbing materials, electrolytic water and the like, and is particularly used for preparing electrode materials of the fuel cells and/or the super capacitors. The lignin-based transition metal-nitrogen-doped carbon material is applied to cathode materials of fuel cells, electrode materials of super capacitors and CO2Adsorption material, electrolytic water material, etc.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention takes lignin as a carbon source, has wide raw material source and low price, can overcome the limit of fossil resource crisis on the development of carbon materials, and can realize the high-value utilization of biomass resources.
(2) According to the carbon material prepared by the coordination reaction of phenolic hydroxyl in the lignin raw material and the transition metal, the active sites are uniformly distributed, and the problems of uneven distribution of the active sites, agglomeration of metal particles and the like caused by the traditional mixed carbonization method can be solved.
(3) The porous carbon material is prepared by the two-step method, the preparation process is simple, the steps are few, the implementation is easy, and the preparation cost of the carbon material can be effectively reduced.
(4) The lignin-based transition metal-nitrogen doped carbon material prepared by the invention has high oxygen reduction catalytic activity, has an initial potential (0.98V) and a half-wave potential (0.837V) equivalent to a platinum carbon electrode, and has a current density (5.19mA cm)–2) Is significantly higher than a platinum carbon electrode (4.89mA cm)–2). The carbon material prepared by the method has excellent super-capacitance performance, the specific capacitance is up to 390F/g (the current density is 0.5A/g), the cycling stability is high, and the capacitance retention value can reach 99.5% after 5000 times of cycling charge and discharge.
Drawings
FIG. 1 is an IR plot (a) and an XPS plot (b) of the hydrothermal precarbonization product of example 1; IR plot (a) of the hydrothermal precarbonization product of comparative example 2;
FIG. 2 shows Fe as a carbon material prepared in example 12-SN4XPS plot of C @900, wherein a is nitrogen spectrum, b is iron spectrum;
FIG. 3 shows Fe as a carbon material prepared in example 12-SN4TEM image (a) and elemental distribution plots (corresponding carbon, nitrogen, sulfur, iron elemental distribution plots, respectively, in FIGS. b-e) for C @ 900;
FIG. 4 shows Fe as a carbon material prepared in example 12-SN4SEM (a) and TEM image (b) of C @ 900;
FIG. 5 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of carbon materials prepared in examples 1, 2 and 3; figure a-nitrogen isothermal adsorption and desorption curve chart; figure b-aperture profile;
FIG. 6 is a linear sweep voltammogram of the carbon materials prepared in examples 1, 2 and 3;
FIG. 7 is a linear sweep voltammogram of the carbon materials prepared in examples 1, 4, 5, and 6;
FIG. 8 is a linear sweep voltammogram of the carbon materials prepared in example 1, comparative example 1, and comparative example 2, and Pt/C.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. The parameter processing which is not mentioned can be carried out by referring to the conventional technique. The water used in the present invention may be distilled water, deionized water or tap water.
Example 1
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of lignosulfonic acid to ferric chloride is 1:2) into ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the lignosulfonic acid/ferric chloride mixed solution obtained in the step (1) into a hot water reaction kettle, heating to 180 ℃, carrying out hydrothermal treatment for 4h, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying (at 60 ℃) to obtain a hydrothermal pre-carbonization product;
(3) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:4, placing the mixture in a tube furnace, heating the mixture to 900 ℃ in an inert atmosphere (nitrogen gas) for carbonization for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the washed product with water to be neutral, drying the washed product (60 ℃) to obtain the lignin-based transition metal-nitrogen doped carbon material marked as Fe2-SN4C@900。
The IR diagram (a) and XPS diagram (b) of the hydrothermal precarbonization product of example 1 are shown in fig. 1. By analyzing the results of infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) of the hydrothermal pre-carbonized product, it can be seen that the metallic iron ions and-OH in lignin form a coordination structure after the hydrothermal treatment, and the metallic iron has been successfully doped in the pre-carbonized product (fig. 1). FIG. 2 shows Fe as a carbon material prepared in example 12-SN4XPS plot of C @900, wherein a is nitrogen spectrum, b is iron spectrum; FIG. 3 shows Fe as a carbon material prepared in example 12-SN4TEM image (a) and elemental distribution plots (corresponding carbon, nitrogen, sulfur, and iron elemental distribution plots, respectively, for C @ 900). From Fe2-SN4XPS testing of C @900 (FIG. 2) shows that Fe is present after mixed carbonization of the pre-carbonized product with melamine2-SN4C @900 forms the active site of iron-nitrogen, and the iron and nitrogen elements are uniformly distributed as can be seen by a Transmission Electron Microscope (TEM) and an element distribution diagram (FIG. 3). FIG. 4 shows Fe as a carbon material prepared in example 12-SN4SEM (a) and TEM image (b) of C @ 900. It can be seen from the figure that the lignin-based carbon material prepared by the method is a sphere-like particle stacked on each other, and a certain amount of nanosheets are distributed around the particle, and no metal particles are obviously agglomerated in the TEM. The nitrogen adsorption and desorption curve and the pore size distribution diagram of the carbon material prepared in the example are shown in fig. 5; figure a-nitrogen isothermal adsorption and desorption curve chart; figure b-aperture distribution plot. By Fe2-SN4The specific surface area of the product is 580m calculated by a nitrogen adsorption and desorption curve of C @9002In terms of/g, and the pore size distribution is reasonable (FIG. 5). The linear sweep voltammograms of the carbon materials prepared in this example are shown in fig. 6-8. On toolThe characteristics of uniformly distributed iron-nitrogen active sites, nitrogen doping, larger specific surface area, reasonable pore size distribution and the like are prepared, and Fe2-SN4C @900 shows excellent oxygen reduction catalytic activity, the initial potential and the half-wave potential are 0.98V and 0.837V respectively, and the current density is as high as 5.19mAcm–2. At the same time, Fe2-SN4C @900 also has excellent supercapacitor performance, and in a three-electrode system, the specific capacitance is 280F/g (the current density is 0.5A/g).
Example 2
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of lignosulfonic acid to ferric chloride is 1:2) into ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the lignosulfonic acid/ferric chloride mixed solution obtained in the step (1) into a reaction kettle, placing the reaction kettle in a muffle furnace, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product;
(3) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:4, placing the mixture in a tube furnace, heating the mixture to 800 ℃ in an inert atmosphere (nitrogen gas) for carbonization for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the washed product with water to be neutral, drying the washed product (60 ℃) to obtain the lignin-based transition metal-nitrogen doped carbon material marked as Fe2-SN4C@800。
The nitrogen adsorption and desorption curve and the pore size distribution diagram of the carbon material prepared in the example are shown in fig. 5; figure a-nitrogen isothermal adsorption and desorption curve chart; figure b-aperture distribution plot. The linear sweep voltammogram of the carbon material prepared in this example is shown in FIG. 6. By Fe2-SN4The specific surface area of the nitrogen adsorption-desorption curve C @800 is 482m2(g), the mesoporous content of 1.6 to 3nm is small, as shown in FIG. 5. Relative to Fe2-SN4C@900，Fe2-SN4C @800 has poor oxygen reduction performance (FIG. 6) and a specific capacitance of 310F/g (current density of 0.5A/g).
Example 3
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of lignosulfonic acid to ferric chloride is 1:2) into ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the lignosulfonic acid/ferric chloride mixed solution obtained in the step (1) into a reaction kettle with a certain volume, placing the reaction kettle in a muffle furnace, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product;
(3) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:4, placing the mixture in a tube furnace, heating the mixture to 1000 ℃ in an inert atmosphere (nitrogen gas) for carbonization for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the washed product with water to be neutral, drying the washed product (60 ℃) to obtain the lignin-based transition metal-nitrogen doped carbon material marked as Fe2-SN4C@1000。
The nitrogen adsorption and desorption curve and the pore size distribution diagram of the carbon material prepared in the example are shown in fig. 5; figure a-nitrogen isothermal adsorption and desorption curve chart; figure b-aperture distribution plot. The linear sweep voltammogram of the carbon material prepared in this example is shown in FIG. 6. By Fe2-SN4The specific surface area of the nitrogen adsorption and desorption curve C @1000 is 457m2(g), the mesoporous content of 1.6 to 3nm is small, as shown in FIG. 5. Relative to Fe2-SN4C@900，Fe2-SN4C @1000 had poor oxygen reduction performance (FIG. 6) and a specific capacitance of 276F/g (current density of 0.5A/g).
Example 4
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of lignosulfonic acid to ferric chloride is 1:2) into ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the lignosulfonic acid/ferric chloride mixed solution obtained in the step (1) into a reaction kettle with a certain volume, placing the reaction kettle in a muffle furnace, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product;
(3) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:2, placing the mixture in a tube furnace, heating the mixture to 900 ℃ in an inert atmosphere (nitrogen gas) for carbonization for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the washed product with water to be neutral, drying the washed product (60 ℃) to obtain the lignin-based transition metal-nitrogen doped carbon material marked as Fe2-SN2C @ 900. The linear sweep voltammogram of the carbon material prepared in this example is shown in FIG. 7. The specific capacitance was 287F/g (current density: 0.5A/g).
Example 5
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of lignosulfonic acid to ferric chloride is 1:2) into ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the lignosulfonic acid/ferric chloride mixed solution obtained in the step (1) into a reaction kettle with a certain volume, placing the reaction kettle in a muffle furnace, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product;
(3) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:6, placing the mixture in a tube furnace, heating the mixture to 1000 ℃ in an inert atmosphere (nitrogen gas) for carbonization for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the washed product with water to be neutral, drying the washed product (60 ℃) to obtain the lignin-based transition metal-nitrogen doped carbon material marked as Fe2-SN6C @ 900. The linear sweep voltammogram of the carbon material prepared in this example is shown in FIG. 7. The specific capacitance is 390F/g (the current density is 0.5A/g), the cycling stability is high, and the capacitance retention value can reach 99.5% after 5000 times of cycling charge and discharge; in a symmetrical electrode system, when the power density is 450W/kg, the energy density can reach 14.7 kW/kg.
Example 6
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of alkali lignin to ferric chloride is 1:2) into the ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the alkali lignin/ferric chloride mixed solution obtained in the step (1) into a reaction kettle with a certain volume, placing the reaction kettle in a muffle furnace, heating to 180 ℃ for hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product;
(3) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:8, placing the mixture in a tube furnace, heating the mixture to 900 ℃ in an inert atmosphere (nitrogen gas) for carbonization for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the carbonized product with water to be neutral, and drying the product (60 ℃) to obtain the lignin-based transition metal-nitrogen doped carbon material marked as Fe2-SN8C @ 900. The linear sweep voltammogram of the carbon material prepared in this example is shown in FIG. 7. The specific capacitance was 196F/g (current density: 0.5A/g).
Comparative example 1
(1) Dissolving ferric chloride in water to obtain a ferric chloride aqueous solution with the concentration of 0.1 g/mL; adding lignosulfonic acid (the mass ratio of lignosulfonic acid to ferric chloride is 1:2) into ferric chloride aqueous solution, and uniformly stirring to obtain lignosulfonic acid/ferric chloride mixed solution;
(2) transferring the lignosulfonic acid/ferric chloride mixed solution obtained in the step (1) into a reaction kettle with a certain volume, placing the reaction kettle in a muffle furnace, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product;
(3) and (3) placing the pre-carbonized product in a tubular furnace, heating to 900 ℃ in an inert atmosphere (nitrogen), carbonizing for 2h, cooling to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing with water to be neutral, and drying to obtain the lignin-based transition metal carbon material. The obtained carbon material was labeled as Fe2-SC @900, which is poor in oxygen reduction performance (FIG. 8). Wire of carbon material prepared in this exampleThe sex sweep voltammogram is shown in FIG. 8. The specific capacitance was only 62F/g (current density 0.5A/g).
Comparative example 2
(1) Adding lignosulfonic acid into water, and uniformly stirring to obtain a lignosulfonic acid solution, wherein the concentration of the lignosulfonic acid solution is 0.1 g/mL;
(2) transferring the lignosulfonic acid solution obtained in the step (1) into a reaction kettle, placing the reaction kettle in a muffle furnace, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling to room temperature after the reaction is finished, washing the solid product with water, and drying at 60 ℃ to obtain a hydrothermal pre-carbonization product; the IR diagram of the hydrothermal precarbonization product is shown in FIG. 1 (a);
(3) and (2) fully and uniformly mixing the pre-carbonized product and melamine according to the mass ratio of 1:4, placing the mixture in a tube furnace, heating the mixture to 900 ℃ in an inert atmosphere (nitrogen), carbonizing the mixture for 2 hours, cooling the mixture to room temperature after the reaction is finished, washing the carbonized product with 1M hydrochloric acid solution, washing the washed product with water to be neutral, and drying the washed product to obtain the lignin-based transition metal-nitrogen doped carbon material. The resulting carbon material is labeled as SN4C @900, which has poor oxygen reduction performance (FIG. 8). The linear sweep voltammogram of the carbon material prepared in this example is shown in FIG. 8. The specific capacitance was only 59F/g (current density 0.5A/g).
In addition, the invention also provides a linear sweep voltammogram of Pt/C as shown in FIG. 8. The carbon materials of the present invention have superior performance by comparing the carbon materials prepared in example 1, comparative example 1 and comparative example 2 with the linear sweep voltammograms of Pt/C.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a lignin-based transition metal-nitrogen doped carbon material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing transition metal salt and lignin in water to obtain lignin/transition metal salt mixed solution; the transition metal salt is a water-soluble salt;
(2) carrying out hydrothermal pre-carbonization treatment on the lignin/transition metal salt mixed solution to obtain a hydrothermal pre-carbonization product; the temperature of the hydrothermal pre-carbonization treatment is 120-300 ℃;
(3) and mixing the hydrothermal pre-carbonization product with a nitrogen source, carbonizing at high temperature in a protective atmosphere, and performing subsequent treatment to obtain the lignin-based transition metal-nitrogen doped carbon material.
2. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 1, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises the following steps: the temperature of the high-temperature carbonization in the step (3) is 600-1000 ℃; the mass ratio of the hydrothermal pre-carbonization product to the nitrogen source in the step (3) is (0.1-5): 1.
3. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 1, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises the following steps: in the step (1), the lignin is more than one of alkali lignin, lignosulfonic acid and organic solvent type lignin;
in the step (1), the transition metal salt is Fe3+Salt formed, Cu2+Salt formed, Co2+Salt formed, Ni2+Salt formed, Mn2+More than one of the salts formed.
4. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 3, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises: the lignin is lignosulfonic acid; the transition metal salt is ferric chloride.
5. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 1, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises the following steps: the mass ratio of the transition metal salt to the lignin in the step (1) is 1 (0.2-5);
the time of the hydrothermal pre-carbonization treatment in the step (2) is 2-24 h;
the high-temperature carbonization time in the step (3) is 0.2-10 h.
6. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 1, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises the following steps: in the step (3), the nitrogen source is more than one of melamine, urea, dicyandiamide, ethylenediamine, thiourea and diammonium hydrogen phosphate;
the concentration of the transition metal salt in the water in the step (1) is (0.05-0.5) g/mL;
the temperature rise rate of the high-temperature carbonization in the step (3) is 0.5-20 ℃/min.
7. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 1, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises the following steps: and (3) performing subsequent treatment, namely carbonizing at high temperature, cooling to room temperature, washing with acid, washing with water to neutrality, and drying to obtain the lignin-based transition metal-nitrogen doped carbon material.
8. The method for preparing the lignin-based transition metal-nitrogen-doped carbon material according to claim 7, wherein the lignin-based transition metal-nitrogen-doped carbon material comprises: the acid is H with the concentration of 0.05-5M2SO4Or a solution of HCl.
9. A lignin-based transition metal-nitrogen-doped carbon material obtained by the production method according to any one of claims 1 to 8.
10. Use of the lignin-based transition metal-nitrogen doped carbon material according to claim 9, wherein: the lignin-based transition metal-nitrogen-doped carbon material is applied to the fields of fuel cells, super capacitors, adsorbing materials and/or electrolyzed water.
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