CN112044461B - Lignin-based bimetallic functionalized carbon material and preparation method and application thereof - Google Patents
Lignin-based bimetallic functionalized carbon material and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 83
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 230000002255 enzymatic effect Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 3
- 230000021523 carboxylation Effects 0.000 abstract description 2
- 238000006473 carboxylation reaction Methods 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 33
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 238000009826 distribution Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 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
- 239000003446 ligand Substances 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of biomass materials, and discloses a lignin-based bimetallic functionalized carbon material and a preparation method and application thereof. Provides a preparation method of a lignin-based metal functionalized carbon material, which is characterized in that lignin is modified by carboxylation and then coordinated with transition metal to form a metal-carboxylated lignin-based supramolecular precursor, and then the metal-carboxylated lignin-based supramolecular precursor is co-doped with non-metal hetero atoms and carbonized at high temperature. The method comprises the following steps: s1, carrying out coordination combination on the carboxylated lignin and a solution of iron and cobalt metal salts to obtain a bi-metal-carboxylated lignin-based supramolecular precursor; s2, carrying out nonmetal doping and high-temperature carbonization treatment on the metal-lignin-based supramolecular precursor to obtain the modified lignin-based metal functionalized carbon material. The electrocatalytic oxygen evolution electrode prepared from the carboxylated lignin-based metal functionalized carbon material prepared by the preparation method disclosed by the invention shows excellent catalytic activity.
Description
Technical Field
The invention relates to the technical field of biomass materials, in particular to a lignin-based bimetallic functionalized carbon material and a preparation method and application thereof.
Background
The high-efficiency catalyst for electrocatalytic hydrogen production is mainly noble metal and its oxide, such as Pt, ir, ru, irO 2 、RuO 2 Etc., but their scarcity and high cost have limited their widespread use. Therefore, research and development of catalysts with abundant resources, low price, and excellent catalytic activity and stability are urgently needed. Although the oxygen evolution performance of materials such as transition metals of iron, cobalt, nickel, manganese and the like is not as good as that of noble metal materials, the transition metals of iron, cobalt, nickel, manganese and the like are widely distributed and have low price, the stability of the transition metals is obviously superior to that of noble metals, the transition metals become potential choices for replacing the noble metal materials gradually, and meanwhile, the coordination of the bimetallic material catalystThe application of the same effect in electrocatalysis has more excellent properties than the corresponding single metal. The biomass carbon material has the unique properties of good chemical stability, large pH value adaptation range, high specific surface area, good conductivity, abundant surface functional groups and the like, and the carbon nano material prepared by using the biomass carbon material as a carbon source has a better prospect.
In the process of preparing the non-noble metal oxygen evolution catalyst, the active group of the carbon material with good conductivity is limited, and the binding force between the metal catalyst and the carbon material is weak, so that the metal cannot be uniformly dispersed and the stability is poor. Therefore, the development of novel carbon skeleton materials with abundant groups (such as carboxyl, hydroxyl and the like) is of great significance for improving the catalytic efficiency of the catalyst.
Chinese patent (CN 109012590A) discloses a preparation method of a lignin-based transition metal-nitrogen doped carbon material, which utilizes a carbon skeleton material lignin containing carboxyl to be mixed with metal salt and then subjected to hydrothermal method and high-temperature calcination to obtain a product, but the obtained product has low metal content, few active sites and long preparation time.
Disclosure of Invention
The invention aims to provide a preparation method of a lignin-based bimetallic functionalized carbon material, and the carbon material obtained by the preparation method has the advantages of high metal content, more active sites, uniform distribution and high catalytic activity.
It is another object of the present invention to provide a lignin-based bimetallic functionalized carbon material.
The invention also aims to provide application of the lignin-based bimetallic functionalized carbon material.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a lignin-based bimetal functionalized carbon material comprises the following steps:
s1, mixing carboxylated lignin with an iron salt solution and a cobalt salt solution, adjusting the pH value to 6-10, standing, and filtering to obtain an iron-cobalt bimetal-carboxylated lignin-based supramolecular precursor;
s2, mixing the iron-cobalt bimetal-carboxylated lignin-based supramolecular precursor with a nitrogen source, and carrying out carbonization treatment at the temperature of 500-900 ℃ for 0.5-3 h in a protective atmosphere to obtain the carboxylated lignin-based functionalized carbon material.
The mass ratio of the carboxylated lignin to the ferric salt to the cobalt salt is (16-1): (4-1): (1-10).
According to the invention, the carboxylated lignin is adopted, the water solubility of the carboxylated lignin is improved, and the reaction sites for forming coordination between the carboxylated lignin and the metal are increased. Iron-cobalt bimetal is adopted to coordinate with the carboxylated lignin, a supramolecular precursor is formed by adjusting the pH value, and finally the supramolecular precursor and a nitrogen source are mixed and carbonized at high temperature to obtain the lignin-based iron-cobalt bimetal functionalized carbon material.
The carboxylated lignin is prepared by the following preparation method, dissolving Enzymatic Hydrolysis Lignin (EHL) in a sodium hydroxide aqueous solution, pouring into a reaction flask and stirring; weighing monochloroacetic acid, dissolving in deionized water, dropwise adding a monochloroacetic acid aqueous solution into a reaction flask, reacting in a constant-temperature water bath, cooling, adjusting the pH value, centrifuging for 10min, washing, centrifuging, and drying to obtain the carboxylated lignin, wherein the carboxylated lignin is uniformly named as EHL-COOH.
Preferably, the mass ratio of the carboxylated lignin, the ferric salt and the cobalt salt in the step S1 is (4-2): (2-1): (1-5).
The iron salt is selected from one or more of ferric chloride, ferric nitrate or ferric sulfate.
The cobalt salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt sulfate or cobalt acetate.
Preferably, the lignin is selected from one or more of enzymatic lignin, alkali lignin, sulphite lignin or lignosulphonate.
Preferably, the lignin is modified with a carboxylating agent to obtain carboxylated lignin.
Preferably, the standing time in the step S1 is 6-24 h.
Preferably, the mass ratio of the iron-cobalt bimetallic-carboxylated lignin-based supramolecular precursor to the nitrogen source in the step S1 is 1 (0.5-4).
Preferably, the nitrogen source in step S2 is one or more of urea, ammonia gas, dicyandiamide, melamine, carbon nitride, cyanamide, and dimethyl imidazole.
Preferably, the protective atmosphere in step S2 is one of nitrogen or inert gas.
A lignin-based bimetallic functionalized carbon material is prepared by the method.
The lignin-based bimetallic functionalized carbon material is applied to electrolytic water oxygen evolution reaction, and the oxygen evolution reaction takes 0V as an initial potential and takes 1 mV.s -1 Is scanned to 1V.
According to the invention, a carboxylated lignin ligand with a coordination function is designed and synthesized by utilizing the surface functional group structure modification of lignin, and is precisely coordinated with iron-cobalt metal ions to form a metal-lignin-based supramolecular precursor, and the metal-lignin-based supramolecular precursor is mixed with a nitrogen source, and then the metal-lignin-based supramolecular precursor is placed in a tubular furnace for in-situ carbonization, so that the lignin-based bi-metal functionalized carbon material is prepared, and the electrochemical activity of a lignin/metal compound is improved. The product obtained by the preparation method has high metal content, short preparation time, uniform metal distribution and no agglomeration.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the invention, carboxyl is introduced by modifying lignin, the carboxylated lignin with a three-dimensional network structure has a large number of active groups such as carboxyl, hydroxyl and the like, and can coordinate with metal to provide active sites, the lignin/bimetal compound with a regular microstructure is formed by coordination with iron salt and cobalt salt metal ions, and finally nitrogen source mixing and calcining are carried out, so that high metal content and uniform metal distribution are obtained, and the prepared pore channel structure is beneficial to the high-efficiency transfer and mass transfer process in the catalysis process, thereby improving the catalysis efficiency. Compared with a commercial Ir/C catalyst, the prepared lignin-based bimetallic functionalized catalyst has a catalytic effect comparable to that of the commercial Ir/C catalyst, and the commercial catalyst is a noble metal.
Drawings
FIG. 1 is an SEM image of a carbon material FeCo-N/C-700 prepared in example 1.
FIG. 2 is an SEM photograph of carbon material N/C-700 prepared in comparative example 6.
FIG. 3 is an XPS map of a carbon material FeCo-N/C-700 prepared in example 1.
FIG. 4 is an XRD pattern of the carbon material FeCo-N/C-700 prepared in example 1 and the carbon material N/C-700 prepared in comparative example 6.
FIG. 5 is a graph of OER test results for carbon materials prepared in example 1, comparative example 5, and comparative example 6 as catalysts versus commercial Ir/C catalysts.
FIG. 6 is a graph of OER test results for carbon materials prepared in example 1, comparative example 2, and comparative example 3 as catalysts versus commercial Ir/C catalysts.
FIG. 7 shows the lignin-based bimetallic functionalized carbon material (FeCo-N/C-700) prepared by the method of example 1 at a current density of 10mA cm -2 OER stability when used.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The raw materials in the examples are all commercially available; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise specified.
The carboxylated lignin used in the examples and comparative examples was prepared by this method: 10.0g of EHL was dissolved in 25g of a 20wt% aqueous NaOH solution, and the solution was poured into a reaction flask, and stirred at 30 ℃ for 30min; weighing 6.0g of monochloroacetic acid, dissolving in 10.0g of deionized water, dropwise adding an aqueous solution of monochloroacetic acid into a reaction flask, reacting in a constant-temperature water bath at 70 ℃ for 90min, cooling, measuring the pH value of the reaction solution, adjusting the pH value of the solution to 5.0 by 2mol/L hydrochloric acid, centrifuging at 8000rpm for 10min, washing, centrifuging, drying the filtrate in an oven at 50 ℃ to obtain the carboxylated lignin, which is collectively named as EHL-COOH.
Example 1
A preparation method of a lignin-based bimetal functionalized carbon material comprises the following steps:
s1, weighing the following substances according to a mass ratio of EHL-COOH, ferric chloride to cobalt nitrate of 2. Dissolving EHL-COOH in 100mL of pure water, dissolving ferric chloride hexahydrate and cobalt nitrate hexahydrate in 50mL of pure water, uniformly stirring by magnetic force, dropwise adding the mixture into an EHL-COOH aqueous solution, stirring for 10min, and measuring the pH value of the mixed solution. And (3) adjusting the pH of the mixed solution to 8.5 by using ammonia water and hydrochloric acid, standing for 12h, filtering, washing and precipitating, centrifuging, drying a sample in a drying oven for 24h, taking out, and weighing to obtain the metal-lignin-based supramolecular precursor, namely EHL-COOH-Fe/Co.
S2, grinding and uniformly mixing EHL-COOH-Fe/Co and urea in a mass ratio of 1:1, carbonizing at a high temperature of 700 ℃ in an Ar atmosphere by a heat stabilizing procedure, keeping at the temperature of 700 ℃ for 1h, and cooling the sample to room temperature. Respectively washing with 1mol/L hydrochloric acid solution and deionized water, and drying at 80 ℃ for 12h to obtain the carboxylated lignin-based bimetallic functionalized carbon material FeCo-N/C-700.
Examples 2 to 10
The preparation of examples 2-10 was identical to that of example 1 except for the amounts of starting materials and parameters, which are listed in Table 1.
TABLE 1 raw materials and parameter settings for examples 2-10
Comparative examples 1 to 7
Comparative examples 1 to 7 were prepared in substantially the same manner as in example 1, and the raw materials and parameters are shown in Table 2
TABLE 2 raw materials and parameters for comparative examples 1 to 7
The lignin-based metal functionalized carbon materials prepared according to the present invention can be used as catalysts for which the catalysts prepared in the above examples and comparative examples were tested for their electrochemical performance and compared to commercial Ir/C catalysts. The electrochemical performance test is carried out on an IVium electrochemical workstation in the Netherlands, a traditional three-electrode system is adopted, a spectral pure graphite rod (with the purity of 99.999%) is used as a counter electrode, and Hg/HgO is used as a reference electrode. The working electrode was prepared by "drop coating" in which 4mg of carbon material powder was added to 200. Mu.L of 0.25% Nafion-ethanol solution, and ultrasonically dispersed for 15min. 50 μ L of the sample dispersion was pipetted onto carbon paper (0.5X 0.5 mm) and oven dried at 60 ℃.
Electrochemical performance tests are carried out in a 1M KOH electrolyte solution, high-purity oxygen is continuously introduced during OER tests, and potentials are compensated by IR through Thale software carried by an instrument. The measurement of the polarization curve is carried out by linear sweep voltammetry, and the oxygen evolution reaction takes 0V as the initial potential and 1mV s -1 Is scanned to 1V. The electrocatalytic activity of the catalyst was determined in a standard three-electrode system, and to exclude the potential gain effect of platinum on the catalyst, the auxiliary electrode was replaced with a spectrally pure graphite rod. Usually, 10mA · cm is used -2 The overpotential under the current density is used for measuring the oxygen evolution catalytic performance of different catalysts, and the lower the overpotential of the catalyst is, the better the oxygen evolution performance of the catalyst is.
Table 3 table for comparing metal contents of example 1 and comparative example 4
| Iron element content | Cobalt element content | |
| Example 1 | 1.4493wt％ | 5.5995wt％ |
| Comparative example 4 | 0.0554wt％ | 0.1915wt％ |
From FeCo-N/C-700 prepared in example 1, the metal content in a FeCo-N/C-700 sample was determined by ICP-OES, wherein the iron element content was 1.4493wt% and the cobalt element content was 5.5995wt%.
And FeCo-N/C prepared by comparative example 4 0 700, determination of FeCo-N/C by ICP-OES 0 -metal content in the 700 sample, wherein the iron element content is 0.0554wt% and the cobalt element content is 0.1915wt%.
It was found that a product with a high metal content, a high number of catalytically active sites and a uniform distribution can be obtained by the carboxylation step.
XPS plots of FeCo-N/C-700 samples prepared in example 1 as shown in FIG. 3. XPS measurement spectrum shows the existence of Co, fe, O, N and C elements.
The electron microscope image of the microstructure of the N/C-700 sample prepared in the comparative example 6 is shown in FIG. 2, the electron microscope image of the microstructure of the FeCo-N/C-700 sample prepared in the example 1 is shown in FIG. 1, and the comparison between FIG. 1 and FIG. 2 shows that the FeCo-N/C-700 sample has a richer pore structure, and the metal particles are in a highly dispersed state, are uniformly distributed, and have no agglomeration phenomenon.
XRD patterns of the N/C-700 sample prepared in comparative example 6 and the FeCo-N/C-700 sample prepared in example 1 are shown in FIG. 4. It can be observed that the characteristic peaks of the N/C-700 sample appear at positions of 24 DEG and 43 DEG 2 theta, respectively, and are assigned to (002) and (100), respectively, representing the diffraction planes of graphitic carbon. In contrast, the FeCo-N/C-700 sample prepared in example 1 showed many new characteristic diffraction peaks, and the diffraction peaks with 2 theta located near 43.7 DEG, 50.8 DEG and 74.9 DEG were respectively compared with: (A), (B)111 The (200) and (220) planes are in one-to-one correspondence and can be classified as Co 5.47 N (PDF # 41-0943). The characteristic diffraction peaks at 45.1 DEG and 65.7 DEG 2 theta can be assigned to Co 0.7 Fe 0.3 (PDF # 48-1818) indicating that the metal is mainly present in the form of an alloy.
TABLE 4 tables of results of electrocatalyst testing for examples 1-10 and comparative examples 1-7
| Overpotential (mV) | |
| Example 1 | 260 |
| Example 2 | 340 |
| Example 3 | 335 |
| Example 4 | 312 |
| Example 5 | 293 |
| Example 6 | 304 |
| Example 7 | 296 |
| Example 8 | 300 |
| Example 9 | 307 |
| Example 10 | 292 |
| Comparative example 1 | 385 |
| Comparative example 2 | 382 |
| Comparative example 3 | 354 |
| Comparative example 4 | 394 |
| Comparative example 5 | 365 |
| Comparative example 6 | 401 |
| Comparative example 7 | 376 |
FIG. 5 is a graph showing the results of OER tests on the carbon materials of example 1, comparative example 5 and comparative example 6 of the present invention as a catalyst and a commercial Ir/C catalyst at a current density of 10mA cm -2 Under the conditions, the overpotential of the FeCo-N/C-700 catalyst in the example 1 is 260mV, the overpotential of the FeCo-C-700 catalyst in the comparative example 5 is 365mV, and the overpotential of the N/C-700 catalyst in the comparative example 6 is 401mV, so that the result shows that the oxygen evolution overpotential can be greatly reduced by doping metal, and the electro-catalysis oxygen generation performance is improved; doped with non-metals can also haveEffectively promoting the promotion of the electrocatalytic oxygen production performance.
The overpotential of commercial Ir/C is 258mV, which shows that the catalyst based on the lignin-based bimetallic functionalized carbon material in example 1 has excellent electrocatalytic oxygen generation performance, can be comparable with the commercial Ir/C catalyst,
FIG. 6 is a graph of the results of OER testing of carbon materials prepared in example 1, comparative example 2, and comparative example 3 as catalysts with a commercial Ir/C catalyst. At a current density of 10mA cm -2 Next, the overpotential of commercial Ir/C was 258mV, the overpotential of the FeCo-N/C-700 catalyst of example 1 was 260mV, the overpotential of the Fe-N/C-700 catalyst of comparative example 1 was 385mV, the overpotential of the Co-N/C-700 catalyst of comparative example 2 was 382mV, and the overpotential of the FeCoNi-N/C-700 catalyst of comparative example 3 was 354mV, indicating that the activity of the bimetallic doped FeCo-N/C-700 catalyst was optimal.
FIG. 7 shows that the overpotential of the FeCo-N/C-700 sample is substantially unchanged after the carbon material prepared in example 1 is circulated for 80000s, and good stability is shown.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a lignin-based bimetal functionalized carbon material is characterized by comprising the following steps:
s1, mixing carboxylated lignin with an iron salt solution and a cobalt salt solution, adjusting the pH value to 6 to 10, standing, and filtering to obtain an iron-cobalt bimetal-carboxylated lignin-based supramolecular precursor;
s2, mixing the iron-cobalt bimetal-carboxylated lignin-based supramolecular precursor with a nitrogen source, and carbonizing at 500-900 ℃ for 0.5-3 h under a protective atmosphere to obtain a carboxylated lignin-based bimetal functionalized carbon material;
the mass ratio of the carboxylated lignin to the ferric salt to the cobalt salt is (16 to 1): (4~1): (1 to 10);
the mass ratio of the iron-cobalt bimetal-carboxylated lignin-based supramolecular precursor to the nitrogen source is 1 (0.5 to 4);
the lignin-based bimetal functionalized carbon material has a rich pore structure, and metal particles are in a highly dispersed state and are uniformly distributed.
2. The method for preparing the lignin-based bimetallic functionalized carbon material according to claim 1, wherein the mass ratio of the carboxylated lignin to the iron salt to the cobalt salt is (4~2): (2~1): (1~5).
3. The method of producing a lignin-based bimetallic functionalized carbon material according to claim 1, wherein the lignin is selected from one or more of enzymatic lignin, alkali lignin, sulfite lignin or lignosulfonate.
4. The method for producing a lignin-based bimetallic functionalized carbon material according to claim 1, wherein the lignin is modified with a carboxylating agent to obtain a carboxylated lignin.
5. The method for preparing a lignin-based bimetallic functionalized carbon material as claimed in claim 1, wherein the standing time in the step S1 is 6 to 24 hours.
6. The method for preparing the lignin-based bimetallic functionalized carbon material as claimed in claim 1, wherein the nitrogen source in step S2 is one or more of urea, ammonia gas, dicyandiamide, melamine, carbon nitride, cyanamide and dimethylimidazole.
7. The method of claim 1, wherein the protective atmosphere in step S2 is one of nitrogen or an inert gas.
8. A lignin-based bimetallic functionalized carbon material prepared by the preparation method of any one of claims 1 to 7.
9. Use of the lignin-based bimetallic functionalized carbon material of claim 8 for oxygen evolution from electrolyzed water.
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