CN115784228A - Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof - Google Patents
Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof Download PDFInfo
- Publication number
- CN115784228A CN115784228A CN202211651728.1A CN202211651728A CN115784228A CN 115784228 A CN115784228 A CN 115784228A CN 202211651728 A CN202211651728 A CN 202211651728A CN 115784228 A CN115784228 A CN 115784228A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- porous carbon
- doped porous
- preparation
- carbon nanosheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002135 nanosheet Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 51
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000000197 pyrolysis Methods 0.000 claims abstract description 48
- 238000000498 ball milling Methods 0.000 claims abstract description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 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 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000002028 Biomass Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000005554 pickling Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 229920001661 Chitosan Polymers 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 150000002829 nitrogen Chemical class 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 238000010000 carbonizing Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Abstract
A double-metal modified nitrogen-doped porous carbon nanosheet and a preparation method and application thereof are disclosed, wherein the preparation method comprises the steps of mixing a biomass carbon source, a nitrogen source and sodium chloride, carrying out first ball milling treatment, then adding ferric nitrate, cobalt nitrate and dimethyl imidazole, carrying out second ball milling treatment, and then dropwise adding a methanol solution for carrying out third ball milling treatment to obtain a mixture of nitrogen-doped double-metal MOF materials; and pyrolyzing the mixture powder in an inert gas or nitrogen atmosphere, pickling and drying a product subjected to pyrolysis, and then carbonizing the product in an argon-hydrogen reducing atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet. The method effectively improves the N doping amount in the final carbon material, and the material has more reaction active sites and good ORR performance.
Description
Technical Field
The invention belongs to the field of catalysis and energy storage, and relates to a bimetal modified nitrogen-doped porous carbon nanosheet and a preparation method and application thereof.
Background
Zinc air cells are considered to be promising candidates for the next generation of clean and sustainable energy storage devices because of their low cost, safety, environmental friendliness and high specific energy density. In zinc-air cells, the air catalyst accelerates the slow Oxygen Reduction Reaction (ORR) and largely controls the overall performance of the cell. Traditional platinum-based materials are the most practical electrocatalysts, but their unreliable stability, lower power density and higher scarcity and cost severely limit their large-scale application.
Among air catalysts, carbon-based materials are considered promising candidates due to their high electrical conductivity, chemical robustness, porous structure and adjustable composition. Heteroatom doping and defect engineering are the main strategies to improve the ORR performance of carbon materials. Theoretical and experimental research shows that the breaking of electric neutrality, the changing of charge and spin distribution by heteroatom doping or defect engineering is beneficial to O 2 Thereby obtaining the best ORR performance. MOFs have been widely used as ideal precursors for the preparation of heteroatom-doped carbon materials with regular framework structures and high surface areas, but direct pyrolysis of MOFs often results in the loss of a large number of carbon and nitrogen species, resulting in low yield of carbon materials and reduced N doping, which in turn affects the electrical properties of the materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a bimetal modified nitrogen-doped porous carbon nanosheet and a preparation method and application thereof, so that the problems that in the prior art, when MOF is used as a precursor of a heteroatom-doped carbon material, direct pyrolysis causes loss of carbon and nitrogen species, and the N doping amount is reduced are solved.
The invention is realized by the following technical scheme:
a preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
s1: mixing a biomass carbon source, a nitrogen source and sodium chloride, performing first ball milling treatment, then adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, and then dropwise adding a methanol solution to perform third ball milling treatment to obtain a mixture of nitrogen-doped bimetallic MOF materials;
s2: and pyrolyzing the mixture powder in an inert gas or nitrogen atmosphere, pickling and drying the product after pyrolysis, and then putting the product into an argon-hydrogen reducing atmosphere for carbonization to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
Preferably, the biomass carbon source is one or a mixture of more than two of chitosan, cellulose and lignin.
Preferably, the nitrogen source is one or a mixture of more than two of melamine, urea and ammonium chloride.
Preferably, the mass ratio of the biomass carbon source to the biomass nitrogen source to the biomass sodium chloride is (0.8-1.4): (3.5-5.5): 6-9.
Preferably, the molar ratio of the ferric nitrate to the cobalt nitrate to the dimethyl imidazole is (0.6-1.3) to (0.7-1.2) to (5.3-7.7).
Preferably, in the step S2, in the pyrolysis process, the temperature rise rate is 2-10 ℃/min, the pyrolysis temperature is 700-1000 ℃, and the pyrolysis time is 0.5-3 h.
Preferably, in step S2, the stirring temperature of the pyrolysis-treated product in the sulfuric acid solution or hydrochloric acid solution is 60 to 80 ℃.
Preferably, in step S2, the carbonization temperature is 700-1000 ℃ and the carbonization time is 0.5-3 h.
A double-metal modified nitrogen-doped porous carbon nanosheet is prepared by the method; the work of the bimetal modified nitrogen-doped porous carbon nanosheetThe specific density is 240-300 mV cm -2 。
The bimetal modified nitrogen-doped porous carbon nanosheet is applied to the field of electrocatalysis.
Compared with the prior art, the invention has the following beneficial technical effects:
a method for preparing a bimetal modified nitrogen-doped porous carbon nanosheet comprises the steps of synthesizing a nitrogen-doped bimetal MOF material in a ball milling mode in the material synthesis process, converting the MOF material into carbon nanosheets in a pyrolysis process, simultaneously converting a biomass carbon source into the carbon nanosheets in a pyrolysis process, interweaving the two carbon nanosheets to form the porous carbon nanosheets, synthesizing MOF in a ball milling mode in the preparation process, carrying out pyrolysis treatment, adding an additional nitrogen source in the synthesis process of the MOF, effectively increasing the N doping amount in the final carbon material through the combination of the two technical means, and effectively forming a salt-sealed reactor through adding a pore-forming agent sodium chloride so that an organic matter is partially decomposed to form defective carbon nanosheets, effectively increasing the pore structure and the specific surface area of the final carbon nanosheets, effectively increasing the reaction active sites of the material and improving the ORR performance of the carbon material when the carbon material is used as a catalyst.
Furthermore, the mass ratio of the biomass carbon source, the nitrogen source and the sodium chloride is (0.8-1.4) to (3.5-5.5) to (6-9), so that the morphology of the material can be effectively controlled, and the material has better electrochemical performance.
Furthermore, the molar ratio of the ferric nitrate to the cobalt nitrate to the dimethyl imidazole is (0.6-1.3) to (0.7-1.2) to (5.3-7.7), so that the bimetallic MOF material can be fully formed, and the electrochemical performance of the material can be effectively improved.
Furthermore, in the pyrolysis process, the heating rate is 2-10 ℃/min, the pyrolysis temperature is 700-1000 ℃, and the pyrolysis time is 0.5-3 h, so that the morphology of the material can be effectively controlled, and the ORR performance of the material can be improved.
Furthermore, the stirring treatment temperature of the product after the pyrolysis treatment in a sulfuric acid solution is 60-80 ℃, and unreacted metal in a reaction system is effectively removed.
Furthermore, in the step S3, the carbonization temperature is 700-1000 ℃, the carbonization time is 0.5-3 h, the morphology of the material can be effectively controlled, and the ORR performance of the material is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic flow chart of a method for preparing a bimetal modified nitrogen-doped porous carbon nanosheet according to the present invention;
fig. 2 is a cyclic voltammetry curve of a bi-metal iron and cobalt modified nitrogen-doped biomass-based porous carbon nanosheet prepared in example 1 of the present invention;
fig. 3 is a discharge curve diagram of the iron and cobalt bimetal modified nitrogen-doped biomass-based porous carbon nanosheet prepared in example 1 of the present invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," "including," "having," or similar terms, shall mean "consisting of 8230; \8230, composition" and "consisting essentially of 8230; \8230, composition" such as "A comprises a" shall mean "A comprises a and the other" and "A comprises a only".
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
As shown in fig. 1, the invention provides a preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet, which is characterized by comprising the following steps:
s1: mixing a biomass carbon source, a nitrogen source and sodium chloride, performing first ball milling treatment, adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, and dropwise adding a methanol solution to perform third ball milling treatment to obtain a mixture of a nitrogen-doped bimetallic MOF material; wherein the biomass carbon source is one or a mixture of more than two of chitosan, cellulose and lignin. The nitrogen source is one or a mixture of more than two of melamine, urea and ammonium chloride. The mass ratio of the biomass carbon source, the biomass nitrogen source and the biomass sodium chloride is (0.8-1.4) to (3.5-5.5) to (6-9). The molar ratio of the ferric nitrate, the cobalt nitrate and the dimethyl imidazole is (0.6-1.3) to (0.7-1.2) to (5.3-7.7). Wherein, sodium chloride is used as a pore-forming agent.
S2: and (3) pyrolyzing the mixture powder in an inert gas or nitrogen atmosphere, wherein in the pyrolysis process, the heating rate is 2-10 ℃/min, the pyrolysis temperature is 700-1000 ℃, and the pyrolysis time is 0.5-3 h. And then, carrying out acid washing and drying on the product after the pyrolysis treatment, specifically, putting the product after the pyrolysis treatment into a sulfuric acid solution or a hydrochloric acid solution, stirring at the temperature of 60-80 ℃, and then putting the product into an argon-hydrogen reducing atmosphere for carbonization treatment for 0.5-3 h at the temperature of 700-1000 ℃ to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The technical problem to be solved by the invention is as follows: in order to find an oxygen reduction reaction electrocatalyst capable of replacing a zinc-air battery, the preparation method solves the problems of high cost, poor ORR reaction performance and low power density of the existing preparation method.
According to the invention, the cost is reduced by selecting the biomass chitosan, the iron and cobalt elements are added for doping modification, the pore-making agent is introduced to generate interface defects, and the interface defects are combined with the high-temperature pyrolysis of the metal organic framework limited in the molten salt under secondary different atmospheres to prepare the bimetal modified nitrogen-doped porous carbon nanosheet material. Compared with commercial Pt/C RuO 2 The cost is lower, the oxygen reduction performance is better, and the power density is higher. The power density of the bimetal modified nitrogen-doped porous carbon nanosheet prepared by the method is 240-300 mV cm -2 。
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
The following examples use instrumentation conventional in the art. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
a. weighing 0.5g of chitosan, 2g of sodium chloride and 4g of ammonium chloride by using an electronic balance, and mixing and recording as A; 1mmol of ferric nitrate, 1mmol of cobalt nitrate and 6mmol of dimethylimidazole are weighed on an electronic balance and mixed to be recorded as B.
b. And ball-milling the mixture A for 10 minutes, adding the mixture B, ball-milling for 10 minutes, taking out, dropwise and slowly adding 2ml of methanol solution, ball-milling for 10 minutes, taking out a product, and drying overnight.
c. The mixture was carbonized in a tube furnace at 900 ℃ for 3h under nitrogen.
d. Dispersing the solid after primary carbonization in 1mol/L sulfuric acid solution, stirring overnight at 80 ℃, washing and drying; and carbonizing the mixture for 1h in a tubular furnace at 800 ℃ and in an argon-hydrogen reducing gas atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The cyclic voltammetry characteristic curve of the bi-metal modified nitrogen-doped porous carbon nanosheet prepared in the embodiment is shown in fig. 2, and the bi-metal modified nitrogen-doped porous carbon electrode material for electrocatalytic oxygen reduction reaction and commercial Pt/C. RuO prepared from the bi-metal modified nitrogen-doped porous carbon electrode material are shown in fig. 2 2 From the comparison of the cyclic voltammograms, it can be seen that the ORR of example 1 is 0.89, compared to commercial Pt/C. RuO 2 The material prepared by the method has more defects and active sites available for electrocatalysis, so that the material has more excellent oxygen reduction performance.
The discharge curve of the bimetal modified nitrogen-doped porous carbon nanosheet prepared in the embodiment is shown in fig. 3, and the bimetal modified nitrogen-doped porous carbon electrode material for electrocatalytic oxygen reduction reaction and commercial Pt/C. RuO prepared from the bimetal modified nitrogen-doped porous carbon nanosheet shown in fig. 3 2 Compared with the discharge curve and the power density curve, the power density of the material prepared in the embodiment is 270mV cm -2 Higher than Pt/C RuO 2 Is more than twice as high as the power density of (c).
Example 2
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
a. weighing 0.5g of chitosan, 1g of sodium chloride and 4g of ammonium chloride by using an electronic balance, and mixing and recording as A; an electronic balance was used to weigh 1mmol of ferric nitrate, 1mmol of cobalt nitrate, and 6mmol of dimethylimidazole, and the mixture was recorded as B.
b. And ball-milling the mixture A for 10 minutes, adding the mixture B, ball-milling for 10 minutes, taking out, dropwise and slowly adding 2ml of methanol solution, ball-milling for 10 minutes, taking out a product, and drying overnight.
c. The above mixture was carbonized in a tube furnace at 900 ℃ for 3h under nitrogen atmosphere.
d. Dispersing the solid after primary carbonization in 1mol/L sulfuric acid solution, stirring overnight at 80 ℃, washing and drying; and carbonizing the mixture for 1h in a tubular furnace at 900 ℃ in an argon-hydrogen reducing gas atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the material prepared in this example was 239mV cm -2 。
Example 3
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
a. weighing 1g of chitosan, 2g of sodium chloride and 8g of ammonium chloride by using an electronic balance, and mixing and recording as A; 1mmol of ferric nitrate, 1mmol of cobalt nitrate and 6mmol of dimethylimidazole are weighed on an electronic balance and mixed to be recorded as B.
b. And ball-milling the mixture A for 10 minutes, adding the mixture B, ball-milling for 10 minutes, taking out, dropwise and slowly adding 2ml of methanol solution, ball-milling for 10 minutes, taking out a product, and drying overnight.
c. The above mixture was carbonized in a tube furnace at 800 ℃ under nitrogen atmosphere for 3h.
d. Dispersing the solid after primary carbonization in 1mol/L sulfuric acid solution, stirring overnight at 80 ℃, washing and drying; and carbonizing the mixture for 1h in a tubular furnace at 800 ℃ in an argon-hydrogen reducing gas atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the material prepared in this example was 245mV cm -2 。
Example 4
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
a. weighing 0.5g of chitosan, 2g of sodium chloride and 4g of ammonium chloride by using an electronic balance, and mixing and recording as A; 1mmol of ferric nitrate, 1mmol of cobalt nitrate and 6mmol of dimethylimidazole are weighed on an electronic balance and mixed to be recorded as B.
b. And ball-milling the mixture A for 10 minutes, adding the mixture B, ball-milling for 10 minutes, taking out, dropwise and slowly adding 2ml of methanol solution, ball-milling for 10 minutes, taking out a product, and drying overnight.
c. The above mixture was carbonized in a tube furnace at 700 ℃ for 2h under nitrogen atmosphere.
d. Dispersing the solid after primary carbonization in 1mol/L sulfuric acid solution, stirring overnight at 80 ℃, washing and drying; and carbonizing the mixture for 1h in a tubular furnace at 800 ℃ in an argon-hydrogen reducing gas atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the material prepared in this example was 255mV cm -2 。
Example 5
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
a. weighing 1g of chitosan, 4g of sodium chloride and 8g of ammonium chloride by using an electronic balance, and mixing and recording as A; 2mmol of ferric nitrate, 2mmol of cobalt nitrate and 12mmol of dimethylimidazole are weighed on an electronic balance and mixed to be recorded as B.
b. And ball-milling the mixture A for 10 minutes, adding the mixture B, ball-milling for 10 minutes, taking out, dropwise and slowly adding 2ml of methanol solution, ball-milling for 10 minutes, taking out a product, and drying overnight.
c. The above mixture was carbonized in a tube furnace at 700 ℃ for 3h under nitrogen atmosphere.
d. Dispersing the solid after primary carbonization in 1mol/L sulfuric acid solution, stirring overnight at 80 ℃, washing and drying; and carbonizing the mixture for 2 hours in a tubular furnace at 800 ℃ in an argon-hydrogen reducing gas atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the material prepared in this example was 255mV cm -2 。
Example 6
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
a. weighing 1g of chitosan, 4g of sodium chloride and 8g of ammonium chloride by using an electronic balance, and mixing and recording as A; an electronic balance was used to weigh 1mmol of ferric nitrate, 1mmol of cobalt nitrate, and 6mmol of dimethylimidazole, and the mixture was recorded as B.
b. And ball-milling the mixture A for 10 minutes, adding the mixture B, ball-milling for 10 minutes, taking out, dropwise and slowly adding 2ml of methanol solution, ball-milling for 10 minutes, taking out a product, and drying overnight.
c. The above mixture was carbonized in a tube furnace at 700 ℃ for 3h under nitrogen atmosphere.
d. Dispersing the solid after primary carbonization in 1mol/L sulfuric acid solution, stirring overnight at 80 ℃, washing and drying; and (3) carbonizing the mixture for 1h in a tubular furnace at 800 ℃ in an argon-hydrogen reducing gas atmosphere to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the material prepared in this example was 260mV cm -2 。
Example 7
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
s1: mixing chitosan, melamine and sodium chloride, performing first ball milling treatment, adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, and dropwise adding a methanol solution to perform third ball milling treatment to obtain a mixture of nitrogen-doped bimetallic MOF materials; wherein the mass ratio of chitosan, melamine and sodium chloride is 0.8. The molar ratio of iron nitrate, cobalt nitrate and dimethyl imidazole is 0.6.
S2: and (3) carrying out pyrolysis treatment on the mixture powder under helium gas, wherein in the pyrolysis process, the heating rate is 2 ℃/min, the pyrolysis temperature is 700 ℃, and the pyrolysis time is 0.5h. And then, carrying out acid washing and drying on the product after the pyrolysis treatment, specifically, placing the product after the pyrolysis treatment in a sulfuric acid solution, stirring at the temperature of 60 ℃, and then placing the product in an argon-hydrogen reducing atmosphere for carbonization treatment for 0.5h at the temperature of 700 ℃ to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the prepared bimetal modified nitrogen-doped porous carbon nanosheet is 300mV cm -2 。
Example 8
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
s1: mixing cellulose, urea and sodium chloride, performing first ball milling treatment, adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, and dropwise adding a methanol solution to perform third ball milling treatment to obtain a mixture of the nitrogen-doped bimetallic MOF material; wherein the mass ratio of the cellulose to the urea to the sodium chloride is 1.0. The molar ratio of iron nitrate, cobalt nitrate and dimethylimidazole is 0.8.
S2: and (3) pyrolyzing the mixture powder under argon gas, wherein the heating rate is 4 ℃/min, the pyrolysis temperature is 950 ℃, and the pyrolysis time is 0.7h in the pyrolysis process. And then, carrying out acid washing and drying on the product after the pyrolysis treatment, specifically, placing the product after the pyrolysis treatment in a hydrochloric acid solution, stirring at 65 ℃, and then placing the product in an argon-hydrogen reducing atmosphere for carbonization treatment for 0.7h at 750 ℃ to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the prepared bimetal modified nitrogen-doped porous carbon nanosheet is 280mV cm -2 。
Example 9
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
s1: mixing lignin, urea, melamine and sodium chloride, performing first ball milling treatment, adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, and dropwise adding a methanol solution to perform third ball milling treatment to obtain a mixture of nitrogen-doped bimetallic MOF materials; wherein the mass ratio of the cellulose to the urea to the sodium chloride is 1.3. The molar ratio of the iron nitrate to the cobalt nitrate to the dimethylimidazole is 1.0.
S2: and (3) pyrolyzing the mixture powder in a nitrogen atmosphere, wherein in the pyrolysis process, the heating rate is 6 ℃/min, the pyrolysis temperature is 980 ℃, and the pyrolysis time is 1.5h. And then, carrying out acid washing and drying on the product after the pyrolysis treatment, specifically, placing the product after the pyrolysis treatment in a sulfuric acid solution, stirring at the temperature of 70 ℃, and then placing the product in an argon-hydrogen reducing atmosphere for carbonization treatment for 1.5h at the temperature of 900 ℃ to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the prepared bimetal modified nitrogen-doped porous carbon nanosheet is 295mV cm -2 。
Example 10
A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet comprises the following steps:
s1: mixing chitosan, lignin, urea, ammonium chloride and sodium chloride, performing first ball milling treatment, adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, dropwise adding a methanol solution, and performing third ball milling treatment to obtain a mixture of the nitrogen-doped bimetallic MOF material; wherein the mass ratio of the cellulose to the urea to the sodium chloride is 1.4. The molar ratio of iron nitrate, cobalt nitrate and dimethyl imidazole is 1.3.
S2: and carrying out pyrolysis treatment on the mixture powder in a nitrogen atmosphere, wherein in the pyrolysis process, the heating rate is 10 ℃/min, the pyrolysis temperature is 1000 ℃, and the pyrolysis time is 3h. And then, carrying out acid washing and drying on the product after the pyrolysis treatment, specifically, placing the product after the pyrolysis treatment in a sulfuric acid solution, stirring at the temperature of 80 ℃, and then placing the product in an argon-hydrogen reducing atmosphere for carbonization treatment for 3 hours at the temperature of 1000 ℃ to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
The power density of the prepared bimetal modified nitrogen-doped porous carbon nanosheet is 287mV cm -2 。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a bimetal modified nitrogen-doped porous carbon nanosheet is characterized by comprising the following steps:
s1: mixing a biomass carbon source, a nitrogen source and sodium chloride, performing first ball milling treatment, then adding ferric nitrate, cobalt nitrate and dimethyl imidazole, performing second ball milling treatment, and then dropwise adding a methanol solution to perform third ball milling treatment to obtain a mixture of nitrogen-doped bimetallic MOF materials;
s2: and pyrolyzing the mixture powder in an inert gas or nitrogen atmosphere, pickling and drying the product after pyrolysis, and then putting the product into an argon-hydrogen reducing atmosphere for carbonization to obtain the bimetal modified nitrogen-doped porous carbon nanosheet.
2. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet according to claim 1, wherein the biomass carbon source is one or a mixture of two or more of chitosan, cellulose and lignin.
3. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet according to claim 1, wherein the nitrogen source is one or a mixture of two or more of melamine, urea and ammonium chloride.
4. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet as claimed in claim 1, wherein the mass ratio of the biomass carbon source, the nitrogen source and the sodium chloride is (0.8-1.4): (3.5-5.5): (6-9).
5. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet as claimed in claim 1, wherein the molar ratio of the ferric nitrate to the cobalt nitrate to the dimethylimidazole is (0.6-1.3) to (0.7-1.2) to (5.3-7.7).
6. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet according to claim 1, wherein in the step S2, in the pyrolysis process, the temperature rise rate is 2-10 ℃/min, the pyrolysis temperature is 700-1000 ℃, and the pyrolysis time is 0.5-3 h.
7. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet according to claim 1, wherein in the step S2, the stirring treatment temperature of the product after pyrolysis treatment in a sulfuric acid solution or a hydrochloric acid solution is 60-80 ℃.
8. The preparation method of the bimetal modified nitrogen-doped porous carbon nanosheet according to claim 1, wherein in step S2, the carbonization temperature is 700-1000 ℃ and the carbonization time is 0.5-3 h.
9. A bimetal modified nitrogen doped porous carbon nanosheet, characterized by being prepared by the method of any one of claims 1 to 8; the power density of the bimetal modified nitrogen-doped porous carbon nanosheet is 240-300 mV cm -2 。
10. Use of the bi-metal modified nitrogen-doped porous carbon nanoplatelets of claim 9 in the field of electrocatalysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211651728.1A CN115784228A (en) | 2022-12-21 | 2022-12-21 | Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211651728.1A CN115784228A (en) | 2022-12-21 | 2022-12-21 | Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115784228A true CN115784228A (en) | 2023-03-14 |
Family
ID=85427664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211651728.1A Pending CN115784228A (en) | 2022-12-21 | 2022-12-21 | Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115784228A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174188A (en) * | 2018-09-07 | 2019-01-11 | 常州大学 | A kind of preparation of Heteroatom doping carbon material/Ni-MOF composite electrocatalyst |
| CN109678146A (en) * | 2019-01-22 | 2019-04-26 | 中国科学院福建物质结构研究所 | A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application |
| CN110289424A (en) * | 2019-07-05 | 2019-09-27 | 北京化工大学 | A kind of preparation method of MOF derived carbon and cellular porous carbon composite |
| CN110444776A (en) * | 2019-07-02 | 2019-11-12 | 清华大学 | A kind of base metal N doping MOF economic benefits and social benefits elctro-catalyst and preparation method thereof |
| KR102086658B1 (en) * | 2018-10-22 | 2020-03-10 | 한국에너지기술연구원 | Biomass carbon-MOF composite, preparation method thereof and super capacitor electrode comprising the same |
| CN111545208A (en) * | 2020-05-26 | 2020-08-18 | 福州大学 | Cobalt-nickel bimetallic catalyst and preparation method thereof |
| CN113460993A (en) * | 2021-06-29 | 2021-10-01 | 湘潭大学 | Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery |
| CN113908874A (en) * | 2021-09-30 | 2022-01-11 | 华中科技大学 | Nitrogen-rich porous composite carbon material, and preparation method and application thereof |
| CN115020122A (en) * | 2022-06-30 | 2022-09-06 | 西安交通大学 | Nitrogen-doped paper fiber porous carbon foam electrode material and preparation method and application thereof |
-
2022
- 2022-12-21 CN CN202211651728.1A patent/CN115784228A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174188A (en) * | 2018-09-07 | 2019-01-11 | 常州大学 | A kind of preparation of Heteroatom doping carbon material/Ni-MOF composite electrocatalyst |
| KR102086658B1 (en) * | 2018-10-22 | 2020-03-10 | 한국에너지기술연구원 | Biomass carbon-MOF composite, preparation method thereof and super capacitor electrode comprising the same |
| CN109678146A (en) * | 2019-01-22 | 2019-04-26 | 中国科学院福建物质结构研究所 | A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application |
| CN110444776A (en) * | 2019-07-02 | 2019-11-12 | 清华大学 | A kind of base metal N doping MOF economic benefits and social benefits elctro-catalyst and preparation method thereof |
| CN110289424A (en) * | 2019-07-05 | 2019-09-27 | 北京化工大学 | A kind of preparation method of MOF derived carbon and cellular porous carbon composite |
| CN111545208A (en) * | 2020-05-26 | 2020-08-18 | 福州大学 | Cobalt-nickel bimetallic catalyst and preparation method thereof |
| CN113460993A (en) * | 2021-06-29 | 2021-10-01 | 湘潭大学 | Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery |
| CN113908874A (en) * | 2021-09-30 | 2022-01-11 | 华中科技大学 | Nitrogen-rich porous composite carbon material, and preparation method and application thereof |
| CN115020122A (en) * | 2022-06-30 | 2022-09-06 | 西安交通大学 | Nitrogen-doped paper fiber porous carbon foam electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108212157B (en) | Metal boride water cracking catalyst, preparation method and application thereof in aspect of electrocatalytic water cracking | |
| CN109759066B (en) | Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst | |
| CN111013634A (en) | Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof | |
| CN109585856B (en) | Preparation method of dual-functional cobalt sulfide and sulfur and nitrogen doped carbon in-situ composite electrode | |
| CN114784299A (en) | Nitrogen-sulfur doped carbon material and preparation method and application thereof | |
| US10947117B2 (en) | Mechanically stable composite electrolyte for intermediate temperature fuel cell with improved proton conductivity and methods thereof | |
| CN113299934A (en) | Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell | |
| CN109772413B (en) | Nitrogen-sulfur co-doped graphdiyne material, preparation method and application thereof, and oxygen evolution reaction catalyst containing nitrogen-sulfur co-doped graphdiyne material | |
| CN115784228A (en) | Bimetal modified nitrogen-doped porous carbon nanosheet and preparation method and application thereof | |
| CN108808026B (en) | Metal-air battery oxygen electrode catalyst material and preparation method and application thereof | |
| KR102465836B1 (en) | A transition metal nitride-carbon catalyst composite, a method for manufacturing the same, a electrode catalyst for fuel cell comprising the transition metal nitride-carbon catalyst composite, a fuel cell comprising the electrode catalyst | |
| CN115058731A (en) | N, S doped porous carbon loaded Co composite material and preparation method and application thereof | |
| CN113584504A (en) | Ru/RuO2/MoO2Composite material and preparation method and application thereof | |
| CN114214663A (en) | Nitrogen vacancy modified nickel nitride electrocatalytic material and preparation method and application thereof | |
| CN108940288B (en) | Preparation method of nickel-coated carbon nanotube efficient hydrogen evolution electrocatalyst | |
| CN113181944A (en) | Preparation method of Ni-based nonmetal doped catalyst | |
| CN111525143A (en) | Preparation method of nitrogen and boron co-doped carbon material and application of nitrogen and boron co-doped carbon material in cathode of microbial fuel cell | |
| CN115125578B (en) | Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst | |
| CN114784292B (en) | Lithium-carbon dioxide battery positive electrode material and preparation method thereof | |
| CN115786964B (en) | Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst, preparation method and application thereof | |
| CN115747874B (en) | Preparation method and application of rare earth element doped 2D RE@Fe-MOF efficient integrated membrane electrode | |
| CN116093346A (en) | Non-noble metal fuel cell catalyst and preparation method and application thereof | |
| GB2611508A (en) | A stable reusable graphite crucible for upscaling of unsupported metal oxides electrocatalysts via a modified Adams fusion method | |
| CN113136588A (en) | Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof | |
| Cui et al. | Pt/C electrocatalysts derived from recycled Pt/Re mixed solutions: synthesis, characterization, and electrochemical behaviour in fuel cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |