CN108722414B - Preparation method of thin-wall graphitized carbon-coated metal core-shell structure material - Google Patents
Preparation method of thin-wall graphitized carbon-coated metal core-shell structure material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 90
- 239000002184 metal Substances 0.000 title claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 239000011258 core-shell material Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002905 metal composite material Substances 0.000 claims abstract description 34
- 229920005610 lignin Polymers 0.000 claims abstract description 33
- 238000003763 carbonization Methods 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000010000 carbonizing Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000011257 shell material Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 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 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 239000010410 layer Substances 0.000 description 23
- 229910052742 iron Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000001241 arc-discharge method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/398—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- 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
Abstract
The invention provides a preparation method of a thin-wall graphitized carbon-coated metal core-shell structure material, which comprises the following steps: the preparation method of the lignin-metal composite material comprises the steps of carbonizing a carbon source and a metal source by a hydrothermal method by taking lignin resin as the carbon source and metal salt as the metal source to obtain the lignin-metal composite material; and a carbonization step, which comprises carbonizing the lignin-metal composite material by adopting an inverse program heating method to obtain a thin-wall graphitized coated metal core-shell material, wherein the metal is a core, and the graphitized carbon is a shell. The invention provides the method for preparing the thin-wall graphitized carbon-coated metal core-shell structure material, which is simple to operate and low in cost, and the performance of the thin-wall graphitized carbon-coated metal core-shell structure material prepared by the method is improved.
Description
Technical Field
The invention relates to the technical field of core-shell structure material preparation, in particular to a preparation method of a thin-wall graphitized carbon-coated metal core-shell structure material.
Background
In recent years, carbon-coated transition metal catalysts, particularly Graphitized Carbon (GC) -coated Transition Metal (TM) type TM @ GC catalysts, have attracted much attention, and in the reaction process, due to introduction of carbon atoms, the metal bond length is increased, so that the metal d band is shrunk, and the state density near the fermi level is increased, so that the metal d band has an electronic structure and catalytic characteristics similar to those of rare noble metal catalysts such as platinum, rhodium, iridium, palladium, ruthenium and the like, and the activity and stability of the "quasi-platinum catalyst" are exhibited in the classical catalytic reactions such as catalytic hydrogenation, oxidation reduction and the like.
Although the preparation methods of TM @ GC catalysts have been reported, the preparation process of the catalysts is difficult to perform fine structure regulation, so that the catalytic performance of the catalysts is easy to degrade, the effective service life of the catalysts is shortened, and the potential application of the catalysts is limited. For example, Fe @ GC is limited by the thickness of the wrapped carbon layer (which affects catalytic activity by reducing surface curvature due to too thick a wrapped carbon layer) in the application of a substituted platinum catalyst to hydrogen production from electrolyzed water. Therefore, the rational design of the carbon wrap of the TM @ GC catalyst plays a critical role for catalytic applications.
At present, the preparation method for preparing the carbon-coated transition metal material mainly comprises the following steps: arc discharge, laser evaporation, solid phase pyrolysis, chemical vapor deposition, and the like. However, the preparation methods for preparing the carbon-coated transition metal material still have the defects that the reaction temperature of the arc discharge method is higher, and the phase purity of the obtained material is low; the size of the metal core in the laser evaporation method is difficult to control, and the thickness of the wrapped carbon layer is not uniform; the solid phase pyrolysis method involves a graphite-based carbon source and is difficult to form graphitized carbon; the thickness of the carbon layer in the chemical vapor deposition method is difficult to control, usually about 20-30 layers, and the catalytic activity is affected because the surface curvature is reduced due to the coated carbon layer being too thick.
Therefore, how to solve the problem that the graphitized carbon coating layer is too thick, and providing a method for preparing a thin-walled graphitized carbon coating metal core-shell structure material with simple operation and low cost becomes a problem to be solved urgently.
Disclosure of Invention
The invention provides a preparation method of a thin-wall graphitized carbon-coated metal core-shell structure material, which comprises the following steps:
a) the preparation method of the lignin-metal composite material comprises the steps of carbonizing a carbon source and a metal source by a hydrothermal method by taking lignin resin as the carbon source and metal salt as the metal source to obtain the lignin-metal composite material;
b) and a carbonization step, which comprises carbonizing the lignin-metal composite material by adopting an inverse procedure temperature rise method to obtain a thin-wall graphitized coated metal core-shell material, wherein the metal is a core, and the graphitized carbon is a shell.
Optionally, step a) includes the following specific steps:
i) mixing the raw materials in a mass ratio of 08-1.2: 0.9-1.5: 0.08-0.15 of lignin, formaldehyde and sodium hydroxide to perform chemical reaction to obtain lignin resin;
ii) weighing the lignin resin obtained in the step i) and 0.1mol/L metal salt solution, uniformly stirring, putting into a hydrothermal kettle, reacting at 160-180 ℃ for 12-24 h, centrifuging, washing and drying to obtain the lignin-metal composite material.
Optionally, the mass ratio of the lignin resin to the metal salt is 1: 0.1 to 0.2.
Optionally, step b) includes: placing the lignin-metal composite material obtained in the step ii) in a tubular furnace or a muffle furnace, carbonizing the lignin-metal composite material by adopting an inverse procedure heating method, and centrifuging, washing and drying the carbonized lignin-metal composite material to obtain the thin-walled graphitized carbon-coated metal core-shell structure material.
Optionally, in the step i), the temperature of the chemical reaction is within a range of 60-90 ℃, and the reaction time is within a range of 3-8 h.
Optionally, the metal salt is ferric nitrate, ferric sulfate, ferric chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, nickel nitrate, nickel sulfate or nickel chloride.
Optionally, the step of placing the lignin-metal composite material obtained in step ii) in a tube furnace or a muffle furnace, and performing carbonization treatment on the lignin-metal composite material by using a reverse-procedure temperature raising method comprises: firstly, the temperature of the tubular furnace or the muffle furnace is raised to a set carbonization temperature, then the lignin-metal composite material is placed in the tubular furnace or the muffle furnace for reaction, and then the temperature is reduced.
Optionally, the specific parameters of the carbonization treatment by the inverse program heating method include: the reaction is carried out for 0.2-1 h at the carbonization temperature of 500-800 ℃, and the speed of the temperature reduction treatment is controlled within the range of 1-5 ℃/min.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
according to the invention, lignin resin is used as a carbon source, metal salt is used as a metal source, a hydrothermal method is adopted for carbonization to obtain a lignin-metal composite material, and then the lignin-metal composite material is subjected to carbonization treatment by reverse temperature programming to obtain a thin-wall graphitized coated metal core-shell material, wherein metal is used as a core, and graphitized carbon is used as a shell. The graphitized coated metal core-shell structure material prepared by the method provided by the invention has 1-10 (0.32-3.2 nm) graphitized carbon coating layers and a high specific surface area, so that the graphitized coated metal core-shell structure material has excellent performance.
In addition, in the preparation method of the thin-wall graphitized carbon-coated metal core-shell material provided by the invention, no other auxiliary material is required to be added, the carbon source can be regenerated, the synthesis method is simple, the production efficiency of the product is improved, and the natural environment is protected.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a graphitized carbon-coated metal core-shell structure material prepared by a conventional carbonization method, wherein the coated metal is iron;
FIG. 2 is a schematic flow chart of a method for preparing a thin-walled graphitized carbon-coated metal core-shell structure material according to an embodiment of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of a thin-walled graphitized carbon-coated metal core-shell structure material according to an embodiment of the present invention, wherein the coated metal is iron;
FIG. 4 is a Transmission Electron Microscope (TEM) image of a thin-walled graphitized carbon-coated metal core-shell structure material according to another embodiment of the present invention, wherein the coated metal is cobalt;
fig. 5 is a Transmission Electron Microscope (TEM) of the thin-walled graphitized carbon-coated metal core-shell structure material according to another embodiment of the present invention, wherein the coated metal is nickel.
Detailed Description
Known from the background art, the method for preparing the graphitized carbon-coated metal core-shell structure material needs to be simplified, the cost needs to be reduced, and the prepared graphitized carbon coating layer needs to be thinned. Referring to fig. 1, fig. 1 shows a perspective electron microscope (TEM) of a graphitized carbon-coated iron core-shell structure material prepared by a conventional carbonization method.
The analysis of the reasons for the above problems includes:
the products obtained by the existing method for preparing the carbon-coated transition metal material can not meet the quality requirements, and the problems are mainly that the thickness of the coated carbon layer is not easy to control, the uniformity of the coated carbon layer is poor, and the thickness of the coated carbon layer is thicker and is usually about 20-30 layers. Since the thickness of the coated carbon layer is relatively thick, the surface curvature of the product is reduced, and the performance of the product is adversely affected, especially the catalytic activity of the product.
In order to solve the problems, the invention provides a preparation method of a thin-wall graphitized carbon-coated metal core-shell structure material, which can enable the thickness of a carbon layer coated by a prepared product to be lower and can be about 1-10 layers (0.32 nm-3.2 nm), thereby being beneficial to obtaining a higher specific surface area and further improving the comprehensive performance of the product.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 2, fig. 2 shows a schematic flow chart of a preparation method of the thin-walled graphitized carbon-coated metal core-shell mechanism material according to the present invention. Specifically, the method comprises the following basic steps:
a) the preparation method of the lignin-metal composite material comprises the steps of carbonizing a carbon source and a metal source by a hydrothermal method by taking lignin resin as the carbon source and metal salt as the metal source to obtain the lignin-metal composite material;
b) and a carbonization step, which comprises carbonizing the lignin-metal composite material by adopting an inverse procedure temperature rise method to obtain a thin-wall graphitized coated metal core-shell material, wherein the metal is a core, and the graphitized carbon is a shell.
The invention will be further explained with reference to the drawings.
Referring to fig. 2, step a) is performed, lignin resin is used as a carbon source, metal salt is used as a metal source, and the carbon source and the metal source are carbonized by a hydrothermal method to obtain the lignin-metal composite material.
In the invention, the mass ratio of the lignin resin is 0.8-1.2: 0.9-1.5: 0.08-0.15 of lignin, formaldehyde and sodium hydroxide. The lignin is an amorphous aromatic high polymer which is widely existed in plants and contains structural units of oxyphenbutamol or derivatives thereof in molecular structure, has low cost and has the advantage of reproducibility.
In the present invention, the temperature of the chemical reaction should not be too high or too low, which would affect the quality of the lignin resin produced. Specifically, the temperature of the chemical reaction is within the range of 60-90 ℃, and the reaction time is within the range of 3-8 h.
In the invention, the metal salt is one of ferric nitrate, ferric sulfate, ferric chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, nickel nitrate, nickel sulfate or nickel chloride. The selection of the metal salt determines the type of the metal core in the thin-walled graphitized carbon-coated metal core-shell structure material. For example, when the metal salt contains iron element, the prepared final product is a thin-walled graphitized coated iron core-shell structure; when the metal salt contains cobalt element, the prepared final product is a thin-wall graphitized wrapped cobalt core-shell structure; when the metal salt contains nickel element, the final product is the thin-wall graphitized wrapped nickel core-shell structure. The materials containing different metal core structures have different properties, and the materials with different properties can be selected in different application environments.
The lignin resin obtained by the above chemical reaction is used as a raw material for preparing a lignin-metal composite material. Specifically, a certain amount of lignin resin is weighed and added into 0.1mol/L metal salt solution, wherein the mass ratio of the lignin resin to the metal salt is 1: 0.1-0.2, stirring until uniform, and reacting at 160-180 ℃ for 12-24 h. And then centrifuging, washing and drying the reactant to obtain the lignin-metal composite material, so as to prepare for the subsequent steps.
Referring to fig. 2, step b) is executed, and a reverse-procedure temperature raising method is adopted to perform carbonization treatment on the lignin-metal composite material, so as to obtain a thin-wall graphitized coated metal core-shell material, wherein the metal is a core, and the graphitized carbon is a shell.
Specifically, the temperature of the tubular furnace or the muffle furnace is increased to a set carbonization temperature, then the lignin-metal composite material is placed in the tubular furnace or the muffle furnace for reaction, and then the temperature is reduced.
The carbonization temperature, the reaction time and the cooling speed of the cooling treatment in the carbonization process of the inverse program heating method all influence the reaction. Through experiments, the carbonization treatment is carried out by adopting the inverse program heating method, the lignin-metal composite material is reacted for 0.2-1 h at 500-800 ℃, and the speed of the temperature reduction treatment is controlled within the range of 1-5 ℃/min. The effect of carrying out the carbonization reaction under the parameter is better.
The main principle of the formation of the thin-wall graphitized carbon-coated metal core-shell structure material is a carbon dissolution and re-precipitation process, namely, a carbon-carbon bond in a carbonization process is broken under the action of metal and then dissolved in the metal to form a metal-carbon mixture, and when the solubility of the carbon in the metal reaches saturation, part of the dissolved carbon tends to be in a low-energy graphite form under the catalytic action of the metal along with the reduction of temperature, so that a graphite layer is precipitated on the surface of the metal. The thickness of the wrapped graphite layer can be effectively controlled by using an inverse temperature programming carbonization process, the formation of a metal carbon compound and the solid solution amount of carbon in the metal carbon compound in the reaction process are controlled through carbonization temperature and reaction time, then the activity of metal is controlled through cooling speed, and further the precipitation thickness carbonization treatment of carbon on the surface of the metal can be further adjusted, and then the thin-wall graphitized carbon wrapped metal core-shell structure material with a thin carbon wrapping layer is obtained through centrifugation, washing and drying.
Example 1
1. Mixing lignin, formaldehyde and sodium hydroxide according to the proportion of 1: 1.3: 0.1, dissolving lignin in an aqueous solution, adding sodium hydroxide, raising the temperature to 60 ℃, slowly adding formaldehyde, and reacting for 3 hours to obtain lignin resin;
2. weighing 1g of lignin resin and 50mL of 0.1mol/L ferric nitrate solution, uniformly stirring, putting into a hydrothermal kettle, reacting at 180 ℃ for 24 hours, centrifuging, washing and drying to obtain the lignin-iron composite material.
3. And (3) placing the product prepared in the step (2) in a tubular furnace, raising the temperature of the tubular furnace to 600 ℃, rapidly placing the lignin-iron composite material in the tubular furnace, carbonizing for 0.5h, cooling at the speed of 1 ℃/min, and finally centrifuging, washing and drying to obtain the core-shell structure material with 2-7 layers of graphitized carbon coated iron.
Referring to fig. 3, fig. 3 shows a Transmission Electron Microscope (TEM) of the thin-walled graphitized carbon-coated iron core-shell structure material obtained by the preparation method described in embodiment 1 of the present invention, and through detection, the particle size of the iron nano is in the range of 6-9nm, and the thickness of the coated graphite layer is in the range of 0.64-2.24nm, compared with the core-shell structure material of graphitized carbon-coated iron prepared by conventional carbonization (as shown in fig. 1), the thickness of the graphite layer is in the range of 9.6-16nm, and the thin-walled graphitized carbon-coated iron core-shell structure material prepared by the present invention has a higher surface curvature, and enhances the electron transfer capability between core shells, thereby improving the catalytic activity thereof.
Example 2
1. Mixing lignin, formaldehyde and sodium hydroxide according to the proportion of 1: 1.3: 0.1, dissolving lignin in an aqueous solution, adding sodium hydroxide, raising the temperature to 70 ℃, slowly adding formaldehyde, and reacting for 4 hours to obtain the lignin resin.
2. Weighing 1g of lignin resin and 50mL of 0.1mol/L cobalt nitrate solution, uniformly stirring, putting into a hydrothermal kettle, reacting at 160 ℃ for 18h, centrifuging, washing and drying to obtain the lignin-cobalt composite material.
3. And (3) placing the product prepared in the step (2) in a tubular furnace, raising the temperature of the tubular furnace to 650 ℃, rapidly placing the lignin-iron composite material in the tubular furnace, carbonizing for 0.2h, cooling at the speed of 1 ℃/min, and finally centrifuging, washing and drying to obtain the core-shell structure material with 3-8 layers of graphitized carbon coated cobalt.
Referring to fig. 4, fig. 4 shows a Transmission Electron Microscope (TEM) of the thin-walled graphitized carbon-coated cobalt core-shell structure material obtained by the preparation method described in embodiment 2 of the present invention, and the particle size of the cobalt nanometer is detected to be in the range of 5-8nm, and the thickness of the coated graphite layer is detected to be in the range of 0.96-2.56 nm.
Example 3
1. Mixing lignin, formaldehyde and sodium hydroxide according to the proportion of 1: 1.3: 0.1, dissolving lignin in an aqueous solution, adding sodium hydroxide, raising the temperature to 90 ℃, slowly adding formaldehyde, and reacting for 3 hours to obtain the lignin resin.
2. Weighing 1g of lignin resin and 50mL of 0.1mol/L nickel nitrate solution, uniformly stirring, putting into a hydrothermal kettle, reacting at 160 ℃ for 20h, centrifuging, washing and drying to obtain the lignin-cobalt composite material.
3. And (3) placing the product prepared in the step (2) in a tubular furnace, raising the temperature of the tubular furnace to 750 ℃, rapidly placing the lignin-iron composite material in the tubular furnace, carbonizing for 0.2h, cooling at the speed of 1 ℃/min, and finally centrifuging, washing and drying to obtain the core-shell structure material with 1-4 layers of graphitized carbon-coated nickel.
Referring to fig. 5, fig. 5 shows a Transmission Electron Microscope (TEM) image of the thin-walled graphitized carbon-coated nickel core-shell structure material obtained by the preparation method described in embodiment 3 of the present invention, and the particle size of the nickel nano-particles is in the range of 8-11nm, and the thickness of the coated graphite layer is in the range of 0.32-1.28 nm.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A preparation method of a thin-wall graphitized carbon-coated metal core-shell structure material is characterized by comprising the following steps:
a) the preparation method of the lignin-metal composite material comprises the steps of carbonizing a carbon source and a metal source by a hydrothermal method by taking lignin resin as the carbon source and metal salt as the metal source to obtain the lignin-metal composite material; the metal salt is ferric nitrate, ferric sulfate, ferric chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, nickel nitrate, nickel sulfate or nickel chloride;
b) a carbonization step, which comprises carbonizing the lignin-metal composite material by adopting an inverse program heating method to obtain a thin-wall graphitized carbon-coated metal core-shell material, wherein the metal is a core, and the graphitized carbon is a shell; the specific parameters of the carbonization treatment by adopting an inverse program temperature rise method comprise: reacting for 0.2-1 h at the carbonization temperature of 500-800 ℃, and controlling the speed of the cooling treatment within the range of 1-5 ℃/min;
the step a) comprises the following specific steps:
i) mixing the raw materials in a mass ratio of 0.8-1.2: 0.9-1.5: 0.08-0.15 of lignin, formaldehyde and sodium hydroxide to perform chemical reaction to obtain lignin resin;
ii) weighing the lignin resin obtained in the step i) and 0.1mol/L metal salt solution, uniformly stirring, putting into a hydrothermal kettle, reacting at 160-180 ℃ for 12-24 h, centrifuging, washing and drying to obtain the lignin-metal composite material.
2. The preparation method of the thin-walled graphitized carbon-coated metal core-shell structure material according to claim 1, wherein the mass ratio of the lignin resin to the metal salt in step ii) is 1: 0.1 to 0.2.
3. The method for preparing the thin-walled graphitized carbon-coated metal core-shell structure material according to claim 1, wherein the step b) comprises: placing the lignin-metal composite material obtained in the step ii) in a tubular furnace or a muffle furnace, carbonizing the lignin-metal composite material by adopting an inverse procedure heating method, and centrifuging, washing and drying the carbonized lignin-metal composite material to obtain the thin-walled graphitized carbon-coated metal core-shell structure material.
4. The method for preparing the thin-walled graphitized carbon-coated metal core-shell structure material according to claim 1, characterized by comprising the steps of
i) The temperature of the chemical reaction is within the range of 60-90 ℃, and the reaction time is within the range of 3-8 h.
5. The method for preparing the thin-walled graphitized carbon-coated metal core-shell structure material according to claim 3, wherein the step of placing the lignin-metal composite material obtained in the step ii) in a tubular furnace or a muffle furnace, and performing carbonization treatment on the lignin-metal composite material by using a reverse-procedure temperature raising method comprises the following steps: firstly, the temperature of the tubular furnace or the muffle furnace is raised to a set carbonization temperature, then the lignin-metal composite material is placed in the tubular furnace or the muffle furnace for reaction, and then the temperature is reduced.
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