CN108722414A - A kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material - Google Patents
A kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material Download PDFInfo
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- CN108722414A CN108722414A CN201810461806.9A CN201810461806A CN108722414A CN 108722414 A CN108722414 A CN 108722414A CN 201810461806 A CN201810461806 A CN 201810461806A CN 108722414 A CN108722414 A CN 108722414A
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- lignin
- shell structure
- coated metal
- structure material
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 88
- 239000002184 metal Substances 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 239000011258 core-shell material Substances 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 44
- 239000010439 graphite Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 229920005610 lignin Polymers 0.000 claims abstract description 31
- 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
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 239000011257 shell material Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 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 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005406 washing 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
- 230000008859 change Effects 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- 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
- 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 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000002560 therapeutic procedure Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 229910052742 iron Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- -1 Shown in Fig. 1) Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000009931 harmful effect Effects 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction 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
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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 present invention provides a kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material, including：Lignin-metallic composite preparation process, including using lignin resin as carbon source, using metal salt as source metal, carbon source and source metal are carbonized using hydro-thermal method to obtain lignin-metallic composite；And carbonization, including charing process is carried out to the lignin-metallic composite using anti-programmed temperature method, Thinwall Graphite coated metal core-shell material is obtained, wherein metal is core, and graphitized carbon is shell.The present invention provides a kind of method for preparing Thinwall Graphite carbon coated metal Core-shell structure material easy to operate, at low cost, the performance of the Thinwall Graphite carbon coated metal Core-shell structure material prepared by this method gets a promotion.
Description
Technical field
The present invention relates to Core-shell structure material preparing technical field, more particularly to a kind of Thinwall Graphite carbon coated metal core
The preparation method of shell structure material.
Background technology
In recent years, carbon wraps up transition-metal catalyst, especially graphitized carbon (graphitized carbon, GC) and wraps up
Transition metal (transition metal, TM) type TM@GC catalyst is widely paid close attention to, during the reaction, due to carbon
The introducing of atom makes metallic bond bond distance increase, and is shunk so as to cause metal d bands and causes the density of states near fermi level in turn
Increase, makes it have the electronic structure and catalysis characteristics similar to the rare precious metals catalyst such as platinum, rhodium, iridium, palladium, ruthenium, urging
Change plus the classics such as hydrogen and redox are catalyzed the activity and stability for having shown " quasi- platinum catalyst " in reaction.
Although TM@GC method for preparing catalyst has many reports, it is difficult to carry out essence in such catalyst preparation process
Fine texture regulates and controls, and causes its catalytic performance to be easy to degenerate, useful working life shortens, and limits its potential application.For example,
Fe@GC receive the limitation of package carbon layers having thicknesses (due to package during replacing platinum catalyst applied to water electrolysis hydrogen production
Carbon-coating is too thick to cause surface curvature to reduce, to affect catalytic activity).Therefore, the reasonable of TM@GC catalyst carbon wrapping layers sets
Meter plays the role of catalytic applications key.
Currently, the preparation method for preparing carbon package transition metal material includes mainly：Arc discharge method, laser evaporization method,
Solid-phase pyrolysis, chemical vapour deposition technique etc..But these preparation methods for preparing carbon package transition metal material still have not
Foot, wherein arc discharge method reaction temperature is higher, and obtained object phase purity is low；And the size of metal core is difficult in laser evaporization method
With control, and the carbon layers having thicknesses wrapped up are uneven；Solid-phase pyrolysis is related to graphite-based carbon source, and is difficult to form graphitized carbon；Change
The thickness for learning carbon-coating in vapour deposition process is difficult to control, and usually at 20-30 layers or so, leads to surface since the carbon-coating of package is too thick
Curvature reduces, to affect catalytic activity.
Therefore, how to solve the problems, such as that above-mentioned graphitized carbon wrapping layer is too thick, a kind of system easy to operate, at low cost is provided
The method of standby Thinwall Graphite carbon coated metal Core-shell structure material, the problem of becoming urgent need to resolve.
Invention content
Problems solved by the invention is to provide a kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material,
Include the following steps：
A) lignin-metallic composite preparation process, including using lignin resin as carbon source, using metal salt as metal
Source carbonizes carbon source and source metal using hydro-thermal method to obtain lignin-metallic composite；
B) carbonization, including charing process is carried out to the lignin-metallic composite using anti-programmed temperature method,
Thinwall Graphite coated metal core-shell material is obtained, wherein metal is core, and graphitized carbon is shell.
Optionally, step a) includes step in detail below：
I) it is 08~1.2 by mass ratio：0.9~1.5:0.08~0.15 lignin, formaldehyde, sodium hydroxide carry out chemistry
Lignin resin is obtained by the reaction；
Ii) weigh the lignin resin and 0.1mol/L that are obtained in step i) metal salt solution stir evenly after, be put into
In water heating kettle, react 12 at 160~180 DEG C~for 24 hours, by centrifugation, washing, it is dry after to obtain the lignin-metal multiple
Condensation material.
Optionally, the mass ratio of the lignin resin and metal salt is 1：0.1~0.2.
Optionally, step b) includes：By step ii) in the obtained lignin-metallic composite be positioned over tubular type
In stove or Muffle furnace, charing process is carried out to it using anti-programmed temperature method, it is described using being obtained after centrifugation, washing, drying
Thinwall Graphite carbon coated metal Core-shell structure material.
Optionally, in step i), the temperature of the chemical reaction is within the scope of 60~90 DEG C, and the reaction time is in 3~8h models
In enclosing.
Optionally, the metal salt be ferric nitrate, ferric sulfate, iron chloride, cobalt nitrate, cobaltous sulfate, cobalt chloride, nickel nitrate,
Nickel sulfate or nickel chloride.
Optionally, by step ii) in the obtained lignin-metallic composite be positioned over tube furnace or Muffle furnace
In, the step of carrying out charing process to it using anti-programmed temperature method includes：First the temperature of tube furnace or Muffle furnace is raised to
The carbonization temperature of setting, then the lignin-metallic composite is placed in tube furnace or is reacted in Muffle furnace, so
After carry out cooling processing.
Optionally, include using the design parameter of anti-programmed temperature method progress charing process：In carbonization temperature 500~800
0.2~1h of reaction is carried out at DEG C, the speed control for the processing that cools down is within the scope of 1~5 DEG C/min.
Compared with prior art, technical solution provided by the invention has the following advantages：
Using lignin resin as carbon source, metal salt is carbonized as source metal by using hydro-thermal method the present invention
Lignin-metallic composite is obtained, then charing process carries out it by anti-temperature programming and obtains Thinwall Graphiteization package gold
Belong to core-shell material, wherein metal is core, and graphitized carbon is shell.The graphitization that the method provided through the invention is prepared
Coated metal Core-shell structure material, graphitized carbon wrapping layer with 1~10 layer (0.32nm~3.2nm) and higher compares table
Area, so that it is with excellent performance.
In addition, in Thinwall Graphite carbon coated metal core-shell material preparation method provided by the invention, it need not add and appoint
What his auxiliary material, and carbon source is renewable, simultaneously synthesizing method is simple, while improving the production efficiency of product, also protects
Natural environment.
Description of the drawings
Fig. 1 is a kind of transmission electron microscope picture of the graphitized carbon coated metal Core-shell structure material prepared using conventional charring
(TEM), wherein the metal wrapped up is iron；
Fig. 2 is that the flow of the preparation method of one embodiment of the invention Thinwall Graphite carbon coated metal Core-shell structure material is shown
It is intended to；
Fig. 3 is the transmission electron microscope picture (TEM) of one embodiment of the invention Thinwall Graphite carbon coated metal Core-shell structure material,
The metal wherein wrapped up is iron；
Fig. 4 is the transmission electron microscope picture of another embodiment of the present invention Thinwall Graphite carbon coated metal Core-shell structure material
(TEM), wherein the metal wrapped up is cobalt；
Fig. 5 is the transmission electron microscope picture of another embodiment of the present invention Thinwall Graphite carbon coated metal Core-shell structure material
(TEM), wherein the metal wrapped up is nickel.
Specific implementation mode
By background technology it is found that the method for preparing graphitized carbon coated metal Core-shell structure material needs to be simplified, cost has
It is to be reduced, and prepare graphitized carbon wrapping layer need it is thinning.With reference to figure 1, Fig. 1 shows a kind of using conventional charring preparation
Graphitized carbon package iron Core-shell structure material perspective electron microscope (TEM).
There are the reason of above problem to include for analysis：
The existing obtained product of carbon package transition metal material method for preparing cannot be satisfied quality requirement, and problem is often
The carbon layers having thicknesses for being primarily due to package are not easily controlled, and the carbon-coating uniformity not only wrapped up is poor, and its thickness is thicker, usually
At 20~30 layers or so.Since the thickness of the carbon-coating of package is thicker, reduce so as to cause the surface curvature of product, and then to product
Performance cause harmful effect, can especially influence its catalytic activity.
To solve the above-mentioned problems, the present invention provides a kind of preparation of Thinwall Graphite carbon coated metal Core-shell structure material
Method enables to the carbon layers having thicknesses that the product prepared is wrapped up to obtain relatively low, can be at 1~10 layer (0.32nm~3.2nm)
The comprehensive performance of product to be conducive to obtain higher specific surface area, and then is improved in left and right.
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
With reference to figure 2, Fig. 2 shows the streams of the preparation method of Thinwall Graphite carbon coated metal nucleocapsid of the present invention mechanism material
Journey schematic diagram.Specifically, including following basic step：
A) lignin-metallic composite preparation process, including using lignin resin as carbon source, using metal salt as metal
Source carbonizes carbon source and source metal using hydro-thermal method to obtain lignin-metallic composite；
B) carbonization, including charing process is carried out to the lignin-metallic composite using anti-programmed temperature method,
Thinwall Graphite coated metal core-shell material is obtained, wherein metal is core, and graphitized carbon is shell.
Below in conjunction with attached drawing, the present invention will be further described.
With reference to figure 2, step a) is executed, using lignin resin as carbon source, using metal salt as source metal, using hydro-thermal method to carbon
Source and source metal are carbonized to obtain lignin-metallic composite.
In the present invention, the lignin resin is by being 0.8~1.2 by mass ratio：0.9~1.5:0.08~0.15 is wooden
Element, formaldehyde, sodium hydroxide carry out chemical reaction acquisition.Lignin be it is a kind of be widely present in plant it is unbodied, point
The armaticity high polymer of phenylpropanol containing oxo or derivatives thereof structural unit, of low cost in minor structure, has reproducible excellent
Point.
In the present invention, the temperature of the chemical reaction is unsuitable excessively high also unsuitable too low, otherwise will influence to generate wooden
The quality of plain resin.Specifically, the temperature of the chemical reaction is within the scope of 60~90 DEG C, and the reaction time is within the scope of 3~8h.
In the present invention, the metal salt is ferric nitrate, ferric sulfate, iron chloride, cobalt nitrate, cobaltous sulfate, cobalt chloride, nitric acid
One kind in nickel, nickel sulfate or nickel chloride.The selection of the metal salt determines Thinwall Graphite carbon coated metal nucleocapsid knot
The type of metal core in structure material.For example, when containing ferro element in the metal salt, the final product of preparation is thin-walled stone
Inkization wraps up iron nucleocapsid；When containing cobalt element in the metal salt, the final product of preparation is Thinwall Graphite packet
Wrap up in cobalt nucleocapsid；When containing nickel element in the metal salt, the final product of preparation is Thinwall Graphiteization package nickel core
Shell structure.The material of the nuclear structure containing different metal has different performances, and dissimilarity can be selected in different application environments
The material of energy.
The lignin resin obtained by above-mentioned chemical reaction is used as raw material and is used for preparing lignin-metallic composite.
Specifically, a certain amount of lignin resin is weighed, is added into the metal salt solution of 0.1mol/L, the lignin resin
Mass ratio with metal salt is 1：0.1~0.2, stirring until uniformly after, make its temperature be 160~180 DEG C at reaction 12~
24h.Then reactant centrifuged again, washed, drying process, obtaining the lignin-metallic composite, for follow-up step
Suddenly it prepares.
With reference to figure 2, step b) is executed, the lignin-metallic composite is carbonized using anti-programmed temperature method
Processing obtains Thinwall Graphite coated metal core-shell material, and wherein metal is core, and graphitized carbon is shell.
Specifically, the temperature of tube furnace or Muffle furnace is first raised to the carbonization temperature of setting, then by the lignin-gold
Category composite material, which is positioned in tube furnace or Muffle furnace, to be reacted, and cooling processing is then carried out.
The cooling rate of carbonization temperature, reaction time and cooling processing is to reacting equal in anti-programmed temperature method charring process
Have an impact.By experiment, charing process is carried out using above-mentioned anti-programmed temperature method, the lignin-metallic composite is existed
0.2~1h of reaction is carried out at 500~800 DEG C, speed control when cooling is handled is within the scope of 1~5 DEG C/min.Under this parameter
The effect for carrying out carbonization reaction is preferable.
The cardinal principle that the Thinwall Graphite carbon coated metal Core-shell structure material is formed is that the dissolving of carbon was precipitated again
Journey, that is to say, that carbon-carbon bond is broken under the action of metal in carbonization process, is then dissolved in metal, and metal-is formed
Carbon mix, when the solubility of carbon in metal reaches saturation, with the reduction of temperature, in the catalytic action lower part of metal
The graphite form for dividing the carbon of dissolving to be intended to low-lying level, in metal surface indigenous graphite layer.It is carbonized using anti-temperature programming
Technique can effectively control the graphite layer thickness of package, first by carbonization temperature and reaction time, control in reaction process
Then the solid solution capacity of carbon in the formation of metcar and metcar controls the activity of metal by cooling rate,
And then carbon can be further adjusted the precipitation thickness charing process of metal surface the step of and then by centrifugation, washing
And it is dry, to obtain the Thinwall Graphite carbon coated metal Core-shell structure material with relatively thin carbon wrapping layer.
Embodiment 1
1. by lignin, formaldehyde, sodium hydroxide according to 1：1.3：0.1 mass ratio, which is thrown into round-bottomed flask, to be reacted,
Lignin is dissolved in aqueous solution first, then puts into sodium hydroxide, temperature is risen to 60 DEG C, slowly puts into formaldehyde, is obtained after reacting 3h
To lignin resin；
After 2. the iron nitrate solution for weighing 1g lignin resins and the 0.1mol/L of 50mL stirs evenly, it is put into water heating kettle
In, after being reacted for 24 hours at 180 DEG C, through centrifugation, washs, is dried to obtain lignin-iron composite material.
3. the product that step 2 is prepared is placed in tube furnace, the temperature of tube furnace is first risen to 600 DEG C, then will be wooden
Quality-iron composite material is placed in tube furnace rapidly, carbonize 0.5h after, the rate using 1 DEG C/min cools down, most afterwards pass through from
The heart, the Core-shell structure material washed, be dried to obtain 2-7 layers of graphitized carbon package iron.
With reference to figure 3, Fig. 3 shows the Thinwall Graphite carbon packet that the preparation method described according to embodiments of the present invention 1 obtains
The transmission electron microscope picture (TEM) of iron Core-shell structure material is wrapped up in, after testing, the grain size of iron nanometer is within the scope of 6-9nm, the graphite of package
Layer thickness is within the scope of 0.64-2.24nm, compared with the graphitized carbon that routinely prepared by charing wraps up the Core-shell structure material of iron (such as
Shown in Fig. 1), for graphite layer thickness within the scope of 9.6-16nm, Thinwall Graphite carbon prepared by the present invention wraps up iron nucleocapsid
Material has higher surface curvature, the electron transmission ability between nucleocapsid is enhanced, to improve its catalytic activity.
Embodiment 2
1. by lignin, formaldehyde, sodium hydroxide according to 1：1.3：0.1 mass ratio, which is thrown into round-bottomed flask, to be reacted,
Lignin is dissolved in aqueous solution first, then puts into sodium hydroxide, temperature is risen to 70 DEG C, slowly puts into formaldehyde, is obtained after reacting 4h
To lignin resin.
After 2. the cobalt nitrate solution for weighing 1g lignin resins and the 0.1mol/L of 50mL stirs evenly, it is put into water heating kettle
In, after reacting 18h at 160 DEG C, through centrifugation, washs, is dried to obtain lignin-cobalt composite material.
3. the product that step 2 is prepared is placed in tube furnace, the temperature of tube furnace is first risen to 650 DEG C, then will be wooden
Quality-iron composite material is placed in tube furnace rapidly, carbonize 0.2h after, the rate using 1 DEG C/min cools down, most afterwards pass through from
The heart, the Core-shell structure material washed, be dried to obtain 3-8 layers of graphitized carbon package cobalt.
With reference to figure 4, Fig. 4 shows the Thinwall Graphite carbon packet that the preparation method described according to embodiments of the present invention 2 obtains
The transmission electron microscope picture (TEM) of the Core-shell structure material of cobalt is wrapped up in, after testing, the grain size of cobalt nanometer is within the scope of 5-8nm, the stone of package
Ink layer thickness is within the scope of 0.96-2.56nm.
Embodiment 3
1. by lignin, formaldehyde, sodium hydroxide according to 1：1.3：0.1 mass ratio, which is thrown into round-bottomed flask, to be reacted,
Lignin is dissolved in aqueous solution first, then puts into sodium hydroxide, temperature is risen to 90 DEG C, slowly puts into formaldehyde, is obtained after reacting 3h
To lignin resin.
After 2. the nickel nitrate solution for weighing 1g lignin resins and the 0.1mol/L of 50mL stirs evenly, it is put into water heating kettle
In, after reacting 20h at a temperature of 160 DEG C, through centrifugation, washs, is dried to obtain lignin-cobalt composite material.
3. the product that step 2 is prepared is placed in tube furnace, the temperature of tube furnace is first risen to 750 DEG C, then will be wooden
Quality-iron composite material is placed in tube furnace rapidly, carbonize 0.2h after, the rate using 1 DEG C/min cools down, most afterwards pass through from
The heart, the Core-shell structure material washed, be dried to obtain 1-4 layers of graphitized carbon package nickel.
With reference to figure 5, Fig. 5 shows the Thinwall Graphite carbon packet that the preparation method described according to embodiments of the present invention 3 obtains
Wrap up in the transmission electron microscope picture (TEM) of the Core-shell structure material of nickel, after testing, the grain size of nickel nanometer within the scope of 8-11nm, package
Graphite layer thickness is within the scope of 0.32-1.28nm.
Although present disclosure is as above, present invention is not limited to this.Any those skilled in the art are not departing from this
It in the spirit and scope of invention, can make various changes or modifications, therefore protection scope of the present invention should be with claim institute
Subject to the range of restriction.
Claims (8)
1. a kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material, which is characterized in that include the following steps：
A) lignin-metallic composite preparation process, including using lignin resin as carbon source, using metal salt as source metal, adopt
Carbon source and source metal are carbonized with hydro-thermal method to obtain lignin-metallic composite；
B) carbonization, including charing process is carried out to the lignin-metallic composite using anti-programmed temperature method, it obtains
Thinwall Graphite coated metal core-shell material, wherein metal are core, and graphitized carbon is shell.
2. the preparation method of Thinwall Graphite carbon coated metal Core-shell structure material according to claim 1, feature exist
In step a) includes step in detail below：
I) it is 0.8~1.2 by mass ratio：0.9~1.5:0.08~0.15 lignin, formaldehyde, sodium hydroxide are chemically reacted
Obtain lignin resin；
Ii it) weighs after the lignin resin that is obtained in step i) stirs evenly with 0.1mol/L metal salt solutions, is put into water heating kettle
In, react 12 at 160~180 DEG C~for 24 hours, by centrifugation, washing, it is dry after obtain the lignin-metallic composite.
3. the preparation method of Thinwall Graphite carbon coated metal Core-shell structure material according to claim 2, feature exist
In step ii) described in the mass ratio of lignin resin and metal salt be 1：0.1~0.2.
4. the preparation method of Thinwall Graphite carbon coated metal Core-shell structure material according to claim 2, feature exist
In step b) includes：By step ii) in the obtained lignin-metallic composite be positioned over tube furnace or Muffle furnace
In, charing process is carried out to it using anti-programmed temperature method, using centrifugation, washing, it is dry after obtain the Thinwall Graphite
Carbon coated metal Core-shell structure material.
5. the preparation method of Thinwall Graphite carbon coated metal Core-shell structure material according to claim 2, feature exist
In in step i), the temperature of the chemical reaction is within the scope of 60~90 DEG C, and the reaction time is within the scope of 3~8h.
6. the preparation method of Thinwall Graphite carbon coated metal Core-shell structure material according to claim 1, feature exist
In the metal salt is ferric nitrate, ferric sulfate, iron chloride, cobalt nitrate, cobaltous sulfate, cobalt chloride, nickel nitrate, nickel sulfate or chlorine
Change nickel.
7. the preparation method of Thinwall Graphite coated metal Core-shell structure material according to claim 4, which is characterized in that
By step ii) in the obtained lignin-metallic composite be positioned in tube furnace or Muffle furnace, using return sequence liter
The step of warm therapy carries out charing process to it include：The temperature of tube furnace or Muffle furnace is first raised to the carbonization temperature of setting,
Lignin-the metallic composite is placed in tube furnace or Muffle furnace again and is reacted, cooling processing is then carried out.
8. the preparation method of Thinwall Graphite coated metal Core-shell structure material according to claim 7, which is characterized in that
Using anti-programmed temperature method carry out charing process design parameter include：Reaction 0.2 is carried out at 500~800 DEG C of carbonization temperature
~1h, the speed control for the processing that cools down is within the scope of 1~5 DEG C/min.
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