CN112938936A - Metal atom loaded nano composite material and preparation method thereof - Google Patents
Metal atom loaded nano composite material and preparation method thereof Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
Abstract
The invention belongs to the technical field of nano composite materials, relates to the field of preparing metal atom loaded nano composite materials by chemical vapor deposition, and discloses a metal atom loaded nano composite material and a preparation method thereof; the preparation method of the metal atom loaded nano composite material comprises the following steps: and dispersing metal atoms in an isolated or atomic cluster form, depositing the metal atoms on the nanocarbon-based material carrier and carbonizing the nanocarbon-based material carrier under the inert gas atmosphere to obtain the metal atom loaded nanocomposite. The metal atom loaded nano composite material with uniform atom distribution and strong bonding capability is prepared; in the preparation process, the complicated physical and chemical treatment steps and the cost of reagents and instruments in the conventional synthesis are avoided, and the preparation method can be used for mass production in industry.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, relates to the field of preparing metal atom loaded nano composite materials by chemical vapor deposition, and particularly relates to a metal atom loaded nano composite material and a preparation method thereof.
Background
Heteroatom-doped carbon materials, such as nitrogen-doped, sulfur-doped, boron-doped, and iodine-doped carbon nanotubes and graphene composites, play a role in electrocatalysis, environmental monitoring, biosensing, and the like, through the use of various innovative synthetic strategies. The metal atom loaded nano composite material has stability, activity and selectivity superior to those of the conventional nano material; for example, Single-atom catalysts (SACs) are a special type of supported metal catalyst, which is intended to mean that all metal components on the support are present in a monoatomic dispersion without metal-metal bonds, or when multiple metals are supported without metal bonds between the same metal.
The preparation of metal atom loaded nanocomposites is a very challenging problem, and the main methods of the current preparation are divided into two main categories, physical methods and chemical methods. The physical methods mainly include methods such as laser sputtering, ball milling and the like; the chemical method mainly comprises the steps of taking Metal Organic Framework (MOF) as a precursor, and preparing the MOF into a Metal atom loading material taking carbon as a carrier after high-temperature calcination. However, these methods have high costs for raw materials and equipment for synthesizing the atom-supported composite material, poor dispersibility and low yield, and the metal atoms of the material tend to agglomerate, and are difficult to be industrially produced.
Disclosure of Invention
The present invention is directed to a metal atom-supported nanocomposite and a method for preparing the same, which solves one or more of the problems set forth above. The metal atom loaded nano composite material with uniform atom distribution and strong bonding capability is prepared; in the preparation process, the complicated physical and chemical treatment steps and the cost of reagents and instruments in the conventional synthesis are avoided, and the preparation method can be used for mass production in industry.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a metal atom loaded nano composite material, which comprises the following steps: and dispersing metal atoms in an isolated or atomic cluster form, depositing the metal atoms on the nanocarbon-based material carrier and carbonizing the nanocarbon-based material carrier under the inert gas atmosphere to obtain the metal atom loaded nanocomposite.
The invention is further improved in that the metal atoms are one or more of iron atoms, cobalt atoms, nickel atoms, copper atoms, manganese atoms, platinum atoms and ruthenium atoms.
The invention has the further improvement that the nano carbon-based material carrier is one or more of nitrogen-doped, sulfur-doped, boron-doped or iodine-doped carbon-based carrier.
In a further improvement of the invention, the specific steps of dispersing, depositing and carbonizing the volatilized metal atoms in isolated or atomic cluster form on the nanocarbon-based material carrier under inert gas atmosphere include:
and (3) heating to a preset temperature at a preset heating speed in an inert gas atmosphere, and preserving heat, so that metal atoms sublimated by the metal organic compound or the bulk metal volatilize to the nanocarbon-based material carrier along with the gas, and are captured, anchored and carbonized by defects on the surface of the carrier.
The further improvement of the invention is that the metal organic compound or the bulk metal is one or more of ferrocene, nickelocene, carbonyl iron, nickel tetracarbonyl, copper foam, nickel foam or cobalt foil;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 1-20%.
The invention is further improved in that the preset temperature rise speed is 1-10 ℃/min, the preset temperature is 800-1000 ℃, and the heat preservation time is 60-120 min.
The invention has the further improvement that when the nano carbon-based material carrier is prepared, the adopted carbon source is one or more of melamine, dicyandiamide, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile or starch; the preparation method is one or more of pyrolysis, ball milling and hydrothermal method.
A further development of the invention is that the inert gas atmosphere is a nitrogen, argon or helium atmosphere.
The invention discloses a metal atom loaded nano composite material prepared by the preparation method.
In a further development of the invention, the nanocomposite comprises a nanocarbon-based material support and metal monoatomic atoms and atomic clusters supported thereby.
Compared with the prior art, the invention has the following beneficial effects:
the method of the invention takes a carbon-based material as a carrier, and disperses and deposits metal atoms volatilized from metal organic compounds or bulk metals and the like on the carrier in an isolated or atomic cluster mode in an inert gas atmosphere, and simultaneously carbonizes the metal atoms to prepare the carbon-based material loaded with the metal atoms. The metal atom loaded nano composite material prepared by the method avoids the complicated physical and chemical treatment steps and the cost of reagents and instruments in the conventional synthesis, and can be produced in large scale in industry.
Specifically, the metal atoms of precursors such as metal organic compounds or bulk metals subjected to high-temperature sublimation are captured and combined by a carrier by utilizing a chemical vapor deposition method and principle, so that the metal atom-loaded nano composite material with uniform atom distribution and strong bonding capability is prepared. At high temperature, metal atoms diffuse to the surface of the carrier along with the gas atmosphere, are captured and anchored by the defects on the surface of the carrier, and are carbonized at the same time, so that the dispersibility and the anchoring capability of the atoms are improved, the anchored metal is dispersed to the maximum extent, the utilization rate of active sites is high, and the performance of the material is finally improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram of the preparation of a metal atom-supported nanocomposite material according to an embodiment of the present invention;
FIG. 2 is a SEM diagram of a material prepared in example 1 of the present invention;
FIG. 3 is a comparison of electrochemical polarization curves of Fe (Fc) -N/S-C and Pt/C in example 1 of the present invention;
FIG. 4 is a schematic diagram of AC HADDF-STEM of Fe (Fc) -N/S-C in example 1 of the present invention;
FIG. 5 is an enlarged schematic view of the boxed area in FIG. 4; wherein the circles mark Fe single atoms.
Detailed Description
In order to make the purpose, technical effect and technical solution of the embodiments of the present invention clearer, the following clearly and completely describes the technical solution of the embodiments of the present invention with reference to the drawings in the embodiments of the present invention; it is to be understood that the described embodiments are only some of the embodiments of the present invention. Other embodiments, which can be derived by one of ordinary skill in the art from the disclosed embodiments without inventive faculty, are intended to be within the scope of the invention.
Referring to fig. 1, a method for preparing a metal atom-supported nanocomposite material by chemical vapor deposition according to an embodiment of the present invention includes the following steps:
step 4, mixing precursors of metal organic compound or bulk metal and the like in a certain mass ratio with the sulfur-doped C obtained in the step 33N4Placing in crucible upstream and downstream of gas flow, and covering with ceramic sheet to obtain a crucible C3N4A gap with the width of about 2mm is left on one side; then heating to 800-1000 ℃ at a certain heating rate in an inert gas atmosphere, and preserving heat for a certain time to enable sublimed metal atoms to volatilize to C along with the gas3N4And finally obtaining the metal atom loaded nano composite material on the carrier.
In the embodiment of the invention, in the step 1, the melamine and the L-cysteine are mixed in a ratio of (2-4): 1, in a mass ratio of 1.
In the embodiment of the invention, the ball-milling balls of the ball mill can be one of agate balls, stainless steel balls, hard alloy balls and zirconia balls; the diameter of the ball grinding ball is 3-20 mm; the ball milling pot can be one of agate, stainless steel, hard alloy and zirconia; the ball milling ball material mass ratio is (200-10): 1.
in the embodiment of the invention, the preparation of the carrier is not limited to one or more of carbon-based carriers such as nitrogen-doped carrier, sulfur-doped carrier, boron-doped carrier, iodine-doped carrier and the like; the carbon source is not limited to one or more of melamine, urea, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, starch and the like; the preparation method of the carrier is not limited to one or more of pyrolysis, ball milling, hydrothermal method and the like.
In step 2 of the embodiment of the invention, the temperature is raised to 600 ℃ at the temperature raising speed of 1-10 ℃/min, and the temperature is kept for 60-120 min.
In step 4 of the embodiment of the present invention, the metal organic compound or the bulk metal is ferrocene; the mass ratio of the metal organic compound or the bulk metal to the carrier is 1-20%; the temperature is raised to 900 ℃ at the temperature rise speed of 1-10 ℃/min, and the temperature is kept for 60-120 min to obtain the prepared composite material; wherein, the metal organic compound or the bulk metal is not limited to one or more of ferrocene, nickelocene, carbonyl iron, nickel tetracarbonyl, copper foam, nickel foam, cobalt foil and the like; the inert gas atmosphere is not limited to one of nitrogen, argon, helium, and the like.
The invention utilizes the chemical vapor deposition method and principle to capture and combine metal atoms of precursors such as metal organic compounds or bulk metals and the like sublimated at high temperature by a carrier, and prepares the metal atom loaded nano composite material with uniform atom distribution and strong combining capability. At high temperature, metal atoms diffuse to the surface of the carrier along with the gas atmosphere, are captured and anchored by the defects on the surface of the carrier, and are carbonized at the same time, so that the dispersibility and the anchoring capability of the atoms are improved, and finally the performance of the material is improved. The metal atom loaded nano composite material prepared by the method avoids the complicated physical and chemical treatment steps and the cost of reagents and instruments in the conventional synthesis, and can be produced in large scale in industry.
The nano composite material prepared by the embodiment of the invention comprises: a nano carbon material carrier and metal single atoms and atom clusters loaded by the nano carbon material carrier; the metal atom comprises one or more of iron atom, cobalt atom, nickel atom, copper atom, manganese atom and the like.
Chemical vapor deposition is a chemical technique for depositing a thin film by exposing a substrate to one or more different precursors and causing a chemical reaction to occur on the surface of the substrate, wherein atomic layer deposition is a method by which a substance can be "plated" onto the surface of the substrate layer by layer as a monoatomic film. The method and the principle of chemical vapor deposition are utilized to capture and combine metal atoms of precursors such as metal organic compounds or bulk metals and the like sublimated at high temperature by a carrier, and the method and the principle are a new idea for preparing the metal atom loaded nano composite material. The invention discloses a method for preparing a metal atom loaded nano composite material by utilizing chemical vapor deposition, and relates to the field of nano composite materials in material preparation. The process comprises taking carbon-based material as carrier, dispersing and depositing volatilized metal atoms of metal organic compound or bulk metal and the like on the carrier in isolated or atomic cluster form in inert gas atmosphere, and carbonizing to prepare the carbon-based material loaded with the metal atoms.
Example 1
Referring to fig. 1 to 5, a method for preparing a metal atom-supported nanocomposite according to an embodiment of the present invention includes the following steps:
8.00g of melamine and 2.00g L-cysteine were mixed in a ball mill for one hour, and the two powders were mixed uniformly; then placing the mixed powder in a crucible, covering a ceramic chip, heating to 600 ℃ at the speed of 2 ℃/min, and preserving heat for 120min to obtain blocky light sulfur-doped C with low density3N4. 500mg of the prepared material was dispersed in 250mL of HNO3(0.5mol L-1) And (4) medium ultrasonic dispersion. Add 3.125mL of GO dispersion (1mg mL)-1) And stirred for 6h to obtain a homogeneous dispersion. The final product was collected by filtration, washed three times with deionized water and ethanol, respectively, and then dried in a lyophilizer for 12 hours to obtain a precursor.
Placing ferrocene with the mass ratio of 5% on one side of a precursor, covering a ceramic chip on a crucible, and leaving a gap of about 2mm on one side of the precursor, so that a sublimated ferrocene product flows out along with protective gas, then heating to 900 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, and preserving heat for 120min to finally obtain an Fe-doped carbon nitrogen material (Fe (Fc) -N/S-C); the scanning electron microscope of the prepared material is shown in figure 2, and the ORR performance test result is shown in figure 3.
From the Scanning Electron Microscope (SEM) results of the material of FIG. 2, it can be seen that the material prepared by the method of example 1 is a nanosheet layered structure which is pyrolyzed in a first step to form C3N4Further carbonisation of the skeletal material provides the possibility, when carbonised, of anchoring migrating metal atoms upstream of the gas flow. According to the electrochemical results measured in FIG. 3, the half-wave potential of the catalyst prepared by the method is 0.872V which is higher than that of commercial Pt/C (0.867V). Meanwhile, FIG. 4 and FIG. 5 show the AC-HADDF-STEM diagram of Fe (Fc) -N/S-C prepared by the present solution, and Fe single atoms in the material can be clearly seen, and no agglomerated particles exist, which indicates that the present solution successfully prepares the metal atom-loaded material. The above results demonstrate the feasibility of the present invention for preparing metal atom-supported nanocomposites.
Example 2
The preparation method of the metal atom loaded nano composite material comprises the following steps: under the inert gas atmosphere, dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonizing to obtain a metal atom loaded nano composite material;
wherein the metal atom is an iron atom.
Example 3
The inventive example differs from example 2 only in that the metal atoms are iron atoms, cobalt atoms and nickel atoms.
Example 4
The preparation method of the metal atom loaded nano composite material comprises the following steps: under the inert gas atmosphere, dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonizing to obtain a metal atom loaded nano composite material;
wherein the nano carbon-based material carrier is doped with nitrogen.
Example 5
The inventive example differs from example 4 only in that the nanocarbon-based material support is nitrogen doped, sulfur doped and boron doped.
Example 6
The preparation method of the metal atom loaded nano composite material comprises the following steps: under the inert gas atmosphere, dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonizing to obtain a metal atom loaded nano composite material;
the specific steps of dispersing, depositing and carbonizing volatilized metal atoms on the nanocarbon-based material carrier in an isolated or atomic cluster mode under the inert gas atmosphere comprise:
heating to a preset temperature at a preset heating speed in an inert gas atmosphere, and preserving heat to enable metal atoms sublimated by the metal organic compound or the bulk metal to volatilize to the nano carbon-based material carrier along with the gas, and to be captured, anchored and carbonized by defects on the surface of the carrier;
the metal organic compound or the bulk metal is ferrocene;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 1%.
Example 7
The embodiment of the invention is different from the embodiment 6 only in that the metal organic compound or the bulk metal is ferrocene or nickelocene; the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 10%.
Example 8
The embodiment of the invention differs from embodiment 6 only in that the metal organic compound or bulk metal is ferrocene, nickelocene, iron carbonyl, nickel tetracarbonyl; the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 20%.
Example 9
The embodiment of the invention is different from the embodiment 6 only in that the preset temperature rise speed is 1 ℃/min, the preset temperature is 800 ℃, and the heat preservation time is 60 min.
Example 10
The embodiment of the invention is different from the embodiment 7 only in that the preset temperature rise speed is 5 ℃/min, the preset temperature is 900 ℃, and the heat preservation time is 80 min.
Example 11
The embodiment of the invention is different from the embodiment 8 only in that the preset temperature rise speed is 10 ℃/min, the preset temperature is 1000 ℃, and the heat preservation time is 120 min.
Example 12
The preparation method of the metal atom loaded nano composite material comprises the following steps: under the inert gas atmosphere, dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonizing to obtain a metal atom loaded nano composite material;
wherein the metal atoms are iron atoms, cobalt atoms, nickel atoms and copper atoms;
the nano carbon-based material carrier is a nitrogen-doped, sulfur-doped, boron-doped or iodine-doped carbon-based carrier;
the specific steps of dispersing, depositing and carbonizing volatilized metal atoms on the nanocarbon-based material carrier in an isolated or atomic cluster mode under the inert gas atmosphere comprise:
heating to a preset temperature at a preset heating speed in an inert gas atmosphere, and preserving heat to enable metal atoms sublimated by the metal organic compound or the bulk metal to volatilize to the nano carbon-based material carrier along with the gas, and to be captured, anchored and carbonized by defects on the surface of the carrier;
the metal organic compound or the bulk metal is ferrocene or nickelocene;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 18 percent;
the preset heating speed is 1-10 ℃/min, the preset temperature is 850 ℃, and the heat preservation time is 100 min;
when the nano carbon-based material carrier is prepared, the adopted carbon sources are melamine and dicyandiamide; the adopted preparation method is pyrolysis; the inert gas atmosphere is helium atmosphere.
Example 13
The preparation method of the metal atom loaded nano composite material comprises the following steps: under the inert gas atmosphere, dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonizing to obtain a metal atom loaded nano composite material;
wherein the metal atom is a ruthenium atom;
the nano carbon-based material carrier is an iodine-doped carbon-based carrier;
the specific steps of dispersing, depositing and carbonizing volatilized metal atoms on the nanocarbon-based material carrier in an isolated or atomic cluster mode under the inert gas atmosphere comprise:
heating to a preset temperature at a preset heating speed in an inert gas atmosphere, and preserving heat to enable metal atoms sublimated by the metal organic compound or the bulk metal to volatilize to the nano carbon-based material carrier along with the gas, and to be captured, anchored and carbonized by defects on the surface of the carrier;
the metal organic compound or the block metal is foam copper or foam nickel;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 8%;
the preset heating speed is 7 ℃/min, the preset temperature is 950 ℃, and the heat preservation time is 90 min;
when the nano carbon-based material carrier is prepared, the adopted carbon source is melamine; the adopted preparation method comprises pyrolysis and ball milling;
the inert gas atmosphere is nitrogen atmosphere.
Example 14
The preparation method of the metal atom loaded nano composite material comprises the following steps: under the inert gas atmosphere, dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonizing to obtain a metal atom loaded nano composite material;
wherein the metal atom is an iron atom;
the nano carbon-based material carrier is doped with nitrogen;
the specific steps of dispersing, depositing and carbonizing volatilized metal atoms on the nanocarbon-based material carrier in an isolated or atomic cluster mode under the inert gas atmosphere comprise:
heating to a preset temperature at a preset heating speed in an inert gas atmosphere, and preserving heat to enable metal atoms sublimated by the metal organic compound or the bulk metal to volatilize to the nano carbon-based material carrier along with the gas, and to be captured, anchored and carbonized by defects on the surface of the carrier;
the metal organic compound or the bulk metal is ferrocene;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 13%;
the preset heating speed is 10 ℃/min, the preset temperature is 1000 ℃, and the heat preservation time is 120 min;
when the nano carbon-based material carrier is prepared, the adopted carbon source is polyvinyl alcohol; the adopted preparation method is a hydrothermal method;
the inert gas atmosphere is nitrogen atmosphere.
Example 15
8.00g of urea powder was placed in a crucible and covered with a ceramic tile, using urea as a carbon and nitrogen source. Heating to 600 deg.C at a rate of 2 deg.C/min, and maintaining for 120min to obtain light sulfur-doped C with small density3N4。
The obtained C3N4Grinding in a ball mill, placing 5% foamed nickel by mass on one side of C3N4, covering a crucible with a ceramic tile, C3N4Leaving a gap of about 2mm on one side, enabling the sublimated ferrocene product to flow out along with protective gas, then heating to 900 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, and preserving heat for 120min to finally obtain the Ni-doped carbon-nitrogen material.
Example 16
The production method of the present embodiment differs from embodiment 15 only in that: the foamed nickel with the mass ratio of 5 percent is cobalt acetylacetonate with the mass ratio of 5 percent.
Example 17
The production method of the present embodiment differs from embodiment 15 only in that: the temperature rise rate of 2 ℃/min to 900 ℃ in the nitrogen atmosphere is changed into the temperature rise rate of 2 ℃/min to 800 ℃.
Example 18
The production method of the present embodiment differs from embodiment 15 only in that: the temperature rise rate of 2 ℃/min to 900 ℃ in the nitrogen atmosphere is changed into the temperature rise rate of 2 ℃/min to 1000 ℃.
The invention discloses a method for preparing a metal atom loaded nano composite material by utilizing chemical vapor deposition, and relates to the field of nano composite materials in material preparation. The process comprises taking carbon-based material as carrier, dispersing and depositing volatilized metal atoms of metal organic compound or bulk metal and the like on the carrier in isolated or atomic cluster form in inert gas atmosphere, and carbonizing to prepare the carbon-based material loaded with the metal atoms.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.
Claims (10)
1. A method for preparing a metal atom-supported nanocomposite material, comprising: and dispersing metal atoms in an isolated or atomic cluster form, depositing the metal atoms on the nanocarbon-based material carrier and carbonizing the nanocarbon-based material carrier under the inert gas atmosphere to obtain the metal atom loaded nanocomposite.
2. The method for preparing a metal atom-supported nanocomposite material according to claim 1, wherein the metal atom is one or more of an iron atom, a cobalt atom, a nickel atom, a copper atom, a manganese atom, a platinum atom and a ruthenium atom.
3. The method for preparing the metal atom supported nano composite material according to claim 1, wherein the nano carbon-based material carrier is one or more of nitrogen-doped, sulfur-doped, boron-doped or iodine-doped carbon-based carrier.
4. The method for preparing a metal atom-supported nanocomposite as claimed in claim 1, wherein the specific steps of dispersing, depositing and carbonizing volatilized metal atoms in isolated or atomic clusters on the nanocarbon-based material support under an inert gas atmosphere comprise:
and (3) heating to a preset temperature at a preset heating speed in an inert gas atmosphere, and preserving heat, so that metal atoms sublimated by the metal organic compound or the bulk metal volatilize to the nanocarbon-based material carrier along with the gas, and are captured, anchored and carbonized by defects on the surface of the carrier.
5. The method for preparing the metal atom-supported nano composite material according to claim 4, wherein the metal organic compound or the bulk metal is one or more of ferrocene, nickelocene, carbonyl iron, nickel tetracarbonyl, copper foam, nickel foam or cobalt foil;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 1-20%.
6. The method for preparing a metal atom-supported nanocomposite material according to claim 4, wherein the predetermined temperature rise rate is 1-10 ℃/min, the predetermined temperature is 800-1000 ℃, and the holding time is 60-120 min.
7. The method for preparing the metal atom-loaded nano composite material according to claim 1, wherein when the nano carbon-based material carrier is prepared, the adopted carbon source is one or more of melamine, dicyandiamide, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile or starch; the preparation method is one or more of pyrolysis, ball milling and hydrothermal method.
8. The method according to claim 1, wherein the inert gas atmosphere is nitrogen, argon or helium.
9. A metal atom-supported nanocomposite material produced by the production method according to claim 1.
10. The metal atom-supported nanocomposite material as claimed in claim 9, wherein the nanocomposite material comprises a nanocarbon-based material support and metal monoatomic atoms and atomic clusters supported thereby.
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| CN114974938A (en) * | 2022-07-08 | 2022-08-30 | 曲靖师范学院 | Preparation of Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material |
| AT525570B1 (en) * | 2021-12-10 | 2023-05-15 | Hydrosolid Gmbh | Process for preparing g-C3N4/metal composite nanoplates |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330059A (en) * | 2003-05-07 | 2004-11-25 | Ube Nitto Kasei Co Ltd | Method for producing metal fine particle-carrying composite material and metal fine particle-carrying composite material obtained by the method |
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| CN103407985A (en) * | 2013-07-16 | 2013-11-27 | 清华大学 | Heteratom doped carbon nano-tube-graphene complex and preparation method thereof |
| CN105642917A (en) * | 2016-03-15 | 2016-06-08 | 苏州赛福德备贸易有限公司 | Preparation method for metal-clad carbon nano tube |
| CN106185885A (en) * | 2016-06-30 | 2016-12-07 | 天津大学 | There is isotropism height heat conduction, elastic three-dimensional grapheme and the preparation method of carbon nano tube compound material |
| CN106683991A (en) * | 2016-12-09 | 2017-05-17 | 华中科技大学 | Interconnection method for the carbon nanotube devices of grapheme/metal combined electrode |
| CN107017412A (en) * | 2017-04-28 | 2017-08-04 | 哈尔滨工业大学 | A kind of sp for having single dispersion metal atom doped2Hydridization carbon material and preparation method thereof |
| CN107321349A (en) * | 2017-06-26 | 2017-11-07 | 华南理工大学 | A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application |
| CN110201662A (en) * | 2019-05-08 | 2019-09-06 | 厦门大学 | The electrochemical preparation method of carbon load monoatomic metal catalyst |
| CN110694669A (en) * | 2019-11-15 | 2020-01-17 | 中国科学技术大学 | Preparation method of monatomic catalyst |
| CN111235545A (en) * | 2020-01-15 | 2020-06-05 | 武汉大学 | Nano-alloy particles and patterning method thereof |
| US20200230589A1 (en) * | 2019-01-18 | 2020-07-23 | Korea Institute Of Science And Technology | Metal single-atom catalyst and method for preparing the same |
| CN111620311A (en) * | 2019-02-28 | 2020-09-04 | 中国科学院化学研究所 | Porous carbon-loaded monoatomic metal nitrogen coordination composite material and preparation method thereof |
| CN111842924A (en) * | 2020-07-16 | 2020-10-30 | 西安交通大学 | Microwave-assisted metal nanoparticle preparation method and system |
| CN112473714A (en) * | 2020-11-26 | 2021-03-12 | 南方科技大学 | Composite material loaded with metal monoatomic, preparation method and application thereof |
-
2021
- 2021-03-17 CN CN202110286350.9A patent/CN112938936B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330059A (en) * | 2003-05-07 | 2004-11-25 | Ube Nitto Kasei Co Ltd | Method for producing metal fine particle-carrying composite material and metal fine particle-carrying composite material obtained by the method |
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| CN103407985A (en) * | 2013-07-16 | 2013-11-27 | 清华大学 | Heteratom doped carbon nano-tube-graphene complex and preparation method thereof |
| CN105642917A (en) * | 2016-03-15 | 2016-06-08 | 苏州赛福德备贸易有限公司 | Preparation method for metal-clad carbon nano tube |
| CN106185885A (en) * | 2016-06-30 | 2016-12-07 | 天津大学 | There is isotropism height heat conduction, elastic three-dimensional grapheme and the preparation method of carbon nano tube compound material |
| CN106683991A (en) * | 2016-12-09 | 2017-05-17 | 华中科技大学 | Interconnection method for the carbon nanotube devices of grapheme/metal combined electrode |
| CN107017412A (en) * | 2017-04-28 | 2017-08-04 | 哈尔滨工业大学 | A kind of sp for having single dispersion metal atom doped2Hydridization carbon material and preparation method thereof |
| CN107321349A (en) * | 2017-06-26 | 2017-11-07 | 华南理工大学 | A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application |
| US20200230589A1 (en) * | 2019-01-18 | 2020-07-23 | Korea Institute Of Science And Technology | Metal single-atom catalyst and method for preparing the same |
| CN111620311A (en) * | 2019-02-28 | 2020-09-04 | 中国科学院化学研究所 | Porous carbon-loaded monoatomic metal nitrogen coordination composite material and preparation method thereof |
| CN110201662A (en) * | 2019-05-08 | 2019-09-06 | 厦门大学 | The electrochemical preparation method of carbon load monoatomic metal catalyst |
| CN110694669A (en) * | 2019-11-15 | 2020-01-17 | 中国科学技术大学 | Preparation method of monatomic catalyst |
| CN111235545A (en) * | 2020-01-15 | 2020-06-05 | 武汉大学 | Nano-alloy particles and patterning method thereof |
| CN111842924A (en) * | 2020-07-16 | 2020-10-30 | 西安交通大学 | Microwave-assisted metal nanoparticle preparation method and system |
| CN112473714A (en) * | 2020-11-26 | 2021-03-12 | 南方科技大学 | Composite material loaded with metal monoatomic, preparation method and application thereof |
Non-Patent Citations (8)
| Title |
|---|
| HIU PING CHU ET AL.: "Metallo-Organic Chemical Vapor Deposition (MOCVD) for the Development of Heterogeneous Catalysts", 《ENERGY & FUELS》 * |
| HIU PING CHU ET AL.: "Metallo-Organic Chemical Vapor Deposition (MOCVD) for the Development of Heterogeneous Catalysts", 《ENERGY & FUELS》, vol. 12, 3 October 1998 (1998-10-03), pages 1109 - 1111 * |
| YANG,ZK ET AL.: "Directly transforming copper (I) oxide bulk into isolated single-atom copper sites catalyst through gas-transport approach", 《NATURE COMMUNICATIONS》 * |
| YANG,ZK ET AL.: "Directly transforming copper (I) oxide bulk into isolated single-atom copper sites catalyst through gas-transport approach", 《NATURE COMMUNICATIONS》, vol. 10, 19 August 2019 (2019-08-19), pages 1 - 5 * |
| 潘旭晨等: "氮掺杂有序介孔碳-Ni纳米复合材料的制备及电化学性能", 《无机化学学报》 * |
| 潘旭晨等: "氮掺杂有序介孔碳-Ni纳米复合材料的制备及电化学性能", 《无机化学学报》, no. 02, 10 February 2015 (2015-02-10), pages 282 - 289 * |
| 陈立飞等: "石墨烯负载金属纳米粒子新功能材料的制备", 《上海第二工业大学学报》 * |
| 陈立飞等: "石墨烯负载金属纳米粒子新功能材料的制备", 《上海第二工业大学学报》, no. 03, 15 September 2015 (2015-09-15), pages 185 - 189 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT525570B1 (en) * | 2021-12-10 | 2023-05-15 | Hydrosolid Gmbh | Process for preparing g-C3N4/metal composite nanoplates |
| AT525570A4 (en) * | 2021-12-10 | 2023-05-15 | Hydrosolid Gmbh | Process for preparing g-C3N4/metal composite nanoplates |
| CN114974938A (en) * | 2022-07-08 | 2022-08-30 | 曲靖师范学院 | Preparation of Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material |
| CN114974938B (en) * | 2022-07-08 | 2023-07-14 | 曲靖师范学院 | Preparation of Mn-Ni double single-atom modulation CN graded carbon tube electrode material |
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