CN112938936B - Metal atom loaded nanocomposite and preparation method thereof - Google Patents
Metal atom loaded nanocomposite and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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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
- 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
- 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
- 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 nanocomposite comprises the following steps: under the inert gas atmosphere, metal atoms are dispersed and deposited on the nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonized, so that the nano composite material loaded by the metal atoms is obtained. The invention prepares the metal atom loaded nano composite material with uniform atom distribution and strong binding capacity; in the preparation process, complicated physical and chemical treatment steps, reagent and instrument costs in the previous synthesis are avoided, and the 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 in particular 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 and other composite materials, play a role in electrocatalysis, environmental monitoring, biosensing and the like by using 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 supported metal catalyst, which means that all metal components on a carrier exist in a Single-atom dispersed form, without metal-metal bonds, or without metal bonds between the same metals when multiple metals are supported.
The preparation of metal atom-loaded nanocomposites is a very challenging problem, and the main methods of preparation currently fall into two broad categories, physical and chemical. The physical method mainly comprises the methods of laser sputtering, ball milling and the like; the chemical method mainly comprises the steps of taking a metal organic framework compound (Metal Organic Framework, MOF) as a precursor, and preparing the metal atom load material taking carbon as a carrier after high-temperature calcination. However, the cost of raw materials and devices for synthesizing the atomic-supported composite material is high, the metal atoms of the material are easy to agglomerate and have poor dispersibility, the yield is low, and the industrial production is difficult to expand.
Disclosure of Invention
The invention aims to provide a metal atom loaded nanocomposite and a preparation method thereof, which are used for solving one or more technical problems. The invention prepares the metal atom loaded nano composite material with uniform atom distribution and strong binding capacity; in the preparation process, complicated physical and chemical treatment steps, reagent and instrument costs in the previous synthesis are avoided, and the method can be used for mass production in industry.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a metal atom loaded nanocomposite, which comprises the following steps: under the inert gas atmosphere, metal atoms are dispersed and deposited on the nano carbon-based material carrier in an isolated or atomic cluster mode, and carbonized, so that the nano composite material loaded by the metal atoms is obtained.
The invention is further improved in that the metal atom is one or more of iron atom, cobalt atom, nickel atom, copper atom, manganese atom, platinum atom and ruthenium atom.
The invention further improves that the nano carbon-based material carrier is one or more of nitrogen-doped, sulfur-doped, boron-doped or iodine-doped carbon-based carriers.
The invention further improves that the specific steps of dispersing and depositing volatilized metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode under the inert gas atmosphere and carbonizing comprise the following steps:
under the inert gas atmosphere, the temperature is increased to a preset temperature at a preset temperature increasing speed, and the heat is preserved, so that metal atoms sublimated by the metal organic compound or the bulk metal volatilize to the nano carbon-based material carrier along with the gas, and the metal atoms are captured, anchored and carbonized by defects on the surface of the carrier.
The invention is further improved in that the metal organic compound or the bulk metal is one or more of ferrocene, nickel-dicyclopentadienyl, carbonyl iron, nickel tetracarbonyl, foam copper, foam nickel 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 rising speed is 1-10 ℃/min, the preset temperature is 800-1000 ℃, and the heat preservation time is 60-120 min.
The invention is further improved in that the carbon source adopted in the preparation of the nano carbon-based material carrier 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 or hydrothermal method.
A further improvement of the invention is that the inert gas atmosphere is a nitrogen, argon or helium atmosphere.
The invention discloses a metal atom loaded nanocomposite prepared by the preparation method.
A further improvement of the present invention is that the nanocomposite comprises a nanocarbon-based material carrier and metal monoatoms and clusters supported thereby.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, a carbon-based material is used as a carrier, metal atoms volatilized from metal organic compounds or bulk metals and the like are dispersed and deposited on the carrier in the form of isolated or atomic clusters in an inert gas atmosphere, and simultaneously carbonized to prepare the carbon-based material loaded by the metal atoms. The metal atom loaded nano composite material prepared by the method avoids complex physical and chemical treatment steps and reagent and instrument costs in the previous synthesis, and can be produced in mass in industry.
Specifically, the invention utilizes the method and principle of chemical vapor deposition to capture and combine metal atoms sublimated at high temperature from precursors such as metal organic compounds or bulk metals by a carrier, and prepares the metal atom loaded nanocomposite with uniform atom distribution and strong combining capability. Under high temperature, metal atoms are diffused to the surface of the carrier along with the gas atmosphere, captured and anchored by defects on the surface of the carrier, and carbonized, so that the dispersibility and anchoring capacity of the atoms are improved, 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 following description of the embodiments or the drawings used in the description of the prior art will make a brief description; it will be apparent to those of ordinary skill in the art that the drawings in the following description are of some embodiments of the invention and that other drawings may be derived from them without undue effort.
FIG. 1 is a schematic illustration of a method for preparing a metal atom-loaded nanocomposite according to an embodiment of the present invention;
FIG. 2 is a SEM schematic of the material prepared in example 1 of the present invention;
FIG. 3 is a graphical representation of the electrochemical polarization curves of Fe (Fc) -N/S-C versus Pt/C for example 1 of the present invention;
FIG. 4 is a schematic representation of an 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 block area in FIG. 4; wherein the circles mark Fe monoatoms.
Detailed Description
In order to make the purposes, technical effects and technical solutions of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it will be apparent that the described embodiments are some of the embodiments of the present invention. Other embodiments, which may be made by those of ordinary skill in the art based on the disclosed embodiments without undue burden, are within the scope of the present invention.
Referring to fig. 1, a method for preparing a metal atom-loaded nanocomposite by chemical vapor deposition according to an embodiment of the invention includes the following steps:
step 1, melamine is used as a nitrogen source and a carbon source, and L-cysteine is mixed in a ball mill for one hour according to a certain mass ratio, and the two powders are uniformly mixed;
step 2, placing the mixed powder in a crucible, covering a ceramic chip, placing the crucible in a tube furnace, heating to 500-600 ℃ at a certain heating rate under the inert gas atmosphere, and preserving heat for a certain time to obtain blocky light sulfur doped C with small density 3 N 4 A carrier;
step 3, the obtained sulfur doped C 3 N 4 Pulverizing into powder with a ball mill;
step 4, mixing a precursor such as a metal organic compound or bulk metal with a certain mass ratio with the sulfur doped C obtained in the step 3 3 N 4 Respectively placing in the crucible at the upstream and downstream of the air flow, and covering with ceramic chip to make C 3 N 4 One side is provided with a gap with the width of about 2 mm; then heating to 800-1000 ℃ at a certain heating rate under inert gas atmosphere, and preserving heat for a certain time to volatilize sublimated metal atoms to C along with gas 3 N 4 And finally obtaining the nano composite material loaded by the metal atoms on the carrier.
In the embodiment of the invention, in the step 1, melamine and L-cysteine are mixed in the following ratio (2-4): 1 by mass ratio.
In the embodiment of the invention, the ball grinding ball of the ball mill can be one of an agate ball, a stainless steel ball, a hard alloy ball and a zirconia ball; the diameter of the ball grinding ball is 3-20 mm; the ball milling tank 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 doping, sulfur doping, boron doping, iodine doping 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 the step 2 of the embodiment of the invention, the temperature rising speed is 1-10 ℃/min, the temperature rises to 600 ℃, 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 rising speed is 1-10 ℃/min, the temperature rises to 900 ℃, and the temperature is kept for 60-120 min, so that the prepared composite material is obtained; wherein the metal organic compound or the bulk metal is not limited to one or more of ferrocene, nickel dichloride, carbonyl iron, nickel tetracarbonyl, foam copper, foam nickel, 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 method and principle of chemical vapor deposition to capture and combine metal atoms sublimated at high temperature by precursors such as metal organic compounds or bulk metals by a carrier, and prepares the metal atom loaded nanocomposite with uniform atom distribution and strong combining capability. At high temperature, metal atoms are diffused to the surface of the carrier along with the gas atmosphere, are captured and anchored by defects on the surface of the carrier, and are carbonized, so that the dispersibility and anchoring capacity 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 complicated physical and chemical treatment steps and reagent and instrument costs in the previous synthesis, and can be produced in mass in industry.
The nanocomposite prepared by the embodiment of the invention comprises: a nano carbon material carrier and metal monoatoms and atom clusters loaded by the nano carbon material carrier; the metal atoms comprise one or more of iron atoms, cobalt atoms, nickel atoms, copper atoms, manganese atoms and the like.
Chemical vapor deposition is a chemical technique in which a substrate is exposed to one or more different precursors and chemical reactions occur on the substrate surface to deposit a thin film, wherein atomic layer deposition is a process by which a substance can be "plated" onto the substrate surface in the form of a monoatomic film. By utilizing the chemical vapor deposition method and principle, metal atoms sublimated by precursors such as metal organic compounds or bulk metals at high temperature are captured and combined by a carrier, and the method is a new thought for preparing the nanocomposite loaded by the metal atoms. The invention discloses a preparation method for preparing a metal atom loaded nanocomposite by chemical vapor deposition, and relates to the field of nanocomposite in material preparation. The process comprises taking carbon-based material as carrier, dispersing metal atoms volatilized from metal organic compound or bulk metal in the form of isolated or atomic clusters on the carrier, and carbonizing to obtain the carbon-based material loaded by metal atoms.
Example 1
Referring to fig. 1 to 5, a method for preparing a metal atom-loaded nanocomposite according to an embodiment of the present invention includes the following steps:
8.00g of melamine and 2.00g of g L-cysteine are mixed for one hour in a ball mill, and the two powders are uniformly mixed; then placing the mixed powder in a crucible, covering with ceramic chip, heating to 600deg.C at 2 deg.C/min, and maintaining the temperature for 120min to obtain blocky light sulfur doped C with small density 3 N 4 . 500mg of the prepared material was dispersed in 250mL of HNO 3 (0.5mol L -1 ) And (5) ultrasonic dispersion. 3.125mL of GO dispersion (1 mg mL was added -1 ) And stir6h to obtain a uniform dispersion. The final product was collected by filtration, washed three times with deionized water and ethanol, respectively, and then dried in a freeze dryer for 12 hours to give the precursor.
Placing ferrocene with the mass ratio of 5% on one side of a precursor, covering a ceramic chip on a crucible, leaving a gap of about 2mm on one side of the precursor, enabling sublimated ferrocene products to flow out along with protective gas, then heating to 900 ℃ at a heating speed of 2 ℃/min under nitrogen atmosphere, and preserving heat for 120min to finally obtain Fe-doped carbon-nitrogen materials (Fe (Fc) -N/S-C); the prepared material scanning electron microscope is shown in figure 2, and the ORR performance test result is shown in figure 3.
As can be seen from the Scanning Electron Microscope (SEM) results of the material of FIG. 2, the material prepared by the method of example 1 has a nano-lamellar structure, which is pyrolyzed in a first step to form C 3 N 4 Further carbonization is performed on the basis of the framework material, and when the lamellar structure is carbonized, the possibility is provided for anchoring the metal atoms which migrate from the upstream of the airflow. The electrochemical results according to FIG. 3 show that the half-wave potential of the catalyst prepared by the scheme is 0.872V, which is higher than that of commercial Pt/C (0.867V). Meanwhile, the AC-HADDF-STEM diagram of Fe (Fc) -N/S-C prepared by the scheme is shown in figures 4 and 5, so that Fe single atoms in the material can be clearly seen, and agglomerated particles are not generated, and the successful metal atom loaded material prepared by the scheme is shown. The above results demonstrate the feasibility of the present invention to prepare metal atom-loaded nanocomposites.
Example 2
The preparation method of the metal atom loaded nanocomposite comprises the following steps: dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode in an inert gas atmosphere, and carbonizing to obtain a metal atom-loaded nano composite material;
wherein the metal atom is an iron atom.
Example 3
The embodiment of the present invention differs from embodiment 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 nanocomposite comprises the following steps: dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode in an inert gas atmosphere, and carbonizing to obtain a metal atom-loaded nano composite material;
wherein the nano carbon-based material carrier is nitrogen doped.
Example 5
The embodiment of the present invention differs from embodiment 4 only in that the nanocarbon-based material carrier is nitrogen-doped, sulfur-doped, and boron-doped.
Example 6
The preparation method of the metal atom loaded nanocomposite comprises the following steps: dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode in an inert gas atmosphere, and carbonizing to obtain a metal atom-loaded nano composite material;
the method comprises the specific steps of dispersing and depositing volatilized metal atoms in isolated or atomic clusters on a nano carbon-based material carrier under an inert gas atmosphere and carbonizing the metal atoms, wherein the specific steps comprise:
under the inert gas atmosphere, heating to a preset temperature at a preset heating rate, and preserving heat to volatilize metal atoms sublimated by the metal organic compound or the bulk metal to the nano carbon-based material carrier along with the gas, and capturing, anchoring and carbonizing the metal atoms 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 present invention differs from embodiment 6 only in that the metal organic compound or bulk metal is ferrocene, nickel-dicyclopentadienyl; 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 present invention differs from embodiment 6 only in that the metal organic compound or bulk metal is ferrocene, nickel-dicyclopentadienyl, 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 difference between the embodiment of the present invention and the embodiment 6 is that the predetermined heating rate is 1 ℃/min, the predetermined temperature is 800 ℃, and the heat preservation time is 60min.
Example 10
The difference between the embodiment of the present invention and the embodiment 7 is that the predetermined heating rate is 5 ℃/min, the predetermined temperature is 900 ℃, and the heat preservation time is 80min.
Example 11
The difference between the embodiment of the present invention and the embodiment 8 is that the predetermined heating rate is 10 ℃/min, the predetermined temperature is 1000 ℃, and the heat preservation time is 120min.
Example 12
The preparation method of the metal atom loaded nanocomposite comprises the following steps: dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode in an inert gas atmosphere, 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 method comprises the specific steps of dispersing and depositing volatilized metal atoms in isolated or atomic clusters on a nano carbon-based material carrier under an inert gas atmosphere and carbonizing the metal atoms, wherein the specific steps comprise:
under the inert gas atmosphere, heating to a preset temperature at a preset heating rate, and preserving heat to volatilize metal atoms sublimated by the metal organic compound or the bulk metal to the nano carbon-based material carrier along with the gas, and capturing, anchoring and carbonizing the metal atoms by defects on the surface of the carrier;
the metal organic compound or the bulk metal is ferrocene or nickel dicyclopentadienyl;
the mass ratio of the metal organic compound or the bulk metal to the nano carbon-based material carrier is 18%;
the preset heating speed is 1-10 ℃/min, the preset temperature is 850 ℃, and the heat preservation time is 100min;
when the nano carbon-based material carrier is prepared, the adopted carbon source is 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 nanocomposite comprises the following steps: dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode in an inert gas atmosphere, and carbonizing to obtain a metal atom-loaded nano composite material;
wherein the metal atom is ruthenium atom;
the nano carbon-based material carrier is an iodine doped carbon-based carrier;
the method comprises the specific steps of dispersing and depositing volatilized metal atoms in isolated or atomic clusters on a nano carbon-based material carrier under an inert gas atmosphere and carbonizing the metal atoms, wherein the specific steps comprise:
under the inert gas atmosphere, heating to a preset temperature at a preset heating rate, and preserving heat to volatilize metal atoms sublimated by the metal organic compound or the bulk metal to the nano carbon-based material carrier along with the gas, and capturing, anchoring and carbonizing the metal atoms by defects on the surface of the carrier;
the metal organic compound or the bulk metal is copper foam and nickel foam;
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 90min;
when the nano carbon-based material carrier is prepared, the adopted carbon source is melamine; the adopted preparation method is pyrolysis and ball milling;
the inert gas atmosphere is a nitrogen atmosphere.
Example 14
The preparation method of the metal atom loaded nanocomposite comprises the following steps: dispersing and depositing metal atoms on a nano carbon-based material carrier in an isolated or atomic cluster mode in an inert gas atmosphere, 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 nitrogen doped;
the method comprises the specific steps of dispersing and depositing volatilized metal atoms in isolated or atomic clusters on a nano carbon-based material carrier under an inert gas atmosphere and carbonizing the metal atoms, wherein the specific steps comprise:
under the inert gas atmosphere, heating to a preset temperature at a preset heating rate, and preserving heat to volatilize metal atoms sublimated by the metal organic compound or the bulk metal to the nano carbon-based material carrier along with the gas, and capturing, anchoring and carbonizing the metal atoms 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 120min;
when the nano carbon-based material carrier is prepared, the adopted carbon source is polyvinyl alcohol; the preparation method is a hydrothermal method;
the inert gas atmosphere is a nitrogen atmosphere.
Example 15
8.00g of urea powder was placed in a crucible covered with ceramic chips using urea as a carbon source and a nitrogen source. Heating to 600 ℃ at a speed of 2 ℃/min, and preserving heat for 120min to obtain blocky light sulfur doped C with small density 3 N 4 。
The C obtained 3 N 4 Grinding in a ball millPlacing foam nickel with mass ratio of 5% on one side of C3N4, covering the crucible with ceramic chip, C 3 N 4 A gap of about 2mm is reserved on one side, so that sublimated ferrocene products flow out along with the shielding gas, then the temperature is raised to 900 ℃ at a speed of 2 ℃/min under the nitrogen atmosphere, and the temperature is kept for 120min, and finally the Ni-doped carbon-nitrogen material is obtained.
Example 16
The production method of this embodiment differs from embodiment 15 only in that: the foamed nickel with the mass ratio of 5% is cobalt acetylacetonate with the mass ratio of 5%.
Example 17
The production method of this embodiment differs from embodiment 15 only in that: the temperature rise rate was changed to 900℃at 2℃per minute under a nitrogen atmosphere to 800℃at 2℃per minute.
Example 18
The production method of this embodiment differs from embodiment 15 only in that: the temperature rise rate of 2 ℃/min to 900 ℃ is changed to 1000 ℃ at the temperature rise rate of 2 ℃/min under the nitrogen atmosphere.
The invention discloses a preparation method for preparing a metal atom loaded nanocomposite by chemical vapor deposition, and relates to the field of nanocomposite in material preparation. The process comprises taking carbon-based material as carrier, dispersing metal atoms volatilized from metal organic compound or bulk metal in the form of isolated or atomic clusters on the carrier, and carbonizing to obtain the carbon-based material loaded by metal atoms.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, one skilled in the art may make modifications and equivalents to the specific embodiments of the present invention, and any modifications and equivalents not departing from the spirit and scope of the present invention are within the scope of the claims of the present invention.
Claims (5)
1. A method for preparing a metal atom-loaded nanocomposite by chemical vapor deposition, comprising the steps of:
step 1, melamine is used as a nitrogen source and a carbon source, and L-cysteine is mixed in a ball mill for one hour according to a certain mass ratio, and the two powders are uniformly mixed;
step 2, placing the mixed powder in a crucible, covering a ceramic chip, placing the crucible in a tube furnace, heating to 500-600 ℃ at a certain heating speed under the inert gas atmosphere, and preserving heat for a certain time to obtain a blocky light sulfur doped C with small density 3 N 4 A carrier;
step 3, the obtained sulfur doped C 3 N 4 Grinding into powder by a ball mill;
step 4, mixing a metal organic compound or a bulk metal precursor with the sulfur doped C obtained in the step 3 according to a certain mass ratio 3 N 4 Respectively placing in the crucible at the upstream and downstream of the air flow, and covering with ceramic chip to make C 3 N 4 One side is left with a gap of about 2mm width; then heating to 800-1000 ℃ at a certain heating rate in inert gas atmosphere, and preserving heat for a certain time to volatilize sublimated metal atoms to C along with gas 3 N 4 Finally obtaining the nano composite material loaded by metal atoms on the carrier;
wherein the prepared nanocomposite comprises: a nano carbon material carrier and metal monoatoms 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 and manganese atom.
2. The method for preparing a metal atom supported nanocomposite by chemical vapor deposition according to claim 1, wherein,
in the step 1, melamine and L-cysteine are mixed in the following ratio (2-4): 1 by mass ratio.
3. The method for preparing a metal atom supported nanocomposite by chemical vapor deposition according to claim 1, wherein,
the ball-milling ball of the ball mill is one of an agate ball, a stainless steel ball, a hard alloy ball and a zirconia ball;
the diameter of the ball grinding ball is 3-20 mm;
the ball milling tank of the ball mill is one of agate, stainless steel, hard alloy and zirconia;
the ball grinding ball material mass ratio is (200-10): 1.
4. the method for preparing a metal atom supported nanocomposite by chemical vapor deposition according to claim 1, wherein,
in the step 2, the temperature rising speed is 1-10 ℃/min, the temperature rises to 600 ℃, and the temperature is kept for 60-120 min.
5. The method for preparing a metal atom supported nanocomposite by chemical vapor deposition according to claim 1, wherein,
in the step 4, the metal organic compound is one or more of ferrocene, nickel-dicyclopentadienyl, carbonyl iron and nickel-tetracarbonyl, and the bulk metal is one or more of foam copper, foam nickel and cobalt foil; the mass ratio of the metal organic compound or the bulk metal to the carrier is 1% -20%; heating to 900 ℃ at a heating speed of 1-10 ℃/min, and preserving heat for 60-120 min to obtain the metal atom loaded nanocomposite; wherein the inert gas atmosphere is one of nitrogen, argon and helium.
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| CN202110286350.9A CN112938936B (en) | 2021-03-17 | 2021-03-17 | Metal atom loaded nanocomposite and preparation method thereof |
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