CN109012733B - g-C3N4Preparation method of core-shell structure nano composite coated with metal - Google Patents
g-C3N4Preparation method of core-shell structure nano composite coated with metal Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/398—
Abstract
The invention belongs to the field of composite nanoparticle synthesis and discloses g-C3N4A preparation method of a core-shell structure nano composite coated with metal. Grinding and uniformly mixing nanoscale metal powder and urea together by using a simple microwave reaction method, heating magnetic nanoparticles by using microwaves in a protective atmosphere to serve as reaction conditions, reacting for 1-10 minutes, placing a sample in the protective atmosphere in liquid nitrogen for rapid cooling, and synthesizing g-C3N4Coating metal spherical shell structure nano particles; the g to C3N4The metal-coated core-shell nano powder has g-C with magnetic metal as core and outer coating3N4. g-C prepared by the invention3N4The metal core-shell type nano powder coating compound has the advantages of simple preparation process, high sample structure uniformity, environmental protection, easiness in large-scale production and the like. Preparation of g-C3N4The coated metal core-shell nano powder has wide application prospect in the fields of research of photocatalysis, electro-catalysis (hydrogen evolution reaction) and the like.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to g-C3N4A preparation method of a core-shell nano composite coated with metal.
Background
The coated metal nano-particles have unique physical and chemical properties, and the coating layer has a protection effect on the coated metal particles, so that the application range of the nano-particle materials is expanded, and the materials have great potential application values in the fields of chemistry, materials, physics and the like. In the field of electricity, the proportion of the coated metal nanoparticles to the interface units is very large, and the coated metal nanoparticles have excellent electrical properties such as high conductivity and high dielectricity due to the size and the interface effect, and the application of the material to an electrical quantum device is a research hotspot at present. In the field of catalysts, coated metal nanoparticles can be used as catalyst carriers, and have made good progress in the aspect of photoelectrocatalysis. In the optical field, the coated metal nano material has special optical performance which the bulk material does not have due to the small size effect. The nonlinear optics, light absorption, light reflection, energy loss in the light transmission process and the like of the material are strongly related to the particle size of the material, and the nanoscale coating type metal material can be applied to optical devices with special performance.
The ion beam method is also an earlier and ideal method for preparing the carbon-coated metal nano material by using ion sputtering co-deposition drilling and carbon to prepare a nano film, and then performing further heat treatment to obtain the carbon-coated nano material.
Disclosure of Invention
The inventionAims to provide a microwave method for quickly and simply preparing g-C3N4The method for coating the metal core-shell nano-composite comprises the steps of firstly preparing nano-scale metal nano-particles, and rapidly preparing g-C with a core-shell structure by uniformly mixing the metal nano-particles and urea under microwave irradiation3N4Coating the metal nanocomposite.
The specific technical scheme is as follows:
graphite phase carbon nitride (g-C)3N4) The preparation method of the metal-coated core-shell structure nano composite comprises the following steps:
And 3, immediately taking out the container after the reaction is finished, and placing the container in a liquid nitrogen or water-cooled environment for cooling.
Further, uniformly mixing the magnetic metal nanoparticles and urea in the step 1 according to a mass ratio of 1: 10; in the step 2, the power of the microwave reactor is adjusted to 1000w, and the reaction time is 1 min.
Further, the method for preparing the magnetic metal nanoparticles in step 1 is to prepare the magnetic metal nanoparticles in situ under the working air pressure by using a plasma arc discharge technology, wherein:
magnetic metal micron powder is uniformly pressed to be used as an anode, and a tungsten rod is used as a cathode; the distance between the cathode and the anode is kept to be 2-20 mm; the voltage of arc discharge is 20-40V; the current is 100A; the working pressure is argon and hydrogen.
Further, the argon partial pressure is 0.01 to 0.3MPa, and the hydrogen partial pressure is 0.01 to 0.3 MPa.
Furthermore, the magnetic metal micron powder in the anode material is one of iron, cobalt and nickel, and the purity of the metal is more than 99.8%.
Further, the anode is cylindrical, and has a diameter of 30 to 50mm and a thickness of 5 to 30 mm.
The invention has the beneficial effects that: provides a method for quickly preparing coated g-C by a microwave method3N4A method of metal nanocomposite. The microwave reaction time is further shortened to optimize the more efficient synthesis. The thickness of the carbon shell can be further regulated and controlled, and more excellent photocatalytic and electrochemical catalytic performances can be obtained. Meanwhile, the method has the advantages of rapid reaction, simple process, resource saving, high purity, low cost and the like.
Drawings
FIG. 1 shows the envelope g-C of the process of the invention3N4Schematic structure of metal nanocomposite.
FIG. 2 shows the inclusion of g-C in the process of the invention3N4A flow chart of a preparation method of the metal nano-composite.
FIG. 3 shows the inclusion of g-C in the process of the invention3N4X-ray diffraction pattern corresponding to the metallic iron nano-particles.
FIG. 4 shows the inclusion of g-C in the process of the invention3N4High resolution projection micrographs corresponding to metallic iron particles.
FIG. 5 shows the inclusion of g-C in the process of the invention3N4Projected EDS line scan corresponding to metallic iron particles. Projection image (a) and line scan image (b).
FIG. 6 shows the inclusion of g-C in the process of the present invention3N4X-ray photoelectron spectrum corresponding to the metal iron particle. (a) Iron XPS graph, and (b) peak separation graph of C element.
FIG. 7 shows the inclusion of g-C in the process of the present invention3N4X-ray diffraction pattern corresponding to metallic cobalt nanoparticles.
FIG. 8 is a graph of the envelope g-C of the process of the present invention3N4Cobalt metal particle instituteCorresponding high resolution projection micrographs.
FIG. 9 shows the inclusion of g-C in the process of the present invention3N4X-ray photoelectron spectrum corresponding to the metal cobalt particle. (a) Cobalt XPS pattern, and (b) peak separation pattern of C element.
FIG. 10 is a graph of the envelope g-C of the process of the present invention3N4X-ray diffraction pattern corresponding to metallic nickel nanoparticles.
FIG. 11 is a graph of the inclusion of g-C in the process of the present invention3N4High-resolution projection micrographs corresponding to metallic nickel particles.
FIG. 12 is a graph of cladding type g-C in the method of the present invention3N4X-ray photoelectron spectrum corresponding to the metal nickel particle. (a) Nickel XPS pattern, and (b) peak separation pattern of C element.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the operation of the present invention is provided with reference to the accompanying drawings and specific examples. It should be understood that the specific examples described herein are for purposes of illustration only and are not intended to limit the scope of the present disclosure.
Example 1
FIG. 1 shows the envelope g-C of the process of the invention3N4Schematic structure of metal nanocomposite. As shown in fig. 1, the core-shell type cladding material nanoparticles include: wherein the outer portion is coated with a carbon nitride shell layer 101; an inner metal core layer 102, in this embodiment Fe nanoparticles.
The carbonitride shell layer 101 is typically g-C3N4Or a carbonitride of similar composition.
The metal core 102 may be prepared by a direct current arc method, and has a particle diameter of 1 to 300 nm.
Further, the nanoparticles 102 of the present example were prepared using hydrogen gas and argon gas, and were cooled using cooling water, and the particle size of the metal nanoparticles was 1 to 200 nm.
Meanwhile, the invention provides a preparation method of the embodiment:
FIG. 2 shows a coated form g-C3N4Flow chart of the method for preparing metal nano-composite.
And step B101, preparing metal nano particles.
According to the preparation process, the core/shell type nano-particles are prepared by using a direct current arc method. In this example, Fe was chosen as the metal, and hydrogen and argon were used as the reactant gases, and the preparation was carried out under arc conditions of 30-90V,90-290A, using cooling water as the cooling means.
And step B102, preparing a mixture of metal nanoparticles and urea.
The direct current arc method is used for preparing nano particles and uniformly mixing the nano particles with urea. In the implementation, the urea powder is firstly ground by agate, and then is uniformly mixed and ground with the nano iron powder according to the proportion of 10:1 to obtain a mixture, and the mixture is placed in a three-mouth beaker.
Step B103, heating the reaction by a microwave reactor. The sample is carried out under the atmosphere of argon as a protective gas, the full power of the microwave reactor (1000w) and the reaction time of 1 minute are set.
And step B104, cooling the prepared sample suspension in a high gradient manner. And (3) quickly pouring a proper amount of liquid nitrogen into the three-mouth beaker after the reaction is finished under the argon protection atmosphere, instantly cooling the three-mouth beaker to a low temperature, and cooling the three-mouth beaker by virtue of high gradient to generate a compound suspension.
And step B105, performing suction filtration on the compound suspension, and then placing the compound suspension in a ventilated environment without pollution for natural drying.
FIG. 3 is a graph of measurements on an X-ray diffractometer of an example of the present invention. As shown in fig. 3, the diffraction peak of the sample at 2 θ ═ 27.8 ° corresponds to g — C3N4(002) lattice plane of the phase. The Fe and the urea can be used for synthesizing g-C by a microwave-assisted method3N4And other substances cannot be synthesized.
FIG. 4 is a high resolution image taken with a high resolution projection microscope in accordance with an embodiment of the present invention. As shown in FIG. 4, the sample is clearly seen to be of a core-shell structure with the outer portion being g-C3N4The distance between the crystal faces corresponding to the (002) crystal face is 0.35nm, and the interior of the crystal face is provided with an Fe core.
FIG. 5 is a graphical representation of a line sweep taken under the EDS mode of a projection microscope according to an embodiment of the present invention. As shown in FIG. 5, the content of Fe, C and N on the sample is changed on line scanning, the content of C and N is obviously increased at the shell, the content of Fe in the inner core is increased, the content of C, N is reduced, and the coated g-C is also authenticated3N4Structure of metal nanocomposite.
FIG. 6 is a graph of measurements on an X-ray photoelectron spectrometer of an example of the present invention. As shown in the left side of fig. 6, the peak positions of the N and C elements can be clearly seen; FIG. 6 right panel, fine X-ray photoelectron spectroscopy of C and simulation, the generation of g-C can be clearly inferred by chemical bond energy3N4。
Example 2
FIG. 1 shows the envelope g-C of the process of the invention3N4Schematic structure of metal nanocomposite. As shown in fig. 1, the core-shell type cladding material nanoparticles include: wherein the outer portion is coated with a carbon nitride shell layer 101; an inner metal core layer 102, in this embodiment Co nanoparticles are selected.
The carbonitride shell layer 101 is typically g-C3N4Or a carbonitride of similar composition.
The metal core 102 may be prepared by a direct current arc method, and has a particle diameter of 1 to 300 nm.
Further, the nanoparticles 102 of the present example were prepared using hydrogen gas and argon gas, and were cooled using cooling water, and the particle size of the metal nanoparticles was 1 to 200 nm.
Meanwhile, the invention provides a preparation method of the embodiment:
FIG. 2 shows a coated form g-C3N4Flow chart of the method for preparing metal nano-composite.
And step B101, preparing metal nano particles.
According to the preparation process, the core/shell type nano-particles are prepared by using a direct current arc method. In this example, Co was chosen as the metal, and hydrogen and argon were used as the reactant gases, and the preparation was carried out under arc conditions of 30-90V,90-290A, using cooling water as the cooling means.
And step B102, preparing a mixture of metal nanoparticles and urea.
The direct current arc method is used for preparing nano particles and uniformly mixing the nano particles with urea. In the implementation, the urea powder is firstly ground by agate, and then is uniformly mixed and ground with the nano iron powder according to the proportion of 10:1 to obtain a mixture, and the mixture is placed in a three-mouth beaker.
Step B103, heating the reaction by a microwave reactor. The sample is carried out under the atmosphere of argon as a protective gas, the power of the microwave reactor is 800w, and the reaction time is set to be 2 minutes.
And step B104, cooling the prepared sample suspension in a high gradient manner. And (3) quickly pouring a proper amount of liquid nitrogen into the three-mouth beaker after the reaction is finished under the argon protection atmosphere, instantly cooling the three-mouth beaker to a low temperature, and cooling the three-mouth beaker by virtue of high gradient to generate a compound suspension.
And step B105, performing suction filtration on the compound suspension, and then placing the compound suspension in a ventilated environment without pollution for natural drying.
FIG. 7 is a graph of measurements on an X-ray diffractometer of an example of the present invention. As shown in fig. 7, since the peak of the nano-metallic cobalt is very sharp and the intensity is very high, the diffraction peak of the sample at 27.8 ° 2 θ is not very obvious.
FIG. 8 is a high resolution image taken with a high resolution projection microscope in accordance with an embodiment of the present invention. As shown in FIG. 8, the sample is clearly seen to be of a core-shell structure with the outer portion being g-C3N4The interplanar spacing of the (002) crystal face is 0.35nm, and the interior is Co core.
FIG. 9 is a graph of measurements on an X-ray photoelectron spectrometer of an embodiment of the present invention. As shown in the left side of fig. 9, the peak positions of the N and C elements are clearly seen; FIG. 9 right panel, fine X-ray photoelectron spectroscopy of C and simulation, the generation of g-C is clearly inferred by chemical bond energy3N4。
Example 3
FIG. 1 shows the envelope g-C of the process of the invention3N4Schematic structure of metal nanocomposite. As shown in fig. 1, the core-shell type cladding material nanoparticles include: wherein the outer bagA coated carbon nitrogen compound shell layer 101; an inner metal core layer 102, in this embodiment Ni nanoparticles are selected.
The carbonitride shell layer 101 is typically g-C3N4Or a carbonitride of similar composition.
The metal core 102 may be prepared by a direct current arc method, and has a particle diameter of 1 to 300 nm.
Further, the nanoparticles 102 of the present example were prepared using hydrogen gas and argon gas, and were cooled using cooling water, and the particle size of the metal nanoparticles was 1 to 200 nm.
Meanwhile, the invention provides a preparation method of the embodiment:
FIG. 2 shows a coated form g-C3N4Flow chart of the method for preparing metal nano-composite.
And step B101, preparing metal nano particles.
According to the preparation process, the core/shell type nano-particles are prepared by using a direct current arc method. In this example, Ni was chosen as the metal, and hydrogen and argon were used as the reactant gases, and the preparation was carried out under arc conditions of 30-90V,90-290A, using cooling water as the cooling means.
And step B102, preparing a mixture of metal nanoparticles and urea.
The direct current arc method is used for preparing nano particles and uniformly mixing the nano particles with urea. In the implementation, the urea powder is firstly ground by agate, and then is uniformly mixed and ground with the nano iron powder according to the proportion of 10:1 to obtain a mixture, and the mixture is placed in a three-mouth beaker.
Step B103, heating the reaction by a microwave reactor. The sample is carried out under the atmosphere of argon as a protective gas, the power of the microwave reactor is 900w, and the reaction time is set to be 4 minutes.
And step B104, cooling the prepared sample suspension in a high gradient manner. And (3) quickly pouring a proper amount of distilled water into the three-mouth beaker after the reaction is finished under the argon protection atmosphere, instantly cooling the three-mouth beaker to a low temperature, and cooling the three-mouth beaker by virtue of a high gradient to generate a compound suspension.
And step B105, performing suction filtration on the compound suspension, and then placing the compound suspension in a ventilated environment without pollution for natural drying.
FIG. 10 is a graph of measurements on an X-ray diffractometer of an example of the present invention. As shown in fig. 10, since the peak of the nano metal nickel is very sharp and the intensity is very high, the diffraction peak of the sample at 27.8 ° 2 θ is not very obvious.
FIG. 11 is a high resolution image taken with a high resolution projection microscope in accordance with an embodiment of the present invention. As shown in FIG. 11, the sample is clearly seen to be of a core-shell structure with the outer portion being g-C3N4The distance between the crystal faces corresponding to the (002) crystal face is 0.35nm, and the inside is a Ni core.
FIG. 12 is a graph of measurements on an X-ray photoelectron spectrometer of an example of the present invention. As shown in the left side of fig. 12, the peak positions of the N and C elements can be clearly seen; FIG. 12, right panel, fine X-ray photoelectron spectroscopy of C and simulations were performed, and g-C was generated by a clear inference of chemical bond energy3N4。
The above embodiments are merely illustrative, not restrictive, of the technical solutions of the present invention, and any technical solutions without departing from the spirit and scope of the present invention should be covered by the claims of the present invention.
Claims (8)
1. g-C3N4The preparation method of the metal-coated core-shell structure nano composite is characterized by comprising the following steps:
step 1, uniformly mixing and grinding magnetic metal nanoparticles and urea according to a mass ratio of 1: 10-30, wherein the size of the magnetic metal nanoparticles is 1-200 nm;
step 2, placing the mixture obtained in the step 1 in a container, introducing argon as a protective gas, placing the container in a microwave reactor, and adjusting the power of the microwave reactor to 800-1000 w for 0.5-10 min;
step 3, immediately taking out the container after the reaction is finished, and placing the container in a liquid nitrogen or water-cooled environment for cooling;
step 4, filtering the product obtained in the step 3, drying the product in vacuum, and drying the sample to obtain g-C3N4A core-shell structure nanocomposite coated with metal.
2. g-C according to claim 13N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that the magnetic metal nanoparticles and urea in the step 1 are uniformly mixed according to the mass ratio of 1: 10; in the step 2, the power of the microwave reactor is adjusted to 1000w, and the reaction time is 1 min.
3. g-C according to claim 1 or 23N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that the preparation method of the magnetic metal nano particles in the step 1 is to prepare the magnetic metal nano particles in situ under working air pressure by utilizing a plasma arc discharge technology, wherein:
magnetic metal micron powder is uniformly pressed to be used as an anode, and a tungsten rod is used as a cathode; the distance between the cathode and the anode is kept to be 2-20 mm; the voltage of arc discharge is 20-40V; the current is 100A, and the working pressure is argon and hydrogen.
4. g-C according to claim 33N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that the partial pressure of argon is 0.01-0.3 MPa, and the partial pressure of hydrogen is 0.01-0.3 MPa.
5. g-C according to claim 33N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that magnetic metal micron powder in an anode material is prepared, wherein the metal is one of iron, cobalt and nickel, and the purity of the metal is more than 99.8%.
6. g-C according to claim 43N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that magnetic metal micron powder in an anode material is prepared, wherein the metal is one of iron, cobalt and nickel, and the purity of the metal is more than 99.8%.
7. g-C according to claim 33N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that the anode is cylindrical, the diameter of the anode is 30-50 mm, and the thickness of the anode is 5-30 mm.
8. g-C according to claim 4 or 5 or 63N4The preparation method of the metal-coated core-shell structure nano composite is characterized in that the anode is cylindrical, the diameter of the anode is 30-50 mm, and the thickness of the anode is 5-30 mm.
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