CN109012733A - A kind of g-C3N4Coat the preparation method of the nuclear shell structure nano compound of metal - Google Patents
A kind of g-C3N4Coat the preparation method of the nuclear shell structure nano compound of metal Download PDFInfo
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- CN109012733A CN109012733A CN201811035478.2A CN201811035478A CN109012733A CN 109012733 A CN109012733 A CN 109012733A CN 201811035478 A CN201811035478 A CN 201811035478A CN 109012733 A CN109012733 A CN 109012733A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000008187 granular material Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 3
- 238000010891 electric arc Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 58
- 239000002105 nanoparticle Substances 0.000 abstract description 19
- 238000005253 cladding Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000011858 nanopowder Substances 0.000 abstract 3
- 239000002131 composite material Substances 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002122 magnetic nanoparticle Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000002082 metal nanoparticle Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 11
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 fields of composite nanoparticle synthesis, disclose a kind of g-C3N4Coat the preparation method of the nuclear shell structure nano compound of metal.Utilize simple microwave reaction method; it by nano level metal powder and urea co-ground and is uniformly mixed under protective atmosphere through microwave for magnetic nanoparticle heating as reaction condition, the reaction 1~sample under gas will be protected to be placed in liquid nitrogen after ten minutes is quickly cooled down and synthesizes g-C3N4Coat metal ball shell structural nano particle；The g-C3N4Metal core-shell type nano powder is coated, is had using magnetic metal as kernel, the g-C of external sheath3N4.G-C prepared by the present invention3N4Metal core-shell type nano powder compound is coated, has many advantages, such as that preparation process is simple, sample structure homogenization is high, environmentally protective, is easy to large-scale production.Prepare g-C3N4Cladding metal core-shell type nano powder has broad application prospects for the research fields such as photocatalysis and electro-catalysis (evolving hydrogen reaction).
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of g-C3N4The core-shell nano for coating metal is multiple
Close object preparation method.
Background technique
Cladded type metal nanoparticle has unique physicochemical properties, and clad is to the metallic coated
With protective effect, the application range of this type nano granular material has been expanded, has led this material in chemistry, material, physics etc.
There is huge potential using value in domain.In electricity field, cladded type metal nanoparticle is because of its boundary element proportion pole
Greatly and size and interfacial effect make it have excellent electric property, and such as high conductivity, high dielectric property, this material exists
Application on electricity quantum device is the previous research hotspot of mesh.In catalyst field, cladded type metal nanoparticle can be made
For catalyst carrier, good progress is had been achieved in terms of photoelectrocatalysis.And in optical field, since cladded type metal is received
Rice material small-size effect, makes it have special optical performance not available for block materials.Material nonlinearity optics, light are inhaled
It receives, light reflection, the energy loss in optical transmission process etc. all have very strong association, nanoscale cladded type gold with material particle size
Belonging to material may be used in the optical device of property.
Up to the present, the preparation method in relation to carbon-clad metal nano material is by wide coverage, wherein relatively common
Method have arc process, ion beam method, laser method, chemical vapour deposition technique, high-temperature process method etc..Wherein, arc process is carbon packet
Cover a kind of most common method in metal nano material preparation method.Carbon-clad metal nano material is initially by U.S.'s Rouff group
It is found when La graphite anode rod is mixed in arc process evaporation gasification.Ion beam method is also that a kind of study earlier, preferably prepares
The method of carbon-clad metal nano material is co-deposited brill using ion sputtering, carbon prepares nano thin-film, then further heat treatment
Obtain carbon coating type nano material.Laser method is to use a laser as the energy, is pyrolyzed carbon source under gas with various protection to prepare
A kind of method of carbon-clad metal nano material.Why laser method had once attracted the concern of numerous researchers, was due to laser
Method can control the output of its energy by the frequency shift of light, so being a kind of easily-controllable method, repeatability is higher, but its
Required equipment is more expensive, so that this method is above greatly limited in application.Chemical vapour deposition technique is to prepare carbon packet
It is a kind of more commonly used to cover nano material, and the method that research is more.Usually using organic gas, liquid as carbon source, in gold
Under the catalytic action of metal nano-particle, is acted on by vapor deposition and generate carbon-clad metal nano material.High-temperature process also by with
In preparing carbon-clad metal nano material.High-temperature process method is pyrolysis copolymer preparation microporous carbon, is intended to coat by infusion process
Metal and microporous carbon formed compound hydrogen gas protection under carry out high temperature pyrolysis processing, finally obtain carbon-clad metal and receive
Rice material.
Summary of the invention
The purpose of the invention is to provide a kind of microwave method and quickly and easily prepares g-C3N4Coat metal core-shell nano complex
Method passes through the metal nanoparticle that will be uniformly mixed under microwave irradiation wherein preparing nanoscale metal nanoparticle first
The g-C of core-shell structure is quickly prepared into urea3N4Coat metal nano compound.
Specific technical solution is as follows:
A kind of graphite phase carbon nitride (g-C3N4) cladding metal nuclear shell structure nano compound preparation method, including such as
Lower step:
Step 1, nano metallic nickel granular material is uniformly mixed into simultaneously co-ground according to the mass ratio of 1:10~30 with urea.
Step 2, mixture step 1 obtained is placed in container, is passed through argon gas as protection gas, then to be placed in microwave anti-
It answers in device, microwave reactor is adjusted to 800~1000w of power, the reaction time is 0.5~10min；It is big by microwave abrupt release
The energy rapid synthesis cladded type g-C of amount3N4/ metal nano compound.
Step 3, it takes out container at once after reaction and is placed in liquid nitrogen or the cooling of water cooling environment.
Step 4, it will be dried in vacuo after the filtering of step 3 products therefrom, dry sample, obtain g-C3N4Coat the nucleocapsid of metal
Structure nano compound.
Further, nano metallic nickel granular material described in above-mentioned steps 1 is uniformly mixed with urea according to the mass ratio of 1:10；
Microwave reactor is adjusted to power 1000w, reaction time 1min in step 2.
Further, the preparation method of nano metallic nickel granular material described in above-mentioned steps 1 is put using plasma arc
Power technology is prepared in situ under operating air pressure, in which:
Using the uniform tabletting of magnetic metal micron powder as anode, tungsten bar is cathode；Between cathode and anode keep 2~
The distance of 20mm；The voltage of arc discharge is 20-40V；Electric current is 100A；Operating air pressure is argon gas and hydrogen.
Further, above-mentioned partial pressure of ar gas is 0.01~0.3MPa, and hydrogen partial pressure is 0.01~0.3MPa.
Further, the magnetic metal micron powder in above-mentioned anode material, wherein metal is one of iron, cobalt, nickel,
Purity is 99.8% or more.
Further, above-mentioned anode is cylinder, a diameter of 30~50mm, with a thickness of 5~30mm.
The beneficial effects of the present invention are: proposing a kind of microwave method quickly prepares cladded type g-C3N4/ metal nano compound
Method.The microwave reaction time further shortens, to optimize more efficient synthesis.Carbon thickness of the shell can further regulate and control, and obtain more
Excellent photocatalysis and electrochemical catalysis performance.Meanwhile this method, with being swift in response, simple process economizes on resources, purity
Height, it is at low cost the advantages that.
Detailed description of the invention
Fig. 1 is cladded type g-C in the method for the present invention3N4The structural schematic diagram of/metal nano compound.
Fig. 2 is cladded type g-C in the method for the present invention3N4/ metal nano compound preparation method flow chart.
Fig. 3 is cladded type g-C in the method for the present invention3N4X-ray diffractogram corresponding to/metal iron nano-particle.
Fig. 4 is cladded type g-C in the method for the present invention3N4High-resolution corresponding to/iron granule projects micrograph.
Fig. 5 is cladded type g-C in the method for the present invention3N4Projection EDS linear sweep graph corresponding to/iron granule.(a) it projects
Figure, (b) linear sweep graph.
Fig. 6 is cladded type g-C in the method for the present invention3N4X-ray photoelectron spectroscopy figure corresponding to/iron granule.(a)
Iron XPS figure, (b) the swarming figure of C element.
Fig. 7 is cladded type g-C in the method for the present invention3N4X-ray diffractogram corresponding to/metal cobalt nano-particle.
Fig. 8 is cladded type g-C in the method for the present invention3N4High-resolution corresponding to/metal cobalt granule projects micrograph.
Fig. 9 is cladded type g-C in the method for the present invention3N4X-ray photoelectron spectroscopy figure corresponding to/metal cobalt granule.(a)
Cobalt XPS figure, (b) the swarming figure of C element.
Figure 10 is cladded type g-C in the method for the present invention3N4X-ray diffractogram corresponding to/metallic nickel nano granule.
Figure 11 is cladded type g-C in the method for the present invention3N4High-resolution corresponding to/metal nickel particle projects micrograph.
Figure 12 is cladded type g-C in the method for the present invention3N4X-ray photoelectron spectroscopy figure corresponding to/metal nickel particle.(a)
Nickel XPS figure, (b) the swarming figure of C element.
Specific embodiment
To be more clear the objectives, technical solutions, and advantages of the present invention, below in conjunction with drawings and concrete examples to this hair
Bright operating process is described in further detail.Need to illustrate, specific example described herein for explaining only the invention, wherein
It is illustrated as illustrative nature, is not intended to limit the scope of the present invention.
Embodiment 1
Fig. 1 is cladded type g-C in the method for the present invention3N4The structural schematic diagram of/metal nano compound.As shown in Figure 1, core
Shell mould covering material nanoparticle includes: the carboritride shell 101 of wherein external cladding；Internal metal seed layer 102, this
Fe nano particle is selected in embodiment.
The carboritride shell 101 is generally g-C3N4, or the carboritride of similar composition.
The metal inner core 102 can be direct current arc method preparation preparation, and its particle diameter is 1 to 300nm.
Further, nano particle 102 described in this example is prepared using hydrogen gas and argon gas in the preparation, and use is cold
But water is cooled down, and the partial size of the metal nanoparticle is 1 to 200nm.
Meanwhile the present invention provides above-described embodiment preparation method:
Fig. 2 show cladded type g-C3N4The flow chart of/metal nano compound preparation method.
Step B101, prepares metal nanoparticle.
According to preparation flow, core/shell type nano particle is prepared using direct current arc method.In the present embodiment, Fe is chosen to make
It for metal, while using hydrogen and argon gas as reaction gas, is prepared at 30-90V, the arcing condition of 90-290A, use is cold
But water is as the type of cooling.
Step B102, prepares metal nanoparticle and urea admixture.
Nano particle and urea is prepared using direct current arc method uniformly to mix.In this embodiment, first by urea powder Ma
Nao grinding, then it is uniformly mixed co-ground according to the ratio of 10:1 with nanometer iron powder, it obtains mixture and is placed into three mouthfuls
In beaker.
Step B103, microwave reactor heating reaction.Sample is in the case where argon gas is to protect the atmosphere of gas, microwave reactor quota
Power (1000w) sets the progress of 1 minute reaction time.
Step B104, the sample suspension of the cooling preparation of high gradient.Three mouthfuls of beakers will have been reacted under argon atmosphere
Suitable liquid nitrogen is poured into rapidly, its moment is made to drop to low temperature, generates compound suspension by high gradient is cooling.
Step B105 is placed in ventilation and will not generate natural in the environment of pollution after being filtered compound suspension
Drying.
The curve graph that Fig. 3 is surveyed on X-ray diffractometer by present example.As shown in figure 3, sample is in 2 θ=27.8 °
The diffraction maximum at place corresponds to g-C3N4(002) lattice plane of phase.Fe and urea can synthesize g-C with microwave assisting method3N4, will not
Synthesize other substances.
The High-Resolution Map that Fig. 4 is clapped by present example in high-resolution projection microscope.As shown in figure 4, sample is apparent
It is seen to be core-shell structure, outside is g-C3N4, the interplanar distance for corresponding to (002) crystal face is 0.35nm, and inside is Fe core.
Fig. 5 is present example in the offline picture figure for sweeping lower bat of projection microscope EDS mode.As shown in figure 5, sample is online
The changes of contents of Fe, C, N for sweeping are obviously increased in the content of the local C and N of shell, and the content of kernel Fe increases, C, N content
It reduces, also has authenticated cladded type g-C3N4The structure of/metal nano compound.
The curve graph that Fig. 6 is surveyed on x-ray photoelectron spectroscopy by present example.It, can be obvious such as Fig. 6 left hand view
See the peak position for having N and C element；Fig. 6 right part of flg carries out the fine x-ray photoelectron spectroscopy figure of C and is simulated, passed through
Chemical bond energy can be inferred significantly and generate g-C3N4。
Embodiment 2
Fig. 1 is cladded type g-C in the method for the present invention3N4The structural schematic diagram of/metal nano compound.As shown in Figure 1, core
Shell mould covering material nanoparticle includes: the carboritride shell 101 of wherein external cladding；Internal metal seed layer 102, this
Co nano particle is selected in embodiment.
The carboritride shell 101 is generally g-C3N4, or the carboritride of similar composition.
The metal inner core 102 can be direct current arc method preparation preparation, and its particle diameter is 1 to 300nm.
Further, nano particle 102 described in this example is prepared using hydrogen gas and argon gas in the preparation, and use is cold
But water is cooled down, and the partial size of the metal nanoparticle is 1 to 200nm.
Meanwhile the present invention provides above-described embodiment preparation method:
Fig. 2 show cladded type g-C3N4The flow chart of/metal nano compound preparation method.
Step B101, prepares metal nanoparticle.
According to preparation flow, core/shell type nano particle is prepared using direct current arc method.In the present embodiment, Co is chosen to make
It for metal, while using hydrogen and argon gas as reaction gas, is prepared at 30-90V, the arcing condition of 90-290A, use is cold
But water is as the type of cooling.
Step B102, prepares metal nanoparticle and urea admixture.
Nano particle and urea is prepared using direct current arc method uniformly to mix.In this embodiment, first by urea powder Ma
Nao grinding, then it is uniformly mixed co-ground according to the ratio of 10:1 with nanometer iron powder, it obtains mixture and is placed into three mouthfuls
In beaker.
Step B103, microwave reactor heating reaction.Sample is in the case where argon gas is to protect the atmosphere of gas, microwave reactor power
For 800w, the progress of 2 minute reaction time is set.
Step B104, the sample suspension of the cooling preparation of high gradient.Three mouthfuls of beakers will have been reacted under argon atmosphere
Suitable liquid nitrogen is poured into rapidly, its moment is made to drop to low temperature, generates compound suspension by high gradient is cooling.
Step B105 is placed in ventilation and will not generate natural in the environment of pollution after being filtered compound suspension
Drying.
The curve graph that Fig. 7 is surveyed on X-ray diffractometer by present example.As shown in fig. 7, due to nano metal cobalt
Peak is very sharp, and intensity is very high, and diffraction maximum of the sample at 2 θ=27.8 ° is not apparent.
The High-Resolution Map that Fig. 8 is clapped by present example in high-resolution projection microscope.As shown in figure 8, sample is apparent
It is seen to be core-shell structure, outside is g-C3N4, the interplanar distance for corresponding to (002) crystal face is 0.35nm, and inside is Co core.
The curve graph that Fig. 9 is surveyed on x-ray photoelectron spectroscopy by present example.It, can be obvious such as Fig. 9 left hand view
See the peak position for having N and C element；Fig. 9 right part of flg carries out the fine x-ray photoelectron spectroscopy figure of C and is simulated, passed through
Chemical bond energy can be inferred significantly and generate g-C3N4。
Embodiment 3
Fig. 1 is cladded type g-C in the method for the present invention3N4The structural schematic diagram of/metal nano compound.As shown in Figure 1, core
Shell mould covering material nanoparticle includes: the carboritride shell 101 of wherein external cladding；Internal metal seed layer 102, this
Ni nano particle is selected in embodiment.
The carboritride shell 101 is generally g-C3N4, or the carboritride of similar composition.
The metal inner core 102 can be direct current arc method preparation preparation, and its particle diameter is 1 to 300nm.
Further, nano particle 102 described in this example is prepared using hydrogen gas and argon gas in the preparation, and use is cold
But water is cooled down, and the partial size of the metal nanoparticle is 1 to 200nm.
Meanwhile the present invention provides above-described embodiment preparation method:
Fig. 2 show cladded type g-C3N4The flow chart of/metal nano compound preparation method.
Step B101, prepares metal nanoparticle.
According to preparation flow, core/shell type nano particle is prepared using direct current arc method.In the present embodiment, Ni is chosen to make
It for metal, while using hydrogen and argon gas as reaction gas, is prepared at 30-90V, the arcing condition of 90-290A, use is cold
But water is as the type of cooling.
Step B102, prepares metal nanoparticle and urea admixture.
Nano particle and urea is prepared using direct current arc method uniformly to mix.In this embodiment, first by urea powder Ma
Nao grinding, then it is uniformly mixed co-ground according to the ratio of 10:1 with nanometer iron powder, it obtains mixture and is placed into three mouthfuls
In beaker.
Step B103, microwave reactor heating reaction.Sample is in the case where argon gas is to protect the atmosphere of gas, microwave reactor power
For 900w, the progress of 4 minute reaction time is set.
Step B104, the sample suspension of the cooling preparation of high gradient.Three mouthfuls of beakers will have been reacted under argon atmosphere
Suitable distilled water is poured into rapidly, its moment is made to drop to low temperature, generates compound suspension by high gradient is cooling.
Step B105 is placed in ventilation and will not generate natural in the environment of pollution after being filtered compound suspension
Drying.
The curve graph that Figure 10 is surveyed on X-ray diffractometer by present example.As shown in Figure 10, due to nano metal nickel
Peak it is very sharp, intensity is very high, and diffraction maximum of the sample at 2 θ=27.8 ° is not apparent.
The High-Resolution Map that Figure 11 is clapped by present example in high-resolution projection microscope.As shown in figure 11, sample is obvious
Be seen to be core-shell structure, outside is g-C3N4, the interplanar distance for corresponding to (002) crystal face is 0.35nm, and inside is Ni core.
The curve graph that Figure 12 is surveyed on x-ray photoelectron spectroscopy by present example.Such as Figure 12 left hand view, Ke Yiming
Aobvious sees the peak position for having N and C element；Figure 12 right part of flg carries out the fine x-ray photoelectron spectroscopy figure of C and is simulated, and leads to
It crosses chemical bond energy and can significantly infer and generate g-C3N4。
Above-mentioned embodiment is only used to illustrate and not limit the technical solutions of the present invention, it is any do not depart from spirit of that invention and
The technical solution of range should all cover in patent claim of the invention.
Claims (8)
1. a kind of g-C3N4Coat the preparation method of the nuclear shell structure nano compound of metal, which is characterized in that including walking as follows
It is rapid:
Step 1, nano metallic nickel granular material is uniformly mixed into simultaneously co-ground according to the mass ratio of 1:10~30 with urea；
Step 2, mixture step 1 obtained is placed in container, is passed through argon gas as protection gas, then be placed in microwave reactor
It is interior, microwave reactor is adjusted to 800~1000w of power, the reaction time is 0.5~10min；
Step 3, it takes out container at once after reaction and is placed in liquid nitrogen or the cooling of water cooling environment；
Step 4, it will be dried in vacuo after the filtering of step 3 products therefrom, dry sample, obtain g-C3N4Coat the core-shell structure of metal
Nano-complex.
2. g-C according to claim 13N4The preparation method of the nuclear shell structure nano compound of metal is coated, feature exists
In nano metallic nickel granular material described in step 1 is uniformly mixed with urea according to the mass ratio of 1:10；Microwave reactor in step 2
It is adjusted to power 1000w, reaction time 1min.
3. g-C according to claim 1 or 23N4The preparation method of the nuclear shell structure nano compound of metal is coated, it is special
Sign is that the preparation method of nano metallic nickel granular material described in step 1 is using plasma arc discharge technology, in work gas
Pressure is prepared in situ, in which:
Using the uniform tabletting of magnetic metal micron powder as anode, tungsten bar is cathode；2~20mm is kept between cathode and anode
Distance；The voltage of arc discharge is 20-40V；Electric current is 100A；Operating air pressure is argon gas and hydrogen.
4. g-C according to claim 33N4The preparation method of the nuclear shell structure nano compound of metal is coated, feature exists
In partial pressure of ar gas is 0.01~0.3MPa, and hydrogen partial pressure is 0.01~0.3MPa.
5. g-C according to claim 33N4The preparation method of the nuclear shell structure nano compound of metal is coated, feature exists
In magnetic metal micron powder in anode material, wherein metal is one of iron, cobalt, nickel, and purity is 99.8% or more.
6. g-C according to claim 43N4The preparation method of the nuclear shell structure nano compound of metal is coated, feature exists
In magnetic metal micron powder in anode material, wherein metal is one of iron, cobalt, nickel, and purity is 99.8% or more.
7. g-C according to claim 33N4The preparation method of the nuclear shell structure nano compound of metal is coated, feature exists
In the anode is cylinder, a diameter of 30~50mm, with a thickness of 5~30mm.
8. according to claim 4 or 5 or 6 g-C3N4The preparation method of the nuclear shell structure nano compound of metal is coated, it is special
Sign is that the anode is cylinder, a diameter of 30~50mm, with a thickness of 5~30mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811035478.2A CN109012733B (en) | 2018-09-06 | 2018-09-06 | g-C3N4Preparation method of core-shell structure nano composite coated with metal |
Applications Claiming Priority (1)
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