CN111185211A - Carbon-coated nickel nanocomposite and preparation method thereof - Google Patents
Carbon-coated nickel nanocomposite and preparation method thereof Download PDFInfo
- Publication number
- CN111185211A CN111185211A CN201811358334.0A CN201811358334A CN111185211A CN 111185211 A CN111185211 A CN 111185211A CN 201811358334 A CN201811358334 A CN 201811358334A CN 111185211 A CN111185211 A CN 111185211A
- Authority
- CN
- China
- Prior art keywords
- carbon
- acid
- coated nickel
- precursor
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 181
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 92
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 71
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 20
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 238000000197 pyrolysis Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 18
- 125000003277 amino group Chemical group 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 239000011162 core material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 239000011258 core-shell material Substances 0.000 abstract description 8
- 239000002149 hierarchical pore Substances 0.000 abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 7
- 125000003368 amide group Chemical group 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 14
- 239000002086 nanomaterial Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Images
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
-
- B01J35/397—
-
- B01J35/613—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A method for preparing a carbon-coated nickel nanocomposite is provided, comprising the steps of: s1, mixing water-soluble fatty acid containing amino group with Ni (NO)3)2Mixing the raw materials in water, heating and stirring the mixture to form a homogeneous solution, removing water, and grinding the obtained solid to form a precursor; and S2, pyrolyzing the precursor at high temperature in an inert protective atmosphere or a reducing atmosphere. The invention also provides a carbon-coated nickel nanocomposite material prepared by the method. The precursor of the high-temperature pyrolysis of the invention is directly prepared from Ni (NO)3)2Phase-stripping with water-soluble fatty acid containing amido at normal pressure and pure waterThe precursor Ni can be obtained by heating and stirring under the condition of a workpiece, and the atom utilization rate of the precursor Ni can reach 100 percent. In addition, the nitrate is decomposed in the pyrolysis process to form a unique hierarchical pore structure in the material, so that the effective regulation and control of the pore structure of the carbon-coated nickel core-shell structure nano-particles are realized.
Description
Technical Field
The invention belongs to the field of preparation and application of carbon-coated metal composite materials, and particularly relates to a nitrogen and oxygen doped carbon-coated nickel nanocomposite material and a preparation method and application thereof.
Background
Nanomaterials have some special physicochemical properties that are different from conventional size materials, including surface effects, dielectric confinement, quantum size, small size effects, and macroscopic quantum tunneling effects. Among them, metal nanoparticles are receiving much attention because of their excellent optical, electrical, and magnetic properties. However, the metal nanoparticles have high activity, are easy to agglomerate or be oxidized or even burn in air, and greatly influence the performance and application of the materials. The nano carbon material has the advantages of acid and alkali corrosion resistance, stable chemical property and the like. In addition, the nano carbon material with defects and heteroatoms also shows excellent catalytic performance in characteristic reaction. Recent studies have shown that the use of single-layer or multi-layer graphite-coated metal nanoparticles can effectively combine the advantages of two materials and exhibit new properties, which has attracted the attention of researchers.
At present, methods for coating metal nanoparticles with carbon mainly include an arc method, a Chemical Vapor Deposition (CVD) method, a high temperature pyrolysis method, and the like. The electric arc method has the disadvantages of complicated equipment, poor operability, high energy consumption and difficulty in realizing large-scale preparation. Compared with the arc method, the CVD method has lower cost, higher yield and productivity, but requires the preparation of metal nanoparticles or compound particles thereof in advance. Generally, such deposition precursors have the disadvantages of non-uniform particle size, difficulty in effective dispersion, complicated preparation, etc., thereby affecting the properties of the final product. Similar to CVD processes, the structure and properties of the pyrolysis products are greatly affected by the precursor materials. However, the pyrolysis method has the advantages of simple process, low cost, high yield, controllable metal content and the like, and is one of the methods with the greatest large-scale preparation prospects at present.
Pyrolysis can be mainly divided into two main types, and the first method directly mixes a carbon source (usually dicyandiamide, melamine, etc.) and a metal source and then carries out high-temperature pyrolysis in an inert or reducing atmosphere. Because carbon sources such as dicyanodiamine and melamine are easy to decompose at high temperature and are directly mixed with metal particles, the interaction is weak, so that the ligand utilization rate is low and the carbonization yield is low. In addition, cyanamide substances are carbon and nitrogen sources, which are easy to generate carbon nanotube coating materials, so that the product is impure. Another method is to form a metal-organic framework (MOF) compound as a precursor by self-assembly connection of metal ions and organic ligands under a characteristic reaction. The preparation of such precursors generally requires the use of organic solvents and high temperature, high pressure reactions in reaction vessels. Unlike the pyrolysis method of cyanamide, the metal in MOF forms uniform dispersion at atomic level, so it is considered as a more ideal precursor for pyrolysis, and has become a hot research focus in recent years in this field. Co (NO: 10.1002/anie.201409524Angewandte Chemie International Edition 2015,54.7:2100-3)2、Ni(NO3)2Is a metal source, adopts ethylene diamine tetraacetic acid tetrasodium as a carbon source, prepares a self-assembly precursor under the conditions of high temperature and high pressure, and prepares the nitrogen and oxygen doped carbon-coated cobalt-nickel alloy through pyrolysis under the Ar atmosphereAnd (3) nanoparticles. An (DOI:10.1039/C6ta02339h, MeObarous Ni @ C hybrids for a high energy a queousasymetric supercapacitor device, Electronic complementary Material (ESI) for journal of Materials Chemistry A) and the like, using iminodiacetic acid as a carbon source, Ni (NO: 10.1039/C6ta02339h, and the like3)2Is a metal source, self-contained precursor is prepared under the conditions of high temperature and high pressure, carbon-coated nickel nano-particles are further prepared by high-temperature pyrolysis under Ar atmosphere, and N is used for preparing the nickel-coated nano-particles2The pore diameter corresponding to the pore diameter distribution peak calculated by the adsorption and desorption isotherm curve is 17.8 nm. In summary, the problems of low preparation efficiency, complex steps, single product pore structure and the like still exist in the preparation of the carbon-coated nickel core-shell structure nano material at present. How to efficiently prepare the carbon-coated nickel core-shell structure nanoparticles and regulate and control the pore structure of the carbon-coated nickel core-shell structure nanoparticles, especially how to prepare a material with rich hierarchical pore structures, and how to have great significance for promoting the application of the carbon-coated nickel core-shell structure nanoparticles.
Disclosure of Invention
In order to overcome the defects, the invention provides a carbon-coated nickel nano composite material and a preparation method thereof.
The invention provides a carbon-coated nickel nano composite material, which comprises carbon-coated nickel nano particles, wherein the carbon-coated nickel nano particles consist of nickel nano particle cores and nitrogen and oxygen-doped graphitized carbon layer shells coated on the surfaces of the nickel nano particles; the composite material has two distribution peaks with the pore diameter of 30-50 nm and 50-300 nm.
According to one embodiment of the present invention, wherein the content of Ni is 5 to 80%, the content of C is 20 to 93%, the content of O is 0.5 to 6%, the content of N is 0.5 to 6%, and the content of H is 0.1 to 2.5% based on the total mass of the composite material.
According to another embodiment of the present invention, wherein the nickel nanoparticle inner core comprises a face centered cubic lattice structure and a hexagonal close lattice structure.
According to another embodiment of the present invention, wherein the composite material has a pickling loss of less than 60%, preferably less than 20%, more preferably less than 10%, most preferably less than 2%.
In another aspect, the present invention provides a method for preparing the carbon-coated nickel nanocomposite, comprising the steps of: s1, mixing water-soluble fatty acid containing amino group with Ni (NO)3)2Mixing the raw materials in water, heating and stirring the mixture to form a homogeneous solution, removing water, and grinding the obtained solid to form a precursor; and S2, pyrolyzing the precursor at high temperature in an inert protective atmosphere or a reducing atmosphere.
According to an embodiment of the invention, wherein the amine group-containing water-soluble fatty acid is one or more of ethylenediaminetetraacetic acid, iminodiacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and 1, 3-propylenediaminetetraacetic acid.
According to another embodiment of the present invention, wherein said Ni (NO)3)2The molar ratio of the amino group-containing water-soluble fatty acid to the amino group-containing water-soluble fatty acid is 1: 0.5-10.
According to another embodiment of the present invention, the heating and stirring temperature is 30 to 150 ℃.
According to another embodiment of the present invention, in the step S2, the inert atmosphere is nitrogen or argon, the high temperature pyrolysis is carried out at a rate of 0.5-30 ℃/min until reaching a constant temperature section, the constant temperature section is kept at a constant temperature for 20-600min, and the temperature of the constant temperature section is 400-800 ℃; preferably, the heating rate is 1-10 ℃/min, the constant temperature time in the constant temperature section is 450-800 ℃, and the temperature in the constant temperature section is 20-480 min.
According to another embodiment of the present invention, the method further comprises: s3, purifying the product obtained in the S2 step in an acid solution to remove incomplete coated Ni inner cores.
According to another embodiment of the present invention, the acidic solution in the purification step is an aqueous solution of one or more of hydrochloric acid, sulfuric acid or hydrofluoric acid, and the concentration is 0.1-3 mol/L.
The precursor of the high-temperature pyrolysis of the invention is directly prepared from Ni (NO)3)2The precursor Ni and water-soluble fatty acid containing amido are heated and stirred under the conditions of normal pressure and pure water phase, and the atom utilization rate of the precursor Ni can reach 100 percent. The preparation process does not need to use dicyanodiamine, melamine and the like commonly used in the traditional methodA ligand which is sublimated or decomposed and easily generates a carbon nanotube; and overcomes the defects that the preparation of the metal organic framework structure precursor in the prior art needs the self-assembly of a high-temperature high-pressure reaction kettle, a large amount of organic solvent is wasted, the purification steps are complicated, and the like. In addition, the nitrate is decomposed in the pyrolysis process to form a unique hierarchical pore structure in the material, so that the effective regulation and control of the pore structure of the carbon-coated nickel core-shell structure nano-particles are realized. Further, the preparation method uses inexpensive Ni (NO)3)2Is a metal source, is directly stirred with water-soluble fatty acid containing amido in a water phase and is evaporated to dryness to obtain a precursor, the operation is simple and convenient, and the industrialized mass production is easy to realize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is an XRD pattern of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 1.
Fig. 2 is a TEM photograph of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 1.
FIG. 3A is N of N-doped carbon-coated nickel nanocomposite prepared in example 12Adsorption and desorption isotherm graphs.
Fig. 3B is a graph of pore size distribution for the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 1.
Fig. 4 is an XRD pattern of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2.
Fig. 5 is an SEM photograph of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2.
Fig. 6 is an XPS spectrum of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2.
Fig. 7 is a graph of pore size distribution for the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2.
Fig. 8 is a graph of pore size distribution of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 3.
Fig. 9 is a pore size distribution curve of the nitrogen-doped carbon-coated nickel nanocomposite prepared in comparative example 1.
Detailed Description
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
The term "core-shell structure" in the invention means that the inner core is cobalt nanoparticles, and the shell layer is an oxygen-doped or nitrogen-oxygen-doped graphitized carbon layer. The graphitized carbon layer refers to a carbon structure which is obviously observed to be layered under a high-resolution transmission electron microscope, but not an amorphous structure, and the interlayer spacing is about 0.34 nm.
The term "oxygen" in the "oxygen-doped graphitized carbon layer" refers to the oxygen element, wherein the "oxygen content" of the nanocomposite refers to the content of the oxygen element, and specifically refers to the oxygen element contained in various forms in the formed graphitized carbon layer during the preparation of the carbon-coated nanocomposite, and the "oxygen content" is the total content of all forms of the oxygen element.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "acid pickling loss ratio" refers to the loss ratio of the transition metal after acid pickling of the prepared carbon-coated transition metal nanocomposite product. Which reflects how tightly the graphitized carbon layer coats the transition metal. If the graphitized carbon layer does not cover the transition metal tightly, the transition metal of the core is dissolved by the acid and lost after the acid treatment. The larger the acid washing loss rate is, the lower the degree of tightness of the transition metal coating by the graphitized carbon layer is, and the smaller the acid washing loss rate is, the higher the degree of tightness of the transition metal coating by the graphitized carbon layer is.
The "pickling loss ratio" was measured and calculated in the following manner:
adding 1g of sample into 20mL of sulfuric acid aqueous solution (1mol/L), treating the sample at 90 ℃ for 8h, then washing the sample to be neutral by using deionized water, weighing and analyzing the sample after drying, and calculating the pickling loss rate according to the following formula.
The acid pickling loss rate is [1- (mass fraction of transition metal in the composite material after acid pickling × mass of the composite material after acid pickling) ÷ (mass fraction of transition metal in the composite material to be pickled × mass of the composite material to be pickled) ] × 100%.
The carbon-coated nickel nano composite material comprises carbon-coated nickel nano particles, wherein the carbon-coated nickel nano particles consist of nickel nano particle inner cores and nitrogen and oxygen doped graphitized carbon layer shells coated on the surfaces of the nickel nano particles; the composite material has two distribution peaks with the mesoporous aperture of 30-50 nm and 50-300 nm.
Preferably, based on the total mass of the composite material, the content of Ni is 5-80%, the content of C is 20-93%, the content of O is 0.5-6%, the content of N is 0.5-6%, and the content of H is 0.1-2.5%
Preferably, the nickel nanoparticle core includes a face centered cubic lattice structure and a hexagonal close lattice structure.
Preferably, the composite has a pickling loss of less than 60%, preferably less than 20%, more preferably less than 10%, most preferably less than 2%.
The carbon-coated nickel nanocomposite material is prepared by the following method, and comprises the following steps: s1, mixing water-soluble fatty acid containing amino group with Ni (NO)3)2Mixing the raw materials in water, heating and stirring the mixture to form a homogeneous solution, removing water, and grinding the obtained solid to form a precursor; and S2, pyrolyzing the precursor at high temperature in an inert protective atmosphere or a reducing atmosphere.
Preferably, the amine group-containing water-soluble fatty acid is one or more of ethylenediaminetetraacetic acid, iminodiacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and 1, 3-propylenediaminetetraacetic acid.
Ni(NO3)2The molar ratio of the amino group-containing water-soluble fatty acid to the amino group-containing water-soluble fatty acid is 1: 0.5-10.
The heating and stirring temperature is 30-150 ℃.
In the step S2, inert atmosphere is nitrogen or argon, high-temperature pyrolysis is carried out to raise the temperature to a constant-temperature section at the speed of 0.5-30 ℃/min, the constant-temperature time is kept at the constant-temperature section for 20-600min, and the temperature of the constant-temperature section is 800 DEG; preferably, the heating rate is 1-10 ℃/min, the constant temperature time in the constant temperature section is 450-800 ℃, and the temperature in the constant temperature section is 20-480 min.
Preferably, the method further comprises: s3, purifying the product obtained in the step S2 in an acid solution to remove incomplete Ni core coating.
Wherein the acidic solution in the purification step is one or more aqueous solutions of hydrochloric acid, sulfuric acid or hydrofluoric acid, and the concentration is 0.1-3 mol/L.
Preparation of carbon-coated nickel nanocomposite
Example 1
Weighing 30mmol Ni (NO)3)2·6H2O and 15mmol of EDTA are added into 100mL of deionized water, the mixture is stirred at 85 ℃ to obtain a homogeneous solution, the homogeneous solution is continuously heated and evaporated to dryness, and the solid is ground to obtain a precursor.
And placing the precursor into a porcelain boat, then placing the porcelain boat in a constant-temperature area of a tube furnace, introducing nitrogen at a flow rate of 100mL/min, heating to 625 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 120min, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated nickel nano material.
And adding the obtained composite material into 50mL of 1mol/L HCl solution, stirring and refluxing at 90 ℃ for 4h, then carrying out suction filtration on the solution, washing the solution to be neutral by using deionized water, and then placing the powder in an oven at 100 ℃ for drying for 2h to obtain the purified carbon-coated nano material.
Example 2
Weighing 20mmol of Ni (NO)3)2·6H2O and 10mmol of EDTA are added into 100mL of deionized water, the mixture is stirred at 85 ℃ to obtain a homogeneous solution, the homogeneous solution is continuously heated and evaporated to dryness, and the solid is ground to obtain a precursor.
And placing the obtained precursor into a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 100mL/min, heating to 700 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 120min, stopping heating, and cooling to room temperature under the nitrogen atmosphere to obtain the carbon-coated nickel nano material.
And adding the obtained composite material into 50mL of 1mol/L HCl solution, stirring and refluxing at 90 ℃ for 4h, then carrying out suction filtration on the solution, washing the solution to be neutral by using deionized water, and then placing the powder in an oven at 100 ℃ for drying for 2h to obtain the purified carbon-coated nano material.
Example 3
Weighing 20mmol of Ni (NO)3)2·6H2O and 20mmol of iminodiacetic acid are added into 100mL of deionized water, the mixture is stirred at the temperature of 80 ℃ to obtain a homogeneous phase solution, the homogeneous phase solution is continuously heated and evaporated to dryness, and the solid is ground to obtain a precursor.
And placing the obtained precursor into a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 100mL/min, heating to 550 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 180min, stopping heating, and cooling to room temperature under a nitrogen atmosphere to obtain the carbon-coated nickel nano material.
The resulting composite was added to 40mL of 1mol/L H2SO4And stirring and refluxing the solution at 85 ℃ for 6 hours, then carrying out suction filtration on the solution, washing the solution to be neutral by using deionized water, and then placing the powder in an oven at 100 ℃ for drying for 2 hours to obtain the purified carbon-coated nano material.
Comparative example 1
60mmol of Ni (OH) are weighed2And adding 30mmol of EDTA into 100mL of deionized water, stirring at 85 ℃ to obtain a homogeneous solution, continuously heating and evaporating to dryness, and grinding the solid to obtain a precursor.
And placing the obtained precursor into a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 100mL/min, heating to 625 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 120min, stopping heating, and cooling to room temperature under a nitrogen atmosphere to obtain the carbon-coated nickel nano material.
And adding the obtained composite material into 50mL of 1mol/L HCl solution, stirring and refluxing at 90 ℃ for 4h, then carrying out suction filtration on the solution, washing the solution to be neutral by using deionized water, and then placing the powder in an oven at 100 ℃ for drying for 2h to obtain the purified carbon-coated nano material.
Characterization of the results
The XRD diffractometer adopted is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and has the XRD test conditions of a Cu target, K α rays (the wavelength lambda is 0.154nm), tube voltage of 40kV, tube current of 200mA and scanning speed of 10 degrees (2 theta)/min.
The surface morphology of the material was observed by Scanning Electron Microscopy (SEM). The adopted Scanning Electron Microscope (SEM) is super 55 field emission scanning electron microscope (Germany Seiss company), and the testing conditions of the SEM are as follows: the thermal field emission type has a working voltage of 20kV and an amplification factor range of 12-900 k.
The adopted X-ray photoelectron spectrum analyzer is an ESCALb 220i-XL type ray electron energy spectrum analyzer which is manufactured by VG scientific company and is provided with Avantage V5.926 software, the X-ray photoelectron spectrum analyzer has the analysis and test conditions that an excitation source is monochromatized A1K α X rays, the power is 330W, and the basic vacuum is 3X 10-9mbar during analysis and test.
The pore structure properties of the material were examined by the BET test method. Specifically, a Quantachrome AS-6B type analyzer is adopted for determination, the specific surface area of the catalyst is obtained by a Brunauer-Emmett-Taller (BET) method, and a pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The analysis of four elements of carbon (C), hydrogen (H), oxygen (O) and nitrogen (N) was performed on an Elementar Micro Cube element analyzer. The specific operation method and conditions are as follows: weighing 1-2mg of sample in a tin cup, placing the sample in an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (for removing atmospheric interference during sample feeding, helium gas is adopted for blowing), and then reducing the combusted gas by using reduced copper to form nitrogen, carbon dioxide and water. The mixed gas is separated by three desorption columns and sequentially enters a TCD detector for detection. The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
The content of the metal elements is the normalized result of the material after the content of carbon, hydrogen, oxygen and nitrogen is removed.
Fig. 1 is an XRD pattern of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 1. In the figure, curve (a) represents the carbon-coated nickel nanocomposite material without purification, and curve (b) represents the carbon-coated nickel nanocomposite material with purification. It can be seen from the figure that the material before and after pickling had distinct phases corresponding to face-centered cubic packed Ni (fcc-Ni) and hexagonal close packed Ni (hcp-Ni), indicating that a significant amount of carbon-coated nickel nanoparticles still existed after pickling. Fig. 2 is a TEM photograph of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 1. It can be clearly seen that the nickel nanoparticles are highly densely distributed on the carbon support, while the outer layer of the nickel nanoparticles is coated with several graphitized carbon layers. FIG. 3A is N of N-doped carbon-coated nickel nanocomposite prepared in example 12Adsorption and desorption isotherm graphs. Fig. 3B is a graph of pore size distribution for the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 1. It can be seen that the nitrogen isothermal adsorption and desorption curve is an isothermal line typical of IV, and the pore size distribution curves respectively have a distribution peak at 40.5nm and 246nm, which proves that a hierarchical pore structure containing abundant macropores is effectively generated on a carbon substrate by utilizing the nitrate-containing precursor in the pyrolysis process. The elemental analyzer determined that the nano-material had a C content of 26.56%, an H content of 2.09%, an N content of 1.44%, an O content of 5.32%, and a normalized Ni content of 64.59%. The acid loss of the composite material obtained in this example before purification was 30% and the acid loss of the composite material after purification was less than 1%, as measured and calculated by the method described in the nomenclature section. The pickling loss rate remains substantially unchanged by continuing to increase the pickling time on the basis of the process described in the nomenclature section.
Fig. 4 is an XRD pattern of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2. It can be seen from the figure that the material after acid washing still has distinct phases corresponding to face-centered cubic packed Ni (fcc-Ni) and hexagonal close packed Ni (hcp-Ni), indicating that a large amount of carbon-coated nickel nanoparticles still exist after acid washing. Fig. 5 is an SEM photograph of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2. It can be clearly seen that there are many obvious holes on the whole material frame, proving that the material has rich hierarchical pore structure. Fig. 6 is an XPS spectrum of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2. It is clear that the peak corresponding to C, N, O, Ni has a surface composition of 78.32% by atomic ratio of C, 3.07% by atomic ratio of N, 8.24% by atomic ratio of O and 10.38% by atomic ratio of Ni. Fig. 7 is a graph of pore size distribution for the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 2. The pore size distribution curves have a peak at 39.2nm and a peak at 109nm, respectively, confirming that the utilization of the nitrate-containing precursor in the pyrolysis process effectively produces a hierarchical pore structure on the carbon substrate containing abundant macropores. The elemental analyzer determined that the content of C in the nanomaterial was 37.14%, the content of H was 1.65%, the content of N was 1.67%, the content of O was 5.12%, and the content of Ni after normalization was 54.42%. The acid loss of the composite material obtained in this example before purification, measured and calculated by the method described in the nomenclature section, was 56%, and the acid loss of the composite material after purification was less than 1%. The pickling loss rate remains substantially unchanged by continuing to increase the pickling time on the basis of the process described in the nomenclature section.
Fig. 8 is a graph of pore size distribution of the nitrogen-doped carbon-coated nickel nanocomposite prepared in example 3. The pore size distribution curves show peaks at 38.1nm and 74.1nm, respectively, and it is also confirmed that the utilization of the nitrate-containing precursor during pyrolysis effectively produces a hierarchical pore structure on the carbon substrate containing abundant macropores. The elemental analyzer determined that the nano material C content was 34.01%, the H content was 2.43%, the N content was 2.81%, the O content was 7.14%, and the normalized Ni content was 53.61%. The acid loss of the composite material obtained in this example before purification, measured and calculated by the method described in the nomenclature section, was 51%, and the acid loss of the composite material after purification was less than 1%. The pickling loss rate remains substantially unchanged by continuing to increase the pickling time on the basis of the process described in the nomenclature section.
Fig. 9 is a pore size distribution curve of the nitrogen-doped carbon-coated nickel nanocomposite prepared in comparative example 1. It can be seen that the pores of the material are mainly mesoporous pores with the pore diameter less than 15nm, and nitrate is not contained in the precursor, so the pore structure of the material is obviously different from the embodiment.
The precursor of the high-temperature pyrolysis of the invention is directly prepared from Ni (NO)3)2The precursor Ni and water-soluble fatty acid containing amido are heated and stirred under the conditions of normal pressure and pure water phase, and the atom utilization rate of the precursor Ni can reach 100 percent. In the preparation process, dicyanodiamine, melamine and the like which are commonly used in the traditional method are not needed to be easily sublimated or decomposed, and the ligand of the carbon nanotube is easily generated; and overcomes the defects that the preparation of the metal organic framework structure precursor in the prior art needs the self-assembly of a high-temperature high-pressure reaction kettle, a large amount of organic solvent is wasted, the purification steps are complicated, and the like. In addition, the nitrate is decomposed in the pyrolysis process to form a unique hierarchical pore structure in the material, so that the effective regulation and control of the pore structure of the carbon-coated nickel core-shell structure nano-particles are realized. Further, the preparation method uses inexpensive Ni (NO)3)2Is a metal source, is directly stirred with water-soluble fatty acid containing amido in a water phase and is evaporated to dryness to obtain a precursor, the operation is simple and convenient, and the industrialized mass production is easy to realize.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A carbon-coated nickel nano composite material comprises carbon-coated nickel nano particles, wherein the carbon-coated nickel nano particles are composed of nickel nano particle inner cores and nitrogen and oxygen doped graphitized carbon layer shells coated on the surfaces of the nickel nano particles; the composite material has two distribution peaks with the pore diameter of 25-50 nm and 50-300 nm.
2. The carbon-coated nickel nanocomposite as claimed in claim 1, wherein the content of Ni is 5 to 80%, the content of C is 20 to 93%, the content of O is 0.5 to 6%, the content of N is 0.5 to 6%, and the content of H is 0.1 to 2.5% based on the total mass of the composite.
3. The carbon-coated nickel nanocomposite material of claim 1, wherein the nickel nanoparticle core comprises a face-centered cubic lattice structure and a hexagonal close lattice structure.
4. The carbon-coated nickel nanocomposite according to claim 1, wherein the composite has a pickling loss ratio of less than 50%, preferably less than 20%, more preferably less than 10%, most preferably less than 2%.
5. A method of making the carbon-coated nickel nanocomposite material of any of claims 1 to 3, comprising the steps of:
s1, mixing water-soluble fatty acid containing amino group with Ni (NO)3)2Mixing the raw materials in water, heating and stirring the mixture to form a homogeneous solution, removing water, and grinding the obtained solid to form a precursor;
and S2, pyrolyzing the precursor at high temperature in an inert protective atmosphere or a reducing atmosphere.
6. The method of claim 5, wherein the amine group-containing water-soluble fatty acid is one or more of ethylenediaminetetraacetic acid, iminodiacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and 1, 3-propanediaminetetraacetic acid.
7. The method of claim 5, wherein the Ni (NO)3)2The molar ratio of the amino group-containing water-soluble fatty acid to the amino group-containing water-soluble fatty acid is 1: 0.5-10.
8. The method according to claim 5, wherein the heating and stirring temperature is 30 to 150 ℃.
9. The method as claimed in claim 5, wherein in the step S2, the inert atmosphere is nitrogen or argon, the high temperature pyrolysis is carried out at a rate of 0.5-30 ℃/min to a constant temperature section, the constant temperature section is kept for 20-600min, and the temperature of the constant temperature section is 400-800 ℃; preferably, the heating rate is 1-10 ℃/min, the constant temperature time in the constant temperature section is 450-800 ℃, and the temperature in the constant temperature section is 20-480 min.
10. The method of claim 5, further comprising:
s3, purifying the product obtained in the S2 step in an acid solution to remove incomplete coated Ni inner cores.
11. The method according to claim 10, wherein the acidic solution in the purification step is an aqueous solution of one or more of hydrochloric acid, sulfuric acid or hydrofluoric acid, and the concentration is 0.1-3 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811358334.0A CN111185211B (en) | 2018-11-15 | 2018-11-15 | Carbon-coated nickel nanocomposite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811358334.0A CN111185211B (en) | 2018-11-15 | 2018-11-15 | Carbon-coated nickel nanocomposite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111185211A true CN111185211A (en) | 2020-05-22 |
| CN111185211B CN111185211B (en) | 2023-06-09 |
Family
ID=70684277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811358334.0A Active CN111185211B (en) | 2018-11-15 | 2018-11-15 | Carbon-coated nickel nanocomposite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111185211B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426490A (en) * | 2020-10-12 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic hydrogenation of unsaturated compounds |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500295A (en) * | 2011-10-26 | 2012-06-20 | 天津大学 | Preparation method of carbon-coated metallic nano-particles |
| CN104209514A (en) * | 2014-09-05 | 2014-12-17 | 南开大学 | Method for preparing Ni@C or Co@C core-shell nanoparticles |
| CN104841924A (en) * | 2014-02-19 | 2015-08-19 | 中国科学院大连化学物理研究所 | Preparation method of carbon entirely-packaged metal nanoparticles |
| CN105478755A (en) * | 2016-01-13 | 2016-04-13 | 合肥工业大学 | Method for preparing non-metallic element doped carbon coated metal nanoparticle magnetic composite |
| CN106622248A (en) * | 2016-11-21 | 2017-05-10 | 清华大学 | Porous nickel and carbon compound and preparation method of porous nickel and carbon compound |
-
2018
- 2018-11-15 CN CN201811358334.0A patent/CN111185211B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500295A (en) * | 2011-10-26 | 2012-06-20 | 天津大学 | Preparation method of carbon-coated metallic nano-particles |
| CN104841924A (en) * | 2014-02-19 | 2015-08-19 | 中国科学院大连化学物理研究所 | Preparation method of carbon entirely-packaged metal nanoparticles |
| CN104209514A (en) * | 2014-09-05 | 2014-12-17 | 南开大学 | Method for preparing Ni@C or Co@C core-shell nanoparticles |
| CN105478755A (en) * | 2016-01-13 | 2016-04-13 | 合肥工业大学 | Method for preparing non-metallic element doped carbon coated metal nanoparticle magnetic composite |
| CN106622248A (en) * | 2016-11-21 | 2017-05-10 | 清华大学 | Porous nickel and carbon compound and preparation method of porous nickel and carbon compound |
Non-Patent Citations (4)
| Title |
|---|
| CUIHUA AN: "Mesoporous Ni@C hybrids for a high energy aqueous asymmetric supercapacitor device", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| JIAO DENG ET AL.: "Enhanced Electron Penetration through an Ultrathin Graphene Layer for Highly Efficient Catalysis of the Hydrogen Evolution Reaction", 《COMMUNICATION》 * |
| 化学工业出版社《化工百科全书》编辑部编: "《冶金和金属材料》", 31 January 2001, 化学工业出版社 * |
| 肖正辉: "炭气凝胶及其改性材料对重金属离子吸附的研究", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426490A (en) * | 2020-10-12 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic hydrogenation of unsaturated compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111185211B (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109309213B (en) | Carbon-coated nickel nano composite material and preparation method and application thereof | |
| CN111185604B (en) | Carbon-coated iron and iron carbide nano composite material and preparation method thereof | |
| CN112705235B (en) | Carbon-coated nickel carbide nanocomposite and preparation method and application thereof | |
| Yang et al. | Construction of core-shell mesoporous carbon nanofiber@ nickel cobaltite nanostructures as highly efficient catalysts towards 4-nitrophenol reduction | |
| WO2021051896A1 (en) | Monolithic catalyst with cobalt oxide nanowire wrapped by nitrogen-doped carbon, and preparation method therefor | |
| Kong et al. | Metal organic framework derived CoFe@ N-doped carbon/reduced graphene sheets for enhanced oxygen evolution reaction | |
| CN111185211B (en) | Carbon-coated nickel nanocomposite and preparation method thereof | |
| Liu et al. | Janus coordination polymer derived PdO/ZnO nanoribbons for efficient 4-nitrophenol reduction | |
| CN115475641B (en) | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof | |
| You et al. | Pd/CNT with controllable Pd particle size and hydrophilicity for improved direct synthesis efficiency of H 2 O 2 | |
| CN113751007B (en) | Catalyst of carbon-coated nickel oxide, preparation method and application thereof | |
| CN113751042B (en) | Carbon-coated nickel oxide nano composite material and preparation method and application thereof | |
| CN112705237B (en) | Carbon-coated nickel carbide and nickel nanocomposite as well as preparation method and application thereof | |
| CN112705234B (en) | Oxygen-doped carbon-based nickel carbide nanocomposite and preparation method and application thereof | |
| CN114426490A (en) | Catalytic hydrogenation of unsaturated compounds | |
| CN113751005A (en) | Catalyst of carbon-coated transition metal oxide and preparation method and application thereof | |
| CN115121252B (en) | Carbon-coated nickel nanocomposite, and preparation method and application thereof | |
| CN112705236A (en) | Carbon-coated nickel carbide nano composite material and preparation method and application thereof | |
| CN112705239B (en) | Nickel carbide nanocomposite and preparation method and application thereof | |
| CN113751041B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof | |
| CN114887646B (en) | Fe monoatomic supported porous carbon nitride photocatalytic material and preparation method and application thereof | |
| CN113750991B (en) | Catalyst of carbon-coated nickel oxide, preparation method and application thereof | |
| CN115966706A (en) | Hierarchical porous graphene material and preparation method and application thereof | |
| CN114887646A (en) | Fe monatomic-loaded porous carbon nitride photocatalytic material and preparation method and application thereof | |
| CN112707802A (en) | Synthetic method of saturated aldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |