CN109465001A - A kind of preparation method and application of carried metal carbon micron chip - Google Patents

A kind of preparation method and application of carried metal carbon micron chip Download PDF

Info

Publication number
CN109465001A
CN109465001A CN201811202288.5A CN201811202288A CN109465001A CN 109465001 A CN109465001 A CN 109465001A CN 201811202288 A CN201811202288 A CN 201811202288A CN 109465001 A CN109465001 A CN 109465001A
Authority
CN
China
Prior art keywords
metal
carbon micron
micron chip
preparation
wax gourd
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.)
Pending
Application number
CN201811202288.5A
Other languages
Chinese (zh)
Inventor
毛武涛
倪萍
张少杰
张子祥
鲍克燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University of Technology
Original Assignee
Jiangsu University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu University of Technology filed Critical Jiangsu University of Technology
Priority to CN201811202288.5A priority Critical patent/CN109465001A/en
Publication of CN109465001A publication Critical patent/CN109465001A/en
Pending legal-status Critical Current

Links

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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of preparation methods of carried metal carbon micron chip, belong to technical field of nano material.Wax gourd particle is immersed in metal salt solution by solwution method by the present invention first using wax gourd and corresponding metal salt as raw material, and the porous carbon micron chip for loading corresponding metal is then made by freeze-drying, pyrolysis carbonization.The utility model has the advantages that the raw material of the porous carbon micron chip of carried metal prepared by the present invention is reproducible natural plants, source is extremely extensive and cheap, experimentation and easy to operate；Method of the invention has preferable universality, the carbon micron chip of various metals load can be prepared, such as ruthenium, rhodium, palladium, nickel, cobalt, silver.

Description

A kind of preparation method and application of carried metal carbon micron chip
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation method of carried metal carbon micron chip and Its application in lithium-sulfur cell and catalytic hydrogenating reduction.
Background technique
Carbon material is the material being most widely used in the world because of its a variety of existence form.Wherein amorphous carbon materials Expect to answer extensively because its special construction with micropore and big specific surface area have in fields such as catalysis, petrochemical industry, food, environmental protection With may be used as catalyst carrier, gas purification, water process etc..Chinese patent CN108097253A describes a kind of carbon nanometer The preparation method for managing metal cobalt loaded nanoparticle catalyst is reacted with 2-methylimidazole using divalent cobalt and generates forerunner Body, then reacted by high temperature cabonization and generate product, and is applied in catalyzing manufacturing of hydrogen, cost of material needed for this method costly, and Largely it will cause environmental pollution using solvent.In recent years, as electrode material or the carrier of sulphur, amorphous carbon material is in lithium sulphur Field of batteries is even more to be demonstrated by more wide application prospect.
Metal nanoparticle (such as gold, silver, iron, cobalt, nickel, palladium) has many beneficial physicochemical properties, is urging Change, in electronics and sensor field using relatively broad.But some noble metal fancy prices limit it and are widely used. Therefore it is met with suitable carrier material, the hybrid material of Development of Novel can not only be obtained than metal ion itself The fields such as performance more outstanding, more catalysis, the magnetic and energy provide a kind of new material, and present broader Economic value.And by metal with porous carbon materials are compound has become a kind of social trend, develop a kind of safety non-pollution, behaviour The porous carbon materials for making simple porous carbon materials and metal-modified are even more to have important environment, economy and society meaning.
Summary of the invention
High, the defect of experimental implementation complexity for solution cost of the existing technology and energy consumption, it is an object of the invention to A kind of preparation method of the porous carbon micron chip of simple carried metal is provided.
Technical solution of the present invention:
A kind of preparation method of carried metal carbon micron chip is to pass through solwution method first using wax gourd and metal salt as raw material Wax gourd particle is immersed in metal salt solution, is then carbonized by freeze-drying, pyrolysis and the carbon micron of carried metal is made Piece specifically comprises the following steps:
(1) in water by dissolving metal salts, metal salt solution is formed；
(2) wax gourd particle is immersed in above-mentioned metal salt solution, stands 24~96h, filtered off upper solution, soaked The wax gourd of metal salt solution was steeped, gained wax gourd is freeze-dried, and is transferred in quartz boat；
(3) above-mentioned quartz boat is placed in tube furnace, is passed through protective gas, kept the temperature after being warming up to predetermined temperature, so After be cooled to room temperature, obtain the porous carbon micron chip of carried metal.
Preferably, the metal salt is one of nickel acetate, cobalt acetate, silver nitrate, ruthenium trichloride and palladium acetate, The concentration of the metal salt solution is 0.005~0.05mol/L, more preferably 0.002~0.02mol/L.
Preferably, protective gas described in step (3) is nitrogen or argon gas, and the air velocity for being passed through protection gas is 20 ~100mL/min, is continually fed into 10~30min.
Preferably, it heats up described in step (3), is to be warming up to 600~900 DEG C with the speed of 2~5 DEG C/min, more preferably It is 750~800 DEG C, preferably 60~240min of soaking time, more preferably 180~240min.
The utility model has the advantages that
(1) raw material that the porous carbon micron chip of carried metal is prepared in the present invention is reproducible natural plants, carrys out source electrode Its is extensive and cheap, experimentation and easy to operate.
(2) method of the invention has preferable universality, can not only prepare simple porous carbon micron chip, can also To prepare the carbon micron chip of various metals load, such as ruthenium, rhodium, palladium, nickel, cobalt, silver.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the SEM figure of porous carbon micron chip made from embodiment 1.
Fig. 2 is the SEM figure of carried metal nickel porous carbon micron chip made from embodiment 3.
Fig. 3 is the SEM figure of metal cobalt loaded porous carbon micron chip made from embodiment 5.
Fig. 4 is the SEM figure of carried metal silver porous carbon micron chip made from embodiment 6.
Fig. 5 is the SEM figure of supported metal ruthenium porous carbon micron chip made from embodiment 7.
Fig. 6 is the circulating effect figure under the lithium-sulfur cell 1C current density condition that embodiment 10 assembles.
Specific embodiment
Below with reference to some specific embodiments, the present invention is further described, but is not intended to limit the present invention.
A kind of embodiment 1: preparation of porous carbon micron chip
Gained white solid addition quartz boat is placed in tube furnace, then passes to nitrogen by the freeze-drying of 200g wax gourd 30min, air velocity 50mL/min are warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 180min, are cooled to room temperature, obtain To black solid, porous carbon micron sheet material is dried to obtain through 10% acetic acid aqueous solution washing.
As shown in Figure 1, products obtained therefrom is thickness 100-200nm, the carbon plate that length and width is 1-10 μm, BET, which is tested, to be shown to compare Surface area is 133m2/g。
A kind of embodiment 2: preparation of carried metal nickel porous carbon micron chip
(1) nickel acetate of corresponding 4.9g is dissolved in 1000mL water, concentration 0.02mol/L stirs 30min, is made into Homogeneous and transparent solution；
(2) wax gourd of 200g is impregnated in the above solution, stands 48h, filter off solution, gained wax gourd is freeze-dried, Obtain absinthe-green fluffy solid；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 180min, are cooled to room temperature, obtain To the carbon micron chip of carried metal nickel.
Products obtained therefrom is thickness 100-200nm, and the carbon plate that length and width is about 1-10 μm, BET, which is tested, shows that specific surface area is 275m2/ g, metal nickel content are 4.6%, particle diameter 20-100nm.
A kind of embodiment 3: preparation of carried metal nickel porous carbon micron chip
(1) nickel acetate of corresponding 12.25g is dissolved in 1000mL water, concentration 0.05mol/L stirs 30min, matches At homogeneous and transparent solution；
(2) wax gourd of 400g is impregnated in the above solution, stands 60h, filter off solution, gained wax gourd is freeze-dried, Obtain absinthe-green fluffy solid；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 750 DEG C with the speed of 2 DEG C/min, and keep the temperature 240min, are cooled to room temperature, obtain To the carbon micron chip of carried metal nickel.
Products obtained therefrom is thickness 100-200nm, and the carbon plate that length and width is about 1-10 μm, BET, which is tested, shows that specific surface area is 185m2/ g, as shown in Fig. 2, metallic nickel is successfully supported in carbon micron chip, and metal nickel content is 7.8%, particle diameter 20- 100nm。
A kind of embodiment 4: preparation of carried metal nickel porous carbon micron chip
(1) nickel acetate of corresponding 0.5g is dissolved in 1000mL water, concentration 0.002mol/L stirs 30min, matches At homogeneous and transparent solution；
(2) wax gourd of 300g is impregnated in the above solution, stands 72h, filter off solution, gained wax gourd is freeze-dried, Obtain absinthe-green fluffy solid；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 750 DEG C with the speed of 2 DEG C/min, and keep the temperature 240min, are cooled to room temperature, obtain To the carbon micron chip of carried metal nickel.
Products obtained therefrom is thickness 100-200nm, and the carbon plate that length and width is about 1-10 μm, BET, which is tested, shows that specific surface area is 252m2/ g, metal nickel content are 0.3%, particle diameter 5-20nm.
A kind of embodiment 5: preparation of metal cobalt loaded porous carbon micron chip
(1) cobalt acetate of corresponding 3.54g is dissolved in 1000mL water, concentration 0.02mol/L stirs 30min, matches At homogeneous and transparent solution；
(2) wax gourd of 300g is impregnated in the above solution, stands 48h, filter off solution, gained wax gourd is freeze-dried, Obtain pink fluffy solid；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 300min, are cooled to room temperature, obtain To metal cobalt loaded carbon micron chip.
Products obtained therefrom is thickness 100-200nm, the carbon plate that length and width is about 1-10 μm, as shown in figure 3, metallic cobalt success is equal It is even to be supported on carbon micron chip surface and inside.
A kind of embodiment 6: preparation of carried metal silver porous carbon micron chip
(1) silver nitrate of corresponding 0.85g is dissolved in 500mL water, concentration 0.01mol/L stirs 30min, is made into Homogeneous and transparent solution；
(2) wax gourd of 100g is impregnated in the above solution, stands 72h, filter off solution, gained wax gourd is freeze-dried, Obtain the fluffy solid of white；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 180min, are cooled to room temperature, obtain To the carbon micron chip of carried metal silver.
Products obtained therefrom is thickness 100-200nm, the carbon plate that length and width is about 1-10 μm, as shown in figure 4, metallic silver particles are equal The surface and inside of even load carbon material.
A kind of embodiment 7: preparation of supported metal ruthenium porous carbon micron chip
(1) ruthenium trichloride of corresponding 0.52g being dissolved in 500mL water, concentration 0.005mol/L stirs 30min, It is made into homogeneous and transparent solution；
(2) wax gourd of 100g is impregnated in the above solution, stands 72h, filter off solution, gained wax gourd is freeze-dried, Obtain the fluffy solid of white；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 900 DEG C with the speed of 2 DEG C/min, and keep the temperature 180min, are cooled to room temperature, obtain To the carbon micron chip of supported metal ruthenium.
Products obtained therefrom is thickness 100-200nm, the carbon plate that length and width is about 1-10 μm, as shown in figure 5, metal Ru particle is equal The surface and inside of even load carbon material.
A kind of embodiment 8: preparation of carried metal palladium porous carbon micron chip
(1) palladium acetate of corresponding 0.35g is dissolved in 500mL water, concentration 0.002mol/L stirs 30min, matches At homogeneous and transparent solution；
(2) wax gourd of 100g is impregnated in the above solution, stands 72h, filter off solution, gained wax gourd is freeze-dried, Obtain the fluffy solid of white；
(3) it obtains dry part wax gourd solid quartz boat is added being placed in tube furnace by above-mentioned, then pass to nitrogen 20min, air velocity 50mL/min are warming up to 850 DEG C with the speed of 2 DEG C/min, and keep the temperature 240min, are cooled to room temperature, obtain To the carbon micron chip of supported metal ruthenium.
Products obtained therefrom is thickness 100-200nm, the carbon plate that length and width is about 1-10 μm, Metal Palladium particle uniform load carbon materials The surface and inside of material.
Embodiment 9: carried metal palladium porous carbon micron chip is reacted for catalytic hydrogenating reduction
Carried metal palladium porous carbon micron chip catalyst prepared by 100mg embodiment 8 is added into hydrogenation reaction cauldron, adds Enter 5mL methanol and make solvent, 5 drop glacial acetic acids are added, the substrate nitro benzene of 0.24g is added, is passed through hydrogen to 0.4MPa, displacement gas Three times, 5h, conversion ratio > 99% is stirred at room temperature in body.It is demonstrated experimentally that the porous carbon micron of nickel-loaded metal made from embodiment 2-4 The catalyst of piece is used equally for catalytic hydrogenation reaction, and conversion ratio > 99%.
Embodiment 10
The porous carbon micron chip of carried metal nickel is surveyed as lithium sulphur positive electrode, specific material preparation and battery assembly Examination the following steps are included:
(1) material and 100mg sulphur powder prepared by 100mg embodiment 2 are uniformly mixed, grind 30min, gained mixture It is placed in test tube, 150 DEG C of heating 12h；
(2) by the above-mentioned resulting materials of 80mg, 10mg Kynoar, 10mg conductive black, few drops of N- crassitudes Ketone, grinding uniformly, by gained slurry are placed in 60 DEG C of dry 12h on clean aluminium foil using scraper manual application；
(3) after dry, the aluminium foil after coating is cut into the positive plate that diameter is 12mm, pole piece unit plane using slicer Long-pending load sulfur content is about 0.8-1.0mg/cm2；
(4) the inner assembled battery of glove box (meter Kai Luo that) of 1ppm is respectively less than in water oxygen content, using the electricity of 2016 models Pond shell, lithium piece (diameter 14mm) is as reference electrode and to electrode, diaphragm model Celgard2400, electrolyte used at It is divided into 1M LiTFSI/DME+DOL (volume ratio 1:1) the mixing ethers organic solution for having dosed 2wt% lithium nitrate；
(5) it will be put into 30 DEG C of insulating boxs after assembled battery standing 12h, utilize blue electrical measurement test system (LANDCT2001A) electro-chemical test is carried out:
As shown in fig. 6, battery described above activates initial discharge specific volume under the current density of 0.2C (335mA/g) Amount is up to 1458.7mAh/g, and after activation 5 is enclosed, under the current density of 1C (1675mA/g), 700 circle specific discharge capacities of circulation are still So keep 466.8mAh/g.

Claims (7)

1. a kind of preparation method of carried metal carbon micron chip, it is characterized in that using wax gourd and metal salt as raw material, first by molten Wax gourd particle is immersed in metal salt solution by liquid method, and the carbon that carried metal then is made by freeze-drying, pyrolysis carbonization is micro- Rice piece.
2. a kind of preparation method of carried metal carbon micron chip according to claim 1, it is characterised in that including walking as follows It is rapid:
(1) in water by dissolving metal salts, metal salt solution is formed；
(2) wax gourd particle is immersed in above-mentioned metal salt solution, stands 24~96h, filtered off upper solution, obtain impregnating gold Belong to the wax gourd of salting liquid, gained wax gourd is freeze-dried, and is transferred in quartz boat；
(3) above-mentioned quartz boat is placed in tube furnace, is passed through protective gas, kept the temperature after being warming up to predetermined temperature, it is then cold But to room temperature, the porous carbon micron chip of carried metal is obtained.
3. a kind of preparation method of carried metal carbon micron chip according to claim 1, which is characterized in that the metal Salt is one of nickel acetate, cobalt acetate, silver nitrate, ruthenium trichloride and palladium acetate, and the concentration of the metal salt solution is 0.005 ~0.05mol/L.
4. a kind of preparation method of carried metal carbon micron chip according to claim 2, which is characterized in that in step (3) The protective gas is nitrogen or argon gas, and the air velocity for being passed through protection gas is 20~100mL/min, it is continually fed into 10~ 30min。
5. a kind of preparation method of carried metal carbon micron chip according to claim 2, which is characterized in that in step (3) The heating is to be warming up to 600~900 DEG C with the speed of 2~5 DEG C/min, keeps the temperature 60~240min.
6. the carbon micron chip of the nickel-loaded metal of method preparation according to claim 1-5 is as lithium-sulfur cell Positive electrode.
7. the nickel-loaded of method preparation according to claim 1-5 or the carbon micron chip of palladium metal add as catalysis The catalyst of hydrogen reduction reaction.
CN201811202288.5A 2018-10-16 2018-10-16 A kind of preparation method and application of carried metal carbon micron chip Pending CN109465001A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811202288.5A CN109465001A (en) 2018-10-16 2018-10-16 A kind of preparation method and application of carried metal carbon micron chip

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811202288.5A CN109465001A (en) 2018-10-16 2018-10-16 A kind of preparation method and application of carried metal carbon micron chip

Publications (1)

Publication Number Publication Date
CN109465001A true CN109465001A (en) 2019-03-15

Family

ID=65664655

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811202288.5A Pending CN109465001A (en) 2018-10-16 2018-10-16 A kind of preparation method and application of carried metal carbon micron chip

Country Status (1)

Country Link
CN (1) CN109465001A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110976899A (en) * 2019-11-12 2020-04-10 中国地质大学（北京） In-situ anchoring co-reduction preparation method of carbon-based supported metal sub-nanoparticles
CN112186164A (en) * 2020-10-10 2021-01-05 宁波大学 Carbon fiber composite material loaded with Co nanoparticles and preparation method and application thereof
CN112186165A (en) * 2020-10-10 2021-01-05 宁波大学 Protein fiber loaded with Ni nanoparticles and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974083A (en) * 2006-11-01 2007-06-06 大连理工大学 Prepn process and application of metal-carbon nanometer composite material
CN104600260A (en) * 2014-12-31 2015-05-06 江苏锋驰绿色电源有限公司 C/Ni/S composite material prepared from absorbent cotton and preparation method and application thereof
CN105322189A (en) * 2014-07-01 2016-02-10 中国科学院大连化学物理研究所 Cathode material used for lithium sulfur battery, preparation and application thereof
CN106082193A (en) * 2016-06-14 2016-11-09 陕西科技大学 A kind of method preparing multilevel hierarchy material with carbon element for carbon source with algae
CN106531476A (en) * 2016-12-29 2017-03-22 湖北文理学院 Preparation method of metal oxide/ carbon composite material
CN106914265A (en) * 2017-03-06 2017-07-04 南京师范大学 A kind of method for preparing N doping porous nano carbon material as carbon source gel method with biomass

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974083A (en) * 2006-11-01 2007-06-06 大连理工大学 Prepn process and application of metal-carbon nanometer composite material
CN105322189A (en) * 2014-07-01 2016-02-10 中国科学院大连化学物理研究所 Cathode material used for lithium sulfur battery, preparation and application thereof
CN104600260A (en) * 2014-12-31 2015-05-06 江苏锋驰绿色电源有限公司 C/Ni/S composite material prepared from absorbent cotton and preparation method and application thereof
CN106082193A (en) * 2016-06-14 2016-11-09 陕西科技大学 A kind of method preparing multilevel hierarchy material with carbon element for carbon source with algae
CN106531476A (en) * 2016-12-29 2017-03-22 湖北文理学院 Preparation method of metal oxide/ carbon composite material
CN106914265A (en) * 2017-03-06 2017-07-04 南京师范大学 A kind of method for preparing N doping porous nano carbon material as carbon source gel method with biomass

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杜娟: "生物质基多级孔碳材料的制备及其吸附和电化学性能", 《万方学位论文数据库》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110976899A (en) * 2019-11-12 2020-04-10 中国地质大学（北京） In-situ anchoring co-reduction preparation method of carbon-based supported metal sub-nanoparticles
CN112186164A (en) * 2020-10-10 2021-01-05 宁波大学 Carbon fiber composite material loaded with Co nanoparticles and preparation method and application thereof
CN112186165A (en) * 2020-10-10 2021-01-05 宁波大学 Protein fiber loaded with Ni nanoparticles and preparation method and application thereof
CN112186164B (en) * 2020-10-10 2021-12-21 宁波大学 Carbon fiber composite material loaded with Co nanoparticles and preparation method and application thereof
CN112186165B (en) * 2020-10-10 2022-01-18 宁波大学 Protein fiber loaded with Ni nanoparticles and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Liu et al. CoOx/CoNy nanoparticles encapsulated carbon-nitride nanosheets as an efficiently trifunctional electrocatalyst for overall water splitting and Zn-air battery
CN106914265A (en) A kind of method for preparing N doping porous nano carbon material as carbon source gel method with biomass
CN109465001A (en) A kind of preparation method and application of carried metal carbon micron chip
Huang et al. Photodegradation of rhodamine B over biomass-derived activated carbon supported CdS nanomaterials under visible irradiation
Fan et al. Oxygen‐Deficient Three‐Dimensional Porous Co3O4 Nanowires as an Electrode Material for Water Oxidation and Energy Storage
CN110444776A (en) A kind of base metal N doping MOF economic benefits and social benefits elctro-catalyst and preparation method thereof
CN103227334A (en) Carbon-containing metal catalyst, preparation method and application thereof
CN109037625A (en) The composite material of a kind of multi-stage porous carbon and cobalt sulfide, preparation method and lithium sulfur battery anode material and lithium-sulfur cell containing it
CN106960962B (en) A kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst and preparation method thereof
CN107649160A (en) A kind of graphene-supported magnesium-yttrium-transition metal single dispersing catalyst atom and its preparation method and application
Yuan et al. Silicon oxide-protected nickel nanoparticles as biomass-derived catalysts for urea electro-oxidation
Halder et al. Electrocatalytic applications of graphene–metal oxide nanohybrid materials
Kiyani et al. Investigation of the effect of carbonaceous supports on the activity and stability of supported palladium catalysts for methanol electro-oxidation reaction
Lv et al. Electrospun foamlike NiO/CuO nanocomposites with superior catalytic activity toward the reduction of 4-nitrophenol
Xu et al. A co-operative protection strategy to synthesize highly active and durable Fe/N co–doped carbon towards oxygen reduction reaction in Zn–air batteries
Liu et al. Cobalt nanoparticles encapsulated in nitrogen-doped carbon nanotube as bifunctional-catalyst for rechargeable Zn-air batteries
Feng et al. Facile synthesis of Cu2O nanoparticle-loaded carbon nanotubes composite catalysts for reduction of 4-nitrophenol
Sun et al. Biomass-derived N, S co-doped 3D multichannel carbon supported Au@ Pd@ Pt catalysts for oxygen reduction
CN111530486A (en) Novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and preparation method thereof
CN107176590A (en) Highly controllable ternary heterojunction structure material of constituent content and preparation method thereof
Zhao et al. Optimizing electrocatalytic oxygen reduction by adjacent COC structure-driven charge separation on FeN4 active sites
Wei et al. Void confinement and doping-modulation of IrNi alloy nanoparticles on hollow carbon spheres for efficient hydrogen oxidation/evolution reactions
Lu et al. Coexisting Fe single atoms and nanoparticles on hierarchically porous carbon for high-efficiency oxygen reduction reaction and Zn-air batteries
CN106410203B (en) A method of using metal alkoxide as precursor preparation spherical shape cobalt acid zinc/carbon composite
Saka et al. A novel hazelnutt bagasse based activated carbon as sodium borohydride methanolysis and electrooxidation catalyst

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20190315

RJ01 Rejection of invention patent application after publication