CN110265677A - A kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays and its preparation and application - Google Patents

A kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays and its preparation and application Download PDF

Info

Publication number
CN110265677A
CN110265677A CN201910583987.7A CN201910583987A CN110265677A CN 110265677 A CN110265677 A CN 110265677A CN 201910583987 A CN201910583987 A CN 201910583987A CN 110265677 A CN110265677 A CN 110265677A
Authority
CN
China
Prior art keywords
nico
nis
composite material
doped carbon
carbon nanometer
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
Application number
CN201910583987.7A
Other languages
Chinese (zh)
Other versions
CN110265677B (en
Inventor
丁倩倩
耿哲
张�杰
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.)
Suzhou Vocational Institute of Industrial Technology
Original Assignee
Suzhou Vocational Institute of Industrial 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 Suzhou Vocational Institute of Industrial Technology filed Critical Suzhou Vocational Institute of Industrial Technology
Priority to CN201910583987.7A priority Critical patent/CN110265677B/en
Publication of CN110265677A publication Critical patent/CN110265677A/en
Application granted granted Critical
Publication of CN110265677B publication Critical patent/CN110265677B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • 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
    • 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

Abstract

The invention discloses a kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays and its preparations and application, the composite material includes NiCo@NiS nano particle, S doped carbon nanometer pipe, NiCo@NiS nano particle is embedded on S doped carbon nanometer pipe, and the partial size of NiCo@NiS nano particle is 11~15nm.The preparation method of the composite material includes: to mix melamine, cysteine, Nickel dichloride hexahydrate, cobalt chloride hexahydrate according to the molar ratio of 40:2:1:1, and then grinding obtains solid powder；Solid powder after grinding is placed in Muffle furnace, the gas of inert atmosphere is then passed through into Muffle furnace, Muffle furnace increases temperature to 550 DEG C, and keeps 2h；Muffle furnace is increased into temperature to 800 DEG C again, and keeps 2h, is regathered after temperature is cooling.The composite material is used for elctro-catalyst, carries out oxygen reduction reaction and evolving hydrogen reaction double-function catalyzing, shows excellent.

Description

A kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays and its preparation and Using
Technical field
The invention belongs to catalyst preparation and its application fields more particularly to a kind of S- doped carbon that NiCo@NiS inlays to receive Mitron composite material and its preparation and application.
Background technique
In recent years, with the consumption of fossil energy, energy demand be continuously increased and environmental-friendly consciousness is constantly mature, Relative clean sustainable energy converter device in countries in the world carries out developmental research, wherein utilizing the energy stores of electrochemical reaction It is greatly paid close attention to converting apparatus by people.Secondary metal-air batteries are simple with preparation, security performance is excellent and environment The advantages that friendly, in terms of economic benefit and environmental protection, zinc-air battery be acknowledged as 21 century it is maximally efficient and One of reliable new energy technology.The theoretical density of especially zinc-air battery is much higher than traditional lithium ion battery, can be with Applied to powerful devices such as electric cars.However, making sky due to still lacking suitable air diffusion motor elctro-catalyst so far The discharge current density in pneumoelectric pond is less than normal, and inefficiency and service life are shorter, to greatly limit the application neck of zinc-air battery Domain and industrialization pace.Currently, the noble metal catalysts such as platinum carbon are still viewed as being the highest electricity of ORR (oxygen reduction reaction) activity Catalyst.However, the noble metal catalysts cost of manufacture such as platinum is quite high, while earth reserves are rare, can not mass production generally make With.In addition, although such catalyst shows good activity to ORR (oxygen reduction reaction), and on OER (oxygen evolution reaction) It performs poor.Thus it is extremely restricted in the large-scale application of reversible air electrode catalyst.Therefore develop it is cheap, There is the bifunctional catalyst of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) to seem especially urgent simultaneously.
Summary of the invention
The first object of the present invention is to provide a kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, and has NiCo@NiS nano particle is embedded in the structure on S doped carbon nanometer pipe, and carbon nanotube portion is graphitized, synchronous to realize The improvement of electronic transmission performance and the regulation of active site；
The second object of the present invention is to provide a kind of preparation of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays Method, preparation method is simple；
The third object of the present invention is to provide a kind of application of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, As catalyst, it to be used for oxygen reduction reaction and evolving hydrogen reaction.
To solve the above problems, the technical solution of the present invention is as follows:
A kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, the composite material include NiS nanometers of NiCo@ Particle, S- doped carbon nanometer pipe, the NiCo@NiS nano particle are embedded on the S- doped carbon nanometer pipe, the NiCo@ The partial size of NiS nano particle is 11~15nm.
The present invention also provides a kind of preparation method of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, packets It includes:
Step 1: by melamine, cysteine, Nickel dichloride hexahydrate, cobalt chloride hexahydrate according to 40:2:1:1 mole Ratio mixing, then grinding obtains solid powder；
Step 2: first stage calcining: the solid powder after grinding in step 1 being placed in Muffle furnace, then to Muffle The gas of inert atmosphere is passed through in furnace, then Muffle furnace increases temperature to 550 DEG C, and keeps 2h；
Step 3: second stage calcining: increasing temperature to 800 DEG C for Muffle furnace again, and keep 2h, after temperature is cooling again It collects.
Preferably, the gas of the inert atmosphere includes nitrogen and/or argon gas and/or helium.
Preferably, the first stage calcining Muffle furnace heating rate is 3 DEG C/min.
Preferably, the second stage calcining Muffle furnace heating rate is 5 DEG C/min.
The present invention also provides a kind of applications of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, and urge for electricity Agent carries out oxygen reduction reaction and evolving hydrogen reaction.
Preferably, the composite material is used for the catalyst of evolving hydrogen reaction under the alkaline condition of pH=12~13.
The present invention due to using the technology described above, makes it have the following advantages that and actively imitate compared with prior art Fruit:
(1) composite material for the S- doped carbon nanometer pipe that NiCo@NiS provided by the invention inlays as catalyst to oxygen also Former and evolving hydrogen reaction shows excellent double-function catalyzing activity.The incorporation of sulphur cooperatively forms NiCo catalytic site, effectively adjusts The electronic structure of carbon nanotube is saved, the catalytic performance of oxygen reduction reaction and evolving hydrogen reaction is improved.The composite material is in alkaline condition It is lower to realize that hydrogen generates and be assembled into the oxygen reduction electrode of Zn-air battery.
(2) trimerization in the preparation method of the composite material for the S- doped carbon nanometer pipe that NiCo@NiS provided by the invention inlays Cyanamide polymerize under 550 degrees Celsius forms graphite carbonitride.Meanwhile the nickel cobalt base nano particle of generation is limited in interlayer. Thermal annealing temperatures are further increased to 800 degrees Celsius, so that the growth of nickel cobalt base nano particle catalysis carbonitride.Finally Obtained product is the S- doped carbon nanometer pipe composite material that NiCo@NiS inlays.The preparation method fabricated in situ, synthetic method Simply, cost is relatively low, therefore the composite material prepared is relatively low as catalyst price, and is not added and appoints in preparation method What poisonous and harmful substance, it is environmentally protective.
Detailed description of the invention
Fig. 1 is that the composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays prepares schematic diagram；
Fig. 2 is the scanning electron microscope diagram piece of the composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays；
Fig. 3 is the grain size distribution of NiCo@NiS nano particle；
Fig. 4 is the picture of the high-resolution-ration transmission electric-lens of the composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays；
Fig. 5 is the high-resolution-ration transmission electric-lens image of NiS；
Fig. 6 is the energy dispersion spectrogram of the composite material for the S- doped carbon nanometer pipe that NiCo NiS inlays；
Fig. 7 is the full spectrogram of XPS of the composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays；
Fig. 8 is the fine spectrogram of XPS of S2P in composite material of the present invention；
Fig. 9 is the fine spectrogram of XPS of Co2p in composite material of the present invention；
Figure 10 is the fine spectrogram of XPS of Ni2p3/2 in composite material of the present invention；
The LSV that Figure 11 is composite material of the present invention as elctro-catalyst and Pt/C oxygen evolution reaction under the same testing conditions Curve；
Figure 12 is LSV curve of the composite material of the present invention as elctro-catalyst oxygen evolution reaction under different rotating speeds；
Figure 13 is to survey composite material of the present invention as elctro-catalyst and the oxygen evolution reaction of business Pt/C catalyst to intersect effect Answer spirogram；
Figure 14 is that composite material of the present invention is surveyed as the stability of elctro-catalyst and the oxygen evolution reaction of business Pt/C catalyst Spirogram；
Figure 15 is that composite material of the present invention is analysed under the same testing conditions as elctro-catalyst and business Pt/C catalyst The LSV curve of hydrogen reaction；
Figure 16 is stability test figure of the composite material of the present invention as the evolving hydrogen reaction of elctro-catalyst.
Specific embodiment
Below in conjunction with the drawings and specific embodiments to a kind of S- doped carbon nanometer that NiCo@NiS inlays proposed by the present invention Pipe composite material and its preparation and application are described in further detail.According to following explanation and claims, of the invention is excellent Point and feature will become apparent from.
In the present embodiment, with reference to Fig. 1, a kind of composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays is by following Step preparation:
(1) by the melamine of 20mmol, the cysteine of 1mmol, the Nickel dichloride hexahydrate and 0.5mmol of 0.5mmol Cobalt chloride hexahydrate mixing, then grinding obtain solid powder；
(2) first stage calcines: the solid powder that step (1) obtains being placed in Muffle furnace, with the heating of 3 DEG C/min Rate is raised to 550 DEG C, keeps the temperature 2 hours；
(3) phase III calcines: and then 800 DEG C are raised to the heating rate of 5 DEG C/min, 2 hours are kept the temperature, it is cooling to temperature It is regathered after to room temperature.
Fig. 1 is the schematic diagram of the preparation method, in short, the composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays It is the simple thermal condensation under 550 degrees Celsius by melamine, cysteine, cobalt chloride hexahydrate and Nickel dichloride hexahydrate, so Hydridization synthesis is heated under 800 degrees celsius afterwards.Melamine polymerize under 550 degrees Celsius forms graphite carbonitride, The nickel cobalt base nano particle generated simultaneously is limited in interlayer.Thermal annealing temperatures are further increased to 800 degrees Celsius, so that The growth of nickel cobalt base nano particle catalysis carbonitride.The product finally obtained is the S- doped carbon nanometer that NiCo@NiS inlays Pipe composite material.The preparation method fabricated in situ, synthetic method is simple, and any poisonous and harmful substance is not added, environmentally protective.
A kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, the composite material include NiCo@NiS nanometers Grain, S doped carbon nanometer pipe, NiCo@NiS nano particle are embedded on S doped carbon nanometer pipe, the partial size of NiCo@NiS nano particle About 13nm (as shown in Figure 3).
Using the microcosmic knot of scanning electron microscope and the composite material of high resolution transmission electron microscope observation preparation Structure, as a result as shown in Fig. 2,3,4,5, composite material is equably made of overlength carbon nano pipe as can be seen from Figure 2, in carbon nanotube It is even to be dispersed with nano particle.The internal diameter of carbon nanotube is about 20nm, is greater than business carbon nanotube (about 7nm).As shown in Figure 3 The size of NiCo@NiS nano particle is about 13 nanometers, and with reference to Fig. 4, Fig. 5, high-resolution-ration transmission electric-lens image is further disclosed The high-crystallinity feature of the composite material for the S- doped carbon nanometer pipe that NiCo@NiS inlays.The side wall table of carbon nanotube after synthesis Reveal irregular and undulatory graphene sample form, there is interlamellar spacing, illustrate that carbon nanotube portion is graphitized.It is embedded in NiCo@NiS nano particle in carbon nanotube shows two groups of lattice fringes, and 0.206nm corresponds to (111) of NiCo alloy phase Crystal face (Fig. 4).High-resolution projection sem image (Fig. 5) of NiS provides 0.25nm spacing of lattice, and corresponding is NiS (021) crystalline substance Face.
Fig. 6 is the energy dispersion spectrogram for the S- doped carbon nanometer pipe composite material that NiCo NiS inlays, can from figure Carbon, cobalt, nickel, sulphur are distributed on entire sheet material out, it was confirmed that the presence of carbon in the composite material, cobalt, nickel and sulphur, and quality accounting Respectively carbon (80.46%), oxygen (8.97%), sulphur (1.44%), nickel (3.88%) and cobalt (5.25%).
Fig. 7 is the full spectrogram of XPS for the S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, and is shown in the composite material There are carbon, oxygen, sulphur, nickel, cobalt elements, almost the same with energy dispersion spectrum analysis.
Fig. 8 is the fine spectrogram of XPS of S2P, is broadly divided into four peaks in Fig. 8, is located at 165.2eV, 163.9eV and 162.4eV corresponds respectively to the S-O key in NiCo@NiS nanoparticle, C-S-C key and Ni-S/Co-S key.Fig. 9 is Co2p's XPS fine spectrogram is primarily present five positioned at 778.6eV, 780.4eV, 786.2eV, 796.5eV and 803.7eV in figure Peak, wherein the strong peak of 786.2eV and 803.7eV is satellites, is attributable to the oscillatory excitation of high-spin Co2+ ion； Peak at 778.6eV and 780.4eV is attributable to the combination energy of the 2p3/2 track of Co species, and the peak at 796.5eV corresponds to The 2p1/2 track of Co species.Peak value at about 780.4eV is attributed to Co-O and Co-S, and the peak value pair at about 778.6eV It should be in Co0 phase.Figure 10 is the fine spectrogram of XPS of Ni2p3/2, and the peak of 855.1eV and 859.6eV can be divided into spectrogram, right It should be in NiO phase and Ni-S/Ni-O component.All these results further demonstrate the formation of NiCo@NiS nano particle, and Element sulphur is successfully entrained in carbon nanotube.
The S- doped carbon nanometer pipe composite material that NiCo@NiS inlays is used for catalyst and carries out electro-chemical test, it is specific real It is for example following to apply mode:
With PINE rotating disk electrode (r.d.e) (RDE) (Pine Instruments Co.Ltd.USA) the electrochemistry work combined It stands and carries out electrochemical measurement on (CHI 760D, CH Instruments, Inc., Shanghai, China).During measurement Use the standard three electrode electrochemical cell equipped with gas flow system.Before measuring, first successively with 5.0 μm of ol/L, 3.0 μm of ol/L and 0.05 μm of ol/L alumina slurries polish rotating disk electrode (r.d.e) (RDE, 5.0 millimeters of diameter), then respectively in water With supersound washing 1 minute in ethyl alcohol.The electrode cleaned with high-purity nitrogen steam drying.By by 5.0 milligrams of the present embodiment Composite powder be distributed to comprising 100 microlitres Nafion (perfluorinated sulfonic acid) solution (0.5wt%) and 900 microlitres of ethyl alcohol it is mixed It closes in object, is ultrasonically treated 2 minutes then to prepare NiCo@NiS/S-CNTs (CNTs refers to carbon nanotube) catalyst ink.So 12 microlitres of catalyst inks are dripped on vitreous carbon (GC) electrode surface afterwards, make every square li of 305 microgram of catalyst loadings Rice.In order to compare, the commercially available Pt/C catalyst ink with same concentrations is also prepared, step is mixed with the NiCo@NiS S- inlayed Miscellaneous carbon nano-tube catalyst ink is identical.
Catalysis is studied by linear sweep voltammetry figure (LSV) measurement in the 0.1mol/LKOH solution that oxygen is saturated The ORR performance of agent.Under the different rotary rate of 625rpm, 900rpm, 1225rpm, 1600rpm and 2025rpm, with 10 millivolts Scan rate measurement LSV curve per second.All current potentials in the work are recorded relative to Ag/AgCl reference electrode.Pass through The electron transfer number (n) of each oxygen molecule during Koutecky-Levich (K-L) equation calculation ORR:
B=0.62nF (D0)2/3υ-1/6C0 (2)
JK=nFkC0 (3)
The current density measured during wherein J is hydrogen reduction, JKIt is dynamic current density, ω is electrode rotary angular speed (π of ω=2 N, N are linear rotational velocities), B are K-L slope of a curves, and n represents the electron transfer number of each oxygen molecule, and F is method Draw constant (F=96485Cmol-1), D0It is O2Diffusion coefficient in 0.1mol/L KOH (1.9 × 10-5cm2s-1), ν It is dynamic viscosity (0.01cm2s-1), C0It is O2Volumetric concentration (1.2 × 10-3mol·L-1)。
Figure 11 is the S- doped carbon nanometer pipe catalyst that NiCo@NiS inlays and Pt/C in O2The 0.1mol/L KOH of saturation With 10mVs in solution-1Sweep speed and 1600rpm rotation speed measuring speed under the conditions of LSV curve, such as Figure 11 institute Show, linear sweep voltammetry figure (LSV) curve and Pt/C electricity for the S- doped carbon nanometer pipe sample that measurement NiCo@NiS inlays are urged Agent is as reference.The S- doped carbon nanometer pipe and business Pt/C that the elctro-catalyst NiCo@NiS of research inlays show respectively- The take-off potential (relative to Ag/AgCl) of 0.01V and -0.03V, -0.14V and -0.15V are respectively elctro-catalyst NiCo@NiS edge The half wave potential of embedding S- doped carbon nanometer pipe and business Pt/C.Of S- doped carbon nanometer pipe and Pt/C that NiCo@NiS inlays Beginning current potential and half wave potential value are very close, show that the S- doped carbon nanometer pipe that NiCo@NiS inlays has excellent hydrogen reduction living Property.In addition, the S- doped carbon nanometer pipe that NiCo@NiS inlays also shows that maximum is investigated potential in all catalyst Electric current in range further shows its excellent hydrogen reduction performance.
Figure 12 is under different rotating speeds from O2The S- that the NiCo@NiS that the 0.1mol/L KOH solution of saturation obtains inlays mixes The LSV curve of miscellaneous carbon nanotube.Based on corresponding Koutecky-Levich (K-L) figure, the S- that NiCo@NiS inlays is adulterated Carbon nanotube is 3.75 in the mean value calculation of the transfer electron number of -0.40V to -0.55V, and approximation is catalyzed relative to Pt/C The theoretical value (n=4.0) of agent shows nearly four electronics hydrogen reduction process.
Figure 13 is the friendship of NiCo@NiS inlays under identical experiment condition S- doped carbon nanometer pipe and Pt/C catalyst Pitch effect, Figure 14 is the durable of NiCo@NiS inlays under identical experiment condition S- doped carbon nanometer pipe and Pt/C catalyst Property measurement, display, the S- doped carbon nanometer pipe that NiCo@NiS inlays has height endurability and good steady to methanol crossover effect It is qualitative.
Evolving hydrogen reaction polarization curve N at room temperature2With 5.0mVs in the 0.1mol/LKOH (PH=12.5) of saturation-1Sweep Retouch rate acquisition.
Figure 15 is the S- doped carbon nanometer pipe that NiCo@NiS inlays and Pt/C in 1600rpm, sweep speed 5mVs-1N2 The linear sweep voltammetry curve being saturated in 0.1mol/L KOH, Figure 16 are the S- doped carbon nanometer pipe inlayed of NiCo@NiS in liberation of hydrogen Stability in reaction.As shown in figure 15, it is for the NiCo@NiS S- doped carbon nanometer pipe inlayed and Pt/C current density 10mAcm-2When measurement current potential be respectively -1.16V and -1.01V；The S- doped carbon nanometer pipe that NiCo@NiS inlays is confirmed respectively Catalytic activity with certain evolving hydrogen reaction.In addition, the S- doped carbon nanometer that NiCo@NiS inlays as can see from Figure 16 Pipe also shows high-durability in evolving hydrogen reaction.
In summary it analyzes, the S- doped carbon nanometer pipe that NiCo@NiS inlays can be used as catalyst in hydrogen reduction In reaction and evolving hydrogen reaction, the S- doped carbon nanometer pipe that NiCo@NiS inlays catalytic performance in oxygen reduction reaction and evolving hydrogen reaction Bi-functional be attributable to NiCo, NiS and S be entrained in carbon nano tube structure generate active site synergistic effect.
Embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned implementations Mode.Even if to the present invention, various changes can be made, if these variations belong to the model of the claims in the present invention and its equivalent technologies Within enclosing, then still fall within the protection scope of the present invention.

Claims (7)

1. a kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, which is characterized in that the composite material includes NiCo@NiS nano particle, S doped carbon nanometer pipe, the NiCo@NiS nano particle are embedded on the S doped carbon nanometer pipe, The partial size of the NiCo@NiS nano particle is 11~15nm.
2. a kind of preparation method for the S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, which is characterized in that this method packet It includes:
Step 1: by melamine, cysteine, Nickel dichloride hexahydrate, cobalt chloride hexahydrate according to 40:2:1:1 molar ratio Mixing, then grinding obtains solid powder；
Step 2: first stage calcining: the solid powder after grinding in step 1 being placed in Muffle furnace, is passed through into Muffle furnace The gas of inert atmosphere, then Muffle furnace increases temperature to 550 DEG C, and keeps 2h；
Step 3: second stage calcining: increasing temperature to 800 DEG C for Muffle furnace again, and keep 2h, regathers after temperature is cooling.
3. the preparation method for the S- doped carbon nanometer pipe composite material that NiCo@NiS according to claim 2 inlays, special Sign is that the gas of the inert atmosphere includes nitrogen and/or argon gas and/or helium.
4. the preparation method for the S- doped carbon nanometer pipe composite material that NiCo@NiS according to claim 2 inlays, special Sign is that the first stage calcining Muffle furnace heating rate is 3 DEG C/min.
5. the preparation method for the S- doped carbon nanometer pipe composite material that NiCo@NiS according to claim 2 inlays, special Sign is that the second stage calcining Muffle furnace heating rate is 5 DEG C/min.
6. a kind of application for the S- doped carbon nanometer pipe composite material that NiCo@NiS inlays, which is characterized in that it is used for elctro-catalyst, Carry out oxygen reduction reaction and evolving hydrogen reaction.
7. the application for the S- doped carbon nanometer pipe composite material that NiCo@NiS according to claim 6 inlays, feature exist In for the catalyst of evolving hydrogen reaction under the alkaline condition of pH=12~13.
CN201910583987.7A 2019-07-01 2019-07-01 NiCo @ NiS-inlaid S-doped carbon nanotube composite material and preparation and application thereof Active CN110265677B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910583987.7A CN110265677B (en) 2019-07-01 2019-07-01 NiCo @ NiS-inlaid S-doped carbon nanotube composite material and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910583987.7A CN110265677B (en) 2019-07-01 2019-07-01 NiCo @ NiS-inlaid S-doped carbon nanotube composite material and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN110265677A true CN110265677A (en) 2019-09-20
CN110265677B CN110265677B (en) 2022-06-03

Family

ID=67923566

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910583987.7A Active CN110265677B (en) 2019-07-01 2019-07-01 NiCo @ NiS-inlaid S-doped carbon nanotube composite material and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN110265677B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110911698A (en) * 2019-12-02 2020-03-24 济南大学 Oxygen reduction catalyst and preparation method thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013008209A2 (en) * 2011-07-14 2013-01-17 Centro De Investigación Y De Estudios Avanzados Del Instituto Politécnico Nacional Methods for the preparation of carbon nanotubes doped with different elements
CN105244482A (en) * 2015-09-12 2016-01-13 复旦大学 Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof
CN105609790A (en) * 2015-12-14 2016-05-25 青岛大学 Preparation method for Ni-Co/carbon nanotube aerogel catalyst of zinc-air battery
CN106669739A (en) * 2016-12-30 2017-05-17 温州大学 Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof
CN107829107A (en) * 2017-09-25 2018-03-23 中国科学院山西煤炭化学研究所 A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application
CN108543545A (en) * 2018-04-26 2018-09-18 大连理工大学 A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications
CN108722460A (en) * 2018-04-08 2018-11-02 湖北大学 NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof
CN108923051A (en) * 2018-07-06 2018-11-30 郑州大学 A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application
CN109530714A (en) * 2018-11-19 2019-03-29 广州大学 A kind of combination electrode material and its preparation method and application
CN109745984A (en) * 2017-11-08 2019-05-14 中国科学院金属研究所 A kind of preparation method of the monatomic doped carbon nanometer pipe of metal
CN109759088A (en) * 2019-02-21 2019-05-17 青岛科技大学 A kind of compound assembled material of 2D NiS/ graphene and preparation method thereof
US20190186029A1 (en) * 2017-08-03 2019-06-20 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Graphene material inlaid with single metal atoms and preparing method and application thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013008209A2 (en) * 2011-07-14 2013-01-17 Centro De Investigación Y De Estudios Avanzados Del Instituto Politécnico Nacional Methods for the preparation of carbon nanotubes doped with different elements
CN105244482A (en) * 2015-09-12 2016-01-13 复旦大学 Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof
CN105609790A (en) * 2015-12-14 2016-05-25 青岛大学 Preparation method for Ni-Co/carbon nanotube aerogel catalyst of zinc-air battery
CN106669739A (en) * 2016-12-30 2017-05-17 温州大学 Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof
US20190186029A1 (en) * 2017-08-03 2019-06-20 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Graphene material inlaid with single metal atoms and preparing method and application thereof
CN107829107A (en) * 2017-09-25 2018-03-23 中国科学院山西煤炭化学研究所 A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application
CN109745984A (en) * 2017-11-08 2019-05-14 中国科学院金属研究所 A kind of preparation method of the monatomic doped carbon nanometer pipe of metal
CN108722460A (en) * 2018-04-08 2018-11-02 湖北大学 NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof
CN108543545A (en) * 2018-04-26 2018-09-18 大连理工大学 A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications
CN108923051A (en) * 2018-07-06 2018-11-30 郑州大学 A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application
CN109530714A (en) * 2018-11-19 2019-03-29 广州大学 A kind of combination electrode material and its preparation method and application
CN109759088A (en) * 2019-02-21 2019-05-17 青岛科技大学 A kind of compound assembled material of 2D NiS/ graphene and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEIGUANG FANG ET AL.: "N- and S-doped porous carbon decorated with in-situ synthesized CoeNi bimetallic sulfides particles: A cathode catalyst of rechargeable Zn-air batteries", 《CARBON》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110911698A (en) * 2019-12-02 2020-03-24 济南大学 Oxygen reduction catalyst and preparation method thereof
CN110911698B (en) * 2019-12-02 2022-05-27 济南大学 Oxygen reduction catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN110265677B (en) 2022-06-03

Similar Documents

Publication Publication Date Title
Meng et al. In situ coupling of Co 0.85 Se and N-doped carbon via one-step selenization of metal–organic frameworks as a trifunctional catalyst for overall water splitting and Zn–air batteries
Li et al. An extremely facile route to Co2P encased in N, P-codoped carbon layers: Highly efficient bifunctional electrocatalysts for ORR and OER
Yu et al. Metal-organic framework derived Co@ NC/CNT hybrid as a multifunctional electrocatalyst for hydrogen and oxygen evolution reaction and oxygen reduction reaction
Liu et al. Facile hydrothermal synthesis of urchin-like NiCo2O4 spheres as efficient electrocatalysts for oxygen reduction reaction
CN107051568B (en) Two cobaltous selenide@N-CT composite catalysts of a kind of analysis oxygen Fe doping and its preparation method and application
Aftab et al. Mixed CoS2@ Co3O4 composite material: An efficient nonprecious electrocatalyst for hydrogen evolution reaction
Zhu et al. Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution
CN106944141B (en) The preparation method of sheet Co-MOF nano material and its application in electro-catalysis
Qian et al. Co3O4 nanoparticles on porous bio-carbon substrate as catalyst for oxygen reduction reaction
Abdelkareem et al. Synthesis and testing of cobalt leaf-like nanomaterials as an active catalyst for ethanol oxidation
Lu et al. Earth-abundant coal-derived carbon nanotube/carbon composites as efficient bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries
Wang et al. GO clad Co3O4 (Co3O4@ GO) as ORR catalyst of anion exchange membrane fuel cell
CN110252335A (en) A kind of carbon-coating nickel ruthenium nano material and its preparation method and application
Sun et al. Enhanced electrocatalytic activity of FeCo2O4 interfacing with CeO2 for oxygen reduction and evolution reactions
Ai et al. Robust interfacial Ru-RuO2 heterostructures for highly efficient and ultrastable oxygen evolution reaction and overall water splitting in acidic media
Xiong et al. Preparation and electrocatalytic properties of spinel CoxFe3-xO4 nanoparticles
CN104810518B (en) A kind of cobalt manganese systems spinel nano material and its preparation method and application
Huang et al. Spinel CoFe2O4/carbon nanotube composites as efficient bifunctional electrocatalysts for oxygen reduction and oxygen evolution reaction
Lan et al. One-pot synthesis of NiFe-MOF/NiFe2O4 hollow spheres and their application as bifunctional ORR/OER electrocatalysts in Zn-air batteries
Song et al. Self-supported amorphous nickel-iron phosphorusoxides hollow spheres on Ni-Fe foam for highly efficient overall water splitting
Ojha et al. In-situ fabrication of manganese oxide nanorods decorated manganese oxide nanosheets as an efficient and durable catalyst for oxygen reduction reaction
Yang et al. Electrochemical deposition of CeO2 nanocrystals on Co3O4 nanoneedle arrays for efficient oxygen evolution
Nie et al. Efficient oxygen evolution reaction in SrCo0. 8Fe0. 2O3-δ perovskite and surface reconstruction for practical zinc-air batteries
Abd-Elrahim et al. Composition dependent electrocatalytic activity of Ni (OH) 2-graphene hybrid catalyst deposited by one-step vacuum kinetic spray technique
Yang et al. Fe3C/C nanoparticles encapsulated in N-doped graphene aerogel: an advanced oxygen reduction reaction catalyst for fiber-shaped fuel cells

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