CN110265677B - NiCo @ NiS-inlaid S-doped carbon nanotube composite material and preparation and application thereof - Google Patents
NiCo @ NiS-inlaid S-doped carbon nanotube composite material and preparation and application thereof Download PDFInfo
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- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 74
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 72
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
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- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
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- 239000007789 gas Substances 0.000 claims abstract description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 5
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- 229910052734 helium Inorganic materials 0.000 claims description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
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- 238000001228 spectrum Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
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- 238000005259 measurement Methods 0.000 description 6
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- 230000000630 rising effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
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- -1 Co2+ ions Chemical class 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229910018553 Ni—O Inorganic materials 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M4/00—Electrodes
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- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses a NiCo @ NiS inlaid S-doped carbon nanotube composite material and a preparation method and application thereof, wherein the composite material comprises NiCo @ NiS nano particles and S-doped carbon nanotubes, the NiCo @ NiS nano particles are inlaid on the S-doped carbon nanotubes, and the particle size of the NiCo @ NiS nano particles is 11-15 nm. The preparation method of the composite material comprises the following steps: mixing melamine, cysteine, nickel chloride hexahydrate and cobalt chloride hexahydrate according to the molar ratio of 40:2:1:1, and then grinding to obtain solid powder; placing the ground solid powder in a muffle furnace, then introducing gas in an inert atmosphere into the muffle furnace, raising the temperature of the muffle furnace to 550 ℃, and keeping the temperature for 2 hours; and raising the temperature of the muffle furnace to 800 ℃, keeping the temperature for 2 hours, and collecting the mixture after the temperature is cooled. The composite material is used for an electrocatalyst to perform double-function catalysis of oxygen reduction reaction and hydrogen evolution reaction, and has excellent performance.
Description
Technical Field
The invention belongs to the field of catalyst preparation and application, and particularly relates to an NiCo @ NiS inlaid S-doped carbon nanotube composite material and preparation and application thereof.
Background
In recent years, with the consumption of fossil energy, the increasing demand for energy, and the maturing of environmental protection consciousness, the development and research of relatively clean and sustainable energy exchange devices in countries of the world have been carried out, and among them, energy storage and conversion equipment using electrochemical reaction has received great attention. The secondary metal-air battery has the advantages of simple preparation, excellent safety performance, environmental friendliness and the like, and the zinc-air battery is known to be one of the most effective and reliable new energy technologies in the 21 st century in terms of economic benefit and environmental protection. Particularly, the theoretical density of the zinc-air battery is greatly higher than that of the traditional lithium ion battery, and the zinc-air battery can be applied to high-power equipment such as electric automobiles and the like. However, the lack of suitable air diffusion electro-mechanical catalysts has led to a lower discharge current density, lower efficiency and shorter service life of the air battery, which greatly limits the application field and industrialization pace of zinc-air batteries. At present, a noble metal catalyst such as platinum-carbon is still regarded as an electrocatalyst having the highest ORR (oxygen reduction reaction) activity. However, noble metal catalysts such as platinum are expensive to produce, have a scarce global reserve, and cannot be mass-produced and commonly used. In addition, such catalysts show good activity for ORR (oxygen reduction reaction) but do not perform well on OER (oxygen evolution reaction). And thus is greatly limited in large-scale application of the reversible air electrode catalyst. Therefore, it is very urgent to develop a low-cost bifunctional catalyst having both Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER).
Disclosure of Invention
The invention provides an S-doped carbon nanotube composite material inlaid with NiCo @ NiS, which has a structure that NiCo @ NiS nanoparticles are inlaid on an S-doped carbon nanotube, and the carbon nanotube is partially graphitized, so that the improvement of electron transmission performance and the regulation and control of a catalytic active site are synchronously realized;
the second purpose of the invention is to provide a preparation method of the S-doped carbon nanotube composite material inlaid with NiCo @ NiS, which is simple and easy to implement;
the third purpose of the invention is to provide the application of the NiCo @ NiS inlaid S-doped carbon nanotube composite material as a catalyst for oxygen reduction reaction and hydrogen evolution reaction.
In order to solve the problems, the technical scheme of the invention is as follows:
the NiCo @ NiS-embedded S-doped carbon nanotube composite material comprises NiCo @ NiS nanoparticles and S-doped carbon nanotubes, wherein the NiCo @ NiS nanoparticles are embedded on the S-doped carbon nanotubes, and the particle size of the NiCo @ NiS nanoparticles is 11-15 nm.
The invention also provides a preparation method of the NiCo @ NiS inlaid S-doped carbon nanotube composite material, which comprises the following steps:
step 1: mixing melamine, cysteine, nickel chloride hexahydrate and cobalt chloride hexahydrate according to the molar ratio of 40:2:1:1, and then grinding to obtain solid powder;
step 2: first-stage calcination: placing the solid powder ground in the step 1 in a muffle furnace, introducing gas in an inert atmosphere into the muffle furnace, raising the temperature of the muffle furnace to 550 ℃, and keeping the temperature for 2 hours;
Preferably, the gas of the inert atmosphere comprises nitrogen and/or argon and/or helium.
Preferably, the temperature rising speed of the first-stage calcining muffle furnace is 3 ℃/min.
Preferably, the temperature rising speed of the muffle furnace for the second-stage calcination is 5 ℃/min.
The invention also provides application of the NiCo @ NiS inlaid S-doped carbon nanotube composite material to an electrocatalyst for carrying out an oxygen reduction reaction and a hydrogen evolution reaction.
Preferably, the composite material is used as a catalyst for hydrogen evolution reaction under the alkaline condition that the pH value is 12-13.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
(1) the NiCo @ NiS-inlaid S-doped carbon nanotube composite material provided by the invention has excellent bifunctional catalytic activity on oxygen reduction and hydrogen evolution reaction when used as a catalyst. The doping of sulfur synergistically forms NiCo catalytic sites, effectively adjusts the electronic structure of the carbon nano tube, and improves the catalytic performance of oxygen reduction reaction and hydrogen evolution reaction. The composite material achieves hydrogen generation under alkaline conditions and can be assembled into an oxygen reduction electrode of a Zn-air battery.
(2) According to the preparation method of the NiCo @ NiS inlaid S-doped carbon nanotube composite material, provided by the invention, melamine is polymerized at 550 ℃ to form graphite carbonitride. At the same time, the nickel/cobalt-based nanoparticles produced are confined within the interlayer. The thermal annealing temperature was further increased to 800 degrees celsius so that the nickel/cobalt based nanoparticles catalyzed the growth of carbonitride. And finally obtaining the product which is the NiCo @ NiS inlaid S-doped carbon nanotube composite material. The preparation method has the advantages of in-situ synthesis, simple synthesis method and low cost, so that the price of the prepared composite material as a catalyst is relatively low, and no toxic or harmful substance is added in the preparation method, so that the preparation method is green and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of NiCo @ NiS inlaid S-doped carbon nanotube composite fabrication;
FIG. 2 is a scanning electron microscope picture of a NiCo @ NiS damascene S-doped carbon nanotube composite;
FIG. 3 is a graph of the particle size distribution of NiCo @ NiS nanoparticles;
FIG. 4 is a high resolution TEM image of a NiCo @ NiS inlaid S-doped carbon nanotube composite;
FIG. 5 is a high resolution transmission electron microscope image of NiS;
FIG. 6 is an energy dispersion spectrum of a NiCo @ NiS damascene S-doped carbon nanotube composite;
FIG. 7 is an XPS survey of a NiCo @ NiS damascene S-doped carbon nanotube composite;
FIG. 8 is an XPS fine spectrum of S2P in a composite material according to the present invention;
FIG. 9 is an XPS fine spectrum of Co2p in a composite material according to the present invention;
FIG. 10 is an XPS fine spectrum of Ni2p3/2 in a composite material according to the present invention;
FIG. 11 is an LSV curve of the oxygen evolution reaction of the composite of the present invention as an electrocatalyst and Pt/C under the same test conditions;
FIG. 12 is an LSV curve of the oxygen evolution reaction of the composite material of the present invention as an electrocatalyst at different rotation speeds;
FIG. 13 is a graph showing the cross-effect of measuring the oxygen evolution reaction of the composite of the present invention as an electrocatalyst with a commercial Pt/C catalyst;
FIG. 14 is a graph of stability measurements of the oxygen evolution reaction of the composite of the present invention as an electrocatalyst with a commercial Pt/C catalyst;
FIG. 15 is a LSV curve of hydrogen evolution reaction of the composite of the present invention as an electrocatalyst with a commercial Pt/C catalyst under the same test conditions;
FIG. 16 is a graph showing the stability test of the hydrogen evolution reaction of the composite material of the present invention as an electrocatalyst.
Detailed Description
The following provides a NiCo @ NiS inlaid S-doped carbon nanotube composite material and its preparation and application in further detail with reference to the accompanying drawings and specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims.
In this example, referring to fig. 1, a NiCo @ NiS mosaic S-doped carbon nanotube composite was prepared as follows:
(1) mixing 20mmol of melamine, 1mmol of cysteine, 0.5mmol of nickel chloride hexahydrate and 0.5mmol of cobalt chloride hexahydrate, and then grinding to obtain solid powder;
(2) first-stage calcination: putting the solid powder obtained in the step (1) into a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2 hours;
(3) and (3) third-stage calcination: then heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and collecting after the temperature is cooled to the room temperature.
FIG. 1 is a schematic diagram of the preparation method, in brief, NiCo @ NiS mosaic S-doped carbon nanotube composite material is synthesized by simple thermal condensation of melamine, cysteine, cobalt chloride hexahydrate and nickel chloride hexahydrate at 550 ℃ and then heating hybridization at 800 ℃. The melamine polymerizes at 550 degrees celsius to form graphitic carbonitride with the resulting nickel/cobalt based nanoparticles confined within the interlayer. The thermal annealing temperature was further increased to 800 degrees celsius so that the nickel/cobalt based nanoparticles catalyzed the growth of carbonitride. And finally obtaining the product which is the NiCo @ NiS inlaid S-doped carbon nanotube composite material. The preparation method has the advantages of in-situ synthesis, simple synthesis method, no addition of any toxic and harmful substances, and environmental protection.
A NiCo @ NiS-inlaid S-doped carbon nanotube composite, the composite comprising NiCo @ NiS nanoparticles, S-doped carbon nanotubes, the NiCo @ NiS nanoparticles being inlaid on the S-doped carbon nanotubes, the NiCo @ NiS nanoparticles having a particle size of about 13nm (as shown in fig. 3).
As a result of observing the microstructure of the prepared composite material using a scanning electron microscope and a high-resolution transmission electron microscope, as shown in fig. 2, 3, 4, and 5, it can be seen from fig. 2 that the composite material is uniformly composed of ultra-long carbon nanotubes on which nanoparticles are uniformly distributed. The inner diameter of the carbon nanotubes is about 20nm, which is larger than commercial carbon nanotubes (about 7 nm). From fig. 3, it can be seen that the size of NiCo @ NiS nanoparticles is about 13nm, and referring to fig. 4 and 5, high resolution transmission electron microscope images further reveal the high crystallinity characteristic of NiCo @ NiS mosaic S-doped carbon nanotube composites. The side walls of the synthesized carbon nanotubes show irregular and corrugated graphene-like morphology with interlayer spacing, indicating that the carbon nanotubes are partially graphitized. NiCo @ NiS nanoparticles embedded on carbon nanotubes exhibit two sets of lattice stripes, 0.206nm corresponding to the (111) crystal plane of the NiCo alloy phase (fig. 4). The high resolution projection electron microscope image of NiS (fig. 5) gives a lattice spacing of 0.25nm, corresponding to the (021) plane of NiS.
Fig. 6 is an energy dispersion spectrum of NiCo @ NiS mosaic S-doped carbon nanotube composite material, from which it can be seen that carbon, cobalt, nickel, and sulfur are distributed throughout the sheet, confirming the presence of carbon, cobalt, nickel, and sulfur in the composite material, and the mass ratios are carbon (80.46%), oxygen (8.97%), sulfur (1.44%), nickel (3.88%), and cobalt (5.25%), respectively.
FIG. 7 is an XPS survey of a NiCo @ NiS-inlaid S-doped carbon nanotube composite showing that carbon, oxygen, sulfur, nickel, and cobalt elements are present in the composite and are substantially consistent with energy dispersive spectroscopy analysis.
FIG. 8 is an XPS fine spectrum of S2P showing the major separation in FIG. 8 into four peaks at 165.2eV,163.9eV and 162.4eV corresponding to the S-O bond, C-S-C bond and Ni-S/Co-S bond in NiCo @ NiS nanoparticles, respectively. FIG. 9 is an XPS fine spectrum of Co2p showing the predominant presence of five peaks at 778.6eV,780.4eV,786.2eV,796.5eV and 803.7eV, with the strong peaks at 786.2eV and 803.7eV being satellite peaks attributable to oscillatory excitation of high spin Co2+ ions; the peaks at 778.6eV and 780.4eV are attributable to the binding energy of the 2p3/2 orbital of the Co species, while the peak at 796.5eV corresponds to the 2p1/2 orbital of the Co species. The peak at about 780.4eV is attributed to Co-O and Co-S, while the peak at about 778.6eV corresponds to the Co0 phase. FIG. 10 is an XPS fine spectrum of Ni2p3/2 showing 855.1eV and 859.6eV peaks corresponding to the NiO phase and Ni-S/Ni-O composition. All these results further confirm the formation of NiCo @ NiS nanoparticles and the successful doping of elemental sulfur in carbon nanotubes.
The NiCo @ NiS inlaid S-doped carbon nanotube composite material is used for electrochemical testing of a catalyst, and the specific implementation mode is as follows:
electrochemical measurements were performed on an electrochemical workstation (CHI 760D, CH Instruments, inc., Shanghai, China) coupled with a PINE Rotating Disk Electrode (RDE) (PINE Instruments co.ltd.usa). A standard three-electrode electrochemical cell equipped with a gas flow system was used during the measurements. Prior to measurement, a rotating disk electrode (RDE, diameter 5.0 mm) was first polished with 5.0. mu. mol/L, 3.0. mu. mol/L, and 0.05. mu. mol/L alumina slurries in this order, and then ultrasonically washed in water and ethanol, respectively, for 1 minute. The cleaned electrode was dried with high purity nitrogen vapor. NiCo @ NiS/S-CNTs (CNTs refers to carbon nanotubes) catalyst ink was prepared by dispersing 5.0 milligrams of the composite powder of this example into a mixture comprising 100 microliters of Nafion (perfluorosulfonic acid) solution (0.5 wt%) and 900 microliters of ethanol, followed by sonication for 2 minutes. Then 12 microliters of catalyst ink was dropped onto the surface of a Glassy Carbon (GC) electrode to a catalyst loading of 305 micrograms per square centimeter. For comparison, a commercial Pt/C catalyst ink having the same concentration was also prepared, which was the same procedure as the NiCo @ NiS damascene S-doped carbon nanotube catalyst ink.
The ORR performance of the catalyst was studied by Linear Scanning Voltammogram (LSV) measurements in a 0.1mol/LKOH solution saturated with oxygen. The LSV curves were measured at scan rates of 10 millivolts per second at different rotation rates of 625rpm, 900rpm, 1225rpm, 1600rpm and 2025 rpm. All potentials in this work were recorded against an Ag/AgCl reference electrode. The number of electron transfers per molecule of oxygen (n) during ORR was calculated by the Koutecky-Levich (K-L) equation:
B＝0.62nF(D0)2/3υ-1/6C0 (2)
JK＝nFkC0 (3)
wherein J is the current density measured during oxygen reduction, JKIs the dynamic current density, ω is the electrode rotation angular velocity (ω 2 π N, N is the linear rotation speed), B is the slope of the K-L curve, N represents the electron transfer number per molecule of oxygen, and F is the Faraday constant (F-96485℃ mol.)-1)，D0Is O2Diffusion coefficient in 0.1mol/L KOH (1.9X 10-5cm2s-1), v is the kinetic viscosity (0.01 cm)2s-1)，C0Is O2Volume concentration of (1.2X 10)-3mol·L-1)。
FIG. 11 is NiCo @ NiS damascene S-doped carbon nanotube catalyst and Pt/C in O2Saturated 0.1mol/L KOH solution at 10 mV. s-1And a rotation speed of 1600rpm, the LSV curve under the speed condition was measured, as shown in fig. 11, the Linear Scanning Voltammogram (LSV) curve of the NiCo @ NiS mosaic S-doped carbon nanotube sample was measured, and the Pt/C electrocatalyst was used as a reference. The studied electrocatalysts NiCo @ NiS-intercalated S-doped carbon nanotubes and commercial Pt/C showed onset potentials (vs. Ag/AgCl) of-0.01V and-0.03V, respectively, -0.14V and-0.15V are the half-wave potentials of the electrocatalysts NiCo @ NiS-intercalated S-doped carbon nanotubes and commercial Pt/C, respectively. The initial potential and half-wave potential values of the NiCo @ NiS inlaid S-doped carbon nanotube and Pt/C are very close, which shows that the NiCo @ NiS inlaid S-doped carbon nanotube has excellent oxygen reduction activity. In addition, NiCo @ NiS-mosaiced S-doped carbon nanotubes also showed the highest current range possible to be investigated in all catalysts, further showing their excellent oxygen reduction properties.
FIG. 12 shows the rotation speed of the rotor from O2LSV curves of NiCo @ NiS-mosaic S-doped carbon nanotubes obtained from saturated 0.1mol/L KOH solutions. S-doped carbon nanotubes for NiCo @ NiS damascene based on the corresponding Koutecky-Levich (K-L) diagramThe average value of the number of transferred electrons at-0.40V to-0.55V was calculated to be 3.75, and an approximate value with respect to the theoretical value of the Pt/C catalyst (n ═ 4.0) indicates near four electron oxygen reduction processes.
Fig. 13 is a graph of the cross effect of NiCo @ NiS tessellated S-doped carbon nanotubes and Pt/C catalyst under the same experimental conditions and fig. 14 is a measurement of the durability of NiCo @ NiS tessellated S-doped carbon nanotubes and Pt/C catalyst under the same experimental conditions, showing that NiCo @ NiS tessellated S-doped carbon nanotubes have high tolerance and good stability to methanol cross effect.
Polarization curve of hydrogen evolution reaction at room temperature N2Saturated 0.1mol/LKOH (pH 12.5) at 5.0mVs-1Is obtained.
FIG. 15 shows NiCo @ NiS damascene S-doped carbon nanotubes and Pt/C at 1600rpm with a scan rate of 5mVs-1N of (A)2Linear sweep voltammogram saturated in 0.1mol/L KOH, fig. 16 is the stability of NiCo @ NiS-mosaiced S-doped carbon nanotubes in hydrogen evolution reactions. As shown in FIG. 15, the current density for NiCo @ NiS damascene S-doped carbon nanotubes and Pt/C is 10mAcm-2The measurement potentials are-1.16V and-1.01V respectively; respectively proves that the NiCo @ NiS inlaid S-doped carbon nano-tube has certain catalytic activity of hydrogen evolution reaction. Furthermore, it can be seen from fig. 16 that NiCo @ NiS mosaic S-doped carbon nanotubes also exhibit high durability in hydrogen evolution reactions.
In summary, the NiCo @ NiS-inlaid S-doped carbon nanotube can be used as a catalyst in an oxygen reduction reaction and a hydrogen evolution reaction, and the dual-functional performance of the NiCo @ NiS-inlaid S-doped carbon nanotube in the oxygen reduction reaction and the hydrogen evolution reaction can be attributed to the synergistic effect of the NiCo, NiS and S doping on the catalytic active sites in the carbon nanotube structure.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (5)
1. The application of the NiCo @ NiS-inlaid S-doped carbon nanotube composite material is characterized in that the composite material is used for an electrocatalyst to perform an oxygen reduction reaction and a hydrogen evolution reaction, the composite material comprises NiCo @ NiS nano particles and S-doped carbon nanotubes, the NiCo @ NiS nano particles are inlaid on the S-doped carbon nanotubes, and the particle size of the NiCo @ NiS nano particles is 11-15 nm;
the preparation method of the composite material comprises the following steps:
step 1: mixing melamine, cysteine, nickel chloride hexahydrate and cobalt chloride hexahydrate according to the molar ratio of 40:2:1:1, and then grinding to obtain solid powder;
step 2: first-stage calcination: placing the solid powder ground in the step 1 in a muffle furnace, introducing gas in an inert atmosphere into the muffle furnace, raising the temperature of the muffle furnace to 550 ℃, and keeping the temperature for 2 hours;
step 3, second-stage calcination: and raising the temperature of the muffle furnace to 800 ℃, keeping the temperature for 2 hours, and collecting the mixture after the temperature is cooled.
2. The use of a NiCo @ NiS mosaic S-doped carbon nanotube composite material as claimed in claim 1, wherein the catalyst is used for hydrogen evolution reaction under basic conditions of pH = 12-13.
3. Use of a NiCo @ NiS mosaic S-doped carbon nanotube composite material according to claim 1, wherein the gas of the inert atmosphere comprises nitrogen and/or argon and/or helium.
4. Use of a NiCo @ NiS tessellated S-doped carbon nanotube composite material according to claim 1, characterized in that the first stage calcination muffle furnace ramp rate is 3 ℃/min.
5. The use of a NiCo @ NiS tessellated S-doped carbon nanotube composite material according to claim 1, wherein the second stage calcination muffle ramp rate is 5 ℃/min.
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