CN113394415A - Oxygen-enriched vacancy NC @ BiOCl-CNTs composite material as well as preparation method and application thereof - Google Patents
Oxygen-enriched vacancy NC @ BiOCl-CNTs composite material as well as preparation method and application thereof Download PDFInfo
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Images
Classifications
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- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- 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
Abstract
The invention relates to the technical field of electrocatalytic oxidation reduction, and in particular relates to an oxygen-enriched air NC @ BiOCl-CNTs composite material as well as a preparation method and application thereof. The oxygen-enriched vacancy NC @ BiOCl-CNTs composite material is prepared by taking a PDA @ Bi-CNTs composite material as a precursor through carbonization and acid leaching. The oxygen-enriched vacancy NC @ BiOCl-CNTs composite material has high-efficiency oxygen reduction performance in an alkaline solution; the NC @ BiOCl-CNTs catalyst is good as a cathode material of a zinc-air batteryGood long-term stability, no fading after 155 hours, high power density of 170.7mW/cm2。
Description
Technical Field
The invention relates to the technical field of electrocatalytic oxidation reduction, and in particular relates to an oxygen-enriched vacancy NC @ BiOCl-CNTs composite material as well as a preparation method and application thereof.
Background
Currently, the demand for energy continues to increase, creating an energy crisis based on fossil fuels, leading to an increased interest in renewable clean energy storage and conversion systems. Among various energy conversion devices, zinc-air batteries have the advantages of high energy density, low cost, zero emission, and the like. However, the key to improving the overall performance of zinc-air cells is to overcome the slow four electron transfer reaction kinetics of oxygen reduction, which greatly limits the rapid development of this field.
Noble metals (Pt, Ir and Ag) and their oxides are well known oxygen reduction catalysts, but their scarcity and high cost limit their large scale application. Therefore, it is desirable to develop a new redox catalyst composite that is efficient, inexpensive, and durable.
Disclosure of Invention
In order to solve the technical problems, the invention provides an oxygen-enriched vacancy NC @ BiOCl-CNTs composite material, a preparation method and application thereof, and the intrinsic catalytic activity of the catalyst is improved through abundant oxygen holes.
One technical scheme of the invention is that the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material takes CNTs as a carrier and a carbon nitride compound with a nano structure net-coated BiOCl nano sheet composite material as a load.
According to the second technical scheme, the preparation method of the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material is characterized in that PDA @ Bi-CNTs are used as precursors, the precursors are carbonized to obtain NC @ Bi-CNTs, and then aqua regia is impregnated to obtain the NC @ BiOCl-CNTs composite material.
According to the preparation method, the NC @ Bi-CNTs precursor is obtained after high-temperature carbonization treatment, the obtained precursor is soaked in aqua regia, and reduced metal ions at high temperature are removed to directly form the NC @ BiOCl-CNTs composite material, so that the preparation method is simple to operate and environment-friendly.
Further, the preparation method of the PDA @ Bi-CNTs precursor comprises the following steps:
the method comprises the steps of taking a pretreated carbon nano tube, F127, bismuth salt and 2-amino terephthalic acid as raw materials, carrying out primary solvothermal reaction, cooling, transferring a product into an acetone solution, dropwise adding a dopamine-acetone solution, and carrying out secondary solvothermal reaction to obtain a PDA @ Bi-CNTs precursor.
F127 is poloxamer with the molecular formula of HO (C)2H4O)m·(C3H6O)nH is a polyoxyethylene polyoxypropylene ether block copolymer.
Further, the preparation of the pretreated carbon nanotube includes: placing the carboxyl multi-walled carbon nanotube into a concentrated nitric acid (commercial concentrated nitric acid with the mass fraction of about 68%) solution, heating and refluxing, and then cleaning to be neutral to obtain a pretreated nanotube;
further, the mixing mass-volume ratio of the carboxyl multi-walled carbon nano-tube to the concentrated nitric acid is 0.2 g: 30mL, the heating thermal reflux treatment temperature is 60 ℃, and the heating treatment time is 4 hours;
furthermore, the addition mass ratio of the pretreated carbon nano tube to the F127 is (5-7) to 100, the addition molar ratio of the bismuth salt to the 2-amino terephthalic acid is (3-4) to 1, and the mass molar ratio of the pretreated carbon nano tube to the bismuth salt is 6g to (6-8) mol;
the reflux treatment is to remove carbon impurities which are easy to oxidize, promote the stability of the carbon tube, modify the carbon tube in a heating environment, and form strong interface combination by utilizing concentrated nitric acid treatment in order to introduce a large amount of hydroxyl and carboxyl.
Further, the solvent in the primary solvent thermal reaction is N, N-dimethylformamide, the reaction temperature is 170-180 ℃, and the reaction time is 6-8 h;
further, the dopamine-acetone solution is a mixture of dopamine hydrochloride and an acetone solution with the mass volume ratio of 0.2: 10mL, and the mass ratio of the dopamine hydrochloride to the pretreated nanotube in the secondary solvothermal reaction system is 10: 3;
further, the reaction temperature of the secondary solvothermal reaction is 170-180 ℃, and the reaction time is 6-8 h.
Further, the carbonization treatment specifically includes: the PDA @ Bi-CNTs precursor and melamine are mixed and ground according to the mass ratio of (1-2) to 10, then the mixture is transferred into an argon atmosphere, and the mixture is heated to 900-950 ℃ at the heating rate of 5 ℃/min and calcined for 2-3h and cooled to obtain NC @ Bi-CNTs.
The prepared sample has higher graphitization degree and conductivity due to the proper calcination temperature, the electron transfer in the electrochemical ORR process is promoted, but the catalyst is easy to sinter to destroy the activity of the catalyst due to the overhigh calcination temperature; the calcination time can affect the structure of the catalyst, so that the combination effect of the load substance and the carrier is changed, and the catalytic effect is affected; the addition of melamine increases the doping amount of N element in the graphitization process, and high N doping forms more active centers and changes the electronegativity of adjacent C atoms, thereby improving ORR activity.
Further, the aqua regia impregnation specifically comprises: and (3) transferring the NC @ Bi-CNTs into aqua regia to be soaked for 8-12h, centrifuging, collecting precipitates, washing the precipitates to be neutral, and drying to obtain the NC @ BiOCl-CNTs composite material with the oxygen-enriched vacancy.
In the third technical scheme of the invention, the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material is used as a catalyst for preparing an electrode material.
Fourth of the technical schemes of the invention, a redox electrode takes the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material as a catalyst material, and the preparation method of the redox electrode comprises the following steps: mixing the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material with isopropanol, water and 5 wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on the surface of the polished working electrode, and drying to obtain the redox electrode.
The fifth technical scheme of the invention is that the cathode electrode of the zinc-air battery takes the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material as a catalyst material, and the preparation method of the cathode electrode of the zinc-air battery comprises the following steps: mixing the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material with isopropanol, water and 5 wt% of perfluorinated sulfonic acid solution to obtain a catalyst ink, dripping the catalyst ink on hydrophilic carbon fiber paper, and drying to obtain the zinc-air battery cathode electrode.
Further, in the preparation process of the redox electrode and the cathode electrode of the zinc-air battery, the mixing mass volume ratio of the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material to isopropanol, water and 5 wt% of perfluorosulfonic acid solution is 4 mg: 245 μ L: 745 μ L: 10 μ L.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method increases the proportion of oxygen vacancies in the composite material, and the high proportion of oxygen vacancies can enhance charge transfer, promote oxygen dissociation reaction and improve ORR performance. During the carbonization process, melamine rich in nitrogen is also introduced, the crystal lattice O is partially substituted by N, so that the electron density of oxygen vacancies is correspondingly increased, and the intrinsic catalytic activity of the catalyst is improved through rich oxygen vacancies. The melamine can increase the active sites of the catalyst, the carbon nano tube is favorable for charge transfer, and the oxygen-containing functional group on the carbon nano tube can be used as an adhesive to anchor the BiOCl nano sheet on a carbon matrix, so that the performance of the material is better.
2. The BiOCl composite material is a photocatalytic material with high activity and is widely applied to the field of photocatalysts. However, in the oxygen reduction process, the main group metals, such as Mg, Al and Bi, are inert and also do not have empty and filled main orbitals critical to catalytic cycling. The high-activity NC @ BiOCl-CNTs catalyst is prepared by a reasonable strategy, and the nitrogen-doped carbon-coated BiOCl catalytic material obtained by soaking in a strong-acid aqua regia solution has good ORR catalytic performance, long stability and high power density when being applied to a zinc-air battery, so that the N-doped carbon-encapsulated BiOCl-CNTs hybrid is prepared by a controllable method, and the excellent performance is attributed to N doping, oxygen vacancy and BiOCl active sites.
3. The oxygen-enriched vacancy NC @ BiOCl-CNTs composite material prepared by the invention has high-efficiency oxygen reduction performance in an alkaline solution; as a zinc-air battery cathode material, the NC @ BiOCl-CNTs catalyst has good long-term stability, does not decline after being kept for 155 hours, has high power density and can reach 170.7mW/cm2。
Drawings
FIG. 1 is an X-ray powder diffraction pattern of NC @ BiOCl-CNTs prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of NC @ BiOCl-CNTs prepared in example 1 of the present invention; the method comprises the following steps of a, etching a piece of NC @ Bi-CNTs material by using aqua regia, b, c, d, e and f, wherein a is a scanning electron microscope picture of the NC @ Bi-OCl-CNTs material before aqua regia etching, b is a scanning electron microscope picture of the NC @ BiOCl-CNTs material after aqua regia etching, c is a transmission electron microscope picture of the NC @ BiOCl-CNTs material after aqua regia etching, d is a high-power transmission electron microscope picture of the NC @ BiOCl-CNTs material after aqua regia etching, e is a high-power transmission electron microscope picture of the corresponding position of the picture d, and f is an element distribution picture of the NC @ BiOCl-CNTs material after aqua regia etching;
FIG. 3 is an X-ray photoelectron spectrum of a composite material prepared in examples 1 to 3 of the present invention;
fig. 4 is a CV curve of the redox electrode prepared in effect verification 1 of the present invention;
FIG. 5 is a RRDE curve of the redox electrode prepared in the verification of the effect 1 of the present invention at a rotation speed of 1600 rpm;
FIG. 6 shows H of the redox electrode prepared in the verification of the Effect 1 of the present invention2O2Yield and electron transfer number;
fig. 7 is a tafel slope of the redox electrode prepared in effect verification 1 of the present invention;
FIG. 8 is a RRDE curve (a) and a K-L graph (b) of an electrode prepared from NC @ BiOCl-CNTs in the effect verification 1 of the invention at different rotating speeds;
FIG. 9 shows the corresponding H of RRDE curves of electrodes prepared from NC @ BiOCl-CNTs in the effect verification 1 of the invention at different rotating speeds2O2Yield and electron transfer number;
fig. 10 is a schematic structural view of a performance diagram of a zinc-air battery in effect verification 2 of the present invention;
fig. 11 is a graph showing the specific capacity of the catalyst in the zinc-air battery in effect verification 2 of the present invention;
fig. 12 is a graph of the discharge polarization and power density of a zinc-air cell with catalyst in the zinc-air cell of effect verification 2 of the present invention;
fig. 13 is a graph of open circuit voltage of a zinc-air battery in effect verification 2 of the present invention;
fig. 14 is a picture of two groups of zinc-air batteries connected in series to light a red LED in the effect verification 2 of the present invention;
FIG. 15 is a discharge curve of a zinc-air battery prepared by using NC @ BiOCl-CNTs as a catalyst in the effect verification 2 of the invention under different current densities;
fig. 16 is a constant current discharge and charge voltage curve of a zinc-air battery in effect verification 2 of the present invention;
fig. 17 is a comparison of voltage differences between the first turn and the last turn of fig. 16 in the effect verification 2 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the following examples of the present invention, a method for preparing pretreated carbon nanotubes comprises:
placing the carboxyl multi-walled carbon nano-tube into a concentrated nitric acid solution according to the mass-volume ratio of 2g to 300mL, carrying out oil bath for 4h at the temperature of 60 ℃, cooling to room temperature, and washing with deionized water to be neutral to obtain the pretreated carbon nano-tube.
Example 1
(1) 0.06g of pretreated carbon nanotube, 1g F127 g of bismuth nitrate pentahydrate, 2.9104g of bismuth nitrate pentahydrate and 0.2717g of 2-aminoterephthalic acid (namely, the molar ratio of bismuth salt to 2-aminoterephthalic acid is 4: 1) are weighed and dissolved in 60mL of DMF solution to prepare a uniform mixed solution;
(2) the homogeneous mixed solution was transferred to a stainless steel autoclave and maintained at 180 ℃ for 8 hours. And (3) after cooling at room temperature, dispersing the obtained brown powder into 65mL of acetone solution, dripping 10mL of 20mg/mL dopamine-acetone solution (0.2g dopamine hydrochloride is added into 10mL acetone solution), stirring for 30 minutes, sealing in an autoclave again, carrying out hydrothermal treatment at 180 ℃ for 8 hours, and collecting the precipitate by a centrifugal method to obtain the PDA @ Bi-CNTs precursor.
(3) 0.1g of PDA @ Bi-CNTs precursor and 1g of melamine are weighed, uniformly ground and calcined for 2 hours at 950 ℃ in an argon atmosphere. And cooling to room temperature, and collecting powder to finish the preparation of NC @ Bi-CNTs.
(4) Soaking the carbonized NC @ Bi-CNTs sample in aqua regia (HNO)3 HCl 1/3), collecting the precipitate by centrifugation, washing the precipitate with deionized water until the solution is neutral, and drying to obtain the final sample NC @ BiOCl-CNTs.
FIG. 1 is an X-ray powder diffraction pattern of NC @ BiOCl-CNTs prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of NC @ BiOCl-CNTs prepared in example 1 of the present invention; wherein a and b are scanning electron microscope pictures, c is a transmission electron microscope picture, d is a high-power transmission electron microscope picture, e is a high-power transmission electron microscope picture of the corresponding position of the picture d, and f is an element distribution picture (a is a picture of an NC @ Bi-CNTs material before aqua regia etching, and b-f is a picture of an NC @ BiOCl-CNTs material after etching);
by analyzing fig. 1 and 2: FIG. 1 shows that the composite material is obtained by converting Bi nanoparticles into BiOCl species after aqua regia etching so as to obtain NC @ BiOCl-CNTs hybrid material. The 4 distinct characteristic peaks at 11.98 °, 25.86 °, 32.50 ° and 33.45 ° are attributed to the (001), (101), (110) and (102) crystal planes of BiOCl (JCPDS: 06-0249). Furthermore, in fig. 2a, the surface of the carbon nanotubes is modified by dense nanoparticles. FIG. 2b shows that the NC @ BiOCl-CNTs catalyst surface becomes relatively smooth after aqua regia etching, probably because most of the Bi particles are dissolved. In fig. 2c, the TEM image shows that the nanoparticles are randomly distributed on the surface of the carbon nanotubes. 2d-e high resolution TEM images, the clear lattice spacing of 0.34nm is typical of the C (002) crystal plane, while the lattice fringes of 0.22 and 0.27nm belong to the (112) and (102) crystal planes of BiOCl, respectively. FIG. 2f is a HAADF-STEM and corresponding element mapping showing that the Bi, Cl, C, N and O elements are well distributed throughout the catalyst structure of NC @ BiOCl-CNTs.
Example 2
The steps (1) and (2) are the same as those in example 1;
(3) weighing 0.1g of PDA @ Bi-CNTs precursor, uniformly grinding, calcining for 2 hours at 950 ℃ in an argon atmosphere, cooling to room temperature, and collecting powder to finish the preparation of C @ Bi-CNTs.
(4) Soaking the carbonized C @ Bi-CNTs sample in aqua regia (HNO)3 HCl 1/3), collecting the precipitate by centrifugation, washing the precipitate with deionized water until the solution is neutral, and drying to obtain the final sample C @ BiOCl-CNTs.
Example 3
(1) 1g F127 g, 2.9104g of bismuth nitrate and 0.2717g of 2-aminoterephthalic acid (i.e., molar ratio 4: 1) were weighed out and dissolved in 60mL of DMF solution to prepare a homogeneous mixed solution.
(2) The homogeneous mixed solution was transferred to a stainless steel autoclave and maintained at 180 ℃ for 8 hours. After cooling at room temperature, dispersing the obtained brown powder into 65mL of acetone solution, dripping 10mL of 20mg/mL dopamine-acetone solution, stirring for 30 minutes, sealing in an autoclave again, carrying out hydrothermal treatment at 180 ℃ for 8 hours, and collecting the precipitate by a centrifugal method to obtain PDA @ Bi.
(3) 0.1g of PDA @ Bi precursor and 1g of melamine are weighed, uniformly ground and calcined for 2 hours at 950 ℃ in an argon atmosphere. And cooling to room temperature, and collecting powder to finish the preparation of NC @ Bi.
(4) Soaking the carbonized sample in aqua regia (HNO)3 HCl 1/3), the precipitate was collected by centrifugation, washed with deionized water until the solution was neutral, and dried to give the final sample NC @ BiOCl.
The X-ray photoelectron spectra of the composite materials prepared in examples 1-3 are shown in FIG. 3; according to the XPS scheme of FIG. 3. The high resolution XPS spectrum of O1s was deconvoluted into BiOCl lattice oxygen (530.0eV), oxygen vacancies (531.1eV), C-O (532.2eV), and adsorbed H2O/C ═ O (533.5 eV). A high proportion of oxygen vacancies can enhance charge transfer, spiking into the dissociation reaction, and thereby improve ORR performance. The oxygen vacancies in the NC @ BiOCl-CNTs and NC @ BiOCl materials were 33.7% and 37.9%, respectively, while the C @ BiOCl-CNTs contained only 18.6%, indicating that N doping promotes the formation of oxygen defects.
The preparation of the redox electrode using the Pt/C catalyst, the composite material of examples 1-3 as the catalyst, and the rotating ring disk electrode as the working electrode, respectively, was as follows:
polishing the working electrode on a felt polishing pad by using 0.05 mu m of alumina, and then cleaning the working electrode for three times by using water, 0.5mol/L sulfuric acid and ethanol for later use;
4mg of the catalyst powder was weighed, mixed with 245. mu.L of isopropanol, 745. mu.L of water and 10. mu.L of a 5 wt% Nafion solution, and sonicated for 30 minutes. 19.610 μ L of catalyst ink was added dropwise to the polished RRDE surface using a pipette and dried in the air. The catalyst loading on the working electrode was 0.318 mg/cm2The Pt/C catalyst load is 0.081mg/cm2。
Oxygen reduction testing was performed on a CHI 760E electrochemical workstation (CH Instruments, Chenhua Co, China) using a three electrode system. A typical three-electrode system is adopted, a carbon rod is taken as a counter electrode, and KCI saturated Ag/AgCl is taken as a reference electrode. Before testing, add O2Bubbling from the electrolyte for 30 minutes, and maintaining the bubbling state during the measurement to maintain O in the solution2The saturated state of (c). Cyclic Voltammetry (CV) test at 50 mV/s sweep in 0.1M KOH solutionAt a drawing rate of N2In a saturated solution. At O2Linear scanning tests (LSV) were performed in saturated 0.1M KOH solutions at different spin rates (400-2025 rpm) and at a scan rate of 10 mV/s. Measurement of the number of electron transfers and H in the ORR at 1600rpm with RRDE2O2Yield. The specific formula is as follows:
wherein iDAnd iRRespectively the disk current and the ring current. N is the collection efficiency of the platinum ring (N ═ 0.37). The results are shown in FIG. 4; wherein a is a CV curve of the redox electrode, b is an RRDE curve of the redox electrode at 1600rpm, and c is H of the redox electrode2O2Yield and electron transfer number, d is the Tafel slope of the redox electrode, e is the RRDE curve of the electrode prepared from NC @ BiOCl-CNTs at different rotating speeds, f is the H corresponding to the RRDE curve of the electrode prepared from NC @ BiOCl-CNTs at different rotating speeds2O2Yield and electron transfer number
From fig. 4-9 it can be derived that: in FIG. 4, NC @ BiOCl-CNTs catalyst is in O2Shows a distinct redox peak in the case of saturation, with a potential of 0.87V, more positive than the reduction peaks of the C @ BiOCl-CNTs and NC @ BiOCl catalysts. Also shown in FIG. 5 is the greater limiting current density of 5.2mA cm for the NC @ BiOCl-CNTs catalyst at 0.2V-2And half-wave potential 0.85V, compared to C @ BiOCl-CNTs and NC @ BiOCl catalysts. FIG. 6 shows NC @ BiOCl-CNTs catalyst H in the range of 0.2-0.8V2O2The yield is lower than 20%, the electron transfer number is close to 4, and the ORR kinetic path is met. The Tafel slope of the NC @ BiOCl-CNTs catalyst in FIG. 7 is 68.7mV dec-1The catalyst is far lower than C @ BiOCl-CNTs and NC @ BiOCl catalysts, and the rapid reaction kinetics is verified. A series of LSV measurements at rotation speeds from 400-2050rpm are made in FIG. 8a, showing the current density as the rotation speed increasesAnd the increase, the average number of transferred electrons in the voltage range of 0.3-0.7V of the NC @ BiOCl-CNTs catalyst calculated from the graph of FIG. 8b K-L is about 4. FIG. 9 further evaluation H2O2The yield and the number of transferred electrons were in accordance with the results of the K-L diagram (note that 20 wt% Pt/C in the diagram is a product type, 0.081 mg/cm)2Is the catalyst loading).
Zinc-air cell testing:
the preparation method of the catalyst ink prepared by the zinc-air battery test is the same as the preparation method of the effect verification 1.
The electrolyte of the zinc-air battery is 6.0M KOH +0.2M Zn (AC)2The mixed solution of (1).
Dropping catalyst ink on hydrophilic carbon fiber paper (1 x 2 cm)2) And using a polished zinc plate as an anode. The catalyst loading was 2.0mg cm-2。
The test results are shown in FIGS. 10-17; fig. 10 is a schematic diagram of a zinc-air battery structure, fig. 11 is a catalyst specific capacity, fig. 12 is a discharge polarization and power density curve of a zinc-air battery with a catalyst, fig. 13 is a zinc-air battery open-circuit voltage graph, fig. 14 is a picture of two groups of zinc-air batteries connected in series and used for lighting red LEDs, fig. 15 is a discharge curve of a zinc-air battery prepared by using NC @ BiOCl-CNTs as a catalyst under different current densities, fig. 16 is a zinc-air battery constant current discharge and charge voltage curve, and fig. 17 is a voltage difference comparison of a first circle and a last circle of fig. 16.
From fig. 10 to 17 it can be derived: in fig. 10 is an assembled zinc-air cell device, exploring the practical application of NC @ BiOCl-CNTs in energy sources. FIG. 11 is a graph of specific catalyst capacity, with a plateau voltage of 1.25V for NC @ BiOCl-CNTs as zinc-air cathode material, which is 1.17V higher than the plateau voltage of Pt/C. In addition, the NC @ BiOCl-CNTs catalyst is at 10mA cm-2At a discharge current density of 724mA h g-1The specific capacity of the composite is higher than that of a Pt/C assembled zinc-air battery. FIG. 12 shows that the power density of the NC @ BiOCl-CNTs catalyst in zinc-air is 170.7mW cm-2Much higher than the Pt/C power density of 129.6mW cm-2. FIG. 13 shows that NC @ BiOCl-CNTs catalyst provides 1.51V stabilization in a zinc-air cellOpen circuit voltage, higher than commercial Pt/C catalyst. FIG. 14 shows that two cells in series can light a 3.0V red Light Emitting Diode (LED) when NC @ BiOCl-CNTs catalyst is used as the cathode material of the cell. FIG. 15 is a graph of NC @ BiOCl-CNTs catalyst maintaining relatively stable discharge capacity at different current densities. When the discharge current density is recovered to 2mA cm-2The plateau voltage recovered 1.27V, indicating good reversibility based on rechargeable zinc-air batteries. The stability of NC @ BiOCl-CNTs in FIGS. 16-17 was evaluated by cycle durability and recharge capability. After 155 hours of long-term operation, the NC @ BiOCl-CNTs-based cell did not show any sign of voltage drop, showing better cycling stability than the commercial Pt/C. These results further demonstrate the potential application of NC @ BiOCl-CNTs catalyst as an oxygen reduction electrocatalyst, making it competitive in practical applications.
In conclusion, it can be concluded that: the invention improves the intrinsic catalytic activity of the catalyst through abundant oxygen vacancies. The oxygen-enriched vacancy NC @ BiOCl-CNTs composite material has efficient oxygen reduction performance in alkaline solution, and is subjected to O-conversion by using cyclic voltammetry and linear scanning2Testing in saturated 0.1M KOH solution showed: a distinct redox peak at 0.87V (vs. rhe); half-wave potential 0.86V (vs. rhe); at 0.2V, the diffusion limiting current density was 5.2mA cm-2(ii) a As a zinc-air battery cathode material, the NC @ BiOCl-CNTs catalyst has good long-term stability, does not decline after being kept for 155 hours, has high power density, and can reach 170.7mW cm-2。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An oxygen-enriched vacancy NC @ BiOCl-CNTs composite material is characterized in that CNTs are used as a carrier, and a carbon nitride compound with a nano structure is coated with a BiOCl nanosheet composite material in a net manner to serve as a load.
2. The preparation method of the oxygen-rich vacancy NC @ BiOCl-CNTs composite material as claimed in claim 1, is characterized in that PDA @ Bi-CNTs are used as precursors, the precursors are carbonized to obtain NC @ Bi-CNTs, and then aqua regia is used for impregnation to obtain the NC @ BiOCl-CNTs composite material.
3. The preparation method of the oxygen-rich vacancy NC @ BiOCl-CNTs composite material as claimed in claim 2, wherein the preparation method of the PDA @ Bi-CNTs precursor comprises the following steps:
the method comprises the steps of taking a pretreated carbon nano tube, F127, bismuth salt and 2-amino terephthalic acid as raw materials, carrying out primary solvothermal reaction, cooling, transferring into an acetone solution, dropwise adding a dopamine-acetone solution, and carrying out secondary solvothermal reaction to obtain a PDA @ Bi-CNTs precursor.
4. The preparation method of the oxygen-rich vacancy NC @ BiOCl-CNTs composite material as claimed in claim 3,
the preparation method of the pretreated carbon nanotube comprises the following steps: placing the carboxyl multi-walled carbon nano-tube in a concentrated nitric acid solution for heating treatment, and then cleaning to be neutral to obtain a pretreated nano-tube;
the addition mass ratio of the pretreated carbon nano tube to the F127 is (5-7) to 100, the addition molar ratio of the bismuth salt to the 2-amino terephthalic acid is (3-4) to 1, and the mass molar ratio of the pretreated carbon nano tube to the bismuth salt is 6g to (6-8);
the solvent in the primary solvent thermal reaction is N, N-dimethylformamide, the reaction temperature is 170-180 ℃, and the reaction time is 6-8 h;
the dopamine-acetone solution is a mixture of dopamine hydrochloride and acetone solution with the mass volume ratio of 0.2g to 10mL, and the mass ratio of the dopamine hydrochloride to the pretreated nanotube in the secondary solvothermal reaction system is 10 to 3;
the reaction temperature of the secondary solvent thermal reaction is 170-180 ℃, and the reaction time is 6-8 h.
5. The preparation method of the oxygen-rich vacancy NC @ BiOCl-CNTs composite material as claimed in claim 2, wherein the carbonization treatment specifically comprises: the PDA @ Bi-CNTs precursor and melamine are mixed and ground according to the mass ratio of (1-2) to 10, then the mixture is transferred into an argon atmosphere, and the mixture is heated to 900-950 ℃ at the heating rate of 5 ℃/min and calcined for 2-3h and cooled to obtain NC @ Bi-CNTs.
6. The preparation method of the oxygen-rich vacancy NC @ BiOCl-CNTs composite material as claimed in claim 2, wherein the aqua regia impregnation specifically comprises: and (3) transferring NC @ Bi-CNTs into aqua regia to be soaked for 8-12 h.
7. Use of the oxygen-rich vacancy NC @ BiOCl-CNTs composite material as defined in claim 1 as a catalyst in the preparation of an electrode material.
8. A redox electrode, characterized in that the oxygen-rich vacancy NC @ BiOCl-CNTs composite material of claim 1 is used as a catalyst material, and the preparation method of the redox electrode comprises the following steps: mixing the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material with isopropanol, water and 5 wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink on the surface of the polished working electrode, and drying to obtain the redox electrode.
9. The cathode electrode of the zinc-air battery is characterized in that the oxygen-rich vacancy NC @ BiOCl-CNTs composite material disclosed by claim 1 is used as a catalyst material, and the preparation method of the cathode electrode of the zinc-air battery comprises the following steps: mixing the oxygen-enriched vacancy NC @ BiOCl-CNTs composite material with isopropanol, water and 5 wt% of perfluorinated sulfonic acid solution to obtain a catalyst ink, dripping the catalyst ink on hydrophilic carbon fiber paper, and drying to obtain the zinc-air battery cathode electrode.
10. The electrode of any one of claims 8-9, wherein the mixed mass-to-volume ratio of the oxygen-rich vacancy NC @ BiOCl-CNTs composite to isopropanol, water, 5 wt% perfluorosulfonic acid solution is 4 mg: 245 μ L: 745 μ L: 10 μ L.
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