CN113394415B - Oxygen-enriched vacancy NC@BiOCl-CNTs composite material and preparation method and application thereof - Google Patents
Oxygen-enriched vacancy NC@BiOCl-CNTs composite material and preparation method and application thereof Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 118
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001301 oxygen Substances 0.000 title claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 50
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- 238000003763 carbonization Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
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- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
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- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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Classifications
-
- 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, in particular to an oxygen-enriched air NC@BiOCl-CNTs composite material, and a preparation method and application thereof. The oxygen-enriched vacancy NC@BiOCl-CNTs composite material is specifically 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 presents high-efficiency oxygen reduction performance in alkaline solution; as a cathode material of a zinc-air battery, the NC@BiOCl-CNTs catalyst has good long-term stability, is kept for 155 hours and does not fade, and has high power density which can reach 170.7mW/cm 2 。
Description
Technical Field
The invention relates to the technical field of electrocatalytic oxidation reduction, in particular to an oxygen-enriched vacancy NC@BiOCl-CNTs composite material, and a preparation method and application thereof.
Background
At present, the continuous growth of energy demand has raised an energy crisis based on fossil fuels, resulting in 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 kinetics of the oxygen reduction reaction, 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 the scarcity and high cost of noble metal catalysts limit their large scale application. Therefore, it is particularly necessary to develop a new efficient, inexpensive, durable redox catalyst composite.
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 rich oxygen holes.
According to one of the technical schemes of the invention, the oxygen-enriched vacancy NC@BiOCl-CNTs composite material takes CNTs as a carrier, and the nano-structure carbon nitride net-coated BiOCl nano-sheet composite material is taken as a carrier.
According to the preparation method of the oxygen-enriched vacancy NC@BiOCl-CNTs composite material, PDA@Bi-CNTs are used as precursors, NC@Bi-CNTs are obtained through carbonization treatment, and then NC@BiOCl-CNTs composite material is obtained through aqua regia impregnation.
According to the preparation method, the NC@Bi-CNTs precursor is obtained after high-temperature carbonization treatment, the obtained precursor is immersed in aqua regia, and the NC@BiOCl-CNTs composite material is directly formed by removing reduced metal ions at high temperature, 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 preparation method comprises the steps of taking a pretreated carbon nano tube, F127, bismuth salt and 2-amino terephthalic acid as raw materials, cooling after primary solvothermal reaction, transferring the product into an acetone solution, and dropwise adding a dopamine-acetone solution for secondary solvothermal reaction to obtain a PDA@Bi-CNTs precursor.
F127 is poloxamer of the formula HO (C 2 H 4 O) m ·(C 3 H 6 O) n H is a polyoxyethylene polyoxypropylene ether block copolymer.
Further, the preparation of the pretreated carbon nanotubes comprises: placing the carboxyl group-based multi-wall carbon nanotube in a concentrated nitric acid (the mass fraction of the commercial concentrated nitric acid is about 68 percent) solution, heating, refluxing, and cleaning to neutrality to obtain a pretreated nanotube;
further, the mass-volume ratio of the carboxyl multiwall carbon nanotube to the concentrated nitric acid is 0.2g to 30mL, the heating thermal reflux treatment temperature is 60 ℃, and the heating treatment time is 4 hours;
further, the adding mass ratio of the pretreated carbon nano tube to F127 is (5-7) to 100, the adding mole ratio of bismuth salt to 2-amino terephthalic acid is (3-4) to 1, and the mass mole 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 stronger interface combination by using concentrated nitric acid to introduce a large amount of hydroxyl and carboxyl.
Further, the solvent in the primary solvothermal reaction is N, N-dimethylformamide, the reaction temperature is 170-180 ℃, and the reaction time is 6-8 hours;
further, the dopamine-acetone solution is specifically a mixture of dopamine hydrochloride and acetone solution with the mass volume ratio of 0.2:10 mL, and the mass ratio of the dopamine hydrochloride to the pretreated nanotubes 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 6-8h.
Further, the carbonization treatment specifically includes: the precursor of PDA@Bi-CNTs and melamine are mixed and ground according to the mass ratio of (1-2) to 10, then the mixture is transferred into argon atmosphere, the temperature is raised to 900-950 ℃ at the heating rate of 5 ℃/min, and the mixture is calcined for 2-3 hours and cooled to obtain NC@Bi-CNTs.
The proper calcination temperature ensures that the prepared sample has higher graphitization degree and conductivity, promotes the electron transfer in the electrochemical ORR process, but is too high to cause the catalyst to be sintered so as to destroy the activity; the calcination time can influence the structure of the catalyst, so that the combination effect of the load substance and the carrier is changed, thereby influencing the catalytic effect; 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 electronegativity of adjacent C atoms, thereby improving ORR activity.
Further, the aqua regia impregnation specifically comprises: transferring NC@Bi-CNTs into aqua regia, immersing for 8-12h, centrifugally collecting precipitate, washing with water to be neutral, and drying to obtain the oxygen-enriched vacancy NC@BiOCl-CNTs composite material.
In the third technical scheme of the invention, the oxygen-enriched vacancy NC@BiOCl-CNTs composite material is applied to preparing electrode materials as a catalyst.
According to the fourth technical scheme, the 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 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink into 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 5wt% of perfluorosulfonic acid solution to obtain catalyst ink drops, and drying the catalyst ink drops on hydrophilic carbon fiber paper to obtain the cathode electrode of the zinc-air battery.
Further, in the preparation process of the redox electrode and the cathode electrode of the zinc-air battery, the mixing volume ratio of the oxygen-enriched vacancy NC@BiOCl-CNTs composite material to isopropanol, water and 5wt% of perfluorinated sulfonic acid solution is 4 mg:245 mu L:745 mu L:10 mu L.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method increases the oxygen vacancy proportion in the composite material, and the high proportion of oxygen vacancies can enhance charge transfer, promote oxygen dissociation reaction and improve ORR performance. In the carbonization process, melamine rich in nitrogen is also introduced, and lattice O is partially replaced by N, so that the electron density of oxygen vacancies is correspondingly increased, and the intrinsic catalytic activity of the catalyst is improved through the rich oxygen vacancies. The melamine can increase the active site 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 the carbon matrix, so that the material has better performance.
2. The BiOCl composite material is a photocatalytic material with high activity and is widely applied to the field of photocatalysts. However, during the oxygen reduction process, the main group metals, such as Mg, al and Bi, are inert and do not have empty and filled main tracks critical to the catalytic cycle. 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, and has longer stability and high power density when 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 vacancies and BiOCl active sites.
3. The oxygen-enriched vacancy NC@BiOCl-CNTs composite material prepared by the method disclosed by the invention has high-efficiency oxygen reduction performance in alkaline solution; as a cathode material of a zinc-air battery, the NC@BiOCl-CNTs catalyst has good long-term stability, is kept for 155 hours and does not fade, and has high power density which can reach 170.7mW/cm 2 。
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; wherein a is a scanning electron microscope picture of NC@Bi-CNTs material before the etching of the water, b is a scanning electron microscope picture of NC@BiOCl-CNTs material after the etching of the water, c is a transmission electron microscope picture of NC@BiOCl-CNTs material after the etching of the water, d is a high-power transmission electron microscope picture of NC@BiOCl-CNTs material after the etching of the water, e is a high-power transmission electron microscope picture at a position corresponding to the picture d, and f is an element distribution picture of NC@BiOCl-CNTs material after the etching of the water;
FIG. 3 is an X-ray photoelectron spectrum of the composite material prepared in examples 1-3 of the present invention;
FIG. 4 is a CV curve of the redox electrode prepared in the effect verification 1 of the present invention;
FIG. 5 is a RRDE curve of the redox electrode prepared in effect test 1 of the present invention at 1600 rpm;
FIG. 6 is a schematic diagram showing H of the redox electrode prepared in effect verification 1 of the present invention 2 O 2 Yield and number of electron transfers;
FIG. 7 is a Tafil slope of the redox electrode prepared in effect verification 1 of the present invention;
FIG. 8 is a graph (a) of RRDE and a graph (b) of K-L of electrodes prepared from NC@BiOCl-CNTs in effect verification 1 of the invention at different rotational speeds;
FIG. 9 shows the corresponding H of RRDE curve of electrodes prepared by NC@BiOCl-CNTs in effect verification 1 of the invention at different rotation speeds 2 O 2 Yield and number of electron transfers;
FIG. 10 is a schematic structural diagram of the performance diagram of the zinc-air cell in effect verification 2 of the present invention;
FIG. 11 is a graph showing the specific capacity of the catalyst in the zinc-air cell of effect verification 2 of the present invention;
FIG. 12 is a graph showing the discharge polarization of a zinc-air cell and its power density for the catalyst in the zinc-air cell of effect verification 2 of the present invention;
FIG. 13 is a graph showing the open circuit voltage of the zinc-air cell in effect verification 2 of the present invention;
FIG. 14 is a photograph showing two sets of zinc-air cells in series with red LEDs in effect verification 2 of the present invention;
FIG. 15 is a graph showing the discharge curves of zinc-air cells prepared with NC@BiOCl-CNTs as catalyst in effect verification 2 of the present invention at different current densities;
FIG. 16 is a graph showing the constant current discharge and charge voltage of the zinc-air cell of effect verification 2 of the present invention;
FIG. 17 is a comparison of the voltage differences between the first and last turns of FIG. 16 in effect verification 2 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In the following examples of the present invention, the preparation method of the pretreated carbon nanotubes:
and (3) placing the carboxyl multiwall carbon nanotube into concentrated nitric acid solution according to the mass volume ratio of 2g to 300mL, carrying out oil bath for 4 hours at 60 ℃, cooling to room temperature, and washing with deionized water until the carbon nanotube is neutral to obtain the pretreated carbon nanotube.
Example 1
(1) Weighing 0.06g of pretreated carbon nano tube, 1g of F127, 2.9104g of bismuth nitrate pentahydrate and 0.2717g of 2-amino terephthalic acid (namely, the molar ratio of bismuth salt to 2-amino terephthalic acid is 4:1), dissolving in 60mL of DMF solution, and preparing a uniform mixed solution;
(2) The homogeneous mixed solution was transferred to a stainless steel autoclave at 180℃for 8 hours. After cooling at room temperature, the obtained brown powder is dispersed into 65mL of acetone solution, 10mL of 20mg/mL dopamine-acetone solution (0.2 g of dopamine hydrochloride is added into 10mL of acetone solution) is dripped, the mixture is stirred for 30 minutes, the mixture is sealed in an autoclave again, hydrothermal is carried out at 180 ℃ for 8 hours, and a precipitation is collected by a centrifugal method to obtain a PDA@Bi-CNTs precursor.
(3) 0.1g of PDA@Bi-CNTs precursor and 1g of melamine are weighed and uniformly ground, and calcined for 2 hours in an argon atmosphere at 950 ℃. And cooling to room temperature, and collecting powder to complete the preparation of NC@Bi-CNTs.
(4) Immersing the carbonized NC@Bi-CNTs sample in aqua regia (HNO) 3 HCl=1/3), collecting precipitate by centrifugation, washing with deionized water until the solution is neutral, and drying to obtain 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 at a position corresponding to the picture d, f is an element distribution picture (a is a picture of NC@Bi-CNTs material before aqua regia etching, and b-f is a picture of NC@BiOCl-CNTs material after etching);
by analyzing fig. 1 and 2: FIG. 1 shows that the composite material is a hybrid material of NC@BiOCl-CNTs by converting Bi nano particles into BiOCl species after aqua regia etching. The 4 characteristic peaks clear at 11.98 °,25.86 °,32.50 ° and 33.45 ° are due 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 with dense nanoparticles. FIG. 2b is that the NC@BiOCl-CNTs catalyst surface became relatively smooth after aqua regia etching, probably because most of the Bi particles were dissolved. In fig. 2c, the TEM image shows that the nanoparticles are randomly distributed on the surface of the carbon nanotubes. FIGS. 2d-e high resolution TEM images, with a clear lattice spacing of 0.34nm being typical of the C (002) plane, and lattice fringes of 0.22 and 0.27nm belonging to the (112) and (102) planes of BiOCl, respectively. FIG. 2f is a HAADF-STEM and corresponding elemental mapping showing that Bi, cl, C, N and O elements are well distributed throughout the catalyst structure of NC@BiOCl-CNTs.
Example 2
Steps (1) and (2) are the same as in example 1;
(3) Weighing 0.1g of PDA@Bi-CNTs precursor, grinding uniformly, calcining for 2 hours in an argon atmosphere at 950 ℃, cooling to room temperature, and collecting powder to complete the preparation of the C@Bi-CNTs.
(4) Immersing carbonized C@Bi-CNTs sample in aqua regia (HNO) 3 HCl=1/3), collecting precipitate by centrifugation, washing with deionized water until the solution is neutral, and drying to obtain final sample C@BiOCl-CNTs.
Example 3
(1) 1g of F127, 2.9104g of bismuth nitrate and 0.2717g of 2-amino terephthalic acid (i.e. molar ratio 4:1) are 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 at 180℃for 8 hours. After cooling at room temperature, the brown powder obtained was dispersed into 65mL of acetone solution, 10mL of 20mg/mL dopamine-acetone solution was added dropwise, stirred for 30 minutes, sealed again in an autoclave at 180 ℃ and hydrothermally heated for 8 hours, and the precipitate was collected by centrifugation to obtain pda@bi.
(3) 0.1g of PDA@Bi precursor and 1g of melamine are weighed and uniformly ground, and calcined for 2 hours in an argon atmosphere at 950 ℃. And cooling to room temperature, and collecting powder to complete the preparation of NC@Bi.
(4) Immersing 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 composites prepared in examples 1-3 are shown in FIG. 3; as shown in XPS according to fig. 3. The high resolution XPS spectrum of O1s was deconvoluted into BiOCl lattice oxygen (530.0 eV), oxygen vacancies (531.1 eV), C-O (532.2 eV) and adsorbed H 2 O/c=o (533.5 eV). A high proportion of oxygen vacancies may enhance charge transfer, piercing dissociation reactions, and thus improve ORR performance. Oxygen vacancies in the NC@BiOCl-CNTs and NC@BiOCl materials were 33.7% and 37.9%, respectively, whereas C@BiOCl-CNTs contained only 18.6%, indicating that N doping promoted the formation of oxygen defects.
Effect verification 1
The oxidation-reduction electrode was prepared by using Pt/C catalyst and the composite material of examples 1-3 as the catalyst and the rotating disk electrode as the working electrode, respectively, as follows:
polishing the working electrode on a polishing pad on a felt by using 0.05 mu m alumina, and then cleaning the working electrode with water, 0.5mol/L sulfuric acid and ethanol for three times for later use;
the catalyst powder, 4mg, was weighed, mixed with 245 μl of isopropanol, 745 μl of water and 10 μl of 5wt% nafion solution, and sonicated for 30 minutes. 19.610 μl of the catalyst ink was added dropwise to the polished RRDE surface with a pipette and dried in the natural environment. The catalyst loading on the working electrode was 0.318 mg/cm 2 Pt/C catalyst loading was 0.081mg/cm 2 。
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 used as a counter electrode, and KCI saturated Ag/AgCl is used as a reference electrode. O is added before testing 2 Bubbling from the electrolyte for 30 minutes, maintaining the bubbling state during the measurement to maintain O in solution 2 Is in a saturated state. Cyclic Voltammetry (CV) test at a scan rate of 50 mV/s in 0.1M KOH solution at N 2 In a saturated solution. At O 2 Linear scan testing (LSV) was performed in saturated 0.1M KOH solution at different spin rates (400-2025 rpm) and scan rates of 10 mV/s. At 1600rpm, the electron transfer number and H in ORR were measured with RRDE 2 O 2 Yield. The specific formula is as follows:
；
wherein i is D And i R The disk current and the ring current, respectively. N is the collection efficiency of the platinum loop (n=0.37). The results are shown in FIG. 4; wherein a is CV curve of the redox electrode, b is RRDE curve of the redox electrode at 1600rpm, and c is H of the redox electrode 2 O 2 Yield and electron transfer number, d is the Tafil slope of the redox electrode, e is the RRDE curve of the electrode prepared by NC@BiOCl-CNTs at different rotation speeds, and f is H corresponding to the RRDE curve of the electrode prepared by NC@BiOCl-CNTs at different rotation speeds 2 O 2 Yield and number of electronic transfers
From fig. 4-9, it can be derived that: in FIG. 4, NC@BiOCl-CNTs catalyst at O 2 The saturation showed a significant redox peak, 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 that the NC@BiOCl-CNTs catalyst has a large limiting current density of 5.2mA cm at 0.2V -2 And 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 0.2-0.8V 2 O 2 The yield is lower than 20%, the electron transfer number is close to 4, and the method accords with the ORR kinetic pathway. FIG. 7 shows that the catalyst NC@BiOCl-CNTs has a Tafil slope of 68.7mV dec -1 Far lower than the catalysts of C@BiOCl-CNTs and NC@BiOCl, the rapid reaction kinetics was verified. A series of LSV measurements at rotational speeds from 400-2050rpm were performed in FIG. 8a, showing an increase in current density with increasing rotational speed, and an average number of transferred electrons of about 4 over a voltage range of 0.3-0.7V for the NC@BiOCl-CNTs catalyst calculated according to FIG. 8b K-L. FIG. 9 further evaluates H 2 O 2 Yield and number of transferred electrons, consistent with the K-L plot results (20 wt% Pt/C in the plot is product model, 0.081 mg/cm) 2 Is the catalyst loading).
Effect verification 2
Zinc-air cell test:
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 cell was 6.0M KOH+0.2M Zn (AC) 2 Is a mixed solution of (a) and (b).
The catalyst ink was dropped onto hydrophilic carbon fiber paper (1 x 2cm 2 ) And (3) 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 view of a zinc-air battery structure, fig. 11 is a specific capacity of a catalyst, fig. 12 is a discharge electrode and power density curve of the zinc-air battery of the catalyst, fig. 13 is an open circuit voltage diagram of the zinc-air battery, fig. 14 is a graph of two groups of zinc-air batteries which are serially lighted with red LEDs, fig. 15 is a discharge curve of the zinc-air battery prepared by nc@biocl-CNTs as catalysts under different current densities, fig. 16 is a constant current discharge and charge voltage curve of the zinc-air battery, and fig. 17 is a voltage difference comparison of the first circle and the last circle of fig. 16.
From fig. 10-17, it can be derived that: in fig. 10, the assembled zinc-air cell device was explored for practical use of nc@biocl-CNTs in energy sources. FIG. 11 is a graph of specific catalyst capacity, where NC@BiOCl-CNTs are used as zinc-air cathode material with a plateau voltage of 1.25V, 1.17V higher than that of Pt/C. In addition, NC@BiOCl-CNTs catalyst was used at 10mA cm -2 Provides 724mA h g at discharge current density of (2) -1 Higher than Pt/C assembled zinc-air batteries. FIG. 12 shows that the power density of the NC@BiOCl-CNTs catalyst in zinc-air is 170.7mW cm -2 Far above Pt/C power density of 129.6mW cm -2 . FIG. 13 shows that the NC@BiOCl-CNTs catalyst provides a stable open circuit voltage of 1.51V in zinc-air cells, which is higher than the commercial Pt/C catalyst. FIG. 14 shows that two cells in series can illuminate a 3.0V red Light Emitting Diode (LED) when NC@BiOCl-CNTs catalyst is used as the cathode material of the cells. FIG. 15 is a graph showing that NC@BiOCl-CNTs catalysts maintain relatively stable discharge capacities at different current densities. When the discharge current density is restored to 2mA cm -2 At this time, the plateau voltage recovered 1.27V, indicating good reversibility based on the rechargeable zinc-air cell. The stability of NC@BiOCl-CNTs in FIGS. 16-17 was evaluated by cycle durability and recharging capacity. After a long run of 155 hours, the NC@BiOCl-CNTs based cell showed no sign of voltage drop, showing better cycling stability than commercial Pt/C. These results further demonstrate the potential use of NC@BiOCl-CNTs catalysts as oxygen reduction electrocatalysts, making them competitive in practical applications.
Summarizing, it can be concluded that: the invention improves the intrinsic catalytic activity of the catalyst through rich oxygen vacancies. Oxygen-enriched vacancy NC@BiOCl-CNTs composite material in alkalineThe solution shows high-efficiency oxygen reduction performance, and the cyclic voltammetry and the linear scanning method are used for generating oxygen in O 2 Testing in saturated 0.1M KOH solution showed that: a clear redox peak appears at 0.87V (vs. rhe); the half-wave potential is 0.86V (vs. rhe); at 0.2V, the diffusion limiting current density was 5.2 mA.cm -2 The method comprises the steps of carrying out a first treatment on the surface of the As a cathode material of a zinc-air battery, the NC@BiOCl-CNTs catalyst has good long-term stability, is kept for 155 hours and does not fade, and has high power density which can reach 170.7mW cm -2 。
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (6)
1. The oxygen-enriched vacancy NC@BiOCl-CNTs composite material is characterized in that CNTs are used as a carrier, and a nano-structure carbon nitride net-coated BiOCl nano-sheet composite material is used as a carrier;
the preparation method of the oxygen-enriched vacancy NC@BiOCl-CNTs composite material comprises the following steps:
taking PDA@Bi-CNTs as a precursor, performing carbonization treatment to obtain NC@Bi-CNTs, and then dipping in aqua regia to obtain NC@BiOCl-CNTs composite material;
the preparation method of the PDA@Bi-CNTs precursor comprises the following steps: taking pretreated carbon nano tubes, F127, bismuth salt and 2-amino terephthalic acid as raw materials, cooling after primary solvothermal reaction, transferring into an acetone solution, and dropwise adding a dopamine-acetone solution for secondary solvothermal reaction to obtain a PDA@Bi-CNTs precursor;
the preparation method of the pretreated carbon nano tube comprises the following steps: placing the carboxyl-based multi-walled carbon nanotube in a concentrated nitric acid solution for heating treatment, and then cleaning to neutrality to obtain a pretreated nanotube;
the mass ratio of the pretreated carbon nano tube to F127 is (5-7) to 100, the mole ratio of the bismuth salt to the 2-amino terephthalic acid is (3-4) to 1, and the mass mole ratio of the pretreated carbon nano tube to the bismuth salt is 6g to (6-8) mol;
the solvent in the primary solvothermal reaction is N, N-dimethylformamide, the reaction temperature is 170-180 ℃, and the reaction time is 6-8 hours;
the dopamine-acetone solution is specifically 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 nano tube in the secondary solvothermal reaction system is 10 to 3;
the reaction temperature of the secondary solvothermal reaction is 170-180 ℃ and the reaction time is 6-8h;
the carbonization treatment specifically comprises: the precursor of PDA@Bi-CNTs and melamine are mixed and ground according to the mass ratio of (1-2) to 10, then the mixture is transferred into argon atmosphere, the temperature is raised to 900-950 ℃ at the heating rate of 5 ℃/min, and the mixture is calcined for 2-3 hours and cooled to obtain NC@Bi-CNTs.
2. The oxygen-enriched vacancy nc@biocl-CNTs composite material according to claim 1, wherein the aqua regia impregnation specifically comprises: transferring NC@Bi-CNTs into aqua regia, and immersing for 8-12h.
3. Use of an oxygen-enriched vacancy nc@biocl-CNTs composite material according to claim 1 as catalyst in the preparation of an electrode material.
4. A redox electrode, characterized in that the oxygen-enriched vacancy NC@BiOCl-CNTs composite material as claimed in 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 5wt% of perfluorinated sulfonic acid solution to obtain catalyst ink, dripping the catalyst ink into the surface of the polished working electrode, and drying to obtain the redox electrode.
5. A zinc-air battery cathode electrode, characterized in that the oxygen-enriched vacancy NC@BiOCl-CNTs composite material as claimed in claim 1 is used as a catalyst material, and the preparation method of the zinc-air battery cathode electrode comprises the following steps: mixing the oxygen-enriched vacancy NC@BiOCl-CNTs composite material with isopropanol, water and 5wt% of perfluorosulfonic acid solution to obtain catalyst ink drops, and drying the catalyst ink drops on hydrophilic carbon fiber paper to obtain the cathode electrode of the zinc-air battery.
6. The electrode of any of claims 4-5 wherein the oxygen-enriched vacancy nc@biocl-CNTs composite material is mixed with isopropanol, water, 5wt% perfluorosulfonic acid solution in a volume ratio of 4 mg:245 μl:745 μl:10 μl.
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