CN114068951A - Preparation method and application of Ni monoatomic-loaded embedded porous Pd-C nanorod - Google Patents
Preparation method and application of Ni monoatomic-loaded embedded porous Pd-C nanorod Download PDFInfo
- Publication number
- CN114068951A CN114068951A CN202111101813.6A CN202111101813A CN114068951A CN 114068951 A CN114068951 A CN 114068951A CN 202111101813 A CN202111101813 A CN 202111101813A CN 114068951 A CN114068951 A CN 114068951A
- Authority
- CN
- China
- Prior art keywords
- naphthylamine
- complex
- embedded porous
- nanorod
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000002073 nanorod Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 25
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 101150003085 Pdcl gene Proteins 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000012467 final product Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- BPJYAXCTOHRFDQ-UHFFFAOYSA-L tetracopper;2,4,6-trioxido-1,3,5,2,4,6-trioxatriarsinane;diacetate Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.[O-][As]1O[As]([O-])O[As]([O-])O1.[O-][As]1O[As]([O-])O[As]([O-])O1 BPJYAXCTOHRFDQ-UHFFFAOYSA-L 0.000 claims description 2
- 102000020897 Formins Human genes 0.000 claims 1
- 108091022623 Formins Proteins 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Images
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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method and application of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms, wherein PdCl is firstly added into an ethanol water solution2And naphthylamine, uniformly mixing, standing to generate a complex, dispersing the complex and NiPc powder in a THF solvent together, stirring, centrifugally drying, collecting solid powder, calcining at high temperature, and cooling to obtain the Ni-monoatomic-loaded embedded porous Pd/C nanorod. The method is simple and easy to implement, the cost of raw materials is low, large-scale production can be realized, and the prepared embedded porous Pd/C nano rod loaded with Ni monoatomic atoms not only has the structural advantages of large specific surface area, good conductivity, strong permeability, high temperature resistance and the like; and has both Ni-Nx and PdThe two metal sites with high activity are used for driving an oxygen evolution reaction and an oxygen reduction reaction respectively, and the high energy conversion efficiency and the strong circulation stability are realized in the performance of the zinc-air battery.
Description
Technical Field
The invention belongs to the technology of air cathode catalysts of zinc-air batteries, and particularly relates to a preparation method and application of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms.
Background
Rechargeable metal-air batteries have received much attention from people because of their high energy density, low cost, good safety and other advantages. Due to the slower kinetics of the reversible oxygen reaction, in metal-air batteries, each charge and discharge process must be catalyzed by a bifunctional catalyst that is active for both Oxygen Evolution (OER) and oxygen reduction (ORR) reactions. Pt-based materials and Ru/Ir-based materials, which have high activities for ORR and OER, respectively, are typically physically mixed to make a dual-function catalyst to meet the charge-discharge requirements of the battery. However, the material produced by this method is difficult to control for uniform mixing due to poor compatibility of the two, and thus is neither efficient nor reliable. In the long term, the high cost of noble metal electrocatalysts, the scarce reserves and the unsatisfactory stability of noble metals would severely limit their large-scale application.
The current research shows that palladium (Pd) and platinum (Pt) have very similar electronic structures in a series of noble metal-based catalysts, are cheaper than platinum (Pt) in price and rich in reserves, and are a platinum (Pt) -based catalyst substitute with great potential. The palladium-based nano material is used as an electrocatalyst for oxygen reduction reaction, the size, the structure and the morphology of the palladium-based nano material are further regulated, and the oxygen reduction activity and the stability of the palladium-based nano material can be comparable to those of Pt. In addition, 3d transition metal nanocatalysts are widely used in OER reactions. It has been shown that based on Ni-NxThe catalyst material of (2) has very high catalytic activity for OER, and due to size effect, the catalytic activity of monatomic Ni shows more excellent performance than Ni nanoclusters and Ni nanoparticles.
However, how to combine Pd-based nanomaterials with Ni-NxThe high catalytic activity of the nano material is combined together, and the design and synthesis have Ni-N simultaneouslyxAnd Pd active center nanomaterials still face significant challenges. This is due to Ni-NxThe preparation of-C nano material is often required to be obtained by adopting a high-temperature reduction method (> 300)oC) Most Pd nano materials do not have high temperature resistance, and the Pd nano particles are easy to agglomerate, reconstruct and combine under the high temperature condition, so that the number of the surface active sites of Pd is obviously reduced. Therefore, it is difficult to realize Ni-N in the same synthesis systemxAnd the simultaneous construction of Pd active centers.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method and application of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms, the embedded porous Pd-C nanorod prepared by the method has high electrochemical activity and stability, and Ni-N is realized in the same synthesis systemxAnd the simultaneous construction of Pd active centers.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps: adding PdCl into the aqueous solution of ethanol2And naphthylamine (C)10H9And N) mixing the two reactants uniformly, standing until a flaky Pd (II) -naphthylamine complex is generated, centrifugally drying a reaction system, dispersing the obtained solid powder and NiPc powder in a THF (tetrahydrofuran) solvent together, stirring uniformly, centrifugally drying, collecting the solid powder, calcining at high temperature in an inert atmosphere, and cooling to obtain the Ni-monoatomic-loaded embedded porous Pd-C nanorod.
Preferably, the preparation method specifically comprises the following steps:
1) synthesis of yellow flaky Pd (II) -naphthylamine Complex
Weighing naphthylamine (C)10H9N), adding the mixture into an ethanol water solution, and performing ultrasonic treatment to fully dissolve the mixture; adding PdCl2Uniformly mixing the water solution, standing to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying to obtain powder;
2) preparation of Green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine Complex
The Pd (II) -naphthylamine complex and NiPc are dispersed in THF solvent together, slowly and uniformly mixed, stirred and centrifugally dried to obtain a powder green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex;
3) preparation of Ni-loaded monatomic embedded porous Pd/C nanorod
The NiPc @ Pd (II) -naphthylamine complex is calcined at high temperature in an inert atmosphere and then cooled to obtain the final product.
The improvement is that the mass fraction of Pd in the Pd (II) -naphthylamine complex in the step 1) is 0.1-90%, and the mass fraction of Pd in the product is obtained by an icp test.
The improvement is that the volume ratio of water to ethanol in the ethanol water solution in the step 1) is (0.1-99): 1.
The improvement is that the mass ratio of the Pd (II) -naphthylamine complex to NiPc in the step 2) is (0.1-99): 1.
the improvement is that the high-temperature calcination treatment in the inert atmosphere in the step 3) is carried out under the atmosphere of nitrogen, argon or helium by temperature programming for 2.5-20 ℃ for min-1Heat treatment is carried out at 200-1000 ℃, and the temperature is kept for 0.5-24 h.
The improvement is that the stirring speed in the step 2) is 120rpm, and the magnetic stirring is carried out for 0.5-24 h.
The embedded porous Pd/C nano rod loaded with Ni monoatomic atoms prepared by the preparation method.
The embedded porous Pd/C nanorod loaded with the Ni monoatomic atoms is applied to a zinc-air battery as an air cathode catalyst.
The working principle is as follows:
the invention firstly utilizes naphthylamine (C)10H9N) as a coordinating molecule with PdCl2A yellow complex precipitate is formed, and the Pd (II) -naphthylamine complex has a regular sheet-like structure. And then, carrying out high-temperature self-reduction on the Pd (II) -naphthylamine complex and NiPc to finally obtain the Ni-monoatomic-loaded embedded porous Pd/C nanorod. The method is simple and easy to implement, has low raw material cost, and can realize large-scale production. The embedded porous Pd/C nano rod loaded with Ni monoatomic atoms prepared by the method not only has large specific surface area and good conductivityStrong permeability, high temperature resistance and other structural advantages; and simultaneously has Ni-NxAnd Pd superfine nanocrystalline (-5.0 nm), which are used for driving OER and ORR reactions respectively. Therefore, the Ni monoatomic supported embedded porous Pd/C nanorod shows bifunctional electrocatalytic activity and has excellent selectivity for oxygen reaction. More significantly, in the performance of the zinc-air battery, the embedded porous Pd/C nanorod loaded with the Ni monoatomic atom as the air cathode catalyst shows higher energy conversion efficiency and stronger cycle stability.
Has the advantages that:
compared with the prior art, the invention provides a novel preparation method of the cathode oxygen reduction catalyst, and the embedded porous Pd/C nano rod loaded with Ni monoatomic atoms is prepared by a high-temperature carbonization self-reduction method which is simple and convenient and can realize large-scale production, and has the following specific advantages:
the invention adopts PdCl2The plate-shaped complex obtained by the coordination reaction with the 1-naphthylamine is taken as a precursor, NiPc with a rigid macrocyclic structure is taken as a Ni source, the NiPc can generate a strong acting force with the plate-shaped complex through a pi-pi stacking effect to be tightly adsorbed on the surface of the plate-shaped complex, a proper pyrolysis temperature is selected, and the embedded porous Pd/C nanorod loaded with the Ni single atom is obtained through carbonization and reduction. The obtained Ni monoatomic embedded porous Pd/C nanorod has the following characteristics: (1) surface rich Ni-NxThe bond can be used as an effective catalytic active site for oxygen evolution reaction; (2) the ultrafine Pd nanoparticles (5.0 nm) are uniformly distributed and have single size, and more oxygen reduction catalytic active sites can be provided; (3) with both Ni-NxAnd Pd superfine nanocrystalline (-5.0 nm) to realize the construction of the bifunctional electrocatalyst. The prepared embedded porous Pd/C nano rod loaded with the Ni monoatomic atom has more excellent bifunctional electrocatalytic activity and selectivity, and the specific capacity (718.6 mAhgzn) of the rechargeable zinc-air battery assembled by taking the embedded porous Pd/C nano rod loaded with the Ni monoatomic atom as an air cathode-1) And energy density (935.8 wh. kgzn)-1) Obviously superior to the traditional Pt/C + RuO2An air cathode; (4) is porousThe nanorod structure is beneficial to the transmission and diffusion of electrolyte, so that the electrocatalytic activity is effectively improved; (5) Ni-NxAnd the embedded structure of the Pd nano particles on the carbon material ensures that the catalyst is not easy to aggregate and dissolve in the catalysis process, thereby having better electrochemical stability. The rechargeable zinc-air battery assembled by taking the embedded porous Pd/C nano rod loaded with Ni monoatomic atoms as an air cathode can stably run for 700 cycles (about 200 hours), and does not have obvious performance attenuation; (6) the selected complex naphthylamine is cheap and easy to obtain, and the method has the advantages of simple and feasible process, low cost and simple equipment, and can realize large-scale production.
Drawings
FIG. 1 is a low power TEM spectrum of an embedded porous Pd/C nanorod supporting Ni monoatomic atoms prepared according to the method of the present invention;
FIG. 2 is an SEM image of Ni-monoatomic supported embedded porous Pd/C nanorods prepared according to the method of the present invention;
FIG. 3 is a high power TEM spectrum of an embedded porous Pd/C nanorod supporting Ni monoatomic atoms prepared according to the method of the present invention;
FIG. 4 is an XRD pattern of Ni-monoatomic supported embedded porous Pd/C nanorods prepared according to the method of the present invention;
FIG. 5 is a BET spectrum of an embedded porous Pd/C nanorod supporting Ni monoatomic atoms prepared according to the method of the present invention;
FIG. 6 is a zinc-air cell assembled with Ni monatomic-supported embedded porous Pd/C nanorods as an air cathode prepared according to the method of the present invention, with a constant current density of 5 mA--2Discharge curve under the condition;
FIG. 7 shows an embedded porous Ni-monatomic-supported Pd/C nanorod prepared according to the method of the present invention as an air cathode in an assembled zinc-air cell with a constant current density of 10 mA--2Charge-discharge voltage distribution under the condition.
Detailed Description
Example 1
The invention will be further described with reference to specific embodiments and the accompanying drawings.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.15g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, and drying in an oven at 40 ℃ for 12h to obtain powder, thus obtaining yellow flaky Pd (II) -naphthylamine complex powder (which is flaky under a 200nm scale electron microscope and the product is yellow);
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 20 mg of the yellow powder prepared in the step 1), simultaneously weighing 10mg of NiPc, jointly dispersing in 40mL of THF, stirring at the speed of 120rpm for 24h, evaporating the solvent, and centrifugally drying to obtain a green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex powder (rod-shaped under a scale electron microscope of 200nm, and green products);
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 2) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 2
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.15g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Mixing the water solution, standing, centrifuging, and drying in oven at 40 deg.C for 12 hr to obtain yellow solutionA lamellar Pd (II) -naphthylamine complex;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 20 mg of the yellow powder prepared in the step 1), simultaneously weighing 20 mg of NiPc, jointly dispersing in 40ml of THF, stirring at the speed of 120rpm for 24h, evaporating the solvent, and centrifugally drying to obtain a green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex powder;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 3
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.15g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, and drying in an oven at 40 ℃ for 12h to obtain a yellow flaky Pd (II) -naphthylamine complex;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 20 mg of the yellow powder prepared in the step 1), simultaneously weighing 30 mg of NiPc, jointly dispersing in 40ml of THF, stirring at the speed of 120rpm for 24h, evaporating the solvent, and centrifugally drying to obtain a green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 4
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.15g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, drying in an oven at 40 ℃ for 12h to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifuging and drying;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 20 mg of the yellow powder prepared in the step 1), simultaneously weighing 40mg of NiPc, jointly dispersing in 40ml of THF, stirring at the speed of 120rpm for 24h, evaporating the solvent, and centrifugally drying to obtain a green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 5
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.15g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, drying in an oven at 40 ℃ for 12h to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifuging and drying;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 20 mg of the yellow powder prepared in the step 1), simultaneously weighing 50mg of NiPc, jointly dispersing in 40ml of THF, stirring at the speed of 120rpm for 24h, evaporating the solvent, and centrifugally drying to obtain a green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex powder;
3) carrying Ni monoatomic atomsPreparing an embedded porous Pd/C nanorod: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 6
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.15g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, drying in an oven at 40 ℃ for 12h to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifuging and drying;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 20 mg of the yellow powder prepared in the step 1), simultaneously weighing 60 mg of NiPc, jointly dispersing the NiPc in 40ml of THF, stirring at the speed of 120rpm for 20 h, evaporating the solvent, and centrifugally drying to obtain a green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex powder;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 7
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.2g of naphthylamine (C) is weighed out10H9N), adding the mixture into 40mL of mixed solvent of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; then 4mL of 0.05 mol L were added-1PdCl of (2)2Mixing the water solution, standing, centrifuging, and drying in oven at 40 deg.C for 12 hr to obtain yellow sheetPd (II) -naphthylamine complex, and centrifugally drying;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 10mg of the yellow powder prepared in the step 1), simultaneously weighing 50mg of NiPc, jointly dispersing the NiPc in 30ml of THF, stirring at the speed of 120rpm for 24h, evaporating the solvent, and centrifugally drying to obtain a green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex powder;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 8
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.2g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 30mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; followed by addition of 4mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, drying in an oven at 40 ℃ for 12h to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifuging and drying;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 40mg of the yellow powder prepared in the step 1), simultaneously weighing 60 mg of NiPc, jointly dispersing the NiPc in 80ml of THF, stirring at the speed of 120rpm for 12h, evaporating the solvent, and centrifugally drying to obtain a green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex powder;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under nitrogen atmosphere at 5 deg.C for min-1Temperature programming to 700 deg.CoC, carrying out heat treatment, keeping the temperature for 2 hours, and then cooling to room temperature to obtain the final product.
Example 9
A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms comprises the following steps:
1) preparation of metal precursor complex: 0.2g of naphthylamine (C) is weighed out10H9N), adding the mixture into a mixed solvent of 20 mL of water and ethanol (the volume ratio of the water to the ethanol is 10: 1), and fully performing ultrasonic treatment to dissolve the mixture; then 3 mL of 0.05 mol-1PdCl of (2)2Uniformly mixing the aqueous solution, standing, centrifuging, drying in an oven at 40 ℃ for 12h to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifuging and drying;
2) preparation of green rod-like intermediate NiPc @ Pd (II) -naphthylamine complex: weighing 40mg of the yellow powder prepared in the step 1), simultaneously weighing 50mg of NiPc, jointly dispersing the NiPc and the NiPc in 80ml of THF, stirring at the speed of 120rpm for 12h, evaporating the solvent, and centrifugally drying to obtain a green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex powder;
3) preparing an embedded porous Pd/C nano rod loaded with Ni monoatomic atoms: fermenting the green powder obtained in step 1) under argon atmosphere at 5 deg.C for min-1Temperature programmed to 600 deg.CoC, carrying out heat treatment, keeping the temperature for 2 hours, and then cooling to room temperature to obtain the final product.
Performance testing
Physical characterization is carried out on the Ni monoatomic-supported embedded porous Pd/C nanorod prepared in example 1 by adopting ways such as TEM, SEM, XRD and BET. From both low power TEM (FIG. 1) and SEM (FIG. 2), it can be seen that the prepared Ni-loaded monatomic embedded porous Pd/C nanorods are porous framework structures, and further enlarged high power TEM (FIG. 3) shows that Pd nanoparticles are uniformly embedded in the porous framework, with a particle size of about 4.2 nm, indicating that the Pd nanoparticles have an ultrafine particle size of less than 5nm, which proves that the present invention is embedded porous nanorods. As can be seen from the XRD spectrum of FIG. 4, the diffraction peak of the Ni-monoatomic-supported embedded porous Pd/C nanorod can be completely matched with the standard card of Pd (JCPDS card, 65-6174), which proves that Pd (II) in the precursor complex is reduced into metal Pd, and Ni-NxIn the form of a single atom. As shown in FIG. 5, N of Ni monoatomic embedded porous Pd/C nanorod2The adsorption isotherm belongs to the IV-type isothermHaving a significant hysteresis loop showing the presence of mesopores, the surface area of the Ni-monoatomic supported embedded porous Pd/C nanorods was 131.31 m2﹒g-1。
And (3) testing the zinc-air battery: the test of the zinc-air battery uses a self-made zinc-air battery. The air cathode comprises hydrophobic carbon paper, a catalyst layer of the hydrophobic carbon paper is positioned on one side close to the electrolyte, and a gas diffusion layer is positioned on one side close to the air. Drop-coating catalyst ink on carbon paper (10 mg. cm-2) Naturally drying to obtain a catalyst layer: air diffusion layer let O2Can effectively diffuse from the surrounding environment to the catalyst layer: a Zn sheet with the thickness of 0.3 mm is used as an anode of the zinc-air battery; 0.2M ZnCl2And the mixed solution of + 6M KOH is used as electrolyte. The cycling stability test of the battery was performed on the LandCT2001A system, with each charge and discharge time set to 10 min.
FIG. 6 shows an embedded porous Ni-loaded Pd/C nanorod as an air cathode assembled zinc-air cell with constant current density of 5 mA--2Under the condition, the discharge curve can find the specific capacity (718.6 mAhgzn) of the rechargeable zinc-air battery assembled by taking the embedded porous Pd/C nano-rod loaded with Ni monoatomic atoms as an air cathode-1) And energy density (935.8 Wh kgzn)-1) Obviously superior to the traditional Pt/C + RuO2And an air cathode. FIG. 7 shows an embedded porous Ni-loaded Pd/C nanorod as an air cathode assembled zinc-air cell with constant current density of 10 mA--2Distribution of charge and discharge voltage under the conditions, it can be seen that the rechargeable zinc-air battery assembled by using the embedded porous Pd/C nanorods loaded with Ni monoatomic atoms as an air cathode can stably operate for 700 cycles (about 200 hours) without significant performance degradation.
Therefore, the embedded porous Pd/C nanorod loaded with Ni monoatomic atoms prepared by the method has the structural advantages of large specific surface area, good conductivity, strong permeability, high temperature resistance and the like; and simultaneously has Ni-NxAnd Pd superfine nanocrystalline (-5.0 nm), which are used for driving OER and ORR reactions respectively. Thus, Ni monoatomic-supported embedded porous Pd/C nanorods were shown to beThe double-function electric catalytic activity has excellent selectivity to oxygen reaction. More significantly, in the performance of the zinc-air battery, the embedded porous Pd/C nanorod loaded with the Ni monoatomic atom as the air cathode catalyst shows higher energy conversion efficiency and stronger cycle stability.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (9)
1. A preparation method of an embedded porous Pd-C nanorod loaded with Ni monoatomic atoms is characterized by comprising the following steps: adding PdCl into the aqueous solution of ethanol2And naphthylamine (C)10H9And N) mixing the two reactants uniformly, standing until a flaky Pd (II) -naphthylamine complex is generated, centrifugally drying a reaction system, dispersing the obtained solid powder and NiPc powder in a THF (tetrahydrofuran) solvent together, stirring uniformly, centrifugally drying, collecting the solid powder, calcining at high temperature in an inert atmosphere, and cooling to obtain the Ni-monoatomic-loaded embedded porous Pd-C nanorod.
2. The method for preparing Ni-monatomic-supported embedded porous Pd-C nanorods according to claim 1, characterized in that it comprises the following steps:
synthesis of yellow flaky Pd (II) -naphthylamine Complex
Weighing naphthylamine (C)10H9N), adding the mixture into an ethanol water solution, and performing ultrasonic treatment to fully dissolve the mixture; adding PdCl2Uniformly mixing the water solution, standing to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying to obtain powder;
preparation of Green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine Complex
The Pd (II) -naphthylamine complex and NiPc are dispersed in THF solvent together, slowly and uniformly mixed, stirred and centrifugally dried to obtain a powder green rod-shaped intermediate NiPc @ Pd (II) -naphthylamine complex;
preparation of Ni-loaded monatomic embedded porous Pd/C nanorod
The NiPc @ Pd (II) -naphthylamine complex is calcined at high temperature in an inert atmosphere and then cooled to obtain the final product.
3. The method for preparing Ni-monatomic-supported embedded porous Pd-C nanorod according to claim 1, wherein the mass fraction of Pd in the Pd (II) -naphthylamine complex in step 1) is 0.1-90%.
4. The method for preparing Ni-monatomic-supported embedded porous Pd-C nanorod according to claim 1, wherein the mass ratio of the Pd (II) -naphthylamine complex to NiPc in step 2) is (0.1-99): 1.
5. the method for preparing the Ni-monatomic-loaded embedded porous Pd-C nanorod according to claim 1, wherein the high-temperature calcination treatment in the inert atmosphere in the step 3) is performed by performing temperature programming for 2.5-20 ℃ for min in the atmosphere of nitrogen, argon or helium-1Heat treatment is carried out at 200-1000 ℃, and the temperature is kept for 0.5-24 h.
6. The method for preparing the Ni-monatomic-supported embedded porous Pd-C nanorod according to claim 1, wherein the volume ratio of water to ethanol in the ethanol aqueous solution in the step 1) is (0.1-99): 1.
7. The method for preparing the Ni-monatomic-loaded embedded porous Pd-C nanorod according to claim 1, wherein the stirring speed in the step 2) is 120rpm, and the magnetic stirring is carried out for 0.5-24 h.
8. An embedded porous Pd/C nanorod supporting Ni monoatomic atoms, prepared based on the preparation method of claim 1.
9. Use of the embedded porous Ni-loaded Pd/C nanorods based on claim 1 or claim 8 as air cathode catalyst in zinc-air cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111101813.6A CN114068951A (en) | 2021-09-18 | 2021-09-18 | Preparation method and application of Ni monoatomic-loaded embedded porous Pd-C nanorod |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111101813.6A CN114068951A (en) | 2021-09-18 | 2021-09-18 | Preparation method and application of Ni monoatomic-loaded embedded porous Pd-C nanorod |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114068951A true CN114068951A (en) | 2022-02-18 |
Family
ID=80234096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111101813.6A Pending CN114068951A (en) | 2021-09-18 | 2021-09-18 | Preparation method and application of Ni monoatomic-loaded embedded porous Pd-C nanorod |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114068951A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986059A (en) * | 2005-12-23 | 2007-06-27 | 中国石油化工股份有限公司 | Preparing process of mercaptol oxidizing catalyst |
| CN109378482A (en) * | 2018-09-25 | 2019-02-22 | 中新国际联合研究院 | The nucleocapsid catalyst of Non-precious Metal Catalysts material load, preparation method and applications |
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing |
| CN111527633A (en) * | 2017-12-26 | 2020-08-11 | 可隆工业株式会社 | Catalyst, method for preparing the same, electrode, membrane-electrode assembly and fuel cell comprising the catalyst |
| CN111682223A (en) * | 2020-06-12 | 2020-09-18 | 山东理工大学 | Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst |
| CN112736257A (en) * | 2020-12-07 | 2021-04-30 | 南京师范大学 | Embedded porous Fe-NxPreparation method of @ Pd-NC nanorod, nanorod prepared by preparation method and application of nanorod |
| CN113394410A (en) * | 2021-05-08 | 2021-09-14 | 南京师范大学 | Nitrogen-doped carbon nanosheet composite material anchored with NiPd/Ni and preparation method and application thereof |
-
2021
- 2021-09-18 CN CN202111101813.6A patent/CN114068951A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986059A (en) * | 2005-12-23 | 2007-06-27 | 中国石油化工股份有限公司 | Preparing process of mercaptol oxidizing catalyst |
| CN111527633A (en) * | 2017-12-26 | 2020-08-11 | 可隆工业株式会社 | Catalyst, method for preparing the same, electrode, membrane-electrode assembly and fuel cell comprising the catalyst |
| CN109378482A (en) * | 2018-09-25 | 2019-02-22 | 中新国际联合研究院 | The nucleocapsid catalyst of Non-precious Metal Catalysts material load, preparation method and applications |
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing |
| CN111682223A (en) * | 2020-06-12 | 2020-09-18 | 山东理工大学 | Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst |
| CN112736257A (en) * | 2020-12-07 | 2021-04-30 | 南京师范大学 | Embedded porous Fe-NxPreparation method of @ Pd-NC nanorod, nanorod prepared by preparation method and application of nanorod |
| CN113394410A (en) * | 2021-05-08 | 2021-09-14 | 南京师范大学 | Nitrogen-doped carbon nanosheet composite material anchored with NiPd/Ni and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| C. ALEGRE, A等: "Investigation of the activity and stability of Pd-based catalysts towards the oxygen reduction (ORR) and evolution reactions (OER) in iron–air batteries", RSC ADVANCES, vol. 5, pages 25424 - 25427 * |
| ZHIJUAN LI等: "Iminodiacetonitrile induce-synthesis of two-dimensional PdNi/Ni@carbon nanosheets with uniform dispersion and strong interface bonding as an effective bifunctional eletrocatalyst in air-cathode", ENERGY STORAGE MATERIALS, vol. 42, pages 118 - 128 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhong et al. | Engineering Pt and Fe dual-metal single atoms anchored on nitrogen-doped carbon with high activity and durability towards oxygen reduction reaction for zinc-air battery | |
| Li et al. | Regulation and mechanism study of the CoS2/Cu2S-NF heterojunction as highly-efficient bifunctional electrocatalyst for oxygen reactions | |
| Wu et al. | Metal-organic framework-derived, Zn-doped porous carbon polyhedra with enhanced activity as bifunctional catalysts for rechargeable zinc-air batteries | |
| Wang et al. | Co single-atoms on ultrathin N-doped porous carbon via a biomass complexation strategy for high performance metal–air batteries | |
| Chen et al. | Rational design of hollow N/Co-doped carbon spheres from bimetal-ZIFs for high-efficiency electrocatalysis | |
| Tian et al. | In-situ cobalt-nickel alloy catalyzed nitrogen-doped carbon nanotube arrays as superior freestanding air electrodes for flexible zinc-air and aluminum-air batteries | |
| Xu et al. | Morphology controlled La2O3/Co3O4/MnO2–CNTs hybrid nanocomposites with durable bi-functional air electrode in high-performance zinc–air energy storage | |
| Wang et al. | Boosting Li-CO2 battery performances by engineering oxygen vacancy on NiO nanosheets array | |
| Zhong et al. | Co/CoOx heterojunctions encapsulated N-doped carbon sheets via a dual-template-guided strategy as efficient electrocatalysts for rechargeable Zn-air battery | |
| Li et al. | Enhancing oxygen reduction performance of oxide-CNT through in-situ generated nanoalloy bridging | |
| Liu et al. | Facile preparation of modified carbon black-LaMnO3 hybrids and the effect of covalent coupling on the catalytic activity for oxygen reduction reaction | |
| Tang et al. | Advanced noble-metal-free bifunctional electrocatalysts for metal-air batteries | |
| Zhang et al. | Isolated transition metal nanoparticles anchored on N-doped carbon nanotubes as scalable bifunctional electrocatalysts for efficient Zn–air batteries | |
| Yang et al. | Interface reinforced 2D/2D heterostructure of Cu-Co oxides/FeCo hydroxides as monolithic multifunctional catalysts for rechargeable/flexible zinc-air batteries and self-powered water splitting | |
| CN111082079B (en) | Bifunctional oxygen electrocatalyst material and preparation method and application thereof | |
| CN112736257B (en) | Embedded porous Fe-NxPreparation method of @ Pd-NC nanorod, nanorod prepared by preparation method and application of nanorod | |
| Bang | Hollow graphitic carbon spheres for Pt electrocatalyst support in direct methanol fuel cell | |
| CN113394410B (en) | Nitrogen-doped carbon nanosheet composite material anchored with NiPd/Ni and preparation method and application thereof | |
| Zhang et al. | Spatial construction of ultrasmall Pt-decorated 3D spinel oxide-modified N-doped graphene nanoarchitectures as high-efficiency methanol oxidation electrocatalysts | |
| CN112002915B (en) | Oxygen electrode bifunctional catalyst, preparation method and application | |
| CN113471452A (en) | Multi-site composite nanotube for hydrogen and oxygen evolution reduction and preparation method and application thereof | |
| Li et al. | Engineering Gd2O3-Ni heterostructure for efficient oxygen reduction electrocatalysis via the electronic reconfiguration and adsorption optimization of intermediates | |
| Tian et al. | Carbon nitride decorated nitrogen doped graphene hollow spheres loaded Ni/Co and corresponding oxides nanoparticles as reversible air electrode catalysts for rechargeable zinc-air batteries | |
| CN113258083A (en) | CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof | |
| Wang et al. | Ni 3 Fe/Ni 3 Fe (OOH) x dynamically coupled on wood-derived nitrogen doped carbon as a bifunctional electrocatalyst for rechargeable zinc–air batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220218 |