CN113270597B - C 3 N 4 Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof - Google Patents
C 3 N 4 Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a C 3 N 4 A coated carbon nano tube loaded NiFe difunctional oxygen electrocatalyst and a preparation method thereof belong to the technical field of electrochemical catalyst materials. The invention takes the carbon nano tube as a carbon skeleton, the NiFe is embedded in the carbon skeleton in the form of nano metal particles, and the carbon nano tube is coated with C 3 N 4 The preparation method comprises the steps of firstly synthesizing Carbon Nano Tube (CNT) loaded bimetal NiFe-MOF by a hydrothermal method, then further mixing and grinding the carbon nano tube loaded bimetal NiFe-MOF with a nitrogen source, and finally obtaining the target catalyst through high-temperature pyrolysis. The composite catalyst of the invention shows good OER and ORR dual electrocatalytic activity in an alkaline medium, has simple preparation method and good application potential in practical energy conversion devices.
Description
Technical Field
The invention relates to the technical field of electrochemical catalyst materials, in particular to a catalyst C 3 N 4 A coated carbon nano tube loaded NiFe bifunctional oxygen electrocatalyst and a preparation method thereof.
Background
Zinc Air Batteries (ZAB) are considered to be one of the most promising energy conversion and storage technologies due to their advantages of high theoretical specific energy, good safety, environmental friendliness, etc. Despite extensive efforts, large-scale commercialization of ZABs is still limited by slow reaction kinetics of Oxygen Evolution Reactions (OERs) and Oxygen Reduction Reactions (ORRs). Noble metals Ru/Ir and Pt based catalysts are generally considered to be efficient electrocatalysts for OER and ORR, respectively. However, the disadvantages of limited resources, high cost, low anti-toxicity capability, poor durability and the like seriously hinder the large-scale application of the compound.
In recent years, many nitrogen-doped carbon-based materials have proven to be a widely accepted potential effective electrocatalyst for catalyzing ORR due to their highly tunable pore structure, good stability, and sufficiently high positive charge density to facilitate adsorption and reduction of oxygen molecules. The problems that the nitrogen content is relatively low and the catalytic activity is low and unstable due to the leaching of nitrogen active sites exist at present. High nitrogen content graphitic carbon nitride (g-C3N4) can be a viable ORR electrocatalyst by providing more active sites than other nitrogen carbon materials. Adding radix Et rhizoma Fagopyri Tatarici into water 3 N 4 The addition of the mesoporous carbon improves the four-electron selectivity (100 percent of four-electron selectivity) of the mesoporous carbon material in the ORR reaction process, and is obviously higher than that of a Pt/C catalyst. Likewise, the three-dimensional conductive porous g-C3N4/rGO mixed supramolecular structure favors O due to rich electrode-electrolyte-gas three-phase boundaries 2 The diffusion of molecules, electrolytes and electrons in the porous framework is beneficial to improving the ORR catalytic performance of the rGO. The nitrogen doping by introducing g-C3N4 improves ORR activity of carbon materials to a certain extent, but OER activity is low, so that the nitrogen-rich carbon-based hybrid is far from meeting the requirement of a high-efficiency dual catalyst.
It has been found that doping or properly introducing a small amount of metal species into the carbon-based material can improve the local electronic structure in the carbon skeleton structure, and reduce the binding energy of the surface adsorbed species OOH and OH, thereby effectively promoting the 4 e-ORR reaction process. Although non-noble metal-doped carbon materials generally exhibit some OER and ORR activities at the same time, since the catalyst preparation process is usually subjected to a pyrolysis process at 800 ℃, -1100 ℃, the metal species in the finally obtained catalyst material tend to form particles with larger size due to agglomeration, so that the surface active sites thereof are limited, and the electron transport between the metal species and the carbon skeleton is limited.
Therefore, there is an urgent need to develop a catalyst having both the oel and ORR electrocatalytic functions, which is highly efficient, inexpensive, and stable in performance.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a C 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst has carbon nanotube as carbon skeleton, NiFe embedded inside the carbon skeleton in the form of nanometer metal particle and coated with C 3 N 4 . The composite material is marked as NiFe/C 3 N 4 @ CNT or NiFe @ C 3 N 4 -CNT。
Specifically, the specific surface area of the catalyst material is 250-450cm 2 g -1 The pore diameter is mainly distributed in 2-10nm and is intensively distributed in 4 nm.
The invention further discloses a preparation method of the bifunctional oxygen electrocatalyst, which comprises the following steps:
(1) weighing a proper amount of carbon nano tubes, adding the carbon nano tubes into an N, N-dimethylformamide solution to completely disperse the carbon nano tubes, adding an organic ligand to uniformly mix, then adding a certain amount of nickel salt and ferric salt to dissolve the nickel salt and the ferric salt to obtain a precursor mixed solution, and carrying out hydrothermal reaction under an alkaline condition to obtain a carbon nano tube precursor loaded with NiFe-MOF (nickel-metal organic framework) namely NiFe-MOF @ CNT;
(2) weighing a proper amount of NiFe-MOF @ CNT, uniformly mixing with a nitrogen source, and carrying out high-temperature pyrolysis to obtain the target catalyst.
Preferably, the carbon nanotubes are subjected to a surface oxidation pretreatment before dispersion.
Specifically, the carbon nanotubes are in H 2 SO 4 And HNO 3 The mixed solution of (3) is subjected to surface oxidation treatment.
Wherein the nickel salt is nickel nitrate, nickel chloride, nickel acetate or nickel sulfate, and the iron salt is ferric chloride, ferric nitrate, ferric sulfate or ferrous chloride
Preferably, the nickel salt is Ni (NO) 3 ) 2 ·6H 2 O, iron salt being FeCl 3 ·6H 2 O。
Wherein the content of CNT in the precursor mixed solution is 1-2 mg/mL.
Wherein the concentration of the metal salt in the precursor mixed solution is 0.02-0.08 mol/L.
Wherein the molar ratio of the bimetallic salt in the step 1 is Ni: fe is 1: 0.4-1: 2.5; preferably Ni: fe is 1.5: 1-0.7: 1; most preferably Ni: fe ═ 1: 1.
Wherein, the hydrothermal reaction temperature in the step 1 is controlled at 100-150 ℃.
Wherein, the nitrogen source in the step 2 is dicyandiamide, melamine or urea.
Wherein the mass ratio of the NiFe-MOF @ CNT in the step 2 to the nitrogen source is 1: 1-1: 10.
Wherein, the high-temperature pyrolysis temperature in the step 2 is controlled at 600-700 ℃.
The invention has the following beneficial effects:
the invention firstly synthesizes Carbon Nano Tube (CNT) loaded bimetal NiFe-MOF by a hydrothermal method, then takes the bimetal NiFe-MOF as a precursor and a structural template, further mixes and grinds the precursor and a nitrogen source, and finally obtains C by high-temperature pyrolysis 3 N 4 Wrapped CNT composite catalyst NiFe/C loaded with bimetallic nano-particle NiFe 3 N 4 @CNT；
The composite catalyst of the invention shows good OER and ORR dual electrocatalytic activity in an alkaline medium, and shows high power density of 137.05mW/cm as a cathode catalyst of a zinc-air battery 2 High energy density 684.65 Wh kg -1 The good application potential of the composite catalyst in the practical energy conversion device is proved;
the invention mainly relates to a two-step process, namely a simple hydrothermal reaction, the process does not relate to any template, the reaction condition is mild, and in addition, the high-efficiency and stable oxygen electrocatalyst can be obtained by adopting lower pyrolysis temperature in the pyrolysis process.
Drawings
FIG. 1 shows a specific example of NiFe/C of the present invention 3 N 4 A process flow diagram for preparing the @ CNT dual-function oxygen electrocatalyst;
FIG. 2 shows a specific NiFe/C of the present invention 3 N 4 @CNT、C 3 N 4 The XRD patterns of @ CNT and O-CNT;
FIG. 3 is an SEM image of one embodiment of the NiFe-MOF @ CNT of the present invention;
FIG. 4 shows Ni of example 1 0.5 Fe 0.5 /C 3 N 4 XPS spectra of @ CNT: ni2p, Fe2p, N1s and C1s spectra;
FIG. 5 a shows a specific NiFe/C of the present invention 3 N 4 SEM image of @ CNT, b and C are NiFe/C 3 N 4 TEM image of @ CNT, d is NiFe/C 3 N 4 In HRTEM image, 0.36nm lattice fringes belonging to (002) crystal plane of graphite carbon and 0.21nm lattice FeNi are observed 3 The (111) crystal face of (a);
in FIG. 6, a is Ni of example 1 0.5 Fe 0.5 /C 3 N 4 @ CNT and comparative example 1C 3 N 4 N of @ CNT 2 Drawing, b is a corresponding aperture distribution diagram;
FIG. 7 is C 3 N 4 @ CNT and Ni of different Ni, Fe proportions x Fe 1-x /C 3 N 4 @CNT(0<x<1) The results were tested in an oxygen-saturated 0.1M KOH electrolyte system: (a) linear sweep voltammograms, (b) the corresponding onset potential (E0), half wave potential (E1/2) and limiting current density Jlim; oxygen evolution performance in 1.0M KOH electrolyte: (c) linear sweep voltammogram, (d) overpotential.
FIG. 8 shows a composition consisting of Ni 0.5 Fe 0.5 /C 3 N 4 @ CNT and 20% Pt/C + RuO 2 The battery performance of the prepared rechargeable zinc-air battery is as follows: (a) a charge-discharge polarization curve and a corresponding power density curve; (b) at a current density of 10mA cm -2 Lower energy density curve; (c) long term charge and discharge curve (20 min/cycle).
Detailed Description
The Metal Organic Frameworks (MOFs) are porous framework structures formed by coordination bonds between organic multiple topological structure elements and metal or metal cluster type secondary building units, can be used as porous structure templates for derivative preparation of porous metal species, and simultaneously, the limited domain separation effect of organic ligands on metal sites is favorable for uniform distribution of the metal sites on a carbon skeleton. Sp2 hybridized one-dimensional Carbon Nanotubes (CNTs) are considered to be ideal carbon-based scaffolds due to their excellent stability, good electrical conductivity, and easy functionalization. The graphitized carbon nitride (g-C3N4) modified carbon material with high nitrogen content is favorable for causing the redistribution of the local electronic structure of the carbon skeleton due to the interaction between the nitrogen-rich carbon structure with high electronegativity and the carbon structure, thereby influencing the intrinsic electrocatalytic activity of the carbon-based material.
The invention utilizes porous NiFe-MOF with dispersed metal nodes as a metal precursor and simultaneously utilizes the optimization of g-C3N4 on the structure and the electronic structure of CNT, and provides a method for efficiently and quickly preparing a bifunctional oxygen reduction catalyst 2 The high-efficiency and low-cost bifunctional oxygen catalyst can be obtained by one-step pyrolysis in the atmosphere.
The invention provides a compound C 3 N 4 The preparation method of the coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst can be specifically carried out according to the following operations:
1. precursor preparation
Weighing a certain amount of carbon nano tube, adding the carbon nano tube into N, N-dimethylformamide solution saturated by nitrogen, carrying out ultrasonic treatment for a period of time to completely disperse the CNT, then adding terephthalic acid, stirring for 0.5h, and then adding a certain amount of Ni (NO) 3 ) 2 ·6H 2 O and FeCl 3 ·6H 2 And continuously performing ultrasonic dispersion on the O to enable the O to be dissolved and uniformly dispersed in the O. Then, 2-3 mL of 0.4M NaOH solution is added and stirred to mix thoroughly. And then transferring the mixed solution into a high-pressure reaction kettle, placing the reaction kettle in an oven, heating to the target temperature (100-.
In a preferred embodiment, the carbon nanotubes are subjected to a surface oxidation pretreatment before dispersion to form oxygen-containing functional groups on the surface of the carbon nanotubes, thereby improving the affinity of the CNTsWater-based while allowing Ni in the reaction process 2+ 、Fe 3+ Ions are easy to adsorb on the surface of the CNT, and further metal ions and ligands of terephthalic acid act, so that NiFe-MOF precursors are generated on the surface of the CNT in situ.
2. Sample preparation
Weighing a certain amount of the precursor, mixing and grinding the precursor and a certain amount of dicyandiamide for 30min to ensure that the NiFe-MOF @ CNT precursor and the dicyandiamide are fully and uniformly mixed, then transferring the mixture into a ceramic crucible, placing the ceramic crucible into a tubular furnace, and N 2 Or heating to 600-.
In the hydrothermal process, metal ions interact with ligands to grow NiFe-MOF on the surface of the CNT in situ. The NiFe-MOF serving as a typical metal organic framework material has good porous network structural characteristics, and bimetallic nodes coordinated with ligands are separated by organic ligands, so that metal agglomeration is prevented, and the metal has high dispersibility; after subsequent high-temperature pyrolysis, the terephthalic acid ligand is decomposed, and NiFe metal sites still keep high dispersity and are attached to the surface of the CNT, so that more catalytic active sites can be exposed, and the ORR and OER activity can be improved.
The principles and features of this invention are described below in conjunction with the drawings and the embodiments, which are set forth to illustrate, but are not to be construed to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1 Ni 0.5 Fe 0.5 /C 3 N 4 @CNT
Surface oxidation treatment of the carbon nano tube: 100mg of carbon nanotubes are added into H 2 SO 4 And HNO 3 The mixed solution (v/v-3/1) was stirred at room temperature for 24 hours. Diluting the CNT solution by about 10-20 times, then carrying out suction filtration to collect solid, repeatedly washing with distilled water, and carrying out suction filtration until the solid is dissolvedAnd (4) collecting a filter cake, placing the filter cake in a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the carbon oxide nanotube (marked as O-CNT).
Preparing a precursor: 25mL of N, N-dimethylformamide was weighed into a 50mL beaker, followed by 44mg of O-CNT, continued sonication at room temperature for 40 minutes, addition of terephthalic acid, mixing well, and addition of 0.135g FeCl 3 ·6H 2 O and 0.145g of Ni (NO) 3 ) 2 ·6H 2 O is uniformly dispersed therein. Then adding a certain amount of sodium hydroxide solution, continuously stirring to fully mix, transferring the mixed solution into a 50mL high-pressure reaction kettle, then placing the reaction kettle in an oven, heating to 120 ℃, and then preserving heat for 8 hours. After natural cooling, the reaction product is poured out, washed and centrifuged, and the product is collected and dried in a vacuum oven at 120 ℃ for 12 hours.
Sample preparation: the precursor prepared above was milled and mixed with 50mg of dicyandiamide, and the mixture was placed in N 2 Heating to 600 deg.C at 2.3 deg.C/min in a tubular furnace, maintaining for 4 hr, naturally cooling to room temperature, taking out black sample as target catalyst sample, and recording the product as Ni 0.5 Fe 0.5 /C 3 N 4 @CNT。
Example 2 Ni 0.3 Fe 0.7 /C 3 N 4 @CNT
Preparing a precursor: 25mL of N, N-dimethylformamide was taken in a 50mL beaker, 44mg of O-CNT was added, ultrasonic treatment was continued at room temperature for 40 minutes to sufficiently disperse the O-CNT, terephthalic acid was added thereto and mixed well, and then 0.087g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.56 mmoleFeCl 3 ·6H 2 O is added into the CNT solution, and ultrasonic uniform dispersion is continued for a period of time. Then 2-2.5 mL of 0.4M NaOH solution is added and stirring is continued to mix thoroughly. And transferring the mixed solution into a 50mL high-pressure reaction kettle, then placing the reaction kettle in an oven, heating to 120 ℃, and then preserving heat for 10 hours. After natural cooling, the reaction product is poured out, washed, centrifuged and dried in a vacuum oven at 120 ℃ for 12 h.
Sample preparation: subjecting the precursor prepared as described above to a reaction with50mg of dicyandiamide were mixed by milling and the mixture was placed in N 2 Heating to 600 deg.C at 2.3 deg.C/min in a tubular furnace in atmosphere, maintaining for 4 hr, naturally cooling to 70 deg.C to obtain black catalyst sample, and recording the product as Ni 0.3 Fe 0.7 /C 3 N 4 @CNT。
Example 3 Ni 0.7 Fe 0.3 /C 3 N 4 @CNT
Preparing a precursor: weighing 44mg of O-CNT, adding into 25ml of N-dimethylformamide solution, ultrasonically dispersing for more than 30min to fully disperse, adding terephthalic acid, mixing well, weighing 0.204g of Ni (NO) 3 ) 2 ·6H 2 O and 0.081g FeCl 3 ·6H 2 O is added to the CNT solution and ultrasonic dispersion is continued for a period of time. Subsequently, 2.5mL of NaOH solution (0.4M) was added, and the mixed solution was stirred at room temperature for another 30min to be sufficiently mixed. And transferring the mixed solution into a 50mL high-pressure reaction kettle, then placing the reaction kettle in an oven, heating to 120 ℃, and then preserving heat for 10 hours. After natural cooling, the reaction product is poured out, washed, centrifuged and dried in a vacuum oven at 120 ℃ for 12 h.
Sample preparation: the precursor prepared above was milled and mixed with 50mg of dicyandiamide, and the mixture was placed in N 2 Heating to 600 ℃ at a speed of 2-2.3 ℃/min in a tubular furnace in the atmosphere, preserving heat for 4h, naturally cooling to 70 ℃ to obtain a black catalyst sample, and recording the product as Ni 0.7 Fe 0.3 /C 3 N 4 @CNT。
Comparative example 1C 3 N 4 @CNT
Mixing and grinding 44mg of oxidized O-CNT and 50mg of dicyandiamide in an agate mortar for 30min, then putting the mixture into a ceramic crucible, placing the ceramic crucible in the center of a tubular furnace, raising the temperature to 600 ℃ at the speed of 2-2.3 ℃/min in a nitrogen atmosphere, and preserving the temperature for 4 h. After allowing to cool naturally, a black sample was taken and recorded as C3N4@ CNT. The XRD analysis is shown in fig. 2.
Comparative example 2 Ni/C 3 N 4 @CNT
Preparing a precursor: 44mg of carbon nano tube is weighed and added into 25mLN, N-dimethylUltrasonic dispersing in formamide solution for more than 30min, adding terephthalic acid, mixing, and weighing 0.291g of Ni (NO) 3 ) 2 ·6H 2 O is added to the CNT solution and ultrasonic dispersion is continued for a period of time. Subsequently, 2.5mL of NaOH solution (0.4M) was added, and the mixed solution was stirred at room temperature for another 30min to be sufficiently mixed. And transferring the mixed solution into a 50mL high-pressure reaction kettle, then placing the reaction kettle in an oven, heating to 120 ℃, and then preserving heat for 10 hours. After natural cooling, the reaction product is poured out, washed, centrifuged and dried in a vacuum oven at 120 ℃ for 12 h.
Sample preparation: and (3) grinding and mixing the prepared precursor and 50mg of dicyandiamide, putting the mixture into a tubular furnace in an N2 atmosphere, heating to 600 ℃ at the speed of 2-2.3 ℃/min, preserving heat for 4h, and naturally cooling to 70 ℃ to obtain a black catalyst sample.
Comparative example 3 Fe/C 3 N 4 @CNT
Preparing a precursor: weighing 44mg of carbon nano tube, adding the carbon nano tube into 25mLN, N-dimethylformamide solution, performing ultrasonic dispersion for more than 30min to fully disperse the carbon nano tube, adding terephthalic acid, uniformly mixing, weighing 0.27g of FeCl 3 ·6H 2 The addition of O to the CNT solution continues the ultrasonic dispersion for a period of time. Subsequently, 2.5mL of NaOH solution (0.4M) was added, and the mixed solution was stirred at room temperature for another 30min to be sufficiently mixed. And transferring the mixed solution into a 50mL high-pressure reaction kettle, then placing the reaction kettle in an oven, heating to 120 ℃, and then preserving heat for 10 hours. After natural cooling, the reaction product is poured out, washed, centrifuged and dried in a vacuum oven at 120 ℃ for 12 h.
Sample preparation: the precursor prepared above was milled and mixed with 50mg of dicyandiamide, and the mixture was placed in N 2 And (3) heating to 600 ℃ at the speed of 2-2.3 ℃/min in a tubular furnace in the atmosphere, preserving heat for 4h, and naturally cooling to 70 ℃ to obtain a black catalyst sample.
Examples of Performance test
Preparing an electrode: 2.0mg of the prepared material is weighed and placed in a sample tube, and then 350 muL of distilled water, 150 muL of isopropanol and 10 muL of Nafion solution are added in sequence and shaken up. And (4) taking out the small test tube after ultrasonic dispersion for 2 h. Accurately measuring 15 mu L of the catalyst mixed solution by using a liquid transfer gun, dripping the catalyst mixed solution on a rotating disc electrode (phi: 5mm), or dripping 4 mu L of the catalyst mixed solution on a glassy carbon electrode (phi: 3mm), placing the glassy carbon electrode at a ventilated place, naturally airing the glassy carbon electrode, and taking the glassy carbon electrode as a working electrode in subsequent tests.
And (3) testing the catalytic performance: the ORR performance test of the catalyst material is carried out on an AUTOLAB electrochemical workstation and a PINE rotating disk electrode, and the test system is a standard three-electrode system, wherein the oxygen reduction performance test process takes the disk electrode (phi: 5mm) loaded with a catalyst coating as a working electrode, Pt wire as a counter electrode, an Ag/AgCl electrode as a reference electrode, and O 2 Saturated 0.1M KOH solution was the electrolyte. Oxygen Evolution (OER) performance was also tested in a standard three-electrode system, in which a glassy carbon electrode (phi: 3mm) supporting a catalyst material was used as the working electrode, a Pt sheet was used as the counter electrode, and an Ag/AgCl electrode was used as the reference electrode.
Assembling a zinc-air battery: the zinc-air battery is formed by assembling an air electrode (anode), a diaphragm and a zinc electrode (cathode), wherein the air electrode is loaded by 1mg cm -2 The NiFe @ C3N4-CNT or noble metal catalyst consists of a carbon sheet, foamed nickel and a waterproof film, and 6.0M KOH electrolyte is used as electrolyte. The assembled zinc-air cell tests were all performed at room temperature. And obtaining a discharge polarization curve of the zinc-air battery by adopting a linear sweep voltammetry at a sweep speed of 10mV s < -1 >. For rechargeable zinc-air batteries, 6.0M KOH +0.20M Zn (Ac) 2 As electrolyte, 1.6V-2.5V over a potential window at a scan rate of 10mV s -1 And obtaining a charging polarization curve of the battery. The zinc-air cells were subjected to galvanostatic discharge and charge-discharge cycling tests (20 min per cycle) on a NEWEI test system.
Results of Performance test
As shown in FIG. 7, the electrochemical results of example 1 showed a catalyst loading of 305.7. mu.g cm -2 When the catalyst is used, the catalytic initial potential is 0.903V (vs. RHE), the half-wave potential is 0.785V (vs. RHE), and the limiting current density reaches 4.98mA cm -2 (ii) a The overpotential during the oxygen evolution reaction is 315 mV. Electric powerThe potential difference is only 0.76V. As shown in FIG. 8, the test results after the zinc-air battery is assembled show that the power density and the energy density can reach 137.05mW cm respectively -2 And 684.65Wh kg -1 . It is at 10mA cm -2 After the current is cycled for 130h, the voltage difference is only increased by 0.19V, which shows good stability, and the stability is better than that of a commercial 20% Pt/C + RuO2 assembled air battery under the same test condition.
As shown in FIG. 7, the electrochemical results of example 2 showed a catalyst loading of 305.7. mu.g cm -2 When the catalyst is used, the catalytic initial potential is 0.903V (vs. RHE), the half-wave potential is 0.761V (vs. RHE), and the limiting current density reaches 5.13mA cm -2 (ii) a The overpotential during the oxygen evolution reaction is 324 mV. The potential difference was 0.793V.
As shown in FIG. 7, the electrochemical results of example 3 showed a catalyst loading of 305.7. mu.g cm -2 When the catalyst is used, the catalytic initial potential is 0.85V (vs. RHE), the half-wave potential is 0.72V (vs. RHE), and the limiting current density reaches 4.58mA cm -2 (ii) a The overpotential during the oxygen evolution reaction is 318 mV. The potential difference was 0.828V.
As shown in FIG. 7, the electrochemical results for comparative example 1C3N4@ CNT showed a catalyst loading of 305.7 μ g cm -2 When the catalyst is used, the catalytic initial potential is 0.707V (vs. RHE), the half-wave potential is 0.50V (vs. RHE), and the limiting current density reaches 4.19mA cm -2 (ii) a The overpotential during the oxygen evolution reaction is 490 mV. The potential difference was 1.22V.
As shown in FIG. 7, the electrochemical results for comparative example 2Ni/C3N4@ CNT showed a catalyst loading of 305.7 μ g cm -2 When the catalyst is used, the catalytic initial potential is 0.852V (vs. RHE), the half-wave potential is 0.767V (vs. RHE), and the limiting current density reaches 3.48mA cm -2 (ii) a The overpotential during the oxygen evolution reaction is 399 mV. The potential difference was 0.862V.
As shown in FIG. 7, the electrochemical results for comparative example 3Fe/C3N4@ CNT showed a catalyst loading of 305.7 μ g cm -2 When the catalyst is used, the catalytic initial potential is 0.903V (vs. RHE), the half-wave potential is 0.756V (vs. RHE), and the limiting current density reaches 4.90mA cm -2 (ii) a The overpotential in the oxygen evolution reaction process is 389 mV. The potential difference was 0.863V.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. C 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: the catalyst material takes a carbon nano tube as a carbon skeleton, NiFe is embedded in the carbon skeleton in the form of nano metal particles, and meanwhile, the carbon nano tube is coated with C 3 N 4 (ii) a The specific surface area of the catalyst material is 250-450m 2 g -1 The aperture is mainly distributed in 2-10 nm; the preparation method of the catalyst material is characterized by comprising the following steps:
(1) weighing a proper amount of carbon nanotubes, dispersing the carbon nanotubes in an N, N-dimethylformamide solution, adding an organic ligand, uniformly mixing, adding a certain amount of nickel salt and ferric salt, dissolving to obtain a precursor mixed solution, and carrying out hydrothermal reaction under an alkaline condition to obtain a NiFe-MOF-loaded carbon nanotube precursor, namely NiFe-MOF @ CNT; the molar ratio of nickel to iron in the precursor mixed solution is Ni: fe =1: 0.4-1: 2.5;
(2) weighing a proper amount of the NiFe-MOF @ CNT, uniformly mixing with a nitrogen source, and carrying out high-temperature pyrolysis to obtain a target catalyst; the nitrogen source is dicyandiamide, melamine or urea, the mass ratio of the NiFe-MOF @ CNT to the nitrogen source is 1: 1-1: 10, and the high-temperature pyrolysis temperature is controlled at 600-700 ℃.
2. C according to claim 1 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: carrying out surface oxidation pretreatment on the carbon nano tube; placing carbon nanotubes in H 2 SO 4 And HNO 3 The mixed solution of (2) is subjected to surface oxidation pretreatment.
3. C according to claim 1 or 2 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: the nickel salt isNickel nitrate, nickel chloride, nickel acetate or nickel sulfate, and the iron salt is ferric chloride, ferric nitrate, ferric sulfate or ferrous chloride.
4. C according to claim 1 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: the content of CNT in the precursor mixed solution in the step 1 is 1-2 mg/mL; the concentration of the metal salt in the precursor mixed solution in the step 1 is 0.02-0.08 mol/L.
5. C according to claim 1 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: step 1, the hydrothermal reaction temperature is controlled at 100-150 ℃.
6. C according to claim 1 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: 1, the molar ratio of nickel to iron in the precursor mixed solution is Ni: fe =1.5:1 to 0.7: 1.
7. C according to claim 6 3 N 4 The coated carbon nanotube supported NiFe bifunctional oxygen electrocatalyst is characterized in that: 1, the molar ratio of nickel to iron in the precursor mixed solution is Ni: fe =1: 1.
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