CN113130922B - Preparation method and application of Ce-Co-S-P nanocrystalline - Google Patents

Preparation method and application of Ce-Co-S-P nanocrystalline Download PDF

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CN113130922B
CN113130922B CN202110281174.XA CN202110281174A CN113130922B CN 113130922 B CN113130922 B CN 113130922B CN 202110281174 A CN202110281174 A CN 202110281174A CN 113130922 B CN113130922 B CN 113130922B
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封飞艳
毛启昕
钱春竹
杨浩
曹佳
段海宝
刘苏莉
陈昌云
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Nanjing Xiaozhuang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract

The invention providesA method for preparing Ce-Co-S-P nanocrystalline comprises the following steps: mixing ammonium ceric nitrate, cobalt acetylacetonate, oleic acid, n-dodecyl mercaptan and tri-n-octyl phosphine, heating to 320 deg.CoAnd C, performing heat preservation reaction, and performing dispersion sedimentation and centrifugal separation on the obtained product to obtain the Ce-Co-S-P nanocrystal. The Ce-Co-S-P nanocrystalline prepared by the method has excellent OER performance and can efficiently catalyze the OER in the fuel cell. The invention adopts a one-pot method, utilizes Ce to effectively adjust the phase change of the Co-S-P nanosheets, simultaneously adjusts the catalytic performance, has simple process, low reaction temperature and short time, is suitable for batch production, and has important guiding significance for the technical development of renewable energy sources.

Description

Preparation method and application of Ce-Co-S-P nanocrystalline
Technical Field
The invention relates to the technical field of nanocrystals, in particular to a preparation method and application of a Ce-Co-S-P nanocrystal.
Background
The hydrogen is taken as an ideal clean energy fuel, and when the hydrogen is applied to energy conversion devices such as fuel cells and the like, the hydrogen has high energy density, does not emit carbon and is environment-friendly. Among various hydrogen production methods, hydrogen production by water electrolysis has the characteristics of environmental friendliness, high efficiency and the like, and is widely concerned by people. The hydrogen production by water electrolysis mainly comprises two half reactions of cathodic Hydrogen Evolution Reaction (HER) and anodic Oxygen Evolution Reaction (OER), wherein the OER becomes a rate determining step due to the slowest electrochemical kinetics process. At present, Pt-group active metal-based materials are still the catalysts with highest catalytic efficiency for HER (Pt, Ir, Ru and the like)/OER (Ir/Ru oxide and the like), but the Pt-group active metal-based materials have high cost and poor stability and seriously influence the development of the water electrolysis hydrogen production industry. Therefore, it has been a focus of attention to find a material with low cost and relatively high performance.
The transition metal phosphide has semimetal characteristics, is relatively stable in acid-base environment, has good light and heat stability, and is a novel catalytic material appearing after transition metal carbide and transition metal nitride. In recent years, transition metal phosphide has exhibited catalytic activity comparable to that of noble metal platinum in reactions such as photo/electrocatalytic decomposition of water for hydrogen evolution, catalytic hydrogenation, dehydrogenation and the like, and is known as a "quasi-platinum catalyst". However, the phosphide prepared by the traditional preparation method such as low-temperature phosphorization, liquid-phase hydrothermal method and the like has large size, catalytic sites are only positioned on the surface of the catalyst, so the utilization rate of the active sites is low, and the prepared single-component phosphide has poor conductivity. Therefore, how to more efficiently utilize the redundant active sites of transition metal phosphide to maximize the utilization rate of the catalyst; how to better improve the conductivity of the phosphide; the problems of further improving the catalytic stability and the like become a plurality of problems which limit the industrial application of the catalyst at present.
Previous studies indicate that transition metal cation doping is an effective means for improving the catalytic activity of phosphide electrocatalysts. However, the performance of triggering phosphide phase transition and regulating electrocatalysis is rarely reported by utilizing the abundant redox performance, good electronic conductivity and flexible coordination capability of the rare earth element cerium.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of Ce-Co-S-P nanocrystalline, which takes the prepared Ce-Co-S-P nanocrystalline as an oxygen evolution reaction catalyst of a fuel cell and has the characteristics of novelty, high efficiency and low price.
The invention provides a preparation method of Ce-Co-S-P nanocrystalline, which comprises the following steps: mixing ammonium ceric nitrate, cobalt acetylacetonate, oleic acid, n-dodecyl mercaptan and tri-n-octyl phosphine, heating to 320 ℃, carrying out heat preservation reaction, and carrying out dispersion sedimentation and centrifugal separation on the obtained product to obtain the Ce-Co-S-P nanocrystal.
Preferably, the time for the incubation reaction is 30 min.
Preferably, the temperature rise is gradual temperature rise according to the speed of 7 ℃/min.
Preferably, the temperature rise is direct temperature rise.
Preferably, the addition ratio of each part of the Ce-Co-S-P nanocrystalline is as follows: 0.375mmol of ceric ammonium nitrate, 0.7mmol of cobalt acetylacetonate, 1.5mL of oleic acid, 8mL of n-dodecyl mercaptan, and 5mL of tri-n-octyl phosphine.
Preferably, the dispersion sedimentation is performed by using an n-heptane and ethanol solution, wherein the operations of dispersion sedimentation and centrifugal separation by using n-heptane and ethanol can be repeated 3-4 times each.
Preferably, the volume ratio of the n-heptane solution to the ethanol solution is 3: 1.
the invention also provides application of the Ce-Co-S-P nanocrystalline as a reaction catalyst of a fuel cell.
Preferably, the reaction is an oxygen evolution reaction.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, Ce is adopted to effectively regulate the phase change of the Co-S-P nanosheets, and the Co-S-P nanocrystals doped with Ce are of twin crystal lamellar structures, have more dislocation and step defect sites, have excellent OER performance and can efficiently catalyze the OER in the fuel cell. The performance of the composite material is detected to be superior to that of the current commercial lrO2The method has important guiding significance for the development of renewable energy development technology.
2. The Ce-Co-S-P nanocrystalline is controllably synthesized at normal pressure and low temperature through solid-liquid phase chemical reaction; meanwhile, the flaky Ce-Co-S-P nano crystal is obtained by adopting a one-pot boiling mode and utilizing a program temperature control mode, the process is simple, the reaction temperature is low, the time is short, and the method is suitable for batch production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM image of Ce-Co-S-P nanocrystals in the examples of the present invention.
FIG. 2 is a HRTEM and Mapping image of the Ce-Co-S-P nanocrystal in the embodiment of the invention.
FIG. 3 is an XRD and XPS diagram of the Ce-Co-S-P nanocrystals in the example of the present invention.
FIG. 4 is an EPR diagram of the Ce-Co-S-P nanocrystals in the examples of the present invention.
FIG. 5 is an OER performance test chart of the Ce-Co-S-P nanocrystals in the examples of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
Examples
203.5mg (0.375mmol) of ceric ammonium nitrate and 178.2mg (0.7mmol) of cobalt acetylacetonate were weighed out at room temperature, and all the raw materials were charged into a dry three-necked round-bottomed flask having a capacity of 250mL together, and 1.5mL of oleic acid, 8mL of n-dodecyl mercaptan and 5mL of tri-n-octyl phosphine were measured out by a rubber head dropper and charged into the three-necked round-bottomed flask, followed by uniform mixing to obtain a solution.
Transferring the three-neck round-bottom flask into a sand bath, raising the temperature to 320 ℃ at the speed of 7 ℃/min under the programmed temperature control, preserving the temperature for 30min, naturally cooling the reactor to the room temperature after the reaction is finished, and adding a proper amount of a solvent with the volume ratio of 3: 1 and dispersing the mixture in n-heptane and ethanol, and centrifuging to separate solid. And washing the solid to obtain a product, namely the Ce-Co-S-P nanocrystalline, and drying the product at 60 ℃ in vacuum for analysis and characterization.
The product was analyzed by XRD, XPS, Mapping, TEM and HRTEM, EPR tests, respectively, and the results are shown in fig. 1 to 4. Fig. 1 is a TEM image of a sample, from which it can be seen that the sample has a sheet-like structure. FIG. 2 isAccording to the HRTEM image of the sample, the sample is of a twin-crystal sheet structure and has more dislocation, steps and other defect sites, literature research shows that the defect sites play an important role in improving the catalytic activity, and Mapping image shows that main elements are Ce, Co, S and P. The XRD pattern of FIG. 3 shows that the synthesized material is Co3S4(JCPDS #3-731) and Co9S8(JCPDS # 19-364). Cubic phase Co3S4The diffraction peaks of (a) are located at 26.71 °, 31.41 °, 38.16 °, 50.25 ° and 55.23 ° belonging to the (220), (311), (400), (511) and (440) crystal planes, respectively; cubic phase Co9S8The diffraction peaks of (a) are located at 30.02 °, 47.99 °, 52.15 °, and are assigned to the (311), (511), and (440) crystal planes, respectively.
XPS (X-ray diffraction) graph shows that two main peaks of Ce-Co-S-P nanosheet Co 2P at the binding energy of 778.5eV and 793.5eV are respectively attributed to Co3+Co 2p of3/2And Co 2p1/2The peaks at the binding energies 780.7eV and 796.5eV are considered to be Co2+Co 2p of (1)3/2And Co 2p1/2. The remaining two peaks are satellite peaks at binding energies 784.5eV and 802.8 eV. The XPS result of Co shows that Co in the Ce-Co-S-P nanosheet2+：Co3+Is 1: 1.36, 1: 1.09, which shows that Ce-Co-S-P nanosheets have S with a low coordination number, confirming the presence of S vacancies. Two peaks centered at 161.5eV and 164.2eV of the Ce-Co-S-P nanosheet S2P correspond to S2-S2 p of3/2And S2 p1/2(ii) a Two peaks at 162.5eV and 163.5eV can be assigned to S2 2-S2 p of3/2And S2 p1/2. The broad peak observed at 168.9eV may be considered to be S oxidation due to air contact. While peaks at 161.4eV and 162.5eV in the XPS spectrum of Co-S-P correspond to S2P3/2And S2 p1/2Indicating the presence of a Co-S bond. Ce-Co-S-P and Co-S-P, wherein the introduction content of P is very small, and the doping content of Ce-Co-S-P nanosheet Ce is very weak compared with that of Co-S-P. The EPR diagram of FIG. 4 shows that compared with Co-S-P, the Ce-Co-S-P nanosheet shows abundant S vacancies, and the EPR signal is stronger at 2.004 g.
Based on the analysis, the obtained crystal product is Ce-Co-S-P nanocrystalline and has a twin-crystal sheet structure.
Test examples
The electrochemical properties of the sample are tested in a three-electrode system by cyclic voltammetry and a polarization curve method, and the specific process is as follows:
the electrochemical experiment was carried out on an AUTOLAB-PGSTAT302N type electrochemical workstation, using a standard three-electrode test system, the corresponding working electrode being a glassy carbon electrode modified with the sample obtained herein, the counter electrode being a platinum sheet, and the reference electrode being mercury oxide (HgO). All potentials in this experiment were relative to HgO, electrolyte solution, 0.1M KOH solution, and all electrochemical tests were performed at 25 ℃. At each experiment, all modified electrodes were tested in 0.1M KOH solution.
The preparation method of the sample modified electrode comprises the following steps:
before each experiment, a rotating disk electrode having a diameter of 5mm was coated with Al of 1.0 μm, 0.3 μm and 0.05 μm in this order2O3Grinding to obtain mirror surface, ultrasonic cleaning, rinsing with redistilled water, and standing at room temperature N2Drying in the atmosphere for later use. 5mg of the product was dispersed in 0.25mL of ethanol and then 0.7mL of water and 0.25mL of 1% naphthol solution were added to obtain a suspension of 5mg/mL of the product. 10 μ L of the suspension and 5 μ L of 0.1% naphthol solution were dispersed successively on the surface of the rotating disk electrode N2And drying in the atmosphere to obtain the product Ce-Co-S-P nanocrystalline modified electrode.
Before OER test, high-purity O is firstly introduced into the solution2For 30min to remove dissolved other gases in the solution and continue to pass O during the experiment2To maintain O of the solution2And (4) atmosphere. LSV is also at O2The electrochemical scanning speed is 10mV/s, the rotating speed is set to 1600rpm, and the scanning range is 0V-1.0V.
See fig. 5 and table 1 for the results of the tests. The test result shows that the catalytic activity of the C-Co-S-P nanocrystal in catalyzing OER is superior to that of the commercially available lrO2A catalyst.
TABLE 1 overpotential of catalyst at different current densities
Figure BDA0002978467320000061
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (6)

1. The preparation method of the Ce-Co-S-P nanocrystal is characterized in that the Ce-Co-S-P nanocrystal is of a twin crystal lamellar structure, and Ce is introduced to adjust the phase change of the Co-S-P nanosheet; the preparation method comprises the following steps: mixing ceric ammonium nitrate, cobalt acetylacetonate, oleic acid, n-dodecyl mercaptan and tri-n-octyl phosphine, wherein the addition ratio of the raw materials is as follows: cerium ammonium nitrate 0.375mmol, cobalt acetylacetonate 0.7mmol, oleic acid 1.5ml, n-dodecyl mercaptan 8ml, tri-n-octyl phosphine 5ml, gradually heating to 320 deg.C/minoAnd C, performing heat preservation reaction, and performing dispersion sedimentation and centrifugal separation on the obtained product to obtain the Ce-Co-S-P nanocrystal.
2. The method of claim 1, wherein the incubation reaction is carried out for a period of 30 min.
3. The process according to claim 1, wherein the dispersion sedimentation is carried out using a solution of n-heptane and ethanol.
4. The method according to claim 3, wherein the volume ratio of the n-heptane solution to the ethanol solution is 3: 1.
5. use of the Ce-Co-S-P nanocrystals prepared according to any one of claims 1 to 4 as a reaction catalyst for fuel cells.
6. Use according to claim 5, wherein the reaction is an oxygen evolution reaction.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108097269A (en) * 2017-12-19 2018-06-01 南京晓庄学院 A kind of ultra-thin porous Ce-Ni-O-S nanometer sheets and its preparation method and application
CN109004239A (en) * 2018-08-10 2018-12-14 南京晓庄学院 A kind of Co of P doping3S4Nanometer sheet and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108097269A (en) * 2017-12-19 2018-06-01 南京晓庄学院 A kind of ultra-thin porous Ce-Ni-O-S nanometer sheets and its preparation method and application
CN109004239A (en) * 2018-08-10 2018-12-14 南京晓庄学院 A kind of Co of P doping3S4Nanometer sheet and its preparation method and application

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