CN115261921A - FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase catalyst and preparation method and application thereof - Google Patents
FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase catalyst and preparation method and application thereof Download PDFInfo
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
Abstract
The invention relates to the field of OER catalysts, in particular to a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst and a preparation method and application thereof. The catalyst of the embodiment comprises a carbon carrier and a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase nano material loaded on the carbon carrier, wherein the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase nano material is obtained by carrying out heat treatment on a FeCoNiMnCr five-element metal organic framework precursor in a reducing atmosphere. The high-entropy alloy structure is adjusted through spontaneous oxidation of 3d transition metal Cr to form the high-entropy alloy/high-entropy oxide heterogeneous phase composite nanomaterial, and the nanomaterial has excellent catalytic activity and stability on OER reaction.
Description
Technical Field
The invention belongs to the technical field of OER electro-catalysts, and particularly relates to a FeCoNiMnCr high-entropy alloy phase structure nano material regulated and controlled by spontaneous oxidation of 3d transition metal Cr, and a preparation method and application thereof.
Background
Under the large background of achieving the goal of carbon peak reaching and carbon neutralization, the development strategy is promoted by the electrochemical decomposition of water to produce novel green hydrogen energy. Research finds that the traditional alloy catalyst applied to the four-electron transfer Oxygen Evolution Reaction (OER) generally has the defects of poor stability and low activity.
The high-entropy alloy (HEA) based on multiple transition metals is a novel catalytic material which is composed of four or more than four metals and has certain configuration entropy. Some studies have shown that HEA has great advantages in terms of OER catalytic activity and stability compared to low-element alloys, whose characteristics of spatial disorder and lattice order can optimize its surface electronic structure.
Although HEAs have potential electrocatalytic performance, part of HEAs can adsorb intermediates too strongly in the electrocatalytic process, so that the performance of the HEAs is poor; on the other hand, many highly stable, highly active HEAS catalysts tend to contain expensive noble metals, limiting the long-term development of these HEAS.
Disclosure of Invention
Aiming at the problems in the prior art, the invention mainly aims to provide a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase catalyst which is low in cost and has high catalytic activity and stability, and a preparation method and application thereof.
In order to achieve the above-mentioned main object, a first aspect of the present invention provides a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst, comprising a carbon carrier and a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous nanomaterial supported on the carbon carrier; the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase nano material is obtained by carrying out heat treatment on a FeCoNiMnCr five-element metal organic framework precursor in a reducing atmosphere.
In the above technical solution, the carbon carrier may be a carbon nanotube.
In the technical scheme, the reducing atmosphere can be argon-hydrogen mixed gas, the temperature of the heat treatment can be 350-450 ℃, and the time can be 2-4 h.
The second aspect of the invention provides a preparation method of a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst, which comprises the following steps:
s1, dissolving 2, 5-dihydroxyterephthalic acid, ferrous salt, cobalt salt, nickel salt, manganese salt and chromium salt in a mixed solvent consisting of ethanol, deionized water and N, N-dimethylformamide according to a preset molar ratio, and performing hydrothermal reaction after adding a carbon carrier to obtain a FeCoNiMnCr five-element metal organic framework precursor product;
s2, carrying out heat treatment on the FeCoNiMnCr five-element metal organic framework precursor product in a reducing atmosphere to obtain the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase nano material loaded on the carbon carrier.
In the above preparation method, the molar ratio of 2, 5-dihydroxyterephthalic acid, ferrous salt, cobalt salt, nickel salt, manganese salt and chromium salt may be 0.34:0.25:0.25:0.25:0.25:0.25.
in the preparation method, the temperature of the hydrothermal reaction can be 100-140 ℃ and the time can be 20-35h.
In the preparation method, the reducing atmosphere can be argon-hydrogen mixed gas, the temperature of the heat treatment can be 350-450 ℃, and the time can be 2-4 h.
In the preparation method, the ferrous salt is ferrous acetate, the cobalt salt is cobalt nitrate, the nickel salt is nickel nitrate, the manganese salt is manganese nitrate, and the chromium salt is chromium nitrate.
In the above preparation method, the volume ratio of ethanol, deionized water and N, N-dimethylformamide may be 1.35:1.35:22.5, the ratio of ferrous salt to ethanol may be 0.25:1.35mmol/mL.
The third aspect of the invention discloses the application of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst in OER reaction.
The invention has the following beneficial effects:
the introduction of 3d transition metal Cr can effectively convert a FeCoNiMnCr high-entropy alloy (HEA) pure metal phase into a high-entropy alloy/high-entropy oxide (HEA-HEO) heterogeneous phase, adjust the electronic structure of an interface site, optimize the adsorption energy of an oxygen-containing intermediate, accelerate the charge transfer process in the OER process, have better and more stable catalytic effect on the reaction process, particularly have higher electrocatalytic activity and stability of oxygen precipitation in an alkaline environment, and have extremely high commercial application prospect.
Drawings
FIG. 1 is a Fourier infrared spectrum (FT-IR) graph of a FeCoNiMn high-entropy alloy prepared in comparative example 1 and a FeCoNiMnCr high-entropy alloy/high-entropy oxide prepared in example 1;
FIG. 2 is a powder X-ray diffraction (XRD) pattern and a comparison of XRD patterns of FeCoNiMn high-entropy alloy prepared by comparative example 1;
FIG. 3 is a powder X-ray diffraction (XRD) contrast spectra of FeCoNiMn high entropy alloy prepared in comparative example 1 and FeCoNiMnCr high entropy alloy/high entropy oxide prepared in example 1;
in FIG. 4, a and c are Field Emission Scanning Electron Microscope (FESEM) images of FeCoNiMnCr high-entropy alloy/high-entropy oxide prepared in example 1, and b and d are Field Emission Scanning Electron Microscope (FESEM) images of FeCoNiMn high-entropy alloy prepared in comparative example 1;
FIG. 5 is a Transmission Electron Microscope (TEM) image of FeCoNiMn high-entropy alloy prepared in comparative example 1;
FIG. 6 is a Transmission Electron Microscope (TEM) image of FeCoNiMnCr high entropy alloy/high entropy oxide prepared in example 1;
FIG. 7 is a comparison of full spectra of high resolution photoelectron spectroscopy (XPS) spectra of FeCoNiMn high entropy alloy prepared in comparative example 1 and FeCoNiMnCr high entropy alloy/high entropy oxide prepared in example 1;
FIG. 8 is a comparison of high resolution photoelectron spectroscopy (XPS) spectra of C1s, co2p, fe2p, ni2p, mn2p and O1s for the FeCoNiMn high entropy alloy prepared in comparative example 1 and the FeCoNiMnCr high entropy alloy/high entropy oxide prepared in example 1;
FIG. 9 is a comparison of Raman (Raman) spectra of FeCoNiMn high-entropy alloy prepared in comparative example 1 and FeCoNiMnCr high-entropy alloy/high-entropy oxide prepared in example 1;
FIG. 10 shows FeCoNiMn high-entropy alloy prepared in comparative example 1, feCoNiMnCr high-entropy alloy/high-entropy oxide catalyst prepared in example 1, and commercial IrO2IR-corrected polarization plots in 1M KOH solution at room temperature;
FIG. 11 shows FeCoNiMn high entropy alloy prepared in comparative example 1, feCoNiMnCr high entropy alloy/high entropy oxide catalyst prepared in example 1, and commercial IrO2A tafel plot during electrocatalytic oxygen evolution reaction;
FIG. 12 shows FeCoNiMn high-entropy alloy prepared in comparative example 1, feCoNiMnCr high-entropy alloy/high-entropy oxide catalyst prepared in example 1, and commercial IrO2Cyclic Voltammetry (CV) graph of (a);
FIG. 13 shows FeCoNiMn high entropy alloy prepared in comparative example 1, feCoNiMnCr high entropy alloy/high entropy oxide catalyst prepared in example 1, and commercial IrO2The electric double layer capacitance of the catalyst;
FIG. 14 shows FeCoNiMn high-entropy alloy prepared in comparative example 1, feCoNiMnCr high-entropy alloy/high-entropy oxide catalyst prepared in example 1, and commercial IrO2Nernst diagram of (a);
FIG. 15 is a chronopotentiometric response (E-t) curve for FeCoNiMnCr high entropy alloy/high entropy oxide catalyst prepared in example 1.
FIG. 16 is a graph of IR-corrected polarization of FeCoNiMnCr high-entropy alloy/high-entropy oxide catalyst prepared in example 1 in 1M KOH at room temperature over 100 hours.
FIG. 17 is a comparison of the powder X-ray diffraction (XRD) pattern of the FeCoNiMnCr high-entropy oxide prepared in comparative example 2 and the XRD pattern of the FeCoNiMnCr high-entropy alloy/high-entropy oxide catalyst in example 1;
FIG. 18 is a graph of IR-corrected polarization curves of FeCoNiMnCr high-entropy oxide prepared in comparative example 2 and FeCoNiMnCr high-entropy alloy/high-entropy oxide catalyst prepared in example 1 in a 1M KOH solution at room temperature.
Detailed Description
Researches show that the adsorption effect of the oxidation site of the 3d transition metal Cr on the intermediate is weak, and the adsorption energy of active sites of some HEAs can be adjusted. The inventor carries out intensive research on the method, and finds that a 3d transition metal Cr is introduced into a FeCoNiMn high-entropy alloy material, a FeCoNiMnCr high-entropy alloy/high-entropy oxide (HEA-HEO) heterogeneous phase is formed by spontaneous oxidation of Cr, the number of HEA active sites can be adjusted, the structure entropy value is increased, and the adsorption of O is enhanced, so that the reaction energy of a potential limiting step is reduced, the charge transfer process in the OER process is accelerated, a better and more stable catalytic effect is achieved on the reaction process, and particularly, the electrocatalytic activity and stability of higher oxygen evolution are achieved in an alkaline environment.
Hereinafter, the details will be described with reference to examples and comparative examples.
Example 1
The preparation method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst in the embodiment 1 comprises the following specific steps:
The application method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst in the OER reaction in the embodiment 1 is as follows: the method comprises the steps of preparing an anode catalytic electrode from a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst, taking a platinum electrode as a cathode, taking a KOH solution with the concentration of 1mol/L as an electrolyte, and reacting for 100 hours under the condition of normal temperature and the control voltage of 0.6V, wherein the catalyst content of the anode catalytic electrode is 1mg/cm2。
Comparative example 1
In order to better compare the structure of FeCoNiMnCr high-entropy alloy/high-entropy oxide and the electrocatalytic OER performance thereof, feCoNiMn high-entropy alloy is synthesized by the comparative example 1, and the method comprises the following specific steps:
Comparative example 2
In order to better compare the structure of FeCoNiMnCr high-entropy alloy/high-entropy oxide and the electrocatalytic OER performance of the FeCoNiMnCr high-entropy oxide, the FeCoNiMnCr high-entropy oxide is synthesized by the comparative example 2, and the method comprises the following specific steps of:
and 2, roasting the five-element metal organic framework precursor product obtained in the step 1 in an air atmosphere, wherein the roasting temperature is 600 ℃, the heating rate is 5 ℃/min, and the roasting time is 3h.
The catalysts of the examples and comparative examples were subjected to structural and morphological characterization, specifically analyzed as follows:
as shown in FIG. 1, no obvious characteristic peak corresponding to an organic matter is found in the FT-IR spectrum, which proves that the synthesized FeCoNiMnCr high-entropy alloy/high-entropy oxide and FeCoNiMn high-entropy alloy catalyst has no organic matter residue.
As shown in FIG. 2, the XRD pattern of FeCoNiMn high entropy alloy shows a peak around 26 degrees, which belongs to carbon (JPCDS 41-1487). The position of the diffraction peak of 43 DEG width is slightly shifted compared with the standard cards of Fe-based alloy and Ni-based alloy (JPCDS 88-1715, PCDS 44-1433 and JPCDS 54-0533). This demonstrates that the resultant material is not a bimetallic alloy. A broad diffraction peak is formed due to the formation of the single-phase multi-metal alloy. 3 diffraction peaks on the map represent crystal faces (111), (200) and (220), and the crystal faces are single-phase FCC structures, so that the FeCoNiMn high-entropy alloy is successfully prepared.
As shown in FIG. 3, the FeCoNiMn HEA/CNT XRD peak formed at 44.0 ° (2 θ) can be assigned to the (111) plane of the Face Centered Cubic (FCC) structure of the high entropy alloy, and no metal oxide peak is detected. After the addition of the fifth transition metal Cr, the new XRD peaks formed by FeCoNiMnCr high-entropy alloy/high-entropy oxide at 35 DEG and 64 DEG (2 theta) can be assigned to spinel oxide (311) and (440) planes. Diffraction peak of FeCoNiMnCr high-entropy alloy/high-entropy oxide composite material and corresponding spinel oxide NiCrMnO4The standard spectrum (JPCDS 71-0854) of (A) was well matched. The diffraction peaks of 44.0 degrees (2 theta) of the FeCoNiMnCr high-entropy alloy/high-entropy oxide are widened, and the crystallinity is low, which is probably due to the increase of disorder degree/entropy, so that a heterogeneous structure is further formed.
As shown in FIG. 4, feCoNiMnCr high-entropy alloy/high-entropy oxide and FeCoNiMn high-entropy alloy samples are both powder particles and have uniformly distributed nano-morphologies. As can be seen from fig. 4, the synthesis catalyst is a combination of carbon nanotubes and nanoparticles.
As shown in fig. 5, a Transmission Electron Microscope (TEM) image of the FeCoNiMn high-entropy alloy shows that the FeCoNiMn high-entropy alloy shows lattice spacings of 0.201nm and 0.208nm, corresponding to the (111) planes of the high-entropy alloy.
As shown in FIG. 6, feCoNiMnCr high entropy alloy/high entropy oxide is selected from FIG. 6a, and more precise analysis and phase contrast are performed on the lattice plane of CNT (220). HRTEM images show FeCoNiMnCr high entropy alloy/high entropy oxide (fig. 6b and c), fig. 6b shows a lattice spacing of 0.209 nm, corresponding to the (111) planes of the high entropy alloy. Fig. 6c clearly identifies the (311) plane of the high entropy oxide with a lattice spacing of 0.253 nm.
As shown in fig. 7, the successful introduction of Cr into the high entropy material was demonstrated in the high resolution XPS spectra of FeCoNiMnCr high entropy alloy/high entropy oxide samples.
As shown in fig. 8, the surface structure of the FeCoNiMnCr high-entropy alloy/high-entropy oxide catalyst was investigated by X-ray photoelectron spectroscopy (XPS). XPS spectra of Fe2p, co2p, ni2p, mn2p, C1s and O1s were collected. High resolution C1s XPS spectra confirmed the composition of C = C/C-C (284.7 eV) of carbon nanotubes (fig. 8 a). Compared with Co2p peak, fe2p peak, ni2p peak and Mn2p peak of FeCoNiMn high-entropy alloy, the combination energy of Co, fe, ni and Mn can generate negative shift, which shows that the surface electronic structure of Co, fe, ni and Mn is changed, and FeCoNiMnCr high-entropy alloy/high-entropy oxide is formed. In XPS Co2p spectrum of FeCoNiMnCr high entropy alloy/high entropy oxide, metal Co 0 2p3/2And Co 0 2p1/2There are two states at 779.2 and 794.3eV, respectively (fig. 8 b). Mainly made of Co2+In the form of (A), co 2+ 2p3/2And 2p1/2The corresponding peak positions are 781.91eV and 796.10 eV respectively. In FIG. 8c, the high resolution Fe2p spectrum demonstrates that the Fe exists in a zero valence state (Fe)0 2p3/2709.9eV, fe 0 2p1/2723.2 eV). Peaks centered at 853.3eV and 870.71eV are metallic Ni, respectively0 2p3/2And Ni 0 2p1/2(FIG. 8 d). The result of XPS analysis shows that FeCoNiMnCr high-entropy alloy contains high-entropy oxide.
As shown in fig. 9, raman spectroscopy further confirmed that the surfaces of the two electrocatalyst particles are two distinct broad peaks rather than narrow peaks. Compared with FeCoNiMn high-entropy alloy, after Cr is added, feCoNiMnCr high-entropy alloy/high-entropy oxide is 550-750 cm-1The peak at (a) is significantly larger, indicating an increase in the oxidation phase after Cr addition, which is consistent with HRTEM results.
As shown in FIG. 10, feCoNiMn high entropy alloy and FeCoNiMnCr high entropy alloy/high entropy oxide samples were saturated with O2Room temperature electrocatalytic OER performance of the three-electrode system in 1.0M KOH solution. According to the polarization curve shown in FIG. 10, at 10mA cm-2At a current density of FeCoNiMnCr, a high-entropy alloy/high-entropy oxideThe minimum overpotential of the sample catalyst is 259mV, which is lower than FeCoNiMn high entropy alloy (286 mV) and IrO2(335 mV) catalyst. As shown in FIG. 11, tafel slope (42.2 mV dec) of FeCoNiMnCr high entropy alloy/high entropy oxide sample-1) Lower than FeCoNiMn high entropy alloy (51.76 mV dec)-1)、IrO2(107.27mV dec-1) And NF (103.26 mV dec)-1)。
The electrochemically active surface area (ECSAs) and electrochemical double layer capacitance (C) of electrocatalysts are well knowndl) In direct proportion, this can be determined by measuring the Cyclic Voltammetry (CV) of the different scan rates of the non-faraday regions. C of FeCoNiMnCr high entropy alloy/high entropy oxide samples as shown in FIGS. 12 and 13dlThe value was 9.83mF cm-2C of other samplesdlThe value is large, which indicates that the FeCoNiMnCr high-entropy alloy/high-entropy oxide sample has more exposed surface active sites, so that the FeCoNiMnCr high-entropy alloy/high-entropy oxide sample has better OER activity.
To further illustrate the kinetics of the electrode reaction in the catalyzed OER process, electrochemical Impedance Spectroscopy (EIS) was performed. The Nyquist plot (see FIG. 14) shows that under alkaline conditions, feCoNiMnCr high entropy alloy/high entropy oxide samples have low charge transfer resistance (R)ct) About 1.81 omega (300 mV overvoltage), which is much smaller than FeCoNiMn high entropy alloy (4.2 omega) and IrO2(18.32 Ω) catalyst, indicating faster charge transfer on the surface of FeCoNiMnCr high entropy alloy/high entropy oxide during electrochemical reaction. These results strongly demonstrate that FeCoNiMnCr high entropy alloys/high entropy oxides have good activity on OER.
As shown in FIG. 15, the chronopotentiometric response (E-t) curve indicates that the FeCoNiMnCr high entropy alloy/high entropy oxide catalyst is at 100mA cm-2Has good durability after 100 hours or more of testing under the OER test condition (2). The polarization curve of the FeCoNiMnCr high-entropy alloy/high-entropy oxide catalyst has no obvious change of overpotential before and after stability test.
As shown in FIG. 16, at 100mA cm-2The overpotential after 100h of the stability test is also reduced by 12mV under the current density of FeCoNiMnCr, which shows that the FeCoNiMnCr high-entropy alloy/high-entropy oxide catalyst has the performanceExcellent long-term stability.
As shown in FIG. 17, the new XRD peaks formed at 35 and 64 (2. Theta.) for FeCoNiMnCr high entropy oxides processed in oxygen-filled muffle furnaces can be assigned to spinel oxide (311) and (440) planes, in contrast to spinel oxide NiCrMnO4The standard spectrum of (JPCDS 71-0854) matched well. Compared with XRD of FeCoNiMnCr high-entropy alloy/high-entropy oxide, the FeCoNiMnCr high-entropy oxide has large diffraction peak intensity at 43.3 degrees (2 theta), higher crystallinity and no obvious alloy peak at 44.0 degrees (2 theta), and proves that the FeCoNiMnCr high-entropy oxide synthesized in a muffle furnace filled with oxygen atmosphere is a pure-phase oxide.
As shown in FIG. 18, feCoNiMnCr high entropy oxide and FeCoNiMnCr high entropy alloy/high entropy oxide samples were saturated with O2Room temperature electrocatalytic OER performance of the three-electrode system in 1.0M KOH solution. According to the polarization curve shown in FIG. 18, at 10mA cm-2Under the current density of FeCoNiMnCr, the minimum overpotential of the FeCoNiMnCr high-entropy alloy/high-entropy oxide sample catalyst is 259mV which is lower than 292mV of the FeCoNiMnCr high-entropy oxide catalyst.
Example 2
The preparation method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst in the embodiment 2 comprises the following specific steps:
FeCoNiMnCr high entropy alloy/high entropy oxide heterogeneous phase in example 2The application method of the catalyst in the OER reaction is as follows: preparing an anode catalytic electrode from FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst, taking a platinum electrode as a cathode, taking KOH solution with the concentration of 6mol/L as electrolyte, and reacting for 20 hours at 85 ℃ under the control of the voltage of 0.5V, wherein the catalyst content of the anode catalytic electrode is 2mg/cm2。
Example 3
The preparation method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst in the embodiment 3 comprises the following specific steps:
The application method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst in the OER reaction in the embodiment 3 is as follows: preparing a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase catalyst into an anode catalytic electrode, taking a platinum electrode as a cathode, taking a KOH solution with the concentration of 4mol/L as an electrolyte, and reacting for 12 hours at 65 ℃ under the control of the voltage of 0.7V, wherein the catalyst content of the anode catalytic electrode is 1mg/cm2。
In summary, the embodiment of the invention forms the high-entropy material with the heterogeneous structure of the alloy phase and the oxide phase by a simple method, so that the physicochemical properties of the material are improved, and the complex wet chemical process is avoided. In addition, the heterogeneous structure of the composite material with rich interfaces can adjust the electronic performance, and realize the optimal combination of the performances of two components, namely the high-entropy alloy phase and the oxide phase, so that the catalytic activity and the stability are greatly improved.
Compared with commercial noble metals, the FeCoNiMnCr high-entropy alloy/high-entropy oxide (HEA-HEO) heterogeneous catalyst provided by the invention has higher stability and stronger activity, can stably run for a long time under high current density, and has extremely high commercial application prospect.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (10)
1. A FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst comprises a carbon carrier and a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous nano-material loaded on the carbon carrier; the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase nano material is obtained by carrying out heat treatment on a FeCoNiMnCr five-element metal organic framework precursor in a reducing atmosphere.
2. A FeCoNiMnCr high entropy alloy/high entropy oxide heterogeneous catalyst according to claim 1; wherein the carbon carrier is a carbon nanotube.
3. A FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst according to claim 1; wherein the reducing atmosphere is argon-hydrogen mixed gas, the temperature of the heat treatment is 350-450 ℃, and the time is 2-4 h.
4. A preparation method of a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst comprises the following steps:
s1, dissolving 2, 5-dihydroxyterephthalic acid, ferrous salt, cobalt salt, nickel salt, manganese salt and chromium salt in a mixed solvent consisting of ethanol, deionized water and N, N-dimethylformamide according to a preset molar ratio, and performing hydrothermal reaction after adding a carbon carrier to obtain a FeCoNiMnCr quinary metal organic framework precursor product;
s2, carrying out heat treatment on the FeCoNiMnCr quinary metal organic framework precursor product in a reducing atmosphere to obtain a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous nano material loaded on the carbon carrier.
5. A method for preparing a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst according to claim 4; wherein the molar ratio of the 2, 5-dihydroxy terephthalic acid, ferrous salt, cobalt salt, nickel salt, manganese salt and chromium salt is 0.34:0.25:0.25:0.25:0.25:0.25.
6. a method for preparing a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst according to claim 4; wherein the temperature of the hydrothermal reaction is 100-140 ℃ and the time is 20-35h.
7. The preparation method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst according to claim 4; wherein the reducing atmosphere is argon-hydrogen mixed gas, the temperature of the heat treatment is 350-450 ℃, and the time is 2-4 h.
8. A method for preparing a FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous catalyst according to claim 4; the iron salt is ferrous acetate, the cobalt salt is cobalt nitrate, the nickel salt is nickel nitrate, the manganese salt is manganese nitrate, and the chromium salt is chromium nitrate.
9. The preparation method of the FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase nano-material according to claim 4; wherein the volume ratio of the ethanol to the deionized water to the N, N-dimethylformamide is 1.35:1.35:22.5, the ratio of the ferrous salt to the ethanol is 0.25:1.35mmol/mL.
10. Use of a FeCoNiMnCr high entropy alloy/high entropy oxide heterogeneous catalyst according to any of claims 1 to 3 in OER reactions.
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| CN116078393A (en) * | 2023-01-18 | 2023-05-09 | 华南农业大学 | Transition metal supported high-entropy oxide low-temperature methane dry reforming catalyst and preparation method and application thereof |
| CN117026257A (en) * | 2023-10-10 | 2023-11-10 | 河南师范大学 | Preparation method of zinc-nitrate radical battery based on high-entropy oxide |
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| CN116078393A (en) * | 2023-01-18 | 2023-05-09 | 华南农业大学 | Transition metal supported high-entropy oxide low-temperature methane dry reforming catalyst and preparation method and application thereof |
| CN117026257A (en) * | 2023-10-10 | 2023-11-10 | 河南师范大学 | Preparation method of zinc-nitrate radical battery based on high-entropy oxide |
| CN117026257B (en) * | 2023-10-10 | 2024-01-09 | 河南师范大学 | Preparation method of zinc-nitrate radical battery based on high-entropy oxide |
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