CN114016066A - Ni-Fe bimetal boride nanosheet array catalyst, and preparation method and application thereof - Google Patents
Ni-Fe bimetal boride nanosheet array catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Ni-Fe bimetal boride nanosheet array catalyst, and a preparation method and application thereof, and belongs to the technical field of hydrogen energy. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst comprises the following steps: step 1: pretreating nickel foam; step 2: preparing a FeNi-precursor solution; and step 3: (Fe)xNi1‑x)2And preparing B/NF. The invention also discloses a Ni-Fe bimetal boride nano-sheet array catalyst and application thereof. The Ni-Fe bimetal boride nanosheet array catalyst prepared by the method has excellent catalytic activity and good stability under alkaline and neutral conditions.
Description
Technical Field
The invention relates to a Ni-Fe bimetal boride nano-sheet array catalyst, a preparation method and application thereof, belonging to the technical field of hydrogen energy.
Background
Hydrogen has an ultra-high gravimetric energy density and is a clean fuel that releases water only when used in fuel cell power generation or when burned directly like natural gas. Hydrogen is produced by water electrolysis, water is used as a raw material to provide high-purity hydrogen, and the hydrogen is successfully commercialized and operated. When the electricity for electrolysis is from a renewable energy source, such as solar energy, the process can convert the energy into hydrogen bonds, thereby efficiently storing, transporting, and utilizing the renewable energy source.
Despite the above advantages, the Oxygen Evolution Reaction (OER) is slower than the Hydrogen Evolution Reaction (HER), and needs to go through a complicated electrical-electrolyte coupling process, which greatly hinders the water electrolysis efficiency. Therefore, there is a strong need for efficient OER electrocatalysts to improve kinetics and drive high current densities at low overpotentials.
Currently, oxides based on the noble metals iridium (Ir) and ruthenium (Ru) are the benchmark OER catalysts at practical current densities, but their widespread use is hampered by the high cost and low abundance. Moreover, under alkaline and neutral conditions, a large amount of overpotential is still required. Therefore, further improvement in the water oxidation efficiency of the electrocatalyst is highly desired. In order to replace the standard noble metal-based OER electrocatalyst used at present, abundant and low-cost transition metals (such as Fe, Co and Ni) are developed, and the preparation of the efficient and robust OER electrocatalyst has important significance. Non-noble metal oxide catalysts, such as nickel (Ni) oxide, cobalt (Co) oxide, manganese (Mn) oxide, and multi-cation perovskites, have also been extensively studied. Despite the tremendous advances made in developing earth-rich element-based OER electrocatalysts, a large number of overpotentials are still required. Therefore, further improvement in water oxidation efficiency of electrocatalysts abundant on earth is highly desired.
Existing studies indicate that Ni-based electrocatalysts are the most promising substitute for noble metal catalysts, since the OER activity of 40% Fe-doped Ni oxide films in alkaline solutions is two orders of magnitude higher than that of nickel films, and three orders of magnitude higher than that of iron layers. OER is the incorporation of Ni and Fe in Fe-Ni compounds that alters the oxidation properties of Ni and further enhances its electrocatalytic activity.
The presence of boron in the transition metal compound has a significant effect on its OER performance. The turnover frequency of cobalt borides is significantly increased compared to the corresponding Co oxides. In view of the significant improvement in OER performance that can be achieved by adding Fe and boron to a transition metal Ni based catalyst, bimetallic Fe-Ni borides are expected to be highly effective OER catalysts. Although transition metal-based electrocatalysts are mostly stable in alkaline electrolytes, it is highly desirable that they function well under neutral conditions. Efficient OER electrocatalysis under neutral conditions is benign and can reduce application costs. However, most reported neutral OER catalysts are cobalt-based compounds. Fe doped borides as a solution to the behaviour of OER catalysts under neutral conditions have not been reported so far.
Therefore, it is necessary to provide a Ni-Fe bimetal boride nanosheet array catalyst, a preparation method and an application thereof, so as to solve the defects of the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a Ni-Fe bimetal boride nano-sheet array catalyst.
The technical scheme for solving the technical problems is as follows: a preparation method of a Ni-Fe bimetal boride nanosheet array catalyst comprises the following steps:
step 1: pretreating nickel foam;
step 2: preparation of FeNi-precursor solution
Adding 6mmol of Ni (NO)3)2·6H2O and Fe (NO)3)3·9H2Dissolving the total O amount, 5mmol of ammonium fluoride and 12mmol of urea in 60mL of deionized water to obtain a FeNi-precursor solution; wherein said Ni (NO)3)2·6H2O and said Fe (NO)3)3·9H2The molar ratio of O is (1-X): x, X ═ 0-1;
and step 3: (Fe)xNi1-x)2Preparation of B/NF
Transferring the FeNi-precursor solution obtained in the step 2 into a stainless steel autoclave lined with polytetrafluoroethylene, adding the nickel foam pretreated in the step 1, and carrying out closed reaction at the temperature of 140-160 ℃ for 4-6 h to obtain a FeNi-precursor/NF;
FeNi-precursor/NF and 2.0g NaH2BO2·H2O is respectively arranged in two ceramic boats, and then the two ceramic boats are respectively arranged at two different positions of a tube type, wherein the NaH2BO2·H2O is positioned above the gas flow, the FeNi-precursor/NF is positioned below the gas flow, the tube furnace is flushed by argon,and under the static argon atmosphere, heating the center of the tubular furnace by a program, and naturally cooling to room temperature to obtain the Ni-Fe bimetal boride nano sheet array catalyst.
The principle of the preparation method of the Ni-Fe bimetal boride nano-sheet array catalyst is as follows:
in step 1 of the present invention, the nickel foam is pretreated to remove oxides on the surface of the nickel foam.
In step 2 of the present invention, (Fe) is obtainedxNi1-x)2B hydroxide precursor, while facilitating X-ray diffraction (XRD) characterization, borides were made on nickel foil using the same method as described above.
In step 3 of the invention, the FeNi precursor solution and the nickel foam pretreated in step 1 are subjected to a closed reaction in a stainless steel autoclave lined with polytetrafluoroethylene, and are used for the hydrothermal growth of a FeNi body.
In addition, the design of the three-dimensional nanostructure array air electrode enables the catalyst to directly grow on the surface of a current collector (nickel foam, carbon cloth, stainless steel mesh and the like) in situ, and the contact interface of the two has chemical bond interaction, so that the interface resistance is greatly reduced; the array has rich pore channel structures, which is beneficial to oxygen and electrolyte to diffuse to the surface of the catalyst; compared with the traditional coating method for preparing the electrode, the exposed quantity of the active sites is more under the condition of the same amount of catalyst, so that the catalytic performance of oxygen evolution and oxygen reduction reaction is obviously improved.
In conclusion, the Ni-Fe bimetal boride nanosheet array catalyst prepared by the method disclosed by the invention has excellent catalytic activity and good stability under alkaline and neutral conditions.
The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst has the beneficial effects that:
1. the Ni-Fe bimetal boride nanosheet array catalyst prepared by the method has excellent catalytic activity and good stability under alkaline and neutral conditions.
2. The bimetallic Ni-Fe-B nanosheet array catalyst prepared by the invention has small particle size of less than 3.14nm,the specific surface area is large and is 0.289mg/cm2。
3. The preparation method disclosed by the invention is easy to operate, low in price, easy to obtain raw materials, wide in market prospect and suitable for large-scale popularization and application.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step 1, the method for pretreating the nickel foam comprises the following steps: soaking nickel foam in hydrochloric acid with the concentration of 10mol/L, performing ultrasonic treatment, taking out, cleaning with deionized water for 3-5 times, soaking in absolute ethyl alcohol, performing ultrasonic treatment, taking out, and then performing vacuum drying to obtain the pretreated nickel foam.
The adoption of the further beneficial effects is as follows: by adopting the operation, the oxide on the surface of the nickel foam can be removed.
Furthermore, the nickel foam is of a porous rectangular structure, the pore diameter is 200-300 mu m, and the porosity is 98%.
The adoption of the further beneficial effects is as follows: the nickel foam adopting the parameters has better performance.
Furthermore, the power of ultrasonic treatment is 16KW-60KW, and the time is 8min-10 min.
The further beneficial effects of the adoption are as follows: by adopting the parameters, the treatment effect is better.
Furthermore, the temperature of the vacuum drying is 80 ℃, and the time is 2 hours.
The further beneficial effects of the adoption are as follows: by adopting the parameters, the drying effect is better.
Further, in step 3, the temperature programming refers to raising the temperature to 4400-4600 ℃ at a rate of 2 ℃/min and keeping the temperature for 1h-2 h.
Further, in step 3, the room temperature is 15-38 ℃.
The second purpose of the invention is to provide a Ni-Fe bimetal boride nano-sheet array catalyst.
The technical scheme for solving the technical problems is as follows: the bimetallic Ni-Fe-B nanosheet array catalyst prepared by the preparation method.
The Ni-Fe bimetal boride nanosheet array catalyst has the beneficial effects that:
the Ni-Fe bimetal boride nanosheet array catalyst disclosed by the invention has excellent catalytic activity and good stability under alkaline and neutral conditions.
The third purpose of the invention is to provide the application of the prepared Ni-Fe bimetal boride nano-sheet array catalyst.
The technical scheme for solving the technical problems is as follows: the prepared Ni-Fe bimetal boride nano-sheet array catalyst is applied to electrolytic water oxygen evolution catalysis.
The application of the Ni-Fe bimetal boride nano-sheet array catalyst has the beneficial effects that:
the Ni-Fe bimetal boride nano-sheet array catalyst prepared by the method is added into NaOH solution of 1mol/L at the concentration of 50mA/cm2After the current density of the catalyst is measured for 24 hours, no obvious reduction of the electrocatalytic activity is observed, which indicates that the catalyst has high-efficiency oxygen evolution catalytic activity; after 1000 scanning cycles, the polarization curve shows no significant decay in current density, indicating good stability of the catalyst. Therefore, the Ni-Fe bimetal boride nano-sheet array catalyst can be used for electrolytic water oxygen evolution catalysis and has wide application prospect. Furthermore, if renewable power such as wind energy, solar energy, hydroelectric power generation and the like is used as fuel, and the activity of the catalyst is improved by using the Ni-Fe bimetal boride nanosheet array catalyst, the wide implementation of water electrolysis is likely to be realized in the near future.
Drawings
FIG. 1 is an OER post-characterization of Fe-Ni boride (enlarged view of embedded amorphous layer) in Experimental example 1 of the present invention.
FIG. 2 shows different ratios of Fe in Experimental example 2 of the present inventionxNi1-x)2Electrocatalytic OER behavior of P/NF in alkaline conditions, and used for comparative nickel foam and RuO2/NF。
FIG. 3 shows (Fe) in Experimental example 2 of the present invention0.4Ni0.6)2Polarization pattern before and after B/NF cycling.
FIG. 4 shows (Fe) in Experimental example 3 of the present invention0.4Ni0.6)2B high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Examples
The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst comprises the following steps:
step 1: pretreatment of nickel foam
The nickel foam is in a porous rectangular structure, the aperture is 200-300 mu m, and the porosity is 98%. Soaking nickel foam in hydrochloric acid with the concentration of 10mol/L, treating for 8-10 min by adopting 16KW-60KW ultrasonic waves, taking out, cleaning for 3-5 times by using deionized water, soaking in absolute ethyl alcohol, treating for 10min by adopting 16KW ultrasonic waves, taking out, and drying for 2h in vacuum at the temperature of 80 ℃ to obtain the pretreated nickel foam.
Step 2: preparation of FeNi-precursor solution
Adding 6mmol of Ni (NO)3)2·6H2O and Fe (NO)3)3·9H2Dissolving the total O amount, 5mmol of ammonium fluoride and 12mmol of urea in 60mL of deionized water to obtain a FeNi-precursor solution; wherein said Ni (NO)3)2·6H2O and said Fe (NO)3)3·9H2The molar ratios of O are 1:0, 0.9:0.1, 0.8:0.2, 0.7:0.3, 0.6:0.4 and 0.5:0.5, respectively.
And step 3: (Fe)xNi1-x)2Preparation of B/NF
And (3) transferring the FeNi-precursor solution obtained in the step (2) into a stainless steel autoclave lined with polytetrafluoroethylene, adding the nickel foam pretreated in the step (1), and carrying out closed reaction for 4-6 h at the temperature of 140-160 ℃ to obtain a FeNi-precursor/NF.
FeNi-precursor/NF and 2.0g NaH2BO2·H2O is respectively arranged in two ceramic boats, and then the two ceramic boats are respectively arranged at two different positions of a tube type, wherein the NaH2BO2·H2And O is positioned above the airflow, the FeNi-precursor/NF is positioned below the airflow, the tubular furnace is flushed by argon, the center of the tubular furnace is heated to 4400-4600 ℃ at the speed of 2 ℃/min and is kept for 1h-2h under the static argon atmosphere, and then the tubular furnace is naturally cooled to the room temperature of 15-38 ℃, so that the Ni-Fe bimetal boride nano sheet array catalyst is obtained.
Experimental example 1
The invention grows mesoporous Fe-Ni boride nano-sheet arrays with adjustable Fe/Ni ratio on nickel foam. (Fe)xNi1-x)2The actual Ni/Fe ratio in B was determined by inductively coupled plasma mass spectrometry (ICP-MS). On nickel foam (Fe)xNi1-x)2B nanoplate arrays are topologically derived from their hydroxide precursors by boronation. From Ni, Fe and B pairs (Fe)0.4Ni0.6)2The element mapping of B proves the uniform distribution of all elements in the whole nano sheet, and the porous structure provides rich active sites for electrochemical reaction due to rich mesopores in the Fe-Ni boride nano sheet.
(Fe0.4Ni0.6)2The B/NF electrode exhibits excellent OER activity under both alkaline and neutral conditions, and specifically, is capable of supplying 20mA/cm in a 0.8mol/L NaOH solution at extremely small overpotentials of 118mV and 215mV, respectively2And 600mA/cm2The current density of (a) is 10mA/cm driven by only 355mV overpotential in 0.2mol/L borate buffer2It also shows significant stability in 0.8mol/L NaOH solution and 0.2mol/L borate buffer. The performance under both basic and neutral conditions is demonstrated (Fe) compared to other non-noble OER electrocatalysts reported so far0.4Ni0.6)2The B/NF has excellent catalytic activity.
As shown in FIG. 1, a thin amorphous layer with a thickness of about 10nm can be observed on the surface of the Ni-Fe bimetal boride nano-sheet array catalyst. Whereas no B was detected in the surface layer due to leaching during OER. Further detailed XBS analysis after OER revealed the disappearance of B binding energy and the presence of OH-. These characterizations indicate that the surface lamellae are dominated mainly by Fe — Ni hydroxide, which is the active form of the OER electrocatalyst. These characterizations provide strong evidence for the Ni redox process in the OER process. Wherein the conversion of Ni-Fe hydroxide from its diselenide is observed after OER catalysis in alkaline medium. The high OER activity of the Fe-Ni boride derived core-shell hybrid may be due to the formation of a heterostructure interface between the derived Fe-Ni hydroxide and the Fe-Ni boride. Such a heterogeneous interface may create more opportunities for adjusting the surface electronic state and its interaction with reaction intermediates, resulting in a more active catalyst.
Experimental example 2
Electrochemical measurements were performed at room temperature using a potentiostat on a standard three-electrode system to obtain (Fe)xNi1-x)2B/NF and bare nickel foam as working electrodes, platinum wire as counter electrode, Ag/AgCl (3M) and Hg/HgO electrode as reference electrode.
The OER test was performed in a 2mol/L NaOH solution (pH 14.0) and a 0.2mol/L borate buffer solution, respectively, at room temperature. Long-term durability tests were performed using chronopotentiometry and Cyclic Voltammetry (CV). CV cycling tests were performed at a scan rate of 100 mV/s. Electrochemical impedance spectroscopy tests were conducted in the frequency range of 100kHz-0.1 Hz.
(Fe) obtained in step 3 of example 1xNi1-x)2B/NF, electrocatalytic OER performance test is carried out under neutral and alkaline conditions, and RuO is adopted2the/NF and nickel foams are referenced. Electrode kinetics were further examined by Electrochemical Impedance Spectroscopy (EIS). Neutral and alkaline OER performance is similar, and the increased Fe incorporation enhances the OER activity of Fe-Ni borides, but suppresses the electrochemical oxidation reaction of Ni. In general, (Fe)xNi1-x)2B/NF electrode exhibits specific RuO2The OER activity was much higher for the/NF. In particular, (Fe)0.4Ni0.6)2B/NF electrodes appear to be superior to other catalyst electrodesOER performance, only a very low overpotential of 355mV is needed to provide 10mA/cm2The current density of (1). The overpotential is superior to the high-performance neutral catalyst in the prior research. As shown in fig. 2.
In a 1mol/L NaOH solution (pH 14.0) at 50mA/cm2No significant decrease in electrocatalytic activity was observed after 24h of current density measurement. After 1000 scan cycles, the polarization curve shows no significant decay in current density, as shown in FIG. 3.
In contrast to other catalyst electrodes, e.g. RuO2(Fe) of/NF and other ratiosxNi1-x)2B/NF，(Fe0.4Ni0.6)2The Electrochemical Surface Area (ECSA) of B/NF is the largest. The Roughness Factor (RF) is used to determine the ratio of ECSA to electrode geometric surface area. To estimate ECSA and RF, the present experimental example measured the double layer capacitance (Cdl) at different scan rates in the non-faraday region by a simple Cyclic Voltammetry (CV) method. Despite the bimetal (Fe)xNi1-x)2The morphology between B/NF is similar, but in fact, (Fe)0.4Ni0.6)2The maximum Cdl of B/NF was 6mF/cm2Indicating that its RF is greater than that of (Fe) in other proportionsxNi1-x)2B/NF. Thus, (Fe)0.4Ni0.6)2The excellent electrocatalytic properties of B/NF can be attributed in part to the high ECSA and thus highly exposed active sites.
Experimental example 3
A scanning electron microscope image and an energy dispersive X-ray spectral image were obtained using the dual beam. X-ray diffraction data was collected on a diffractometer.
On nickel foam (Fe)xNi1-x)2B nanoplate arrays are topologically derived from their hydroxide precursors by boronation. During the synthesis, the color of the electrode changed from yellow brown to black. The entire nickel foam is completely coated with a boride layer. Despite the slight volume shrinkage, the nanostructures retain their bulk properties after boronation. Interconnected electrolyte channels in the Fe-Ni boride layer can provide shorter ion diffusionThe dispersion/exchange path, thereby improving the catalytic efficiency. Inductively coupled plasma mass spectrometry (ICP-MS) analysis showed (Fe)0.4Ni0.6)2The Fe/Ni molar ratio of B is highest. On the nickel foam, the amount gradually decreases with increasing Fe content. From Ni, Fe and B pairs (Fe)0.4Ni0.6)2The element mapping of B proves the uniform distribution of all elements in the whole nano sheet, and the porous structure provides rich active sites for electrochemical reaction due to rich mesopores in the Fe-Ni boride nano sheet. As shown in fig. 4. A large number of mesopores can be observed on the surface of the nanosheet. Boride fragments were stripped from the nickel foam under sonication.
Experimental example 4
A thin amorphous layer with a thickness of about 10nm was observed on the surface of the Fe-Ni boride nanoplate. Whereas no B was detected in the surface layer due to leaching during OER. Further detailed XBS analysis after OER revealed the disappearance of B binding energy and the presence of OH-.
These characterizations indicate that the thin layer of the surface is dominated mainly by Fe — Ni hydroxide, which is the active form of the OER electrocatalyst. Furthermore, these characterizations provide strong evidence for the Ni redox process in the OER process. Wherein the conversion of Ni-Fe hydroxide from its diselenide is observed after OER catalysis in alkaline medium. The high OER activity of the Fe-Ni boride derived core-shell hybrid may be due to the formation of a heterostructure interface between the derived Fe-Ni hydroxide and the Fe-Ni boride. Such a heterogeneous interface may create more opportunities for adjusting the surface electronic state and its interaction with reaction intermediates, resulting in a more active catalyst.
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 (9)
1. A preparation method of a Ni-Fe bimetal boride nanosheet array catalyst is characterized by comprising the following steps:
step 1: pretreating nickel foam;
step 2: preparation of FeNi-precursor solution
Adding 6mmol of Ni (NO)3)2·6H2O and Fe (NO)3)3·9H2Dissolving the total O amount, 5mmol of ammonium fluoride and 12mmol of urea in 60mL of deionized water to obtain a FeNi-precursor solution; wherein said Ni (NO)3)2·6H2O and said Fe (NO)3)3·9H2The molar ratio of O is (1-X): x, X ═ 0-1;
and step 3: (Fe)xNi1-x)2Preparation of B/NF
Transferring the FeNi-precursor solution obtained in the step 2 into a stainless steel autoclave lined with polytetrafluoroethylene, adding the nickel foam pretreated in the step 1, and carrying out closed reaction at the temperature of 140-160 ℃ for 4-6 h to obtain a FeNi-precursor/NF;
FeNi-precursor/NF and 2.0g NaH2BO2·H2O is respectively arranged in two ceramic boats, and then the two ceramic boats are respectively arranged at two different positions of a tube type, wherein the NaH2BO2·H2And O is positioned above the airflow, the FeNi-precursor/NF is positioned below the airflow, the tubular furnace is flushed by argon, the center of the tubular furnace is heated by program under the static argon atmosphere, and then the tubular furnace is naturally cooled to room temperature, so that the Ni-Fe bimetal boride nanosheet array catalyst is obtained.
2. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst as defined in claim 1, wherein in step 1, the method of pretreatment of the nickel foam is: soaking nickel foam in hydrochloric acid with the concentration of 10mol/L, performing ultrasonic treatment, taking out, cleaning with deionized water for 3-5 times, soaking in absolute ethyl alcohol, performing ultrasonic treatment, taking out, and then performing vacuum drying to obtain the pretreated nickel foam.
3. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst of claim 2, wherein the nickel foam is of a porous rectangular structure with a pore size of 200 μ ι η to 300 μ ι η and a porosity of 98%.
4. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst of claim 2, wherein the power of the ultrasonic treatment is 16KW-60KW, and the time is 8min-10 min.
5. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst of claim 2, wherein the temperature of the vacuum drying is 80 ℃ and the time is 2 h.
6. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst of claim 2, wherein in step 3, the temperature programming refers to raising the temperature to 4400-4600 ℃ at a rate of 2 ℃/min and maintaining for 1h-2 h.
7. The preparation method of the Ni-Fe bimetal boride nanosheet array catalyst of claim 2, wherein in step 3, the room temperature is 15-38 ℃.
8. The bimetallic Ni-Fe-B nanosheet array catalyst prepared by the above-described preparation method of any one of claims 1-7.
9. The use of the Ni-Fe bimetal boride nano-sheet array catalyst prepared by the preparation method of any one of claims 1 to 7 in electrolytic water oxygen evolution catalysis.
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