Preparation method of bi-component selenide with three-dimensional interwoven structure and application of bi-component selenide in technical field of catalysis for hydrogen production by full water splitting
By constructing a two-component selenide catalyst with a three-dimensional interwoven structure on nickel foam, the interface synergistic effect of FeSex and NiSe2 is used to solve the problems of high cost and poor stability of precious metal catalysts, and an efficient and stable electrochemical water cracking reaction is achieved.
Patent Information
- Application Number
- CN202411318993.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-21
- Publication Date
- 2024-12-20
AI Technical Summary
The existing electrocatalysts have high cost and poor stability. A single functional catalyst increases the cost of a fully decomposed water electrolytic cell. The method of making transition metal selenide is complex and structurally difficult to regulate, which limits the electrochemical water cracking efficiency.
A two-component selenide catalyst using a three-dimensional interwoven structure is constructed on foam nickel by two-step electrochemical deposition method. The interface synergistic effect of amorphous FeSex and crystalline NiSe2 is used to form a two-component catalyst of amorphous phase and crystalline phase to achieve HER and OER dual activity.
It achieves efficient full hydrolysis catalytic performance and high stability, reduces the cost of electrocatalysts, and significantly improves the efficiency and stability of electrolytic water reaction.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of catalytic technology for producing hydrogen through complete water splitting, a method for preparing a two-component selenide with a three-dimensional interwoven structure and application of the same in the technical field of catalytic technology for producing hydrogen through complete water splitting. Background Art
[0002] Electrochemical water splitting has been a subject of extensive research due to its great potential to store intermittent renewable energy in the form of hydrogen, which is a promising fuel cell energy carrier and an important raw material for the production of ammonia and hydrogenation processes. However, the performance of the above clean renewable energy reactions is usually limited by the inefficient kinetics of the anode OER and the cathode HER, which leads to large overpotentials. The efficiency of current water splitting devices highly relies on catalysts at the anode and cathode to accelerate the slow kinetics of HER and OER, respectively. Existing commercial electrocatalysts are mainly precious metal-based catalysts, including IrO2 and Pt / C, which can be used as OER and HER electrocatalysts, respectively, due to their excellent catalytic activity and high current density. However, the high cost and relatively poor stability of these precious metal-based catalysts will limit their practical application in industrial production, and the single-functional catalyst will increase the cost of the full water electrolyzer, so it is necessary to construct high-performance and highly stable bifunctional electrocatalysts. Transition metal selenides such as Ni x Se y and Fe x Se y Due to its inherent metallic properties and high conductivity, it has attracted a lot of attention in the field of electrocatalytic water splitting. However, most reports on the preparation of transition metal selenides are through high-temperature gas-solid reaction methods or hydrothermal selenization of metal hydroxides, and the structure of the prepared selenides is almost completely dependent on the precursor structure. Therefore, it is of great research significance to develop simple and harmless methods for the preparation of selenides and achieve structural regulation. Summary of the invention
[0003] 1. A method for preparing a two-component selenide with a three-dimensional interwoven structure and its application in the field of catalytic technology for hydrogen production from complete water splitting. The preparation process is as follows:
[0004] (1) Pre-treating the carrier to remove oxides and oil stains on the surface;
[0005] (2) preparing 100 mL of a solution containing ferric nitrate nonahydrate and selenium dioxide, and stirring the mixture magnetically until the mixture is fully mixed to obtain a mixed solution A;
[0006] (3) The pretreated support is subjected to a three-electrode system electrochemical deposition process in the mixed solution A, and then washed and air-dried to obtain amorphous iron selenide (FeSe x )Foam nickel precursor of nanospheres;
[0007] (4) Prepare 100 mL of a solution containing nickel chloride hexahydrate and selenium dioxide, stir magnetically until fully mixed, and obtain a mixed solution B, and then add the amorphous FeSe coated solution obtained in step (3) to the solution. x The nickel foam precursor of the nanospheres is subjected to a three-electrode system electrochemical deposition process in a mixed solution B; the reaction product is washed and dried in air to obtain a two-component selenide complete water splitting catalyst FeSe x -NiSe2 / NF.
[0008] 2. According to the method for preparing a two-component selenide with a three-dimensional interwoven structure and its application in the field of catalytic technology for hydrogen production by comprehensive water splitting as described in claim 1, the molar ratio of the two metal salts in steps (2) and (4) is controlled to be 1:0.3, 1:0.5, 1:1, 1:2, 1:3.
[0009] 3. According to the method for preparing a two-component selenide with a three-dimensional interwoven structure and its application in the field of catalytic technology for hydrogen production by comprehensive water splitting as described in claim 1, the deposition potential in steps (3) and (5) is -0.9V vs.Ag / AgCl and the deposition time is 10min.
[0010] The advantages of the present invention are as follows: the present invention uses a simple two-step deposition method to construct a two-component selenide layer with a three-dimensional interwoven structure on nickel foam. x Due to the interfacial synergistic effect with crystalline NiSe2 and the three-dimensional interwoven nanostructure, the prepared electrocatalyst has dual HER and OER activities, and exhibits excellent overall hydrolysis catalytic performance and high stability.
[0011] The innovation of the method of the present invention compared with the prior art is that the present invention constructs an amorphous phase and a crystalline two-component selenide interface through a two-step deposition method, which can effectively regulate the electronic structure of the metal site, accelerate the interfacial electron transfer, give the catalyst excellent catalytic performance, and systematically study its HER, OER and complete water splitting performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 : FeSe prepared in Example 1 of the present invention x / NF、FeSe x -SEM image of NiSe2 / NF.
[0013] Figure 2 : FeSe prepared in Example 1 of the present invention x / NF、FeSe x -XRD spectrum of NiSe2 / NF.
[0014] Figure 3: HER linear polarization curve of Example 1 of the present invention.
[0015] Figure 4 : OER linear polarization curve of Example 1 of the present invention.
[0016] Figure 5 : It is FeSe prepared in Example 1 of the present invention x -Linear polarization curve of NiSe2 / NF for complete water splitting under alkaline conditions.
[0017] Figure 6 : FeSe prepared in Example 1 of the present invention x -IT curve of complete water splitting of NiSe2 / NF under alkaline conditions. Specific implementation methods
[0019] In order to more clearly illustrate the present invention, the following embodiments are listed, but they do not limit the scope of the present invention in any way. The technical solutions in the embodiments of the present invention are clearly and completely described in conjunction with the drawings of the specification. The described embodiments are only part of the embodiments of the present invention, not all of the embodiments.
[0020] Embodiment 1:
[0021] (1) Add 0.665 g of selenium dioxide to 50 mL of deionized water to prepare solution 1, and then add 3.232
[0022] 1 g of ferric nitrate nonahydrate was added to 50 mL of deionized water to prepare solution 2, and the mixture was magnetically stirred for 10 min until it was completely dissolved. Finally, solution 1 was slowly poured into solution 2 and stirred again for 2 min to mix them evenly, to obtain a mixed solution A.
[0023] (2) The pretreated nickel foam (1 cm*1.5 cm) was subjected to electrochemical deposition in mixed solution A (three-electrode system), with an area of 1 cm*1 cm immersed in the solution, and deposited at a constant potential of -0.9 V vs. Ag / AgCl for 10 min; the obtained product was alternately washed with deionized water and ethanol, and dried in air to obtain FeSe x / NF nanosphere precursor;
[0024] (3) Dissolve 0.665 g of selenium dioxide and 3.803 g of nickel chloride in 100 mL of deionized water and stir for 10 min until completely dissolved to obtain a mixed solution B. x The precursor of the / NF nanospheres was placed in solution B and deposited at a constant potential of -0.9 V vs. Ag / AgCl for 10 min. After washing and drying, FeSe x -NiSe2 / NF-1 sample.
[0025] Embodiment 2:
[0026] (1) Add 0.665 g of selenium dioxide to 50 mL of deionized water to prepare solution 1, and then add 3.232
[0027] 1 g of ferric nitrate nonahydrate was added to 50 mL of deionized water to prepare solution 2, and the mixture was magnetically stirred for 10 min until it was completely dissolved. Finally, solution 1 was slowly poured into solution 2 and stirred again for 2 min to mix them evenly, to obtain a mixed solution A.
[0028] (2) The pretreated nickel foam (1 cm*1.5 cm) was subjected to electrochemical deposition in mixed solution A (three-electrode system), with an area of 1 cm*1 cm immersed in the solution, and deposited at a constant potential of -0.9 V vs. Ag / AgCl for 10 min; the obtained product was alternately washed with deionized water and ethanol, and dried in air to obtain FeSe x / NF nanosphere precursor;
[0029] (3) Dissolve 0.665 g of selenium dioxide and 1.901 g of nickel chloride in 100 mL of deionized water and stir for 10 min until completely dissolved to obtain a mixed solution B. x The precursor of the / NF nanospheres was placed in solution B and deposited at a constant potential of -0.9 V vs. Ag / AgCl for 10 min. After washing and drying, FeSe x -NiSe2 / NF-2 sample.
[0030] Embodiment 3:
[0031] (1) Add 0.665 g of selenium dioxide to 50 mL of deionized water to prepare solution 1, and then add 3.232
[0032] 1 g of ferric nitrate nonahydrate was added to 50 mL of deionized water to prepare solution 2, and the mixture was magnetically stirred for 10 min until it was completely dissolved. Finally, solution 1 was slowly poured into solution 2 and stirred again for 2 min to mix them evenly, to obtain a mixed solution A.
[0033] (2) The pretreated nickel foam (1 cm*1.5 cm) was subjected to electrochemical deposition in mixed solution A (three-electrode system), with an area of 1 cm*1 cm immersed in the solution, and deposited at a constant potential of -0.9 V vs. Ag / AgCl for 10 min; the obtained product was alternately washed with deionized water and ethanol, and dried in air to obtain FeSe x / NF nanosphere precursor;
[0034] (3) Dissolve 0.665 g of selenium dioxide and 5.704 g of nickel chloride in 100 mL of deionized water and stir for 10 min until completely dissolved to obtain a mixed solution B. x The precursor of the / NF nanospheres was placed in solution B and deposited at a constant potential of -0.9 V vs. Ag / AgCl for 10 min. After washing and drying, FeSe x -NiSe2 / NF-3 sample.
[0035] Application Example 1:
[0036] The HER and OER catalytic activities of the prepared catalysts were tested by a three-electrode system. x -NiSe2 / NF, for example, has excellent HER and OER activity in 1M KOH. For HER performance, it reaches 10mAcm -2 The current density only requires 40 mV overpotential. For OER performance, 50 mA cm-2 can be achieved at an overpotential of 220 mV. -2 This indicates that the material developed by the present invention has excellent bifunctional water electrolysis catalytic performance.
[0037] Application Example 2:
[0038] FeSe prepared in Example 1 x -NiSe2 / NF are used as cathode and anode terminals respectively to form a complete water electrolysis cell. The present invention can achieve 10mA cm with only 1.45V voltage. -2 The current density of the present invention is significantly better than that of the commercial Pt / C and RuO2-based water electrolyzer. -2 It can be maintained for 240 hours at a current density of 1.54 W, demonstrating its excellent stability.
Claims
1. A method for preparing a two-component selenide with a three-dimensional interwoven structure and its application in the field of catalytic technology for hydrogen production from complete water splitting. The preparation process is as follows: (1) Pre-treat the carrier to remove oxides and oil stains on the surface; (2) Prepare 100 mL of a solution containing ferric nitrate nonahydrate and selenium dioxide, and stir the mixture magnetically until it is fully mixed to obtain a mixed solution A; (3) subjecting the pretreated support to a three-electrode system electrochemical deposition process in the mixed solution A, followed by washing and air drying to obtain a foamed nickel precursor coated with amorphous iron selenide (FeSex) nanospheres; 100 mL of a solution containing nickel chloride hexahydrate and selenium dioxide was prepared and magnetically stirred until fully mixed to obtain a mixed solution B. Then, the foam nickel precursor coated with amorphous FeSex nanospheres obtained in step (3) was subjected to a three-electrode system electrochemical deposition process in the mixed solution B; the reaction product was washed and dried in air to obtain a two-component selenide complete water splitting catalyst FeSex-NiSe2 / NF.
2. According to the method for preparing a two-component selenide with a three-dimensional interwoven structure and its application in the field of catalytic technology for hydrogen production by comprehensive water splitting, the molar ratio of the two metal salts in steps (2) and (4) is controlled to be 1:0.3, 1:0.5, 1:1, 1:2, or 1:
3.
3. According to claim 1, a method for preparing a two-component selenide with a three-dimensional interwoven structure and its application in the field of hydrogen production by comprehensive water splitting technology, the deposition potential in steps (3) and (5) is -0.9 V vs. Ag / AgCl, and the deposition time is 10 min.