A nanocone structure hydrogen evolution electrode with a dichromium trisulfide / trinickel disulfide interface and a preparation method and application thereof
By growing a nanoconical coating at the interface of chromium trisulfide/nickel trisulfide in situ on a nickel mesh, the problem of hydrogen atom desorption from nickel trisulfide catalyst was solved, improving the efficiency and catalytic activity of hydrogen production by water electrolysis, reducing overpotential, and achieving efficient and low-cost hydrogen evolution.
Patent Information
- Application Number
- CN202411557963.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-04
- Publication Date
- 2026-01-16
- Estimated Expiration
- 2044-11-04
AI Technical Summary
In existing water electrolysis hydrogen production technologies, nickel disulfide catalysts are difficult to desorb hydrogen atoms during the hydrogen evolution reaction, resulting in reduced catalytic activity. Furthermore, precious metal catalysts are expensive and scarce.
Using a nickel mesh as a conductive substrate, a nanoconical coating at the interface of chromium trisulfide/nickel trisulfide is grown in situ via electrochemical deposition to optimize catalyst activity, increase active sites, and reduce the overpotential for water splitting.
It improves hydrogen evolution efficiency, reduces the overpotential of water splitting, enhances catalyst stability and activity, and reduces preparation costs.
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Figure CN119640312B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of water electrolysis hydrogen evolution electrode, and particularly relates to a nano-cone structure hydrogen evolution electrode with a dichromic sulfide tri-sulfide / nickel tri-sulfide interface as well as a preparation method and application thereof. BACKGROUND
[0002] Due to increasingly severe energy and environmental problems, energy supply and demand are increasingly tight, and we urgently need to seek a new type of energy. Water electrolysis hydrogen production technology is a simple, safe and sustainable high-purity hydrogen production approach, which is expected to replace fossil fuels in the extraction of oxygen and hydrogen and play an important role in future sustainable energy supply. However, the high cost of water electrolysis hydrogen production technology limits its development. Therefore, it is necessary to study catalysts with high catalytic activity and low cost.
[0003] Platinum group noble metal-based materials have strong electrocatalytic effect on hydrogen evolution reaction (HER) due to their inherent high activity, but they are expensive and scarce in resources, which cannot be applied on a large scale. Nickel tri-sulfide (Ni3S2) has been extensively studied in the field of HER due to its high abundance of earth storage, high conductivity and excellent activity. However, in the process of HER catalytic reaction, hydrogen atoms are easily adsorbed on the active s site, greatly increasing the adsorption of hydrogen, forming a strong S-Hads bond, making it difficult to desorb Hads, and thus reducing the catalytic activity of HER. SUMMARY
[0004] The present application provides a nano-cone structure hydrogen evolution electrode with a dichromic sulfide tri-sulfide / nickel tri-sulfide interface and a preparation method and application thereof to solve the problems in the prior art. A nano-cone structure coating with a dichromic sulfide tri-sulfide / nickel tri-sulfide interface is in-situ grown on a nickel mesh as a conductive substrate by electrochemical deposition as a hydrogen evolution catalyst. The dichromic sulfide tri-sulfide / nickel tri-sulfide interface layer has high water decomposition activity, which optimizes the problem of difficult hydrogen atom desorption of the nickel tri-sulfide catalytic coating, introduces more active sites, greatly reduces the overpotential required for water decomposition, and effectively improves the hydrogen evolution efficiency.
[0005] To solve the above technical problems, the present application provides a nano-cone structure hydrogen evolution electrode with a dichromic sulfide tri-sulfide / nickel tri-sulfide interface in the first aspect, which comprises a conductive substrate and a nano-cone structure catalytic coating with a dichromic sulfide tri-sulfide / nickel tri-sulfide interface in-situ grown on the conductive substrate.
[0006] The hydrogen evolution electrode comprises a conductive substrate and a nano-cone structure catalytic coating with a dichromic sulfide / trinickel disulfide interface, the conductive substrate adopts a nickel mesh, the dichromic sulfide / trinickel disulfide interface in the catalytic coating has high water decomposition activity, optimizes the problem of difficult hydrogen atom desorption of the trinickel disulfide catalytic coating, introduces more active sites, greatly reduces the overpotential required for water decomposition, and effectively improves the hydrogen evolution efficiency.
[0007] Further, the thickness of the catalytic coating is 20-45 mu m, and the size of the nano-cone structure is 50-200 nm.
[0008] Further, the catalytic coating comprises the following components in terms of molar percentage: 49.57%-55.38% of nickel, 2.02%-4.74% of chromium and 42.22%-46.72% of sulfur.
[0009] The second aspect of the present application provides a preparation method of the nano-cone structure hydrogen evolution electrode with a dichromic sulfide / trinickel disulfide interface according to the first aspect, comprising the following steps:
[0010] S1, dissolving a soluble nickel salt, a soluble chromium salt and a soluble sulfur salt in a solvent, adjusting the pH and temperature to obtain a precursor solution;
[0011] S2, placing a conductive substrate in the precursor solution for electrochemical deposition, in-situ growing a nano-cone structure catalytic coating with a dichromic sulfide / trinickel disulfide interface to obtain the nano-cone structure hydrogen evolution electrode with a dichromic sulfide / trinickel disulfide interface.
[0012] The present application adopts a one-step electrodeposition method to in-situ grow a nano-cone structure coating with a dichromic sulfide / trinickel disulfide interface on the surface of a conductive substrate, and the preparation method is simple and efficient, and the catalyst has strong stability.
[0013] Further, in S1, the soluble nickel salt is selected from one or more of nickel sulfate, nickel chloride and nickel nitrate; the soluble chromium salt is selected from one or more of chromium sulfate, chromium chloride and chromium nitrate; and the soluble sulfur salt is selected from thiocyanate and / or sodium sulfide.
[0014] Further, in S1, the concentration of nickel ions in the precursor solution is 1-5 mmol / L, the concentration of chromium ions is 0.5-3 mmol / L, and the concentration of sulfur ions is 10-40 mmol / L.
[0015] Further, in S1, the pH of the precursor solution is 4-5, and the temperature is 80-95 DEG C.
[0016] Further, in S1, the solvent is deionized water.
[0017] Further, in S2, the electrochemical deposition is completed by a standard three-electrode system, the standard three-electrode system comprising a working electrode, a counter electrode and a reference electrode, wherein the conductive substrate is used as the working electrode, a platinum sheet is used as the counter electrode, and an Ag / AgCl electrode is used as the reference electrode.
[0018] Further, in S2, the current density of the electrochemical deposition is -5 to -20 mA / cm 2 , and the electrochemical deposition time is 30 to 90 min.
[0019] Further, in S2, the electrochemical deposition further comprises a washing and drying step.
[0020] Further, before S2, the conductive substrate is sequentially placed in anhydrous ethanol, hydrochloric acid and distilled water for cleaning to remove surface oil and oxides, and the conductive substrate is a nickel mesh.
[0021] The third aspect of the present application provides an application of the nanocone structure hydrogen evolution electrode with a chromium trisulfide / nickel trisulfide interface in a catalytic alkaline electrolytic water hydrogen evolution reaction.
[0022] The present application has the following beneficial effects:
[0023] The present application uses a nickel mesh as a conductive substrate, and in-situ grows a nanocone structure coating with a chromium trisulfide / nickel trisulfide interface on the nickel mesh as a hydrogen evolution catalyst, wherein the chromium trisulfide / nickel trisulfide interface layer has a high water decomposition activity, optimizes the problem of difficult hydrogen atom desorption of the nickel trisulfide catalytic coating, introduces more active sites, greatly reduces the overpotential required for water decomposition, and effectively improves the hydrogen evolution efficiency.
[0024] The present application uses a one-step electrochemical deposition method, and has the advantages of simple and efficient preparation method, strong catalyst stability, and wide application prospect of the prepared hydrogen evolution electrode in the field of alkaline electrolytic water hydrogen production. BRIEF DESCRIPTION OF DRAWINGS
[0025] In order to more clearly illustrate the technical solutions of the present application, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings described below are only embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.
[0026] Figure 1 is a preparation flowchart of the nanocone structure hydrogen evolution electrode with a chromium trisulfide / nickel trisulfide interface of the present application;
[0027] Figure 2are scanning electron microscope (SEM) surface morphology images of the Cr-Ni3S2 electrode and the Ni3S2 electrode prepared in Example 1 and Comparative Example 1 of the present application, wherein a1 and a2 are the surface morphology images of the Ni3S2 electrode prepared in Comparative Example 1, and b1 and b2 are the surface morphology images of the Cr-Ni3S2 electrode prepared in Example 1;
[0028] Figure 3 are transmission electron microscope (TEM) images of the Cr-Ni3S2 electrode and the Ni3S2 electrode prepared in Example 1 and Comparative Example 1 of the present application, wherein a1, a2, a3 are the TEM images of the Ni3S2 electrode prepared in Comparative Example 1, and b1, b2, b3 are the TEM images of the Cr-Ni3S2 electrode prepared in Example 1;
[0029] Figure 4 are X-ray diffraction patterns of the Cr-Ni3S2 electrode and the Ni3S2 electrode prepared in Example 1 and Comparative Example 1 of the present application;
[0030] Figure 5 are Raman images of the Cr-Ni3S2 electrode and the Ni3S2 electrode prepared in Example 1 and Comparative Example 1 of the present application;
[0031] Figure 6 are X-ray photoelectron spectroscopy analyses of the Cr-Ni3S2 electrode and the Ni3S2 electrode prepared in Example 1 and Comparative Example 1 of the present application;
[0032] Figure 7 are current density-potential curve diagrams of the electrodes tested in a three-electrode system in Examples 1-4 of the present application;
[0033] Figure 8 are current density-potential curve diagrams of the electrodes tested in a three-electrode system in Example 1 and Comparative Examples 1-2 of the present application. DETAILED DESCRIPTION
[0034] The technical solutions of the present application will be described clearly and completely below in combination with specific embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.
[0035] The present embodiment provides a nanocone structure hydrogen evolution electrode with a chromium trisulfide / nickel disulfide interface, which comprises a conductive substrate and a nanocone structure catalytic coating layer with a chromium trisulfide / nickel disulfide interface grown in situ on the conductive substrate.
[0036] As a specific example, the thickness of the catalytic coating is 20-45 μm, the size of the nanocone structure is 50-200 nm; the catalytic coating comprises the following components in terms of molar percentage: 49.57%-55.38% of nickel, 2.02%-4.74% of chromium and 42.22%-46.72% of sulfur.
[0037] The following is a specific preparation method embodiment of the nanocone structure hydrogen evolution electrode with the dichromic sulfide / trinickel disulfide interface.
[0038] Embodiment 1
[0039] This embodiment relates to a preparation method of a nanocone structure hydrogen evolution electrode with a dichromic sulfide / trinickel disulfide interface, referring to Figure 1 , comprising the following steps:
[0040] S1, cut the nickel mesh into 1*1 cm 2 pieces, sequentially wash in anhydrous ethanol and hydrochloric acid for 15 minutes, and finally wash in distilled water for 10 minutes under ultrasonic, to obtain a pretreated nickel mesh.
[0041] S2, place 5 mmol of nickel sulfate hexahydrate, 40 mmol of thiourea and 1 mmol of chromium nitrate nonahydrate in a 1L beaker, add deionized water to 1L and stir uniformly, adjust the pH to 5, and heat to 95℃, to obtain a catalyst electrodeposition precursor solution.
[0042] S3, electrochemically deposit using a three-electrode system, place the pretreated nickel mesh of S1 in the catalyst electrodeposition precursor solution as a working electrode, use a platinum sheet as a counter electrode, and deposit at a current density of-5 mA / cm 2 for 60 min. After deposition, rinse with deionized water and dry, to obtain a nanocone structure hydrogen evolution electrode with a dichromic sulfide / trinickel disulfide interface, wherein the molar percentages of Cr, Ni and S elements in the deposition coating are 2.84%, 52.50% and 44.66%, respectively.
[0043] Embodiment 2
[0044] This embodiment relates to a preparation method of a nanocone structure hydrogen evolution electrode with a dichromic sulfide / trinickel disulfide interface, comprising the following steps:
[0045] S1, cut the nickel mesh into 1*1 cm 2 pieces, sequentially wash in anhydrous ethanol and hydrochloric acid for 15 minutes, and finally wash in distilled water for 10 minutes under ultrasonic, to obtain a pretreated nickel mesh.
[0046] S2, 5mmol of nickel sulfate hexahydrate, 40mmol of thiourea and 0.5mmol of chromium nitrate nonahydrate were placed in a 1L beaker, deionized water was added to 1L and stirred uniformly, the pH was adjusted to 5, the temperature was raised to 95℃, and a catalyst electrodeposition precursor solution was obtained.
[0047] S3, electrochemical deposition was carried out by using a three-electrode system, the nickel mesh pretreated in S1 was placed in the catalyst electrodeposition precursor solution as the working electrode, a platinum sheet was used as the counter electrode, and deposition was carried out at a current density of-5mA / cm 2 for 60min. After deposition, the electrode was washed with deionized water and dried, and a nanocone structure hydrogen evolution electrode with a dichromium trisulfide / three-nickel disulfide interface was obtained, wherein the molar percentages of Cr, Ni and S elements in the deposition coating were 2.24%, 54.64% and 43.12%, respectively.
[0048] Example 3
[0049] The present embodiment relates to a preparation method of a nanocone structure hydrogen evolution electrode with a dichromium trisulfide / three-nickel disulfide interface, comprising the following steps:
[0050] S1, the nickel mesh was cut into 1*1cm 2 pieces, and was sequentially cleaned in anhydrous ethanol and hydrochloric acid for 15min, and finally was cleaned in distilled water for 10min under ultrasonic cleaning to obtain a pretreated nickel mesh.
[0051] S2, 5mmol of nickel sulfate hexahydrate, 40mmol of thiourea and 2mmol of chromium nitrate nonahydrate were placed in a 1L beaker, deionized water was added to 1L and stirred uniformly, the pH was adjusted to 5, the temperature was raised to 95℃, and a catalyst electrodeposition precursor solution was obtained.
[0052] S3, electrochemical deposition was carried out by using a three-electrode system, the nickel mesh pretreated in S1 was placed in the catalyst electrodeposition precursor solution as the working electrode, a platinum sheet was used as the counter electrode, and deposition was carried out at a current density of-5mA / cm 2 for 60min. After deposition, the electrode was washed with deionized water and dried, and a nanocone structure hydrogen evolution electrode with a dichromium trisulfide / three-nickel disulfide interface was obtained, wherein the molar percentages of Cr, Ni and S elements in the deposition coating were 3.64%, 51.56% and 44.80%, respectively.
[0053] Example 4
[0054] The present embodiment relates to a preparation method of a nanocone structure hydrogen evolution electrode with a dichromium trisulfide / three-nickel disulfide interface, comprising the following steps:
[0055] S1, the nickel mesh was cut into 1*1cm 2small pieces, sequentially placed in anhydrous ethanol, hydrochloric acid for 15 minutes, and finally placed in distilled water for ultrasonic cleaning for 10 minutes to obtain the pretreated nickel mesh.
[0056] S2, 5 mmol of nickel sulfate hexahydrate, 40 mmol of thiourea, and 3 mmol of chromium nitrate nonahydrate were placed in a 1L beaker, deionized water was added to 1L and stirred uniformly, the pH was adjusted to 5, and the temperature was raised to 95°C to obtain a catalyst electrodeposition precursor solution.
[0057] S3, electrochemical deposition was carried out using a three-electrode system, the pretreated nickel mesh of S1 was placed in the catalyst electrodeposition precursor solution as the working electrode, a platinum sheet was used as the counter electrode, and deposition was carried out at a current density of -5mA / cm 2 for 60 min. After deposition, deionized water was used for rinsing and drying to obtain a nano-cone structure hydrogen evolution electrode with a chromium disulfide / three-nickel disulfide interface, wherein the molar percentages of Cr, Ni, and S elements in the deposition coating were 4.54%, 50.39%, and 45.07%, respectively.
[0058] Comparative Example 1
[0059] This comparative example relates to a method for preparing a three-nickel disulfide electrode, comprising the following steps:
[0060] S1, the nickel mesh was cut into 1*1cm 2 small pieces, sequentially placed in anhydrous ethanol, hydrochloric acid for 15 minutes, and finally placed in distilled water for ultrasonic cleaning for 10 minutes to obtain the pretreated nickel mesh.
[0061] S2, 5 mmol of nickel sulfate hexahydrate, 40 mmol of thiourea, and 3 mmol of chromium nitrate nonahydrate were placed in a 1L beaker, deionized water was added to 1L and stirred uniformly, the pH was adjusted to 5, and the temperature was raised to 95°C to obtain a catalyst electrodeposition precursor solution.
[0062] S3, electrochemical deposition was carried out using a three-electrode system, the pretreated nickel mesh of S1 was placed in the catalyst electrodeposition precursor solution as the working electrode, a platinum sheet was used as the counter electrode, and deposition was carried out at a current density of -5mA / cm 2 for 60 min. After deposition, deionized water was used for rinsing and drying to obtain a nano-cone structure hydrogen evolution electrode with a chromium disulfide / three-nickel disulfide interface, wherein the molar percentages of Cr, Ni, and S elements in the deposition coating were 4.54%, 50.39%, and 45.07%, respectively.
[0063] Comparative Example 2
[0064] This comparative example is a Raney nickel electrode, which is widely used as an electrode for industrial electrolytic water hydrogen production, and the preparation method is not described in detail.
[0065] Test Example 1
[0066] The hydrogen evolution electrode with a nanoconical structure at the chromium trisulfide / nickel trisulfide interface prepared in Example 1 (denoted as Cr-Ni3S2 electrode) and the nickel trisulfide (Ni3S2) electrode prepared in Comparative Example 1 were analyzed by scanning electron microscopy (SEM). Figure 2 As shown, where, Figure 2 a1 and Figure 2 a2 is a surface morphology diagram of the Ni3S2 electrode prepared in Comparative Example 1. Figure 2 b1 and 2b2 are surface morphology images of the Cr-Ni3S2 electrode prepared in Example 1. The comparison shows that the Cr-Ni3S2 catalyst formed after the introduction of Cr element forms a smaller and denser microconical structure compared to the pure Ni3S2 catalyst. The size of the microcones changes from 400 nm-1 μm to 50-200 nm, and this structural change greatly increases the active area of the catalyst.
[0067] The Cr-Ni3S2 electrode prepared in Example 1 and the Ni3S2 electrode prepared in Comparative Example 1 were analyzed by transmission electron microscopy (TEM). Figure 3 As shown, where, Figure 3 a1、 Figure 3 a2 and Figure 3 a3 is a TEM image of the Ni3S2 electrode prepared in Comparative Example 1. Figure 3 b1、 Figure 3 b2 and Figure 3 b3 is a TEM image of the Cr-Ni3S2 electrode prepared in Example 1. From Figure 3 a1、 Figure 3 a2 and Figure 3 In a3, the (110) and (113) crystal planes of Ni3S2 can be observed, with lattice spacings of 0.287 nm and 0.183 nm, respectively, indicating that the Ni3S2 catalyst was successfully formed on the nickel mesh. Figure 3 b1、 Figure 4 b2 and Figure 5 As can be seen from b3, after the introduction of Cr, the catalyst forms an interfacial heterojunction between Ni3S2 and Cr2S3, namely the (110) crystal plane of Ni3S2 with an interplanar spacing of 0.287 nm and the (11-3) crystal plane of Cr2S3 with an interplanar spacing of 0.261 nm. The Ni3S2 / Cr2S3 interfacial heterojunction formed by these two crystals can effectively improve the electrochemical activity of the catalyst.
[0068] X-ray diffraction (XRD) analysis was performed on the Cr-Ni3S2 electrode prepared in Example 1 and the Ni3S2 electrode prepared in Comparative Example 1. (Refer to...) Figure 6As shown in the figure, by comparison, the half-peak width of the Ni3S2 diffraction peak in the Cr-Ni3S2 electrode is reduced compared to the half-peak width of the Ni3S2 diffraction peak in the Ni3S2 electrode. This is because the introduction of Cr causes the catalyst to form more S vacancies, which can effectively improve the electrochemical activity of the catalyst.
[0069] The Cr-Ni3S2 electrode prepared in Example 1 and the Ni3S2 electrode prepared in Comparative Example 1 were subjected to Raman analysis, and reference was made to Figure 7 As shown in the figure, by comparing the Raman images, it can be seen that the introduction of Cr indeed reduces the Ni-S bond in the catalyst, and forms Cr-S bonds, Cr-OH bonds and surface adsorbed water peaks. The formation of such Cr-OH bonds can improve the adsorption capacity of the catalyst surface to water, further improving the water electrolysis catalytic performance.
[0070] The Cr-Ni3S2 electrode prepared in Example 1 and the Ni3S2 electrode prepared in Comparative Example 1 were subjected to X-ray photoelectron spectroscopy analysis (XRS), and reference was made to Figure 8 As shown in the figure, by comparison, it can be found that the Ni 2+ of the Cr-Ni3S2 catalyst has a positive shift of 0.1 eV, while the S 2- has a negative shift. This indicates that after the introduction of Cr, the electrons are transferred from Ni to S.
[0071] Test Example 2
[0072] The hydrogen evolution electrodes with Cr2S3 / Ni3S2 interface nanocone structure prepared in Examples 1-4, the Ni3S2 electrode prepared in Comparative Example 1 and the Raney nickel electrode of Comparative Example 2 were subjected to overpotential test, and the specific test method was as follows:
[0073] Under the condition of 80℃, linear sweep voltammetry was used with 30wt% KOH as electrolyte. Among them, the electrodes of the examples and the comparative examples were working electrodes, 60 mesh pure nickel mesh (1cm*1cm) was used as counter electrode, and Ag / AgCl was used as reference electrode. The current density-potential curve of the hydrogen evolution electrode prepared in Examples 1-4 relative to the reversible hydrogen electrode is shown in Example As shown in the figure, when the doping amount of chromium nitrate in Example 1 reaches 1mmol / L, the catalytic effect of the hydrogen evolution electrode reaches the best (500mA / cm 2 The overpotential at current density is only 0.253V). In Examples 3 and 4, as the concentration of chromium nitrate increases, the synthesis of Ni3S2 in the catalyst is affected, and the catalyst activity decreases; while in Example 2, the concentration of chromium nitrate is too low to form the interface heterojunction of Cr2S3 and Ni3S2, affecting the kinetics of the catalytic reaction.
[0074] Reference to the current density-potential curve of the hydrogen evolution electrode of Example 1, Comparative Example 1-2 Mole percentage of Cr, Ni, S elements As shown in the figure, it can be seen that the nanocone structure hydrogen evolution electrode with the Cr2S3 / Ni3S2 interface of Example 1 has a current density of 500 mA / cm 2 The overpotential at the current density of 500 mA / cm The overpotential at the current density of 500 mA / cm
[0075] In order to further prove the beneficial effects of the present application, the electrodes obtained in Examples 1-4 and Comparative Example 1 were used as working electrodes, platinum pieces as counter electrodes, and Ag / AgCl electrodes as reference electrodes, and the hydrogen evolution catalytic performance for water decomposition was detected in 30wt% KOH aqueous solution at 80℃ by linear sweep voltammetry at a scanning speed of 5 mVs -1 The potential measured was corrected according to V RHE = V Ag / AgCl + ph x 0.059 V + 0.197 V, and finally the measured results were relative to the standard hydrogen electrode potential. The test results are shown in Table 1. It can be seen that the hydrogen evolution electrodes prepared in Examples 1-4 have excellent catalytic activity, and in particular, the nanocone structure hydrogen evolution electrode with the Cr2S3 / Ni3S2 interface prepared in Example 1 has an overpotential of only 253 mV at 500 (mAcm -2 ) corresponding to the overpotential of 311 mV of the Ni3S2 electrode prepared in Comparative Example 1 at 500 (mAcm -2 ) corresponding to the overpotential of 311 mV of the Ni3S2 electrode prepared in Comparative Example 1 at 500 (mAcm
[0076] Table 1
[0077] Example 1 Cr 2.84%, Ni 52.50%, S 44.66% 500 (mA cm -2 ) corresponding overpotential mV Example 2 Cr 2.24%, Ni 54.64%, S 43.12% 253 Example 3 Cr 3.64%, Ni 51.56%, S 44.80% 268 Example 4 Cr 4.54%, Ni 50.39, S 45.07% 282 Comparative Example 1 Cr 0.00%, Ni 58.08%, S 41.92 296 311
[0078] In summary, the present application uses a nickel mesh as a conductive substrate, and in-situ grows a nanocone structure coating with a Cr2S3 / Ni3S2 interface on the nickel mesh as a hydrogen evolution catalyst. The Cr2S3 / Ni3S2 interface layer has a higher water decomposition activity, optimizes the problem of difficult hydrogen atom desorption of the Ni3S2 catalytic coating, introduces more active sites, greatly reduces the overpotential required for water decomposition, and effectively improves the hydrogen evolution efficiency. The one-step electrochemical deposition method is simple and efficient, the catalyst has strong stability, and the prepared hydrogen evolution electrode has a broad application prospect in the field of alkaline water electrolysis hydrogen production.
[0079] The present application is described in detail above with reference to specific embodiments and exemplary examples, but these are not to be understood as limiting the present application. It is understood by a person skilled in the art that various equivalent substitutions, modifications or improvements can be made to the technical solutions of the present application and the embodiments thereof without departing from the spirit and scope of the present application, and these all fall within the scope of the present application. The scope of protection of the present application is defined by the appended claims.
Claims
1. A method for preparing a nano-taper structure hydrogen evolution electrode with a chromium disulfide / tri-nickel disulfide interface, characterized in that, The method comprises the following steps: S1, dissolving the soluble nickel salt, the soluble chromium salt and the soluble sulfur salt in a solvent, adjusting the pH and the temperature to obtain a precursor solution; the concentration of nickel ions in the precursor solution is 1-5 mmol / L, the concentration of chromium ions is 0.5-3 mmol / L, and the concentration of sulfur ions is 10-40 mmol / L; S2, electrochemically depositing the conductive substrate in the precursor solution to in-situ grow a nanocone structure catalytic coating with a dichromic trisulfide / three-nickel disulfide interface, to obtain the nanocone structure hydrogen evolution electrode with the dichromic trisulfide / three-nickel disulfide interface; the current density of the electrochemical deposition is -5 ~ -20 mA / cm 2 , and the electrochemical deposition time is 30-90 min.
2. The method for preparing the hydrogen evolution electrode with a nanoconical structure having a chromium trisulfide / nickel trisulfide interface as described in claim 1, characterized in that, In S1, the soluble nickel salt is selected from one or more of nickel sulfate, nickel chloride and nickel nitrate; the soluble chromium salt is selected from one or more of chromium sulfate, chromium chloride and chromium nitrate; and the soluble sulfur salt is selected from thiourea and / or sodium sulfide.
3. The method for preparing the hydrogen evolution electrode with a nanoconical structure having a chromium trisulfide / nickel trisulfide interface as described in claim 1, characterized in that, In S1, the pH of the precursor solution is 4-5, and the temperature is 80-95℃.
4. The method for preparing the hydrogen evolution electrode with a nanoconical structure having a chromium trisulfide / nickel trisulfide interface as described in claim 1, characterized in that, S2 further comprises: sequentially cleaning the conductive substrate in anhydrous ethanol, hydrochloric acid and distilled water; and the conductive substrate is a nickel mesh.
5. The nano-tapered structure hydrogen evolution electrode with CrS2 / NiS3 interface prepared by the method of any one of claims 1-4, characterized in that, The catalytic coating layer comprises a conductive substrate and a nano-cone structure with a dichromium trisulfide / trinickel disulfide interface grown in situ on the conductive substrate.
6. The nano-tapered structure hydrogen evolution electrode with Cr2S3 / NiS2 interface according to claim 5, wherein, The thickness of the catalytic coating layer is 20-45 μm, and the size of the nano-cone structure is 50-200 nm.
7. The hydrogen evolution electrode with a nanoconical structure having a chromium trisulfide / nickel trisulfide interface as described in claim 5, characterized in that, In terms of molar percentage, the catalytic coating layer comprises the following components: 49.57%-55.38% of nickel, 2.02%-4.74% of chromium and 42.22%-46.72% of sulfur.
8. Use of the nano-cone structure hydrogen evolution electrode with a dichromium trisulfide / trinickel disulfide interface according to any one of claims 5-7 in a catalytic alkaline electrolytic water hydrogen evolution reaction.