A kind of foamed nickel loaded polyacid derivative molybdenum nickel sulfide electrocatalytic hydrogen evolution material and preparation
By synthesizing a MoS2/Ni3S2 heterojunction interface on nickel foam, the problems of low specific surface area and poor stability of electrocatalytic hydrogen evolution catalysts were solved, achieving high efficiency and low cost electrocatalytic hydrogen evolution performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HARBIN UNIV OF SCI & TECH
- Filing Date
- 2026-03-25
- Publication Date
- 2026-06-05
Smart Images
Figure CN122147385A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrocatalytic hydrogen evolution, and particularly to a foamed nickel-supported polyacid-derived molybdenum-nickel sulfide, its preparation method, and its application in electrocatalytic hydrogen evolution. Background Technology
[0002] Traditional fossil fuels (such as coal, oil, and natural gas) face resource depletion challenges due to their dwindling reserves and increasing extraction difficulties during long-term large-scale exploitation and use. Furthermore, their combustion emits large amounts of pollutants such as carbon dioxide, nitrogen oxides, and particulate matter, causing a series of severe environmental problems. To achieve sustainable economic and social development, building a clean, low-carbon, safe, and efficient energy system is urgently needed. Hydrogen energy, as a widely available, high-energy-density, clean, carbon-free, storable, and transportable secondary energy source, is gradually becoming an important direction for global energy transformation. Among these, the electrochemical hydrogen evolution reaction (HER) is a clean, simple, and renewable pathway that can effectively alleviate energy demand. Currently, high-performance catalysts mostly rely on precious metals (such as platinum and iridium), but the scarcity, high price, and low specific surface area of precious metals keep the cost of electrocatalytic HER preparation high, severely limiting its large-scale commercial application. Transition metal sulfides, especially cobalt / molybdenum-based sulfides, have become a research hotspot in the field of hydrogen evolution reaction catalysts due to their high catalytic activity, low cost, and abundant reserves. Polyacids possess well-defined, atomically precise metal-oxygen cluster structures, along with strong Brønsted acidity and redox reactivity. Polyatomic atoms (such as Mo, W, and V) can reversibly accept and donate multiple electrons without structural disruption. Polyacids exhibit good chemical stability and high thermal stability in both solid and solution states. Their elemental composition can be substituted and adjusted, and they can form polyacid-based organic-inorganic hybrid materials with organic compounds to regulate their structure. Polyacids can also be loaded onto other materials with high conductivity or large specific surface area to synthesize composite materials, improving their electrochemical performance. Therefore, using polyacids as precursors to prepare highly active, high-specific-surface-area, and highly stable sulfides is of great significance. Summary of the Invention
[0003] To overcome the problems of low specific surface area, high price, and poor stability and conductivity of polyacids as raw materials in existing electrocatalytic hydrogen evolution catalysts, this invention provides a simple and inexpensive method for preparation. The prepared polyacid-derived molybdenum-nickel sulfide supported on nickel foam has advantages such as high specific surface area, high electrocatalytic performance, and good stability as an electrocatalytic hydrogen evolution catalyst material.
[0004] The objective of this invention is achieved as follows:
[0005] The preparation of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide includes the following steps:
[0006] (1) The nickel foam was cut into 1 cm × 1 cm pieces and ultrasonically cleaned sequentially with acetone, hydrochloric acid, ethanol, and deionized water to remove surface oil and oxide layers. Finally, it was vacuum dried at 60 °C for later use. 98 mg ammonium fluoride (NH4F), 200 mg urea (CO(NH2)2), and 194 mg nickel nitrate hexahydrate (Ni(NO3)2·6H2O) were dissolved in 12 mL of deionized water. A pre-cleaned conductive nickel foam substrate was then immersed in the prepared solution. The solution was added to a sealed reactor and placed in an oven at 120 °C for 10–12 h, then cooled to room temperature. The product was washed several times with distilled water. Finally, NiO nanorod arrays (NF-MO) were obtained by calcining the precursor in a tube furnace at 500 °C under N2 atmosphere.
[0007] (2) Dissolve 50 g of Na2MoO4·2H2O in 200 mL of deionized water and heat to 60 °C. Then, add 20 mL of concentrated hydrochloric acid (density: 1.18 g / cm³) under vigorous magnetic stirring. While stirring continuously, dissolve 5 g of Na2SiO3 in 50 mL of water and add it to the above reaction solution. Then, add 60 mL of concentrated hydrochloric acid dropwise and filter to remove the silicic acid precipitate. Cool the filtrate and extract and purify it with 50-60 mL of diethyl ether. Redissolve the product in a mixture of 50 mL of water and 15 mL of concentrated hydrochloric acid and extract again with diethyl ether. Carefully concentrate the yellow extract at 40 °C to obtain crystals (silicomolybdic acid).
[0008] (3) Add 0.11 g of molybdic acid (H4[SiMo) 12 O 40 ], denoted as SiMo 12 0.22 g of thiourea (CH4N2S) was dissolved in 10 mL of deionized water and magnetically stirred for 20–40 minutes at room temperature to ensure complete dissolution. The homogeneous solution was then transferred to a 20 mL stainless steel autoclave lined with polytetrafluoroethylene. A pre-fabricated NF-MO template (1 cm × 1 cm) was carefully immersed in the reaction solution. The autoclave was sealed and kept in a temperature-controlled oven at 180 °C for 10–12 h, followed by natural cooling to room temperature. The resulting product was collected and washed sequentially with deionized water and anhydrous ethanol (3 times each) to remove residual reactants. Finally, the sample was dried under vacuum at 60 °C for 6 h to obtain the MoS2 / Ni3S2@NF-MO composite material.
[0009] (4) The preparation of MoS2 / Ni3S2@NF composite material follows the same synthesis steps as MoS2 / Ni3S2@NF-MO in step (3). The only modification is to replace the NF-MO template with a piece of pretreated nickel foam (NF, 1cm×1cm).
[0010] The aforementioned applications of foamed nickel supported polyacid-derived molybdenum nickel sulfide are mainly in the electrocatalytic splitting of water to produce hydrogen.
[0011] The above application method is as follows: A standard three-electrode system was used, employing a 1.0 M KOH electrolyte. The working electrode was MoS2 / Ni3S2@NF-MO, the counter electrode was a carbon rod, and the reference electrode was a saturated calomel electrode to evaluate the HER performance of the prepared material. The current density was 10 mA cm⁻¹. -2 At that time, MoS2 / Ni3S2@NF-MO exhibited a low overpotential of 67 mV, at 10 mA cm⁻¹. -2 It operates stably for 100 hours at the specified current density.
[0012] Compared with the prior art, the present invention has the following characteristics:
[0013] This invention successfully synthesized a MoS2 / Ni3S2@NF-MO catalyst using a template-based synthesis strategy, exhibiting multiple significant advantages. Structurally, the unique hydrangea-like three-dimensional nanostructure effectively prevents the aggregation of active components, significantly improving catalytic stability and greatly increasing the specific surface area, exposing abundant active sites. In terms of composition, the successfully constructed MoS2 / Ni3S2 heterojunction interface exhibits tight contact, optimizing the electronic structure and accelerating electron transfer, thereby enhancing intrinsic catalytic activity. This three-dimensional structure, guided by an ordered nanorod array template, allows the internal heterojunction to directly contact the reactants, greatly improving the utilization rate of active sites. Comparative experiments confirm that this synthesis strategy is highly effective in controlling material morphology and optimizing structure to improve performance. When used as a catalyst for electrocatalytic hydrogen evolution, at a current density of 10 mA cm⁻¹, [the catalyst exhibits excellent performance]. -2 At that time, MoS2 / Ni3S2@NF-MO exhibited a low overpotential of 67 mV, and at 10 mA cm⁻¹, it showed a low overpotential of 67 mV. -2 It operates stably for 100 hours at a current density without significant changes in morphology and composition, demonstrating excellent stability. Attached Figure Description
[0014] Figure 1 The image shows the XRD pattern of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide prepared in Example 1 of this invention.
[0015] Figure 2This is a scanning electron microscope image of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide prepared in Example 1 of the present invention.
[0016] Figure 3 This is a high-resolution transmission electron microscope image of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide prepared in Example 1 of the invention.
[0017] Figure 4 Hydrogen evolution polarization curves of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide and other commercial catalysts prepared in Example 1 of the invention.
[0018] Figure 5 Tafel slopes for a foamed nickel-supported polyacid-derived molybdenum nickel sulfide and other commercial catalysts prepared in Example 1 of the invention.
[0019] Figure 6 A polyacid-derived molybdenum nickel sulfide supported on foamed nickel prepared in Example 1 of the invention was prepared at 10 mAcm⁻¹. -2 Stability graph showing stable operation for 100 hours at a given current density.
[0020] Figure 7 This is a flowchart illustrating the preparation process of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide prepared according to Example 1 of the invention. Detailed Implementation
[0021] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.
[0022] Example 1, a foamed nickel-supported polyacid-derived molybdenum-nickel sulfide, comprising the following preparation steps:
[0023] (1) The nickel foam was cut into 1 cm × 1 cm pieces and ultrasonically cleaned sequentially with acetone, hydrochloric acid, ethanol, and deionized water to remove surface oil and oxide layers. Finally, it was vacuum dried at 60 °C for later use. 98 mg ammonium fluoride (NH4F), 200 mg urea (CO(NH2)2), and 194 mg nickel nitrate hexahydrate (Ni(NO3)2·6H2O) were dissolved in 12 mL of deionized water. A pre-cleaned conductive nickel foam substrate was then immersed in the prepared solution. The solution was added to a sealed reaction vessel and placed in an oven at 120 °C for 10–12 h, then cooled to room temperature. The product was washed several times with distilled water. Finally, NiO nanorod arrays (NF-MO) were obtained by calcining the precursor in a tube furnace at 500 °C under N2 atmosphere.
[0024] (2) Dissolve 50 g of Na2MoO4·2H2O in 200 mL of deionized water and heat to 60 °C. Then, add 20 mL of concentrated hydrochloric acid (density: 1.18 g / cm³) under vigorous magnetic stirring. While stirring continuously, dissolve 5 g of Na2SiO3 in 50 mL of water and add it to the above reaction solution. Then, add 60 mL of concentrated hydrochloric acid dropwise and filter to remove the silicic acid precipitate. Cool the filtrate and extract and purify it with 50-60 mL of diethyl ether. Redissolve the product in a mixture of 50 mL of water and 15 mL of concentrated hydrochloric acid and extract again with diethyl ether. Carefully concentrate the yellow extract at 40 °C to obtain crystals (silicomolybdic acid).
[0025] (3) Add 0.11 g of molybdic acid (H4[SiMo) 12 O 40 ], denoted as SiMo 12 0.22 g of thiourea (CH4N2S) was dissolved in 10 mL of deionized water and magnetically stirred for 20–40 minutes at room temperature to ensure complete dissolution. The homogeneous solution was then transferred to a 20 mL stainless steel autoclave lined with polytetrafluoroethylene. A pre-prepared NF-MO template (1 cm × 1 cm) was carefully immersed in the reaction solution. The autoclave was sealed and kept in a temperature-controlled oven at 180 °C for 10–12 h, followed by natural cooling to room temperature. The resulting product was collected and washed sequentially with deionized water and anhydrous ethanol (3 times each) to remove residual reactants. Finally, the sample was dried under vacuum at 60 °C for 6 h to obtain the MoS2 / Ni3S2@NF-MO composite material.
[0026] (4) The preparation of MoS2 / Ni3S2@NF composite material follows the same synthesis steps as MoS2 / Ni3S2@NF-MO in step (3), with the only modification being that the NF-MO template is replaced with a piece of pretreated nickel foam (NF, 1cm×1cm).
[0027] The present invention will be further described below with reference to the accompanying drawings and embodiments:
[0028] Figure 1 The image shows the XRD pattern of a polyacid-derived molybdenum nickel sulfide supported on nickel foam. Characteristic peaks of MoS2 (JCPDS No. 37-1492) and Ni3S2 (JCPDS No. 76-1870) are observed in the figure, confirming the successful preparation of the target material.
[0029] Figure 2The image shows a scanning electron microscope (SEM) image of a polyacid-derived molybdenum-nickel sulfide supported on nickel foam. The image reveals that the product after sulfidation exhibits hydrangea-like nanoflowers. This unique three-dimensional structure, assembled from low-dimensional structures, not only prevents self-aggregation during the reaction process and improves reaction stability, but also increases the specific surface area of the material, provides abundant active sites, accelerates electron transfer, and enhances the electrocatalytic activity of the catalyst.
[0030] Figure 3 The image shows a high-resolution transmission electron microscope (TEM) image of a polyacid-derived molybdenum nickel sulfide supported on nickel foam. The image reveals clear lattice fringes and a close contact between Ni3S2 (111) and MoS2 (100), further confirming the formation of a heterojunction. Elemental mapping shows a uniform distribution of Ni, Mo, and S elements in MoS2 / Ni3S2@NF-MO.
[0031] Figure 4 The figure shows the hydrogen evolution polarization curves of a foamed nickel-supported polyacid-derived molybdenum-nickel sulfide and other commercial catalysts. The polarization was achieved at a current density of 10 mA cm⁻¹. -2 At that time, MoS2 / Ni3S2@NF-MO exhibited a low overpotential of 67 mV, significantly better than bare-NF (179 mV), NF-MO (179 mV), and MoS2 / Ni3S2@NF (95 mV), and close to that of commercial Pt / C (40 mV). This further demonstrates that the heterostructure constructed by the template method is beneficial for improving the electrocatalytic reaction activity.
[0032] Figure 5 The figure shows the Tafel slopes for a nickel foam-supported polyacid-derived molybdenum nickel sulfide and other commercial catalysts, with relatively low Tafel slope values (53 mV dec). -1 The results indicate that the kinetics are relatively fast, which also suggests that MoS2 / Ni3S2@NF-MO promotes the Volmer-Heyrovsky mechanism of HER.
[0033] Figure 6 The image shows a foamed nickel-supported polyacid-derived molybdenum nickel sulfide at 10 mA cm⁻¹. -2 The stability diagram shows that MoS2 / Ni3S2@NF-MO operates stably for 100 h at a given current density. This demonstrates that MoS2 / Ni3S2@NF-MO exhibits good structural stability during long-term electrocatalytic operation.
[0034] Figure 7 The diagram shows a process flow chart for preparing a polyacid-derived nickel molybdenum sulfide supported on nickel foam. As shown in the figure, nanorod arrays (NF-MO) are prepared by hydrothermal synthesis, and then used as sacrificial templates with SiMo. 12MoS2 / Ni3S2@NF-MO composite material was obtained by high-temperature reaction with thiourea; nickel foam and SiMo were then grown in situ using an in-situ method. 12 The reaction with thiourea yielded a MoS2 / Ni3S2@NF composite material, which was then compared with the MoS2 / Ni3S2@NF-MO composite material.
Claims
1. Preparation of a polyacid-derived molybdenum nickel sulfide supported on nickel foam, wherein the polyacid precursor for preparing the sulfide is self-prepared silicomolybdic acid (H4[SiMo)). 12 O 40 ], denoted as SiMo 12 The NiO nanorod array prepared by nickel foam was used as a sacrificial template, and thiourea was used as a sulfur source.
2. A method for preparing a polyacid-derived molybdenum nickel sulfide supported on nickel foam, the method comprising the following steps: (1) The nickel foam was cut into 1 cm × 1 cm pieces and ultrasonically cleaned sequentially with acetone, hydrochloric acid, ethanol and deionized water to remove surface oil and oxide layer. Finally, it was vacuum dried at 60 °C for later use. 98 mg ammonium fluoride (NH4F), 200 mg urea (CO(NH2)2) and 194 mg nickel nitrate hexahydrate (Ni(NO3)2·6H2O) were dissolved in 12 mL of deionized water. Then, a pre-cleaned conductive nickel foam substrate was immersed in the prepared solution. The solution was added to a sealed reaction vessel and placed in an oven at 120 °C for 10-12 h. After cooling to room temperature, the product was washed several times with distilled water. Finally, the precursor was calcined in a tube furnace at 500 °C under N2 atmosphere to obtain NiO nanorod arrays (NF-MO).
3. (2) Dissolve 50 g of Na2MoO4·2H2O in 200 mL of deionized water, heat to 60 °C, and then add 20 mL of concentrated hydrochloric acid (density: 1.18 g / cm³) under vigorous magnetic stirring. 3 Under continuous stirring, 5 g of Na2SiO3 was dissolved in 50 mL of water and added to the above reaction solution; 60 mL of concentrated hydrochloric acid was added dropwise, and the silicic acid precipitate was removed by filtration. The filtrate was cooled and purified by extraction with 50-60 mL of diethyl ether; the product was redissolved in a mixture of 50 mL of water and 15 mL of concentrated hydrochloric acid and extracted with diethyl ether again; the yellow extract was carefully concentrated at 40°C to obtain crystals (silicomolybdic acid).
4. (3) Add 0.11 g of molybdic acid (H4[SiMo) 12 O 40 ], denoted as SiMo 12 0.22 g of thiourea (CH4N2S) was dissolved in 10 mL of deionized water and magnetically stirred for 20-40 minutes at room temperature to ensure complete dissolution. The homogeneous solution was then transferred to a 20 mL stainless steel high-pressure reactor lined with polytetrafluoroethylene. A pre-made NF-MO template (1 cm × 1 cm) was carefully immersed in the reaction solution. The reactor was sealed and kept at 180 °C for 10-12 h in a temperature-controlled oven, followed by natural cooling to room temperature. The resulting product was collected and washed sequentially with deionized water and anhydrous ethanol (3 times each) to remove residual reactants. Finally, the sample was dried under vacuum at 60 °C for 6 h to obtain the MoS2 / Ni3S2@NF-MO composite material.
5. (4) The preparation of the MoS2 / Ni3S2@NF composite material follows the same synthesis steps as MoS2 / Ni3S2@NF-MO in step (3), with the only modification being that the NF-MO template is replaced with a piece of pretreated nickel foam (NF, 1cm×1cm).
6. The application of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide prepared by the preparation method according to claim 2, characterized in that, A foamed nickel-supported polyacid-derived molybdenum nickel sulfide is applied in the field of electrocatalytic water splitting for hydrogen production.
7. The application of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide according to claim 2, characterized in that, The application method is as follows: A standard three-electrode system was used, employing 1.0 M KOH electrolyte. The working electrode was MoS2 / Ni3S2@NF-MO, the counter electrode was a carbon rod, and the reference electrode was a saturated calomel electrode to evaluate the HER performance of the prepared material. The current density was 10 mA cm⁻¹. -2 At that time, MoS2 / Ni3S2@NF-MO exhibited a low overpotential of 67 mV, which was significantly better than bare-NF (179 mV), NF-MO (179 mV), and MoS2 / Ni3S2@NF (95 mV), and close to that of commercial Pt / C (40 mV). This indicates that the foamed nickel-supported polyacid-derived molybdenum nickel sulfide of the present invention is a highly efficient catalyst for electrocatalytic water splitting to produce hydrogen.
8. The application of a foamed nickel-supported polyacid-derived molybdenum nickel sulfide according to claim 2, characterized in that, At 10 mA cm -2 The fact that it operates stably for 100 h at a given current density indicates that the foamed nickel-supported polyacid-derived molybdenum-nickel sulfide of the present invention is a stable catalyst for electrocatalytic water splitting to produce hydrogen.