A ternary metal prussian blue analogue partially converted sulfur phosphatizing electrocatalyst, and a preparation method and application thereof

Abstract

This invention relates to the field of electrocatalytic materials technology, specifically to a ternary metal Prussian blue analogue-based partial conversion sulfur phosphating electrocatalyst, its preparation method, and its application. A CoMoO4 nanorod array is grown on a nickel foam surface via a hydrothermal method, further generating an in-situ FeCoNi-PBA precursor to form a hollow, embedded cubic structure. Hydrothermal sulfidation yields hollow, porous NiCo2S4 nanorods; subsequent low-temperature gas-phase phosphating achieves partial conversion of NiCo2S4, generating a NiCoP shell in-situ on the surface, forming a core-shell heterogeneous interface with the core, resulting in a NiCoP / NiCo2S4 / NF electrocatalyst. Compared to traditional bifunctional electrocatalyst preparation methods, this invention utilizes a two-step "sulfidation followed by phosphating" method to construct a stable heterogeneous interface in-situ on a conductive substrate, enabling the resulting catalyst to exhibit both good hydrogen evolution and oxygen evolution activity and long-term stability under high current in alkaline water electrolysis.

Description

Technical Field

[0001] This invention relates to the field of electrocatalytic materials technology, specifically to a ternary metal Prussian blue analogue partial conversion sulfur phosphating electrocatalyst, its preparation method, and its application. Background Technology

[0002] Hydrogen energy, as a clean energy carrier, differs from hydrogen production through fossil fuel reforming. Water electrolysis produces no carbon dioxide emissions, making it a green and sustainable hydrogen production technology. However, traditional water electrolysis relies on high-purity freshwater. Given the increasing scarcity of freshwater resources, developing efficient and stable water electrolysis hydrogen production technologies is crucial. The water electrolysis process involves two half-reactions: the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). The OER, involving a four-electron transfer process, is kinetically slow and is a bottleneck limiting the overall efficiency of water electrolysis. While alkaline water electrolysis systems avoid corrosion problems associated with acidic media, challenges remain, such as insufficient catalytic activity and poor stability at high current densities. Therefore, developing highly active and stable bifunctional electrocatalysts is key to advancing the industrialization of alkaline water electrolysis technology.

[0003] Prussian blue analogues (PBAs) are a class of three-dimensional porous coordination polymers formed by bridging transition metal ions and cyanide ions. They possess advantages such as atomically uniform distribution of metal ions, tunable composition, and controllable structure, making them ideal precursors for high-performance electrocatalysts. Through post-treatment methods such as pyrolysis, phosphating, and sulfidation, PBAs can be converted into transition metal phosphides, sulfides, and their heterostructures. Transition metal phosphides (such as Ni₂P, CoP, and NiCoP) have attracted considerable attention due to their tunable electronic structure, excellent conductivity, and hydrogenase-like catalytic mechanism; transition metal sulfides (such as NiCo₂S₄ and MoS₂) also exhibit good catalytic potential due to their unique electronic structure and abundant active sites. However, existing PBA-derived catalysts are mostly concentrated in binary metal systems, with limited research on ternary metal systems. Furthermore, conventional conversion methods struggle to directly construct heterointerfaces with high-density contacts on conductive substrates. In addition, how to control the morphology and structure of PBA precursors to expose more active sites remains a significant challenge in this field.

[0004] To address the aforementioned issues, some studies have proposed preparing transition metal phosphides for water electrolysis using a PBA derivatization strategy. For example, Chinese patent CN113275027A discloses a method for preparing bimetallic phosphides derived from Prussian blue analogues on nickel foam. First, Ni(OH)₂ / NF is hydrothermally grown on nickel foam. Then, NiFe-PBA / NF is prepared using potassium ferricyanide as a raw material. Finally, the bimetallic phosphide is obtained through phosphating. While this method achieves in-situ growth of PBA derivatives on a conductive substrate, the resulting material has a single phase, being only a bimetallic phosphide, lacking the synergistic effect of the heterogeneous interface between the sulfide and phosphide, making it difficult to simultaneously optimize the catalytic performance of HER and OER. Furthermore, this technical route does not involve fine-tuning the morphology of the PBA precursor, resulting in limited exposure of active sites. Therefore, developing an electrocatalyst capable of in-situ construction on a conductive substrate with a high-density heterogeneous interface and excellent bifunctional activity for both HER and OER remains a pressing technical challenge in this field.

[0005] Based on the above, the focus of this invention is to construct a unique hollow embedded cubic structure through the confined growth of ternary metal PBA, and to achieve partial conversion of NiCo2S4 using a two-step method of "sulfidation followed by phosphating". A coral-like NiCoP shell is then grown in situ on the surface of the nanorods, forming a high-density core-shell heterostructure interface with the core. This heterostructure interface can induce the formation of a built-in electric field, effectively promoting charge transfer. This invention is the first to combine the confined growth of ternary metal PBA with the construction of an incompletely converted heterostructure, providing a new technical solution for designing highly active and stable bifunctional catalysts for alkaline water electrolysis. Summary of the Invention

[0006] 1. The purpose of this invention is to provide a ternary metal Prussian blue analogue partial conversion sulfur phosphating electrocatalyst, its preparation method, and its application, addressing the problems of insufficient overall performance or poor performance stability of existing bifunctional electrocatalytic materials. A CoMoO4 nanorod array is grown on nickel foam using a hydrothermal method, followed by in-situ generation of FeCoNi-PBA via a hydrothermal reaction. This is then processed through a two-step process of hydrothermal sulfidation and low-temperature gas-phase phosphating to finally obtain a NiCoP / NiCo2S4 / NF heterojunction electrocatalyst. Compared with traditional preparation methods, this invention utilizes the confined growth of this ternary PBA to construct a unique hollow embedded cubic structure as a reaction precursor. The incomplete conversion of NiCo2S4 is achieved through a two-step "sulfidation followed by phosphating" method, generating a coral-like NiCoP shell in situ on the nanorod surface, forming a high-density core-shell heterojunction interface with the core. Benefiting from this, the catalyst exhibits excellent HER and OER bifunctional activity in alkaline water electrolysis and maintains long-term stability at high current densities, providing possibilities for subsequent industrial applications.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing a ternary metal Prussian blue analogue-based electrocatalyst for the partial conversion of sulfur to phosphorus, which can be achieved through the following technical route: S1 Pretreatment: After cutting the nickel foam into appropriate sizes, it is immersed in hydrochloric acid, acetone and deionized water respectively for ultrasonic treatment to remove surface oxides and organic matter, and then dried in a vacuum oven.

[0008] S2 Hydrothermal Preparation of Nanorod Substrates: Co(NO3)2 3)2 ·6H2O and (NH4)6Mo7O 24 • Dissolve 4H2O in deionized water, stir well, transfer to a reaction vessel, add two pieces of pretreated nickel foam, and hydrothermally react at 140~160℃ for 4~8 hours. After natural cooling, remove, rinse with deionized water, and dry to obtain CoMoO4 / NF.

[0009] S3 In-situ hydrothermal preparation of ternary metal PBA: K3[Fe(CN)6] was dissolved in deionized water, two pieces of CoMoO4 / NF were added, and the reaction was carried out at 70~100℃ for 1~3 hours. After natural cooling, the mixture was taken out, rinsed with deionized water, and dried to obtain FeCoNi-PBA / CoMoO4 / NF.

[0010] S4 hydrothermal sulfidation: Dissolve Na2S in deionized water, add two pieces of FeCoNi-PBA / CoMoO4 / NF, and hydrothermally react at 140~160℃ for 2~5 hours. After natural cooling, remove the product, rinse with deionized water, and dry to obtain NiCo2S4 / NF.

[0011] S5 Gas-phase phosphating: Two NiCo2S4 / NF sheets are placed downstream of a tube furnace, and NaH2PO2·H2O is placed upstream. Under an inert atmosphere, the furnace is heated to 300~400℃ at a heating rate of 1~5℃ / min, held for 1~3 hours, and then removed after natural cooling to obtain the NiCoP / NiCo2S4 / NF heterojunction electrocatalyst.

[0012] According to the preparation method of the technical route, the characteristic is that: in step (1), the size of the nickel foam is 15×10×1.6 mm, and it is immersed in hydrochloric acid, acetone and deionized water respectively, ultrasonically treated for 10~20 min and then dried to remove organic matter and oxides on the surface of the nickel foam.

[0013] According to the preparation method of the technical route, the characteristic is that: the amount of Co(NO3)2·6H2O used in step (2) is 0.3~0.5 g, and (NH4)6Mo7O 24The amount of ·4H2O was 0.3~0.5 g, dissolved in 30 ml of deionized water, and the hydrothermal reaction temperature was 150℃ for 6 hours to synthesize CoMoO4 nanorod arrays with uniform morphology.

[0014] According to the preparation method of the technical route, the characteristic is that: in step (3), the amount of K3[Fe(CN)6] is 0.1~0.2 g, the hydrothermal temperature is 85℃, it is dissolved in 30 ml of deionized water, the reaction time is 2 hours, and FeCoNi-PBA is grown in situ inside the CoMoO4 nanorod to form a hollow embedded cubic structure.

[0015] According to the preparation method of the technical route, the characteristic is that: in step (4), the amount of Na2S is 0.1~0.2 g, the hydrothermal reaction temperature is 150℃, it is dissolved in 40 ml of deionized water, and the reaction time is 3.5 hours, so as to obtain hollow porous NiCo2S4 nanorods.

[0016] According to the preparation method of the technical route, the characteristic is that: in step (5), the amount of NaH2PO2·H2O is 0.5~1.5 g, the phosphating temperature is 350℃, the heating rate is 2℃ / min, and the holding time is 2 hours. By controlling the phosphating conditions, the incomplete conversion of NiCo2S4 is achieved, and a coral-like NiCoP shell is generated on the surface of the nanorod, forming a core-shell heterostructure with the unconverted NiCo2S4 inside.

[0017] This invention also provides the application of the NiCoP / NiCo2S4 / NF electrocatalyst described in the above technical solution in alkaline water electrolysis.

[0018] As a further feature of the present invention, the NiCoP / NiCo2S4 / NF material prepared by the above method, as a bifunctional electrocatalyst, exhibits excellent HER and OER bifunctional electrocatalytic performance in an alkaline electrolyte (1 mol / L KOH). At 100 mA cm⁻¹ -2 At current density, the OER overpotential is only 179 mV, and the HER overpotential is only 173 mV; at 500 mAcm -2 It can operate stably for over 100 hours at high current densities with minimal potential fluctuations, demonstrating excellent long-term stability. In the total water splitting test, this catalyst requires only a cell voltage of 1.7 V to reach 500 mA cm⁻¹ in a 1 mol / L KOH electrolyte. -2 The current density, 100 mA cm⁻¹ -2 It can operate stably for 100 hours at current density.

[0019] This invention provides a method for preparing a ternary metal Prussian blue analogue-based partial conversion sulfur phosphating electrocatalyst. A CoMoO4 nanorod array is grown on nickel foam via hydrothermal treatment, followed by in-situ hydrothermal generation of FeCoNi-PBA. The confined growth of ternary PBA within the nanorods is achieved using a "dissolution-diffusion-precipitation" mechanism, forming a hollow, embedded cubic structure. Hydrothermal sulfidation then yields hollow, porous NiCo2S4 nanorods. Finally, incomplete conversion of NiCo2S4 is achieved through low-temperature gas-phase phosphating, resulting in the in-situ growth of a coral-like NiCoP shell on the nanorod surface, forming a high-density core-shell heterogeneous interface with the core. Compared to traditional bifunctional electrocatalyst preparation methods, this invention maintains excellent catalytic stability under high current density conditions while ensuring high catalytic efficiency, making it valuable for practical applications in alkaline water electrolysis. Attached Figure Description

[0020] Figure 1 SEM image of the FeCoNi-PBA / CoMoO4 / NF electrode material obtained in Example 1; Figure 2 SEM image of the NiCoP / NiCo2S4 / NF electrode material obtained in Example 1; Figure 3 HRTEM image of the NiCoP / NiCo2S4 / NF electrode material obtained in Example 1; Figure 4 XRD pattern of the NiCoP / NiCo2S4 / NF electrode material obtained in Example 1; Figure 5 XPS image of the electrode material sample in the test example (Ni 2p).

[0021] Figure 6 XPS image (S 2p) of the electrode material sample in the test example.

[0022] Figure 7 LSV diagram of hydrogen evolution and oxygen evolution reactions of the electrode material sample obtained in the experimental example.

[0023] Figure 8 EIS diagrams of hydrogen evolution and oxygen evolution reactions of the electrode material samples in the experimental example.

[0024] Figure 9 : Long-term stability (constant current) of hydrogen evolution and oxygen evolution of the NiCoP / NiCo2S4 / NF electrode material obtained in Example 1. Detailed Implementation

[0025] The technical features of this invention are described below with reference to specific experimental schemes and accompanying drawings, but this invention is not limited thereto. Unless otherwise specified, the experimental methods described in the following embodiments are conventional methods; the instruments and materials described, unless otherwise specified, are all commercially available. Example

[0026] A method for synthesizing a ternary metal Prussian blue analogue partial conversion sulfur phosphorization electrocatalyst (NiCoP / NiCo2S4 / NF) includes the following steps: S1 Pretreatment: In this embodiment, nickel foam with a size of 15×10×1.6 mm is cut, and the nickel foam is placed in hydrochloric acid, acetone and deionized water and ultrasonicated for 10 min respectively. After vacuum drying, it is ready for use.

[0027] S2 Hydrothermal Preparation of Nanorod Substrates: Weigh 0.349 g Co(NO3)2·6H2O (approximately 1.2 mmol) and 0.371 g (NH4)6Mo7O 24 ·4H₂O (approximately 0.3 mmol) was dissolved in 30 mL of deionized water and stirred thoroughly at room temperature. The solution was transferred to a 100 mL polytetrafluoroethylene-lined reactor, and two pieces of pretreated nickel foam were added. The reactor was then subjected to hydrothermal reaction at 150 °C for 6 h. After natural cooling, the sample was removed, washed with deionized water, and dried in a vacuum drying oven at 50 °C for 6 h to obtain CoMoO₄ / NF.

[0028] S3 In-situ hydrothermal preparation of ternary metal PBA: Weigh 0.12 g K3[Fe(CN)6] and dissolve it in 30 mL of deionized water, stirring thoroughly at room temperature. Immerse two pieces of CoMoO4 / NF in the above solution, transfer to a 100 mL polytetrafluoroethylene-lined reactor, and hydrothermally react in an oven at 85℃ for 2 h. After natural cooling, remove the sample, wash with deionized water, and dry in a vacuum drying oven at 50℃ for 6 h to obtain FeCoNi-PBA / CoMoO4 / NF.

[0029] S4 Hydrothermal Vulcanization: Weigh 0.156 g Na2S (approximately 2 mmol) and dissolve it in 40 mL of deionized water, stirring thoroughly at room temperature. Immerse two FeCoNi-PBA / CoMoO4 / NF sheets in the above solution, transfer them to a 100 mL polytetrafluoroethylene-lined reactor, and perform a hydrothermal reaction at 150 °C for 3.5 h. After natural cooling, remove the sample, wash it with deionized water, and dry it in a vacuum drying oven at 50 °C for 6 h to obtain NiCo2S4 / NF.

[0030] S5 Gas-phase phosphating: The two NiCo2S4 / NF sheets were placed in a ceramic boat downstream of a tube furnace, with 1 g of NaH2PO2·H2O placed upstream. Under Ar atmosphere protection, the temperature was increased to 350℃ at 2℃ / min, held for 2 h, and then naturally cooled before being removed to obtain the NiCoP / NiCo2S4 / NF heterojunction electrocatalyst.

[0031] Comparative Example 1 A method for synthesizing NiCo2S4 / NF electrocatalyst differs from Example 1 in that the phosphating treatment in step S5 is omitted, and the NiCo2S4 / NF obtained in step S4 is used directly as the final sample.

[0032] The specific steps include: (1) pretreatment of the nickel foam substrate, (2) preparation of CoMoO4 / NF, (3) preparation of FeCoNi-PBA / CoMoO4 / NF, and (4) preparation of NiCo2S4 / NF, the same as steps S1-S4 in Example 1. The final NiCo2S4 / NF electrocatalyst is obtained. Comparative Example 2 A method for synthesizing a NiCoP / NF electrocatalyst differs from Example 1 in that: the PBA construction in step S3 and the sulfidation treatment in step S4 are omitted, and the CoMoO4 / NF obtained in step S2 is directly phosphated.

[0033] The specific steps include: (1) pretreatment of nickel foam substrate, the same as step S1 in Example 1; (2) preparation of CoMoO4 / NF, the same as step S2 in Example 1; (3) placing the two pieces of CoMoO4 / NF in the downstream ceramic boat of the tube furnace, placing 1 g of NaH2PO2·H2O upstream, heating to 350℃ at 2℃ / min under Ar atmosphere protection, holding for 2 h, and taking it out after natural cooling to obtain NiCoP / NF electrocatalyst.

[0034] Test case Samples: Example 1 (NiCoP / NiCo2S4 / NF), Comparative Example 1 (NiCo2S4 / NF), Comparative Example 2 (NiCoP / NF) (1) Electrode materials prepared in Example 1 and Comparative Examples 1 and 2 were analyzed by electrochemical impedance spectroscopy (EIS). Compared with Comparative Examples 1 and 2, the electrode material sample in Example 1, due to the use of a ternary metal PBA precursor, formed a high-density core-shell heterostructure interface during sulfidation and phosphating. This interface can induce the formation of a built-in electric field, promote interfacial charge transfer, and significantly reduce its charge transfer resistance (Rct). The comparison of these three samples reflects the influence and contribution of the core-shell heterostructure on the bifunctional catalytic performance of HER and OER. (2) The FeCoNi-PBA / CoMoO4 / NF electrode material sample obtained in step S3 of Example 1 was observed and analyzed using a scanning electron microscope (SEM). Figure 1 As shown, the originally solid CoMoO4 nanorods were transformed into hollow structures, filled with a large number of uniformly sized cubic particles, forming a unique "nanorrod-embedded cubic" morphology. This hollow embedded structure facilitates the exposure of more active interfaces, providing abundant reaction sites for subsequent sulfurization reactions.

[0036] The final electrode material sample from Example 1 was observed and analyzed using a scanning electron microscope (SEM), such as... Figure 2 As shown, a coral-like NiCoP shell grows on the surface of the nanorods, while the interior contains a hollow, porous NiCo2S4 core, forming a core-shell heterostructure. This structure creates a multi-level pore network, which facilitates electrolyte penetration and rapid bubble desorption, thus reducing concentration polarization.

[0037] Observation and analysis were performed using high-resolution transmission electron microscopy (HRTEM), such as... Figure 3 As shown, the core-shell crystal planes of NiCoP and NiCo2S4 are clearly visible, forming a coral-like core-shell heterostructure that allows electrons to be transported rapidly at the interface.

[0038] Phase analysis is performed using X-ray diffraction (XRD), such as... Figure 4 As shown, the sample of Example 1 contains characteristic diffraction peaks of both NiCoP and NiCo2S4, confirming the successful construction of the heterostructure.

[0039] X-ray photoelectron spectroscopy (XPS) is used for detection and analysis, such as... Figure 5 and Figure 6 As shown, in the Ni 2p spectrum, the main peak of Ni2p3 / 2 shifts 0.56 eV towards higher binding energy compared to Comparative Example 1, indicating a decrease in electron density at Ni sites; in the S 2p spectrum, the S2p3 / 2 peak shifts 0.15 eV towards lower binding energy, indicating electron flow towards S atoms. These electron transfer directions confirm the existence of a built-in electric field at the heterojunction.

[0040] The linear sweep voltammetry (LSV) method was used for detection and analysis, such as... Figure 7 As shown, by comparison, it can be found that the catalytic activity of the electrode material prepared in Example 1 is significantly better than that of Comparative Example 1 and Comparative Example 2.

[0041] Electrochemical impedance spectroscopy (EIS) was used for detection and analysis, such as... Figure 8 As shown, the EIS spectrum of Example 1 is an arc with the smallest radius. The Rct after equivalent circuit fitting is significantly lower than that of Comparative Example 1 and Comparative Example 2, indicating that the core-shell heterostructure effectively reduces the charge transfer impedance. (3) Electrode material samples from Example 1, Comparative Example 1, and Comparative Example 2 were taken respectively, and their electrochemical performance was tested. The results are summarized in Table 1 below: As can be seen from Table 1 above: In 1 M KOH, the electrode material sample of Example 1 was subjected to a reaction at 100 mA cm⁻¹. -2 The overpotential of OER was 179 mV and the overpotential of HER was 173 mV, significantly better than Comparative Example 1 (single sulfide) and Comparative Example 2 (single phosphide), reflecting and confirming the synergistic enhancement effect of the core-shell heterogeneous interface. At 500 mA cm⁻¹ -2 At this point, the OER overpotential is 382 mV and the HER overpotential is 335 mV, with a gradual potential rise, indicating low polarization characteristics even at high current densities. Furthermore, at 1000 mA cm⁻¹... -2 Under these conditions, the OER overpotential is only 496 mV, indicating that the heterostructure supports continuous operation with high current density. The Tafel slope of Example 1 (OER 36.8 mV dec) -1 HER 116.3 mV dec -1 The apparent kinetics were significantly reduced compared to the control system; the constant current was 500 mA cm⁻¹. -2 The average operation time is ≥100 hours, and the potential fluctuation is small. Figure 9 As shown, the core-shell heterogeneous interface is firmly bonded and maintains structural integrity under strong bubble erosion.

[0043] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing and applying a ternary metal Prussian blue analogue-based electrocatalyst for the partial conversion of sulfur and phosphorus, comprising the following steps: S1 is used for cleaning and pretreatment of nickel foam; S2 grows CoMoO4 nanorod arrays on nickel foam using a hydrothermal method; S3 is then used to generate FeCoNi-PBA in situ via hydrothermal method, and a hollow embedded cubic structure is formed by utilizing the "dissolution-diffusion-precipitation" mechanism; S4 was then subjected to hydrothermal sulfidation to obtain hollow porous NiCo2S4 nanorods; Finally, incomplete conversion of NiCo2S4 was achieved through low-temperature gas-phase phosphating, resulting in the in-situ formation of a coral-like NiCoP shell on the nanorod surface, which forms a high-density core-shell heterogeneous interface with the core, thus obtaining the NiCoP / NiCo2S4 / NF electrocatalyst.

2. The pretreatment method according to claim 1, characterized in that, In step S1, the nickel foam is cut into appropriate sizes and then immersed in hydrochloric acid, acetone, and deionized water for ultrasonic cleaning for 10-20 minutes each. It is then placed in a vacuum drying oven to dry for later use.

3. The preparation method according to claim 1, characterized in that, In step S2, 0.3~0.5 g of Co(NO3)2·6H2O and 0.3~0.5 g of (NH4)6Mo7O are added. 24 • Dissolve 4H2O in 30 ml of deionized water, transfer to a reaction vessel, add pretreated nickel foam, and hydrothermally react at 140~160℃ for 4~8 hours. After natural cooling, wash and dry to obtain CoMoO4 / NF.

4. The preparation method according to claim 1, characterized in that, In step S3, 4 mg / ml K3[Fe(CN)6] is dissolved in deionized water, CoMoO4 / NF is added, and the reaction is carried out at 70~100℃ for 1~3 hours. After natural cooling, the mixture is washed and dried, and FeCoNi-PBA is grown in situ inside the CoMoO4 nanorods to form a special structure with hollow embedded cubic blocks.

5. The preparation method according to claim 1, characterized in that, In step S4, 0.1~0.2 g Na2S is dissolved in 40 ml of deionized water, FeCoNi-PBA / CoMoO4 / NF is added, and the mixture is subjected to hydrothermal reaction at 140~160℃ for 2~5 hours. After natural cooling, the mixture is washed and dried to obtain hollow porous NiCo2S4 / NF.

6. The preparation method according to claim 1, characterized in that, In step S5, NiCo2S4 / NF is placed downstream of a tube furnace, and 1 g of NaH2PO2·H2O is placed upstream. The temperature is increased to 300-400℃ at 1-5℃ / min under an inert atmosphere, held for 1-3 hours, and then naturally cooled to obtain the NiCoP / NiCo2S4 / NF heterojunction electrocatalyst.

7. A bifunctional electrocatalyst for the partial conversion of molybdenum ternary metal Prussian blue analogue to sulfur phosphating, prepared by the preparation method according to any one of claims 1 to 6.

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