A highly efficient and sustainable osmotic energy system and method for hydrogen production

Abstract

The application discloses a kind of efficient sustainable permeation energy hydrogen production system and method.The system includes: seawater and fresh water;Channel surface is decorated with the asymmetric membrane of phytic acid molecule;Alkaline electrolyte;Electrolytic cell;Metallic palladium nanocluster loaded electrode and commercial ruthenium dioxide loaded electrode;Wire.In the application, channel surface is decorated with the asymmetric membrane of phytic acid molecule and metallic palladium nanocluster loaded electrode and commercial ruthenium dioxide loaded electrode are connected in series through wire to form a closed loop.Channel surface is decorated with the asymmetric membrane of phytic acid molecule captures the osmotic energy of seawater and fresh water interface and converts it into electrical energy, and current is transmitted to the hydrolysis electrode at the other end through wire, and the hydrolysis electrode is immersed in electrolyte, when the osmotic energy voltage reaches the minimum voltage value required for electrode hydrolysis, hydrogen will be generated on the surface of metallic palladium nanocluster loaded electrode.The application directly produces hydrogen using osmotic energy in the ocean, which is green and simple, solves the problem of high power consumption in the prior art of water electrolysis hydrogen production, and meets the carbon neutral development goal.

Description

Technical Field

[0001] This invention belongs to the fields of electrochemistry, thin films and metal materials technology, and specifically relates to a highly efficient and sustainable permeation energy hydrogen production system and method. Background Technology

[0002] Hydrogen is a non-toxic gas with an extremely high calorific value, and its combustion product is only water, making it an ideal resource for reducing carbon dioxide emissions. Currently, hydrogen production still largely relies on the consumption of fossil fuels. However, this leads to the release of large amounts of greenhouse gases, which is detrimental to sustainable development. From a sustainable development perspective, directly utilizing renewable energy to produce hydrogen would be the optimal solution. Electrocatalytic water splitting is an ideal hydrogen production method due to its production flexibility, environmental friendliness, and high hydrogen purity. However, this technology is very energy-intensive, and most of the current electricity supply still relies on thermal power generation, which also requires the combustion of large amounts of fossil fuels. Permeable energy is a renewable energy source with predictable and stable output, while producing no waste or carbon dioxide emissions and being unaffected by weather conditions. Theoretically, the permeable energy at the seawater-freshwater interface is estimated at 0.8 kWh / m³. -3 The total global permeable energy is approximately 30 terawatts. Therefore, permeable energy is an ideal renewable energy source for hydrogen production. Summary of the Invention

[0003] This invention addresses the aforementioned problems by providing a highly efficient and sustainable method for hydrogen production via permeation energy. The invention utilizes an asymmetric membrane with phytic acid molecules modified on its surface to capture permeation energy, supplying power to electrodes loaded with palladium nanoclusters to complete an alkaline water electrolysis reaction. This achieves stable and efficient hydrogen production using sustainable energy. Furthermore, this invention directly produces hydrogen using permeation energy from the ocean, a green and simple method that solves the problem of high energy consumption in existing water electrolysis hydrogen production technologies.

[0004] The technical solution of the present invention is described in detail below.

[0005] This invention provides a highly efficient and sustainable permeation energy hydrogen production system, comprising seawater, freshwater, an ion exchange membrane, an alkaline electrolyte, a hydrolysis electrode, and wires. Seawater and freshwater are respectively contained in seawater and freshwater tanks. The ion exchange membrane is positioned at the interface between the seawater and freshwater tanks, and the ion exchange membrane and the hydrolysis electrode are connected in series via wires to form a closed loop. The hydrolysis electrode is immersed in an electrolytic cell containing the alkaline electrolyte. During operation, the ion exchange membrane captures the permeation energy at the seawater and freshwater interface and converts it into electrical energy. The current is transmitted to the hydrolysis electrode via wires. When the permeation energy voltage reaches the minimum voltage required for electrode hydrolysis, hydrogen gas is released from the electrode surface loaded with palladium nanoclusters. The ion exchange membrane is an asymmetric membrane with phytic acid molecules modified on its channel surface.

[0006] In this invention, the asymmetric membrane with phytic acid molecules modified on the channel surface is prepared by the following method: (1) ZIF-8 powder was prepared using 2-methylimidazole and Zn(NO3)2·6H2O as raw materials; (2) Heat treatment was carried out in a H2 / Ar mixed atmosphere at a temperature of 950-1050℃ to obtain a nitrogen-doped carbon framework derived from ZIF-8, denoted as CF; (3) After fully dispersing CF in an aqueous solution of phytic acid PA, react at 100-105℃ for 10-15 hours. After the reaction is completed, take out the powder, wash and dry it to obtain sample PA-CF. (4) Disperse PA-CF powder in a mixed solvent of ethanol and deionized water to obtain a dispersion. Then, under vacuum directional driving force, pass the dispersion through an anodized aluminum oxide film (AAO) to assemble PA-CF nanoparticles on one side of the AAO surface. Finally, let it dry naturally to obtain an asymmetric film with phytic acid molecules modified on the channel surface.

[0007] The asymmetric membrane structure modified with phytic acid molecules on the channel surface used in this invention is stable, has superhydrophilicity and strong electronegativity, and can rapidly and selectively transport cations such as sodium ions.

[0008] In this invention, in step (3), the mass-to-volume ratio of CF and phytic acid is 1:10~1:30 g / mL; in step (4), the volume ratio of ethanol and deionized water is 1:2~2:1, and the concentration of PA-CF powder in the dispersion is 0.5-1.5 mg / mL.

[0009] In this invention, the hydrolysis electrodes are an electrode loaded with palladium nanoclusters and an electrode loaded with commercial ruthenium dioxide, respectively; wherein the electrode loaded with palladium nanoclusters is prepared by the following method: Step 1: PdCl2 powder was ultrasonically dissolved in deionized water, and hydrochloric acid was added to form a transparent mixed solution C; 100 mg of ZIF-8-derived nitrogen-doped carbon framework CF was ultrasonically dispersed in 20-40 mL of deionized water to form a transparent mixed solution D; Solution D was ultrasonically treated, while solution C was poured into solution D and the pH of the solution was adjusted to 2-3 with HCl. After continuous ultrasonic treatment for 10-30 minutes, the mixture was freeze-dried, and the dried sample was washed with deionized water and ethanol. Finally, the washed solid was dried at 50-80 °C to obtain the nano-cluster Pd-CF catalyst. Step 2: Dissolve 5-15 mg of Pd-CF in 800-1000 mL of ethanol-water solution and add 50 mL of Nafion solution. Then sonicate the mixture for 10-30 minutes to completely disperse the Pd-CF. Finally, uniformly deposit the mixture on the surface of a glassy carbon electrode (GCE) and allow it to dry naturally to obtain an electrode loaded with palladium nanoclusters.

[0010] In this invention, the salinity of seawater is between 26-35‰, and the salinity of freshwater is between 0.01-0.6‰.

[0011] In this invention, the alkaline electrolyte is a 0.1-1.0 mol / L potassium hydroxide solution.

[0012] In this invention, seawater and freshwater are respectively contained in seawater pools and freshwater pools, and ion exchange membranes are disposed at the interface between the seawater pools and freshwater pools, forming a device consisting of several sets connected in series. In a specific embodiment, 10 sets were used for relevant tests.

[0013] The present invention further provides an efficient and sustainable permeation energy hydrogen production method based on the above system.

[0014] Compared with the prior art, the beneficial technical effects of the present invention are as follows: The efficient and sustainable permeation energy hydrogen production method of the present invention achieves efficient and sustainable permeation energy hydrogen production by connecting an asymmetric membrane with phytic acid molecules modified on the surface of a channel located at the seawater-freshwater interface and an electrode loaded with palladium nanoclusters in an alkaline electrolyte in the same circuit. This solves the problem of high energy consumption in the existing technology of water electrolysis for hydrogen production.

[0015] In a specific embodiment provided by this invention, the asymmetric membrane with phytic acid molecules modified on the channel surface can achieve a maximum permeation output power of up to 28.3 W / m² under an artificially simulated seawater-freshwater salinity gradient. -2 The open-circuit voltage is 184 mV, and it can operate stably for more than 12 days; the output voltage of the 10 asymmetric films with phytic acid molecules modified on their surfaces, connected in series, can reach 1.84 V and can operate stably for more than 12 days; the electrode loaded with palladium nanoclusters achieves a hydrogen evolution current density of 10 mA cm⁻¹ during water electrolysis in 1.0 M potassium hydroxide solution. -2The overpotential required is only 29 mV, and the reaction can be stable for more than 12 days. At a hydrogen evolution overpotential of 50 mV, the mass activity of the electrode loaded with palladium nanoclusters in this invention in 1.0 M potassium hydroxide solution is approximately 51 times that of a commercial palladium-carbon electrode. Ten sets of asymmetric membranes with phytic acid molecules modified on the channel surface were placed at the seawater and freshwater interface. These sets were then connected in series with a pair of alkaline hydrolyzing devices consisting of an electrode loaded with palladium nanoclusters and an electrode loaded with commercial ruthenium dioxide. The integrated permeation energy hydrogen production system achieved a hydrogen production rate exceeding 300 L / m³. -2 h -1 It can operate stably for more than 12 days. Attached Figure Description

[0016] Figure 1 This is a conceptual diagram of the permeation energy hydrogen production technology in this embodiment.

[0017] Figure 2 This is a scanning electron microscope (SEM) image of the asymmetric membrane with phytic acid molecules modified on the channel surface obtained in Example 1 of the present invention.

[0018] Figure 3 This is a scanning electron microscope cross-sectional image of the asymmetric membrane with phytic acid molecules modified on the channel surface obtained in Example 1 of the present invention.

[0019] Figure 4 This is a transmission electron microscope image of the palladium nanoclusters prepared in Example 2 of the present invention.

[0020] Figure 5 The content percentages of several elements analyzed and the calculated coverage of phytic acid molecules were obtained after the channel surface of the X-ray photoelectron spectroscopy test Example 1 was modified with an asymmetric film containing phytic acid molecules.

[0021] Figure 6 This is a contact angle test photograph of the asymmetric membrane with phytic acid molecules modified on the channel surface in Example 1.

[0022] Figure 7 The curve shows the change in power generation of the asymmetric membrane with phytic acid molecules on the channel surface in Example 1 as a function of the applied resistance.

[0023] Figure 8 The image shows the electrolysis hydrogen evolution polarization curve of the electrode loaded with palladium nanoclusters in Example 2 in a 1.0 M potassium hydroxide solution.

[0024] Figure 9 This is the curve showing the hydrogen production rate over time of the integrated permeable energy hydrogen production device in Example 3. Detailed Implementation

[0025] To make the technical means and effects of the present invention easy to understand, the present invention will be specifically described below in conjunction with embodiments and accompanying drawings.

[0026] This invention provides a highly efficient and sustainable permeation energy hydrogen production system, comprising: The interface between seawater and freshwater contains abundant osmotic energy; An asymmetric membrane with phytic acid molecules is used to capture the osmotic energy at the seawater-freshwater interface and convert it into electrical energy. Alkaline electrolyte, raw material for alkaline water electrolysis to produce hydrogen; An electrolytic cell is used to hold alkaline electrolyte. Electrodes loaded with palladium nanoclusters and electrodes loaded with commercial ruthenium dioxide are used for catalytic water electrolysis reactions; A wire is used to connect an asymmetric film with phytic acid molecules on its surface and an electrode loaded with palladium nanoclusters in series in the same circuit.

[0027] Figure 1 This is a conceptual diagram of the permeation energy hydrogen production technology of the present invention, as shown below. Figure 1 As shown, an asymmetric membrane with phytic acid molecules on the channel surface captures the permeation energy at the seawater-freshwater interface and converts it into electrical energy to supply the electrode loaded with palladium nanoclusters at the other end. When the voltage at the power supply end reaches the minimum voltage required for electrode hydrolysis, the water electrolysis reaction occurs at the same time, producing hydrogen gas, thus realizing the direct hydrogen production from permeation energy.

[0028] The permeation energy hydrogen production method of the present invention includes: preparation of an asymmetric membrane with phytic acid molecules modified on the channel surface; preparation of an electrode loaded with palladium nanoclusters; and permeation energy hydrogen production.

[0029] Example 1: Preparation of an asymmetric membrane with phytic acid molecules modified on the channel surface Step 1: Weigh 12.06 g of 2-methylimidazole powder into a 100 mL beaker, add 60 mL of CH3OH, and stir and sonicate to form a clear solution A. Weigh 10.92 g of Zn(NO3)2·6H2O into a 500 mL round-bottom flask, add 360 mL of CH3OH, and stir and sonicate to form a clear solution B. Quickly pour solution A into solution B. Stir the mixture at room temperature for 24 hours, centrifuge, and wash five times consecutively with CH3OH. Then, dry the precipitate obtained after centrifugation under vacuum at 70 °C overnight. The dried sample is designated ZIF-8.

[0030] Step 2: Place the ZIF-8 powder in a 5% H2 / Ar mixed atmosphere, set the tube furnace heating program to 5 °C / min, raise the temperature to 1000 °C and hold for 3 hours. After the furnace body cools to room temperature, remove the heat-treated material, which is the nitrogen-doped carbon framework derived from ZIF-8, denoted as CF.

[0031] Step 3: Measure 38 mL of deionized water into a 50 mL Erlenmeyer flask using a graduated cylinder. Add 2 mL of phytic acid (PA) solution, stir for 5 minutes, and then sonicate for 5 minutes to obtain a homogeneous, transparent solution. Add 100 mg of CF to the transparent solution, stir for 2 minutes, and then sonicate for another 5 minutes to ensure complete dispersion of CF. After sonication, continue stirring for 1 hour and then transfer the mixture to a 10 cm diameter glass petri dish. Place the petri dish in a 100°C drying oven for 12 hours. After the reaction is complete, remove the petri dish, wash the dried powder repeatedly with deionized water and ethanol, and finally dry the washed solid powder at 70°C. The dried sample is designated PA-CF.

[0032] Step 4: PA-CF powder was introduced into a 1:1 volume ratio mixture of ethanol and deionized water, and then dispersed uniformly by ultrasonication. The sample concentration of the dispersion was 1 mg / mL. Subsequently, under vacuum directional driving force, the dispersion was slowly passed through an anodized aluminum oxide film (AAO) with a pore size of ~80 μm and a thickness of ~100 μm, allowing PA-CF nanoparticles to assemble on one side of the AAO surface. The hybrid film was then naturally dried in a ventilated hood to obtain an asymmetric film with phytic acid molecules modified on the channel surface.

[0033] The asymmetric membrane with phytic acid molecules modified on the channel surface obtained in Example 1 was characterized by scanning electron microscopy. The characterization results are as follows: Figure 2 As shown in Figure 3. Figure 2 This is a scanning electron microscope (SEM) image of the asymmetric membrane with phytic acid molecules modified on the channel surface obtained in Example 1 of the present invention. Figure 3 This is a scanning electron microscope cross-sectional image of the asymmetric film with phytic acid molecules modified on the channel surface obtained in Example 1 of the present invention. Figure 2 and 3 As shown, the asymmetric membrane surface modified with phytic acid molecules is smooth, and the phytic acid-modified channel and the AAO channel form an asymmetric heterogeneous interface.

[0034] Surface X-ray photoelectron spectroscopy was performed on the asymmetric film with phytic acid molecules modified on the channel surface in Example 1. The results are as follows: Figure 5 As shown. Figure 5 This refers to the content percentage of several elements analyzed and the calculated coverage of phytic acid molecules after the channel surface was modified with an asymmetric film containing phytic acid molecules in Example 1 of X-ray photoelectron spectroscopy. For example... Figure 5As shown, the phytic acid coverage of the asymmetric membrane with phytic acid molecules on the channel surface is as high as 10.66 at.

[0035] The contact angle of the asymmetric film with phytic acid molecules modified on the channel surface in Example 1 was tested, and the results are as follows: Figure 6 As shown. Figure 6 These are contact angle test photographs of the asymmetric film with phytic acid molecules modified on the channel surface in Example 1. Figure 6 As shown, the asymmetric membrane with phytic acid molecules modified on the channel surface exhibits superhydrophilicity.

[0036] The asymmetric membrane with phytic acid molecules modified on the channel surface in Example 1 was subjected to a permeation energy power generation test, and the results are as follows: Figure 7 As shown. Figure 7 This is the curve showing the change in power generation from the permeation of the asymmetric membrane with phytic acid molecules modified on the channel surface in Example 1, as a function of applied resistance. Figure 7 As shown, the asymmetric membrane with phytic acid molecules modified on the channel surface achieves a maximum output power of 28.3 W / m² under an artificially simulated seawater-freshwater salinity gradient. -2 .

[0037] Example 2: Fabrication of an electrode loaded with palladium nanoclusters Step 1: PdCl2 powder was ultrasonically dissolved in deionized water, and a small amount of hydrochloric acid was added to form a transparent mixed solution C. 100 mg of prepared CF was ultrasonically dispersed in 28 mL of deionized water to form a transparent mixed solution D. Solution D was ultrasonically treated, while solution C was slowly poured into solution D, and the pH of the solution was adjusted to 2.4 with HCl. After continuous ultrasonic treatment for 20 minutes, the mixture was freeze-dried, and the dried sample was washed with deionized water and ethanol. Finally, the washed solid was dried at 70 °C to obtain nanoclusters of Pd-CF catalyst with a particle size of 0.9 nm.

[0038] Step 2: Dissolve 10 mg of Pd-CF in 950 mL of an ethanol-water solution (water:ethanol = 1:1), and add 50 mL of Nafion solution. Then, sonicate the mixture for 20 minutes to completely disperse the Pd-CF. Finally, uniformly deposit a small amount of the mixture onto the surface of a glassy carbon electrode (GCE) and allow it to air dry to obtain an electrode loaded with palladium nanoclusters. The loading amount of Pd-CF on the GCE surface was 1 mg cm⁻¹. -2 .

[0039] The palladium nanoclusters prepared in Example 2 were characterized by transmission electron microscopy, and the characterization results are as follows: Figure 4 As shown. Figure 4 This is a transmission electron microscope (TEM) image of the palladium nanoclusters prepared in Example 2 of the present invention. Figure 4As shown, the white bright spots are palladium clusters with a particle size of approximately 0.9 nm.

[0040] The electrode loaded with palladium nanoclusters in Example 2 was subjected to alkaline water electrolysis hydrogen evolution test, and the results are as follows: Figure 8 As shown. Figure 8 The image shows the electrolysis hydrogen evolution polarization curve of the electrode loaded with palladium nanoclusters in Example 2 in a 1.0 M potassium hydroxide solution. Figure 8 As shown, the electrode loaded with palladium nanoclusters achieved a hydrogen evolution current density of 10 mA cm⁻¹ during water electrolysis in a 1.0 M potassium hydroxide solution. -2 The overpotential is only 29 mV.

[0041] Example 3: Efficient and Sustainable Hydrogen Production via Osmosis Step 1: Place an asymmetric membrane with phytic acid molecules on the surface of the channel at the interface between seawater and freshwater, and connect 10 sets in series with wires; the salinity of seawater is 29‰ and the salinity of freshwater is 0.58‰.

[0042] Step 2: The electrode loaded with palladium nanoclusters and the electrode loaded with commercial ruthenium dioxide are combined to form a full water splitting device, and the electrolyte is a 1.0 M potassium hydroxide solution.

[0043] Step 3: Connect the components from Step 1 and Step 2 in series with wires to form an integrated device for hydrogen production through permeation.

[0044] The stability of the permeation energy hydrogen production rate of the integrated device in Example 3 was tested, and the test results are as follows: Figure 9 As shown. Figure 9 This is the hydrogen production rate versus time curve of the integrated permeation energy hydrogen production device in Example 3. Figure 9 As shown, the hydrogen production rate of the integrated permeation energy hydrogen production device remained stable at 300 L / m² for up to 12 days. -2 h -1 above.

[0045] In summary, this invention provides an efficient and sustainable method for hydrogen production via permeation energy. The process is simple, utilizing an asymmetric membrane with phytic acid molecules modified on the channel surface to capture permeation energy and supply power to an electrode loaded with palladium nanoclusters to complete the alkaline water electrolysis reaction, thereby achieving stable and efficient hydrogen production from sustainable energy sources.

[0046] The above embodiments are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention.

Claims

1. A high efficiency sustainable permeation energy system for hydrogen production, characterized in that, It includes seawater, freshwater, an ion-exchange membrane, an alkaline electrolyte, a hydrolysis electrode, and wires. Seawater and freshwater are respectively contained in seawater and freshwater tanks. The ion-exchange membrane is positioned at the interface between the seawater and freshwater tanks, and the ion-exchange membrane and the hydrolysis electrode are connected in series via wires to form a closed loop. The hydrolysis electrode is immersed in an electrolytic cell containing the alkaline electrolyte. During operation, the ion-exchange membrane captures the osmotic energy at the seawater and freshwater interface and converts it into electrical energy. The current is transmitted to the hydrolysis electrode through the wires. When the osmotic energy voltage reaches the minimum voltage required for electrode hydrolysis, hydrogen gas is released from the electrode surface loaded with palladium nanoclusters. Specifically, the ion-exchange membrane is an asymmetric membrane with phytic acid molecules modified on its channel surface, and the hydrolysis electrodes are an electrode loaded with palladium nanoclusters and an electrode loaded with commercial ruthenium dioxide, respectively. The asymmetric membrane with phytic acid molecules modified on the channel surface was prepared by the following method: (1) ZIF-8 powder was prepared using 2-methylimidazole and Zn(NO3)2·6H2O as raw materials; (2) Heat treatment was carried out in a H2 / Ar mixed atmosphere at a temperature of 950-1050℃ to obtain a nitrogen-doped carbon framework derived from ZIF-8, denoted as CF; (3) After fully dispersing CF in an aqueous solution of phytic acid PA, react at 100-105℃ for 10-15 hours. After the reaction is completed, take out the powder, wash and dry it to obtain sample PA-CF. (4) Disperse PA-CF powder in a mixed solvent of ethanol and deionized water to obtain a dispersion. Then, under vacuum directional driving force, pass the dispersion through an anodized aluminum oxide film (AAO) to assemble PA-CF nanoparticles on one side of the AAO surface. Finally, let it dry naturally to obtain an asymmetric film with phytic acid molecules modified on the channel surface. The electrode loaded with palladium nanoclusters was prepared by the following method: Step 1: PdCl2 powder was ultrasonically dissolved in deionized water, and hydrochloric acid was added to form a transparent mixed solution C; 100 mg of ZIF-8-derived nitrogen-doped carbon framework CF was ultrasonically dispersed in 20-40 mL of deionized water to form a transparent mixed solution D; Solution D was ultrasonically treated, while solution C was poured into solution D and the pH of the solution was adjusted to 2-3 with HCl. After continuous ultrasonic treatment for 10-30 minutes, the mixture was freeze-dried, and the dried sample was washed with deionized water and ethanol. Finally, the washed solid was dried at 50-80 °C to obtain the nano-cluster Pd-CF catalyst. Step 2: Dissolve 5-15 mg of Pd-CF in 800-1000 mL of ethanol-water solution and add 50 mL of Nafion solution; then sonicate the mixture for 10-30 minutes to completely disperse the Pd-CF; finally, uniformly deposit the mixture on the surface of the glassy carbon electrode GCE and allow it to dry naturally to obtain an electrode loaded with palladium nanoclusters.

2. The efficient and sustainable permeation energy hydrogen production system according to claim 1, characterized in that, In step (3), the mass-to-volume ratio of CF and phytic acid is 1:10~1:30 g / mL; in step (4), the volume ratio of ethanol and deionized water is 1:2~2:1, and the concentration of PA-CF powder in the dispersion is 0.5-1.5 mg / mL.

3. The efficient and sustainable permeation energy hydrogen production system according to claim 1, characterized in that, The salinity of seawater is between 26 and 35‰, while the salinity of freshwater is between 0.01 and 0.6‰.

4. The efficient and sustainable permeable hydrogen production system according to claim 1, characterized in that, The alkaline electrolyte is a 0.1-1.0 mol / L potassium hydroxide solution.

5. The efficient and sustainable permeation energy hydrogen production system according to claim 1, characterized in that, The device consists of several sets of seawater and freshwater pools respectively, with ion exchange membranes installed at the interface between the seawater and freshwater pools.

6. A sustainable permeation energy hydrogen production method based on the permeation energy hydrogen production system of claim 1, characterized in that, Ion exchange membranes are used to capture the permeation energy at the seawater-freshwater interface and convert it into electrical energy. The current is transmitted to the hydrolysis electrode through wires. When the permeation energy voltage reaches the minimum voltage required for electrode hydrolysis, hydrogen gas is released on the electrode surface loaded with palladium nanoclusters. The ion exchange membrane is an asymmetric membrane with phytic acid molecules modified on the channel surface.

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