Process for the preparation of a self-supporting air-breathing cathode based on asymmetric wettability

Abstract

The application discloses a preparation method of a self-supporting air self-breathing cathode based on asymmetric wettability, which comprises the following steps: (1) pretreating carbon cloth; (2) performing surface hydrophilic treatment on the carbon cloth; (3) depositing polypyrrole nanowires on the carbon cloth by using an electrodeposition method; (4) growing ZIF-67 on the carbon cloth in situ by using a submersion method; (5) performing high-temperature carbonization treatment on the carbon cloth, so that the polypyrrole nanowires are converted into a nano carbon needle array, the ZIF-67 is converted into a Co-N-C high-activity ORR catalyst, and an electrode is successfully prepared; (6) performing hydrophobic treatment on one side of the electrode and continuously maintaining the hydrophilic property of the other side, so that the electrode has asymmetric wettability; and (7) performing heat treatment on the electrode, and finally obtaining the self-supporting air self-breathing cathode based on asymmetric wettability. The self-supporting air self-breathing cathode based on asymmetric wettability prepared by the application has the characteristics of high mass transfer efficiency, strong catalytic activity and reliable and stable performance, and can well meet the application requirements of fuel cells.

Description

Technical Field

[0001] This invention relates to the field of fuel cell technology, and in particular to a method for preparing an asymmetric wettable self-supporting air-breathing cathode. Background Technology

[0002] Polymer electrolyte membrane fuel cells (PEMFCs) are a clean energy conversion technology that directly converts the chemical energy stored in fuel and oxidant into electrical energy. They offer advantages such as high energy density, long power generation time (no recharging required), wide availability of fuel, ease of integration, and stability and reliability, making them a promising option for next-generation unconventional power sources. In PEMFCs, the cathode oxygen reduction reaction (ORR) involves multiple electron transfer steps and various reaction intermediates, resulting in relatively slow ORR kinetics and thus becoming a key step limiting battery performance. Currently, precious metal (PGM) catalysts, especially Pt-based materials, are considered the most effective ORR electrocatalysts. However, these PGM catalysts suffer from high cost, limited reserves, and poor stability, hindering widespread application. Therefore, it is necessary to develop a high-performance, low-cost non-precious metal ORR catalyst.

[0003] In recent years, Co- and N co-doped porous carbon catalysts (Co-NC) have attracted much attention due to their high catalytic activity, good stability, absence of Fenton-like reactions, and high electrocatalytic selectivity. Among various precursors for preparing Co-NC catalysts, ZIF-67 (Zeolitic imidazolate framework-67) has become a popular precursor due to its high porosity, large specific surface area, unique morphology, and stable chemical properties. After high-temperature carbonization, the Co nodes and N-containing organic ligands in ZIF-67 can be transformed into Co nanoparticles and N co-doped porous carbon particles, in which the Co nanoparticles are in-situ encapsulated in the N-doped porous carbon. The Co-NC catalyst derived from ZIF-67 not only inherits many advantages of the precursor in structure (such as well-developed pores, high specific surface area, and robust framework structure), but also contains abundant ORR active sites (such as Pyridinic-N, Graphitic-N, Co-Nx, and Co nanoparticles).

[0004] Currently, most research focuses on enhancing the intrinsic catalytic activity of ZIF-67 derived catalysts. For example, this involves mechanically mixing ZIF-67 derived catalyst particles with conductive additives (such as carbon black) and using polymer binders (such as Nafion solution) to fix the catalyst particles onto the electrode surface, thereby fabricating an air cathode. However, the use of conductive additives and polymer binders leads to the following problems:

[0005] (1) Blocking reactive sites reduces the utilization rate of active materials;

[0006] (2) The adhesive has poor conductivity, which seriously hinders electron / ion transport;

[0007] (3) Adhesives will weaken the diffusion process of O2, which is not conducive to ORR kinetics;

[0008] (4) The prepared catalyst layer has low mechanical strength and poor stability.

[0009] It is evident that existing methods for preparing air cathodes cannot fully utilize the performance of ORR catalysts and are insufficient to meet the current application requirements of fuel cells. Summary of the Invention

[0010] To address the shortcomings of the existing technologies, this invention provides a method for preparing an asymmetric wettable self-supporting air-breathing cathode, which features high mass transfer efficiency, strong catalytic activity, and reliable and stable performance, thus well meeting the application requirements of fuel cells.

[0011] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0012] The preparation method based on the asymmetric wettability self-supporting air-breathing cathode includes the following steps:

[0013] (1) Pre-treat the carbon cloth for cleanliness;

[0014] (2) The pretreated carbon cloth is subjected to surface hydrophilic treatment;

[0015] (3) Polypyrrole nanowires were deposited on carbon cloth using an electrodeposition method;

[0016] (4) The ZIF-67 was grown in situ on carbon cloth using the immersion method;

[0017] (5) The carbon cloth was subjected to high-temperature carbonization treatment to transform the polypyrrole nanowires into a nano carbon needle array, and ZIF-67 was transformed into a Co-NC high-activity ORR catalyst, and the electrode was successfully prepared.

[0018] (6) The side of the electrode facing the air is hydrophobic, while the side facing the electrolyte remains hydrophilic, so that the electrode has asymmetric wetting properties.

[0019] (7) The electrode is heat-treated to obtain an asymmetric wettable self-supporting air-breathing cathode.

[0020] The specific steps (1) are as follows: the carbon cloth is pretreated in an acetone and ethanol solution to remove surface oil and impurities, then the carbon cloth is cleaned with deionized water and dried for later use.

[0021] The specific steps (2) are as follows: the carbon cloth is placed in a mixed solution of concentrated nitric acid and concentrated sulfuric acid, and ultrasonically treated to increase its surface hydrophilicity. Then, the carbon cloth is cleaned with deionized water to remove the residual strong acid solution on the surface, and the cleaned carbon cloth is dried for later use. The mass fractions of the concentrated nitric acid and concentrated sulfuric acid are 67 wt% and 98 wt%, respectively, and the volume ratio of the two solutions when mixed is 1:1 to 3.

[0022] Specifically, step (3) includes the following steps:

[0023] (31) Preparation of electroplating solution: Disodium hydrogen phosphate and sodium dihydrogen phosphate are dissolved in deionized water, and then sodium p-toluenesulfonate and pyrrole are added to obtain the electroplating solution; wherein the mass fractions of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium p-toluenesulfonate and pyrrole are 2.5-3 wt%, 2-2.5 wt%, 1.5-2 wt% and 0.5-0.8 wt%, respectively.

[0024] (32) Preparation of polypyrrole nanowires: The electroplating solution was poured into the electrolytic cell, and polypyrrole nanowires were prepared by electrodeposition of carbon cloth as working electrode, platinum mesh as counter electrode and saturated calomel electrode as reference electrode using a three-electrode system.

[0025] Furthermore, in step (32), the electroplating method used is the chronoamperometry method, the working electrode potential is set to 0.7 to 0.9 V, and the electrodeposition time is 10 to 60 minutes.

[0026] The specific steps (4) are as follows: cobalt nitrate hexahydrate and 2-methylimidazole are dissolved in methanol solution to form a mixture, and carbon cloth with polypyrrole nanowires deposited is immersed in the mixture and left to stand for 1 to 4 hours to allow ZIF-67 to grow in situ on the carbon cloth; the methanol purity is 98%, and the mass fractions of cobalt nitrate hexahydrate and 2-methylimidazole in the prepared solution are 2 to 3 wt% and 4 to 5 wt%, respectively.

[0027] Furthermore, in step (5), the carbon cloth is placed in a tube furnace for high-temperature carbonization treatment, wherein the heating rate of the tube furnace is 1-5℃ / min, the carbonization temperature is 700-900℃, the calcination time is 1-4 hours, and the gas atmosphere is one or both of nitrogen and argon.

[0028] Specifically, in step (6), hydrophobic treatment of the air-facing side of the electrode means uniformly immersing one side of the electrode in a PTFE solution to make the electrode side hydrophobic.

[0029] Preferably, the PTFE has a mass fraction of 1-5 wt%, and the electrode is immersed 5-10 times, with each immersion involving 5-15 μL of PTFE solution.

[0030] Preferably, in step (7), the heat treatment temperature is 300-400°C, the heat treatment time is 20-40 minutes, and the gas atmosphere is one or both of nitrogen and argon.

[0031] The design principle of this invention is as follows:

[0032] Using carbon cloth as a substrate, an array of carbon nanoneedles was electrodeposited as an electron transport channel to promote electron transfer; ZIF-67 was grown in situ on the surface of the carbon nanoneedles and then carbonized to prepare a highly active ORR catalyst.

[0033] Building upon the above, the air-facing side of the electrode (i.e., the gas diffusion layer) is hydrophobically treated to make it superaerobic, promoting rapid O2 transport; while the electrolyte-facing side (i.e., the catalytic layer) retains its original hydrophilicity, ensuring rapid ion transfer during the reaction. Therefore, the prepared electrode exhibits high mass transfer efficiency and strong catalytic activity.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) This invention uses an asymmetric wetting method to make the side of the electrode facing the air hydrophobic and the side facing the electrolyte hydrophilic, thereby enhancing the transfer of oxygen, ions and electrons required for the electrode reaction, greatly improving the redox performance of the electrode, providing a technical reference for the research and development of fuel cells and metal-air batteries, and having important application significance.

[0036] (2) The electrode preparation method of this invention, through reasonable raw material selection and step design, achieves an electrode with a nano-carbon needle array and ORR catalyst. Furthermore, it removes conductive additives and polymer binders during the preparation process, allowing the active sites of the catalytic reaction to be better exposed, expanding the three-phase interface of the ORR reaction, and thus further improving the ORR activity of the electrode. Therefore, this invention, through ingenious design, achieves a good balance between technology, cost, and performance, making it very suitable for large-scale application in the fuel cell field. Attached Figure Description

[0037] Figure 1This is a schematic diagram of the electrode preparation process in Example 1 of the present invention.

[0038] Figure 2 This is a schematic diagram of the asymmetric wettability self-supporting air-breathing cathode prepared in Example 1 of the present invention.

[0039] Figure 3 Microscopic morphology of the asymmetric wettability self-supporting air-breathing cathode prepared in Example 1 of the present invention.

[0040] Figure 4 EDS energy dispersive spectroscopy analysis diagram of the asymmetric wettability self-supporting air self-breathing cathode prepared in Example 1 of the present invention.

[0041] Figure 5 The surface wettability of the electrode catalyst layer prepared in Example 1 of this invention is characterized.

[0042] Figure 6 Surface wettability characterization of the electrode gas diffusion layer prepared in Example 1 of the present invention.

[0043] Figure 7 XPS analysis characterization of the electrode prepared for Example 1 of the present invention.

[0044] Figure 8 ORR activity characterization of the electrode prepared for Example 1 of the present invention. Detailed Implementation

[0045] The present invention will be further described below with reference to the accompanying drawings and embodiments. The embodiments of the present invention include, but are not limited to, the following embodiments.

[0046] Example 1

[0047] This embodiment provides an asymmetric wettability-based self-supporting air-breathing cathode, which can be widely used in energy, chemical, and environmental protection fields. Figure 1 As shown, the preparation of the above-mentioned self-breathing cathode in this embodiment mainly includes the following steps: pretreatment of the carbon cloth for cleanliness, surface hydrophilic treatment of the carbon cloth, deposition of polypyrrole nanowires on the carbon cloth by electrodeposition, in-situ growth of ZIF-67 on the carbon cloth by immersion method, electrode preparation, electrode hydrophobic treatment, and electrode heat treatment.

[0048] Each step will be explained in detail below.

[0049] I. Pre-treatment of carbon cloth for cleaning

[0050] A 4cm×2cm carbon cloth (CC) was placed in an acetone and ethanol solution and sonicated for 30 minutes to remove oil and impurities from the surface of the carbon cloth. Then, the carbon cloth was cleaned with a large amount of deionized water and dried for later use.

[0051] II. Surface hydrophilic treatment of carbon cloth

[0052] A mixed solution of concentrated nitric acid and concentrated sulfuric acid with a volume ratio of 1:3 and mass fractions of 67 wt% and 98 wt%, respectively, was prepared. The carbon cloth was immersed in this mixed solution and ultrasonically treated for 1 hour to increase its surface hydrophilicity. Subsequently, the treated carbon cloth was washed with a large amount of deionized water to remove residual acid solution from the surface, and the washed carbon cloth was dried for later use.

[0053] III. Deposition of polypyrrole nanowires on carbon cloth using electrodeposition method

[0054] First, 6.11 g of disodium hydrogen phosphate and 4.8 g of sodium dihydrogen phosphate were dissolved in 200 mL of deionized water, and then 3.9 g of sodium p-toluenesulfonate and 1.4 mL of pyrrole were added to obtain the electroplating solution.

[0055] Then, the electroplating solution was poured into the electrolytic cell. Using carbon cloth as the working electrode, a platinum mesh as the counter electrode, and a saturated calomel electrode as the reference electrode, electrodeposition of the carbon cloth was performed using a chronoamperometry method. The working electrode potential was set to 0.75 V, and the electrodeposition time was 30 minutes. The final product was carbon cloth (denoted as PA / CC) with polypyrrole nanowire arrays (PA) deposited on its surface. The obtained PA / CC was rinsed with plenty of deionized water and air-dried for later use.

[0056] IV. Using the immersion method to grow ZIF-67 in situ on carbon cloth

[0057] 0.71 g of cobalt nitrate hexahydrate and 1.61 g of 2-methylimidazole were dissolved in 40 mL of methanol and magnetically stirred for 15 minutes to ensure complete dissolution and obtain a mixed solution. The obtained PA / CC was immersed in the mixed solution and allowed to stand for 2 hours to allow ZIF-67 to grow in situ onto the PA / CC, ultimately obtaining ZIF-67 / PA / CC. ZIF-67 / PA / CC was thoroughly washed with methanol solution and then vacuum dried for later use.

[0058] V. Electrode Preparation

[0059] Under a nitrogen atmosphere, ZIF-67 / PA / CC was placed in a tube furnace for carbonization treatment. The temperature was increased to 800℃ at a rate of 1℃ / min and calcined for 2 hours. After natural cooling, electrode C-ZIF-67 / CA / CC was obtained.

[0060] VI. Electrode hydrophobic treatment

[0061] The air-facing side of the prepared C-ZIF-67 / CA / CC was uniformly impregnated with a PTFE solution (1 wt%) to perform hydrophobic treatment. Each impregnation involved 10 μL of PTFE solution, and the impregnation was repeated 10 times to make the air-facing side of C-ZIF-67 / CA / CC (i.e., the gas diffusion layer side) hydrophobic.

[0062] VII. Electrode Heat Treatment

[0063] The C-ZIF-67 / CA / CC electrode, after being wetted, is placed in a tube furnace and heat-treated at 350°C for 30 minutes in a nitrogen atmosphere to obtain an asymmetric wettable self-supporting air-breathing cathode. Figure 2 As shown.

[0064] Performance verification

[0065] 1. The prepared asymmetric wetted air cathode was characterized using scanning electron microscopy (SEM), such as... Figure 3 As shown. Elemental analysis of the electrode surface was performed using energy-dispersive X-ray spectroscopy (EDS), such as... Figure 4 As shown in Table 1, the electrode is mainly composed of four elements: C, O, N, and Co. The content percentages of the four elements are shown in Table 1, with C, O, N, and Co accounting for 64.72%, 3.29%, 1.00%, and 30.99%, respectively.

[0066] Table 1

[0067]

[0068] 2. Figure 5 and 6 The wettability of the two sides of the electrode is characterized. It can be seen that the electrode exhibits asymmetric wettability, that is, the catalyst layer side (facing the electrolyte) is hydrophilic with a contact angle of 28.1°; the gas diffusion layer side (facing the air) is hydrophobic with a contact angle of 137.1°. Therefore, the electrode prepared in this embodiment has the characteristic of simultaneously enhancing ion and oxygen transport. Figure 7XPS characterization of the electrode was performed by deconvolution analysis of the N 1s spectrum. Four functional groups—Pyridinic-N, Co-Nx, Pyrrolic-N, and Graphitic-N—were fitted at binding energies of 398.7, 399.2, 400, and 401.3 eV. Relevant literature has confirmed that Pyridinic-N, Graphitic-N, and Co-Nx can serve as active sites for ORR (Oriented Reduction) and play a crucial role in improving the ORR activity of the catalyst. Cyclic voltammetry (CV) tests were conducted on the prepared electrode using a three-electrode system to evaluate its ORR activity. Figure 8 As shown, the electrode did not exhibit a significant reduction peak in a KOH solution saturated with N2. In contrast, the electrode showed a distinct ORR peak in a KOH solution saturated with O2, indicating that the electrode prepared in this embodiment possesses high ORR activity.

[0069] Example 2

[0070] The difference from Example 1 is that:

[0071] 1. Carbon cloth was electrodeposited using the chronoamperometry method, with the working electrode potential set at 0.8V and the electrodeposition time at 10 minutes, resulting in carbon cloth PA / CC with polypyrrole nanowires deposited on the surface.

[0072] 2. Immerse the carbon cloth with deposited polypyrrole nanowires in the mixed solution and let it stand for 1 hour to allow ZIF-67 to grow in situ on the carbon cloth, thus obtaining ZIF-67 / PA / CC.

[0073] 3. Under an argon atmosphere, ZIF-67 / PA / CC was placed in a tube furnace for carbonization treatment. The temperature was increased to 750℃ at a heating rate of 2℃ / min and calcined for 3 hours. After natural cooling, electrode C-ZIF-67 / CA / CC was obtained.

[0074] 4. The air-facing side of the prepared C-ZIF-67 / CA / CC is uniformly impregnated with PTFE solution (3 wt%) to perform hydrophobic treatment. Each impregnation uses 5 μL of PTFE solution and is repeated 5 times.

[0075] 5. Place the impregnated C-ZIF-67 / CA / CC electrode into a tube furnace and heat-treat it at 300°C for 20 minutes in an argon atmosphere.

[0076] The electrode prepared in this embodiment also has the characteristic of simultaneously enhancing ion and oxygen transport, but the ORR activity of the electrode is slightly worse than that in Example 1.

[0077] Example 3

[0078] The difference from Example 1 is that:

[0079] 1. Carbon cloth was electrodeposited using the chronoamperometry method, with the working electrode potential set at 0.9V and the electrodeposition time at 60 minutes, resulting in carbon cloth PA / CC with polypyrrole nanowires deposited on the surface.

[0080] 2. Immerse the carbon cloth with deposited polypyrrole nanowires in the mixed solution and let it stand for 4 hours to allow ZIF-67 to grow in situ on the carbon cloth, thus obtaining ZIF-67 / PA / CC.

[0081] 3. Under the atmosphere of nitrogen and argon mixed gas, ZIF-67 / PA / CC was placed in a tube furnace for carbonization treatment. The temperature was raised to 900℃ at a heating rate of 5℃ / min and calcined for 4 hours. After natural cooling, electrode C-ZIF-67 / CA / CC was obtained.

[0082] 4. The air-facing side of the prepared C-ZIF-67 / CA / CC was uniformly impregnated with PTFE solution (5 wt%) to perform hydrophobic treatment. Each impregnation was performed with 15 μL of PTFE solution, and the number of impregnations was 8.

[0083] 5. Place the impregnated C-ZIF-67 / CA / CC electrode into a tube furnace and heat-treat it at 400°C for 40 minutes in a mixed atmosphere of nitrogen and argon.

[0084] The electrode prepared in this embodiment also has the characteristic of simultaneously enhancing ion and oxygen transport, and the ORR activity of the electrode is between that of Example 1 and Example 2.

[0085] In summary, each step of this invention is interconnected and mutually reinforcing. Only through creative effort can an electrode with high mass transfer efficiency, strong catalytic activity, and stable reliability be prepared in a simple and ingenious manner, thus providing a technical reference for the research and development of fuel cells and metal-air batteries. Therefore, compared with existing technologies, this invention has outstanding substantive features and significant progress, making it highly suitable for large-scale application.

[0086] The above embodiments are merely one of the preferred embodiments of the present invention and should not be used to limit the scope of protection of the present invention. Any modifications or refinements made to the main design concept and spirit of the present invention that are not of substantial significance, but solve the same technical problem as the present invention, should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an asymmetric wettability self-supporting air-breathing cathode, characterized in that, Includes the following steps: (1) Pre-treat the carbon cloth for cleanliness; (2) The pretreated carbon cloth is subjected to surface hydrophilic treatment; (3) Polypyrrole nanowires were deposited on carbon cloth using an electrodeposition method; (4) The ZIF-67 was grown in situ on carbon cloth using the immersion method; (5) The carbon cloth was subjected to high-temperature carbonization treatment to transform the polypyrrole nanowires into a nano carbon needle array, and ZIF-67 was transformed into a Co-NC high-activity ORR catalyst, and the electrode was successfully prepared. (6) The side of the electrode facing the air is hydrophobic, while the side facing the electrolyte remains hydrophilic, so that the electrode has asymmetric wettability. (7) The electrode is heat-treated to obtain an asymmetric wettable self-supporting air-breathing cathode; The specific steps (2) are as follows: the carbon cloth is placed in a mixed solution of concentrated nitric acid and concentrated sulfuric acid, and ultrasonically treated to increase its surface hydrophilicity. Then, the carbon cloth is cleaned with deionized water to remove the residual strong acid solution on the surface, and the cleaned carbon cloth is dried for later use. The mass fractions of the concentrated nitric acid and concentrated sulfuric acid are 67 wt% and 98 wt%, respectively, and the volume ratio of the two solutions when mixed is 1:1 to 3. Step (3) includes the following steps: (31) Preparation of electroplating solution: Disodium hydrogen phosphate and sodium dihydrogen phosphate are dissolved in deionized water, and then sodium p-toluenesulfonate and pyrrole are added to obtain the electroplating solution; wherein the mass fractions of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium p-toluenesulfonate and pyrrole are 2.5-3 wt%, 2-2.5 wt%, 1.5-2 wt% and 0.5-0.8 wt%, respectively. (32) Preparation of polypyrrole nanowires: The electroplating solution was poured into the electrolytic cell, and polypyrrole nanowires were prepared by electrodeposition of carbon cloth as working electrode, platinum mesh as counter electrode and saturated calomel electrode as reference electrode using a three-electrode system.

2. The method for preparing a self-supporting air-breathing cathode based on asymmetric wettability according to claim 1, characterized in that, The specific steps (1) are as follows: the carbon cloth is pretreated in an acetone and ethanol solution to remove surface oil and impurities, then the carbon cloth is cleaned with deionized water and dried for later use.

3. The method for preparing a self-supporting air-breathing cathode based on asymmetric wetting properties according to claim 1 or 2, characterized in that, In step (32), the electroplating method used is the chronoamperometry method, the working electrode potential is set to 0.7 to 0.9V, and the electrodeposition time is 10 to 60 minutes.

4. The method for preparing a self-supporting air-breathing cathode based on asymmetric wettability according to claim 1 or 2, characterized in that, The specific steps (4) are as follows: cobalt nitrate hexahydrate and 2-methylimidazole are dissolved in methanol solution to form a mixture, and carbon cloth with polypyrrole nanowires deposited is immersed in the mixture and left to stand for 1 to 4 hours to allow ZIF-67 to grow in situ on the carbon cloth; the mass fractions of cobalt nitrate hexahydrate and 2-methylimidazole in the prepared solution are 2 to 3 wt% and 4 to 5 wt%, respectively.

5. The method for preparing a self-supporting air-breathing cathode based on asymmetric wettability according to claim 4, characterized in that, In step (5), the carbon cloth is placed in a tube furnace for high-temperature carbonization treatment. The heating rate of the tube furnace is 1-5℃ / min, the carbonization temperature is 700-900℃, the calcination time is 1-4 hours, and the gas atmosphere is one or both of nitrogen and argon.

6. The method for preparing a self-supporting air-breathing cathode based on asymmetric wettability according to claim 5, characterized in that, In step (6), hydrophobic treatment of the air-facing side of the electrode means uniformly immersing one side of the electrode in a PTFE solution to make the electrode side hydrophobic.

7. The method for preparing a self-supporting air-breathing cathode based on asymmetric wettability according to claim 6, characterized in that, The electrode is wetted 5 to 10 times, with each wettation consisting of 5 to 15 μL of PTFE solution.

8. The method for preparing a self-supporting air-breathing cathode based on asymmetric wettability according to claim 6, characterized in that, In step (7), the heat treatment temperature is 300-400℃, the heat treatment time is 20-40 minutes, and the gas atmosphere is one or both of nitrogen and argon.

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