Preparation And Characterization of a New Proton-Exchange Membrane On The Basis of The Modification of Sulfonated Polystyrene With MIL-53 (Al)-NH2 For Applying in The Direct-Methanol Fuel Cell

doi:10.21203/rs.3.rs-1014698/v1

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Preparation And Characterization of a New Proton-Exchange Membrane On The Basis of The Modification of Sulfonated Polystyrene With MIL-53 (Al)-NH₂ For Applying in The Direct-Methanol Fuel Cell

https://doi.org/10.21203/rs.3.rs-1014698/v1

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On the basis of the sulfonated polystyrene, a new proton-exchange membrane was prepared in this study. In order to be applied in the direct-methanol fuel cells (DMFCs), the modification of sulfonated polystyrene was conducted by MIL-53(Al)-NH₂. Membranes were fabricated using sulfonated polystyrene, polyethylene, and different amounts of MIL-53(Al)-NH₂, then they were briefly illustrated by SPS-PE-MIL-53. The membranes were characterized using the FT-IR, SEM, and TGA. The proton conductance, water uptake, oxidative resistance, ionic conductance, and the permeability of methanol were measured to assess its performance in a DMFC with a cation-exchange membrane. The SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane showed relatively better performance than the other membranes. The selectivity factor for this membrane was 7.17 × 10⁴S.s.cm^-3. To assess the performance, the fabricated membranes were used in a fuel cell. All membranes fabricated in the fuel cell performed well, but the SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane performed better than the other membranes.

DMFC on the basis of SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane had a maximum peak power density of 17.04 mAcm^-2with a maximum current density of 115.38 mAcm^-2. In general, the prepared membranes performed well than similar membranes.

Materials Chemistry

Metal-organic framework

MIL-53

Proton-exchange membrane

Selectivity factor

Direct methanol fuel cell (DMFC)

Fuel cells are an emerging technology that offers a brighter future for developing global energy sources with environmental and economic advantages [1]. The fuel cell is a promising source of electrochemical energy that can provide the currently required energy by directly converting a fuel's chemical energy to electrical energy [2-3].

High energy efficiency, high energy density, low noise, almost emission-free, and short-term charging are the advantages of this efficient and clean energy source leading to using this energy to generate electricity [4-7]. Due to their advantages in using low-cost raw materials, high energy conversion efficiency, and low operational temperatures, DMFCs have received more attention than other fuel cells [8-11]. DMFC's efficiency depends on the electrolyte membrane, also the proton-exchange membrane (PEM) plays the role of a separator between the anode and the cathode. It also facilitates the transfer of protons. PEM has some important advantages, including the high thermal, mechanical and chemical resistance, besides preventing the passage of fuel during the fuel cell operation [12].

DMFCs use regenerative methanol as fuel. One of the significant barriers to the broad commercial use of DMFCs on a large scale is methanol crossover (MCO). Methanol penetration from the anode to the cathode using the polymer electrolyte membrane can severely degrade the activity of the cathode catalyst, which limits the use of PEMs in DMFCs [13-15]. Given the above, researchers have made great efforts to develop the PEMs to minimize the methanol crossover problem [16-17].

Various kinds of sulfonated polymers are used as polymer electrolyte membranes, including Nafion, sulfonated arylene ether sulfone, polyether ketone, sulfonated polysulfone, etc. [18-22]. Because of Nafion’s properties, such as the excellent mechanical, thermal and chemical resistance along with high proton conductance [23-24], it is mainly used as a conductor of proton. However, using the Nafion membrane in DMFC faces some obstacles, including the complex synthesis methods, high costs, unavailability of the environment, and high crossover of methanol [25-27].

The membranes were fabricatd as a composite to improve their performance. To fabricate the composite membranes, many organic and in-organic materials have been used as a booster, including sodium dodecylbenzene sulfonate, graphene oxide (GO), poly(styrenesulfonic acid) (PSSA), carbon nanotube (CNT), sulfonated polyimide, sulfonated polybenzimidazoles, sulfonated polysulfone and sulfonated poly (phenylene oxide), zirconia, clays, zeolites, metal-organic frameworks (MOFs), etc. [28-34].

Considering the materials mentioned above, MOFs have attracted great attention because of their interesting structure-related properties and an indefinite number of possible structures [35-36].

For instance, MIL-53 has a good proton conductance [37]. Given that one of the most important properties we expect from DMFC membranes is that they pass protons well, so adding this organic metal framework to the membrane can develop the membranes' performance. Therefore, in this study, we synthesized a type of MIL-53 and prepared composite membranes with sulfonated polystyrene and this organic metal framework. FT-IR, SEM, TGA, and XRDwere used to characterize the membrane. To assess the membrane performance in a DMFC with a cation-exchange membrane, water uptake, proton conductance, oxidative resistance, ionic conductivity, and the permeability of methanol were measured.

Characterization and measurement

All materials and reagents such as dichloromethane, acetic anhydride, sulfuric acid 98 %, Al (NO₃)₃.9H₂O, 2-aminoterephthalic acid, N, N´-dimethylformamide, p-Xylene C, and polystyrene (PS) were purchased from Merck, Germany. Linear low-density polyethylene (LDPE) with a density of 0.92 g. cm³, the surface hardness of SD48, the tensile strength of 20 Mpa, the linear expansion of 20×10^-5 °C, the water adsorption of 0.01 %, the volume resistivity of 10¹⁶Ω.cm and melting temperature range between 120-160 °C was purchased from Bandar Imam Petrochemistry, Iran.

Using a JASCO-460 FT-IR spectrometer, FT-IR spectra of the materials and membranes were taken. They had a spectral range between 400-4000 cm^-1. Through the scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis equipped with an SEM instrument (MIRA3 TESKAN), the surface morphology and the sample's status were studied. After cooling in the liquid nitrogen, the dry membranes were manually fractured. The samples were sputter-coated with 15 nm thickness gold. Also, they were imaged on SEM at 5kV. A thermal gravimetric analysis was conducted by a TGA/DSC 1 (TGA Q50) with a heating rate of 10 K min^-1 in the atmosphere of N₂ at a flow rate of about 50 mLmin^-1. A four-probe method was used to measure the proton conductance of the membrane by the electrochemical impedance spectroscopy (EIS) with a Zahner potentiostat/galvanostat electrochemical workstation model PGSTAT on the frequency range of 4MHz-1Hz with an oscillating voltage of 5 mV.

Preparation of SPS

The method introduced by Makowski et al. was used to prepare sulfonated polystyrene [38-39]. First, acetyl sulfate solution was prepared, then the solution was mixed with an equal amount of dichloromethane and acetic anhydride under the nitrogen atmosphere. Next, it was cooled to 273 K, then the sulfuric acid 98 % was gradually added. After that, the mixture was stirred at room temperature until it resulted in a clear homogeneous solution. To clear any trace of water, extra acetic anhydride was used. Before each sulfonation reaction, the acetyl sulfate was prepared freshly.

In a round-bottomed flask, 20 g of PS were dissolved in 500 mL of CH2Cl2 for the sulfonation reaction. To obtain the total stability of PS, the flask with the solution was heated to 313 K, and it was cleaned with N₂ for 40 min. Then, the acetyl sulfate solution was added to the reaction mixture. The mixture was kept at 313°K while stirring for 2 hours. After adding the sulfonating agent, a transparent yellow solution was produced. The reaction was terminated when an excess of 2-propanol was added for 30 minutes and cooled at room temperature. Ultimately SPS was isolated. The reactions related to the production of acetyl sulfate and SPS have been presented in Fig. 1A and 1B, respectively.

Synthesis of MIL-53(Al)-NH₂[Al(OH)(O₂C–C₆H₃(NH₂)–CO₂) (H₂O)]

For synthesizing the MIL-53(Al)–NH₂, we used the method that was performed as described elsewhere [37]. 2 g of Al(NO₃)₃.9H₂O, 1 g of 2-aminoterephthalic acid, and 15 mL of water were added to 100 mL Teflon-lined steel autoclave. The autoclave was heated for 5 hours in an oven at 423 K. The solution was filtered, and the compound was refluxed in N, N´-dimethylformamide at 423 K for 12 hours, and then it was dried for one day in an oven at 423 K. A yellow powder of MIL-53(Al)–NH₂ was obtained.

Preparation of SPS-PE-MIL-53 membrane

To form a homogeneous solution, 1 g of LDPE was first dissolved in 30 mL p-xylene, then it was stirred at 300 rpm for 2 hours and 373 K. Also, 1 g of SPS with (0.1, 0.25, 0.5) g of MIL-53(Al)–NH₂ had been added, mixed, and dissolved in p-xylene to provide a yellow polymer solution. The solutions were poured onto the glass plates, and they were dried at 318 K for 24 hours, then at 348 K in a vacuum for 12 hours. The membrane was peeled off and designated as SPS-PE-MIL-53. Before using this PEM “SPS-PE-MIL-53” in DMAFC, it was transformed to the H⁺ through boiling it first in the deionized water for half-hour and then in 1 M H₂SO₄ for 24 hours. After that, extra H₂SO₄ was removed by rinsing and boiling in the deionized water.

Evaluating the properties of membrane

To recognize the improved overall performance of the proposed membrane as a component of the proton exchange membrane, various properties, including the water uptake rate, ion exchange capacity, the permeability of methanol, and selectivity, had significant influences, and they should be measured.

To measure the membrane's water retention capability, the water uptake was calculated. By measuring the change in the weight before and after hydration, it was determined. First, the membrane was immersed and saturated in the doubly distilled water (DDW) for 24 hours. After removing the surface water, the membrane was weighted fast to determine the wetted membrane weight (W_w). When the membrane was dried at 373 K for 2 hours, the dry membrane weight (w_d) was determined. Equation (4) was used for calculating the water uptake [40]:

Water uptake (%) = ×100 (4)

The back-titration method was used to determine the ion exchange membrane (IEC). The sample was dried until the weight was constant, then the sample was immersed in 50 mL of saturated NaCl for 24 hours to release the H+ ions into the solution using the ion-exchange reaction with Na+ ions. Using phenolphthalein as an indicator, the ion-exchanged solution was titrated with 0.01 M NaOH. The IEC was calculated by equation (5):

IEC = (5)

In this equation, W_dry (g) is the membrane's dry mass, V_NaOH (L) is the titrated NaOH solution volume, and C_NaOH (mol L^-1) is the NaOH molar concentration in the solution.

To examine the membrane resistance to the free radical species, a piece of membrane was immersed into the Fenton’s reagent under stirring (3% H₂O₂ aqueous solution with 2 ppm FeSO₄) for 1 hour at 80 °C. The oxidative durability was assessed by measuring the time necessary to completely dissolve and maintaining the membrane weight after 2 hours.

The proton conductance of the membrane was measured by a four-probe method [40] by EIS with a Zahner potentiostat/galvanostatat electrochemical workstation model (PGSTAT) over a frequency range of 4MHz-1Hz with the oscillating voltage of 5 mV. 2 inner platinum (Pt) wires (with 0.2 mm diameter) serving as voltage sensors and 2 outer platinum (Pt) wires (with 0.2 mm diameter) serving as AC injectors were used for this four-probe method. The membrane sample (size of ca. 3×1.0 cm²) was squeezed between the two Teflon blocks, and held in its place using the nylon screws. Prior to this test, the membranes were soaked in a 1.0 M HCl solution for 12 hours for activation. After that, they were washed using deionized water until their pH became 7. The proton conductance was measured within the temperature range of 30°C in the liquid water. Equation (6) was used to calculate the proton conductance from the impedance data:

σ = (6)

In the equation (6), σ is the proton conductance (S/cm), L is the distance between potential-sensing electrodes (cm), R is the resistance associated with the ionic conductance of a membrane from the impedance data (Ω), W is the width of membrane (cm), and d is the thickness of membrane (cm).

The permeability of methanol through the membrane was measured by a two-compartment diffusion cell. The membrane between the two glass compartments was vertically clamped, and each one contained a magnetic stirring bar to agitate the solution. The feed part was filled with 5 M methanol, and the receiving one was filled with deionized water. Also, the concentration of the methanol within the receiving compartment was evaluated. Besides, the membrane permeability was calculated using the equation(7) [41-42]:

P = (7)

In equation (7), P is the methanol diffusion permeability of the membrane (cm² s^-1), C_A is the methanol concentration in the cell A (mol L^-1), ∆C_B(t)/Δt is the slope of the molar concentration variation of methanol in the cell B as a time function (mol L^-1 s^-1), V_B is the volume of each diffusion reservoir (cm³), A is the membrane area (cm²), and L is the thickness of membrane (cm).

At last, the selectivity factor (the ratio of proton conductance to the methanol permeability) was determined using the equation below [41-42]:

Selectivity =

SEM characterization

The membranes' structure and morphology were characterized using SEM measurements. The SEM micrographs of MIL-53 and SPS-PE-MIL-53 membranes have been depicted in Fig. 2. The SEM image of particles of MIL-53 has been shown in Fig. 2a. The surface of MIL-53 particles is porous without any agglomeration. The porosity of the metal-organic framework (MIL-53) causes more functional groups to be incorporated into the network, and these functional groups (COOH) and (NH₂) will facilitate the better transfer of protons through the membrane. Fig. 2b shows that the hybrid SPS-PE-MIL-53 with a uniform matrix membrane had a dense structure, whereas the presence of fine micrograph parts on the membrane surface observed in the SEM image confirms the presence of SO₃^-, COOH, and NH₂ groups in the SPS-PE-MIL-53 membranes. The dense homogeneous surface of the prepared membranes is ascribed to the harmony between the polymer and the particle that provides a simple pathway for proton conduction through the ionic channels present in the polymer matrix.

The characterization of FT-IR

In the previous work, we explained the FT–IR key bands of the PE and SPS [40-42]. Fig. 3. shows the FT-IR curve for MIL-53 and SPS-PE-MIL-53. Fig. 3 (a) presents the FT-IR curve for MIL-53. The centralization of the very strong bands at 3421 cm^-1 that could be due to the functional groups of the COOH and NH2 has been clearly depicted in the figure. The width of this peak implies that these functional groups are abundant on the MIL-53 structure. These groups can create hydrogen bonds with water and absorb some water. The amount of water content of the membrane in a DMFC is very important because it is directly related to the amount of proton conduction by the membrane. The strong bands at 1615 cm^-1 are due to the C=O stretching of COOH groups, whereas the bands at 1434 cm^-1 are due to the O–H deformation of C–OH groups. Fig. 3 (b) indicates the FT-IR curve for SPS-PE-MIL-53 membrane. The figure clearly shows that the centralization of the strong bands at 3420 cm^-1could be due to the functional groups of COOH and NH₂. Considering the low amount of the MIL-53 in the membrane fabrication, this bond is weaker than the same band in Fig. 3 (a). The aliphatic C-H stretching absorbance of methylene and methylene groups in the main chain leads to the bands at 2849-3081 cm–1. At 1372 cm–1, SO2 asymmetric stretching occurs. The bands at 1797 cm^-1 appear because of the C=O stretching of COOH groups, and the bands at 1451 and 1492 cm^-1 appear because of the O–H deformation of C–OH groups. The four peaks at 1007 cm^–1, 1030 cm^–1, 1125 cm^–1, 1155 cm^–1 are attributed to the symmetric stretching of SO₃.

Water uptake

The fuel cell membranes are able transfer protons from the anode side to the cathode side of the membrane. Therefore, the higher the water absorption by the membrane is, the better the transfer of protons is from the anode side to the cathode side. But the role of water absorbed by the membrane is like a double-edged sword because the water absorbed by the membrane can swell the membrane and undermine its mechanical properties. Fig. 4 shows the water content of the prepared composite membranes, which was equilibrated with 100% air relative humidity at 25 ^°C. Also, it was immersed in liquid water at the same temperature. As it has been shown in Fig. 4, the order of the membranes’ water content is as SPS-PE-MIL-53 (1:1:0.5 w:w:w) > SPS-PE-MIL-53 (1:1:0.25 w:w:w) > SPS-PE-MIL-53 (1:1:0.1 w:w:w). This indicates that the greater the amount of MOF content, the more water is absorbed. But the amount of water absorbed by the SPS-PE-MIL-53 (1:1:0.5) membrane is very close to that of SPS-PE-MIL-53 (1:1:0.25) membrane. Functional groups in the MOF structure, such as the COOH and NH₂ groups, could help the membrane to absorb more water because of the hydrogen bonding which they could form with water.

Proton conductance

One of the main properties of the membranes used DMFCs is their ability to easily transfer the protons from the anode side to the cathode side. Different functional groups could be applied to the prepared membranes to facilitate proton transfer from them. Operative groups such as sulfonic acid, amine, and carboxylic acid are the three important groups that can be utilized for this purpose. In the present study, all of these three functional groups have been used. These functional groups help to the absorption of more water in the membrane through forming hydrogen bonds with the water molecules. More absorption of water by the membrane would lead to better proton transfer through the membrane. Proton conductance is also expected to increase with the increment of MIL-53 in the prepared membranes. Different proton conductance of the membranes at different temperatures has been depicted in Fig. 5. The figure clearly shows that by enhancing the temperature from 20 ° C to 80 ° C, the proton conductance increases. Also, as it has been shown in Fig. 5, when the amount of MIL-53 used in membranes’ preparation increased from 0.1 g to 0.25 g, the proton conductance increased as well, which could be due to the increasing number of COOH and NH₂ functional groups inside the membrane. However, the proton conductivity decreases when the value is increased from 0.25 g to 0.5 g. The increase in MIL53 in the membranes from a certain amount further, increases the resistance to the proton mass transmission through the membrane, which may be due to the bonds formed between the COOH and NH₂ functional groups of the MIL-53 and the polystyrene sulfonic groups. However, the optimum value of 0.25 g of the MIL-53 for the preparation of membrane was chosen in this work.

Methanol permeability, selectivity factor, ion exchange capacity, and oxidative stability

Table 1 summarizes the IEC, proton conductance, methanol permeability, selectivity, and oxidative stability of the composite membranes. The IEC displays the ability of the membrane for proton transmission from the anodic to the cathodic side in DMFC. For determining the aggregation of proton exchangeable groups and also the proton conductance of the membranes, the ion exchange capacity is an appropriate parameter. According to the instructions, we measured the IEC for the prepared membranes. The results of IEC measurements indicated that all composite membranes exhibited high IEC values which shows that the proton transferability of membranes is good.

We estimated the conductance of the protons by the membrane samples at 20 ° C and a relative humidity of 100%. Moreover, for one day, we performed the composite membranes’ test with water. Table 1 shows that the composite membranes had good proton conductivity [43]. By a 5 M solution of methanol, we measured the permeability of methanol of the membrane samples at room temperature. The permeability values of methanol in the composite membranes have been shown in Table 1. The results of the measurements of permeability of methanol indicate that the order of the permeability of methanol in the synthesized membranes is as follows: SPS-PE-MIL-53 (1:1:0.5 w:w:w) > SPS-PE-MIL-53 (1:1:0.25 w:w:w) > SPS-PE-MIL-53 (1:1:0.1 w:w:w). It means that by increasing the amount of MIL-53 in the membranes, the permeability of methanol increases, but the values of methanol permeability are very close to each other. A low methanol permeability membrane is beneficial for DMFC use. Since the goal of DMFC membranes is to increase the conductance of protons and decrease the permeability of methanol, the selectivity factor (the ratio of the conductance of protons and the permeability of methanol) can be used as a guide to develop better DMFC properties. The higher selectivity factor leads to better performance of DMFC. The results of the selectivity factor have been presented in Table 1.

Also, the results of the research on the oxidation stability of the composite membranes were tested in Fenton's reagent at 80 ° C (Table 1). As the results show, these membranes had good stability, as more than 98% of its weight was retained after 1 hour. The great performance of the membrane in terms of oxidative stability could be attributed to the cross-linking network developed between the SPS-PE and the metal-organic functional group framework (MIL-53).

Table 1. IEC, proton conductance, the permeability of methanol, selectivity, and oxidative stability factor of the composite membranes

Membrane	IEC (meq.g^-1)	σ (S.cm^-1)	P (cm².s^-1)	σ / P (S.s.cm^-3)	Oxidative stability (Wt %)
SPS-PE-MIL-53 (1:1:0.1 w:w:w)	0.95	3.16 × 10^-2	5.96 × 10^-7	5.30× 10⁴	˃ 98
SPS-PE-MIL-53 (1:1:0.25 w:w:w)	0.97	4.54 × 10^-2	6.33 × 10^-7	7.17 × 10⁴	˃ 98
SPS-PE-MIL-53 (1:1:0.5 w:w:w)	0.97	3.77 × 10^-2	6.61 × 10^-7	5.70 × 10⁴	˃ 98

TGA characterizations

Fig. 6 shows the TGA curves for the membranes produced by the SPS-PE-MIL-53. All the three synthesized membranes showed very good thermal resistance, which was very close to each other (see Fig. 6). However, the membranes’ thermal resistance is reduced slightly as the amount of MIL-53 added to the membranes increases. The parameters related to this weight-loss area degrade in four weight zones for all membranes. The first weight-loss zone occurs around 85–140°C. Because membranes are known to absorb a lot of water, the weight-loss might be due to the loss of the absorbed water. The next major weight-loss zone occurs around 360-500. In this zone, there are weight losses of 60 -70%. The highest mass loss accompanies this observed zone of weight loss. Therefore, it is called the main stage. As a result, this mass loss is attributed to the full thermal degradation of the composite's skeletal chain structure. Weight-loss over 600 °C for SPS-PE-MIL-53 membranes can be used for the organic moieties removal. The decomposition of MIL-53 and polystyrene leads to the weight-loss within the temperature range of 700–800 ^◦C.

The performances of single-cell

Single-cell tests for the composite membranes for CH3OH/O2 are performed to understand the proposed membrane performance. The performance of the proposed system relies on the membrane’s composition, the electrochemical reaction efficiency at the interface between the solid phases of electrodes and the liquid and gas phases in the anode and cathode sides, the temperature of fuel cell, the flow rate, and the concentration of methanol in the carrier stream. Fig.7 illustrates the findings of single-cell testing with MEAs produced by SPS-PE-MIL-53 (1:1:0.5 w:w:w), SPS-PE-MIL-53 (1:1:0.25 w:w:w), and SPS-PE-MIL-53 (1:1:0.1 w:w:w) inside Oxygen in the cathode and the aqueous solution of 2M methanol in the anode side at 80ºC with 1 mL.min-1 flow rate. As it could be observed, the DMFC based on SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane has a maximum peak power density of 17.04 mWcm^-2, with a maximum current density of 115.38 mAcm^-2 ; while the DMFC equipped with the SPS-PE-MIL-53 (1:1:0.5 w:w:w) membrane has a maximum peak power density of 17.41 mWcm^-2 with a maximum current density of 97.86 mAcm^-2 and the DMFC equipped with the SPS-PE-MIL-53 (1:1:0.1 w:w:w) membrane has a maximum peak power density of 12.97 mWcm^-2 with a maximum current density of 85.50 mAcm^-2. Because of the increased selectivity in the produced membranes, the proton exchange and the permeability of methanol through the membranes in DMFCs have a direct influence on the OCV. It was found that the OCV in SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane (0.91V) is higher than SPS-PE-MIL-53 (1:1:0.1 w:w:w), and similar to SPS-PE-MIL-53 (1:1:0.5 w:w:w).

Throughout this study, we successfully incorporated MIL-53(Al)-NH2 particles into the membranes through casting, and we prepared the composite membranes. In this work, different amounts of MIL-53(Al)-NH₂ (0.1, 0.25, and 0.5 g) were used to prepare the membranes. Various parameters such as the proton conductance, the water uptake, the permeability of methanol were studied for different membranes. The SPS-PE-MIL-53 (1:1:0.5 w:w:w) membrane had more water uptake than the other two membranes. The proton conductance in the SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane was higher than the other membranes. SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane also showed good resistance to the permeability of methanol compared to the other membranes. Thermal resistance was evaluated through examining the TGA diagram, which showed that all of the prepared membranes had proper thermal resistance. The fuel cell performance test was performed for the prepared membranes, and the synthesized membranes worked well. The SPS-PE-MIL-53 (1:1:0.25 w:w:w) membrane showed relatively better performance than the other membranes.

Acknowledgements

We thank the Central lab of University of Gonābād and University of Yāsuj for the financial support.

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Preparation And Characterization of a New Proton-Exchange Membrane On The Basis of The Modification of Sulfonated Polystyrene With MIL-53 (Al)-NH₂ For Applying in The Direct-Methanol Fuel Cell

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