A low-cost and eco-friendly fabrication of an MCDI-utilized PVA/SSA/GA cation exchange membrane

Hoang Long Ngo; Ngan Tuan Nguyen; Thi Thanh Nguyen Ho; Hoang Vinh Pham; Thanh Nhut Tran; Le Thanh Nguyen Huynh; Thi Nam Pham; Thanh Tung Nguyen; Thai Hoang Nguyen; Viet Hai Le; Dai Lam Tran

doi:10.1515/gps-2022-0056

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A low-cost and eco-friendly fabrication of an MCDI-utilized PVA/SSA/GA cation exchange membrane

Hoang Long Ngo , Ngan Tuan Nguyen , Thi Thanh Nguyen Ho , Hoang Vinh Pham , Thanh Nhut Tran , Le Thanh Nguyen Huynh , Thi Nam Pham , Thanh Tung Nguyen , Thai Hoang Nguyen , Viet Hai Le and Dai Lam Tran

Published/Copyright: May 31, 2022

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From the journal Green Processing and Synthesis Volume 11 Issue 1

Abstract

The alternative desalination technique of membrane capacitive deionization (MCDI) has emerged in the last 15 years and received a lot of research attention since then. By using a voltage applied between two electrodes covered with ion-exchange membranes, MCDI has attempted to challenge established methods such as reverse osmosis or electrodialysis. In this study, through the crosslinking of sulfosuccinic acid (SSA) and glutaric acid (GA) with polyvinyl alcohol (PVA), cation exchange membrane preparation and characterization were introduced. For the CDI system, membranes were chosen based on their water absorption and ion exchange properties. The PVA/SSA/GA composite (mass ratio of 100:5:5) had the best water adsorption and charge efficiencies that could be utilized for CDI application. The membrane’s ability to desalinate water was assessed using electrical properties such as total resistance, specific capacitance, and electro adsorption coated with the best ratio composite CEM. The salt absorption capacity of 19.06 mg·g⁻¹ with stable performance was found to be encouraging.

Keywords: cation exchange membrane; capacitive deionization; polyvinyl alcohol; sulfosuccinic acid; glutaric acid

1 Introduction

Climate change and global warming are now the most crucial problems leading to many issues all over the world. In Vietnam, there are sea-level rise and salinization, together with drought, flood, and critical weather [1]. Especially, it can affect the quantity and quality of the water, resulting in the lack of water in many regions, typically the agricultural regions such as The Mekong Delta or The Long Xuyen Quadrangle in the dry season. According to the recent reports, the salinization level of the Mekong Delta reached 25 km of 10–30 g·L⁻¹ [2]. Therefore, desalination is becoming more and more critical, in terms of both agriculture and people’s life quality assurance.

In recent years, there have been a lot of desalination technologies that have been utilized in a large scale for agriculture all over the world, including various thermal, electrical, and osmotic technologies [3]. Reverse osmosis (RO) was used in agriculture in Europe from the 1960s. Despite its high cost, this technology was applied for the growth of highly economic vegetables and was usually employed in the greenhouse [4]. In addition, RO technology is remarkably effective when applied in the brackish water, as well as high membrane stability and good salt recovery; however, the price is very expensive due to its high cost of energy, installation, and operation. Nanofiltration (NF) uses the membranes with the pore size of 0.5–1.5 nm, which is able to work at lower pressure, higher water flux, and lower cost, and is utilized for water softening or organic compound removal from brackish water [5]. Electrodialysis (ED) is the technology to separate the ions from the solution using ion exchange membrane under the potential gradient [5], where the cations (Na⁺, K⁺, NH₄ ⁺) will come to the cathode and the anions (Cl^–, SO₄ ^2–, PO₄ ^3–) will come to the anode. Cation exchange membranes (CEM) or anion exchange membranes (AEM) are also employed to enhance the ion removal capability and improve clean water supply [6]. ED technology is usually used for brackish water filtration to provide clean drinkable water with very low-energy usage [7]. Ion exchange (IX) uses ion exchange resins to filter and remove the contaminants from water and other solutions. These cation- or anion-exchange resins can be regenerated using the corresponding acids or bases [5]. IX technology has many advantages, namely, low cost, high quality of water, simple operation and equipment, and reduced energy and labor requirement. However, the ion exchange-based desalination process may encounter a drawback, which is the regeneration process greatly depending on the chemicals.

Besides the aforementioned desalination technologies, capacitive deionization (CDI) is emerging as an advanced technology that has been attracting significant attention in the recent years, thanks to its low cost and reduced energy demand compared to the conventional technologies such as reverse osmosis or electrodialysis. CDI can desalinate water by storing ions in an electrical double layer (EDL) on the electrode surface, which can also be utilized in various water treatment processes such as water softening and waste water treatment [8,9,10]. However, there are also some downsides in the CDI technology. One of them is the electrode deterioration as an amount of ions cannot be washed completely from the electrode, leading to performance degradation [11,12]. To solve this problem, membrane capacitive deionization (MCDI), an upgrade from the traditional CDI, was proposed [13,14]. MCDI utilizes the ion exchange membrane with high ion selectivity that can block the reverse adsorption and prevent the co-ion transportation. In MCDI, anion exchange membrane (AEM) is put before anode to prevent the moving of cations, and cation exchange membrane (CEM) is placed before cathode to inhibit the transfer of the anions, reducing the co-ion effect and ameliorating the salt removal efficiency, as well as preventing the faradaic reactions on the electrode surface [15,16]. MCDI is becoming more noticeable, not only in the fields of desalination and water treatment but also in the food industry and the fuel cell fabrication [17,18,19]. Compared to the conventional CDI, MCDI exhibits better salt removal efficiency [18,20,21,22], faster desalination rate [18], higher current efficiency [9,21,22,23], and lower energy consumption [9,24]. Furthermore, MCDI can operate at thermodynamic efficiencies comparable to that of RO [25].

Nevertheless, there are two distinct disadvantages that hinder the performance and the commercialization of MCDI: the high cost of the ion exchange membranes, and the high bulk resistance caused by the adhesive between the electrode and the ion exchange membrane [26]. As a result, many scientists have focused on the materials for ion exchange membrane with better mechanical properties, higher chemical resistance, and lower cost [27]. Among the researched materials, polyvinyl alcohol (PVA) is popular, easy to dissolve in water, and environmentally friendly, and has been utilized in many membrane fabrication processes [28,29] thanks to its excellent film forming ability, high thermal and chemical stability, and good cross-linking capability [30,31,32]. The PVA cross-linking process helps modify its physical properties, flexibility, thermal stability, as well as its solubility in water, water uptake, and water swelling ability [33,34,35]. However, due to the lack of the functional groups, PVA normally exhibits low ionic conductivity [36]; thus, it is usually necessary to provide the organic functional groups such as hydroxyl (–OH), carboxylate (–COOH), sulfonate (–RSO₃), amine (–NH₂), and quaternary ammonium (–NR₄) [37]. The compounds with multiple functional groups are also able to go through cross-linking reaction with the hydroxyl groups in PVA to form a network structure [38,39]. Sulfosuccinic acid (SSA), as a cross-linking agent (–COOH) as well as a hydrophilic functional group donor (–SO₃H), can also be employed to manufacture cation exchange membrane together with PVA to enhance the desalination efficiency of CDI [21,40]. In addition, citric acid (CA) can also be utilized to reduce the cost of cation exchange membrane, as the CA/SSA/PVA membrane exhibited high desalination efficiency thanks to the sulfonic acid (–SO₃H) and carboxyl (–COOH) groups that did not participate in the cross-linking process [41]. There are many cross-linking agents that can provide PVA with hydrophilic functional groups, such as poly(4-styrene sulfonic acid-co-maleic acid) (PSSA_MA) [42], glutaric acid (GA) [43], and sulfonated PVA (sPVA) [44] and polysulfone (SPSf) [44].

In this research, we present a low-cost and environmentally friendly fabrication of PVA/SSA/GA membrane and its application as cation exchange membrane. Physical, mechanical, and chemical properties of the membranes were examined; electrochemical properties and desalination efficiency were also investigated.

2 Materials and methods

2.1 Materials and chemicals

Polyvinyl alcohol (98%, M = 146,000–186,000 g·mol⁻¹) and glutaric anhydride (95%) were purchased from Acros, Belgium. Commercial activated carbon was supplied from Trabaco (Vietnam). Multiwalled carbon nanotube (MWCTN) was supplied from Ntherm (USA). Sulfosuccinic acid (SSA), concentrated nitric acid, concentrated sulfuric acid, hydrochloric acid (37%), and ammonia solution (25%) were acquired from Sigma Aldrich (USA) and were used without any further purification. Graphite sheet (thickness of 200 µm) was supplied by Mineral Seal (USA).

2.2 Preparation of composite membrane electrode

Glutaric anhydride (GA) was added into the 6% PVA solution, and the mixture was stirred for 1 h. Then, MWCNT was added, and the mixture continued to be stirred for another 1 h. The resultant mixture was homogenized in 5 min at 15,000 rpm, and then, AC was added at the ratio suggested in the published literature [45], and the mixture was further homogenized in 5 min. The mixture was then coated on a graphite sheet (200 mm × 300 mm, thickness of 200 µm). Finally, the composite membrane electrode was dried at 120°C in 4 h.

2.3 Preparation of PVA/SSA/GA membrane

First, PVA was dissolved in H₂O at 80–90°C until the solution became clear. Next, sulfosuccinic acid (SSA) solution was added, and the mixture was continually stirred at 50°C for 4 h. The resultant solution was the composite obtained from the reaction between PVA and SSA. This composite solution could be directly coated on the electrode surface or spread on a petri dish to receive the ion exchange membrane. The composite solution or the PVA/SSA membrane could be further mixed with glutaric anhydride (GA) for the cross-linking reaction to modify the properties of the membrane.

To fabricate the free-standing ion exchange membrane, the PVA/SSA composite solution was spread on a petri dish and dried at 40°C to obtain a dry membrane and then continued to be dried at 80°C in 1 h for the high-temperature cross-linking reaction to proceed. Next, the membrane was immersed in the distilled water in 6 h for three times to remove the unreacted components and then was dried at 60°C for 4 h. The GA and SSA concentrations were varied as specified in Table 1. This free-standing ion exchange membrane was utilized to investigate the properties such as water uptake or ion exchange capacity.

Table 1

Composition of the composite membranes by molar ratio

Sample name	PVA	SSA	GA
PVA	100	0	0
G-PVA	100	0	5
SG-PVA	100	5	5

PVA/SSA composite gel solution was also coated on the electrode by the doctor blade with the dried thicknesses of 20–30 µm. The composite membrane electrode was dried at 120°C in 4 h.

2.4 Membrane characterization method

FT-IR spectra were recorded on Cary 630 FT-IR (Agilent Technologies Inc., Santa Clara, CA) in the range of 4,000–650 cm⁻¹ using the free-standing membrane in the ATR mode. The morphology of the materials was investigated using a scanning electron microscope (SEM; JSM-6510LV instrument JOEL).

2.5 Water uptake capacity

The composite membrane was soaked in water for 24 h at room temperature, and then, it was taken out, and the excess water on the surface was blotted quickly. The soaked sample was weighed (m _w) and then dried at 45–50°C until unchanged weight (m _d). Water uptake capacity of composite membrane was calculated based on the following formula:

(1) MC ( % ) = m w − m d m d

where m _w and m _d (g) were the wet and dry membrane mass, respectively.

2.6 Cation-exchange capacity

The cation exchange capacity is an essential electrochemical property of an ion-exchange membrane and is a measure of the number of fixed charges per unit weight of the dry membrane. To determine CEC, the membrane was immersed in H₂SO₄ for 24 h to convert it to H⁺ forms and then rinsed with distilled water to remove the excess acid. Finally, the membrane was soaked in NaCl for 24 h, and the released H⁺ amount was titrated with NaOH in the presence of phenolphthalein. The cation exchange capacity (CEC; mmol·g⁻¹) was calculated from the following equation:

(2) CEC = C NaOH × V NaOH g

where m is the mass of the dry membrane, C _NaOH is the concentration of the NaOH solution, and V _NaOH is the volume of the NaOH solution.

2.7 Salt adsorption on composite membrane electrode

To investigate the desalination performance, the MCDI system was set up as described in Figure 1, consisting of a CDI cell, a peristaltic pump, and a conductivity meter. The CDI cell is composed of a pair of parallel electrodes (3.0 cm × 2.5 cm, thickness of 100–300 µm) separated from each other by an insulating silicone plate. The feed water of 200 ppm NaCl solution was pumped through the CDI cell at a constant rate of 10 mL·min⁻¹. The conductivity (G) of the inlet solution was observed until remain unchanged (G ₀). Next, the potential of 1.2 V was applied to the CDI cell, and the decreasing specific conductivity (G _t) was noted every 30 s until remain unchanged (G _c).

Figure 1

Schematic illustration of CDI system.

Salt adsorption capacity (SAC) was calculated from the following formula:

(3) SAC = ( C 0 − C t ) × V m

The following formula determined the salt adsorption rate (SAR):

(4) SAR = SAC t

where SAC (mg·g⁻¹) is the salt adsorption capacity; SAR (mg·g⁻¹·min⁻¹) is the salt adsorption rate; C ₀ and C _t (mg·L⁻¹) are the concentrations of the NaCl solution, which were calculated from the conductivity of the solution at the beginning and at t (min), respectively; V (L) is the volume of the NaCl solution; m (g) is the mass of the electrode; and t (min) is the adsorption time.

3 Results and discussion

3.1 FT-IR analysis

The incorporation of sulfosuccinic acid (SSA) onto the PVA chain was determined using Fourier-transform infrared spectroscopy (FTIR), and the results are displayed in Figure 2 and are consistent with the previous researches [46,47]. Particularly speaking, the peaks at 3,500–3,300 and 3,000–2,800 cm⁻¹ are attributed to the –OH and the –CH groups of PVA, respectively. In the presence of GA and/or SSA, the peak at 1,735–1,715 cm⁻¹ appeared, which is ascribed to the C═O bond of the carboxyl group (–COO–) [46], confirming that the cross-linking reaction happened in the G-PVA and SG-PVA samples. Furthermore, a new peak at 1,040–1,020 cm⁻¹ can also be observed, which is accredited to the S–O bond of the sulfonic acid group (–SO₃) of SSA, verifying the successful addition of SSA to the PVA structure, as cross-linking agent as well as functional group donor.

Figure 2

FT-IR spectra of PVA, G-PVA, and SG-PVA.

3.2 Water uptake capacity

Water uptake capacity is one of the most important factors to assess the performance of the ion exchange membrane, as water is mostly utilized as the working environment. The swelling behavior investigation was performed at room temperature, and the water uptake capacities of PVA, G-PVA, and SG-PVA samples are shown in Figure 3. The water uptake capacity recorded a dramatic 70% drop in the presence of the cross-linking agents (from 635.70% of PVA to 175.20% and 137.40% of G-PVA and SG-PVA, respectively). This phenomenon can be elucidated by the cross-linking reaction between SSA and GA with PVA as displayed in Scheme 1, where the carboxylic groups of GA and the anhydride carboxylic groups of SSA reacted with the hydroxyl groups of PVA, reducing the number of –OH groups in the PVA chain and thus diminishing the hydrophilicity of the PVA-based composite membrane. Furthermore, there is a chance that the remaining free uncross-linked hydroxyl groups could also be blocked by the cross-linked ones, leading to limited contact with H₂O and consequently inferior water uptake capacity of G-PVA and SG-PVA compared to the pure PVA membrane.

Figure 3

Water uptake capacity of PVA, G-PVA, and SG-PVA.

Scheme 1

Expected cross-linking reaction between SSA with PVA.

3.3 Ion exchange capacity

The ionic conductivity and ion exchange capacity of an ion exchange membrane are two of their most important properties: the ionic conductivity specifies how easy the ions can transport through the membrane, while the ion exchange capacity indicates the amount of replaceable ions in the membrane. In this case, ion exchange capacity is determined by the number of active sites or the number of functional group possessing the ion exchange ability, which in this research is the sulfonic group. As observed in Figure 4, in the case of PVA and G-PVA membranes, without the ion exchange groups, the IEC values were very low (0.0168 and 0.0224 mmol·g⁻¹, respectively). In the presence of the –SO₃ functional group from SSA, the IEC value of SG-PVA increased to 2.423 mmol·g⁻¹, proving the successful incorporation of SSA onto the PVA chain and consequently the improvement of the ion exchange capacity of the composite membrane.

Figure 4

Cation exchange capacity of PVA, G-PVA, and SG-PVA.

3.4 Scanning electron microscopy analysis

Figure 5 displays the SEM image of the SG-PVA membrane electrode, showing its differences with the carbon electrode. It can also be observed that direct coating of the PVA/SSA/GA composite onto the electrode surface provided good contact between the membrane and the electrode, resulting in lower bulk resistance compared to when using free-standing membrane.

Figure 5

SEM image of SG-PVA membrane electrode.

3.5 Deionization tests

To determine the salt adsorption capability of the fabricated cation exchange membranes, the deionization tests were performed in the aforementioned MCDI system as illustrated in Figure 1. Figure 6 represents the salt adsorption capacity (SAC) of PVA, G-PVA, and SG-PVA membrane electrodes as a function of the desalination time. It can be observed that the SAC value increased rapidly within the first 15 min and then became saturated after 30 min at 1.2 V and a flow rate of 10 mL·min⁻¹. PVA displayed the highest SAC value of 9 mg·g⁻¹, higher than that of G-PVA (4 mg·g⁻¹) but lower than that of SG-PVA (19 mg·g⁻¹). It is clearly observed that the incorporation of SSA into PVA enhanced the salt adsorption capability of the membrane through the sulfonic groups (–SO₃H). Conversely, the cross-linking with GA consumed and reduced the number of hydroxyl groups (–OH) in the PVA chain, leading to the deterioration of the salt removal capability of MCDI. These results are also consistent with the conductivity test demonstrated in Figure 7, where SG-PVA membrane electrode reduced around 75% of the conductivity (from 400 to 100 μS), higher than pure PVA (325 μS), and G-PVA (250 μS).

Figure 6

The SAC as a function of desalination time for all PVA membrane electrodes (voltage: 1.2 V; flow rate: 10 mL·min⁻¹).

Figure 7

The conductivity as a function of desalination time for all PVA membrane electrodes (voltage: 1.2 V; flow rate: 10 mL·min⁻¹).

The salt adsorption rate (SAR), which describes the rate of adsorption, is also an important parameter in CDI applications. The performance of a CDI system becomes evidently clear when the SAR is plotted against SAC, which is also known as the Ragone plot. Obviously, an ideal state is that the curve appears in the upper and right corner of the graph, which means higher electrosorption capacity and faster electrosorption rate simultaneously. The Ragone plots for three-membrane electrodes of PVA, G-PVA, and SG-PVA are exhibited in Figure 8. Among the curves, SG-PVA appears in the most upper and right corner in this group, indicating that SG-PVA membrane electrode displayed the highest salt adsorption capacity and fastest electrosorption rate compared to other electrodes.

Figure 8

Ragone plots of all PVA membrane electrodes.

4 Conclusion

In this study, to develop a CDI cell with ion-exchange membrane, a PVA-based composite was synthesized and the desalination performance on the NaCl adsorption was investigated. According to the results, the salt adsorption of the PVA/SSA/GA composite membrane appeared to be superior to that of the PVA and PVA/GA. The Ragone plot shows that the electrode coated by SG-PVA membrane exhibited higher adsorption ability and higher charge rate. Water and ion conductivity were improved by the incorporation of SSA into the PVA backbone. Overall, this study sheds light on the introduction of a low-cost and long-lasting ion-exchange membrane for MCDI systems used in the desalination process.

Funding information: The research is funded by The Graduate University of Science and Technology under grant number: GUST.STS. ĐT2020-HH08.
Author contributions: Hoang Long Ngo: methodology, writing – original draft; Ngan Tuan Nguyen: investigation, visualization; Thi Thanh Nguyen Ho: software, visualization; Hoang Vinh Pham: investigation; Thanh Nhut Tran: methodology; Le Thanh Nguyen Huynh: investigation; Thanh Tung Nguyen: writing – original draft; Thi Nam Pham: project administration, funding acquisition; Thai Hoang Nguyen: resources, supervision; Viet Hai Le: writing – review and editing, supervision; Dai Lam Tran: funding acquisition.
Conflict of interest: The authors state no conflict of interest.
Data availability statement: Available data are presented in the manuscript.

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Received: 2022-01-15

Revised: 2022-04-21

Accepted: 2022-05-02

Published Online: 2022-05-31

This work is licensed under the Creative Commons Attribution 4.0 International License.

Articles in the same Issue

https://doi.org/10.1515/gps-2022-0056

Keywords for this article

cation exchange membrane; capacitive deionization; polyvinyl alcohol; sulfosuccinic acid; glutaric acid

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