Quaternary Ammonium Compound Functionalized Activated Carbon

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Quaternary Ammonium Compound Functionalized Activated Carbon Electrode for Capacitive Deionization Disinfection Jigang Wang, Gang Wang, Tingting Wu, Di Wang, Yuyu Yuan, Jianren Wang, Tian Liu, Lili Wang, and Jieshan Qiu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b04573 • Publication Date (Web): 14 Nov 2018 Downloaded from http://pubs.acs.org on November 14, 2018

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ACS Sustainable Chemistry & Engineering

Quaternary Ammonium Compound Functionalized Activated Carbon Electrode for Capacitive Deionization Disinfection Jigang Wang †, Gang Wang

‡, 

Tingting Wu †, Di Wang §, Yuyu Yuan §,

Jianren Wang †, Tian Liu §, , Lili Wang §, Jieshan Qiu †, †



School of Chemical Engineering, Dalian University of Technology, Dalian

116024, Liaoning, China. ‡

Research Center for Eco-Environmental Engineering, Dongguan

University of Technology, Dongguan, Guangdong 523106, China §

School of Life Science and Biotechnology, Dalian University of

Technology, Dalian 116024, Liaoning, China. E-mail address of all authors: Jigang Wang: [email protected]; Gang Wang: [email protected]; Tingting Wu: [email protected];

Di

Wang:

[email protected];

Yuyu

Yuan:

[email protected]; Jianren Wang: [email protected]; Tian Liu: [email protected]; Lili Wang: [email protected]; Jieshan Qiu: [email protected]

Corresponding author. E-mail: [email protected] (G. Wang). Corresponding author. E-mail: [email protected] (T. Liu) Corresponding author. Tel: 0086-411-84986080. E-mail: [email protected] (J.S. Qiu). 1

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Abstract: New water disinfection technologies should be developed because current methods usually produce disinfection by-products and are expensive. Here, we demonstrated the use of a contact-active activated carbon electrode functionalized by quaternary ammonium compound for capacitive deionization disinfection (CDID) at a contaminant concentration of 104 CFU/mL. The effects of cell voltage, flow rate, and ion concentration on the disinfection performance of CDID electrode were investigated. The electrode can kill 99% of Escherichia coli or Pseudomonas aeruginosa (with a concentration of 104 CFU/mL) at a relatively low cell voltage (1.2 V) and a relatively high flow rate (5 mL/min). The damage on cell membranes was proved to be the killing mechanism. Furthermore, the CDID system exhibited high cyclic stability and its kill rate was maintained approximately 90% after five regeneration cycles. Thus, CDID electrode presented in this work has promising application prospect in water disinfection. Keywords:

quaternary

ammonium

compound;

activated

deionization; water disinfection; contact-active

2


carbon;

capacitive

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Introduction Insufficient clean and fresh water is one of the crucial challenges that threaten life on earth. More than 1 billion people on the planet do not have access to safe drinking water, and millions of people die every year from diseases related to water borne pathogenic microorganisms.1, 2 In 2015, only 71% of the global population (5.2 billion people) had access to a safely managed drinking-water service.3 Although many chemical disinfectants (chlorine, chloramines, ozone, chlorine dioxide, UV, silver, zinc oxide, and others) are effective for killing pathogenic microorganisms in drinking water, they may produce disinfection by-products (DBPs), which are harmful to human health.4,

5

For instance, the reaction of chlorine with

dissolved natural organic matter produces toxic compounds, such as trihalomethanes and haloacetic acids.6 Nanoparticles, such as silver and zinc oxide, have attracted significant attention because dissolving heavy mental ions are toxic to human bodies.7, 8

Water disinfection processes based on UV treatment are expensive due to their high

power consumption.9 Therefore, new disinfection technologies with low DBP, toxicity, power consumption, and high disinfection efficiency should be developed. Capacitive deionization (CDI) has attracted significant attention as an emerging technique for brackish water desalination because of its high energy efficiency and environmental friendliness.10, 11 CDI is an electrochemical process based on electrical double layer theory. Ions or other charged species in water are adsorbed and stored in the electric double layer of electrodes when an external voltage is applied between porous electrodes.12,

13

Generally, bacterial cells are negatively charged due to the

presence of carboxylate and phosphate on the surface.14 Thus, bacterial cells can be adsorbed onto the surface of the anode under the electric field force, which are functionalized with contact-active antibacterial materials and are killed. Recently, several studies on disinfection via CDI are reported. For example, activated carbon cloth electrodes are used for water desalination and disinfection via CDI.15 However, bacteria are only captured on the electrodes, and 63% of them are 3



still alive in the disinfected water. Activated carbons coated with graphene oxide graft quaternized chitosan and graphene electrodes modified with quaternary ammonium cellulose were also reportedly used for capacitive deionization disinfection (CDID); these exhibited ultrahigh disinfection performance of more than 99% killing of Escherichia coli (E. coli).16, 17 In addition, nitrogen doped AC/SnO2 nanocomposite electrode was used for CDID, but the viability of E. coli only declined by less than 40%.18 Some electrochemical reactions may generate disinfectants that enhance CDID performance when the cell voltage was higher than 2 V.19 All these studies proved that CDID is a feasible application for water disinfection. Among the contact-active antibacterial materials, quaternary ammonium compounds (QAC), which contain four alkyl groups covalently attached to a central nitrogen atom (R4N+), are the most commonly reported antibacterial materials.20-22 Usually, QAC are attached to substrates to ensure that they are not removed in disinfection.23 Quaternized poly (4-vinylpyridine), which is a typical QAC, can efficiently kill airborne bacteria on contact after it is attached to glass slides.24 The development and functionalization of carbon electrodes attracts great interest for CDI.25-28 Moreover, many reports are found on water disinfection by using activated carbon functionalized with antibacterial materials.29-31 In this study, a contact-active activated carbon electrode functionalized by quaternized poly (4-vinylpyridine) was prepared for CDID. The effect of QAC coating density on antibacterial performance was determined. Morphology and fluorescent staining analysis were performed to investigate the antibacterial mechanism. The antibacterial properties of prepared materials and the effects of different operating conditions on disinfection performance were discussed. Experimental section Material synthesis The commercial activated carbon was purchased from Nanjing Linda Activated Carbon Company Limited and was boiled for 4 h. 4-vinylpyridine (96%, Aladdin 4


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Reagent Co., Ltd.) and 1-Bromohexane (Aladdin Reagent Co., Ltd.) were used as received without purification. The active composite was prepared using a modified method reported in our previous work.32 First, 5 g activated carbon and 4 mL 4-vinylpyridine were dispersed in 200 mL water under ultrasound. Then, the mixture was transferred in a three-neck flask and was heated to 90 °C. A total of 36 mg potassium persulfate was added, and the reaction was maintained at 90 °C in a slow current of nitrogen for 24 h. The product was washed with methanol, recovered by filtration, and dried at 60 °C for 12 h. The obtained composite was dispersed in 50 mL N,N-dimethyl formamide, to which 1.5 g 1,4-dibromobutaneas cross-linking agent was added, and the mixture was stirred at 65 °C for 48 h under nitrogen protection. The mixture was washed with methanol and water, and reacted with 12 g 1-bromohexane in 50 mL of methanol for 48 h. The prepared quaternary ammonium compound functionalized activated carbon (AC-QPVP-2) was washed with water and methanol and was dried at 60 °C for 12 h. AC-QPVP-1 preparation followed the same procedure above, except that the initial monomer and 1-bromohexane were applied at half dose. CDID cells fabrication To prepare the electrodes, active materials, carbon black, and polyvinylidene fluoride (mass ratio = 8:1:1) were mixed with N,N-dimethylacetamide to produce a homogeneous slurry. Then, the slurry was coated with a piece of graphite paper to produce a film about 200 μm thick and was dried at 80 °C overnight. After the solvent removal, the obtained electrodes were cut into 5 ⨉ 7 cm2. A CDID cell was assembled for disinfection tests using two pieces of the as-prepared electrodes, a piece of non-woven fabric as the separator, a silicon sheet (∼1.3 mm thick), two titanium strips as the current collectors and two poly (methyl methacrylate) plates as the support (Figure S1). Characterizations Fourier transform infrared (FTIR) spectra were scanned by Thermo Scientific 5



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6700. Thermogravimetric analysis (TGA) was performed using Shimadzu, DRG-60 at a heating rate of 10 °C/min under nitrogen atmosphere. Elemental analysis on the materials was conducted on Vario EL III Elemental Analyzer (Element, Germany). The morphologies of material samples and bacteria were characterized by FESEM (FEI NOVA NanoSEM 450). The staining method was used for antibacterial test using confocal laser scanning microscopy (CLSM, OLympus FV1000, Japan). Antibacterial tests Time-killing tests were performed to determine the antibacterial performance of the materials. E. coli BL21 and Pseudomonas aeruginosa (P. aeruginosa) were provided by Dr. Tian Liu and Dr. Lili Wang (Dalian University of Technology), respectively. E. coli BL21 and P. aeruginosa were grown overnight in Lysogeny Broth (LB) medium (1% tryptone, 1% sodium chloride, and 0.5% yeast extract) and were shaken (180 rpm) at 37 °C. After incubation, the bacterial cells were resuspended in sterilized water and diluted to 106 CFU/mL. A total of 3 mL bacterial dispersions were incubated with different materials (AC, AC-QPVP-1, and AC-QPVP-2) at 6 mg in the desired time at 37 °C in shaking condition (180 rpm). Water samples were collected every hour, and the number of bacteria was determined by the plate colony counting method. Loss of cell viability was determined using the equation below. Loss of cell viability = (cell number of control − cell number of samples)/(cell number of control) ⨉ 100%.

(1)

Antibacterial mechanisms FESEM and CLSM images were captured to elucidate the involved mechanisms. E. coli BL21 were grown and resuspended as mentioned above. Bacterial cells were cultured in the presence of AC-QPVP-2 dispersions (2 mg/mL) at 37 °C for 1 h. Then, the bacteria were fixed with 2.5% glutaraldehyde at 4 °C for 4 h, and were dehydrated in a series of ethanol solutions with different concentrations (30%, 50%, 70%, 90%, and 100%) for 10 min. The samples were dried and coated with gold, and were 6


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observed with FESEM (FEI NOVA NanoSEM 450). E. coli BL21 was grown and resuspended as mentioned above. Bacterial cells were cultured in the presence of AC-QPVP-2 dispersions (2 mg/mL) at 37 °C for 1 h. Then, the bacteria were stained with 20 μL acridine orange (AO)/propidium iodide (PI) fluorescent dye at room temperature in the dark for 10 min to view bacterial cells using CLSM (OLympus FV1000, Japan). Water disinfection tests To investigate the disinfection performance of AC-QPVP-1 and AC-QPVP-2 in CDID, batch-mode experiments were conducted in a continuous recycling system. Typically, bacterial cells were grown overnight in LB medium and shaken (180 rpm) at 37 °C. After incubation, the bacterial cells were resuspended in sterilized water and diluted to 104 CFU/mL as the starting solution. A 50 mL starting solution was pumped through the CDID cell by using a peristaltic pump, and the effluent returned to the unit cell. An electrochemical workstation (CHI 760E) was used to supply the needed voltage. After disinfection, the water samples were collected every half hour. Schematic diagram of the CDID setup used in this work is illustrated in Figure S2. The electrodes were washed with sterilized water without any applied voltage, and the regeneration of CDID was performed for another test. The number of bacteria was determined by the plate colony counting method. Loss of cell viability was determined using equation (1). Results and discussion Characterization of materials Figure S3 shows the morphologies of AC, AC-QPVP-1, and AC-QPVP-2. The pristine AC was in granule form of different sizes, i.e., from 1 μm to 10 μm. After the quaternary ammonium compound modification, the morphologies of AC-QPVP-1 and AC-QPVP-2 did not change significantly. Figure 1a shows the FTIR spectra of the samples. AC had no significant adsorption bands. The FTIR spectra of AC-QPVP-1 and AC-QPVP-2 exhibited a new 7



absorption band at 1635 cm−1, which corresponded to the C-N stretching vibration of the quaternized pyridine groups.33 The absorption bands at 1080, 1045, and 880 cm−1 were assigned to the C-H in-plane and out-of-plane bending vibration.34, 35 The FTIR spectra confirmed that the quaternary ammonium compound was bonded to AC successfully. TGA and elemental analysis were performed to determinate the amount of QPVP coated. Figure 1b shows the TGA curves of AC, AC-QPVP-1, and AC-QPVP-2. No significant weight loss was observed for AC given that the temperature gradually increases to 600 °C. A sharp weight loss between 215 °C and 320 °C was observed for AC-QPVP-1 and AC-QPVP-2, which can be attributed to the decomposition of the coated QPVP. The amount of QPVP on AC-QPVP-2 was calculated at approximately 21.5%, which was higher than that of AC-QPVP-1 (16.5%).36 The modification of QPVP was further verified by the elemental analysis results (Table S1), which indicated that the nitrogen content of AC-QPVP-2 (2.05%) was higher than that of AC-QPVP-1 (1.69%) and AC (0.34%). After calculation, the amount of QPVP in AC-QPVP-2 was 22.53%, whereas that in AC-QPVP-1 was 17.64%, which agreed well with the TGA results. Therefore, the weight ratio of QPVP in AC-QPVP-2 was approximately 22%, which was about 5% higher than that in AC-QPVP-1. The high coating density of QPVP generated a high positive charge density of an antibacterial surface, which could be more effective in disinfection tests.23 Antibacterial performance of the materials Figures 2a and 2b shows the time-killing tests of different materials for E. coli and P. aeruginosa, respectively. The loss of E. coli and P. aeruginosa viability could be maintained at 10% without any treatment after incubating for 7 h. The kill rate increased to 40% after the addition of 2 mg/mL pristine AC. Thus, pristine AC had little antibacterial property to E. coli and P. aeruginosa. However, AC-QPVP-1 and AC-QPVP-2 exhibited obvious antibacterial performance. The kill rate of the two 8


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kinds of bacteria for AC-QPVP-2 increased more rapidly compared with AC-QPVP-1. The difference of kill rate between the two functionalized ACs was attributed to the difference of QAC coating density. After incubating for 7 h, kill rate of P. aeruginosa was as high as 99.9%, whereas that of E. coli was 96.9% for AC-QPVP-2. The time-killing tests proved that QAC functionalized AC had good antibacterial performance and could be used in CDID. Antibacterial mechanisms For the detailed investigation of the antibacterial performance of the material, the morphology of E. coli cells incubated with 2 mg/mL AC-QPVP-2 dispersion was observed (Figure 3a) and found to be significantly different with that of the control (Figure 3b). After AC-QPVP-2 treatment, significant physical deformation and disruption can be seen with E. coli, which is the reason that bacterial cells are inactivated. The physical deformation of cells is caused by the interactions of the positively charged quaternary ammonium groups of AC-QPVP-2 with the lipid bilayer structures of bacterial membranes, which led to the death of bacteria and the highly contact-active antibacterial performance of AC-QPVP-2.37, 38 The CLSM images of the control and E. coli cells treated with AC-QPVP-2 are shown in Figure 4. PI and AO were used as the fluorescent stains, both of which are stain nucleic acids and can indicate the integrity of cell membranes. For the control sample, E. coli cells were homogeneously distributed in the bright field (Figure 4c), and almost all of them were stained green (Figure 4a), which meant that cell membranes of them were intact. E. coli cells were agglomerated around the AC-QPVP-2 granule due to electrostatic attraction (Figure 4f) after AC-QPVP-2 treatment for 1 h, and most of the cells were stained red, which indicated the damage of cell membranes. The CLSM images indicated that the killing mechanism of AC-QPVP-2 for E. coli was the disruption of cell membranes, which was consistent with the FESEM images. Water disinfection by CDID 9



To investigate water disinfection performance, the electrodes with AC-QPVP-1 or AC-QPVP-2 as the active materials were used as the anodes, and pristine AC electrodes were used as the cathodes. The electrodes were assembled into asymmetric CDID cells. Figure 5a shows the disinfection performance of different electrodes. The AC-QPVP-2 electrode can kill >99% E. coli in 210 min. The killing rate of the AC electrode was less than 60%. With low contact-active QAC contents, the AC-QPVP-1 electrode achieved a killing rate between the AC and AC-QPVP-2 electrodes (94.1%). P. aeruginosa, a common pathogenic microorganism in water, was also used to investigate the broad-spectrum antibacterial property of the AC-QPVP-2 electrode. Compared with E. coli, P. aeruginosa was more vulnerable, and its killing rate was slightly higher (Figure 5b). AC-QPVP-2 electrode exhibited efficient water disinfection performance for E. coli and P. aeruginosa. Cell voltage is one of the most important factors affecting disinfection efficiency. The disinfection efficiency of the AC-QPVP-2 electrode was evaluated at the cell voltage of 0, 0.4, 0.8, and 1.2 V, respectively (Figure 5c). Without cell voltage, bacteria were adsorbed onto the electrode through physical adsorption and killed by active materials, which only achieves 39.4% killing rate of E. coli at the end of the disinfection. Electric forces between the electrodes were higher as the voltage increases. Thus, more bacteria were adsorbed onto the surface of the anode and killed. The killing rate increased to 71.4% at the cell voltage of 0.4 V and 93.9% at the cell voltage of 0.8 V. The killing rate of E. coli reached 99.1% when the cell voltage increases to 1.2 V. Three flow rates of 1, 3, and 5 mL/min were used to determine the effects of flow rate on bacteria disinfection. Figure 5d shows that >99% of bacteria were eventually killed at all flow rates after disinfection for 210 min, which indicated that flow rate was not a crucial factor in the disinfection system. However, the killing rate of bacteria at the flow rate of 5 mL/min was slightly higher than the other flow rates because the probability of bacteria to be adsorbed onto the surface of the anode 10


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increased with the flow rate in batch-mode operation. To study the influence of ion concentration on the disinfection process, 0, 100, and 200 mg/L NaCl along with 104 CFU/mL E. coli was used as the influent. Figure 5e exhibits the CDID performance of the AC-QPVP-2 electrode under different NaCl concentrations (cell voltage: 1.2 V; flow rate: 5 mL/min). The killing rate decreased slightly when the NaCl concentration increased from 0 to 200 mg/mL. Moreover, the killing rate fluctuated slightly when the NaCl concentration was 200 mg/mL, which was attributed to the competitive adsorption of Cl− ions and E. coli. However, the kill rate reaches >99% in every NaCl concentration after disinfection for 210 min, which indicates that the ion concentration has a little impact on the CDID performance. CDID performance with bacterial concentrations of 104, 105 and 106 CFU/mL were shown in Figure S4. As the increase of bacterial concentration, the killing rate decrease a little. But it still can reach above to 92% with a bacterial concentration of 106 CFU/mL. The recyclability of the electrodes was vital to CDID. The alternating of voltage between 1.2 and 0 V was carried out to investigate the cyclic stability of the AC-QPVP-2 electrode. Figure 5f shows that the killing rate of E. coli slightly decreased during cycling, but it nearly reached 90% after five regeneration cycles, thereby demonstrating that the QAC functionalized electrode in this work could be used in CDID for a long time. Conclusions A quaternary ammonium compound functionalized activated carbon electrode was prepared for water disinfection via capacitive deionization. Compared with pristine AC, AC-QPVP with about 22% QAC showed distinct antibacterial property to E. coli and P. aeruginosa in the time-killing tests. Moreover, AC functionalized with high QAC coating density showed improved antibacterial performance. The physical disruption of cell membranes caused by the contact between E. coli and AC-QPVP was considered as the killing mechanism. The kill rate of E. coli reached 11



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above 99% under low voltage (1.2 V). The disinfection performance was maintained at an extremely high level and at relatively high flow rate (5 mL/min). Ion concentration had no obvious effect on the disinfection performance. The killing rate of E. coli reached approximately 90% after five regeneration cycles. Acknowledgments The authors acknowledge financial support from National Science Foundation of China (Nos. 21878049, 21336001) and the Qaidam Salt Lake Chemical Joint Research Fund Project of NSFC and Qinghai Province State People's Government (No. U1507103). Supporting Information Electronic supplementary information (ESI) available: Characterization of materials and schematic diagram of CDID.

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Figure Captions: Figure 1. (a) FTIR spectra of AC, AC-QPVP-1, and AC-QPVP-2 (b) TGA curves of AC, AC-QPVP-1, and AC-QPVP-2. Figure 2. Time-killing tests of (a) E. coli and (b) P. aeruginosa cultured with materials. Error bars are S.D. values. Figure 3. FESEM images of (a) E. coli and (b) E. coli treated with AC-QPVP-2. Figure 4. CLSM images of E. coli control stained with AO (a), stained with PI (b), and bright field (c) and E. coli treated with AC-QPVP-2 stained with AO (d), stained with PI (e), and bright field (f). Figure 5. (a) CDID performance with different materials (bacteria: E. coli, cell voltage: 1.2 V, and flow rate: 5 mL/min), (b) CDID performance with different bacteria (cell voltage: 1.2 V and flow rate: 5 mL/min), (c) CDID performance with different cell voltages (bacteria: E. coli and flow rate: 5 mL/min), (d) CDID performance with different flow rates (bacteria: E. coli and cell voltage: 1.2 V), (e) CDID performance with different ion concentrations (cell voltage: 1.2 V and flow rate: 5 mL/min), (f) CDID regeneration performance. Error bars are S.D. values.

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Figure 1. (a) FTIR spectra of AC, AC-QPVP-1, and AC-QPVP-2 (b) TGA curves of AC, AC-QPVP-1, and AC-QPVP-2.

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Figure 2. Time-killing tests of (a) E. coli and (b) P. aeruginosa cultured with materials. Error bars are S.D. values.

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Figure 3. FESEM images of (a) E. coli and (b) E. coli treated with AC-QPVP-2.

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Figure 4. CLSM images of E. coli control stained with AO (a), stained with PI (b), and bright field (c) and E. coli treated with AC-QPVP-2 stained with AO (d), stained with PI (e), and bright field (f).

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Figure 5. (a) CDID performance with different materials (bacteria: E. coli, cell voltage: 1.2 V, and flow rate: 5 mL/min), (b) CDID performance with different bacteria (cell voltage: 1.2 V and flow rate: 5 mL/min), (c) CDID performance with different cell voltages (bacteria: E. coli and flow rate: 5 mL/min), (d) CDID performance with different flow rates (bacteria: E. coli and cell voltage: 1.2 V), (e) CDID performance with different ion concentrations (cell voltage: 1.2 V and flow rate: 5 mL/min), (f) CDID regeneration performance. Error bars are S.D. values. 23



Graphical abstract

A new water disinfection technology via capacitive deionization was demonstrated by functionalized carbon electrode with quaternary ammonium compound.

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Quaternary Ammonium Compound Functionalized Activated Carbon

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