The long-term sustainability of beneficial effects resulting from the modification of polyamide thin-film composite (PATFC) membranes with zwitterionic poly(sulfobetaine methacrylate) (pSBMA) and silver nanoparticles (AgNPs) in real-world application scenarios remains uncertain. This study used response surface methodology and innovative anti-biofouling evaluation method to optimize the conditions for AgNP- and pSBMA-co-modified PATFC membranes, with reverse osmosis seawater desalination as the test application scenario. A 180-day continuous seawater treatment test was conducted to evaluate the long-term sustainability of anti-biofouling resistance. Results indicated that loading AgNPs before grafting pSBMA enhanced their stability during use and cleaning. Co-modification under optimal conditions led to a 6.3% improvement in membrane flux reduction over long-term operation. The effect of AgNPs was significant for 30 days, while pSBMA remained effective until the end of the test. Water contact angle measurements, confocal laser scanning microscopy, and quorum sensing signal molecule analysis revealed anti-bioflouling improvements due to the hydration layer and electrostatic barrier from pSBMA, as well as quorum sensing inhibition and disinfection from AgNPs. These findings confirm the discount effectiveness and feasibility of the pSBMA and AgNPs co-modification technique during long working time, offering valuable insights into modification operations and anti-biofouling mechanisms.

  • Co-modification resulted in a 24.2% improvement in anti-biofouling performance.

  • The pSBMA modification has a more lasting effect compared to AgNPs modification.

  • pSBMA mitigates the functional failure of AgNPs caused by halide ions.

Polyamide thin-film composite (PATFC) membranes are widely used in mainstream membrane technologies such as reverse osmosis (RO) and nanofiltration (Pan et al. 2016), but they are susceptible to biological fouling during application (Suresh et al. 2022). The development of biofouling-resistant membranes not only inhibits the formation and growth of biofilms at their source but also alleviates the pressure on pretreatment and membrane cleaning processes, reduces the use of chemical reagents, and minimizes byproduct formation (Lin et al. 2010). Therefore, this approach is considered the most effective method for preventing and managing biofouling in membranes.

There are two commonly used approaches for preparing anti-biofouling membranes. One method involves incorporating hydrophilic materials during membrane fabrication via interfacial polymerization (Agnihotri et al. 2013; Mariën & Vankelecom 2018; Vatanpour et al. 2022), while the other entails grafting hydrophilic materials onto the membrane surface post-fabrication (Firouzjaei et al. 2020; Zhao et al. 2021). The latter approach is particularly advantageous as it allows for simple and facile surface modification while maintaining the structural properties of the substrate membranes. Moreover, post-fabrication modification enables large-scale modification of commercially available membranes that are of consistent quality and available at a low cost. Hydrophilic polymers and nanomaterials are two types of hydrophilic materials that have been widely studied for enhancing the fouling resistance of PATFC (pressure-assisted thin-film composite) membranes.

Among hydrophilic polymeric materials, polyethylene glycol (PEG)-based polymers have been the most extensively explored for antifouling membrane surface modification. The neutral charge of PEG reduces the interactions between foulants and the membrane, thereby effectively preventing foulant adsorption (Kang et al. 2007; Zhang et al. 2019). However, PEG tends to oxidize in complex media, compromising its antifouling property and suitability for long-term applications (Ray et al. 2017). Zwitterionic polymers (ZPs) have emerged as promising alternatives to PEG derivatives for low-fouling surfaces, as they form denser and tighter hydration layers than other hydrophilic materials (Lin et al. 2019). Consequently, PATFC membranes coated with ZPs exhibit significantly reduced adsorption of proteins and bacteria (He et al. 2016; Cui et al. 2020). While ZPs can delay or prevent microbial attachment, they cannot inactivate bacterial cells. Thus, to combat biofouling, several studies propose the fabrication of dual-function membranes by combining ‘offensive’ and ‘defensive’ strategies (Zou et al. 2021). These strategies rely on strong antimicrobial agents, such as organic antimicrobial compounds or biocidal nanoparticles, to inhibit bacterial proliferation, which is considered a promising solution to biofouling in membrane-based technologies.

Surface modification using hydrophilic nanomaterials has been actively investigated to impart ‘offensive’ biofouling resistance to TFC membranes. Various nanomaterials, including metal oxide nanoparticles and carbon-based nanomaterials, have been used to develop antifouling TFC membranes (Zhang et al. 2017; Pejman et al. 2020; Liu et al. 2021; Ngo et al. 2022; Feng et al. 2023). Silver nanoparticles (AgNPs) have received particular attention due to their broad-spectrum antimicrobial activity (Dakal et al. 2016; Salleh et al. 2020). Unlike organic antimicrobial agents that inactivate bacterial cells through contact-mediated mechanisms, AgNPs' toxicity is driven by the release of Ag+ ions (Durán et al. 2016). The physicochemical properties of AgNPs can be tailored to achieve improved reactivity, and their dissolution-dependent mechanism of toxicity makes them less susceptible to the presence of other chemical foulants in the feed stream (Ben-Sasson et al. 2016). Despite concerns about their long-term efficiency, the regenerative capability of AgNPs has proven to be a key element in the preferential design of silver-modified membranes for biofouling mitigation (Liu et al. 2017).

Studies on the co-modification of PATFC membranes with ZPs and AgNPs for anti-biofouling applications show promising results but reveal significant gaps (Liu et al. 2021; Zhang et al. 2018; Yi et al. 2019)). First, there is a lack of systematic optimization of modification conditions (e.g., reaction time of the grafting initiator, loading sequence, and the ratio of zwitterions to nanoparticles) specifically for seawater reverse osmosis (SWRO) desalination, the most common application of PATFC RO membranes. Second, current research typically evaluates the performance of modified membranes using short-term static contact experiments with Escherichia coli and NaCl filtration tests. However, these methods fail to account for variables such as shear forces from water flow, background water composition, and physiological differences between E. coli and other microorganisms that contribute to membrane fouling. Third, the long-term anti-biofouling efficacy of membranes co-modified with ZPs and AgNPs remains largely unexplored. Fourth, while membrane stability has been examined under mild conditions (e.g., NaCl or NaHCO₃), it has yet to be tested under more rigorous chemical cleaning processes. Finally, there is limited mechanistic insight into the biofouling resistance of AgNP- and ZPs-co-modified membranes, with the resistance often attributed to Ag+ disinfection and surface hydrophilicity and roughness, without deeper exploration of interactions with biofilm and ZPs/AgNPs.

To address the above issues, taking SWRO desalination as the design application scenario, PATFC membranes modified with zwitterionic poly(sulfobetaine methacrylate) (pSBMA) and AgNPs were prepared and used to study the following aspects: (1) aiming for anti-biofouling while also considering salt rejection rate, water flux, and resistance to organic fouling, the key modification parameters (AgNO3 concentration, contact time of membrane with initiator, and atom transfer radical polymerization (ATRP) reaction time) were optimized using response surface methodology (RSM) through an improved anti-biofouling testing method and (2) the optimized modified membranes were subjected to long-term continuous run test with RO unit feed water from actual SWRO desalination plant to evaluate the durability of the positive effects of the co-modification on the PATFC membrane. Our results will provide a valuable theoretical and technical reference for AgNPs or/and pSBMA modification technology for the preparation of anti-biofouling membranes applied in SWRO desalination.

Chemicals

All reagents (Text S1, Supporting Information) were used as received without further purification. All solutions were prepared with reagent-grade chemicals and purified water (18.2 MΩ cm) produced by a Smart-N system.

Modification of TFC RO membranes

The PATFC RO membrane used in the experiment was obtained by disassembling the LC-LE 4040 roll-type membrane assembly. The membrane was then cut to an appropriate size and soaked in a 25% aqueous solution of isopropyl alcohol (IPA) for 30 min to remove the surface coating of the commercial film. The membrane was subsequently rinsed with ultra-pure water for more than 24 h, with the water being changed several times during the process. The pretreated membranes were stored in a refrigerator at 4 °C prior to use.

The ARGET ATRP method was used for the grafting of the amphoteric polymer pSBMA on PATFC membranes (Min & Matyjaszewski 2005). The AgNPs were loaded on PATFC membranes through AgNO3 reduction with NaBH4 (Ben-Sasson et al. 2014). Successful loading of AgNPs can be confirmed by SEM, EDS, and XPS analysis (Figure S1(a)–(b), Supporting Information), while successful grafting of pSBMA can be verified by XPS and FTIR analysis (Figure S1(b)–(c), Supporting Information). Modification parameters include AgNO3 concentration ([AgNO3]0), contact time of membrane with α-bromoisobutyryl bromide (BiBB) and dopamine hydrochloride (DA) (TBiBB-DA), and ATRP reaction time (TATRP). The adjustment range of [AgNO3]0 (2–5 mM), TBiBB-DA (2–10 min), and TATRP (30–90 min) is initially determined by pre-experiments (Figure S2–S4, Supporting Information). Experiments have shown that the loading order of AgNPs and pSBMA has little effect on membrane performance (Figure S5, Supporting Information), which differs from the findings reported by Liu et al. (2017). To reduce the leaching of AgNPs, the sequence of loading AgNPs first and then grafting pSBMA for the preparation of AgNPs–pSBMA–PATFC membrane was adopted.

Experimental procedure

Performance evaluation for PATFC membrane modification optimization

The common predominant bacteria (sphingobacteriia) in the RO membrane biofilm community (Nagaraj et al. 2017a, b) served as the test strain to examine bacterial adsorption and growth on the membrane surface. The antimicrobial properties of PATFC membranes, both pre- and post-modification, were assessed employing the plate counting method. Given that the commonly used 3-h static contact experiment overlooks factors such as hydraulic shear and microbial growth and metabolism on the membrane surface, which are often crucial in membrane biofouling, dynamic cross-flow contact test device was built (Figure 1). The test device operated in a constant transmembrane pressure (TMP). Marine agar medium (DSMZ Medium 604) was mixed with sphingobacteriia (1.0 × 106 CFU/mL) to prepare the test solution, which was introduced into the membrane module using a peristaltic pump at a flow rate of 10 mL/min. Unmodified PATFC, AgNPs–PATFC, pSBMA–PATFC, and AgNPs–pSBMA–PATFC are subjected to a 7-d experiment. The pour plate count of bacteria on the original PATFC membrane surface (N0) and modified membrane surface (Ni) was determined. The contaminated membranes from the three parallel tandem membrane modules were collected individually and vortexed in 0.5 mL of saline solution for 30 s each. To count colony-forming units (CFU), 100 μL of the bacterial suspension was inoculated onto R2A agar plates and incubated at 25 °C for 5 days. The bacteria inhibition rate (R) of the modified membranes can be calculated as Equation (1) and the final result was taken as the average of the measurements from three membrane samples.
(1)
Figure 1

Dynamic cross-flow contact test device.

Figure 1

Dynamic cross-flow contact test device.

Close modal

A high-pressure flat membrane equipment (TQFM-24, Shanghai Tongqin Environmental Protection Technology Co., Ltd) was employed for continuous flow testing experiments. The membrane cell area of this high-pressure flat testing apparatus is 24 cm2 (4 cm), with an adjustable filtration pressure range of 1–60 bar and a cross-flow rate of 1 L/min with a recovery rate of 60%. Integrated with a thermostatic water bath (25 °C), electronic balance, and computer, this setup allows for filtration experiments at specified temperatures and pressures while measuring membrane flux. The water flux and salt rejection rate was determined using a 2,000 mg/L NaCl test solution (Text S2, Supporting Information).

Long-term continuous flow test that simulate actual application scenarios

In order to investigate the performance of AgNPs–pSBMA–PATFC membranes during long-term operation, the TQFM-24 high-pressure flat membrane equipment was used for continuous flow testing of AgNPs–pSBMA–PATFC membranes for a period of 6 months. RO feed water from SWRO desalination plant (Table S1, Supporting Information) was used for testing. The membrane flux and desalination rate were recorded during the operation. Since it was not possible to pause the operation to cut membrane samples, only the membrane samples at the end of the operation were characterized.

Additionally, at the end of the operation, the membranes were subjected to a simulated cleaning process. The experiments followed the chemical cleaning agent recommendations provided in the technical documentation of FilmTec RO membranes (Dupont 2023). A cleaning method preferred by inorganic colloids, silica, biofilm, organic foulants was selected. Specifically, modified membrane samples (2 cm × 2 cm) were sequentially immersed in cleaning solutions 0.2% HCI (25 °C and pH 1) and 0.1% NaOH and 0.025% sodium salt of dodecylsulfate (Na-DSS) for 2 h each. The container for cleaning solution was placed on a shaker (35 °C and 150 rpm) to ensure adequate contact between the cleaning solution and the membrane. Residual AgNPs on the membrane surface were dissolved using 10 mL of 10% HNO3, and the resulting Ag+ concentration was determined by ICP-MS. Changes in pSBMA loading were evaluated by comparing the intensity of its characteristic FTIR peaks.

Analysis of bacterial and associated organics on the membrane surface

The biofilm on the membrane surface was characterized by the confocal laser scanning microscopy (LSM780, ZEISS, Germany) after staining with SYTO9 and propidium iodide (PI) (LIVE/DEAD Biofilm Viability kit, FilmTracer). Live microorganisms are displayed with green fluorescence and dead with red fluorescence. The obtained images were analyzed using ZEN2010 (Carl Zeiss Microscopy GmbH, Jena, Germany). Extracellular polymeric substances (EPSs) were analyzed by fluorescence excitation and emission matrix (EEM) spectra (Liu et al. 2023). Parallel factor analysis (PARAFAC) was performed via MATLAB 9.11 using the drEEM toolbox.

Acyl-homoserine-lactones (AHLs) were concentrated using liquid–liquid extraction with ethyl acetate followed by rotary evaporation (Liu et al. 2022). The residue was then recovered with 0.5 mL of methanol for testing. Signal molecules were analyzed using HPLC-MS/MS (Agilent 6400, USA), with a linear gradient of solvent A (methanol) and solvent B (0.1% formic acid and 2 mM acetonitrile) as the mobile phase. The flow rate was maintained at 0.3 mL/min, and mass spectra were measured in ESI mode. To confirm the identity of the putative AHLs, a full scan (m/z 100–350) coupled with a SIM scan was performed. The obtained mass spectra were compared with reference standards.

Preparation optimization and performance testing of AgNPs–pSBMA–PATFC

In order to facilitate rapid optimization of the preparation conditions, the inhibition rate obtained from 3-h static contact experiments was used as an indicator to represent the anti-biofouling performance of the modified membranes. The water flux and salt rejection rate was used to characterize the separation ability of membrane.

Optimization of modification conditions

Figure 2 presents the co-modified membranes' performance under different modification conditions. The best biofouling resistance (93.6%) was obtained under the condition of [AgNO3]0 = 5 mM, TBiBB-DA = 10 min, and TATRP = 60 min (Figure 2(a)). Although extending the TATRP to 120 min can increase the bacteria inhibition rate from 93.6 to 95.0%, this duration may lead to a 10% decline in water flux (Figure 2(b)). Notably, the best modified condition yielded a 33.7% decrease in water flux compared to the case without modification. By comparing the flux data of membranes modified with AgNPs or pSBA alone (Figure S2 and S3, Supporting Information), it is easy to understand that the decline in flux is primarily caused by the grafting of pSBA. Interestingly, [AgNO3]0, TBiBB-DA, and TATRP hardly affect the salt rejection rate (Figure 2(b)), which is consistent with the observations from the one-factor experiment (Figure S3–S5, Supporting Information). However, increase of TBiBB-DA and TATRP significantly decrease the water flux (4.1–41.5%).
Figure 2

Performance of modified membranes under different modification conditions: (a) separation capability and (b) biofouling resistance. Constant pressure filtration mode (TMP 12.5 bar) was applied. TBiBB-DA: contact time of BiBB-DA solution with membrane; TBiBB-DA: ATRP reaction time.

Figure 2

Performance of modified membranes under different modification conditions: (a) separation capability and (b) biofouling resistance. Constant pressure filtration mode (TMP 12.5 bar) was applied. TBiBB-DA: contact time of BiBB-DA solution with membrane; TBiBB-DA: ATRP reaction time.

Close modal

In order to obtain the optimal modification parameters with the antibacterial rate and water flux as the response variable and [AgNO3]0 (A), TBiBB-DA (B), and TATRP (C) as influencing factors, RSM was employed to analyze the optimal modification parameters (Text S1 and Tables S1–S3, Supporting Information). The optimal recommended values for [AgNO3]0, TBiBB-DA, and TATRP are 5 mM, 10 min, and 44.4 min, respectively (Table S4, Supporting Information). Under these optimized modification conditions, the experimental measurements for antimicrobial activity and water flux were respectively 93.0% and 4.35 L m−2 h−1 bar−1, which were consistent with the model predictions.

Considering that the organic foulants may co-exist with biofoulant, whether the increase in anti-biofouling comes at the expense of loss of resistance to organic matter needs further evaluation. Therefore, organic fouling experiments for optimized AgNPs–pSBMA–PATFC were conducted in the presence of BSA (protein contaminant), SA (polysaccharide contaminant), and HA (as a representative of natural organic matter). As depicted in Figure 3, AgNPs–pSBMA–PATFC membrane demonstrated a significantly slower decline in specific flux (0–13.4%) when exposed to BSA, SA, and HA solutions during a 100-min treatment process, in contrast to the pristine PATFC membrane that experienced an evident reduction in specific flux (0–13.4%). Notably, AgNPs–pSBMA–PATFC membrane exhibited almost negligible change in flux when subjected to HA-containing solutions. By assessing the HA resistance of different membranes, including PATFC, AgNPs–PATFC, pSBMA–PATFC, and AgNPs–pSBMA–PATFC (Figure 3(c)), it can conclude that pSBMA is the main contributor, owing to its hydrophilicity regulation effect (Figure S5, Supporting Information) and charged structure effectively prohibiting the adhesion of electrostatically charged HA molecules. Similarly, grafting of pSBMA also contributes to the resistance of BSA and SA.
Figure 3

Organic fouling resistance of the optimal AgNPs–pSBMA–PATFC in the presence of different organic foulants: (a) BSA; (b) SA; (c) HA. Experimental conditions: [BSA]0 = [SA]0 = [HA]0 = 50 mg/L, 25 °C, constant pressure filtration mode (TMP 12.5 bar), initial water flux 4.35 L m−2 h−1 bar−1. Test solution was prepared with saline (2,000 mg/L NaCl).

Figure 3

Organic fouling resistance of the optimal AgNPs–pSBMA–PATFC in the presence of different organic foulants: (a) BSA; (b) SA; (c) HA. Experimental conditions: [BSA]0 = [SA]0 = [HA]0 = 50 mg/L, 25 °C, constant pressure filtration mode (TMP 12.5 bar), initial water flux 4.35 L m−2 h−1 bar−1. Test solution was prepared with saline (2,000 mg/L NaCl).

Close modal

Practical application testing for optimized AgNPs–pSBMA–PATFC

Water production stability

In order to verify the water production stability of AgNPs–pSBMA–PATFC in practical applications, a 180-d continuous flow test experiment using real pretreated sea water was carried out (Figure 4). At the end of the operation, PATFC, AgNPs–PATFC, pSBMA–PATFC, and AgNPs–pSBMA–PATFC showed water flux declines of 9.9, 12.9, 15.5, and 16.3%, respectively. The AgNPs–PATFC demonstrated some ability to improve water flux decline during the first 30 days, but after 30 days, its performance was almost identical to that of PATFC. This may be related to the reduction in soluble silver released by AgNPs due to the presence of a large number of halogen ions in the feedwater. In comparison to AgNPs modification, pSBMA modification exhibited a significant ability to improve water flux decline throughout the entire 180-day operation period. This indicates that pSBMA modification contributes more to maintaining water flux stability during long-term operation. Coupled with the superior performance of AgNPs–pSBMA–PATFC over pSBMA–PATFC, one can infer that although AgNPs modification does not provide long-lasting effects, it can alter the initial deposition of foulants on the membrane and the construction of the filter cake layer. It should be noted that the aforementioned water flux data reflects overall membrane fouling rather than biofouling alone. Therefore, the following discussion specifically addresses biofouling.
Figure 4

Water production performance of AgNPs–pSBMA–PATFC membrane in continuous flow test using real feedwater of RO module in SWRO desalination plant. Experimental conditions: initial flux 40 L m−2 h−1.

Figure 4

Water production performance of AgNPs–pSBMA–PATFC membrane in continuous flow test using real feedwater of RO module in SWRO desalination plant. Experimental conditions: initial flux 40 L m−2 h−1.

Close modal

Biofouling resistance

Further biofilm analysis using CLSM (Figure 5(a)) revealed that the total biovolume on the pSBMA–PATFC membrane was significantly lower than that on the PATFC membrane (Figure 5(b)), indicating the ‘passive’ anti-biofouling effect induced by pSBMA modification (Ma et al. 2020). The gap between the staining layer and the membrane surface as well as the decreased water contact angle ( Figure S5, Supporting Information) shows that the hydration layer acted as a physical barrier to prevent bacteria from approaching the membrane surface. The AgNPs–PATFC membrane also displayed a reduced total biovolume (TOC biovolume) compared to the PATFC membrane, indicating the ‘active’ anti-biofouling effect of AgNPs, which led to a thinner biofilm thickness and a higher volume of dead bacteria. In the case of the AgNPs–pSBMA–PATFC membrane, the biofilm thickness and total biovolume were reduced by 71.9 and 24.2%, respectively, in comparison to the PATFC membrane. Notably, the volume of live bacteria on the AgNPs–pSBMA–PATFC membrane decreased by 68.4% in comparison to the PATFC membrane, signifying the contribution of the ‘active’ anti-biofouling effect. Moreover, the TOC volume of the AgNPs–pSBMA–PATFC membrane was 37.8% lower than that of the PATFC membrane, indicating a lower metabolic intensity of microorganisms on the membrane surface. This was further confirmed by the EEM analysis of organic metabolic products (Figure 5(b)). The lowest soluble microbial metabolites on AgNPs–pSBMA–PATFC membrane surface also supported the ‘passive’ anti-biofouling effect of the modification (Figure 6 and Fig. 6S). Additionally, the co-modification of AgNPs and pSBMA displayed a synergistic effect on the membrane surface, resulting in a greater reduction in average biofilm thickness than the individual effect of each modification. It should be noted that in such a synergistic effect, the outward-facing negative charge barrier of pSBMA partially inhibits halide ions from competing with silver ion released by AgNPs (Liu et al. 2017), thereby ensuring the active anti-biofouling effect of AgNPs. This can be verified by the faster Ag leaching from AgNPs–PATFC compared to AgNPs–pSBMA–PATFC when both were soaked in NaCl solution (Figure S7, Supporting Information).
Figure 5

Biofilm on the membrane surface after 180 days of operation: (a) CLSM images and (b) biofilm thickness and biovolume.

Figure 5

Biofilm on the membrane surface after 180 days of operation: (a) CLSM images and (b) biofilm thickness and biovolume.

Close modal
Figure 6

Microbial metabolites (EEM region IV) on membrane surface after 180 days of operation. EEM region IV (Ex/Em: 250–280/280–380).

Figure 6

Microbial metabolites (EEM region IV) on membrane surface after 180 days of operation. EEM region IV (Ex/Em: 250–280/280–380).

Close modal
Additionally, considering that the reduction in biomass may be related to quorum sensing inhibition, the signal molecules on the membrane surface were also measured. As shown in Figure 7, the surface of the AgNPs–pSBMA–PATFC membrane had the lowest amount of signal molecules (especially AHLs with 12–14 carbon atoms). According to the report by Chen et al. (2024), the introduction of the quorum sensing inhibitor methyl anthranilate into seawater RO membranes enhanced their biofouling resistance. This improvement was attributed to a reduction in the relative abundance of dominant bacteria associated with polysaccharide and protein metabolism on the membrane surface, resulting from quorum sensing inhibition. This is similar to the phenomenon observed in this study. Therefore, when explaining the mechanism by which AgNPs and pSBMA co-modification enhances the biofouling resistance of pSBMA membranes, the quorum sensing inhibition effects of AgNPs and pSBMA should not be overlooked. With the negative charge barrier of pSBMA, the quorum sensing inhibition effect of AgNPs is better realized.
Figure 7

The concentration of signal molecules on membrane surface after 180 days of operation.

Figure 7

The concentration of signal molecules on membrane surface after 180 days of operation.

Close modal

Stability of modified components

Considering the possible detachment or deterioration of modified components due to hydraulic or chemical cleaning of the membrane, simulated cleaning tests were conducted, and observations were made on the modified components (AgNPs and pSBMA). As shown in Figure 8(a), after 180 days of operation, the loading of AgNPs for the AgNPs–PATFC membrane was found to be almost completely depleted after acid cleaning and alkaline cleaning, with only 2.3% of the original amount remaining. Unlike AgNPs–PATFC, AgNPs–pSBMA–PATFC membranes retained 21.3% AgNPs. This suggests that grafting of pSBMA onto the membrane surface after loading AgNPs at bottom can effectively reduce the detachment of AgNPs, although previous studies suggested that AgNPs on top of the polymer brush could better enhance anti-adhesive and antimicrobial properties (Liu et al. 2017). After washing with 0.2% HCl and 0.1% NaOH (0.025% Na-DSS), the characteristic absorption peaks for pSBMA, the carbonyl group (–COO–) at 1,724 cm−1 and the sulfonic acid group at 1,040 cm−1, remained prominent and did not exhibit significant changes (Figure 8(b)). Moreover, the amide groups (N–C = O at 1,666 cm−1 and C–N–H at 1,539 cm−1) on the pristine PATFC membrane surface showed no significant alterations after acid and alkaline washing. Notably, due to the leaching of AgNPs, the anti-biofouling performance of AgNPs–PATFC and AgNPs–pSBMA–PATFC showed significant decline. These results indicate that grafted pSBMA on the AgNPs–pSBMA–PATFC membrane remains unaffected even after prolonged operation and chemical cleaning, while AgNPs, although partially protected by pSBMA, still experience substantial loss over time. This means that the AgNPs on the surface of the AgNPs–pSBMA–PATFC membrane will require periodic regeneration. Since pSBMA is located on top of the AgNPs, the regeneration process faces the challenge of penetrating through the pSBMA ‘forest’ to reload AgNPs onto the surface of the PATFC membrane.
Figure 8

Stability evaluation of AgNPs and pSBMA components on the membrane surface used for 180 days: (a) AgNPs remaining after cleaning; (b) pSBMA remaining after cleaning; and (c) antimicrobial activity pSBMA remaining after cleaning. Cleaning conditions: 0.2% HCl (25 °C and pH 1) soaking for 2 h and 0.1% NaOH + 0.025% Na-DSS for 2 h.

Figure 8

Stability evaluation of AgNPs and pSBMA components on the membrane surface used for 180 days: (a) AgNPs remaining after cleaning; (b) pSBMA remaining after cleaning; and (c) antimicrobial activity pSBMA remaining after cleaning. Cleaning conditions: 0.2% HCl (25 °C and pH 1) soaking for 2 h and 0.1% NaOH + 0.025% Na-DSS for 2 h.

Close modal

The study has demonstrated that the sequential modification of PATFC membranes with AgNPs and pSBMA is an effective approach for enhancing biofouling resistance from a short-term operational perspective (>90% improvement) but not significantly effective from a long-term operational perspective (<25%, based on biovolume). The modification optimization results indicate that the selection of test solutions (including microorganisms and background components) and test methods needs to be specifically designed to ensure that the performance parameters obtained from batch experiments are more accurately translated to actual operational performance. When both AgNPs and pSBMA are loaded onto the PATFC membrane, the AgNPs exhibit different functions compared to when AgNPs are loaded alone. In the former case, the improvement is due to the quorum sensing inhibition and the bactericidal action of silver ions released by AgNPs. In the latter case, the bactericidal action of silver ions is shielded by halide ions competition. Besides forming a hydration layer on the membrane surface, pSBMA also provides a negative charge barrier that weakens the impact of halide ions in seawater on AgNPs. Although this study improved the testing methods for anti-biofouling modifications, the significant differences between performance data from batch experiments and actual operational indicate that the existing testing methods require substantial changes. Moreover, the 180-day operation period in this study only corresponds to one cleaning cycle of an actual SWRO desalination plant. Subsequent research needs to evaluate the AgNPs–pSBMA–PATFC membrane from a full life-cycle perspective. Finally, based on the experimental results, it is recommended that AgNPs be loaded onto the membrane before pSBMA to ensure the effectiveness of AgNPs. However, this poses challenges for the replenishment of AgNPs loss over time.

This research is funded by the National Key R&D Program of China (No. 2023YFF0614501), Zhejiang Public welfare technology research program (No. LGG21E080011), and the Jiyang 533 Talent Program (No. JY21E0102).

All relevant data are included in the paper or its Supplementary Information.

The authors declare there is no conflict.

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