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Introduction

The availability of clean water has become a global problem because of the continuously increasing costs of energy and increasing scarcity of water resources1. This problem has been exacerbated in recent years in the so-called century of water. By far, the domestic ro membrane process persists as the most reliable and cost-effective water desalination technique and numerous large-scale RO plants have been constructed around the world2,3. A wide range of polymers have shown potential for fabricating desalination membranes to be used in RO4. However, PA-based membranes tend to exhibit the best performance in terms of selectivity, flow, chemical stability and ease of large-scale fabrication. PA membrane technology was developed in the mid-70 s and has become the commercial benchmark in RO membranes5. In order to improve the membrane performances, the recent trend in polymer-based membrane research has been to investigate various types of nanocomposite films as an active layer of RO membrane, so-called nanocomposite membranes, in which these films are fabricated using a nanosized filler such as MWCNT, graphene, graphene oxide, silica, or zeolite6. In this regard, MWCNT·PA-based membranes have been prepared by several groups and in general, these membranes have exhibited some level of improved performance7,8,9,10,11,12. The advantages claimed for these membranes range from increased salt rejection, large fluxes, greater durability and even antimicrobial properties.

MWCNT synthesized by catalytic chemical vapour deposition13,14 have been widely studied due to their fascinating chemical and physical properties and among all nanocarbon materials, they can be mass-produced for commercially available applications, such as the electrode additives in high performance lithium ion batteries15. Interestingly, while the structure of the fully aromatic PA-based commercial ro membrane derived from m-phenylendiamine (MPD)-trimesoyl chloride (TMC) is constrained due to its stoichiometry; the addition of MWCNT can significantly vary their performance due to their unique features such as dispersability diameter, length, straightness and chemical functionalities, among many others. Therefore, although these past reports acknowledge the key role of MWCNT in aromatic PA nanocomposite membranes, still little attention has been devoted to the mechanisms related to the improvement of flow rate, selectivity and chlorine tolerance2. Carbon nanotubes inducing chlorine tolerance are particularly interesting because chlorine sensitivity has been recognized as a major drawback of PA-based RO membranes16,17. During long-term operation, chlorine is often added as a pre-treatment to reduce algae biofouling18 and is particularly needed for drinking water purification. Moreover, high-concentration short-term exposure to chlorine is also common during domestic nf membrane backwashing. For these reasons, several studies have been carried out and the degradation mechanism of aromatic PA membranes during chlorine exposure is relatively well-known19,20. Recently, our group demonstrated that the addition of MWCNT to rubber can considerably reduce the chlorine-induced degradation of the polymer matrix21. Although the degradation mechanism of rubber by chlorine is different from that of PA, particularly due to the lack of hydrolysis, covalent chlorination is a common problem for both polyamide and rubber. For rubber, we found that MWCNT effectively restricted the adsorption of chlorine within the polymer matrix, thus resulting in a limited exposure of the polymer to this reactive reagent and thereby decreasing the oxidative degradation. For these reasons, we believe MWCNT are not only promising composite fillers with chlorine protective properties, but might also help to provide mechanical robustness to PA-based RO membranes.