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Hybrid Polymer Materials for Water Purification and Wastewater Treatment

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (20 October 2022) | Viewed by 41528

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Dr. Artur Valente

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Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal
Interests: transport phenomena; surfactants; biopolymers; polysaccharides; supramolecular chemistry
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Adam M. Paruch

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Division of Environment and Natural Resources, Norwegian Institute of Bioeconomy Research (NIBIO), Elizabeth Stephansens vei 23, 1433 Aas, Norway
Interests: antibiotic resistance genes; DNA-based markers; emerging pathogens; microbial quality assessment

Dr. Tanta-Verona Iordache

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National Institute for Research & Development in Chemistry and Petrochemistry ICECHIM, Splaiul Independentei no. 202, 060021 Bucharest, Romania
Interests: molecularly imprinted polymers; hybrid materials; environmental applications

Special Issue Information

Dear Colleagues,

Water, despite covering 70% of the Earth’s surface, is a scarce commodity. According to the World Health Organization, about 663 million people worldwide do not have access to improved drinking water, corresponding to ca. 9% of the world population. Despite that, the use of water in anthropogenic activities (e.g., mining and farming) along with the fact that 2.6 billion people do not have adequate water sanitation and sewage treatment infrastructure, leads to just 71% of the global population that uses a safely managed drinking-water service. Thus, management of water and wastewater requires integrated policies and tangible strategies for optimizing drinking water purification and wastewater treatment processes. These represent great challenges to regulatory authorities, sanitary engineers, and scientific communities due to the multitude of contaminants, including microorganisms, especially pathogens, drugs (e.g., antibiotics and anti-inflammatories), pesticides and metal ions, and other emerging pollutants such as bacteria with antibiotic-resistant genes. This Special Issue is focused on recent developments in hybrid materials, such as imprinted polymer networks, metal organic frameworks, carbon organic frameworks, and clay organic nanocomposites, among others, for effective biological and chemical water purification and wastewater treatment, ranging from fundamentals to applications.

Prof. Dr. Artur Valente
Prof. Dr. Adam M. Paruch
Dr. Tanta-Verona Iordache
Guest Editors

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Keywords

wastewater treatment
water purification
advanced materials
hybrid polymers
composites

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Published Papers (10 papers)

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Research

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20 pages, 4768 KiB

Open AccessArticle

Antifouling and Water Flux Enhancement in Polyethersulfone Ultrafiltration Membranes by Incorporating Water-Soluble Cationic Polymer of Poly [2-(Dimethyl amino) ethyl Methacrylate]

by Raja Muhammad Asif Khan, Nasir M. Ahmad, Habib Nasir, Azhar Mahmood, Mudassir Iqbal and Hussnain A. Janjua

Polymers 2023, 15(13), 2868; https://doi.org/10.3390/polym15132868 - 29 Jun 2023

Cited by 7 | Viewed by 1585

Abstract

Novel ultrafiltration (UF) polymer membranes were prepared to enhance the antifouling features and filtration performance. Several ultrafiltration polymer membranes were prepared by incorporating different concentrations of water-soluble cationic poly [2-(dimethyl amino) ethyl methacrylate] (PDMAEMA) into a homogenous casting solution of polyethersulfone (PES). After adding PDMAEMA, the effects on morphology, hydrophilicity, thermal stability, mechanical strength, antifouling characteristics, and filtration performance of these altered blended membranes were investigated. It was observed that increasing the quantity of PDMAEMA in PES membranes in turn enhanced surface energy, hydrophilicity, and porosity of the membranes. These new modified PES membranes, after the addition of PDMAEMA, showed better filtration performance by having increased water flux and a higher flux recovery ratio (FRR%) when compared with neat PES membranes. For the PES/PDMAEMA membrane, pure water flux with 3.0 wt.% PDMAEMA and 0.2 MPa pressure was observed as (330.39 L·m⁻²·h⁻¹), which is much higher than that of the neat PES membrane with the value of (163.158 L·m⁻²·h⁻¹) under the same conditions. Furthermore, the inclusion of PDMAEMA enhanced the antifouling capabilities of PES membranes. The total fouling ratio (TFR) of the fabricated PES/PDMAEMA membranes with 3.0 wt.% PDMAEMA at 0.2 MPa applied pressure was 36 percent, compared to 64.9 percent for PES membranes. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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21 pages, 4022 KiB

Open AccessArticle

A Highly Efficient Polystyrene-Based Cationic Resin to Reduce Bacterial Contaminations in Water

by Anna Maria Schito, Debora Caviglia, Gabriella Piatti and Silvana Alfei

Polymers 2022, 14(21), 4690; https://doi.org/10.3390/polym14214690 - 3 Nov 2022

Cited by 4 | Viewed by 1987

Abstract

Nowadays, new water disinfection materials attract a lot of attention for their cost-saving and ease of application. Nevertheless, the poor durability of the matrices and the loss of physically incorporated or chemically attached antibacterial agents that can occur during water purification processes considerably limit their prolonged use. In this study, a polystyrene-based cationic resin (R4) with intrinsic broad-spectrum antibacterial effects was produced without needing to be enriched with additional antibacterial agents that could detach during use. Particularly, R4 was achieved by copolymerizing 4-ammonium-butyl-styrene (4-ABSTY) with N,N-dimethylacrylamide (DMAA) and using N-(2-acryloylamino-ethyl)-acrylamide (AAEA) as a cross-linker. The R4 obtained showed a spherical morphology, micro-dimensioned particles, high hydrophilicity, high-level porosity, and excellent swelling capabilities. Additionally, the swollen R4 to its maximum swelling capability, when dried with gentle heating for 3 h, released water following the Higuchi’s kinetics, thus returning to the original structure. In time–kill experiments on the clinical isolates of multidrug-resistant (MDR) pathogens of fecal origin, such as enterococci, Group B Salmonella species, and Escherichia coli, R4 showed rapid bactericidal effects on enterococci and Salmonella, and reduced E. coli viable cells by 99.8% after 4 h. When aqueous samples artificially infected by a mixture of the same bacteria of fecal origin were exposed for different times to R4 in a column, simulating a water purification system, 4 h of contact was sufficient for R4 to show the best bacterial killing efficiency of 99%. Overall, thanks to its physicochemical properties, killing efficiency, low costs of production, and scalability, R4 could become a cost-effective material for building systems to effectively reduce bacterial, even polymicrobial, water contamination. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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26 pages, 3924 KiB

Open AccessArticle

Immobilization of Horseradish Peroxidase on Magnetite-Alginate Beads to Enable Effective Strong Binding and Enzyme Recycling during Anthraquinone Dyes’ Degradation

by Marko Jonović, Branimir Jugović, Milena Žuža, Verica Đorđević, Nikola Milašinović, Branko Bugarski and Zorica Knežević-Jugović

Polymers 2022, 14(13), 2614; https://doi.org/10.3390/polym14132614 - 28 Jun 2022

Cited by 10 | Viewed by 2511

Abstract

The aim of this study was to investigate covalent immobilization of horseradish peroxidase (HRP) on magnetic nanoparticles (Mag) encapsulated in calcium alginate beads (MABs) for color degradation, combining easy and fast removal of biocatalyst from the reaction mixture due to its magnetic properties and strong binding due to surface alginate functional groups. MABs obtained by extrusion techniques were analyzed by optical microscopy, FEG-SEM and characterized regarding mechanical properties, magnetization and HRP binding. HRP with initial concentration of 10 mg/g_carrier was successfully covalently bonded on MABs (diameter ~1 mm, magnetite/alginate ratio 1:4), with protein loading of 8.9 mg/g_carrier, immobilization yield 96.9% and activity 32.8 U/g. Immobilized HRP on MABs (HRP-MABs) was then used to catalyze degradation of two anthraquinonic dyes, Acid Blue 225 (AB225) and Acid Violet 109 (AV109), as models for wastewater pollutants. HRP-MABs decolorized 77.3% and 76.1% of AV109 and AB225, respectively after 15 min under optimal conditions (0.097 mM H₂O₂, 200 mg of HRP-MABs (8.9 mg/g_carrier), 0.08 and 0.1 g/mg beads/dye ratio for AV109 and AB225, respectively). Biocatalyst was used for 7 repeated cycles retaining 75% and 51% of initial activity for AB225 and AV109, respectively, showing potential for use in large scale applications for colored wastewater treatment. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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23 pages, 4627 KiB

Open AccessArticle

Adsorption of Cationic Contaminants by Cyclodextrin Nanosponges Cross-Linked with 1,2,3,4-Butanetetracarboxylic Acid and Poly(vinyl alcohol)

by Ekkachai Martwong, Santi Chuetor and Jatupol Junthip

Polymers 2022, 14(2), 342; https://doi.org/10.3390/polym14020342 - 16 Jan 2022

Cited by 23 | Viewed by 3265

Abstract

Cationic organic pollutants (dyes and pesticides) are mainly hydrosoluble and easily contaminate water and create a serious problem for biotic and abiotic species. The elimination of these dangerous contaminants from water was accomplished by adsorption using cyclodextrin nanosponges. These nanosponges were elaborated by the cross-linking between 1,2,3,4-butanetetracarboxylic acid and β-cyclodextrin in the presence of poly(vinyl alcohol). Their physicochemical characteristics were characterized by gravimetry, acid-base titration, TGA, ¹³C NMR, ATR-FTIR, Raman, X-ray diffraction, and Stereomicroscopy. The BP5 nanosponges displayed 68.4% yield, 3.31 mmol/g COOH groups, 0.16 mmol/g β-CD content, 54.2% swelling, 97.0% PQ removal, 96.7% SO removal, and 98.3% MG removal for 25 mg/L of initial concentration. The pseudo-second-order model was suitable for kinetics using 180 min of contact time. Langmuir isotherm was suitable for isotherm with the maximum adsorption of 120.5, 92.6, and 64.9 mg/g for paraquat (PQ), safranin (SO), and malachite green (MG) adsorption, respectively. Finally, the reusability performance after five regeneration times reached 94.1%, 91.6%, and 94.6% for PQ, SO, and MG adsorption, respectively. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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15 pages, 2156 KiB

Open AccessArticle

Polyvinyl Alcohol Polymer Functionalized Graphene Oxide Decorated with Gadolinium Oxide for Sequestration of Radionuclides from Aqueous Medium: Characterization, Mechanism, and Environmental Feasibility Studies

by Lakshmi Prasanna Lingamdinne, Janardhan Reddy Koduru, Yoon-Young Chang, Mu. Naushad and Jae-Kyu Yang

Polymers 2021, 13(21), 3835; https://doi.org/10.3390/polym13213835 - 6 Nov 2021

Cited by 15 | Viewed by 2442

Abstract

Uranium (U(VI)) and thorium (Th(IV)) ions produced by the nuclear and mining industries cause water pollution, thereby harming the environment and human health. In this study, gadolinium oxide-decorated polyvinyl alcohol-graphene oxide composite (PGO–Gd) was developed using a simple hydrothermal process to treat U(VI) and Th(IV) ions in water. The developed material was structurally characterized by highly advanced spectroscopy and microscopy techniques. The effects of pH, equilibration time and temperature on both radionuclides (U(VI) and Th(IV)) adsorption by PGO–Gd were examined. The PGO–Gd composite adsorbed both metal ions satisfactorily, with adsorption capacities of 427.50 and 455.0 mg g⁻¹ at pH 4.0, respectively. The adsorption properties of both metal ions were found to be compatible with the Langmuir and pseudo–second-order kinetic models. Additionally, based on the thermodynamic characteristics, the adsorption was endothermic and spontaneous. Furthermore, the environmental viability of PGO–Gd and its application was demonstrated by studying its reusability in treating spiked surface water. PGO–Gd shows promise as an adsorbent in effectively removing both radionuclides from aqueous solutions. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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15 pages, 3792 KiB

Open AccessArticle

Copolyamide–Clay Nanotube Polymer Composite Nanofiber Membranes: Preparation, Characterization and Its Asymmetric Wettability Driven Oil/Water Emulsion Separation towards Sewage Remediation

by Sneha Bhagyaraj, Patrik Sobolčiak, Mohammad A. Al-Ghouti and Igor Krupa

Polymers 2021, 13(21), 3710; https://doi.org/10.3390/polym13213710 - 27 Oct 2021

Cited by 8 | Viewed by 2041

Abstract

To address the problem of ever-increasing oily wastewater management, due to its directional liquid transport property, membranes with asymmetric wettability can be effectively used for emulsion separation. This study reports the synthesis of electrospun polymer–clay nanocomposite nanofibers, using co-polyamide polymer (COPA) and halloysite nanotubes (HA) as filler. The influence of clay content on the morphological, thermal and dielectric properties of the polymer composite nanofiber was investigated comprehensively to address the material characteristics of the developed system. The surface structure analysis and contact angle measurements of the electrospun composite nanofibers confirms the change in surface roughness and wettability when the fillers are added to the polymer. The porosity of the composite electrospun nanofiber membrane was found to be 85% with an oil adsorption capacity of 97% and water permeability of 6265 L/m² h. Furthermore, the asymmetric wettability-driven oil/water emulsion separation abilities of the as-synthesized membranes shows that the separation efficiency of the composite fiber membrane is 10% improved compared to that of the neat fiber membrane, with improved separation time. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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21 pages, 5223 KiB

Open AccessArticle

Preparation of Porous Hydroxyapatite Using Cetyl Trimethyl Ammonium Bromide as Surfactant for the Removal of Lead Ions from Aquatic Solutions

by Silviu-Adrian Predoi, Carmen Steluta Ciobanu, Mikael Motelica-Heino, Mariana Carmen Chifiriuc, Monica Luminita Badea and Simona Liliana Iconaru

Polymers 2021, 13(10), 1617; https://doi.org/10.3390/polym13101617 - 17 May 2021

Cited by 24 | Viewed by 3077

Abstract

In the present study, a new low-cost bioceramic nanocomposite based on porous hydroxyapatite (HAp) and cetyl trimethyl ammonium bromide (CTAB) as surfactant was successfully obtained by a simple chemical co-precipitation. The composition and structure of the HAp-CTAB were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscope (SEM) equipped with an energy dispersive X-ray (EDX) spectrometer, and N₂ adsorption/desorption analysis. The capacity of HAp-CTAB nanocomposites to remove the lead ions from aqueous solutions was studied by adsorption batch experiments and proved by Langmuir and Freundlich models. The Pb²⁺ removal efficiency of HAp-CTAB biocomposite was also confirmed by non-destructive ultrasound studies. The cytotoxicity assays showed that the HAp-CTAB nanocomposites did not induce any significant morphological changes of HeLa cells after 24 h of incubation or other toxic effects. Taken together, our results suggests that the obtained porous HAp-CTAB powder could be used for the decontamination of water polluted with heavy metals, such as Pb²⁺. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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8 pages, 402 KiB

Open AccessCommunication

Mitigating Antibiotic Resistance Genes in Wastewater by Sequential Treatment with Novel Nanomaterials

by Lisa Paruch, Adam M. Paruch, Tanta-Verona Iordache, Andreea G. Olaru and Andrei Sarbu

Polymers 2021, 13(10), 1593; https://doi.org/10.3390/polym13101593 - 15 May 2021

Cited by 6 | Viewed by 2778

Abstract

Wastewater (WW) has been widely recognized as the major sink of a variety of emerging pathogens (EPs), antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs), which may disseminate and impact wider environments. Improving and maximizing WW treatment efficiency to remove these microbial hazards is fundamentally imperative. Despite a variety of physical, biological and chemical treatment technologies, the efficiency of ARG removal is still far from satisfactory. Within our recently accomplished M-ERA.NET project, novel functionalized nanomaterials, i.e., molecularly imprinted polymer (MIP) films and quaternary ammonium salt (QAS) modified kaolin microparticles, were developed and demonstrated to have significant EP removal effectiveness on both Gram-positive bacteria (GPB) and Gram-negative bacteria (GNB) from WW. As a continuation of this project, we took the further step of exploring their ARG mitigation potential. Strikingly, by applying MIP and QAS functionalized kaolin microparticles in tandem, the ARGs prevalent in wastewater treatment plants (WWTPs), e.g., blaCTXM, ermB and qnrS, can be drastically reduced by 2.7, 3.9 and 4.9 log (copies/100 mL), respectively, whereas sul1, tetO and mecA can be eliminated below their detection limits. In terms of class I integron-integrase I (intI1), a mobile genetic element (MGE) for horizontal gene transfer (HGT), 4.3 log (copies/100 mL) reduction was achieved. Overall, the novel nanomaterials exhibit outstanding performance on attenuating ARGs in WW, being superior to their control references. This finding provides additional merit to the application of developed nanomaterials for WW purification towards ARG elimination, in addition to the proven bactericidal effect. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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Review

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31 pages, 7237 KiB

Open AccessReview

The Separation of Oil/Water Mixtures by Modified Melamine and Polyurethane Foams: A Review

by Sarah Mohammed Hailan, Deepalekshmi Ponnamma and Igor Krupa

Polymers 2021, 13(23), 4142; https://doi.org/10.3390/polym13234142 - 27 Nov 2021

Cited by 31 | Viewed by 5548

Abstract

Melamine (MA) and polyurethane (PU) foams, including both commercial sponges for daily use as well as newly synthesized foams are known for their high sorption ability of both polar and unipolar liquids. From this reason, commercial sponges are widely used for cleaning as they absorb a large amount of water, oil as well as their mixtures. These sponges do not preferentially absorb any of those components due to their balanced wettability. On the other hand, chemical and physical modifications of outer surfaces or in the bulk of the foams can significantly change their original wettability. These treatments ensure a suitable wettability of foams needed for an efficient water/oil or oil/water separation. MA and PU foams, dependently on the treatment, can be designed for both types of separations. The particular focus of this review is dealt with the separation of oil contaminants dispersed in water of various composition, however, an opposite case, namely a separation of water content from continuous oily phase is also discussed in some extent. In the former case, water is dominant, continuous phase and oil is dispersed within it at various concentrations, dependently on the source of polluted water. For example, waste waters associated with a crude oil, gas, shale gas extraction and oil refineries consist of oily impurities in the range from tens to thousands ppm [mg/L]. The efficient materials for preferential oil sorption should display significantly high hydrophobicity and oleophilicity and vice versa. This review is dealt with the various modifications of MA and PU foams for separating both oil in water and water in oil mixtures by identifying the chemical composition, porosity, morphology, and crosslinking parameters of the materials. Different functionalization strategies and modifications including the surface grafting with various functional species or by adding various nanomaterials in manipulating the surface properties and wettability are thoroughly reviewed. Despite the laboratory tests proved a multiply reuse of the foams, industrial applications are limited due to fouling problems, longer cleaning protocols and mechanical damages during performance cycles. Various strategies were proposed to resolve those bottlenecks, and they are also reviewed in this study. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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37 pages, 3937 KiB

Open AccessReview

Covalent Organic Frameworks: Synthesis, Properties and Applications—An Overview

by Tiago F. Machado, M. Elisa Silva Serra, Dina Murtinho, Artur J. M. Valente and Mu. Naushad

Polymers 2021, 13(6), 970; https://doi.org/10.3390/polym13060970 - 22 Mar 2021

Cited by 57 | Viewed by 14386

Abstract

Covalent Organic Frameworks (COFs) are an exciting new class of microporous polymers with unprecedented properties in organic material chemistry. They are generally built from rigid, geometrically defined organic building blocks resulting in robust, covalently bonded crystalline networks that extend in two or three dimensions. By strategically combining monomers with specific structures and properties, synthesized COF materials can be fine-tuned and controlled at the atomic level, with unparalleled precision on intrapore chemical environment; moreover, the unusually high pore accessibility allows for easy post-synthetic pore wall modification after the COF is synthesized. Overall, COFs combine high, permanent porosity and surface area with high thermal and chemical stability, crystallinity and customizability, making them ideal candidates for a myriad of promising new solutions in a vast number of scientific fields, with widely varying applications such as gas adsorption and storage, pollutant removal, degradation and separation, advanced filtration, heterogeneous catalysis, chemical sensing, biomedical applications, energy storage and production and a vast array of optoelectronic solutions. This review attempts to give a brief insight on COF history, the overall strategies and techniques for rational COF synthesis and post-synthetic functionalization, as well as a glance at the exponentially growing field of COF research, summarizing their main properties and introducing the numerous technological and industrial state of the art applications, with noteworthy examples found in the literature. Full article

(This article belongs to the Special Issue Hybrid Polymer Materials for Water Purification and Wastewater Treatment)

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