Perfluorinated conjugated microporous polymer for targeted capture of Ag(I) from contaminated water.

The maximum targeted capture silver from contaminated water is urgently necessary for sustainable development. Herein, the perfluorination conjugated microporous polymer adsorbent (F-CMP) has been fabricated by Sonogashira-Hagihara coupling reaction and employed to remove Ag(I) ions. Characterizations of NMR, XPS and FT-IR indicate the successful synthesis of F-CMP adsorbent. The influence factors of F-CMP on Ag(I) adsorption behavior are studied, and the adsorption capacity of Ag(I) reaches 251.3 mg/g. The experimental results of isothermal adsorption and kinetic adsorption are consistent with the Freundlich model and pseudo-second-order isothermal adsorption model, which follows a multilayer adsorption behavior on the uniform surface of the adsorbent, and the chemical adsorption becomes the main rate-limiting step. Combined with DFT calculation, the adsorption mechanism of Ag(I) by F-CMP is elucidated. The peaks shift of sp before and after adsorption is larger than that of F1s, suggesting that the -CC- on the F-CMP becomes the dominant chelation site of Ag(I). Furthermore, F-CMP exhibits specific adsorption for Ag(I) in polymetallic complex water, with the maximum selectivity coefficient of 31.5. Our study may provide a new possibility of perfluorinated CMPs for effective capture of Ag(I) ions to address environmental issues.

Insights into ion imprinted membrane with a delayed permeation mechanism for enhancing Cd2+ selective separation.

Ion imprinted polymers exhibit great potential in ion separation from wastewater. However, the difficulty of ion separation by membrane is proverbial, which severely restricts the application of membrane in metal resource recovery from industrial wastewater. Herein, a rational molecular-level design approaches for membrane fabrication was developed to modify a layer of ion imprinted polymer onto the PVDF membrane. Batch rebind and permeation experiments suggest that specific host-guest binding sites had been fabricated along the membrane pore in ion imprinted membranes (IIM). A higher monomer dose leads to a higher rejection of Cd2+, and the more bind sites in IIM. The binding of IIM to Cd2+ was 1.84 times that of non-ion imprinted membranes (NIM). Permselectivity factors (γ) of IIM are larger than 5.39 in mixture ions solutions. Chemical characterization and density functional theory (DFT) calculation reveal that the Cd2+ recognition sites of functional groups are C-S and C˭S. Cd2+ mass transport in IIM suggest that the imprint effects provide a binding force that would delay Cd2+ to permeate through IIM, so as to selectively separate Cd2+ with other ions. The imprint effects may enlighten a novel molecular-level design approaches for membrane fabrication to enhance the selectivity of ion-ion.

Conducting polymer hydrogels as a sustainable platform for advanced energy, biomedical and environmental applications.

Environmentally friendly polymeric materials and derivative technologies play increasingly important roles in the sustainable development of our modern society. Conducting polymer hydrogels (CPHs) synergizing the advantageous characteristics of conventional hydrogels and conducting polymers are promising to satisfy the requirements of environmental sustainability. Beyond their use in energy and biomedical applications that require exceptional mechanical and electrical properties, CPHs are emerging as promising contaminant adsorbents owing to their porous network structure and regulable functional groups. Here, we review the currently available strategies for synthesizing CPHs, focusing primarily on multifunctional applications in energy storage/conversion, biomedical engineering and environmental remediation, and discuss future perspectives and challenges for CPHs in terms of their synthesis and applications. It is envisioned to stimulate new thinking and innovation in the development of next-generation sustainable materials.

High exposure effect of the adsorption site significantly enhanced the adsorption capacity and removal rate: A case of adsorption of hexavalent chromium by quaternary ammonium polymers (QAPs).

Enhancing the performance of adsorbents to the utmost extent is an objective but challenging in applying adsorption technology to wastewater treatment. In this work, novel quaternary ammonium polymers (QAPs) with high density adsorption site (i.e., quaternized N, confirmed by FT-IR results) were designed and prepared for rapid selective removal of Cr(VI) from water. The results of EDS analysis indicated the maximum exposure rate of N on the surface of QAPs was as high as 86.1%, which almost doubled comparing to that of Cr(VI) ions imprinted polymers (Cr(VI)-IIP) (46.2%). Interestingly, the maximum adsorption capacity (211.8 mg/g) and initial adsorption rate (h0, 66.6 mg/ (g·min)) of QAPs (i.e., 5:1(TRIM)) for Cr(VI) are about 3.6 times and 4.9 times those of Cr(VI)-IIP (63.0 mg/g and 13.5 mg/(g·min)), respectively. Impressively, flow-through adsorption experiments demonstrated 5:1(TRIM) can completely remove 5 mg/L of Cr(VI) within five seconds. Additionally, 5:1(TRIM) exhibited a remarkable selectivity for Cr(VI) adsorption, and high purity (100%) of chromium can be readily obtained. The proposed idea of high exposure effect of the adsorption site can provide a valuable guidance for designing rapid selective adsorbents to remove and reclaim Cr(VI) from wastewater.

Comparison of novel functionalized nanofiber forward osmosis membranes for application in antibacterial activity and TRGs rejection.

Antibiotic resistance genes (ARGs) are serious pollutants in municipal sewage treatment plants and may cause significant harm to ecological systems, microbial fouling is also inevitable in membrane process. Herein, novel forward osmosis (FO) membranes made of electrospun nanofibers (TFN0) and further impregnated with titanium dioxide (TiO2) (TFN1) nanoparticles and titanium dioxide/silver composite nanoparticles (TiO2/AgNPs) (TFN2). The FO membranes were used to compare the antimicrobial performance and rejection of tetracycline-resistant genes (TRGs). Characterizations revealed that the TiO2/AgNPs were evenly scattered in the polysulfone (PSf) nanofibers and resulted in a TFN2 membrane that exhibited excellent physicochemical properties, filtration, and antibiofouling performance in real wastewater. The cell viability analysis revealed that the antibacterial effect of the TFN2 membranes was significantly better than that of TFN1, as indicated by about 65 % of E. coli cells killed after contact with the TFN2 membrane. TFN2 membranes had greater rejection rates of TRB and TRGs than TFN1. The TRG permeation rates of the TFN2 membrane in the FO mode (active layer facing the feed solution) were 39.62 % and 33.02 % lower than the TFN0 and TFN1 membranes, respectively. FO membranes modified by the TiO2/AgNPs nanocomposites hold promise to remove ARGs and pathogens from wastewater treatment plant effluents.

Building electrode with three-dimensional macroporous interface from biocompatible polypyrrole and conductive graphene nanosheets to achieve highly efficient microbial electrocatalysis.

Bioelectrochemical systems (BESs) possess a great potential for simultaneous wastewater treatment and energy recovery. Rational construction of electrode materials could significantly improve the BESs performance. Three-dimensional macroporous electrode interface with high conductivity is highly desirable but challenging. In this work, we report a hierarchically nanostructured reduced graphene oxide nanosheets-polypyrrole (rGO@PPy) electrode via one-step electrodeposition technique. The prepared electrode was comprehensively studied by scanning/transmission electron microscopy, Raman spectroscopy, X-ray diffraction and electrochemical measurements, which showed that the rGO@PPy possessed a three-dimensional macroporous interconnecting scaffold with superior conductivity. The rGO@PPy electrode was utilized in Geobacter sulfurreducens inoculated BESs, and the maximum current density was 4.10 ±â€¯0.02 mA cm-2, which is 8-fold higher than that of a rGO electrode (0.51 ±â€¯0.03 mA cm-2), and is among the best performance reported for two-dimensional electrodes. The improved performance is ascribed to ultrahigh biomass concentration induced by "best match scale" between rGO@PPy and microbes, excellent extracellular electron transfer, as well as enhanced microbial affinity through the adequate exposure of biocompatible PPy layers. This work demonstrated a synergistic effect between rGO and PPy for the BESs performance improvement, and provided a new insight to design and fabricate a high-performance bioelectrode.

Development of an anion imprinted polymer for high and selective removal of arsenite from wastewater.

A novel cyclic functional monomer (CFM) was used to develop an As(III)-ion imprinted polymer (As-IIP). CFM possesses a positively charged imidazolium moiety and its specific cyclic size matches that of As(III). Batch adsorption experiments showed that the As-IIP has a maximum As(III) adsorption capacity of 55 mg/g, while that of the control polymer (CP) is only 25 mg As(III)/g. Adsorption isotherms for As(III) agree with the Langmuir model, suggesting monolayer adsorption. Kinetic studies showed that the adsorption process followed pseudo-second-order kinetics. The relative selectivity coefficients of As-IIP compared to CP for Cl-/H2AsO3-, SO42-/H2AsO3-, HPO42-/H2AsO3-, NO3-/H2AsO3-, and Mo7O246-/H2AsO3- are 1.03, 1.95, 2.55, 1.52 and 2.51, respectively. The removal efficiency of As-IIP for As(III) in actual industrial wastewater was nearly 100%, which confirms that As-IIP has a high adsorption capacity as well as selectivity for the removal of As(III) from wastewater.

Visible-light photocatalytic degradation performances and thermal stability due to the synergetic effect of TiO2 with conductive copolymers of polyaniline and polypyrrole.

Conductive polypyrrole-polyaniline/TiO2 nanocomposites (PPy-PANI/TiO2) were prepared by in situ oxidative copolymerization of pyrrole and aniline monomers in the presence of TiO2. For comparison studies, polypyrrole/TiO2 (PPy/TiO2) and polyaniline/TiO2 (PANI/TiO2) were also prepared. The samples were characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, zeta potential analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis and photocurrent tests. In contrast to PPy/TiO2 and PANI/TiO2, PPy-PANI/TiO2 exhibits obvious absorption in the visible-light range, and is much superior to PPy/TiO2 and PANI/TiO2 in thermal stability. It is found that PPy-PANI/TiO2 performs well in the visible-light photocatalytic degradation of 4-nitrophenol. The optimized pyrrole : aniline : TiO2 molar ratio for best performance is 0.75 : 0.25 : 100. The efficacy of PPy-PANI/TiO2 is attributed to its conductivity, conjugated structure, as well as to the synergy amidst polypyrrole, polyaniline and TiO2.

Removal of water-soluble acid dyes from water environment using a novel magnetic molecularly imprinted polymer.

Novel magnetic and hydrophilic molecularly imprinted polymers (mag-MIPs) were prepared by an inverse emulsion-suspension polymerization to remove water-soluble acid dyes from contaminated water with 1-(α-methyl acrylate)-3-methylimidazolium bromide (1-MA-3MI-Br) being utilized as a new functional monomer. The thermal stability, chemical structure and magnetic property of the 1-MA-3MI-Br-mag-MIPs were characterized by the thermal-gravimetric analyzer (TGA), Fourier transform infrared spectrometer (FT-IR) and vibrating sample magnetometer (VSM), respectively. Moreover, effect of concentration and pH value of water-soluble acid dye solutions was optimized. Compared with the methyl acrylic acid and 4-vinylpyridine modified mag-MIPs, the 1-MA-3MI-Br-mag-MIPs showed enhanced removal efficiency. Kinetic studies depicted that the adsorption process on 1-MA-3MI-Br-mag-MIPs followed pseudo-second-order rate mechanism. Investigation results of 5 times removal-regeneration cycles by employing the 1-MA-3MI-Br-mag-MIPs showed that the resulting material was with high stability.

Novel Cu (II) magnetic ion imprinted materials prepared by surface imprinted technique combined with a sol-gel process.

A novel Cu (II) magnetic ion-imprinted polymer (MIIP) was synthesized by surface imprinting technique combined with a sol-gel process. The adsorbent of Cu (II)-MIIP shows higher capacity and selectivity than that of magnetic non-imprinted polymers (MNIP). Adsorption capacities of Cu (II)-MIIP and MNIP are 24.2 and 5.2mg/g for Cu (II) ions, respectively. The selectivity coefficients of the Cu (II)-MIIP for Cu (II)/Zn (II) and Cu (II)/Ni (II) are 91.84 and 133.92, respectively. Kinetics studies show that the adsorption process obeys pseudo-second-order rate mechanism with an initial adsorption rate of 132.48 for Cu (II)-MIIP and 2.41mgg(-1)min(-1) for MNIP. In addition, no obvious decrease was observed after up to five adsorption cycles, indicating that the Cu (II)-MIIP is of high stability.