The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

The development of high-temperature PEM fuel cells (working at 150–200 °C) is pursued worldwide in order to solve some of the problems of current cells based on Nafion® (CO tolerance, improved kinetics, water management, etc.). Polybenzimidazole membranes nanoimpregnated with phosphoric acid have been studied as electrolytes in PEMFCs for more than a decade. Commercially available polybenzimidazole (PBI) has been the most extensively studied and used for this application in membranes doped with all sorts of strong inorganic acids. In addition to this well-known polymer we also review here studies on ABPBI and other polybenzimidazole type membranes. More recently, several copolymers and related derivatives have attracted many researchers' attention, adding variety to the field. Furthermore, besides phosphoric acid, many other strong inorganic acids, as well as alkaline electrolytes have been used to impregnate benzimidazole membranes and are analyzed here. Finally, we also review different hybrid materials based on polybenzimidazoles and several inorganic proton conductors such as heteropoly acids, as well as sulfonated derivatives of the polymers, all of which contribute to a quickly-developing field with many blooming results and useful potential which are the subject of this critical review (317 references).

Proton-conducting membranes based on benzimidazole polymers for high-temperature PEM fuel cells. A chemical quest

In nature, the biological membrane can selectively transport essential small molecules/ions through facilitated diffusion via carrier proteins. Intrigued by this phenomenon and principle, membrane researchers have successfully employed synthetic carriers and carrier-mediated reversible reactions to enhance the separation performance of synthetic membranes. However, the existing facilitated transport membranes as well as the relevant facilitated transport theories have scarcely been comprehensively reviewed in the literature. This tutorial review primarily covers the two aspects of facilitated transport theories: carrier-mediated transport mechanisms and facilitated transport chemistries, including the design and fabrication of facilitated transport membranes. The applications of facilitated transport membranes in energy-intensive membrane processes (gas separation, pervaporation, and proton exchange membrane fuel cells) have also been discussed. Hopefully, this review will provide guidelines for the future research and development of facilitated transport membranes with high energy efficiency.

Facilitated transport of small molecules and ions for energy-efficient membranes

Anti-fouling and anti-bacterial polyethersulfone (PES) membranes were developed by the addition of poly(2-dimethylaminoethyl methacrylate) grafted silica nanoparticles (SiO2-g-PDMAEMA NPs) and further post-quaternization. The SiO2-g-PDMAEMA NPs were first synthesized by grafting PDMAEMA brushes from SiO2 NPs via surface-initiated, reversible addition fragmentation chain transfer (RAFT) polymerization. PES/SiO2-g-PDMAEMA hybrid ultrafiltration (UF) membranes were then prepared from the blending solutions of PES and SiO2-g-PDMAEMA NPs via non-solvent induced phase separation (NIPS) process. The PDMAEMA chains incorporated into the PES membranes were further quaternized by reacting with 1,3-propane sultone (1,3-PS) and methyl iodide (CH3I), respectively. After treatment with 1,3-PS, the resulting zwitterionic PES membranes exhibited excellent hydrophilicity, water permeability, solute rejection and protein anti-fouling properties. The cationic membranes obtained from CH3I treatment showed strong anti-bacterial activity against Escherichia coli (E. coli) and Staphyloccocus aureus Rosenbach (S. aureus). This work presents a convenient strategy for anti-biofouling modification of polymer membranes via surface quaternization of the reactive SiO2-g-PDMAEMA NPs additive.

Anti-fouling and anti-bacterial polyethersulfone membranes quaternized from the additive of poly(2-dimethylamino ethyl methacrylate) grafted SiO2 nanoparticles

High temperature operation of proton exchange membrane fuel cells under ambient pressure has been achieved by using phosphoric acid doped polybenzimidazole (PBI) membranes. To optimize the membrane and fuel cells, high performance polymers were synthesized of molecular weights from 30 to 94 kDa with good solubility in organic solvents. Membranes fabricated from the polymers were systematically characterized in terms of oxidative stability, acid doping and swelling, conductivity, mechanical strength and fuel cell performance and durability. With increased molecular weights the polymer membranes showed enhanced chemical stability towards radical attacks under the Fenton test, reduced volume swelling upon the acid doping and improved mechanical strength at acid doping levels of as high as about 11 mol H3PO4 per molar repeat polymer unit. The PBI-78kDa/10.8PA membrane, for example, exhibited tensile strength of 30.3 MPa at room temperature or 7.3 MPa at 130 °C and a proton conductivity of 0.14 S cm–1 at 160 °C. Fuel cell tests with H2 and air at 160 °C showed high open circuit voltage, power density and a low degradation rate of 1.5 μV h–1 at a constant load of 300 mA cm–2.

High Molecular Weight Polybenzimidazole Membranes for High Temperature PEMFC

Despite the myriad studies on polybenzimidazole based polymer electrolyte membranes for fuel cells operating above 100 °C, the development of membranes with higher proton conductivity without compromising mechanical stability has continued to be the prime challenge. In this article, organic/inorganic hybrid nanocomposites of poly (4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI) were prepared with surface functionalized silica nanoparticles to address this key issue. Structural and morphological studies probed by SAXS, WAXD and TEM, respectively revealed the formation of self-assembled clusters of nanoparticles when the OPBI nanocomposites were made with amine modified silica (AMS) whereas a well dispersed structure was obtained for OPBI and the unmodified silica (UMS) composite. The OPBI/AMS nanocomposites displayed a significant enhancement in the thermal stabilities compared to the pristine OPBI and OPBI/UMS nanocomposite. The OPBI/AMS nanocomposite membranes exhibited a larger mechanical reinforcement than the pristine OPBI and OPBI/UMS nanocomposite. The formation of nanoparticle clusters in the OPBI matrix in the case of OPBI/AMS was found to be the driving force for the higher thermal and mechanical stability of OPBI/AMS than those of OPBI/UMS. The incorporation of AMS in the OPBI matrix shielded the polymer chains from the attack of oxidative radicals, resulting in a huge enhancement of oxidative stability of the nanocomposite membranes compared to the pure OPBI membrane. The OPBI/AMS nanocomposite membranes have significantly higher phosphoric acid (PA) loading compared to the pure OPBI membrane which resulted in the higher proton conductivities of the former. The self-assembled clusters of AMS in the OPBI matrix facilitated the proton transport process.

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Polybenzimidazole/silica nanocomposites: Organic-inorganic hybrid membranes for PEM fuel cell

In this work, a series of poly(4,4′-diphenylether-5,5′-bibenzimidazole)s (OPBIs) were synthesized from 4,4′-oxybis(benzoic acid) and 3,3′,4,4′-tetraaminobiphenyl through the variation of the initial monomer concentration with a solution polycondensation technique in a poly(phosphoric acid) medium. The resulting polymers were characterized by various techniques such as infrared (IR), nuclear magnetic resonance, dynamic mechanical analysis (DMA), and thermogravimetric analysis. The initial monomer concentration in the polymerization mixture played an important role in controlling the molecular weight of the resulting polymers. A temperature-dependent IR study showed that the free movement of the NH group of the imidazole ring was blocked by the absorbed moisture. The DMA study showed that the glass-transition temperature (Tg) varied with the molecular weight, and the presence of the ether linkage in the OPBI polymer backbone had a significant influence on Tg. A high-molecular-weight OPBI polymer tended to form a supramolecular organization, which influenced the thermal characteristic of the polymer. Photophysical studies demonstrated the fluorescent characteristics of the OPBI polymers in both solid and solution states. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

How the monomer concentration of polymerization influences various properties of polybenzimidazole: A case study with poly(4,4′‐diphenylether‐5,5′‐bibenzimidazole)

Polybenzimidazole gel membrane for the use in fuel cell

Polymer nanocomposites of poly (4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI) were prepared with two structurally different organoclays, namely, montmorillonite (OMMT) and kaolinite (OKao), to evaluate the effect of clay structures on the nanocomposites morphology, structure, and the properties. Solid State 13C cross-polarization magic-angle spinning nuclear magnetic resonance, small-angle X-ray diffraction, and transmission electron microscopy studies suggested the formation of exfoliated structure for OPBI/OMMT, whereas and intercalated structure was obtained for OPBI/OKao. Both the nanocomposites displayed significant enhancement in the thermal stabilities compared to the pristine OPBI, and the higher thermal stability of OPBI/OMMT than that of OPBI/OKao was attributed to the higher degree of dispersion of the nanoclay into the OPBI matrix owing to the exfoliated structure of the former. Both the nanocomposites membranes exhibited large mechanical reinforcement by the clays and the superior mechanica...

Sandip Ghosh

Papers

Polybenzimidazole/silica nanocomposites: Organic-inorganic hybrid membranes for PEM fuel cell

How the monomer concentration of polymerization influences various properties of polybenzimidazole: A case study with poly(4,4′‐diphenylether‐5,5′‐bibenzimidazole)

Polybenzimidazole gel membrane for the use in fuel cell

Role of Clays Structures on the Polybenzimidazole Nanocomposites: Potential Membranes for the Use in Polymer Electrolyte Membrane Fuel Cell

N-alkyl polybenzimidazole: Effect of alkyl chain length