Synthesis and characterization of poly(para-phenylene disulfonic acid), its copolymers and their n-alkylbenzene grafts as proton exchange membranes: high conductivity at low relative humidity

Si, Kun; Dong, Daxuan; Litt, Morton H.

doi:10.1039/c2jm33066k

Cited by 51 publications

(74 citation statements)

References 35 publications

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“…[ 38 ] Following the fi t line in Figure 4 , we can predict that sensitivities of ≈0.66 nm/% RH should be achievable for the same cubes on thinner Nafi on fi lms, with even greater enhancements possible using larger NCs with sharper corners and new materials with greater expansion coeffi cients. [ 39 ] Another approach to measuring RH change is to illuminate the sample with monochromatic light with a resonance chosen so that under ambient conditions the illumination wavelength falls approximately half way up the scattering peak ( Figure 5 a). Using monochromatic light allows for faster and more precise observation of a signal change, and is a more scalable method as it does not require a bulky and expensive spectrometer to measure shifts.…”

Section: Full Paper Full Paper Full Papermentioning

confidence: 99%

Plasmonic Gas Sensing Using Nanocube Patch Antennas

Powell

Coles

Taylor

et al. 2016

Advanced Optical Materials

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of interest and be as sensitive as possible to small changes in the local environment. While individual particle resonances can be effectively tuned through size, shape and material choice, [ 2,12 ] coupled modes between two or more nanoparticles have been shown to exhibit far greater electric fi eld enhancements and produce more sensitive detectors. [13][14][15][16][17][18] However, these are extremely diffi cult to fabricate, with many top-down lithographic and FIBbased examples being unrealistic for scaling up, and bottom-up techniques that generally produce randomly oriented particle pairs with no control over the alignment, which is key as the resonances of such dimers are highly sensitive to the polarization of incident illumination. Henzie et al. made some important progress in this fi eld by using a gravity-driven technique to assemble nanoparticles in shallow pits in a substrate, which allows excellent control over orientation and positioning of any number of particle sets. [ 19 ] Another elegant solution to the fabrication problem is the placement of a metallic particle above a metal sheet separated by a thin spacer. A "mirror particle" is excited in the metal plane, which produces a strong coupling effect without having to align two separate particles, drastically simplifying the production process. [ 22 ] There is a growing body of work investigating the properties of silver nanocubes (NCs) above metal fi lms, to tune their scattering properties, [ 21 ] produce controlled-refl ectance surfaces, [ 22 ] and to control and enhance the radiative processes of fl uorophores within the spacer material, [ 23,24 ] as well as theoretical studies looking to build a complete description of the structure. [ 25,26 ] This system can be considered an optical patch antenna, where gap plasmon modes are supported between the metal sheet and the NC. [ 21 ] The resonant modes of these antennae are extremely sensitive to the properties of the spacer layer separating the NC and the silver sheet, and any environmental changes that infl uence the refractive index (RI), or more importantly the thickness of the chosen material will produce signifi cant changes in the plasmon resonance. As long as spacer materials which expand in response to a given analyte are available, this design can be utilized to detect any number of chemicals. This forms the basis for a new type of sensor, which can operate equally well in a gaseous or liquid setting (depending on spacer choice) and that is scalable from the sub-wavelength scale (the footprint of one nanocube) up to a large-surface area metamaterial.In this paper, we demonstrate the operation of the nanocube patch antenna system as a gas sensor for the fi rst time, usingThe ability of individual nanocube patch antennas, consisting of a silver nanocube separated from an Ag sheet by a thin fl uoropolymer spacer, to act as subwavelength sensing elements is demonstrated. An increase in relative humidity (RH) causes the spacer to expand, which alters the resonance of the plasmon cavity mode fo...

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Section: Full Paper Full Paper Full Papermentioning

confidence: 99%

Plasmonic Gas Sensing Using Nanocube Patch Antennas

Powell

Coles

Taylor

et al. 2016

Advanced Optical Materials

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“…Another approach is PEMs with high IEC; increasing the IEC is an effective way to increase the conductivity at low RH because it increases the charge carrier concentration and the diffusion coefficient of water, greatly influencing the ionic mobility. Recently, very high IEC (3−8 mequiv/g) PEMs based on sulfonated poly(phenylene sulfone), 53,105 polyphenylene, 63,64 and poly(arylene ether sulfone) 106,107 were reported, which exhibited proton transport nanochannels. However, they tend to be extremely brittle in the dry state and are either soluble or swell excessively in water.…”

Section: Proton Exchange Membranesmentioning

confidence: 99%

Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers

2014

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/npsi/ctrl?lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?lang=fr Access and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1021/ma402254h Macromolecules, 47, 7, pp. 2175Macromolecules, 47, 7, pp. -2198Macromolecules, 47, 7, pp. , 2014 Ion transport by nanochannels in ion-containing aromatic copolymers Li, Nanwen; Guiver, Michael D. Ion Transport by Nanochannels in Ion-Containing Aromatic CopolymersThe search for the next generation of highly ion-conducting polymer electrolyte membranes has been a subject of intense research because of their potential applications in energy storage and transformation devices, such as fuel cells, vanadium flow batteries, membrane-based artificial photosynthesis, water electrolysis, or water treatment processes such as electrodialysis desalination. Nanochannels that contain ionic groups, through which "hydrated" ions can pass, are believed to be of key importance for efficient ion transport in polymer electrolytes membranes. In this Perspective, we present an overview of the approaches to induce ion-conducting nanochannel formation by selfassembly, using polymer architecture such as block or combshaped copolymers. The transport properties of ion-containing aromatic copolymers are examined to obtain an insight into the fundamental behavior of these materials, which are targeted toward applications in fuel cells and other electrochemical devices. Challenges in obtaining well-defined nanochannel morphologies, and possible strategies to improve transport properties in aromatic copolymers having structures with the potential to withstand operation in electrochemical/chemical devices, are discussed. Opportunities for the application of ion-containing aromatic copolymer membranes in fuel cells, vanadium flow batteries, membrane-based artificial photosynthesis, electrolysis, and electrodialysis are also reviewed. Research needs for further improvements in ionic conductivity and durability, and their applications are identified.

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“…Even a slight change in the polymer structures, e.g., architectures (random, 14,15 block, 16,17 graft, 18,19 etc.) or chain types (main chain, 20 such as the dramatic swelling, which might be the biggest challenge for practical application of those membranes.…”

Section: Introductionmentioning

confidence: 99%

Polymer Electrolyte Membranes Based on Multiblock Poly(phenylene ether ketone)s with Pendant Alkylsulfonic Acids: Effects on the Isomeric Configuration and Ion Transport Mechanism

Zhang

Dong

et al. 2015

J. Phys. Chem. C

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Two structural variations of multi-block poly(phenylene ether ketone)s (bSPPEKs) with pendant alkylsulfonic acids were prepared by a polycondensation reaction between oligomeric difluoroand diphenoxide-precursors, followed by successive demethylation and sulfonation processes.Two isomers, bis[4-fluoro-3-(4'-methoxylbenzoyl)]biphenyl (p-BFMBP) and bis[5-fluoro-2-(4'-methoxylbenzoyl)]biphenyl (m-BFMBP), were prepared as the difluoro-starting monomers. The corresponding polymer membranes were obtained with good mechanical stability to facilitate the further characterizations. The morphology of bSPPEKs was confirmed by atomic force microscopy (AFM), from which the distinct phase separation could be identified with the average hydrophilic domain size of ca. 15-20 nm for the m-bSPPEKs. It is worth noting that both m-and p-bSPPEKs show quite comparable, or even better, ion conduction capacities than commercially available Nafion membrane, especially under low relative humidity conditions (30-50%), suggesting their promising future as polymer electrolyte membrane candidates.Meanwhile, the proton conductivities of all the m-bSPPEKs were found to be greater than those of the p-bSPPEKs over the entire relative humidity range, indicating better water-retention capacity and lower resistance to the ion transport. In addition, molecular dynamics simulation (MDS) was employed to extensively explore the structure-property relationship between the two polymers. The length, angle and torsion distribution results clearly reveal their steric configurations, i.e., a longer length and smaller angle in the side chain, together with a smaller torsion angle in the main chain for m-bSPPEKs, which produces slightly more free volume inside the polymer matrix. Analysis of the diffusion coefficients and coordination numbers shows that there is more water clustering around the sulfonic acid groups in the meta-polymers, than in the para-polymers.

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Synthesis and characterization of poly(para-phenylene disulfonic acid), its copolymers and their n-alkylbenzene grafts as proton exchange membranes: high conductivity at low relative humidity

Cited by 51 publications

References 35 publications

Plasmonic Gas Sensing Using Nanocube Patch Antennas

Plasmonic Gas Sensing Using Nanocube Patch Antennas

Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers

Polymer Electrolyte Membranes Based on Multiblock Poly(phenylene ether ketone)s with Pendant Alkylsulfonic Acids: Effects on the Isomeric Configuration and Ion Transport Mechanism

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