Nanosized Proton Conductor Array with High Specific Surface Area Improves Fuel Cell Performance at Low Pt Loading.

The use of ordered catalyst layers, based on micro-/nanostructured arrays such as the ordered Nafion array, has demonstrated great potential in reducing catalyst loading and improving fuel cell performance. However, the size (diameter) of the basic unit of the most existing ordered Nafion arrays, such as Nafion pillar or cone, is typically limited to micron or submicron sizes. Such small sizes only provide a limited number of proton transfer channels and a small specific area for catalyst loading. In this work, the ordered Nafion array with a pillar diameter of only 40 nm (D40) was successfully prepared through optimization of the Nafion solvent, thermal annealing temperature, and stripping mode from the anode alumina oxide (AAO) template. The density of D40 is 2.7 × 1010 pillars/cm2, providing an abundance of proton transfer channels. Additionally, D40 has a specific area of up to 51.5 cm2/cm2, which offers a large area for catalyst loading. This, in turn, results in the interface between the catalyst layer and gas diffusion layer becoming closer. Consequently, the peak power densities of the fuel cells are 1.47 (array as anode) and 1.29 W/cm2 (array as cathode), which are 3.3 and 2.9 times of that without array, respectively. The catalyst loading is significantly reduced to 17.6 (array as anode) and 61.0 µg/cm2 (array as cathode). Thus, the nanosized Nafion array has been proven to have high fuel cell performance with low Pt catalyst loading. Moreover, this study also provides guidance for the design of a catalyst layer for water electrolysis and electrosynthesis.

Specially Treated Aramid Fiber Stabilized Gel-Emulsions: Preparation of Porous Polymeric Monoliths and Highly Efficient Removing of Airborne HCHO.

Porous polymeric monoliths with densities as low as ≈0.060 g cm-3 are prepared in a gel-emulsion template way, of which the stabilizer employed is a newly discovered acidified aramid fiber that is so efficient that 0.05% (w/v, accounts for continuous phase) is enough to gel the system. The porous monoliths as obtained can be dried at ambient conditions, avoiding energy-consuming processes. Importantly, the monoliths show selective adsorption to HCHO, and the corresponding adsorption capacity (M6) is ≈2700 mg g-1 , the best result that is reported until now. More importantly, the monoliths can be reused after drying.

Salt Tunable Rheology of Thixotropic Supramolecular Organogels and Their Applications for Crystallization of Organic Semiconductors.

Physical gelation behaviors of a series of novel bisurea-based derivatives bearing fatty alkyl tertiary amine moieties have been explored in water and common organic solvents. One of these amines exhibits very good thixotropic gels in apolar aromatic solvents (e.g., xylenes). The corresponding sol-gel transition is instantaneous and could be repeated for at least 50 cycles. Interestingly, the elasticity and strength of the resulting gels can be remarkably enhanced initially by the addition of a trace amount of tetrabutylammonium acetate (TBA) followed by a subsequent drop with further salt addition. Temperature-dependent 1H NMR confirmed that hydrogen bonding is the main driving force for the physical gelation. TEM, rheology, 1H NMR titration, and examination of critical gelation concentration (CGC) reveal that the phenomenon is due to the dominated effects, the salting out effect at lower TBA concentration, or the anion-urea hydrogen bonding at higher TBA concentration. Furthermore, the obtained transparent gels in this work can be used as good media for growing crystals of several organic semiconductors.

New solvatochromic probes: performance enhancement via regulation of excited state structures.

A new fluorescent conjugate (PNBD) with a structure of D-π-A was designed and synthesized, where the donor (D), the acceptor (A) and the bridge (π) are naphthalyl, dicyanovinyl and phenylethynyl-phenylethynyl, respectively. To improve the solubility of the conjugate, two long alkyl chains were introduced as substituents of the central aromatic ring. Spectroscopic studies demonstrated that PNBD is a strongly solvatochromic probe which is characterized by a large molar absorption coefficient (>32 000 cm-1 M-1), long wavelength absorption (>410 nm), large solvatochromic emission range (470-650 nm), high photochemical stability, and good solubility in common organic solvents. The fluorescent quantum yield of PNBD is limited in some polar solvents due to dual emission, a phenomenon ascribed to radiative decay from a higher excited singlet state. To eliminate dual emission, a covalently bound dimer (BPNBD) of PNBD characterized by weak vibronic coupling, was designed and synthesized. The dimer constituents are linked by a single bond between the naphthalyl moieties of the two PNBD monomers. As expected, BPNBD maintains almost all the strong points of the monomer, exhibits a substantial increase in fluorescence quantum yield, and eliminates dual emission by facilitating efficient internal conversion. Importantly, the use of PNBD and BPNBD in concert provides unprecedented discrimination among solvents of similar structures, such as (CH2Cl2, CHCl3, CCl4), (ethyl ether, THF, dioxane), or (methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol), allowing rapid and selective visual identification.