RESUMEN
Metal-organic frameworks (MOFs) are promising materials because of their high designability of pores and functionalities. Especially, MOF thin films and their properties have been investigated toward applications in nanodevices. Typically, MOF thin films are fabricated by using a bottom-up method such as layer-by-layer (LbL) growth in air. Because the water molecules can coordinate and be replaced with organic linkers during synthesis, humidity conditions will be expected to influence the LbL growth processes. In this study, we fabricated MOF thin films composed of Zn2+, tetrakis-(4-carboxyphenyl)-porphyrin (TCPP), and 4,4'-bipyridyl (bpy) at 10 and 40% relative humidity (RH) conditions. Then, we investigated the humidity effects on chemical compositions of TCPP and bpy, periodic structure, orientation, and surface morphology. At high RH, coordination replacement of water with the organic linkers becomes more competitive than that at low RH, resulting in a different TCPP/bpy composition ratio between the two RH conditions. Also, more frequent coordination replacements of water with the organic linkers at high RH led to the formation of phases other than that observed at low RH, loss of growth orientation, and rough surface. The findings clarified the importance of controlling the RH condition during LbL growth to obtain the desired coordination networks.
RESUMEN
We report dual-stimuli, thermo- and photostimuli, responsive chiral assemblies, of planar-chiral pillar[5]arenes with azobenzene groups on their rims. The azobenzene-substituted planar-chiral pillar[5]arenes were synthesized by copper(I)-catalyzed alkyne-azide cycloaddition "click" reaction of azide-substituted planar-chiral pillar[5]arenes containing S or R stereogenic carbon atoms with an alkyne-substituted azobenzene. These decaazides with stereogenic carbons could act as starting points for a large library of planar-chiral pillar[5]arenes. Homeotropic alignment of azobenzenes, caused by the mesogenic property of the azobenzene groups, was induced by annealing a film of the azobenzene-substituted planar-chiral pillar[5]arenes. The alignment resulted in chiral propagation from the planar-chiral pillar[5]arene cores to the azobenzene area and caused significant chiral amplification consequently. These aligned chiral assemblies were collapsed by trans to cis photoisomerization of the azobenzene groups, resulting in chiral amplification off, and reconstructed by cis to trans thermo-isomerization, again turning on the chiral amplification.
RESUMEN
Nanometer thin films of Nafion ionomer interfaced with platinum form the functional electrodes in many electrochemical devices including fuel cells and electrolyzers. To impart facile proton conduction in a Nafion ionomer, sufficient hydration of the Nafion ionomer is necessary to create a percolating network of water-filled nanometer-sized hydrophilic domains that manifest as macroscopic swelling. This hydration behavior of the ionomer thin films is poorly understood especially for films confined on electrochemically relevant Pt substrates. In this work, we present the evolution of hydration-dependent microscopic hydrophilic domains and macroscopic expansion of a 55 nm thin Nafion film on a Pt substrate. The cross-correlation among the film macro-expansion from ellipsometry, the micro-expansion from GISAXS, and the water distribution from neutron reflectometry (NR) explains the observed non-affine behavior of the film which can be attributed to the randomly and spatially non-uniform distribution of water domains. A correlation between the macroscopic factor (ε/τ) for protonic conductivity, and the domain size and swelling is presented for the first time. In addition, interfacial water between Pt and the ionomer interface is estimated at 75% and 84% RH, and an increase in domain size with RH is discussed to explain the increased activity and oxygen diffusivity with RH.