An ideal material for photon harvesting must allow control of the exciton diffusion length and directionality. This is necessary in order to guide excitons to a reaction center, where their energy can drive a desired process. To reach this goal both of the following are required; short- and long-range structural order in the material and a detailed understanding of the excitonic transport. Here we present a strategy to realize crystalline chromophore assemblies with bespoke architecture. We demonstrate this approach by assembling anthracene dibenzoic acid chromophore into a highly anisotropic, crystalline structure using a layer-by-layer process. We observe two different types of photoexcited states; one monomer-related, the other excimer-related. By incorporating energy-accepting chromophores in this crystalline assembly at different positions, we demonstrate the highly anisotropic motion of the excimer-related state along the [010] direction of the chromophore assembly. In contrast, this anisotropic effect is inefficient for the monomer-related excited state.
Development of surface coatings with high antimicrobial activity is urgently required to fight bacteria and other microorganisms on technical and hygiene relevant surfaces. Control over structure and topology of the surface coatings, combined with the ability to include functional molecules within the structure, is crucial for optimizing their performance. Herein, we describe a novel strategy to synthesize structurally well-defined porphyrin polymer thin films via a template approach. In this approach, bisazido-functionalized porphyrin molecules are preorganized within a metal-organic framework (MOF) structure. Afterward, porphyrin units within the MOF are covalently connected via a secondary linker. Removal of the metal ions of the MOF results in water-stable porphyrin polymer thin films that demonstrate high antibacterial activity against pathogens via visible-light-promoted generation of reactive oxygen species. In addition, this approach offers the inherent possibility to incorporate guest molecules within the structures, to functionalize the surface with biomolecules, and to create hierarchically structured materials.
In this work, microporous layer (MPL) degradation was investigated through the characterization of polymer electrolyte membrane (PEM) fuel cell performance and in situ liquid water visualizations. While both the MPL and carbon fiber substrate underwent ex situ carbon corrosion-based degradation, the degradation of the MPL has the most significant impact on the electrochemical performance and the liquid water distribution within the operating PEM fuel cell. Specifically, MPL degradation resulted in larger quantities of liquid water accumulation within the gas diffusion layer (GDL), and we attributed this accumulation to the loss of MPL hydrophobicity caused by the carbon corrosion-based degradation process. The increased liquid water accumulation led to increased mass transport resistances and performance losses at high operating current densities (> 1.5 A/cm 2 ). With increasing current density, the liquid water saturation profile converged to an upper threshold within GDLs with MPLs, whereas an upper liquid water saturation threshold was not observed for GDLs without MPLs. Predictions of long-term performance characteristics of PEM fuel cells should be informed by the proneness of the MPL to carbon corrosion degradation.
This paper discusses the potential of polymer networks, templated by crystalline metal–organic framework (MOF), as novel selective layer material in thin film composite membranes. The ability to create mechanically stable membranes with an ultra-thin selective layer of advanced polymer materials is highly desirable in membrane technology. Here, we describe a novel polymeric membrane, which is synthesized via the conversion of a surface anchored metal–organic framework (SURMOF) into a surface anchored gel (SURGEL). The SURGEL membranes combine the high variability in the building blocks and the possibility to control the network topology and membrane thickness of the SURMOF synthesis with high mechanical and chemical stability of polymers. Next to the material design, the transfer of membranes to suitable supports is also usually a challenging task, due to the fragile nature of the ultra-thin films. To overcome this issue, we utilized a porous support on top of the membrane, which is mechanically stable enough to allow for the easy membrane transfer from the synthesis substrate to the final membrane support. To demonstrate the potential for gas separation of the synthesized SURGEL membranes, as well as the suitability of the transfer method, we determined the permeance for eight gases with different kinetic diameters.
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