En route towards panchromatic light harvesting: photophysical and electrochemical properties of Bodipy–porphyrazine conjugates

The concept of panchromatic light harvesting, that is, broad absorption cross sections throughout most of the visible range and excited state funnelling, has been realized in a novel set of porphyrazines. On one hand, zinc, copper, or magnesium ions were complexed by porphyrazines to tune their ground and excited state features. On the other hand, up to eight Bodipys were covalently attached to the periphery of the porphyrazines to enhance the ground state absorption. The corresponding star-shaped conjugates were probed by advanced photophysical measurements, that is, time-resolved fluorescence and femtosecond transient absorption spectroscopy. From the latter we derive spectroscopic and kinetic evidence in support of a fast and unidirectional energy transfer from the photoexcited Bodipy at the periphery to the porphyrazine at the core. In addition, the impact of the different metal centers is demonstrated

Influence of water content in a proton-conducting ionic liquid on the double layer properties of the Pt/PIL interface

The influence of the water content of 2-sulfoethylmethylammonium trifluoromethanesulfonate [2-Sema][TfO] on the double layer properties of the interface of platinum and the proton conducting ionic liquid (PIL) is investigated by means of impedance spectroscopy and cyclic voltammetry. By fitting the impedance spectra as complex capacitances, up to four differential double layer capacitances and corresponding time constants are obtained, depending on the potential (U = 0–1.6 V/RHE), water content (0.7–6.1 wt%) and temperature (T = 70–110 °C). Within the whole potential range investigated, a high frequency capacitance, C1, and a low frequency capacitance, C2, can be calculated. In the potential region of hydrogen underpotential deposition (HUPD), C1 can be separated into two parts, C1a and C1b. Whereas the high frequency capacitive processes can mainly be attributed to ion transport processes in the double layer, the low frequency process is ascribed to changes in the interfacial layer, including ad-/desorption and Faradaic processes. Alternative interpretations regarding the reorientation of ions, reconstruction of the metal surface and partial electron transfer between anions and Pt are considered

Local Evaluation of Processed Membrane Electrode Assemblies by Scanning Electrochemical Microscopy

Gas diffusion electrodes (GDEs) for high-temperature polymer electrolyte fuel cells with different sizes of the used binder particles were evaluated by scanning electrochemical microscopy (SECM) with shear force (SF) supplement. The SF data provide means of checking the substrate morphology with respect to cracks formed during the drying process and with respect to aggregates from used binder of poly(fluoroethylene) (PTFE) simultaneously to the electrochemical data. Electron microscopy results show that a GDE prepared with smaller PTFE particles exhibits less PTFE aggregation and more regular cracks. The SECM images show a more homogeneous distribution and higher level of oxygen reduction reaction activity for the GDE prepared with smaller PTFE particles. The quantitative comparison is enabled by the SF setup that maintains a constant working distance toward the sample in the variant of the redox competition mode, in which a cyclic voltammogram was recorded for every grid position of the microelectrode probe. Mass transport limitations of oxygen during the experiment are avoided by dedicated shape of the microelectrode body. Images of microelectrode currents at specific potentials were extracted to map the local electrocatalytic activity of the GDE. The GDEs were processed to membrane electrode assemblies and applied in HT-PEFC single cell tests. The polarization curve agree with the SECM results that GDEs produced with smaller PTFE particles favor the MEA performance