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Organisationseinheit der BAM
Herein, we present a detailed investigation of the electrochemically triggered formation and dissolution processes of α- and β-sulfur crystals on a monolithic carbon cathode using operando high-resolution synchrotron radiography (438 nm/pixel).
The combination of visual monitoring with the electrical current response during cyclic voltammetry provides valuable insights into the sulfur formation and dissolution mechanism. Our observations show that the crystal growth process is mainly dictated by a rapid equilibrium between long-chain polysulfides on one side and solid sulfur/short-chain polysulfides on the other side, which is consistent with previous studies in this field. The high temporal and spatial resolution of synchrotron imaging enables the observation of different regimes during the sulfur formation and dissolution process. The appearance of short-chain polysulfides after the first anodic CV peak initiates a rapid dissolution process of α-sulfur crystals on the cathode. The increase in the long-chain lithium polysulfide concentration at the cathode surface during charge results in an increased crystal growth rate, which in turn produces imperfections in α- and β-sulfur crystals. There are strong indications that these defects are fluid inclusions, which may trap dissolved polysulfides and therefore reduce the electrochemical cell capacity.
Systems containing multiple photochromic units possibly display a synergistic interplay of individual switching events and hence potentially give rise to unprecedented photoresponsive behavior. Among such systems photoswitchable foldamers are attractive as the photoisomerization events are coupled to the helixcoil conformational transition. To gain comprehensive insight into the role of the number of switching units (statistics) as well as their specific location and relative orientation in the helix backbone, several series of foldamers have been synthesized and characterized. In these series of foldamers, the local environment of the photoswitchable units was precisely tuned as π,π-stacking interactions were enforced to occur between specific pairs, i.e. azobenzene–azobenzene, azobenzene–tolane, or phenylene–phenylene units. These particular arrangements are reflected not only in the stability of the helical conformation, but also affect the photoresponsive behavior, i.e. the rate of photoisomerization and extent of denaturation. Furthermore, determining the intramolecular spin–spin distance in a series of TEMPO-labeled foldamers with variable chain lengths and different spatial locations of the spin-labels deduced an independent verification of the photoinduced helix–coil transition by ESR spectroscopy. Quantitative analysis of the corresponding ESR spectra shows an excellent correlation of the extent of intramolecular spin–spin coupling and the intensity of the Cotton effect in CD spectroscopy. From all of these results an unusual relationship between the rate of photoisomerization and the extent of photoinduced denaturation could be unraveled, as they are not going hand-in-hand but compete with each other, i.e. the easier the individual switching event is, the harder it becomes to achieve a high degree of unfolding. This insight into the effect of microenvironment on the ease of individual switching events and the role of statistics on the resulting degree of the overall conformational transition is of general interest for the design of multi-switch architectures with improved photoresponse.
Hydroliquefaction is a possible pathway to produce liquid transportation fuels from solid feedstocks like coal or biomass. Though much effort has been put into the investigation of maximizing the oil yield using expensive catalysts and pasting oils in batch setups, little is known about how to commercialize the process. This work aims at the demonstration of lignin hydroliquefaction under conditions interesting for commercial operation. The results from hydroliquefaction experiments of two different lignin types using a cheap iron-based catalyst and anthracene oil as the pasting oil in a semibatch system are presented here. Oil yields of above 50% are reached without observing coke formation. Extensive analyses of the feedstocks and product oils were performed. The process supplies high-quality oil, while differences in the decomposition path of both lignin types are observed. An high heating value of 39 400 J/g and H/C and O/C ratios of up to 1.6 and 0.1, respectively, are detected for the produced bio-oils.