In Situ ATR-FTIR Investigation of Photodegradation of 3,4-Dihydroxybenzoic Acid on TiO2

The catalytic photo-oxidation of 3,4-dihydroxybenzoic acid on TiO2 has been studied by in situ ATR-FTIR in flowing water and in flowing wet air/nitrogen gas. In flowing water it was difficult to observe photodegradation intermediates despite photocatalytic action during UV illumination. In the flowing wet air/nitrogen system carboxylic acids and carbonates were observed. It was shown that water plays an important role in the formation of oxidation active species. Oxygen shows a prominent role for carboxylic acid degradation, but the photogenerated hole plays the important role for the 3,4-dihydroxybenzoic acid ring cleavage

Functionalized silicate nanochannels: towards applications in drug delivery and solar energy conversion

The defined pore networks of silicate-based molecular sieves are attractive for the development of highly organized inorganic/organic hybrid materials. Efficient energy transfer systems are obtained upon inclusion of dye molecules into the one-dimensional channels of zeolite L. The resulting host-guest materials form the basis for an advanced luminescent solar concentrator. The selective functionalization of the channel entrances with zinc phthalocyanine offers further possibilities in terms of employing the dye-zeolite composites for the sensitization of organic solar cells. Having larger pore sizes than zeolites as well as highly modifiable channel walls, mesoporous silicas have recently emerged as versatile starting materials for the synthesis of drug delivery devices. One of the most challenging aspects in this context is the control and the analysis of the functional group distribution. This topic is discussed on the basis of our recent work on the reaction of aminopropylalkoxysilanes with mesoporous silica MCM-41

Designing dye–nanochannel antenna hybrid materials for light harvesting, transport and trapping

We discuss artificial photonic antenna systems that are built by incorporating chromophores into one-dimensional nanochannel materials and by organizing the latter in specific ways. Zeolite L (ZL) is an excellent host for the supramolecular organization of different kinds of molecules and complexes. The range of possibilities for filling its one-dimensional channels with suitable guests has been shown to be much larger than one might expect. Geometrical constraints imposed by the host structure lead to supramolecular organization of the guests in the channels. The arrangement of dyes inside the ZL channels is what we call the first stage of organization. It allows light harvesting within the volume of a dye-loaded ZL crystal and also the radiationless transport of energy to either the channel ends or center. One-dimensional FRET transport can be realized in these guest–host materials. The second stage of organization is realized by coupling either an external acceptor or donor stopcock fluorophore at the ends of the ZL channels, which can then trap or inject electronic excitation energy. The third stage of organization is obtained by interfacing the material to an external device via a stopcock intermediate. A possibility to achieve higher levels of organization is by controlled assembly of the host into ordered structures and preparation of monodirectional materials. The usually strong light scattering of ZL can be suppressed by refractive-index matching and avoidance of microphase separation in hybrid polymer/dye–ZL materials. The concepts are illustrated and discussed in detail on a bidirectional dye antenna system. Experimental results of two materials with a donor-to-acceptor ratio of 33:1 and 52:1, respectively, and a three-dye system illustrate the validity and challenges of this approach for synthesizing dye–nanochannel hybrid materials for light harvesting, transport, and trapping

In Situ ATR-IR Study on the Photocatalytic Decomposition of Amino Acids over Au/TiO 2 and TiO 2

The photocatalytic degradation of l-asparagine and l-glutamic acid over Au/TiO2 and TiO2 catalysts was investigated in situ by attenuated total reflection infrared (ATR-IR) in combination with modulation excitation spectroscopy. Oxalate was detected on the catalyst surface, which has not been reported before for degradation of amino acids by studies focusing on intermediates in solution. The ATR-IR spectra provide valuable information on the fate of the nitrogen. Ammonium was detected, in agreement with previous studies. Most importantly, strong signals of cyanide were observed, and this assignment has been corroborated by 15N labeling experiments. Cyanide was not reported before, to the best of our knowledge, for the photocatalytic degradation of amino acids. Cyanide was formed in the presence and the absence of gold particles on the TiO2 surface. The cyanide leads to leaching of gold via Au(CN)2− species that were detected in solution by mass spectrometry