Upon light excitation MOF-5 behaves as a semiconductor and undergoes charge separation (electrons and holes) decaying in the microsecond time scale. The actual conduction band energy value was estimated to be 0.2 V versus NHE with a band gap of 3.4 eV. Photoinduced electron transfer processes to viologen generates the corresponding viologen radical cation, while holes of MOF-5 oxidizes N,N,N',N'-tetramethyl-p-phenylenediamine. One application investigated for MOF-5 as a semiconductor has been the shape-selective photocatalyzed degradation of phenol in aqueous solutions.
Starting from colloidal TiO2 nanoparticles in combination with tetraethyl orthosilicate using neutral Pluronic or cationic cetyltrimethylammonium as templates, a series of structured mesoporous silicas has been obtained. The structure of the mesoporous titania was confirmed by isothermal gas adsorption, transmission electron microscopy, and X-ray diffraction. The pore diameter ranged between 3.8 and 10.9 nm, and the BET surface area varied from 99 to 584 m2 g(-1). The photocatalytic activity of these samples for the degradation of phenol in aqueous solution has been compared with that of standard P-25 TiO2. Even though the activity of these new mesostructured materials is lower that those found for P-25 TiO2, the turnover frequency of the photocatalytic activity (moles of phenol degraded per Ti atom present at initial reaction time) is much higher for the mesoporous titania, particularly with low titanium contents for those materials (mpTiO2-5 and TiO2SBA15-5).
We have prepared two complementary series of SubPc-C(60) (SubPc=subphthalocyanine) electron/energy donor-acceptor systems, in which the two constituents are linked through ortho-, meta-, or para-substituted phenoxy spacers. In one of the series (1 a) the SubPc units bear iodine atoms, while in the other series (1 b) diphenylamino groups are linked to the SubPc macrocycles. The iodine atoms and diphenylamino groups both influence the resulting oxidation potentials of the electron-donating SubPc. They also modulate the outcome of excited state interactions, namely, energy and/or charge transfer. In addition, we have studied the impact that the substitution pattern in the phenoxy spacer exerts onto intramolecular processes in the ground and excited states. Although some of these processes are governed by the spatial separation between both components, the different electronic coupling through ortho-, meta-, or para- connections also plays decisive roles in some cases.
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