RESUMO
Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of 'extra adsorption domains'-that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.
RESUMO
The performance of dye-sensitized solar cells (DSCs) critically depends on the efficiency of electron transport within the TiO2-dye-electrolyte interface. To improve the efficiency of the electron transfer the conventional structure of the working electrode (WE) based on TiO2 nanoparticles (NPs) was replaced with TiO2 nanotubes (NTs). Sol-gel method was used to prepare undoped and Nb-doped TiO2 NPs and TiO2 NTs. The crystallinity and morphology of the WEs were characterized using XRD, SEM and TEM techniques. XPS and PL measurements revealed a higher concentration of oxygen-related defects at the surface of NPs-based electrodes compared to that based on NTs. Replacement of the conventional NPs-based TiO2 WE with alternative led to a 15% increase in power conversion efficiency (PCE) of the DSCs. The effect is attributed to the more efficient transfer of charge carriers in the NTs-based electrodes due to lower defect concentration. The suggestion was confirmed experimentally by electrical impedance spectroscopy measurements when we observed the higher recombination resistance at the TiO2 NTs-electrolyte interface compared to that at the TiO2 NPs-electrolyte interface. Moreover, Nb-doping of the TiO2 structures yields an additional 14% PCE increase. The application of Nb-doped TiO2 NTs as photo-electrode enables the fabrication of a DSC with an efficiency of 8.1%, which is 35% higher than that of a cell using a TiO2 NPs. Finally, NTs-based DSCs have demonstrated a 65% increase in the PCE value, when light intensity was decreased from 1000 to 10 W/m2 making such kind device be promising alternative indoor PV applications when the intensity of incident light is low.