The adsorption of benzene, toluene, ethylbenzene, and xylene isomers, also known as BTEX, from the gas phase into porous thin films of the metal–organic framework UiO-66-X, where X = H, NH2, and NO2, was measured to quantify adsorption capacity. The thin films were grown by a vapor-conversion method onto Au-coated quartz microbalance crystals. The MOF thin films were characterized by IR and Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The thin films were activated by heating under high vacuum and exposed to each gas to calculate the Henry’s constant. The results demonstrate that the functional groups in the organic linker and missing-linkers both play important roles in the adsorption capacity. Several trends can be observed in the data. First, all the compounds in the BTEX family have lower Henry’s constants in the UiO-66-H films compared to the UiO-66-NH2 and UiO-66-NO2 films, which can largely be attributed to the absence of a functional group on the linker. Second, at 25 °C, the Henry’s constants for all the BTEX compounds in UiO-66-NO2 films are larger than UiO-66-NH2 films. Third, the role of missing linkers is addressed by comparing the measured adsorption capacity to ideal pore filling. The results show that the UiO-66-H films are the most defect-free and the UiO-66-NO2 films have the most missing linker defects.
A new family of highly uniform, cubic-shaped Cu3VSxSe4−x (CVSSe; 0 ≤ x ≤ 4) nanocrystals based on earth-abundant materials with intermediate bandgaps (IB) in the visible range is reported, synthesized via a hot-injection method. The IB transitions and optical band gap of the novel CVSSe nanocrystals are investigated using ultraviolet-visible spectroscopy, revealing tunable band gaps that span the visible and near-infrared regimes. The composition-dependent relationships among the crystal phase, optical band gap, and photoluminescence properties of the novel IB semiconductors with progressive substitution of Se by S are examined in detail. High-resolution transmission electron microscopy and scanning electron microscopy characterization confirm the high crystallinity and uniform size (~19.7 nm × 17.2 nm for Cu3VS4) of the cubic-shaped nanocrystals. Density functional theory (DFT) calculations based on virtual crystal approximation support the experimental findings, showing good agreement in lattice parameters and band gaps across the CVSSe series and lending confidence that the targeted phases and compositions have been successfully realized. A current conversion efficiency, i.e., incident photon-to-current efficiency, of 14.7% was achieved with the p-type IB semiconductor Cu3VS4. These novel p-type IB semiconductor nanocrystals hold promise for enabling thin film solar cells with efficiencies beyond the Shockley–Queisser limit by allowing sub-band-gap photon absorption through intermediate-band transitions, in addition to the conventional direct-band-gap transition.