The development of new functional materials based on metal–organic frameworks (MOFs) for adsorption and catalytic applications is one of the promising trends of modern materials science. The Zr-based MOFs, specifically UiO-66, are considered as the supports for metallic catalysts for the 5-hydroxymethylfurfural platform molecule reduction into valuable products. The present work focused on the effect of NH2 modification of UiO-66 on its structure and functional properties. The samples were prepared by a solvothermal method. The structure of the obtained materials was studied by X-ray diffraction, IR spectroscopy, UV–visible spectroscopy, and low-temperature nitrogen adsorption. Basic properties were investigated by HCl and CH3COOH adsorption, and electrokinetic properties were studied by electrophoretic light scattering. UiO-66-NH2 samples with different contents of aminoterephthalate linkers were successfully prepared. A gradual decrease in the specific surface area and the fraction of micropores with a diameter of ~0.9 nm was observed with an increase in the aminoterephthalate content. A proportional increase in the total number of basic sites in UiO-66-NH2 samples was established with an increase in the aminoterephthalate content up to 75%. At the same time, a noticeable decrease in the total number of basic sites and an increase in their strength with higher aminoterephthalate content was observed.
12 August 2019 in The Journal of Physical Chemistry C
The development of visible-light active titanium dioxide is one of the key challenges in photocatalysis that stimulates the development of TiO2-based composite materials and methods for their synthesis. Here, we report the use of pristine and Pt-modified dark titanium dioxide prepared via pulsed laser ablation in liquid (Nd:YAG laser, 1064 nm, 7 ns) for photocatalytic hydrogen evolution from alcohol aqueous solutions. The structure, textural, optical, photoelectrochemical, and electrochemical properties of the materials are studied by a complex of methods including X-ray diffraction, low-temperature nitrogen adsorption, electrophoretic light scattering, diffuse reflection spectroscopy, photoelectrochemical testing, and electrochemical impedance spectroscopy. Both the thermal treatment effect and the effect of modification with platinum on photocatalytic properties of dark titania materials are studied. Optimal compositions and experimental conditions are selected, and high photocatalytic efficiency of the samples in the hydrogen evolution reaction (apparent quantum yield of H2 up to 0.38) is demonstrated when irradiated with soft UV and blue LED, i.e., 375 and 410 nm. The positive effect of low platinum concentrations on the increase in the catalytic activity of dark titania is explained.