ABSTRACT
Gas sensors based on the multi-sensor platform MSP 632, with thin nanocomposite films based on tin dioxide with a low content of zinc oxide (0.5-5 mol.%), were synthesized using a solid-phase low-temperature pyrolysis technique. The resulting gas-sensitive ZnO-SnO2 films were comprehensively studied by atomic force microscopy, Kelvin probe force microscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, scanning transmission electron microscopy, energy dispersive X-ray spectrometry, and X-ray photoelectron spectroscopy. The obtained films are up to 200 nm thick and consist of ZnO-SnO2 nanocomposites, with ZnO and SnO2 crystallite sizes of 4-30 nm. Measurements of ZnO-SnO2 films containing 0.5 mol.% ZnO showed the existence of large values of surface potential, up to 1800 mV, leading to the formation of a strong surface electric field with a strength of up to 2 × 107 V/cm. The presence of a strong surface electric field leads to the best gas-sensitive properties: the sensor's responsivity is between two and nine times higher than that of sensors based on ZnO-SnO2 films of other compositions. A study of characteristics sensitive to NO2 (0.1-50 ppm) showed that gas sensors based on the ZnO-SnO2 film demonstrated a high sensitivity to NO2 with a concentration of 0.1 ppm at an operating temperature of 200 °C.
ABSTRACT
Functionalization of metal-organic frameworks (MOFs) with noble metal nanoparticles (NPs) is a challenging task. Conventional impregnation by metals often leads to agglomerates on the surface of MOF crystals. Functional groups on linkers interact with metal precursors and promote the homogeneous distribution of NPs in the pores of MOFs, but their uncontrolled localization can block channels and thus hinder mass transport. To overcome this problem, we created nucleation centers only in the defective pores of the UiO-66 MOF via the postsynthesis exchange. First, we have introduced defects into UiO-66 using benzoic acid as a modulator. Second, the modulator was exchanged for amino-benzoic acid. As a result, amino groups have decorated mainly the defective pores and attracted the Pd precursor after impregnation. The interaction of the metal precursor with amino groups and the growth of NPs were monitored by in situ infrared spectroscopy. Three processes were distinguished: the gaseous HCl release, NH2 reactivation, and growth of extended Pd surfaces. Uniform Pd NPs were located in the pores because of the homogeneous distribution of the precursor and pore diffusion-limited nucleation rate. Our work demonstrates an alternative approach of controlled Pd incorporation into UiO-66 that is of great importance for the rational design of heterogeneous catalysts.
ABSTRACT
Platinum-carbon catalysts are widely used in the manufacturing of proton-exchange membrane fuel cells. Increasing Pt/C activity and stability is an urgent task and the optimization of their structure seems to be one of the possible solutions. In the present paper, Pt/C electrocatalysts containing small (2-2.6 nm) nanoparticles (NPs) of a similar size, uniformly distributed over the surface of a carbon support, were obtained by the original method of liquid-phase synthesis. A comparative study of the structural characteristics, catalytic activity in the oxygen electroreduction reaction (ORR), and durability of the synthesized catalysts, as well as their commercial analogs, was carried out. It was shown that the uniformity of the structural and morphological characteristics of Pt/C catalysts makes it possible to reduce the negative effect of the small size of NPs on their stability. As a result, the obtained catalysts were significantly superior to their commercial analogs regarding ORR activity, but not inferior to them in terms of stability.