Validation of in situ applicable measuring techniques for analysis of the water adsorption by stone

As the water adsorbing behaviour (WAB) of stone is a key factor for most degradation processes, its analysis is a decisive aspect when monitoring deterioration and past conservation treatments, or when selecting a proper conservation treatment. In this study the performance of various non-destructive methods for measuring the WAB are compared, with the focus on the effect of the variable factors of the methods caused by their specific design. The methods under study are the contact-sponge method (CSM), the Karsten tube (KT) and the Mirowski pipe (MIR). Their performance is compared with the standardized capillary rise method (CR) and the results are analysed in relation to the open porosity of different lithotypes. Furthermore the effect of practical encumbrances which could limit the application of these methods was valuated. It was found that KT and CSM have complementary fields of investigation, where CSM is capable of measuring the initial water uptake of less porous materials with a high precision, while KT was found commodious for measuring longer contact times for more porous lithotypes. MIR showed too many discommodities, leading to unreliable results. To adequately compare the results of the different methods, the size of the contact area appears to be the most influential factor, whereas the contact material and pressure on the surface do not indicate a significant influence on the results. The study of these factors is currently being extended by visualization of the water adsorption process via X-ray and neutron radiography in combination with physico-mathematical models describing the WAB

Comparison of non-destructive techniques for analysis of the water absorbing behavior of stone

Existing non-destructive techniques for analysis of the water absorbing behavior of stone material have a different nature. This leads to discrepancies in practical application and measuring area, resulting in difficulties when comparing results of different methods. The present study focuses on the comparison of different non-destructive methods in terms of practical application, influence of variable factors and accuracy in relation to the open porosity and the capillary rise measurements. The comparison was based on repetitive measurements and X-ray and neutron radiography of the water absorption by lithotypes with a varying open porosity. The methods under study are the Karsten tube (KT), the contact sponge method (CSM) and the Mirowski pipe (MIR). It can be concluded that KT and CSM have complementary fields of investigation, whereas MIR produces unreliable results due to practical discommodities. The most significant variable factor influencing the measurements is the surface of the contact area. A study of analytical models describing the capillary water absorption as reference for interpretation of results of the different methods is currently ongoing

Photocatalytic Inactivation of Plant Pathogenic Bacteria Using TiO2 Nanoparticles Prepared Hydrothermally

Exploitation of engineered nanomaterials with unique properties has been dynamically growing in numerous fields, including the agricultural sector. Due to the increasing resistance of phytopathogenic microbes, human control over various plant pathogens in crop production is a big challenge and requires the development of novel antimicrobial materials. Photocatalytic active nanomaterials could offer an alternative solution to suppress the plant pathogens. In this work, titanium dioxide nanoparticles (TiO2 NPs) with high photocatalytic activity were synthesized by hydrothermal post-treatment of amorphous titania at different temperatures (250 °C or 310 °C) without using any additives or doping agents. The obtained samples were investigated through X-ray diffraction, N2-sorption measurements, diffuse reflectance UV-Vis spectroscopy, transmission electron microscopy, electron paramagnetic resonance spectroscopy, and X-ray photoelectron spectroscopy. The applied hydrothermal treatment led to the formation of TiO2 nanocrystallites with a predominant anatase crystal phase, with increasing crystallinity and crystallite size by prolonging treatment time. The photocatalytic activity of the TiO2 NPs was tested for the photo-degradation of phenol and applied for the inactivation of various plant pathogens such as Erwinia amylovora, Xanthomonas arboricola pv. juglandis, Pseudomonas syringae pv. tomato and Allorhizobium vitis. The studied bacteria showed different susceptibilities; their living cell numbers were quickly and remarkably reduced by UV-A-irradiated TiO2 NPs. The effectiveness of the most active sample prepared at 310 °C was much higher than that of commercial P25 TiO2. We found that fine-tuning of the structural properties by modulating the time and temperature of the hydrothermal treatment influenced the photocatalytic properties of the TiO2 NPs considerably. This work provides valuable information to the development of TiO2-based antimicrobial photocatalysts

Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity : the role of the hemilabile linker

The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of a-pinene oxide. This reaction is particularly sensitive to the Bronsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Bronsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Bronsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity