RESUMEN

Pd speciation induced by the combined effect of CO and water on Pd/SSZ-13 samples prepared by both impregnation and ion exchange was examined by FT-IR spectroscopy of CO adsorbed at room temperature and at liquid nitrogen temperature on anhydrous and hydrated samples. Starting from the literature findings related to the CO reducing effect on Pd cations, the present work gives precise spectroscopic evidences on how water is necessary in this process not only for compensating with H+ the zeolite exchange sites set free by Pd reduction, but also for mobilizing isolated Pd2+/Pd+ cations and making possible the reduction reactions. The aggregation of some Pd+ sites, just formed by the reduction and mobilized by the hydration, gives rise to the formation of Pd2O particles. Also, Pd0(100) sites are observed with CO on hydrated sample, formed by the aggregation and reduction of isolated Pd cations. Moreover, Pd0(111) sites are formed on the surface of PdOx particles during CO outgassing. The observation of the combined effect of water and CO allowed to define assignments of IR bands related to carbonyls of Pd in different oxidation states and coordination degrees.

RESUMEN

Understanding the water-involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water-promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water-dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO-SnO2 imparts water-resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water-promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C-H and C-C cleavage. Consequently, the tailored CoO-C-SnO2 showcases a remarkable 60-fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high-humidity conditions.

RESUMEN

The coupling effect of moisture content and temperature on the elastic modulus of concrete is experimentally investigated. The elastic modulus of dry concrete exhibits a clear temperature-weakening effect, while the elastic modulus of wet concrete exhibits a water-strengthening effect at room temperature. Under humidity-heat conditions, the elastic modulus of wet concrete declines with the temperature rise. When the temperature is 20 °C, 200 °C, 400 °C, 520 °C, and 620 °C, the humidity-heat coupling factors of the elastic modulus change rate DI˙F with moisture content are 0.08, 0.07, 0.04, 0.01, and -0.03, respectively, and the declining rate increases with the rise of moisture content. The relation between the humidity-heat coupling factor DIF, moisture content, and temperature was established; The equivalent relation between the water-strengthening effect and the temperature-weakening effect of the elastic modulus was obtained. The temperature range of the strengthening effect and "apparent weakening effect" of water stored inside concrete before heating on elastic modulus was determined; The evolutionary mechanism of the competition between the microcrack expansion and healing of concrete under combined humidity and heat conditions was revealed.

RESUMEN

In the field of nitrogen oxides (NOx) abatement, developing selective catalytic reduction (SCR) catalysts that can operate stably in the practical conditions remains a big challenge because of the complexity and uncertainty of actual flue gas emissions. As water vapor is unavoidable in the actual flue gas, it is indispensable to explore its effect on the performance of SCR catalysts. Many studies have proved that the effects of H2O on de-NOx activity of SCR catalysts were indeed observed during SCR reactions operated under wet conditions. Whether the effect is promotive or inhibitory depends on the reaction conditions, catalyst types and reducing agents used in SCR reaction. This review focuses on the effect of H2O on SCR catalysts and SCR reaction, including promoting effect, inhibiting effect, as well as the effecting mechanism. Besides, various strategies for developing a water-resistant SCR catalyst are also included. We hope that this work can give a more comprehensive insight into the effects of H2O on SCR catalysts and help with the rational design of water-resistant SCR catalysts for further practical application in NOx abatement field.

RESUMEN

Humic acid (HA) and water play an important role in polycyclic aromatic hydrocarbons (PAHs) adsorption and biodegradation in soil. In this work, molecular dynamics (MD) and electrostatic potential surfaces (EPSs) simulations are conducted to research the contribution of quartz surface, leonardite humic acid (LHA), and water to PAH adsorption. The adsorption energies between PAHs and LHA are much higher than that between PAHs and quartz. Simulation shows that the hydroxyl and carboxyl groups' attraction by LHA is the main adsorption force between PAHs and LHA. The π-π interaction between PAHs and LHA also contributes to the adsorption process. In addition, the mobility of water on quartz surface is much higher than that of LHA. Water should be regarded as an adsorbate in the system as well as PAHs. However, the presence of water has a remarkable negative effect on the adsorption of PAHs on LHA and quartz. The bridging effect of water could only enhance the stability of the aggregation system. The adsorption contribution of quartz and LHA to PAHs in the soil model tends to 0 if the water layer reaches 2.0 nm. Graphical abstract.

Asunto(s)

RESUMEN

The water effect on the performance of perovskite solar cells has been intensively studied in recent years. However, the conflicting conclusions derived from different studies make it impossible to fully understand the mechanism involved. Besides, all studies have concentrated on single methylammonium cation perovskites. As a consequence, the effects of water on formamidinium and cesium perovskites are still unclear. Herein, we introduce water during the fabrication of triple-cation hybrid perovskites. By controlling the water content, we demonstrate that an optimal concentration of water contributes to a better crystallized and more uniform hybrid perovskite film without impurities, resulting in significant enhancement in power conversion efficiency and long-term stability. In addition, two forms of water (hydrate water and bulk water) are found in the hybrid perovskite film. Hydrate water induces a recrystallization process, whereas bulk water leads to decomposition of the perovskite. These distinct phases are considered to form the basic mechanism affecting the performance of the cells.

RESUMEN

An efficient stereoselective three-component reaction for the synthesis of functionalized spiro[4H-pyran-3,3'-oxindole] derivatives was realized through an organocatalyzed domino Knoevenagel/Michael/cyclization reaction using a cinchonidine-derived thiourea as the catalyst. Using water as the additive was found to improve the product ee values significantly. Under the optimized conditions, the reactions between isatins, malononitrile, and 1,3-dicarbonyl compounds yield the desired spirooxindole products in good yields (71-92%) and moderate to high ee values (up to 87% ee).

RESUMEN

The objective of this study was to determine whether the water effect ratio (WER) or biotic ligand model (BLM) could be applied to efficiently develop water quality criteria (WQC) in Korea. Samples were collected from 12 specific sites along the Yeongsan River (YSR), Korea, including two sewage treatment plants and one estuary lake. A copper toxicity test using Daphnia magna was performed to determine the WER and to compare to the BLM prediction. The results of the WER from YSR samples also indicated significantly different copper toxicities in all sites. The model-based predictions showed that effluent and estuary waters had significantly different properties in regard to their ability to be used to investigate water characteristics and copper toxicity. It was supposed that the slight water characteristics changes, such as pH, DOC, hardness, conductivity, among others, influence copper toxicity, and these variable effects on copper toxicity interacted with the water composition. The 38% prediction was outside of the validation range by a factor of two in all sites, showing a poor predictive ability, especially in STPs and streams adjacent to the estuary, while the measured toxicity was more stable. The samples that ranged from pH 7.3-7.7 generated stable predictions, while other samples, including those with lower and the higher pH values, led to more unstable predictions. The results also showed that the toxicity of Cu in sample waters to D. magna was closely proportional to the amounts of acidity, including the carboxylic and phenolic groups, as well as the DOC concentrations. Consequently, the acceptable prediction of metal toxicity in various water samples needs the site-specific results considering the water characteristics such as pH and DOC properties particularly in STPs and estuary regions.

Asunto(s)

RESUMEN

A series of well-mixed Ce-containing MgAlCe rare earth catalysts derived from layered double hydroxides were synthesized and tested for H2S selective catalytic oxidation. Particularly, no chemisorption O-vacancies but intrinsic defect sites were present on catalyst surface. Significantly, the catalysts exhibited excellent catalytic activity, reasonable durability, and outstanding sulfur selectivity (100%) at relatively low temperatures. Furthermore, the catalyst followed a step-wise mechanism, and the catalyst deactivation was due mainly to the slower oxidation rate of Ce3+ to Ce4+ by O2 as compared to the reduction rate of Ce4+ to Ce3+ by H2S. Particularly, the added water, a Lewis base, can compete with inefficient S8 catalyst for the occupation of Lewis acid sites and active sites. Meanwhile, it can change the characteristics of catalyst surface, resulting in sulfur existing form transforming from inefficient S8 catalyst to inactive S3. Thus, lead to a decrease of deposited inefficient S8 catalyst content. Consequently, decrease the catalytic activity.

RESUMEN

A two-step melt blending procedure was used to produce binary systems composed of thermoplastic starch (TPS) and poly(butylene adipate-co-terephthalate) (PBAT). To improve the properties of the blends, two different layered silicates, viz. bentonite (BT) and organically modified montmorillonite (oMMT) were incorporated. First, TPS and its layered silicate nanocomposites were prepared via extrusion compounding during which starch was plasticized with glycerol and water. In the second step, PBAT was added to TPS/layered silicate to produce blends in a batch-type mixer. Mechanical and thermal properties were determined. The blends showed acceptable ductility over 50wt.% PBAT content, although at the cost of strength and stiffness. By contrast to oMMT the BT became intercalated in TPS and TPS/PBAT blends. The reinforcing effect of BT and oMMT was most prominent for the glassy states of both TPS and TPS/PBAT blends. Thermal, and thermooxidative properties were not significantly affected by the presence of layered silicates.

RESUMEN

Flexible displays are a systematic revolution in the field of display, in which high-performance and high-barrier polymer substrates are considered to be one of the most important key materials. In this work, high water vapor barrier polyimides containing amide moieties were synthesized via the ternary polymerization of 4,4'-diaminobenzailide (DABA), 4,4'-diaminodipheny ether (ODA), and 3,3',4,4'-biphenyl-tetracarboxylic acid dianhydride (BPDA) followed by thermal imidization. The relationship between the content of amide moieties and the water vapor barrier property of the prepared polyimides was studied by means of density test, water absorbing test, water contact angle test, water vapor permeation test, fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), thermogravimetry coupled with fourier transform infrared spectrometry (TG-FTIR), wide-angle X-ray diffraction analysis (WXRD), mechanical performance test, etc. The results show that the introduction of amide groups into polyimide (PI) main chains can improve the water vapor barrier properties of the polyimides effectively. The water vapor transmission rate (WVTR) of the polyimide films can be improved from 8.2365 g·(m²·24 h)-1 to 0.8670 g·(m²·24 h)-1 with the increasing content of amide moieties.

RESUMEN

Thermoplastic starch (TPS) biocomposites modified with cellulose microfibers and/or natural rubber were prepared via extrusion compounding. Glycerol and water served as plasticizers for starch. The dielectric properties of the TPS composites were examined via broadband dielectric spectroscopy in the temperature and frequency ranges of 30°C-65°C and 0.1Hz-10MHz, respectively. Each specimen was tested twice in order to study the effect of absorbed water. The hydrophobic/hydrophilic character of the modifiers governed the dielectric performance of the corresponding TPS biocomposites. Conducted analysis revealed two relaxation processes attributed to matrix-water-reinforcement interfacial polarization and glass to rubber transition of the TPS. Evaporation of water significantly affected the first process and only slightly the second one. Energy density, prior and after water evaporation, was also determined at constant field. By employing dielectric reinforcing function the contributions of water-assisted and constituents' originated interfacial phenomena could be separated.

Asunto(s)

RESUMEN

This study presents the effect of core length on the saturated (UPVsat) and dry (UPVdry) P-wave velocities of four different biomicritic limestone samples, namely light grey (BL-LG), dark grey (BL-DG), reddish (BL-R) and yellow (BL-Y), using core samples having different lengths (25-125mm) at a constant diameter (54.7mm). The saturated P-wave velocity (UPVsat) of all core samples generally decreased with increasing the sample length. However, the dry P-wave velocity (UPVdry) of samples obtained from BL-LG and BL-Y limestones increased with increasing the sample length. In contrast to the literature, the dry P-wave velocity (UPVdry) values of core samples having a length of 75, 100 and 125mm were consistently higher (2.8-46.2%) than those of saturated (UPVsat). Chemical and mineralogical analyses have shown that the P wave velocity is very sensitive to the calcite and clay minerals potentially leading to the weakening/disintegration of rock samples in the presence of water. Severe fluctuations in UPV values were observed to occur between 25 and 75mm sample lengths, thereafter, a trend of stabilization was observed. The maximum variation of UPV values between the sample length of 75mm and 125mm was only 7.3%. Therefore, the threshold core sample length was interpreted as 75mm for UPV measurement in biomicritic limestone samples used in this study.

RESUMEN

Given the widely varying types of aquatic ecosystems and bioavailability of chemicals, it is important to develop site-specific water quality criteria (WQC) to ensure criteria are neither over- nor under-protective. In the study, using pentachlorophenol (PCP) as an example, several approaches to derive site-specific WQC were investigated, including the conventional species sensitivity distribution (SSD), weighted SSD based on the proportion of each trophic level, and water effect ratio (WER) method. When corrected to a pH of 7.8, the conventional SSD approach resulted in criteria maximum concentration (CMC) and criteria continuous concentration (CCC) of 18.11 and 1.74 µg/L, respectively. If SSD was weighted according to the current species composition in Tai Lake, the CMC and CCC were 32.81 and 4.48 µg/L, respectively. However, available data suggest that many sensitive species inhabiting Tai Lake during 1980s were disappeared. Considering the species composition of the healthier ecosystem in 1980s, the CMC and CCC were 10.99 and 0.38 µg/L, respectively, which provide more protective water quality standards. Water effect ratio (WER) was further used to correct for co-occurrence of other toxicants and factors affecting bioavailability of PCP. A final WER of 4.72 was applied to adjust the criteria derived by using the weighted SSD for the 1980s aquatic community, and the final CMC and CCC obtained were 51.87 and 1.79 µg/L, respectively, at a pH of 7.8. Water quality criteria derived using the 1980s species composition and adjusted with WER were deemed the most appropriate WQC for water management and aquatic life protection. Merits of the various approaches for developing WQC for protection of aquatic species were discussed.

Asunto(s)

RESUMEN

A MnOx-NbOx-CeO2 catalyst for low temperature selective catalytic reduction (SCR) of NOx with NH3 was prepared by a sol-gel method, and characterized by NH3-NO/NO2 SCR catalytic activity, NO/NH3 oxidation activity, NOx/NH3 TPD, XRD, BET, H2-TPR and in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The results indicate that the MnOx-NbOx-CeO2 catalyst shows excellent low temperature NH3-SCR activity in the temperature range of 150-300°C. Water vapor inhibits the low temperature activity of the catalyst in standard SCR due to the inhibition of NOx adsorption. As the NO2 content increases in the feed, water vapor does not affect the activity in NO2 SCR. Meanwhile, water vapor significantly enhances the N2 selectivity of the fresh and the aged catalysts due to its inhibition of the decomposition of NH4NO3 into N2O.

Asunto(s)

RESUMEN

The complex structure of the macroscopic assemblies of carbon nanotubes and variable intrinsic piezoresistivity of nanotubes themselves lead to highly interesting piezoresistive performance of this new type of conductive material. Here, we present an in-depth study of the piezoresistive effect in carbon nanotube fibers, i.e., yarnlike assemblies made purely of aligned carbon nanotubes, which are expected to find applications as electrical and electronic materials. The resistivity changes of carbon nanotube fibers were measured on initial loading, through the elastic/plastic transition, on cyclic loading and on stress relaxation. The various regimes of stress/strain behavior were modeled using a standard linear solid model, which was modified with an additional element in series to account for the observed creep behavior. On the basis of the experimental and modeling results, the origin of piezoresistivity is discussed. An additional effect on the resistivity was found as the fiber was held under load which led to observations of the effect of humidity and the associated water adsorption level on the resistivity. We show that the equilibrium uptake of moisture leads to the decrease in gauge factor of the fiber decrease, i.e., the reduction in the sensitivity of fiber resistivity to loading.

RESUMEN

The bioavailability and toxicity of copper (Cu) in Shelter Island Yacht Basin (SIYB), San Diego, CA, USA, was assessed with simultaneous toxicological, chemical, and modeling approaches. Toxicological measurements included laboratory toxicity testing with Mytilus galloprovincialis (Mediterranean mussel) embryos added to both site water (ambient) and site water spiked with multiple Cu concentrations. Chemical assessment of ambient samples included total and dissolved Cu concentrations, and Cu complexation capacity measurements. Modeling was based on chemical speciation and predictions of bioavailability and toxicity using a marine Biotic Ligand Model (BLM). Cumulatively, these methods assessed the natural buffering capacity of Cu in SIYB during singular wet and dry season sampling events. Overall, the three approaches suggested negligible bioavailability, and isolated observed or predicted toxicity, despite an observed gradient of increasing Cu concentration, both horizontally and vertically within the water body, exceeding current water quality criteria for saltwater.

Asunto(s)

RESUMEN

The tautomerism of curcumin has been investigated in ethanol/water binary mixtures by using UV-Vis spectroscopy and advanced quantum-chemical calculations. The spectral changes were processed by using advanced chemometric procedure, based on resolution of overlapping bands technique. As a result, molar fractions of the tautomers and their individual spectra have been estimated. It has been shown that in ethanol the enol-keto tautomer only is presented. The addition of water leads to appearance of a new spectral band, which was assigned to the diketo tautomeric form. The results show that in 90% water/10% ethanol the diketo form is dominating. The observed shift in the equilibrium is explained by the quantum chemical calculations, which show that water molecules stabilize diketo tautomer through formation of stable complexes. To our best knowledge we report for the first time quantitative data for the tautomerism of curcumin and the effect of the water.

Asunto(s)

RESUMEN

Silk fibroin, a natural multi-domain protein, has attracted great attention due to its superior mechanical properties such as ultra-high strength and stretchability, biocompatibility, as well as its versatile biodegradability and processability. It is mainly composed of ß-sheet crystallites and amorphous domains. Although its strength is well known to be controlled by the dissociation of protein chains from ß-sheet crystallites, the way that water as the solvent affects its strength and the reason that its theoretically predicted strength is several times higher than experimental measurement remain unclear. We perform all-atom molecular dynamics simulations on a ß-sheet crystallite of Bombyx mori silk. We find that water solvent reduces the number and strength of hydrogen bonds between ß-chains, and thus greatly weakens the strength of silk fibroin. By dissociating protein chains at different locations from the crystallite, we also find that the pulling strength for the interior chains is several times higher than that for the surface/corner chains, with the former being consistent with the theoretically predicted value, while the latter on par with the experimental value. It is shown that the weakest rupture strength controls the failure strength of silk fibre. Hence, this work sheds light on the role of water in the strength of silk fibroin and also provides clues on the origin of the strength difference between theory and experiment.

Asunto(s)

RESUMEN

The water effect ratio (WER) procedure developed by the US Environmental Protection Agency is commonly used to derive site-specific criteria for point-source metal discharges into perennial waters. However, experience is limited with this method in the ephemeral and intermittent systems typical of arid climates. The present study presents a regression model to develop WER-based site-specific criteria for a network of ephemeral and intermittent streams influenced by nonpoint sources of Cu in the southwestern United States. Acute (48-h) Cu toxicity tests were performed concurrently with Daphnia magna in site water samples and hardness-matched laboratory waters. Median effect concentrations (EC50s) for Cu in site water samples (n=17) varied by more than 12-fold, and the range of calculated WER values was similar. Statistically significant (α=0.05) univariate predictors of site-specific Cu toxicity included (in sequence of decreasing significance) dissolved organic carbon (DOC), hardness/alkalinity ratio, alkalinity, K, and total dissolved solids. A multiple-regression model developed from a combination of DOC and alkalinity explained 85% of the toxicity variability in site water samples, providing a strong predictive tool that can be used in the WER framework when site-specific criteria values are derived. The biotic ligand model (BLM) underpredicted toxicity in site waters by more than 2-fold. Adjustments to the default BLM parameters improved the model's performance but did not provide a better predictive tool compared with the regression model developed from DOC and alkalinity.

Asunto(s)