Accelerated Synthesis of Nanolayered MWW Zeolite by Interzeolite Transformation.

Hierarchical zeolites can offer substantial benefits over bulk zeolites in catalysis. A drawback towards practical implementation is their lengthy synthesis, often requiring complex organic templates. This work describes an accelerated synthesis of nanolayered MWW zeolite based on the combination of interzeolite transformation (IZT) with a dual-templating strategy. FAU zeolite, hexamethyleneimine (HMI), and cetyltrimethylammonium bromide (CTAB) were respectively employed as Al source and primary zeolite, structure directing agent, and exfoliating agent. This approach allowed to reduce the synthesis of nanolayered MWW to 48 h, which is a considerable advance over the state of the art. Tracking structural, textural, morphological, and chemical properties during crystallization showed that 4-membered-ring (4MR) units derived from the FAU precursor are involved in the faster formation of MWW in comparison to a synthesis procedure from amorphous precursor. CTAB restricts the growth of the zeolite in the c-direction, resulting in nanolayered MWW. Moreover, we show that this approach can speed up the synthesis of nanolayered FER. The merits of nanolayered MWW zeolites are demonstrated in terms of improved catalytic performance in the Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to p-xylene compared to bulk reference MWW sample.

Synthesis, Characterization, and NH3-SCR Catalytic Performance of Fe-Modified MCM-36 Intercalated with Various Pillars.

Two series of MCM-36 zeolites intercalated with various pillars and modified with iron were synthesized, analyzed with respect to their physicochemical properties, and tested as catalysts for the NH3-SCR process. It was found that the characteristic MWW morphology of MCM-36 can be obtained successfully using silica, alumina, and iron oxide as pillars. Additionally, one-pot synthesis of the material with iron resulted in the incorporation of monomeric Fe3+ species into the framework positions. The results of catalytic tests revealed that the one-pot synthesized sample intercalated with silica and alumina was the most efficient catalyst of NO reduction, exhibiting ca. 100% activity at 250 °C. The outstanding performance of the material was attributed to the abundance of Lewis acid sites and the beneficial influence of alumina on the distribution of iron species in the zeolite. In contrast, the active centers originating from the Fe2O3 pillars improved the NO conversion in the high-temperature range. Nevertheless, the aggregated particles of the metal oxide limited the access of the reacting molecules to the inner structure of the catalyst, which affected the overall activity and promoted the formation of N2O above 300 °C.

Catalytic Performance and Sulfur Dioxide Resistance of One-Pot Synthesized Fe-MCM-22 in Selective Catalytic Reduction of Nitrogen Oxides with Ammonia (NH3-SCR)-The Effect of Iron Content.

The catalytic performance of Fe-catalysts in selective catalytic reduction of nitrogen oxides with ammonia (NH3-SCR) strongly depends on the nature of iron sites. Therefore, we aimed to prepare and investigate the catalytic potential of Fe-MCM-22 with various Si/Fe molar ratios in NH3-SCR. The samples were prepared by the one-pot synthesis method to provide high dispersion of iron and reduce the number of synthesis steps. We have found that the sample with the lowest concentration of Fe exhibited the highest catalytic activity of ca. 100% at 175 °C, due to the abundance of well-dispersed isolated iron species. The decrease of Si/Fe limited the formation of microporous structure and resulted in partial amorphization, formation of iron oxide clusters, and emission of N2O during the catalytic reaction. However, an optimal concentration of FexOy oligomers contributed to the decomposition of nitrous oxide within 250-400 °C. Moreover, the acidic character of the catalysts was not a key factor determining the high conversion of NO. Additionally, we conducted NH3-SCR catalytic tests over the samples after poisoning with sulfur dioxide (SO2). We observed that SO2 affected the catalytic performance mainly in the low-temperature region, due to the deposition of thermally unstable ammonium sulfates.

Catalytic Performance of One-Pot Synthesized Fe-MWW Layered Zeolites (MCM-22, MCM-36, and ITQ-2) in Selective Catalytic Reduction of Nitrogen Oxides with Ammonia.

The application of layered zeolites of MWW topology in environmental catalysis has attracted growing attention in recent years; however, only a few studies have explored their performance in selective catalytic reduction with ammonia (NH3-SCR). Thus, our work describes, for the first time, the one-pot synthesis of Fe-modified NH3-SCR catalysts supported on MCM-22, MCM-36, and ITQ-2. The calculated chemical composition of the materials was Si/Al of 30 and 5 wt.% of Fe. The reported results indicated a correlation between the arrangement of MWW layers and the form of iron in the zeolitic structure. We have observed that one-pot synthesis resulted in high dispersion of Fe3+ sites, which significantly enhanced low-temperature activity and prevented N2O generation during the reaction. All of the investigated samples exhibited almost 100% NO conversion at 250 °C. The most satisfactory activity was exhibited by Fe-modified MCM-36, since 50% of NO reduction was obtained at 150 °C for this catalyst. This effect can be explained by the abundance of isolated Fe3+ species, which are active in low-temperature NH3-SCR. Additionally, SiO2 pillars present in MCM-36 provided an additional surface for the deposition of the active phase.

Combining Soft- and Hard-Templating Approaches in MWW-Type Zeolites.

A combination of hard-templating (HT) and soft-templating (ST) approaches was studied to obtain MWW-type materials with intermediate physicochemical properties. The HT methodology involved the introduction of carbon particles as hard templates during gel synthesis to obtain a layered zeolitic precursor (LZP) with particles possessing a microspherical morphology. The LZP obtained was treated with surfactants as soft templates to expand the layers of the LZP, followed by a pillaring procedure. The materials were characterized by X-ray diffraction, transmission and scanning electron microscopy, elemental analysis and N2 adsorption. The results demonstrate that the obtained material possesses intermediate properties from both approaches, with interparticle mesopores/macropores and pore sizes between 18 and 46 Å. However, the ST procedure causes a partial disruption of some microspheres, forming small crystallite aggregates, and results in a decrease in the number of interparticle mesopores/macropores previously formed by the HT method. All synthesized solids presented catalytic activity, which was evaluated by the cracking of low-density polyethylene (LDPE) as a probe reaction.

Current State and Perspectives of Exfoliated Zeolites.

Zeolites are highly efficient industrial catalysts and sorbents with microporous framework structures. Approximately 10% of the frameworks, but eventually all in the long run, have produced both 3D crystals and 2D layers. The latter can be intercalated and expanded like all 2D materials but proved difficult to exfoliate directly into suspensions of monolayers in solution as precursors for unique synthetic opportunities. Successful exfoliations have been reported recently and are overviewed in this perspective article. The discussion highlights 3 primary challenges in this field, namely finding suitable 2D zeolite preparations that exfoliate directly in high yield, proving uniform layer thickness in solution and identifying applications to exploit the unique synthetic capabilities and properties of exfoliated zeolite monolayers. Four zeolites have been confirmed to exfoliate directly into monolayers: 3 with known structures-MWW, MFI, and RWR and one unknown, bifer with a unit cell close to ferrierite. The exfoliation into monolayers is confirmed by the combination of 5-6 characterization techniques including AFM, in situ and in-plane XRD, and microscopies. The promising areas of development are oriented films and membranes, intimately mixed zeolite phases, and hierarchical nanoscale composites with other active species like nanoparticles and clusters that are unfeasible by solid state processes.

Wastewater-based epidemiology approach: The learning lessons from COVID-19 pandemic and the development of novel guidelines for future pandemics.

Wastewater-based epidemiology (WBE) provides a comprehensive real-time framework of population attitude and health status. This approach is attracting the interest of medical community and health authorities to monitor the prevalence of a virus (such as the severe acute respiratory syndrome coronavirus 2, SARS-CoV-2) among a community. Indeed, WBE is currently fine-tuning as environmental surveillance tool for coronavirus disease 2019 (COVID-19) pandemic. After a bibliometric analysis conducted to discover the research trends in WBE field, this work aimed to side-by-side compare the conventional method based on clinical testing with WBE approach. Furthermore, novel guidelines were developed to apply the WBE approach to a pandemic. The growing interest on WBE approach for COVID-19 pandemic is demonstrated by looking at the sharp increase in scientific papers published in the last years and at the ongoing studies on viral quantification methods and analytical procedures. The side-by-side comparison highlighted the ability of WBE to identify the hot-spot areas faster than the conventional approach, reducing the costs (e.g., rational use of available resources) and the gatherings at medical centers. Contrary to clinical testing, WBE has the surveillance capacity for preventing the virus resurgence, including asymptomatic contribution, and ensuring the preservation of medical staff health by avoiding the exposure to the virus infection during clinical testing. As extensively reported, the time in collecting epidemiological data is crucial for establishing the prevention and mitigation measures that are essential for curbing a pandemic. The developed guidelines can help to build a WBE system useful to control any future pandemic.

A semi-industrial scale AnMBR for municipal wastewater treatment at ambient temperature: performance of the biological process.

A semi-industrial scale AnMBR plant was operated for more than 600 days to evaluate the long-term operation of this technology at ambient temperature (ranging from 10 to 27 ○C), variable hydraulic retention times (HRT) (from 25 to 41 h) and influent loads (mostly between 15 and 45 kg COD·d-1). The plant was fed with sulfate-rich high-loaded municipal wastewater from the pre-treatment of a full-scale WWTP. The results showed promising AnMBR performance as the core technology for wastewater treatment, obtaining an average 87.2 ± 6.1 % COD removal during long-term operation, with 40 % of the data over 90%. Five periods were considered to evaluate the effect of HRT, influent characteristics, COD/SO42--S ratio and temperature on the biological process. In the selected periods, methane yields varied from 70.2±36.0 to 169.0±95.1 STP L CH4·kg-1 CODinf, depending on the influent sulfate concentration, and wasting sludge production was reduced by between 8 % and 42 % compared to conventional activated sludge systems. The effluent exhibited a significant nutrient recovery potential. Temperature, HRT, SRT and influent COD/SO42--S ratio were corroborated as crucial parameters to consider in maximizing AnMBR performance.

Controlled direct synthesis of single- to multiple-layer MWW zeolite.

The minimized diffusion limitation and completely exposed strong acid sites of the ultrathin zeolites make it an industrially important catalyst especially for converting bulky molecules. However, the structure-controlled and large-scale synthesis of the material is still a challenge. In this work, the direct synthesis of the single-layer MWW zeolite was demonstrated by using hexamethyleneimine and amphiphilic organosilane as structure-directing agents. Characterization results confirmed the formation of the single-layer MWW zeolite with high crystallinity and excellent thermal/hydrothermal stability. The formation mechanism was rigorously revealed as the balanced rates between the nucleation/growth of the MWW nanocrystals and the incorporation of the organosilane into the MWW unit cell, which is further supported by the formation of MWW nanosheets with tunable thickness via simply changing synthesis conditions. The commercially available reagents, well-controlled structure and the high catalytic stability for the alkylation of benzene with 1-dodecene make it an industrially important catalyst.

Total Oxidation of Toluene and Propane over Supported Co3O4 Catalysts: Effect of Structure/Acidity of MWW Zeolite and Cobalt Loading.

A set of supported Co3O4 catalysts have been designed and prepared to study the effect of textural characteristics and Brønsted acid sites concentration of MWW zeolite support, as well as cobalt loading on catalyst activity. Detailed characterization of the catalysts with a thorough study on their performance in the total oxidation of toluene and propane revealed that MCM-22 is the optimal support and that increasing Si/Al and decreasing external surface of MCM-22 positively affect the activity of supported Co3O4 catalysts, which is determined by their low-temperature reducibility. The activity of the Co/MCM-22 catalysts increased with cobalt content (5-20 wt %), consistent with enhancing the amount of low-temperature reducible Co3O4. The optimized catalyst containing 20% Co supported on dealuminated MCM-22 presented high turnover frequency (TOF) values in both toluene (2.6 × 10-5 s-1 at 270 °C) and propane (3.9 × 10-5 s-1 at 215 °C) oxidation and was characterized by outstanding cycling stability, long-term durability, water tolerance, and sintering resistance.

Computational advances of tumor marker selection and sample classification in cancer proteomics.

Cancer proteomics has become a powerful technique for characterizing the protein markers driving transformation of malignancy, tracing proteome variation triggered by therapeutics, and discovering the novel targets and drugs for the treatment of oncologic diseases. To facilitate cancer diagnosis/prognosis and accelerate drug target discovery, a variety of methods for tumor marker identification and sample classification have been developed and successfully applied to cancer proteomic studies. This review article describes the most recent advances in those various approaches together with their current applications in cancer-related studies. Firstly, a number of popular feature selection methods are overviewed with objective evaluation on their advantages and disadvantages. Secondly, these methods are grouped into three major classes based on their underlying algorithms. Finally, a variety of sample separation algorithms are discussed. This review provides a comprehensive overview of the advances on tumor maker identification and patients/samples/tissues separations, which could be guidance to the researches in cancer proteomics.

A DFT study on catalytic oxidative desulfurization with H2O2 over Ti-MWW zeolite.

The catalytic mechanism of Ti-MWW in oxidative desulfurization with H2O2 was investigated by quantum chemical calculations. A defect model (Ti-d) and a perfect model (Ti-p) were proposed for Ti-MWW, and two possible reaction pathways starting from Ti-d and Ti-p were considered. On Ti-d, the hydroperoxy bidentate intermediate TiOOH (η2) was formed by activating H2O2 at the Ti center. Afterwards, aromatic sulfides were oxidized to sulfoxides and to ultimate sulfones by TiOOH (η2). The order of oxidation reactivity was benzothiophene > dibenzothiophene > thiophene, conforming to experimental observations. The Ti-p pathway proposed for oxidation of sulfides with H2O2 resulted in higher energy barriers compared to the Ti-d pathway. Natural bond orbital charge analysis was carried out to understand the charge distribution. This work showed that the defective Ti-MWW model for oxidative desulfurization was more active than the perfect model. Graphical abstract Catalytic oxidative desulfurizationwith H2O2 over Ti-MWW zeolite.

Hydrophobic Nanosized All-Silica Beta Zeolite: Efficient Synthesis and Adsorption Application.

All-silica beta zeolite, synthesized by conventional hydroxide route, usually possesses small crystal size of a few hundred nanometers but poor hydrophobicity, whereas the fluoride-mediated one exhibits to be highly hydrophobic but microsized. To obtain nanosized all-silica beta zeolite with excellent hydrophobicity, an innovative and efficient hydrothermal route via interzeolite transformation for synthesizing all-silica beta zeolite is proposed in present study. With the assistance of beta seeds and tetraethylammonium hydroxide as the structure-directing agent, siliceous beta zeolite is well-crystallized at a high solid yield via dissolution-recrystallization of all-silica ITQ-1 crystals at an extremely low water content (H2O/SiO2 molar ratio of 1). The obtained all-silica beta crystals are composed of 30-70 nm nanoparticles and highly hydrophobic just next to siliceous beta-F zeolite synthesized by environmentally unfriendly fluoride route, which is derived from relatively small amounts of internal defect sites. Thus, this beta zeolite is superior to other pure silica beta zeolites in the adsorption of large-sized volatile organic compounds (VOCs), which is mainly attributed to its high total pore volume and specific surface area as well as excellent hydrophobicity.

Kinetics and microbial ecology of batch sulfidogenic bioreactors for co-treatment of municipal wastewater and acid mine drainage.

The kinetics and microbial ecology in sulfidogenic bioreactors used in a novel two-stage process for co-treatment of acid mine drainage (AMD) and municipal wastewater (MWW) were investigated. Michaelis-Menten modeling of COD oxidation by sulfate reducing bacteria (SRB) (Vmax=0.33mgL(-1)min(-1), Km=4.3mgL(-1)) suggested that the Vmax can be reasonably achieved given the typical COD values in MWW and anticipated mixing with AMD. Non-competitive inhibition modeling (Ki=6.55mgL(-1)) indicated that excessive iron level should be avoided to limit its effects on SRB. The COD oxidation rate was positively correlated to COD/sulfate ratio and SRB population, as evidenced by dsrA gene copies. Phylogenetic analysis revealed diverse microbial communities dominated by sulfate reducing delta-proteobacteria. Microbial community and relative quantities of SRB showed significant differences under different COD/sulfate ratios (0.2, 1 and 2), and the highest dsrA gene concentration and most complex microbial diversity were observed under COD/sulfate ratio 2. Major species were associated with Desulfovirga, Desulfobulbus, Desulfovibrio, and Syntrophus sp. The reported COD kinetics, SRB abundances and the phylogenetic profile provide insights into the co-treatment process and help identify the parameters of concerns for such technology development.

Generalization of vestibular learning to earth-fixed targets is possible but limited when the polarity of afferent vestibular information is changed.

To maintain perception of the world around us during body motion, the brain must update the spatial presentation of visual stimuli, known as space updating. Previous studies have demonstrated that vestibular signals contribute to space updating. Nonetheless, when being passively rotated in the dark, the ability to keep track of a memorized earth-fixed target (EFT) involves learning mechanism(s). We tested whether such learning generalizes across different EFT eccentricities. Furthermore, we ascertained whether learning transfers to similar target eccentricities but in the opposite direction. Participants were trained to predict the position of an EFT (located at 45° to their left) while being rotated counterclockwise (i.e., they press a push button when they perceived that their body midline have cross the position of the target). Overall, the results indicated that learning transferred to other target eccentricity (30° and 60°) for identical body rotation direction. In contrast, vestibular learning partly transferred to target location's matching body rotation but in the opposite rotation direction. Generalization of learning implies that participants do not adopt cognitive strategies to improve their performance during training. We argue that the brain learned to use vestibular signals for space updating. Generalization of learning while being rotated in the opposite direction implies that some parts of the neural networks involved in space updating is shared between trained and untrained direction.

The six-minute walk test and body weight-walk distance product in healthy Brazilian subjects

We assessed the 6-min walk distance (6MWD) and body weight x distance product (6MWw) in healthy Brazilian subjects and compared measured 6MWD with values predicted in five reference equations developed for other populations. Anthropometry, spirometry, reported physical activity, and two walk tests in a 30-m corridor were evaluated in 134 subjects (73 females, 13-84 years). Mean 6MWD and 6MWw were significantly greater in males than in females (622 ± 80 m, 46,322 ± 10,539 kg.m vs 551 ± 71 m, 36,356 ± 8,289 kg.m, P < 0.05). Four equations significantly overestimated measured 6MWD (range, 32 ± 71 to 137 ± 74 m; P < 0.001), and one significantly underestimated it (-36 ± 86 m; P < 0.001). 6MWD significantly correlated with age (r = -0.39), height (r = 0.44), body mass index (r = -0.24), and reported physical activity (r = 0.25). 6MWw significantly correlated with age (r = -0.21), height (r = 0.66) and reported physical activity (r = 0.25). The reference equation devised for walk distance was 6MWDm = 622.461 - (1.846 x Ageyears) + (61.503 x Gendermales = 1; females = 0); r2 = 0.300. In an additional group of 85 subjects prospectively studied, the difference between measured and the 6MWD predicted with the equation proposed here was not significant (-3 ± 68 m; P = 0.938). The measured 6MWD represented 99.6 ± 11.9 percent of the predicted value. We conclude that 6MWD and 6MWw variances were adequately explained by demographic and anthropometric attributes. This reference equation is probably most appropriate for evaluating the exercise capacity of Brazilian patients with chronic diseases.