Tailoring the Electronic Metal-Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation.

Metal-modified catalysts have attracted extraordinary research attention in heterogeneous catalysis due to their enhanced geometric and electronic structures and outstanding catalytic performances. Silver (Ag) possesses necessary active sites for ethylene epoxidation, but the catalyst activity is usually sacrificed to obtain high selectivity towards ethylene oxide (EO). Herein, we report that using Al can help in tailoring the unoccupied 3d state of Ag on the MnO2 support through strong electronic metal-support interactions (EMSIs), overcoming the activity-selectivity trade-off for ethylene epoxidation and resulting in a very high ethylene conversion rate (~100 %) with 90 % selectivity for EO under mild conditions (170 °C and atmospheric pressure). Structural characterization and theoretical calculations revealed that the EMSIs obtained by the Al modification tailor the unoccupied 3d state of Ag, modulating the adsorption of ethylene (C2H4) and oxygen (O2) and facilitating EO desorption, resulting in high C2H4 conversion. Meanwhile, the increased number of positively charge Ag+ lowers the energy barrier for C2H4(ads) oxidation to produce oxametallacycle (OMC), inducing the unexpectedly high EO selectivity. Such an extraordinary electronic promotion provides new promising pathways for designing advanced metal catalysts with high activity and selectivity in selective oxidation reactions.

Volatile organic compounds (VOCs) emissions from internal floating-roof tank in oil depots in Beijing: Influencing factors and emission reduction strategies analysis.

The internal floating-roof tank is the main type of storage tank for refined oil products. The volatile organic compounds (VOCs) emission from the internal floating-roof tank plays a dominant role in the unorganized emission source of the oil depot. In this study, we selected six typical oil depots in Beijing to investigate VOC emission characteristics from the tank top vent hole using infrared imaging technology and flame ionization detector (FID). The results reveal that infrared thermal imager is efficient in quickly identifying the emission level of the tank discharge point. The ambient temperature and wind speed have a direct effect on sealing loss, the turnover can greatly influence the wall hanging loss, and the concentration of VOCs emitted from the tank top vent hole is negatively correlated with liquid height. Furthermore, the influence of accessories type of the internal floating-roof tank on the concentration of VOCs emission from the top vent hole is also studied when other parameters remain unchanged, and find the floating deck type and sealing mode have a significant influence on their VOCs emissions, of which the combination of pontoon type floating deck and secondary seal are effective in controlling the concentration of VOCs emitted from the tank top vent hole. Finally, based on our experimental results, several feasible emission reduction strategies are proposed in terms of source prevention and process control in order to achieve the fine management of the whole process. This paper provides important technical support and policy thoughts for VOCs emission control during oil storage.

Rapid Detection of Potential Natural Food Preservatives and Identification of Artemisia Species via High-Sensitivity Photoionization Mass Spectrometry.

Natural food preservatives are being sought extensively as a safe alternative to chemical food preservatives. This study aimed to identify potential natural preservatives from herbs using single-photon ionization time-of-flight mass spectrometry (SPI-TOF-MS). Five Artemisia species and four other herbs were analyzed, and the random forest (RF) algorithm was used to simulate olfaction and distinguish the Artemisia species by identifying the characteristic peaks of volatile terpenoids (VTPs). Results showed that the terpenoid synthase (TPS) gene family was expanded in Artemisia species, potentially contributing to the increased production of VTPs, which have potential as natural preservatives and specifically identify these species. The limits of detections (LODs) for principle VTPs in Artemisia species were as low as 22-39 parts-per-trillion-by-volume (pptv) using SPI-TOF-MS. This study highlights the potential for headspace mass spectrometry to be used in the development of natural preservatives and the identification of plant species.

Oxygen vacancy-engineered titanium-based perovskite for boosting H2O activation and lower-temperature hydrolysis of organic sulfur.

Modulation of water activation is crucial to water-involved chemical reactions in heterogeneous catalysis. Organic sulfur (COS and CS2) hydrolysis is such a typical reaction involving water (H2O) molecule as a reactant. However, limited by the strong O-H bond in H2O, satisfactory CS2 hydrolysis performance is attained at high temperature above 310 °C, which is at the sacrifice of the Claus conversion, strongly hindering sulfur recovery efficiency improvement and pollution emissions control of the Claus process. Herein, we report a facile oxygen vacancy (VO) engineering on titanium-based perovskite to motivate H2O activation for enhanced COS and CS2 hydrolysis at lower temperature. Increased amount of VO contributed to improved degree of H2O dissociation to generate more active -OH, due to lower energy barrier for H2O dissociation over surface rich in VO, particularly VO clusters. Besides, low-coordinated Ti ions adjacent to VO were active sites for H2O activation. Consequently, complete conversion of COS and CS2 was achieved over SrTiO3 after H2 reduction treatment at 225 °C, a favorable temperature for the Claus conversion, at which both satisfying COS and CS2 hydrolysis performance and improved sulfur recovery efficiency can be obtained simultaneously. Additionally, the origin of enhanced hydrolysis activity from boosted H2O activation by VO was revealed via in-depth mechanism study. This provides more explicit direction for further design of efficacious catalysts for H2O-involved reactions.

Bacterial Communities in the Endophyte and Rhizosphere of White Radish (Raphanus sativus) in Different Compartments and Growth Conditions.

Endophyte resources have important research value in multiresistance breeding, ecological protection, germicide development, and other fields. In this study, high-throughput sequencing (Illumina-MiSeq) technology was employed to analyse the diversity and community composition of white radish (Raphanus sativus) endophytes and rhizosphere bacteria in different compartments and cultivation conditions, including greenhouse and open field cultivation, at both the phylum and genus levels. Alpha diversity index analysis showed that the bacterial richness and diversity values of rhizosphere bacteria were higher than those of endophytes in different compartments. NMDS analysis and microbial co-occurrence network analysis showed that apart from the similarity in the endophytic bacterial composition of the leaf and root endosphere, the endophytic bacterial composition in flesh and epidermis of radish were also more similar. The dominant endophytic bacteria in white radish were Proteobacteria, Bacteroidetes, and Actinomycetes at the phylum level. We analyzed the effects of different ecological compartments and two cultivation environments on radish microorganisms, and found that ecological compartments played an important role, which was related to the mechanism of microbial assembly in plants. The same facility cultivation can also improve the diversity of radish microorganisms in different ecological compartments, and change the biomarkers that play a major role in rhizosphere microorganisms and endophytes of radish. Bacteria plays an important role in the process of plant growth, and the study of endophytes enriches the understanding of microbial diversity in white radish, which helps to provide insight into the ecological function and interaction mechanisms of plants and microorganisms.

Chitosan-based recyclable composite aerogels for the photocatalytic degradation of rhodamine B.

TiO2 based photocatalyst with sufficient reusability for the degradation of water pollutants remains a challenge. Here, we report a composite chitosan-based aerogel containing TiO2 nanoparticles, multiwalled carbon nanotubes and layered silicate rectorite with sufficient mechanical strength for Rhodamine B degradation. The aerogels with homogeneous oriented lamellar structure were successfully prepared via a unidirectional freeze-casting technique. As-prepared aerogels showed specific surface area of 84.59 m2/g. The addition of rectorite and carbon nanotubes accelerated the photodegradation and rectorite significantly enhanced the overall mechanical performance. Rapid degradation of rhodamine B (95% in 100 min) was observed on aerogels with 2 wt% and 4 wt% of rectorite. After 3 cycles, 75% degradation of Rhodamine B was achieved with CTCR4, confirming its reusability. Thus, the composite chitosan aerogels show high photocatalytic degradation efficiency towards Rhodamine B during cycle use.

[Hydrolysis of COS over MgAl Mixed Oxides Derived from Hydrotalcites].

A series of MgAl hydrotalcite-derived composite oxides were prepared by co-precipitation methods. The effects of calcination temperature, reaction temperature, water vapor volume fraction, and alkali metal addition on the hydrolysis activity of the samples were investigated. The crystal structure, specific surface area, pore structure, and basic position distribution of the composite oxides were characterized using XRD, BET, TPD, and XPS. The results shown that the catalytic activity firstly increased and then decreased with the rise of calcination temperature. Furthermore, the sample that calcined at 650℃ can achieve the best catalytic activity (complete removal of COS lasted for 180 min). Increasing the reaction temperature improved the catalytic activity, which can present excellent catalytic activity and stability at temperatures above 70℃. In addition, the doping of the alkali metal Cs improved the catalytic activity, the complete removal time for COS can be maintained for 480 min.

Egg source natural proteins LBL modified cellulose nanofibrous mats and their cellular compatibility.

Natural-based nanocomposites are competitive and promising materials for biomedical applications due to their biocompatibility. Herein, a novel natural-based composite was fabricated by alternately depositing lysozyme (LY) and albumin egg (AE) on electrospun cellulose nanofibrous mats via layer-by-layer self-assembly (LBL) technology. To indicate the successful deposition process and investigate the variations of the mats during LBL process, the surface morphology, physical property, chemical composition, wetting behavior and thermal stability were systematically studied. The results showed that the surface morphology and composition of the mats were significantly influenced by LBL process, which further resulted in the variation of wetting behavior. Besides, the mechanical properties were enhanced after LBL modification. In addition, the LBL structured nanofibrous mats exhibited antibacterial activity and excellent biocompatibility with L929 fibroblasts. In brief, LY and AE coated LBL structured cellulose nanofibrous mats, especially the 15 bilayers coated mats, have considerably potential applications in the biomedical field.

Insight into the H2S selective catalytic oxidation performance on well-mixed Ce-containing rare earth catalysts derived from MgAlCe layered double hydroxides.

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.