ABSTRACT
In-situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water-gas shift (RWGS) reaction. Surface oxygen atoms in various Mo-based catalysts are removed in H2-containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt-dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol·gcatal-1·h-1 at 600 °C has been achieved over in-situ carbonized H-intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3% is observed.
ABSTRACT
BACKGROUND: It is necessary to evaluate the risk factors of secondary bleeding after tonsillectomy in children, to provide reference for clinical children management and care. METHODS: Children who underwent tonsillectomy from January 1, 2018, to December 31, 2022, in our hospital were retrospectively included. The characteristics of children with and without secondary bleeding were analyzed. RESULTS: A total of 1068 children undergoing tonsillectomy were included, and the incidence of secondary bleeding children undergoing tonsillectomy was 4.87%. Age ≥ 9 years old (odds ratio [OR] = 2.609, 95% confidence interval [CI] = 2.112-3.437), type of surgery (OR = 1.764, 95% CI = 1.148-2.291), and degree of tonsil embedding (OR = 2.116, 95% CI = 1.805-2.644) were the risk factors of secondary bleeding after tonsillectomy in children (all P < .05). CONCLUSION: Medical staff should proactively monitor and address the identified risk factors by implementing timely warning systems and preventive strategies to reduce the postoperative bleeding following tonsillectomy.
ABSTRACT
Rapid urbanization and industrialization have greatly contributed to boosting regional economic growth and mitigating the problem of poverty, but blind expansion of cities and towns has not only caused the inefficient use of urban land resources but also caused the deterioration in the urban ecological environment. Within the current context of emphasizing high-quality development, achieving synergy between the efficient use of urban land and ecological environmental protection is an urgent task for promoting new urbanization construction. In this study, cities in the upper reaches of the Yangtze River (URYR) were adopted as the research object, a theoretical analysis framework for the urban land use efficiency (ULUE) and ecological environment quality (EEQ) was established, the ULUE was measured by using the Slacks-Based Measure (SBM) model, the coupling coordination and interactive corresponding response relationship between the ULUE and EEQ were analyzed, and the influencing factors of the coupling coordination between these two systems were explored by using the random forest model. The following conclusions can be obtained: in 2020, compared with those in 2006, both the ULUE and EEQ were improved, and the two systems exhibited interactions and significant spatiotemporal heterogeneity. The coupling coordination degree (CCD) between the ULUE and EEQ could facilitate maintaining the original state, and the transfer of the CCD exhibited a significant spatial correlation with the state of neighbouring cities. The effect of the ULUE on the EEQ indicated nonlinear characteristics, while the effect of the EEQ on the ULUE was manifested as inhibition initially and then promotion. The random forest regression results showed that the population density, landscape agglomeration and connectivity, market conditions, government intervention, and industrial institutions are the key influencing factors of the CCD. Finally, this study provides policy implications for innovative urban land use modelling, environmental regulation, and industrial transformation and upgrading.
Subject(s)
Cities , Conservation of Natural Resources , Urbanization , Models, Theoretical , Ecosystem , ChinaABSTRACT
Sintering of active metal species often happens during catalytic reactions, which requires redispersion in a reactive atmosphere at elevated temperatures to recover the activity. Herein, we report a simple method to redisperse sintered Cu catalysts via O2-H2O treatment at room temperature. In-situ spectroscopic characterizations reveal that H2O induces the formation of hydroxylated Cu species in humid O2, pushing surface diffusion of Cu atoms at room temperature. Further, surface OH groups formed on most hydroxylable support surfaces such as γ-Al2O3, SiO2, and CeO2 in the humid atmosphere help to pull the mobile Cu species and enhance Cu redispersion. Both pushing and pulling effects of gaseous H2O promote the structural transformation of Cu aggregates into highly dispersed Cu species at room temperature, which exhibit enhanced activity in reverse water gas shift and preferential oxidation of carbon monoxide reactions. These findings highlight the important role of H2O in the dynamic structure evolution of supported metal nanocatalysts and lay the foundation for the regeneration of sintered catalysts under mild conditions.
ABSTRACT
An enclosed nanospace often shows a significant confinement effect on chemistry within its inner cavity, while whether an open space can have this effect remains elusive. Here, we show that the open surface of TiO2 creates a confined environment for In2O3 which drives spontaneous transformation of free In2O3 nanoparticles in physical contact with TiO2 nanoparticles into In oxide (InOx) nanolayers covering onto the TiO2 surface during CO2 hydrogenation to CO. The formed InOx nanolayers are easy to create surface oxygen vacancies but are against over-reduction to metallic In in the H2-rich atmospheres, which thus show significantly enhanced activity and stability in comparison with the pure In2O3 catalyst. The formation of interfacial In-O-Ti bonding is identified to drive the In2O3 dispersion and stabilize the metastable InOx layers. The InOx overlayers with distinct chemistry from their free counterpart can be confined on various oxide surfaces, demonstrating the important confinement effect at oxide/oxide interfaces.
ABSTRACT
The activity of active oxygen species on supported Ag atoms can be effectively modulated by metal-support interactions using different oxide supports. The strong interaction between Ag and Al2O3 with more electrons transferred from Ag to Al2O3 leads to the formation of more Ag-O2- (superoxide) species, responsible for the selective oxidation of ethylene to ethylene oxide. The relatively weak interaction between Ag and SiO2 induces the generation of Ag-O (atomic oxygen) and Ag-O22- (peroxide) species, which are more active for complete oxidation of CO and ethylene to CO2. This work is of significance for deep understanding of active surface species in atomically dispersed metal catalysts.
ABSTRACT
OBJECTIVES: To explore the intervention mechanism of combining Polygala tenuifolia (PT) with Magnolia officinalis (MO) on gastrointestinal motility disorders caused by PT. METHODS: Urine and faeces of rats were collected; the effects of PT and MO on the gastric emptying and small intestine advancing rates in mice were analysed via ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS) to determine the potential metabolites. Changes in the metabolic profiles of the urine and faeces were revealed by untargeted metabolomics, followed by multivariate statistical analysis. The integration of urine and faeces was applied to reveal the intervention mechanism of PT-MO on PT-induced disorders. KEY FINDINGS: PT + MO (1:2) improved the gastrointestinal function in mice suffering from PT-induced gastrointestinal motility disorder. Metabolomics indicated that the PT-MO mechanism was mainly associated with the regulations of 17 and 12 metabolites and 11 and 10 pathways in urine and faeces, respectively. The common metabolic pathways were those of tyrosine, purine, tricarboxylic acid cycle, pyruvate and gluconeogenesis, which were responsible for the PT-MO intervention mechanism. CONCLUSIONS: The PT-MO (1:2) couple mechanism mitigated the PT-induced disorders, which were related to the energy, amino acid and fatty metabolisms.
Subject(s)
Gastrointestinal Motility/drug effects , Magnolia/chemistry , Plant Extracts/pharmacology , Polygala/chemistry , Amino Acids/metabolism , Animals , Chromatography, High Pressure Liquid , Energy Metabolism/drug effects , Fatty Acids/metabolism , Feces , Female , Male , Mass Spectrometry , Metabolomics/methods , Mice , Plant Extracts/toxicity , Rats , Rats, Sprague-DawleyABSTRACT
The engineering of highly stable metal-organic frameworks (MOFs) will unveil the intrinsic potential of these materials for practical applications, especially for heterogeneous catalyzes. However, it is fairly challenging to rationally design robust MOFs serving as highly effective and reusable heterogeneous catalysts. Here, for the first time, we report the construction of four robust UiO-type chiral zirconium-metallosalen frameworks, denoted ZSF-1-4. Single-crystal X-ray-diffraction reveals that the frameworks consist of twelve-connected Zr6O8 clusters with privileged chiral metallosalen ligands anchored at ideal positions, generating confined chiral cages that enable synergistic activation. Unlike UiO-68 that is highly sensitive to aqueous solutions, ZSF-1-4 exhibit excellent chemical stability in aqueous solutions with a wide range of pH owing to the abundant hydrophobic groups within metallosalen ligands. These features render ZSF-1 and ZSF-2 to be excellent recycled heterogeneous catalysts for the conversion of imitated industrial CO2 with epoxides into cyclic carbonates with the highest reported turnover numbers in Zr-MOFs. With regard to asymmetric catalysis, ZSF-3 and ZSF-4 can effectively catalyze C-H azidation reaction in water medium with ee value up to 94%. Moreover, these robust ZSFs can be further extended to other analogues with various metal centers through demetallization-remetallization strategy, which renders them to be an excellent platform for broader fields.
ABSTRACT
Metal-organic frameworks (MOFs) imbedded privileged molecular catalysts are of particular interest due to their higher catalytic activities derived from the MOFs pore/channel confinement effect, improved lifetime through eliminating intermolecular deactivation pathway, and the recyclability based on their heterogeneity. In this work, a 3D chiral metallosalen-based MOF [Cd2(Cu(salen))(DMF)3]·DMF·3H2O (1) with a 1D open channel was synthesized and characterized by single-crystal X-ray diffraction and other physicochemical methods. Upon postsynthetic reduction modification with NaBH4, the conversion from imino to amino group on salen cores of 1 generates the reduction product 2 with a more flexible chiral group and more alkaline backbone, meanwhile still maintaining the original porous framework. 2 can be used as an efficient heterogeneous catalyst for the asymmetric Henry reaction with broad substrate applicability and exhibits higher activity and enantioselectivity (ee up to 98%) compared with the unreduced 1. Note that 2 can accelerate the Henry reaction of pyridine-2-carboxaldehyde possessing a potential coordination atom with excellent ee value; however, the homogeneous counterpart does not. In addition, the bulky aldehydes show a decrease in activity but almost the same enantioselectivity with an increase in the molecular size of substrates as a result of the chiral confinement effect of 2, indicating the size-dependent selectivity. To the best of our knowledge, this is the highest enantioselectivity for asymmetric Henry reaction catalyzed by MOF-based catalysts.
ABSTRACT
The development of well-defined multimetallic porous metal-organic frameworks (MOFs) will add a new dimension to the application of MOF catalysis. From this perspective, the understanding and tailoring of the catalytic metal sites in MOFs are key fundamental challenges that could reveal the intrinsic potential of these materials. In this work, a series of porphyrin-salen chiral MOFs (ps-CMOFs 2-7) have been synthesized through postsynthetic metalation (PSMet) of the parent ps-CMOF via single-crystal to single-crystal transformation. Crystal structures of these ps-CMOF analogues revealed the same topological structure but varied metal entities compared to those of the parent framework. Note that the PSMet process involves three methods involving cation exchange at the nodes, cation exchange at the metalated porphyrin, and cation addition at the free porphyrin, which has been systematically investigated using single-crystal X-ray diffraction and other physicochemical methods. The N2 adsorption tests, thermogravimetric analysis, and powder X-ray diffraction of 2-7 showed curves or patterns similar to those of 1, indicating the maintenance of the crystallinity, porosity, and thermal stability of the framework during the PSMet process. In addition, 2-7 showed distinctly improved adsorption capacities and isosteric heats of adsorption (Qst) for CO2 compared to those of their parent counterpart. Lastly, as a representative example of the ps-CMOF catalytic platform, 5 proved to be an efficient recyclable heterogeneous catalyst for the asymmetric addition reaction of CO2 with epoxides under mild conditions. Furthermore, because of the constrained chiral environment within ps-CMOF, the enantioselectivity of this reaction appears to be dependent on substrate size.