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Catalytic direct deoxygenation (DDO) of phenolic compounds to aromatics is an appealing approach for utilization of biomass‐lignin with minimal amount of H2 consumption. Metal/reducible metal oxide catalysts provide two functionalities, i. e., C−H bond formation (hydrogenation) and C−O bond breakage (deoxygenation), required for this reaction that takes place at the interfacial perimeter sites. Strong metal‐support interactions (SMSI) can profoundly alter the density and property of such sites. This short review summarized recent advances in tuning SMSI for enhancing DDO of phenolics. The approaches of varying reduction temperature, modulation of crystal facets and crystal phases of metal oxide, and reduction of mixed metal oxide were discussed for the origin for formation of SMSI, the degree of SMSI, and its consequence on the DDO performance. The analysis revealed that intermediate degree of SMSI with maximal density of metal/oxide interfacial perimeter site enhances DDO while minimizing unfavorable side reactions. This short review highlights the concept of tuning the interfacial perimeter sites via SMSI for reactions which require multiple functionalities and take place at the metal/oxide interface. [ABSTRACT FROM AUTHOR]

The inverse synthetic aperture radar (ISAR) image is a kind of target feature data acquired by radar for moving targets, which can reflect the shape, structure, and motion information of the target, and has attracted a great deal of attention from the radar automatic target recognition (RATR) community. The identification of ISAR image components in radar satellite identification missions has not been carried out in related research, and the relevant segmentation methods of optical images applied to the research of semantic segmentation of ISAR images do not achieve ideal segmentation results. To address this problem, this paper proposes an ISAR image part recognition method based on semantic segmentation and mask matching. Furthermore, a reliable automatic ISAR image component labeling method is designed, and the satellite target component labeling ISAR image samples are obtained accurately and efficiently, and the satellite target component labeling ISAR image data set is obtained. On this basis, an ISAR image component recognition method based on semantic segmentation and mask matching is proposed in this paper. U-Net and Siamese Network are designed to complete the ISAR image binary semantic segmentation and binary mask matching, respectively. The component label of the ISAR image is predicted by the mask matching results. Experiments based on satellite component labeling ISAR image datasets confirm that the proposed method is feasible and effective, and it has greater comparative advantages compared to other classical semantic segmentation networks. [ABSTRACT FROM AUTHOR]

A mechanistic understanding of catalytic reactions at solid‐liquid interface is limited both experimentally and theoretically but attracts much interest. Using density functional theory calculations (DFT) and ab initio molecular dynamics (AIMD) simulations, we investigated the effect of liquid water on α‐H abstraction, C−C coupling, and dehydration steps of aldol condensation of formaldehyde and acetone on an anatase TiO2(101) surface. The existence of the aqueous phase lowered the Gibbs energy of activation of dehydration step pronouncedly from 187 to 74 kJ/mol through proton transfer mechanism, making the hydrogenation pathway more favorable in the aqueous phase. In contrast, a mixed route prevails in the vapor phase. This work provides insights into the effect of the bulk water through a proton transfer mechanism on the dehydrogenation, C−C coupling, and dehydration steps. [ABSTRACT FROM AUTHOR]

Abstract: A comparative study of the hydrodeoxygenation of guaiacol, a phenolic compound derived from the lignin fraction of biomass with both hydroxyl and methoxyl functional groups, was performed on HBeta, Pt/SiO2, and Pt/HBeta at 350 °C and atmospheric pressure. The reaction pathway and the roles of the acid and metal sites were studied. Acid sites catalyze transalkylation and dehydroxylation reactions to produce monohydroxyl phenolics (phenol, cresols, and xylenols) as the major final products. Pt sites catalyze demethylation to result in catechol as the primary product, which can either be deoxygenated to phenol followed by phenol to benzene, or decarbonylated to cyclopentanone and further to butane. The close proximity of Pt and acid sites in bifunctional Pt/HBeta improves transalkylation and deoxygenation (or dehydroxylation) reactions and inhibits demethylation and decarbonylation reactions significantly, which leads to aromatics as the major final products with a total yield >85 %. Both the activity and stability of bifunctional Pt/HBeta during the hydrodeoxygenation of guaiacol are improved compared to those of HBeta and Pt/SiO2. The addition of water to the feed further improves the activity and stability through the hydrolysis of the O−CH3 bond of guaiacol on acid sites and the removal of coke around Pt. [ABSTRACT FROM AUTHOR]

The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal–organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C–H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production. [ABSTRACT FROM AUTHOR]

Water is typically treated as an implicit solvent in modeling electrochemical reactions in an aqueous environment. Such treatment may not be adequate, as a series of concerted or sequential proton-electron transfer steps that explicitly involve water molecules are likely to play important roles in a reaction, such as the electrochemical hydrogenation of CO2. Herein, we use the electrochemical hydrogenation of CO2 on the Sn(112) surface as a model, and employ the density functional theory (DFT) method to examine the effect of up to 12 explicit water molecules on the stability of the hydrogenation intermediates. Our results show that six water molecules are needed to account for the local interaction between an intermediate and the water solvent. Furthermore, the hydrogen bonding interaction between the explicit water molecules and intermediates causes a significant stabilization to the O-containing intermediates, such as the HCOO* and CHO* + OH* species. The inclusion of explicit water molecules also altered the prediction of the potential-limiting step from the formation of H* atoms without the explicit water molecules to the formation of H2COO* in the presence of water molecules and increased selectivity towards methane. This work provides useful insights into the electrocatalytic hydrogenation of CO2, emphasizing the importance of including explicit water molecules to account for the hydrogen bonding interaction between solvent water molecules and the reaction intermediates. [ABSTRACT FROM AUTHOR]

Abstract: Partial oxidation of ethanol with air was carried out in a pulsed discharge plasma reactor at low temperature and atmospheric pressure. Effects of O2:ethanol ratio, ethanol flow rate, and discharge current were investigated. H2 and CO are the major products (>86%). Increases of O2:ethanol ratio promote CO formation at the expense of C2 hydrocarbons. H2 selectivity and H2 + CO selectivity are maximized at O2:ethanol ratios of 0.3 and 0.5, respectively. Increases of feed flow rate accompanied by current increases allow the reactor to operate with high throughput. The LHV energy efficiency is increased with increasing feed flow rate, reaching 85% at high ethanol flow rates, conditions that also increase throughput. In contrast to catalytic and homogenous reactions, not all O2 is consumed at high O2:ethanol ratio for the low temperature plasma reaction. A radical reaction pathway of H abstraction from –OH and the α-H in ethanol to form CH3CHO followed by C–C scission is proposed. The produced hydrogen rich gas can be potentially used in fuel cells and engines. [Copyright &y& Elsevier]

Abstract: An argon glow discharge plasma was used for the reduction of carbon-supported Au catalysts at ambient temperature. The plasma-reduced Au/C sample produced 7–8nm Au particles that were highly dispersed on carbon. The surface oxygen species on carbon were increased by plasma treatment. Most interestingly, the metal particles were recessed into the carbon substrate. The stronger anchoring enhanced the stability of the active metal loaded on the support. The Au/C catalysts were tested for selective oxidation of glucose to gluconic acid compared with conventional hydrogen reduced catalysts. A significant improvement in glucose oxidation was achieved by the plasma-reduced sample. [Copyright &y& Elsevier]

Abstract: The catalytic conversion of anisole (methoxybenzene), a phenolic model compound representing a thermal conversion product of biomass lignin, to gasoline-range molecules has been investigated over a bifunctional Pt/HBeta catalyst at 400°C and atmospheric pressure. The product distribution obtained on the bifunctional catalyst was compared with those obtained on monofunctional catalysts (HBeta and Pt/SiO2). This comparison indicates that the acidic function (HBeta) catalyzes the methyl transfer reaction (transalkylation) from methoxyl to the phenolic ring, yielding phenol, cresols, and xylenols as the major products. The metal function catalyzes demethylation, hydrodeoxygenation, and hydrogenation in sequence, resulting in phenol, benzene, and cyclohexane. On the bifunctional catalyst, both methyl transfer and hydrodeoxygenation are achieved at significantly higher rates than over the monofunctional catalysts, leading to the formation of benzene, toluene, and xylenes with lower hydrogen consumption and a significant reduction in carbon losses, in comparison with the metal function alone. In addition, on the bifunctional Pt/HBeta, the rate of deactivation and coke deposition are moderately reduced. [Copyright &y& Elsevier]

Abstract: Sodium (1–10wt.%)-promoted 1wt.% Pt/TiO2 catalysts were prepared by a co-impregnation method and tested for the water gas shift (WGS) reaction under differential reaction conditions. Significantly higher intrinsic activity is achieved with 2–4wt.% Na addition, when 2–4 layers of NaO x are deposited on the support and the Pt particles are partially covered by NaO x , with moderate surface basicity and exposed Pt surface areas. In addition to the physical coverage, XPS data suggest that interactions between Pt and NaO x may occur by Pt electron donation to O in NaO x through Pt–O–Na. The strong metal–promoter interactions provide highly active sites for the WGS reaction at the periphery of the Pt–NaO x interface and also inhibit Pt particles from sintering. Optimal 4wt.% Na (Na/Pt=34) improves the intrinsic reaction rate and turnover frequency of Pt/TiO2 at 300°C by 8 and 11 times, respectively, and appears to be significantly higher than reported in the literature. The catalysts were characterized by X-ray diffraction, N2 adsorption, CO chemisorption, transmission electron microscopy, H2 temperature-programmed reduction, CO2 temperature-programmed desorption, and X-ray photoelectron spectroscopy. [Copyright &y& Elsevier]

Abstract: The conversion of propanal on large (2–5µm) and small (0.2–0.5µm) crystallite HZSM-5 at 400°C and atmospheric pressure has been studied. Improved catalyst stability was observed on small crystallites due to faster removal of products with the shorter diffusion path length, reducing the formation of coke precursors. As previously shown, C9 aromatics are the initial aromatics produced from propanal via aldol condensation followed by cyclization and these have less opportunity to crack to lighter aromatics on the small crystallites. Thus, a higher ratio of C9/(C8+C7) aromatics was observed on the small crystallites. The main isomer of the C8 aromatic products observed on small crystallites was the initial cracking product of the C9 aromatics, and thermodynamically preferred, meta-xylene, while the shape-selective preferred para-xylene was the predominant product on large crystallites. The higher internal diffusion rate of the para isomer results in greater shape selectivity with the longer path of the large crystallite zeolite. It is concluded that the use of smaller crystallite HZSM-5 improves results for production of alkyl aromatics from light oxygenates at mild conditions that may prove useful for bio-oil upgrading. [Copyright &y& Elsevier]

Abstract: Conversion of anisole, a typical component of bio-oil, was studied over an HZSM-5 zeolite at varying space times (W/F), reaction temperatures, type of carrier gas, and concentration of water in the feed. Several bimolecular and unimolecular reactions are proposed to explain the evolution of products observed. The bimolecular reactions include the following transalkylation reactions: (a) anisoles to phenol and methylanisole; (b) phenol and methylanisole to cresols; (c) phenol and anisole to cresol and phenol; (d) methylanisole and cresol to phenol and xylenol. A pseudo first-order kinetic model based on these bimolecular reactions was found to describe well the observed product distribution as a function of W/F. It is observed that shape selectivity effects prevail over electrophilic substitution and thermodynamic equilibrium effects in the formation of methylanisole isomers. However, the opposite is true for the distribution of cresol isomers. The kinetic analysis indicates that the contribution of unimolecular reactions such as isomerization is much lower than that of bimolecular reactions. The carrier gas composition was found to have a moderate effect on catalyst activity. When H2 was used as a carrier, catalyst stability showed a moderate improvement in comparison to the runs under He. However, a remarkable increase in catalytic activity was observed upon the addition of water in the feed. [Copyright &y& Elsevier]

Abstract: The reactivities of propanal and propylene have been compared over HSZM-5 zeolites (Si/Al=45 and 25). Propanal is found to be much more reactive than propylene and to form mostly 2-methyl-2-pentenal and C9 aromatics as early products in the reaction network. Propylene, in contrast, requires more severe conditions to form C6 and C7 aromatics. It is proposed that propanal undergoes acid-catalyzed aldol condensation to form 2-methyl-2-pentenal. This dimer undergoes further condensation to form the aldol trimer, which subsequently dehydrates and cyclizes into C9 aromatics. In contrast, it is well known that propylene, like other olefins, undergoes aromatization via oligomerization and formation of a hydrocarbon pool. While in the conversion of propanal, propylene is also produced, it appears that it does not play a major role in the formation of aromatics under conditions of shorter space times and lower temperatures, at which propanal produces aromatics in significant amounts. [Copyright &y& Elsevier]

Abstract: Conversion of propanal to gasoline-range molecules was investigated over a series of HZSM-5 catalysts with controlled mesoporosity generated by desilication. Characterization of the structure of the solid by powder X-ray diffraction (XRD), scanning electronic microscopy (SEM), ammonia and isopropylamine temperature programmed desorption (TPD), and n-butane diffusivity measurements confirmed the development of various degrees of mesoporosity in the zeolites. This structural modification seems to have little influence on Brønsted acid density. The catalyst stability was improved upon desilication due to an increase in coke tolerance. The product distribution of the propanal conversion was found to vary with the severity of the desilication. Increasing the extent of desilication gradually reduced the aromatization and cracking reactions, due to a reduction in the fraction of micropores and in the diffusion path length. Mildly desilicated samples were found to exhibit the best stability on stream and inhibited coke formation. [Copyright &y& Elsevier]

Abstract: Bio-ethanol reforming was studied using a plasma-catalytic reactor for hydrogen production at low temperature and atmospheric pressure without diluent gas or external heating. The plasma applied was a DC pulse discharge (corona) plasma. The water gas shift (WGS) catalyst was put just below the cathode electrode. The discharge generated heat was effectively used for feed vaporization and the WGS reaction. The large amounts of CO (∼30%) in the H2 rich gas formed in plasma reforming of ethanol (H2O/ethanol=6) was successfully reduced to ∼0.8% when a Pt/TiO2 and Pt–Re/TiO2 stacked bed were used for in situ WGS catalysis with a gas hourly space velocity up to 12,000cm3 g−1 h−1. The resultant gases contain ∼73% H2 and ∼23% CO2, with small amounts of CO, CH4, and C2H6, that is suitable for H2 fuel cell use after residual CO removal. Stability tests with daily startup–shutdown showed both plasma and catalyst are stable. The plasma-catalytic system is promising for low CO content H2 production, and could be extended to other applications. [Copyright &y& Elsevier]

Abstract: This study is derived from the innate concerns of electrospun poly(DL-lactide) (PDLLA) fibers as tissue engineering scaffolds: hydrophobic surface, surface erosion and dimensional shrinkage, which are not favorable to trigger the initial adhesion and further growth and population of cells. Blending electrospinning of PDLLA and poly(ethylene glycol) (PEG) with different PEG contents was evaluated for optimal tissue engineering scaffolds. The surface hydrophilicity was improved, and the degradation patterns of PDLLA/PEG mats changed from surface erosion to bulk degradation with the increase in PEG contents. The dimensional shrinkage was alleviated through the formation of crystal regions of PEG in the fiber matrix. The PDLLA/PEG fibrous mats were slightly weakened with the increase in the PEG contents, but a significant decrease in the tensile strength could be found for those with PEG contents of over 40%. Human dermal fibroblasts (HDFs) interacted and integrated well with the surrounding fibers containing 20 and 30% PEG, which provided significantly better environment for biological activities of HDFs than electrospun PDLLA mats. It indicated that electrospun mats containing 30% PEG exhibited the most balanced properties, including moderately hydrophilic surface, minimal dimensional changes, adaptable bulk biodegradation pattern and enhancement of cell penetration and growth within fibrous mats. [Copyright &y& Elsevier]

Na promoted Pt/TiO2 catalysts have been studied under high severity, near equilibrium, conditions for use as a single stage WGS catalyst. Addition of 3 wt% Na to a 1 wt% Pt/TiO2 catalyst has been found to improve water gas shift activity significantly compared to Pt/TiO2, Pt/CeO2, and Pt–Re/TiO2 catalysts. This catalyst is stable when the reaction temperature is higher than 250 °C. Deactivation occurred when the reaction temperature was lower than 250 °C, however, returning the temperature to higher than 250 °C fully recovered activity. TEM observations revealed that addition of Na inhibited Pt particle sintering. These results suggest that Na promoted Pt/TiO2 is a promising single stage water gas shift catalyst for small scale hydrogen production. [ABSTRACT FROM AUTHOR]

• Chemical isotope labeling liquid chromatography–mass spectrometry was used to analyze irradiated whole blood. • Taurine and hypotaurine metabolism changed after irradiation in plasma may repair the damage of irradiation. • The changes of adenine and hypoxanthine after irradiation in PBMCs may be related to the dysfunction of DNA synthesis. • The decreased AMP level after irradiation in RBCs may interfere with RBC storage lesions. Irradiated blood is a new type of blood product used to prevent transfusion-associated graft-versus-host disease. However, the effects of irradiation on the metabolism of plasma, red blood cells (RBCs), and peripheral blood mononuclear cells (PBMCs) are largely unknown. We developed a workflow for testing metabolic changes in whole blood to determine the impact of irradiation by chemical isotope labeling liquid chromatography-mass spectrometry (CIL LC–MS). Blood parameters, PBMC proliferation and apoptosis were examined before and after irradiation. Next, the amine/phenol metabolites in the blood components were assayed by 12C- and13C-dansylation labeling LC–MS. We identified 1654, 1730, and 1666 peak pairs in plasma, RBCs, and PBMCs, respectively. We screened out 367, 177, and 219 significant metabolites in plasma, RBCs, and PBMCs, respectively, by principle component analyses, volcano plots, and Venn plots. Metabolic pathway analyses showed that irradiation modulated taurine and hypotaurine metabolism in plasma and purine metabolism in RBCs and PBMCs. Changes in potential biomarkers, including an increase in hypoxanthine level and a decrease in adenine level, may be related to the dysfunction of DNA synthesis in PBMCs. The decreased AMP level in RBCs may interfere with RBC storage lesions. Our research provides a more comprehensive perspective on blood metabolism associated with irradiation. [ABSTRACT FROM AUTHOR]

Abstract: The glow discharge plasma treated Ni/Al2O3 catalyst showed an excellent anti-coke property for CO2 reforming of methane. Characterizations using X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR), transmission electron microscopy (TEM), and CO adsorbed infrared spectroscopy (IR) were conducted to investigate the structure and reactivity of the plasma treated Ni/Al2O3 catalyst for CO2 reforming of methane. It confirms that the plasma treatment of Ni precursor at room temperature followed by calcination thermally has a significant influence on the surface characteristics of the active phase. The plasma treated catalyst contains high concentration of close packed plane with improved Ni dispersion and enhanced Ni-alumina interaction, which lead to high catalytic activity and excellent resistance to formations of filamentous carbon and encapsulating carbon. [Copyright &y& Elsevier]

Abstract: In this work, diffuse reflectance infrared Fourier transformation (DRIFT) spectroscopy of adsorbed CO was studied to investigate the stability of Pt/ZrO2 catalysts for partial oxidation of methane. The studies confirmed that the preparation method has a significant effect on the catalyst performance and the catalyst treatment using argon glow discharge plasma improves the catalyst stability. TG analysis showed that coke formation is not significant on both samples with and without glow discharge plasma treatment, indicating the coke formation is not responsible for the catalyst deactivation. The IR band intensity of adsorbed CO decreases remarkably with increasing calcination temperature, suggesting the sintering of Pt particles in the presence of O2. The sintering of plasma treated sample is slower than that of the untreated sample, especially at higher temperature, which indicates that the plasma treated sample is more resistant to sintering under the oxidizing atmosphere. [Copyright &y& Elsevier]

Pd/HZSM-5 catalyst prepared via glow discharge plasma reduction followed by calcination thermally showed enhanced stability for methane combustion. In order to investigate the plasma catalyst preparation mechanism, oxygen glow discharge, initiated at room temperature, has been employed for reduction of Pd/HZSM-5 catalyst. The catalyst characterization using XRD and XPS analyses demonstrates that oxygen glow discharge plasma is also able to reduce Pd/HZSM-5 catalyst. This suggests that the electronic effect plays an important role in the treatment of catalyst using glow discharge. This also confirms that the thermal effect of the glow discharge reduction can be ignored. A highly durable catalyst for methane combustion has been obtained from calcination of the glow discharge reduced sample. [ABSTRACT FROM AUTHOR]

CO adsorbed infrared spectroscopy study was conducted in this work in order to better understand the significantly improved anti-coke performance of Ni/Al2O3 catalyst obtained via argon glow discharge plasma treatment. The present study revealed a significant decrease of linear to bridge (L/B) adsorbed CO for glow discharge plasma treated Ni/Al2O3, compared to that for untreated Ni/Al2O3, indicating an enhancement of close packed plane concentration. This structure change leads to lower methane turnover frequency (TOF) and better balance of carbon formation-gasification, resulting in better anti-coke property of Ni/Al2O3 for CO2 reforming of methane. [ABSTRACT FROM AUTHOR]

Abstract: Ni/Al2O3 catalyst was first treated by argon glow discharge plasma followed by calcination in air. The catalyst prepared this way exhibits an improved low-temperature activity for carbon dioxide reforming of methane, compared to the catalyst prepared without plasma treatment. The catalyst characterization using XRD, chemisorption and TEM analyses show that the plasma treatment followed by calcination thermally induces a generation of specific nickel species on the support. This kind of “plasma” metal species is highly dispersed on the support and can remain stable during reforming reactions. The average size of the “plasma” metal particles is ca. 5nm. The plasma treatment can also enhance the anti-carbon deposition performance of the catalyst. The formation of carbon species that is responsible for catalyst deactivation can be inhibited. The catalyst stability is therefore improved. [Copyright &y& Elsevier]

Understanding structural transformation and phase transition accompanying reactions in a solid as a catalyst or oxygen carrier is important to the design and optimization of many catalytic or chemical looping reaction processes. Herein, we combined density functional theory calculation with the stochastic surface walking global optimization approach to track the structural transformation accompanying the reduction of CuO upon releasing oxygen. We then used machine learning (ML) methods to correlate the structural properties of CuOx with varying x. By decomposing a reduction step into oxygen detachment and structural reconstruction, we identified two types of pathways: (1) uniform reduction with minimal structural changes; (2) segregated reduction with significant reconstruction. The results of ML analysis showed that the most important feature is the radial distribution functions of Cu–O at a percentage of oxygen vacancy [C(OV)] < 50% and Cu–Cu at C(OV) > 50% for CuOx formation. These features reflect the underlying physicochemical origin, i.e., Cu–O breaking and Cu–Cu formation in the respective stage of reduction. Phase diagram analysis indicates that CuO will be reduced to Cu2O under a typical oxygen uncoupling condition. This work demonstrates the complexity of solid structural transformation and the potential of ML methods in studying solid state materials involved in many chemical processes. [ABSTRACT FROM AUTHOR]

Simple Summary: Cholangiocarcinoma (CCA) accounts for approximately 15% of primary liver cancers. CCA has a poor prognosis and, thus, more effective systemic treatments are needed. We tested opaganib and upamostat, drugs that target sphingosine kinase 2 and multiple serine proteases, primarily trypsins, which are highly expressed in CCA tumors. This study demonstrates the results of inhibiting these novel targets with these drugs individually and in combination in a patient-derived CCA xenograft mouse model. Upamostat is an orally available small-molecule serine protease inhibitor that is a highly potent inhibitor of trypsin 1, trypsin 2, trypsin 3 (PRSS1/2/3), and the urokinase-type plasminogen activator (uPA). These enzymes are expressed in many cancers, especially during tissue remodeling and subsequent tumor cell invasion. Opaganib (ABC294640), a novel, orally available small molecule is a selective inhibitor of the phosphorylation of sphingosine to sphingosine-1-phosphate (S-1-P) by sphingosine kinase 2 (SPHK2). Both sphingosine kinase 1 (SPHK1) and SPHK2 are known to regulate the proliferation-inducing compound S-1-P. However, SPHK2 is more critical in cancer pathogenesis. The goal of this project was to investigate the potential antitumor effects of upamostat and opaganib, individually and in combination, on cholangiocarcinoma (CCA) xenografts in nude mice. PAX165, a patient-derived xenograft (PDX) from a surgically resected CCA, expresses substantial levels of SPHK2, PRSS1, PRSS2, and PRSS3. Four groups of 18 mice each were treated with upamostat, opaganib, both, or vehicle. Mouse weights and PAX165 tumor volumes were measured. Tumor volumes in the upamostat, opaganib, and upamostat plus opaganib groups were significantly decreased compared to the control group. [ABSTRACT FROM AUTHOR]

[Display omitted] • Recent advances in vapor phase hydrodeoxygenation (HDO) of phenolics are reviewed. • Reaction network of HDO on group 10 metals (Ni, Pd and Pt) are discussed. • Reaction mechanism of HDO on group 10 metals are compared. • Novel strategies on selective deoxygenation to aromatics are reviewed. Catalytic hydrodeoxygenation (HDO) of phenolics is a crucial step to convert lignin-biomass to chemicals and fuels. Catalysts based on group 10 metals (Ni, Pd and Pt) are widely used in HDO of phenolics. However, achieving a high yield toward the desirable product remains a challenge since a number of competing reactions take place at the same time, resulting in a complex product distribution. Herein, we review the recent advances in understanding the reaction mechanism on group 10 metal based catalysts and the novel strategies for selective deoxygenation of phenolics to aromatics on these catalysts under mild conditions (intermediate temperature and atmospheric pressure). Typically, HDO on Ni, Pd and Pt involves three main reaction pathways: a) hydrogenation to cyclohexanones/cyclohexanols; b) deoxygenation to aromatics, and c) C − C hydrogenolysis to CH 4. Among the possible mechanisms proposed for deoxygenation to aromatics, the partial hydrogenation mechanism shows the lowest barrier for C − O cleavage, and is therefore most likely to happen. Strategies such as increasing affinity to the O atom of phenols on the surface of Ni, Pd and Pt based catalysts by either reducing the particle sizes, alloying with an oxophilic metal, modifying the metal catalyst with a reducible oxide, or combining with an acidic zeolite have been reviewed. These strategies have been shown to improve the selectivity of HDO to aromatics over the hydrogenation and C − C hydrogenolysis products and are expected to provide useful guidance for rational design of the selective HDO catalysts. [ABSTRACT FROM AUTHOR]

The selective photocatalytic reduction of CO2 to CH4 remains a challenge because there is a need for not only strong adsorption sites for the intermediates, but also optimal proton-feeding sites on the photocatalyst surface. Herein, a synergistic dual-site function between in situ-generated Ni0 and Ni2P on carbon nitride nanosheets (CN) for photocatalytic reduction of CO2 to CH4 is presented. The highest CH4 production rate of 69.03 μmol g−1 h−1 is achieved on Ni2P/CN-0.5 in an aqueous suspension. Detailed analyses show that the promotion of CH4 is closely correlated with the formation of Ni0 sites due to light irradiation, which is confirmed by tracking the compositions of Ni2P/CN-0.5 through XPS and HRTEM characterization. Density functional theory calculations have been combined with CO-TPD and in situ FTIR spectra to reveal the synergy between in situ-generated Ni0 sites and Ni2P. It shows that the Ni0 sites can stabilize the key intermediate *CO, while the Ni0–Ni2P interface can promote *H transfer from Ni2P to Ni0. Therefore, the CO intermediates are rapidly protonated to form CHO* instead of being desorbed from the surface to produce CO, and subsequently CHO* will be converted into CH4. This work demonstrates a new strategy of designing highly efficient photocatalysts with synergistic catalytic sites for CO2 conversion to hydrocarbons. [ABSTRACT FROM AUTHOR]

Selective hydrodeoxygenation (HDO) of biomass lignin derived phenolics to aromatics is an attractive approach for utilization of biomass lignin, since minimal H 2 is consumed. Herein, bimetallic Ni-Cu/SiO 2 catalysts with varying Cu/Ni molar ratios were synthesized by a modified homogeneous precipitation-deposition method and tested for HDO of m-cresol at 350 °C and atmospheric pressure. Characterizations indicate the formation of Ni-Cu alloys with an enrichment of Cu on the surface, which breaks the contiguous surface Ni atoms and reduces the Ni ensemble size. Despite bare Ni/SiO 2 favors both C-C hydrogenolysis to CH 4 and direct deoxygenation (DDO) to toluene, Ni-Cu/SiO 2 makes DDO the dominant pathway (yield of 7.6% at conversion of 9.6% and yield of 90.4% at conversion of 95.2%) while suppresses the C-C hydrogenolysis to a very minor one. Ni-Cu/SiO 2 with an optimal Cu/Ni molar ratio of 0.5 produced a turnover frequency (TOF) of 3.09 min−1 for m-cresol conversion. The TOF for toluene formation on Ni-Cu/SiO 2 increases by ∼3 times to 2.24 min−1 from that on bare Ni/SiO 2 whereas the TOF of CH 4 formation is reduced by ∼10 times to 0.16 min−1. This study demonstrates that dilution of Ni by an inert metal such as Cu can effectively enhance DDO through inhibiting C-C hydrogenolysis during HDO of phenolics at atmospheric pressure. [Display omitted] • Hydrodeoxygenation of m-cresol was investigated at 350 °C and atmospheric pressure. • The formation Ni-Cu alloy reduces the ensemble size of Ni. • The optimal Cu/Ni molar ratio is 0.5. • C-C hydrogenolysis is inhibited on Ni-Cu/SiO 2 catalyst. • Direct deoxygenation is the dominant pathway on Ni-Cu/SiO 2. [ABSTRACT FROM AUTHOR]

Aim: Postpartum depression is prevalent worldwide and seriously endangers maternal and child health. Previous studies have demonstrated the effectiveness of psychological and psychosocial intervention programmes in preventing postpartum depression. However, the literature offers limited practice guidance. Therefore, this study aimed to deeply analyse prior findings to gather rich evidence‐based information on this topic. Methods: Using the distillation and matching model, we conducted a systematic review of psychological and psychosocial interventions used to effectively prevent postpartum depression. Four researchers trained in coding system independently read eligible studies and identified reliable (Cohen's kappa >0.40) and frequently occurring (frequency ≥3 winning study groups) practice elements. Results: Our review included 36 studies containing 37 winning study groups. Fourteen practice elements were identified and subsequently divided into six categories: postpartum practical problems‐related, social support‐related, interpersonal psychotherapy‐related, cognitive behavioural therapy‐related, labour trauma‐related and non‐specific techniques. The most common practice elements were baby care skills and mother–infant bonding/interaction enhancement. Inter‐rater reliability averaged 0.86, ranging from 0.48 to 1. Conclusion: The practice elements identified in this study provide rich evidence‐based information that can guide clinical practitioners in selecting or developing effective, realistically available intervention programmes. [ABSTRACT FROM AUTHOR]

ASPEN PLUS is an important tool for process design. But in the biomass gasification-gas turbine combustion field, ASPEN PLUS has not been extensively studied. In this paper, the operation unit in the biomass gasification-gas turbine combustion power generation system was introduced. Based on ASPEN PLUS, an integrated system model for power generation by biomass gasification-gas turbine combustion was developed. The model consists of biomass gasification and gas-cleaning system, gas turbine combustion system, and power generation system. The main aim of this research was to develop an integrated power generation system model, to predict the gasifier performance and power generation under various operating conditions. Parameters such as temperature, equivalence ratio (ER), and catalyst affected the syngas composition and heating value. The results show that the simulated data are consistent with the experimental data. Considering M701F gas turbine as the research object, the process of integrated power generation system was described. The simulation of biomass gasification-gas turbine combustion integrated power generation system can simulate the integrated system and obtain the main parameters of gas turbine. The system model based on ASPEN PLUS can be used to predict power generation capacity from biomass gasification-gas turbine combustion system. [ABSTRACT FROM AUTHOR]

A clear understanding of the structural transformation of copper-oxide-based oxygen carriers accompanying their reduction by fuels helps to design more efficient oxygen carriers for chemical looping combustion. Herein, density functional theory calculations have been performed on the bulk CuO, CuO(111) surface, and (CuO)32 cluster models with the same number of CuO molecular units to investigate structural transformation accompanying the reduction. The results showed that the averaged reaction energies of desorbing an oxygen molecule from the bulk and surface models are roughly the same [246.2 kJ/(mol O2) and 245.9 kJ/(mol O2), respectively]. The slab model does not significantly lower the overall reaction energy compared to the bulk model. In contrast, the averaged reaction energy using the cluster model is significantly lower [127.5 kJ/(mol O2)] than that of bulk and slab models. The key structural difference is the obvious Cu–Cu bond formation in the cluster model, which would result in nucleation of a metallic Cu phase. The results also showed that different states can be reached by desorbing different number oxygen atoms in a single step, corresponding to different reaction rates, when the system reaches the same level of reduction. These results demonstrate the complexity of reactions involving solid state materials and are consistent with the structural diversity observed experimentally. This study illustrates the importance of particle sizes and reaction conditions in the formation of suboxides during CuO reduction. [ABSTRACT FROM AUTHOR]

Reverse water gas shift (RWGS) reaction is an attractive approach to convert CO2 with renewable H2 to produce CO. However, this reaction is always accompanied by undesirable methanation reaction lowering the CO selectivity, particularly, at low reaction temperature and on Ni catalysts. Herein, a strategy of deposition of inert Ag on the surface of Ni to block methanation reaction during RWGS for selective conversion of CO2 toward CO was reported. Characterizations showed that in contrast to formation of bulk Ni−Ag alloy, both Ag particle and highly dispersed Ag are direct contacting with Ni particle. Surface Ag modifies the property of Ni geometrically and electronically, resulting in reduced accessible surface Ni sites and Ni ensemble size, as well as electron transfer from Ni to Ag. Consequently, both the amount and strength of CO adsorption are reduced, which facilitates CO desorption and reduces CO methanation activity. The Ag modification tunes Ni/SiO2 from selective methanation to selective RWGS, with 100 % CO selectivity on Ni‐0.3 Ag/SiO2 (Ag/Ni=0.3) at 400 °C with gas hourly space velocity (GHSV) >300 L g−1 h−1 and CO selectivity is >80.7 % even at a low GHSV of 15 L g−1 h−1. Moreover, the Ni‐0.3 Ag/SiO2 appears to be very stable for RWGS reaction. [ABSTRACT FROM AUTHOR]

[Display omitted] • The strong metal-support interaction (SMSI) of Pt/TiO 2 is dependent on TiO 2 facet. • The order of encapsulation degree is Pt/TiO 2 -100 > Pt/TiO 2 -001 > Pt/TiO 2 -101. • Encapsulation correlates well with reduction degree of TiO 2 and location of oxygen vacancy. • The highest reaction rate and turnover frequency were achieved on Pt/TiO 2 -001. Metal/reducible metal oxide catalysts are widely used in hydrodeoxygenation (HDO) reactions for upgrading bio-oil to produce chemicals and fuel components. Under such strong reducing condition, the strong metal-support interaction (SMSI) should take place, however, few work has been devoted to understand the effect of facet of metal oxide on the SMSI and its consequence on HDO performance. Herein, Pt supported on anatase TiO 2 with varying dominative exposed facets of (1 0 1), (1 0 0) and (0 0 1) were prepared and tested in HDO of m-cresol at 350 °C and atmosphere H 2 pressure. The degree of SMSI of Pt/TiO 2 is strongly dependent on the facet of TiO 2 when reduced at 350 °C, and the degree of encapsulation decreases following the order of Pt/TiO 2 -100 > Pt/TiO 2 -001 > Pt/TiO 2 -101. The encapsulation correlates well with the reduction degree of TiO 2 and the location of oxygen vacancy, which are resulted from varied oxygen vacancy formation and anisotropic diffusion rates in different facets. The intermediate SMSI is achieved on TiO 2 -001, which creates the maximal density of Pt-O v -Ti3+ sites at the interfacial perimeter of TiO x /Pt for deoxygenation of m-cresol, resulting in the highest reaction rate and turnover frequency (TOF) while the lowest activation energy (E a). In contrast, the maximum SMSI on TiO 2 -100 leads to the lowest deoxygenation rate while the highest E a. This work provides insight into facet dependent SMSI of Pt/TiO 2 and indicates the HDO activity can be finely tailored by tuning the facet of TiO 2. [ABSTRACT FROM AUTHOR]

Tin oxide (SnO x ) formation on tin-based electrode surfaces during CO 2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnO x in CO 2 reduction using a SnO monolayer on the Sn(1 1 2) surface as a model for SnO x . Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H 2 O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO 2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO 3 (t) ∗ ) intermediate, which can then be reduced to either formate (HCOO ∗ ) by hydrogenating the carbon atom or carboxyl (COOH ∗ ) by protonating the oxygen atom. Both steps involve a simultaneous C O bond breaking. Further reduction of HCOO ∗ species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH ∗ will decompose to CO and H 2 O via protonation. Whereas the oxygen vacancy (V O ) in the oxide monolayer maybe formed by the reduction, it can be recovered by H 2 O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO 2 reduction than the hydroxylated V O surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of −0.20 V (RHE), lower than that for the latter (−0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnO x monolayer on the electrode under the operating conditions promotes CO 2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH ∗ to the CO formation, although formic acid is still the major reduction product. [ABSTRACT FROM AUTHOR]

[Display omitted] • C-H activation on Cr/TiO 2 is mediated by surface-stabilized hydroperoxyl. • The production of OH radicals via Fenton mechanism is energetically unfavorable. • The C-H activation proceeds through a homolytic mechanism with a barrier of 0.44 eV. • The relative strength between the acidic and basic site determines the reactivity. • The presence of water does not alter the reaction pathways. Direct conversion of methane to methanol is an attractive alternative to the indirect, energy-intensive syngas production and conversion route. Herein, we present a comprehensive density functional theory (DFT) study of converting methane directly into methanol over the Cr single atom catalyst (SAC) on anatase TiO 2 (1 0 1) surface. Cr species stabilize in the form of CrO with H 2 O 2 as oxidant, on which methane reacts with the deprotonated H 2 O 2 via an Eley–Rideal mechanism. The formation of a three-centered transition-state structure is observed in the rate-determining C H bond activation step with an activation barrier of 0.44 eV. The H 2 O 2 not only serves as the oxidant for the formation of the most stable and reactive CrO species, but also enters the coordination sphere of the Cr center and acts as a highly effective H acceptor, which significantly lowers the activation barrier for C H bond cleavage. Over different Cr-O pairs, methane C H bond activation energy is found to linearly correlate with the energy difference between the d-bond center (ε d) of Cr and p-band center of O (ε p). The presence of water changes the relative stability of the reaction intermediates but does not alter the reaction pathways. This study demonstrated the ability of Cr SACs for catalyzing direct conversion of methane to methanol under mild conditions and would stimulate further interests in designing active Cr catalysts for methane conversion. [ABSTRACT FROM AUTHOR]

A series of rutile TiO2-supported Ni catalysts with varying Ni sizes were prepared and reduced at 650 °C to explore the effect of Ni size on the strong metal–support interactions (SMSI) and its consequences on the hydrodeoxygenation (HDO) of m-cresol at 350 °C and atmospheric pressure. When the Ni size increases from 4 to 29.1 nm, the SMSI becomes stronger, e.g., the thickness of the TiOx overlayer and the coverage extent of TiOx on the Ni particle surface increase. Direct deoxygenation to toluene is the dominant pathway on Ni/TiO2 catalysts with varying Ni loadings, with almost no CH4 being formed. These results indicate that the TiOx overlayer significantly alters the property of Ni. That is, the C-C hydrogenolysis activity on bare Ni is completely inhibited due to SMSI, while the deoxygenation activity is improved at the Ni-TiOx interfacial perimeter sites. Meanwhile, the turnover frequency of HDO on small Ni particles of 4 nm is > 2 times higher than that on large Ni particles of 29.1 nm, indicating that the small Ni particle with moderate SMSI appears to be optimal for the direct deoxygenation of m-cresol to toluene. The results suggest HDO activity may be enhanced by tuning the metal particle size and SMSI degree. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ni properties can be modified by tuning the SMSI with anatase and rutile TiO 2. • The overall HDO activity is significantly reduced due to excess SMSI on Ni/a-TiO 2. • Moderate SMSI occurs on Ni/r-TiO 2 only after reduction at 650 °C. • Ni/r-TiO 2 becomes selective for DDO toward toluene with inhibited C-C hydrogenolysis. • TOF of DDO on Ni/r-TiO 2 is improved by >10 times due to moderate SMSI. The relatively cheap and abundant Ni as a catalyst for hydrodeoxygenation (HDO) of biomass lignin-derived phenolics at 350 °C and atmospheric pressure suffers from unfavorable C-C hydrogenolysis toward CH 4 with a lower direct deoxygenation (DDO) activity. Herein, we demonstrate that the activity and selectively of Ni for HDO of m-cresol can be modified through the differences of strong metal-support interaction (SMSI) on anatase and rutile TiO 2. Characterizations showed that the presence of SMSI depended strongly on the crystal phase of TiO 2. The SMSI dominates on Ni/a-TiO 2 after reduction at 350 °C, resulting in Ni particles partially covered by a TiO x overlayer, and this overlayer became sufficiently thick at 650 °C, causing a significant reduction of CO chemisorption. Although the catalyst became selective for DDO to toluene, the overall HDO activity was significantly reduced because of excessive SMSI. In contrast, the Ni/r-TiO 2 catalyst reduced at 350 °C exhibited little SMSI and was active for C-C hydrogenolysis like a bare Ni catalyst. Increasing reduction temperature to 650 °C, the Ni/r-TiO 2 catalyst showed moderate SMSI and became selective to toluene through DDO while completely inhibited CH 4 formation. The toluene and total aromatics yields were 84.8 and 92.2%, respectively, at full conversion. More importantly, the turnover frequency for DDO (2.43 min−1) on the Ni/r-TiO 2 catalyst reduced at 650 °C was ∼40 and ∼14 times higher than that of Ni on rutile and anatase, respectively, reduced at 350 °C. This study provides an example of "Goldilocks principle" in catalysis, i.e., the best performing catalyst offers a balanced SMSI! [ABSTRACT FROM AUTHOR]

Hydrolytic hydrogenation of cellulose requires both functionalities of a metal and acid site. HZSM-5 has strong acid sites inside the micropores. However, those sites are not easily accessible to large molecules derived from cellulose. In this work, NaOH treatment of ZSM-5 was applied to introduce mesopores to the crystallite of ZSM-5. Characterizations showed that mesopores of 4-20 nm were successfully created on the surface of ZSM-5, and mesopore volume and total acid density (particularly Lewis acid density) increased as the severity of treatment increased. Loading of Ru on the mesoporous HZSM-5 resulted in a highly active and selective catalyst for conversion of cellulose to hexitols. The optimized hexitols yield of 39.4 % is 6 times higher than that of Ru supported on the parent HZSM-5. Model reaction studies (hydrolysis of cellobiose and hydrogenation of glucose) indicated that the enhanced acid density (particularly Lewis acid in mesopores) promotes the hydrolysis of oligosaccharides from primary depolymerization of cellulose. Furthermore, the uniform dispersion of smaller Ru nanoparticles due to the increased surface area caused by the mesopore enhanced the activity of the hydrogenation reaction. Consequently, a high yield of hexitols with reduced yield of small polyols was achieved on the optimized mesoporous Ru/HZSM-5. [ABSTRACT FROM AUTHOR]

Surface morphology of Cu-based catalysts is considered as an important factor affecting both activity and product selectivity of electrochemical reduction of CO2. In this work, surface cavity effect on C2H4 formation was investigated using Cu2O cubes: solid cubes, cavity cubes, and broken cubes, typically representing smooth surface, cavity surface, and rough surface. With respect of C2H4 selectivity, cavity cubes show the significantly enhanced faradaic efficiency (FE) of C2H4, which is 2.7 and 1.7 times higher than those for solid cubes and broken cubes respectively. Moreover, a ratio of CO produced by CO2 reduction reaction (CO2RR) converted to CH4 and C2H4 was calculated to assess the extent of CO further reduction for a catalyst. As noted, cavity cubes exhibited a highest ratio of 29.5%, in contrast with the lower ratio of 13.0% on broken cubes and 14.9% on solid cubes. Consequently, the role of surface cavity is reflected in two effects, the increased CO formation due to higher electrochemical surface area as compared to the smooth surface, and meanwhile the increased ratio of CO converted to hydrocarbons and alcohols due to porous feature as compared to the rough surface with a comparable high electrochemical active surface area (ECSA). What's more, when applied in a flow cell reactor with a gas diffusion electrode, cavity cubes also achieved much higher C2 selectivity of 37.7% FEC2 than solid cubes and broken cubes. Our work provides a facile strategy for improving the catalytic C2+ product selectivity of Cu2O-based catalysts for CO2RR through modifying surface morphology. [ABSTRACT FROM AUTHOR]

Ru supported on zirconia-modified SBA-15 as a catalyst for selective conversion of cellobiose has been prepared and characterized using X-ray diffraction, N 2 adsorption, transmission electron microscopy, and temperature programmed desorption of NH 3 . Coating SBA-15 with zirconia generates acid sites as well as improves Ru dispersion in the mesopore. At a Zr/Si ratio of 0.25 (∼1.4 monolayer coverage of zirconia on the SBA-15 surface), the mesoporous structure of SBA-15 was well preserved in zirconia-modified SBA-15. Increasing the amount of zirconia beyond Zr/Si = 0.5 resulted in narrowing of the mesopores and, eventually, pore blockage. Mechanistic study of cellobiose conversion on the catalyst indicates that the reaction proceeds sequentially through (a) hydrogenolysis/hydrogenation of cellobiose to 3-β- d -glucopyranosyl- d -glucitol, (b) hydrolysis to sorbitol and glucose, and (c) glucose hydrogenation to hexitols, with the hydrolysis step being the rate-determining step for hexitols formation. A complete conversion of cellobiose with a hexitols yield of 72% has been achieved at 140 °C in 1 h with the optimal Zr/Si ratio of 0.25. A comparison with the more acidic Ru/HZSM-5 catalyst demonstrated the importance of the mesopores of SBA-15 to the catalytic reactivity of Ru/Zr-SBA-15(0.25). [ABSTRACT FROM AUTHOR]

[Display omitted] • The oxygen site of supported CuO exhibits a characteristic of a radical anion. • The radical anionic oxygen enables homolytic C-H cleavage, resulting in a •CH 3. • The CH 3 radical captured by the Cu site enables the CH 3 -OH coupling to form CH 3 OH. • SnO 2 offers a balanced reactivity for C-H activation and C-O formation. Direct conversion of methane into methanol is an attractive strategy for the production of manifold value-added chemicals. Herein, we investigated the conversion of methane to methanol over CuO supported on the rutile metal oxides (TiO 2 , SnO 2 and RuO 2) based on results of density functional theory (DFT) calculations. The results show that the oxygen site of the supported CuO exhibits the characteristics of a radical anion. This radical anionic oxygen site enables homolytic C-H cleavage by abstracting the hydrogen atom, resulting in a CH 3 radical. The CH 3 radical captured by the Cu site next to the radical anionic oxygen enables the coupling of CH 3 and OH to form a C-O bond, resulting in methanol. The free energy of activation for C-H activation and C-O formation were found to correlate linearly with the p band center of the radical anionic oxygen, but the slope has the opposite signs, i.e., a lower free energy of activation for C-H scission corresponds to a higher free energy formation for C-O formation. Among rutile oxides studied, SnO 2 offers a balanced reactivity for C-H activation and C-O formation. These findings demonstrate the presence of the radical anionic oxygen on rutile oxide-supported CuO catalyst and their crucial role in regulating the reactivity for direct methane to methanol conversion. The mechanistic insights from this study will benefit the development of supported copper oxide catalysts for effective methane conversion. [ABSTRACT FROM AUTHOR]

A series of CeO 2 catalysts with varying Na content were tested for vapor-phase ketonization of propionic acid at 350 °C. Na+ diffuses into the CeO 2 lattice and excess NaO x accumulates on the surface, which dilutes surface contiguous and partially covers Ce-O acid-base pairs. The intrinsic reaction rate in terms of surface area always decreased with increasing Na, likely originated from the altered acid-base property and the increased distance and steric hindrance between enolate and carboxylate for C-C coupling. On the other hand, the stability was significantly improved, with almost no deactivation being observed for Na 0.1 Ce 0.9 O x. This improvement is resulted from the dilution and/or coverage effects of NaO x , which significantly reduces accumulation of inactive bidentate propionate. This work demonstrates a strategy of dilution and/or coverage of surface acid-base pairs by alkaline metal oxides to reduce bidentate carboxylate and therefore to enhance the stability of metal oxide catalysts toward ketonization of carboxylic acids. [Display omitted] • Na dilutes surface contiguous and partially covers Ce-O acid-base pairs. • Doping Na significantly enhanced the stability of CeO 2 for ketonization reaction. • Na dilution and coverage effects reduced coverage of bidentate propionate. • Reduced coverage of bidentate propionate led to improved stability. [ABSTRACT FROM AUTHOR]

Selective hydrodeoxygenation (HDO) of biomass lignin‐derived phenolic compounds to aromatics is a demanding reaction. Oxophilic Ru based catalysts can catalyze direct deoxygenation but suffer from competing C−C hydrogenolysis to CH4 at 350 °C and hydrogenation of phenyl ring at 250 °C under atmospheric pressure. In this work, a solid solution Ru0.05Ce0.95O2 catalyst was hydrothermally synthesized, characterized and tested for HDO of m‐cresol. The Ru species is highly dispersed in the solid solution as isolated atoms and/or subnanometer clusters as a result of strong Ru−O−Ce interaction, and the catalyst shows high concentration of oxygen vacancies. In contrast to nonselective Ru/SiO2, Ru0.05Ce0.95O2 selectively catalyzes deoxygenation to toluene while significantly inhibits C−C hydrogenolysis and hydrogenation. Moreover, the overall intrinsic HDO rate on Ru0.05Ce0.95O2 is 2.2 and 8.8 times higher than those on Ru/CeO2 and Ru/SiO2, respectively. The Ru−OV−Ce sites were proposed to be the active sites for deoxygenation. Inhibition of C−C hydrogenolysis and phenyl hydrogenation can be ascribed to the reduced size of the Ru ensembles due to the strong interaction in the solid solution. [ABSTRACT FROM AUTHOR]

We demonstrate resonant slot nanoantennas on Ag film for surface plasmon (SP) radiation in optical frequency range. Radiation spectra of the nanoantennas and resonant mode patterns for different mode orders with high spatial resolution are obtained using cathodoluminescence spectroscopy. The dispersions are obtained from the experimental data, and the far-field angular distributions of the radiation are simulated for the four lowest modes. The nanoantennas, which can realize resonant conversion between free space light and SPs at nanoscale, should find applications in nanophotonic devices and integrated optical circuits. [ABSTRACT FROM AUTHOR]

A novel catalyst preparation for NO reduction by CH4 has been conducted using a glow discharge plasma treatment followed by calcinations thermally. Such plasma prepared Pt/NaZSM-5 catalyst exhibits a high dispersion of metal active species. A remarkable improvement in the activity and stability, compared to the catalysts prepared conventionally, has been achieved. Especially, an excellent low temperature activity over the plasma-treated Pt/NaZSM-5 catalyst has been obtained. For example, the conventional 0.1 wt% Pt/NaZSM-5 catalyst shows no activity at temperatures below 673 K, while at 673 K, the NO conversion to nitrogen reaches 61.3% over the plasma-treated 0.1 wt% Pt/NaZSM-5 catalyst. The initiated temperature for the plasma-treated 0.1 wt% Pt/NaZSM-5 catalyst can be as low as 548 K. [Copyright &y& Elsevier]

Electrochemical reduction of carbon dioxide to fuels has been recognized as a perspective way to address the environmental and energy issues. Herein, the novel Au decorated Cu2O electrocatalysts were synthesized via the galvanic replacement reaction and the successive pre‐reduction by linear voltammetry (LSV) method. In contrast to Cu2O, CO formation became dominant over HCOOH and H2 on AuxCu2O, and a remarkably enhanced selectivity of C2H4 was obtained beyond −1.1 V vs. RHE. Among them, Au0.02Cu2O exhibited the highest Faraday efficiency (FE) of C2H4 of 24.4 % at −1.3 V vs. RHE, which was as high as 2∼2.5 and 5 times of those on other two AuxCu2O and bare Cu2O, respectively. Meanwhile, it is demonstrated that the optimal ratio of Au/Cu was essential for effective sequential catalysis between Au and Cu2O to enhance C−C coupling. Furthermore, the effect of copper states resulting from different pre‐reduction methods on the selectivity of C2H4 was explored. A half decrease of C2H4 FE was observed on HPR‐Au0.02Cu2O (high potential reduced) relative to the LSV reduced Au0.02Cu2O, which was ascribed to the different content of Cu0 and residual Cu+ in two catalysts. Our results demonstrate an effective approach to construct Cu2O based bimetallic catalysts for ethylene formation from CO2. [ABSTRACT FROM AUTHOR]

The morphology of catalysts is a key factor influencing their photocatalytic performance. Herein, we prepared three W 18 O 49 photocatalysts with different morphologies of sea urchin (W 18 O 49 SU), nanorod (W 18 O 49 NR) and hollow sphere (W 18 O 49 HS), and evaluate their performances in photocatalytic hydrolysis of ammonia borane (AB). Remarkably, W 18 O 49 SU exhibited an impressive photocatalytic H 2 production rate with the highest TOF of 53.1 min−1 under visible light, which is 10.4 and 7.5 times higher than those of W 18 O 49 HS and W 18 O 49 NR, respectively. The comprehensive characterizations and control experiments revealed that the unique sea urchin-like morphology enabled the strong light harvesting by multiple light scattering, fast separation of photogenerated charges and directional electron enrichment by nanotip effect, which collaboratively boost the photocatalytic activity. Moreover, the enhancement effect of sea urchin-like morphology is again approved well on Nb 2 O 5 photocatalysts. This work opens a paradigm to synergistically improve light harvesting and charge separation efficiency through rational design of photocatalyst nanostructure. Sea urchin-like W 18 O 49 showed excellent photocatalytic activity for H 2 production from AB, which is attributed to enhanced light harvesting, fast separation of photogenerated charges and directional electron enrichment caused by multiple light scattering and nanotip effect. [Display omitted] • Morphological W 18 O 49 was evaluated in AB hydrolysis. • Sea urchin W 18 O 49 enables strong light harvesting by multiple light scattering. • Nanotip effect promotes separation of charge carriers and electron enrichment. [ABSTRACT FROM AUTHOR]

[Display omitted] • Au/Cu 2 O composed of Au nanoparticles on Cu 2 O hollow nanospheres were successfully synthesized. • Au/Cu 2 O catalysts have an earlier onset potentials for ethanol production than Cu 2 O. • CH 3 CH 2 OH formation is favored over C 2 H 4 on Au/Cu 2 O and increases as Au amount increased. • Enhanced ethanol formation is due to more CO formation on Au sites to promote C–C coupling. Electrochemical CO 2 reduction (CO 2 RR) to ethanol is a way to advance CO 2 utilization toward a renewable chemical feedstock and fuel. In present study, an approach to promote ethanol production is employed through adding Au, which is favorable toward CO formation, onto Cu 2 O catalysts. Namely, the Cu 2 O hollow nanospheres with a size of 150−180 nm were synthesized by a soft template method, and then Au nanoparticles of ∼7 nm were loaded to obtain Au x /Cu 2 O composites. The Au x /Cu 2 O catalysts have an earlier onset for ethanol production than Cu 2 O. Besides, Au x /Cu 2 O catalysts display the significantly enhanced Faraday efficiencies (FEs) of CO and ethanol, the suppressed hydrogen evolution reaction and the slightly weakened HCOOH formation. Among them, Au 0.17 /Cu 2 O stands out with the highest FEs of ethanol from 10.8%–16.2% throughout the measuring potentials, suggesting an optimal amount of Au. Furthermore, it is found that the FEs of ethanol increase as the atomic ratio of Au/Cu increases at the medium reduction potentials (-1.1 V to -1.3 V). Besides, it is demonstrated that ethanol formation is more favorable over ethylene formation, evidenced by the ratio of FE ethanol /FE ethylene reaching 2.0, 3.3, 4.1 on three Au x /Cu 2 O catalysts, respectively. This correlation between the ethanol production and the Au amount reflects that Au plays a crucial role in promoting ethanol formation. The enhanced ethanol formation is ascribed to more CO formation on Au sites to promote C–C coupling. Our study demonstrates an effective approach to develop Cu-based electrocatalysts for ethanol formation from CO 2. [ABSTRACT FROM AUTHOR]

Background: Anxiety is common during pregnancy. The 7-item Generalized Anxiety Disorder scale (GAD-7) is a self-rating scale for detecting anxiety and has been validated in various populations, but it has not been validated in pregnant Chinese women. The objective of this study was to validate the GAD-7 as a screening tool to detect anxiety during pregnancy among Chinese women.Methods: The GAD-7 and the anxiety subscale of the Hospital Anxiety and Depression scale (HADS-A) were administered to 140 pregnant Chinese women to evaluate the Cronbach's alpha and the criterion-related validity. Additionally, a diagnostic study (n=170) was conducted by using the Mini International Neuropsychiatric Interview (MINI) as a gold standard to examine the screening performance of the GAD-7. We calculated the sensitivity, specificity, and area under the curve (AUC) by receiver operating characteristic (ROC) analysis.Results: Cronbach's alpha for the GAD-7 was 0.84. The Pearson correlation coefficient between GAD-7 and HADS-A scores was 0.66 (P<0.01). At the maximum Youden Index of 0.53, the optimal cutoff score for the GAD-7 among pregnant women was 7, and an AUC of 0.83, a sensitivity of 96.8%, and a specificity of 56.1% were obtained.Limitation: The majority of the participants were in the first trimester, and thus, the findings cannot be generalized to all pregnant women.Conclusions: The GAD-7 is a suitable screening instrument for detecting antenatal anxiety in mainland China. Further validation is warranted in women in different trimesters of pregnancy. [ABSTRACT FROM AUTHOR]