Polyphenylene as an Active Support for Ru-Catalyzed Hydrogenolysis of 5-Hydroxymethylfurfural

Selective transformation of biomass feedstocks to platform molecules is a key pursuit for sustainable chemical production. Compared to petrochemical processes, biomass transformation requires the defunctionalization of highly polar molecules at relatively low temperatures. As a result, catalysts based on functional organic polymers may play a prominent role. Targeting the hydrogenolysis of the platform chemical 5-hydroxymethylfurfural (5-HMF), here, we design a polyphenylene (PPhen) framework with purely sp2-hybridized carbons that can isolate 5-HMF via π–π stacking, preventing hemiacetal and humin formation. With good swellability, the PPhen framework here has successfully supported and dispersed seven types of metal particles via a newly developed swelling-impregnation method, including Ru, Pt, Au, Fe, Co, Ni, and Cu. Ru/PPhen is studied for 5-HMF hydrogenolysis, achieving a 92% yield of 2,5-dimethylfuran (DMF) under mild conditions, outperforming the state-of-the-art catalysts reported in the literature. In addition, PPhen helps perform a solventless reaction, achieving direct 5-HMF to DMF conversion in the absence of any liquid solvent or reagent. This approach in designing support–reactant/solvent/metal interactions will play an important role in surface catalysis

Synergy of Ag and AgBr in a Pressurized Flow Reactor for Selective Photocatalytic Oxidative Coupling of Methane

Oxidation of methane into valuable chemicals, such as C2+ molecules, has been long sought after but the dilemma between high yield and high selectivity of desired products remains. Herein, methane is upgraded through the photocatalytic oxidative coupling of methane (OCM) over a ternary Ag-AgBr/TiO2 catalyst in a pressurized flow reactor. The ethane yield of 35.4 μmol/h with a high C2+ selectivity of 79% has been obtained under 6 bar pressure. These are much better than most of the previous benchmark performance in photocatalytic OCM processes. These results are attributed to the synergy between Ag and AgBr, where Ag serves as an electron acceptor and promotes the charge transfer and AgBr forms a heterostructure with TiO2 not only to facilitate charge separation but also to avoid the overoxidation process. This work thus demonstrates an efficient strategy for photocatalytic methane conversion by both the rational design of the catalyst for the high selectivity and reactor engineering for the high conversion

Progress and perspective of interface design in garnet electrolyte-based all-solid-state batteries

Inorganic solid-state electrolytes (SSEs) are nonflammable alternatives to the commercial liquid-phase electrolytes. This enables the use of lithium (Li) metal as an anode, providing high-energy density and improved stability by avoiding unwanted liquid-phase chemical reactions. Among the different types of SSEs, the garnet-type electrolytes witness a rapid development and are considered as one of the top candidates to pair with Li metal due to their high ionic conductivity, thermal, and electrochemical stability. However, the large resistances at the interface between garnet-type electrolytes and cathode/anode are the major bottlenecks for delivering desirable electrochemical performances of all-solid-state batteries (SSBs). The electrolyte/anode interface also suffers from metallic dendrite formation, leading to rapid performance degradation. This is a fundamental material challenge due to the poor contact and wettability between garnet-type electrolytes with electrode materials. Here, we summarize and analyze the recent contributions in mitigating such materials challenges at the interface. Strategies used to address these challenges are divided into different categories with regard to their working principles. On one hand, progress has been made in the anode/garnet interface, such as the successful application of Li-alloy anode and different artificial interlayers, significantly improving interfacial performance. On the other hand, the desired cathode/garnet interface is still hard to reach due to the complex chemical and physical structure at the cathode. The common methods used are nanostructured cathode host and sintering additives for increasing the contact area. On the basis of this information, we present our views on the remaining challenges and future research of electrode/garnet interface. This review not only motivates the need for further understanding of the fundamentals, stability, and modifications of the garnet/electrode interfaces but also provides guidelines for the future design of the interface for SSB

Selective catalytic oxidation of ammonia over nano Cu/zeolites with different topologies

The selective catalytic oxidation of ammonia (NH3-SCO) is the last mitigation step in exhaust treatment using a 4-way catalytic converter to convert any excess and unreacted NH3 (that was used as a reductant of NOx) into environmentally benign N2 and H2O. Here, we report a series of highly reactive and selective nano Cu/zeolites for the NH3-SCO reaction. The NH3-SCO activity was found in the order nano Cu/ZSM-5 (MFI topology) > Cu/Beta (BEA) > Cu/MCM-49 (MWW) > Cu/Y (FAU) > Cu/Mordenite (MOR) > Cu/Ferrierite (FER). The best catalyst, i.e., nano Cu/ZSM-5, achieves 98% NH3 conversion at 250 °C with the N2 yield maintained at >98% even at up to 500 °C. When assessed under practical exhaust conditions in the presence of moisture (5% H2O) as well as that after hydrothermal aging (5% H2O, 850 °C, 8 h), the nano Cu/ZSM-5 exhibited only minor deactivation as a result of its good retention of Cu dispersion, pore structure and specific surface area. Furthermore, small micropore (10-membered ring, 10-MR) topologies were found to be crucial in maintaining high N2 yields. For Cu/Y and Cu/Mordenite, composed of 12-MR pores that are non-interconnected with smaller pores, their N2 yields were compromised by forming NOx at temperatures above 400 °C. Based on the in situ DRIFTS study, the iSCR mechanism appears to be applicable for all fresh and aged Cu/zeolites with the exception of fresh Cu/MCM-49 that follows the imide mechanism

Global behavior of cosmological dynamics with interacting Veneziano ghost

In this paper, we shall study the dynamical behavior of the universe accelerated by the so called Veneziano ghost dark energy component locally and globally by using the linearization and nullcline method developed in this paper. The energy density is generalized to be proportional to the Hawking temperature defined on the trapping horizon instead of Hubble horizon of the Friedmann-Robertson-Walker (FRW) universe. We also give a prediction of the fate of the universe and present the bifurcation phenomenon of the dynamical system of the universe. It seems that the universe could be dominated by dark energy at present in some region of the parameter space.Comment: 8 pages, 7 figures, accepted for publication in JHE

Enhancement of cell-specific transgene expression from a Tet-Off regulatory system using a transcriptional amplification strategy in the rat brain

10.1002/jgm.1178Journal of Gene Medicine105583-592JGME

Effective Activation of Strong C−Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo-Coupling

Carbon-carbon (C−C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal-ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C−C coupling of chloride substrates is rare due to the extremely high bond energy of C−Cl bond (327 kJ mol−1). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo-coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C−C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species

UV-IR luminosity functions and stellar mass functions of galaxies in the Shapley supercluster core

We present a panchromatic study of luminosity functions (LFs) and stellar mass functions (SMFs) of galaxies in the core of the Shapley supercluster at z=0.048, in order to investigate how the dense environment affects the galaxy properties, such as star formation (SF) or stellar masses. We find that while faint-end slopes of optical and NIR LFs steepen with decreasing density, no environment effect is found in the slope of the SMFs. This suggests that mechanisms transforming galaxies in different environments are mainly related to the quench of SF rather than to mass-loss. The Near-UV (NUV) and Far-UV (FUV) LFs obtained have steeper faint-end slopes than the local field population, while the 24$\mu$m and 70$\mu$m galaxy LFs for the Shapley supercluster have shapes fully consistent with those obtained for the local field galaxy population. This apparent lack of environmental dependence for the infrared (IR) LFs suggests that the bulk of the star-forming galaxies that make up the observed cluster IR LF have been recently accreted from the field and have yet to have their SF activity significantly affected by the cluster environment.Comment: 5 pages, 3 figures, JENAM 2010, Symposium 2. Conference proceeding

Versatile Preparation of Mesoporous Single-Layered Transition-Metal Sulfide/Carbon Composites for Enhanced Sodium Storage

Transition metal sulfides are promise electrochemical energy storage materials due to their abundant active sites, large inter-layer space and high theoretical capacities. Especially for sodium storage. However, the low conductivity and poor cycling stability at high current densities hampered their applications. Herein, we report a versatile dual-templates method to elaborate ordered mesoporous single layered MoS2 /carbon composite with high specific area, uniform pore size and large pore volume. The single layered MoS2 is confined in the carbon matrix. The mesopores between the composite nanorods provide fast electrolyte diffusion. The obtained nanocomposite shows a high sodium storage capability, excellent rate capacity, and very good cycling performance. A 310 mAh g-1 capacity can remains at 5.0 A g-1 after 2500 cycles. Furthermore, a SIB full cell composed the MoS2 /carbon composite anode and a Na3 V2 (PO4 )3 (NVP) cathode maintains a specific capacity of 330 mA h g-1 at 1.0 A g-1 during 100 cycles. The mechanism is investigated by in situ and ex situ characterizations as well as density functional theory (DFT) calculations. This article is protected by copyright. All rights reserved

Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation

RuII compounds are widely used in catalysis, photocatalysis, and medical applications. They are usually obtained in a reductive environment as molecular O2 can oxidize RuII to RuIII and RuIV. Here we report the design, identification and evolution of an air‐stable surface [bipy‐RuII(CO)2Cl2] site that is covalently mounted onto a polyphenylene framework. Such a RuII site was obtained by reduction of [bipy‐RuIIICl4]− with simultaneous ligand exchange from Cl− to CO. This structural evolution was witnessed by a combination of in situ X‐ray and infrared spectroscopy studies. The [bipy‐RuII(CO)2Cl2] site enables oxidation of CO with a turnover frequency of 0.73×10−2 s−1 at 462 K, while the RuIII site is completely inert. This work contributes to the study of structure–activity relationship by demonstrating a practical control over both geometric and electronic structures of single‐site catalysts at molecular level