A Low-Noble-Metal Ru@CoMn2O4 Spinel Catalyst for the Efficient Oxidation of Propane.

Noble metals have become a research hotspot for the oxidation of light alkanes due to their low ignition temperature and easy activation of C-H; however, sintering and a high price limit their industrial applications. The preparation of effective and low-noble-metal catalysts still presents profound challenges. Herein, we describe how a Ru@CoMn2O4 spinel catalyst was synthesized via Ru in situ doping to promote the activity of propane oxidation. Ru@CoMn2O4 exhibited much higher catalytic activity than CoMn2O4, achieving 90% propane conversion at 217 °C. H2-TPR, O2-TPD, and XPS were used to evaluate the catalyst adsorption/lattice oxygen activity and the adsorption and catalytic oxidation capacity of propane. It could be concluded that Ru promoted synergistic interactions between cobalt and manganese, leading to electron transfer from the highly electronegative Ru to Co2+ and Mn3+. Compared with CoMn2O4, 0.1% Ru@CoMn2O4, with a higher quantity of lattice oxygen and oxygen mobility, possessed a stronger capability of reducibility, which was the main reason for the significant increase in the activity of Ru@CoMn2O4. In addition, intermediates of the reaction between adsorbed propane and lattice oxygen on the catalyst were monitored by in situ DRIFTS. This work highlights a new strategy for the design of a low-noble-metal catalyst for the efficient oxidation of propane.

Evolution of the Composition and Melting Behavior of Spinnable Pitch during Incubation.

The physical and chemical properties of spinnable pitch showed a huge impact on the performance of resultant pitch carbon fiber even if its physical and chemical properties were slightly changed. Various polycyclic aromatic compounds and abundant free radicals existed in spinnable pitch, and there are many interactions among molecules and free radicals. The molecular structure and composition of spinnable pitch were investigated during incubation, and the effect of molecular evaluation on rheological properties of spinnable pitch was illustrated using various characterization methods in this work. It indicated that n-hexane soluble fraction mainly occurred condensation or cleavage, and a small number of heavy components were generated after a long period. The fraction of n-hexane insoluble/toluene soluble underwent molecular condensation and cross-linking in the presence of oxygen-containing radicals and aromatic hydrocarbon radicals, while toluene insoluble/tetrahydrofuran soluble fraction tended to change in large molecules of polycyclic aromatic hydrocarbons. Lastly, tetrahydrofuran insoluble fraction was condensed due to its high aromaticity during the incubation process, and the content of aromatic carbon increased. These changes of composition and structure of spinnable pitch led to its softening point, increase in viscosity and flow activation energy, and deterioration of the rheological property.

Plant elicitor peptide signalling confers rice resistance to piercing-sucking insect herbivores and pathogens.

Rice is a staple food crop worldwide, and its production is severely threatened by phloem-feeding insect herbivores, particularly the brown planthopper (BPH, Nilaparvata lugens), and destructive pathogens. Despite the identification of many BPH resistance genes, the molecular basis of rice resistance to BPH remains largely unclear. Here, we report that the plant elicitor peptide (Pep) signalling confers rice resistance to BPH. Both rice PEP RECEPTORs (PEPRs) and PRECURSORs of PEP (PROPEPs), particularly OsPROPEP3, were transcriptionally induced in leaf sheaths upon BPH infestation. Knockout of OsPEPRs impaired rice resistance to BPH, whereas exogenous application of OsPep3 improved the resistance. Hormone measurement and co-profiling of transcriptomics and metabolomics in OsPep3-treated rice leaf sheaths suggested potential contributions of jasmonic acid biosynthesis, lipid metabolism and phenylpropanoid metabolism to OsPep3-induced rice immunity. Moreover, OsPep3 elicitation also strengthened rice resistance to the fungal pathogen Magnaporthe oryzae and bacterial pathogen Xanthamonas oryzae pv. oryzae and provoked immune responses in wheat. Collectively, this work demonstrates a previously unappreciated importance of the Pep signalling in plants for combating piercing-sucking insect herbivores and promises exogenous application of OsPep3 as an eco-friendly immune stimulator in agriculture for crop protection against a broad spectrum of insect pests and pathogens.

SnO x /graphene anode material with multiple oxidation states for high-performance Li-ion batteries.

Tin and its oxides are promising anode materials owing to their high theoretical capacity, rich resource, and environmental benignity. To achieve low cost and green synthesis, a facile synthetic route of SnO x /graphene composites is proposed, using a simple galvanic replacement method to quickly obtain abundant foamed tin as raw material and ball milling method to realize a mechanochemical reaction between SnO x (0 ≤ x ≤ 2) and graphene. Under different annealing conditions, the foamed tin is converted to tin oxides with multiple oxidation states (Sn3O4, SnO, and SnO2). These unique components can greatly affect the electrochemical performance of the electrode in LIBs. The as-prepared electrode (SnO x -300/G) obtained by annealing foamed tin at 300 °C for 4 h and combining SnO x powders with graphene via ball milling shows great cycling stability, retaining a high capacity of 786 mA h g-1 at 0.1 A g-1 after 150 cycles, and its initial Coulombic efficiency can reach 84.03%. Thus, this facile synthesis can provide an environmentally friendly route for commercial production of high-performance energy storage materials.

Enhancement in external quantum efficiency of light-emitting diode based on colloidal silicon nanocrystals.

Herein, we report an enhanced red emission from colloidal silicon nanocrystals (c-Si NCs) solution-processed light-emitting diode. c-Si NCs were synthesized by facile femtosecond laser ablation. Based on the structural characterization and opto-electrics properties analysis, both photoluminescence and electroluminescence arise from the radiative recombination of carriers due to quantum confined effect. The optical power density and highest external quantum efficiency have been obtained to be 0.79 mW cm-2and âˆ¼6.6%, respectively. These results indicate that Si NCs are very attractive as a potential optical source for future integrated chips.

Porous 3D graphene aerogel co-doped with nitrogen and sulfur for high-performance supercapacitors.

Heteroatom-doped carbon materials with a high specific area, a well-defined porous structure is important to high-performance supercapacitors (SCs). Here, S and N co-doped three-dimensional porous graphene aerogel (NS-3DPGHs) have been synthesized in a facile and efficient self-assembly process with thiourea acting as the reducing and doping agent solution. Operating as a SC electrode, fabricated co-doping graphene, i.e. the sample of NS-3DPGH-150 exhibits the highest specific capacitance of 412.9 F g-1 under 0.5 A g-1 and prominent cycle stabilization with 96.4% capacitance retention in the back of 10 000 cycles. Furthermore, based on NS-3DPGH-150, the symmetrical supercapacitor as-prepared in 6 M KOH displays a superior energy density of 12.9 Wh kg-1 under the power density of 249 W kg-1. Hence, NS-3DPGHs could be considered as an excellent candidate for SCs.

Flexible all-solid-state supercapacitors based on PPy/rGO nanocomposite on cotton fabric.

Polypyrrole (PPy) has high electrochemical activity and low cost, so it has great application prospects in wearable supercapacitors. Herein, we have successfully prepared polypyrrole/reduced graphene oxide (PPy/rGO) nanocomposite cotton fabric (NCF) by chemical polymerization, which exhibits splendid electrochemical performance compared with the individual. The addition of rGO can block the deformation of PPy caused by the expansion and contraction. The as-prepared PPy-0.5/rGO NCF electrode exhibits the brilliant specific capacitance (9300 mF cm-2at 1 mA cm-2) and the capacitance retention with 94.47% after 10 000 cycles. At the same time, the superior capacitance stability under different bending conditions and reuse capability have been achieved. All-solid-state supercapacitor has high energy density of 167µWh cm-2with a power density of 1.20 mW cm-2. Therefore, the PPy-0.5/rGO NCF electrode has a broad application prospect in high-performance flexible supercapacitor fabric electrode.

Overexpression of an Osa-miR162a Derivative in Rice Confers Cross-Kingdom RNA Interference-Mediated Brown Planthopper Resistance without Perturbing Host Development.

Rice is a main food crop for more than half of the global population. The brown planthopper (BPH, Nilaparvata lugens) is one of the most destructive insect pests of rice. Currently, repeated overuse of chemical insecticides represents a common practice in agriculture for BPH control, which can induce insect tolerance and provoke environmental concerns. This situation calls for innovative and widely applicable strategies for rice protection against BPH. Here we report that the rice osa-miR162a can mediate cross-kingdom RNA interference (RNAi) by targeting the NlTOR (Target of rapamycin) gene of BPH that regulates the reproduction process. Through artificial diet or injection, osa-miR162a mimics repressed the NlTOR expression and impaired the oviposition of BPH adults. Consistently, overproduced osa-miR162a in transgenic rice plants compromised the fecundity of BPH adults fed with these plants, but meanwhile perturbed root and grain development. To circumvent this issue, we generated osa-miR162a-m1, a sequence-optimized osa-miR162a, by decreasing base complementarity to rice endogenous target genes while increasing base complementarity to NlTOR. Transgenic overexpression of osa-miR162a-m1 conferred rice resistance to BPH without detectable developmental penalty. This work reveals the first cross-kingdom RNAi mechanism in rice-BPH interactions and inspires a potentially useful approach for improving rice resistance to BPH. We also introduce an effective strategy to uncouple unwanted host developmental perturbation from desirable cross-kingdom RNAi benefits for overexpressed plant miRNAs.

Structural evolution and effective improvement of emission quantum yields for silicon nanocrystals synthesized by femtosecond laser ablation in HF-contained solution.

Stable luminescent colloidal silicon (Si) nanocrystals (NCs) with sufficient surface protection are prepared through femtosecond laser ablation in organic solvent containing diverse concentrations of HF solution. The average size of Si NCs shows the decreasing tendency from 6.5 to 2.7 nm when the concentration of HF varies from 0 to 11.1 vol% (volume ratio). In line with the structural evolution, UV-visible absorption, photoluminescence (PL) excitation spectra, and time-resolved PL, we propose that room temperature blue emission peaks at 412 and 440 nm originate from alkyl-related radiative recombination centers. The enhanced PL quantum yield of colloidal Si NCs from 16.3% to 76.5% has been attributed to the effective passivation and suppression of non-radiative defect centers with increasing HF concentration from 0 to 11.1 vol%.

Engineered Artificial MicroRNA Precursors Facilitate Cloning and Gene Silencing in Arabidopsis and Rice.

Plant genome sequences are presently deciphered at a staggering speed, due to the rapid advancement of high-throughput sequencing technologies. However, functional genomics significantly lag behind due to technical obstacles related to functional redundancy and mutant lethality. Artificial microRNA (amiRNA) technology is a specific, reversible, and multiplex gene silencing tool that has been frequently used in generating constitutive or conditional mutants for gene functional interrogation. The routine approach to construct amiRNA precursors involves multiple polymerase chain reactions (PCRs) that can increase both time and labor expenses, as well as the chance to introduce sequence errors. Here, we report a simplified method to clone and express amiRNAs in Arabidopsis and rice based on the engineered Arabidopsis miR319a or rice miR528 precursor, which harbor restriction sites to facilitate one-step cloning of a single PCR product. Stem-loop reverse-transcriptase quantitative PCR (RT-qPCR) and functional assays validated that amiRNAs can be accurately processed from these modified precursors and work efficiently in plant protoplasts. In addition, Arabidopsis transgenic plants overexpressing the modified miR319a precursor or its derived amiRNA could exhibit strong gene silencing phenotypes, as expected. The simplified amiRNA cloning strategy will be broadly useful for functional genomic studies in Arabidopsis and rice, and maybe other dicotyledon and monocotyledon species as well.

Arabidopsis Aspartic Protease ASPG1 Affects Seed Dormancy, Seed Longevity and Seed Germination.

Seed storage proteins (SSPs) provide free amino acids and energy for the process of seed germination. Although degradation of SSPs by the aspartic proteases isolated from seeds has been documented in vitro, there is still no genetic evidence for involvement of aspartic proteases in seed germination. Here we report that the aspartic protease ASPG1 (ASPARTIC PROTEASE IN GUARD CELL 1) plays an important role in the process of dormancy, viability and germination of Arabidopsis seeds. We show that aspg1-1 mutants have enhanced seed dormancy and reduced seed viability. A significant increase in expression of DELLA genes which act as repressors in the gibberellic acid signal transduction pathway were detected in aspg1-1 during seed germination. Seed germination of aspg1-1 mutants was more sensitive to treatment with paclobutrazol (PAC; a gibberellic acid biosynthesis inhibitor). In contrast, seed germination of ASPG1 overexpression (OE) transgenic lines showed resistant to PAC. The degradation of SSPs in germinating seeds was severely impaired in aspg1-1 mutants. Moreover, the development of aspg1-1 young seedlings was arrested when grown on the nutrient-free medium. Thus ASPG1 is important for seed dormancy, seed longevity and seed germination, and its function is associated with degradation of SSPs and regulation of gibberellic acid signaling in Arabidopsis.

One-step synthesis of colloidal CH3NH3PbBr3 nanoplatelets via chlorobenzene to realize nonsolvent crystallization.

Ligand-assisted reprecipitation (LARP) is a convenient and low-cost method to synthesize perovskite nanoplatelets (NPLs) with great optoelectronic properties. However, it still suffers from delicate purification and passivation. Here, we report the synthesis of perovskite NPLs via a simple one-step method through using chlorobenzene as poor solvent. These as-prepared NPLs exhibit good lateral-size homogeneity and emission wavelength tunability. Controlled experiment indicates that compared to the commonly used toluene, chlorobenzene is advantaged to enhance photoluminescence quantum yield (PLQY) and decay time of the perovskite NPLs. Raman spectra, x-ray photoelectron spectroscopy and energy dispersive spectra have shown that it is the passivation of chlorine atoms which suppresses nonradiative recombination and enhances PLQY. These results demonstrate that chlorobenzene is an alternative poor solvent to realize both the simplification of the LARP technique and the passivation of perovskite NPLs.

Freestanding carbon nanodots/poly (vinyl alcohol) films with high photoluminescent quantum yield realized by inverted-pyramid structure.

Carbon nanodots (C-dots) have attracted great attention for their biocompatibility and strong tunable photoluminescence (PL). However, aggregation-induced PL quenching blocks their practical application in solid-state optoelectronics. Here, we report a luminescent C-dots freestanding film with a substantially enhanced high quantum yield (QY) of 72.3%. A facile template method, rather than complicate lithography and etching technique is proposed to fabricate the C-dots composite films with large-area (8 inch × 8 inch) ordered micro-scale inverted-pyramid patterns on the surface. The control experiment and theoretical analysis demonstrate the key success to QY enhancement lies in the separation of C-dots and the pattern of surface inverted-pyramid structure. This work realizes the QY enhancement simply by geometrical optics, not the chemical treatment of luminescent particles. It provides a general approach to fabricate large-area freestanding luminescent composite film with high QY.

Nickel skeleton three-dimensional nitrogen doped graphene nanosheets/nanoscrolls as promising supercapacitor electrodes.

A novel nickel skeleton 3D nitrogen doped graphene (N-GR/NF) superstructure with interconnected graphene nanosheets and nanoscrolls was synthesized using a facile two-step method. By varying the precursor concentration, the assembly of a graphene aerogel can be easily regulated, yielding different micro-structures and morphologies which accelerate the fast electron/ion transportation. The N-GR/NF composites demonstrate enhanced capacitance of 250 F g-1 at 5 A g-1, good rate performance (237 F g-1 at the current density of 12 A g-1) and cycle stability (90.9% retention after 5000 cycles) in 1 M KOH electrolyte. This study provides a new strategy for the microporous engineering of graphene gel, promising for further exploitation in various other applications.

Galvanic displacement assembly of ultrathin Co3O4 nanosheet arrays on nickel foam for a high-performance supercapacitor.

High-performance supercapacitors are very desirable for many portable electronic devices, electric vehicles and high-power electronic devices. Herein, a facile and binder-free synthesis method, galvanic displacement of the precursor followed by heat treatment, is used to fabricate ultrathin Co3O4 nanosheet arrays on nickel foam substrate. When used as a supercapacitor electrode the prepared Co3O4 on nickel foam exhibits a maximum specific capacitance of 1095 F g-1 at a current density of 1 A g-1 and good cycling stability of 71% retention after 2000 cycling tests. This excellent electrochemical performance can be ascribed to the high specific surface area of each Co3O4 nanosheet that comprises numerous nanoparticles.

Controllable in situ photo-assisted chemical deposition of CdSe quantum dots on ZnO/CdS nanorod arrays and its photovoltaic application.

Compound semiconductors have been widely applied in the energy field as light-harvesting materials, conducting substrates and other functional parts. Nevertheless, to effectively grow them in various forms toward objective applications, limitations have often been met to achieving high growth rate, simplicity of method and controllability of growing processes simultaneously. In this work, we have grown a uniform CdSe layer on ZnO/CdS nanorod arrays by a novel in situ photo-assisted chemical deposition method. The morphology and quality of the as-formed material could be significantly influenced by tuning the optical parameters of the injected light. Due to the effect of injected light on the key reactions during the growth, a modified natural light with removal of the UV and IR components seems to be more suitable than monochromic light. An efficiency of 3.59% was achieved without any additional treatment, significantly higher than the efficiency of 2.88% of the sample by conventional CBD method under similar conditions with growth rate one order of magnitude higher. In general, the result has suggested its potential importance for other compound materials and opto-electronic devices.

Size dependence of phosphorus doping in silicon nanocrystals.

Doping of silicon nanocrystals (Si-NCs) is one of the major challenges for silicon nanoscale devices. In this work, phosphorus (P) doping in Si-NCs which are embedded within an amorphous silicon matrix is realized together with the growth of Si-NCs by plasma-enhanced chemical vapor deposition under a tunable substrate direct current (DC) bias. The variation of phosphorus concentration with substrate bias can be explained by the competition of bonding processes of Si-Si and P-Si bonds. The formation of Si-Si and P-Si bonds is differently influenced by the ion bombardment controlled by the substrate bias, due to their bonding energy difference. We have studied the influences of grain size on P doping in Si-NCs. Free carrier concentration, which is provided by activated P atoms, decreases with decreasing grain size due to increasing formation energy and activation energy of P atoms incorporated in Si-NCs. Furthermore, we have studied the P locations inside Si-NCs and hydrogen passivation of P in the form of P-Si-H complexes using the first-principles method. Hydrogen passivation of P can also contribute to the reduced free carrier concentration in smaller Si-NCs. These results provide valuable understanding of P doping in Si-NCs.

InP nanopore arrays for photoelectrochemical hydrogen generation.

We report a facile and large-scale fabrication of highly ordered one-dimensional (1D) indium phosphide (InP) nanopore arrays (NPs) and their application as photoelectrodes for photoelectrochemical (PEC) hydrogen production. These InP NPs exhibit superior PEC performance due to their excellent light-trapping characteristics, high-quality 1D conducting channels and large surface areas. The photocurrent density of optimized InP NPs is 8.9 times higher than that of planar counterpart at an applied potential of +0.3 V versus RHE under AM 1.5G illumination (100 mW cm(-2)). In addition, the onset potential of InP NPs exhibits 105 mV of cathodic shift relative to planar control. The superior performance of the nanoporous samples is further explained by Mott-Schottky and electrochemical impedance spectroscopy ananlysis.

A simple strategy for synthesizing highly luminescent carbon nanodots and application as effective down-shifting layers.

We propose a novel strategy to prepare highly luminescent carbon nanodots (C-dots) by employing a hydrothermal method with citric acid as the carbon source and ethylenediamine as the nitrogen source, together with adding moderate ammonia water (AW) to achieve both appropriate inner structure and excellent N passivation. The effect of pH value and AW amount on the luminescence properties has been thoroughly investigated. The photoluminescence quantum yield of the resultant C-dots reaches as high as 84.8%, which is of 10.56% higher than that of the C-dots synthesized in the absence of AW in the reaction precursors. We have further combined the highest luminescent C-dots with polyvinyl alcohol to form luminescent down-shifting layers on silicon nanowire solar cells. An effective enhancement of short-circuit current density has been realized and the contribution of the down-shifting has been extracted quantitatively from the deterioration of surface reflectance and the gain of the optical absorption redistribution by means of a theoretical model on external quantum efficiency analysis.

Visible light photocatalytic H2-production activity of wide band gap ZnS nanoparticles based on the photosensitization of grapheme.

Visible light photocatalytic H(2) production from water splitting is considered an attractive way to solve the increasing global energy crisis in modern life. In this study, a series of zinc sulfide nanoparticles and graphene (GR) sheet composites were synthesized by a two-step hydrothermal method, which used zinc chloride, sodium sulfide, and graphite oxide (GO) as the starting materials. The as-prepared ZnS-GR showed highly efficient visible light photocatalytic activity in hydrogen generation. The morphology and structure of the composites obtained by transmission electron microscope and x-ray diffraction exhibited a small crystallite size and a good interfacial contact between the ZnS nanoparticles and the two-dimensional (2D) GR sheet,which were beneficial for the photocatalysis. When the content of the GR in the catalyst was 0.1%, the ZG0.1 sample exhibited the highest H(2)-production rate of 7.42 µmol h(−1) g(−1), eight times more than the pure ZnS sample. This high visible-light photocatalytic H(2) production activity is attributed to the photosensitization of GR. Irradiated by visible light, the electrons photogenerated from GR transfer to the conduction band of ZnS to participate in the photocatalytic process. This study presents the visible-light photocatalytic activity of wide bandgap ZnS and its application in H(2) evolution.