Electronic Oxide-Metal Strong Interaction (EOMSI).

Strong metal-support interaction of supported metal catalysts is an important concept to describe the effect of metal-support interactions on the structures and catalytic performances of supported metal particles. By using an example of CeOx adlayers supported on Ag nanocrystals, herein a concept of electronic oxide-metal strong interaction (EOMSI) is put forward; this interaction significantly affects the electronic structures of oxide adlayers through metal-to-oxide charge transfer. The EOMSI can stabilize oxide adlayers in a low oxidation state under ambient conditions, which individually are not stable; moreover, the oxide adlayers experiencing the EOMSI are resistant to high-temperature oxidation in air to a certain extent. Such an EOMSI concept helps to generalize the strong influence of oxide-metal interactions on the structures and catalytic performance of oxide/metal inverse catalysts, which have been attracting increasing attention.

Pentacoordinated Al3+ -Stabilized Active Pd Structures on Al2 O3 -Coated Palladium Catalysts for Methane Combustion.

Supported Pd catalysts are active in catalyzing the highly exothermic methane combustion reaction but tend to be deactivated owing to local hyperthermal environments. Herein we report an effective approach to stabilize Pd/SiO2 catalysts with porous Al2 O3 overlayers coated by atomic layer deposition (ALD). 27 Al magic angle spinning NMR analysis showed that Al2 O3 overlayers on Pd particles coated by the ALD method are rich in pentacoordinated Al3+ sites capable of strongly interacting with adjacent surface PdOx phases on supported Pd particles. Consequently, Al2 O3 -decorated Pd/SiO2 catalysts exhibit active and stable PdOx and Pd-PdOx structures to efficiently catalyze methane combustion between 200 and 850 °C. These results reveal the unique structural characteristics of Al2 O3 overlayers on metal surfaces coated by the ALD method and provide a practical strategy to explore stable and efficient supported Pd catalysts for methane combustion.

Nanoporous PdCr alloys as highly active electrocatalysts for oxygen reduction reaction.

A simple and convenient dealloying method is used to prepare nanoporous (NP) PdCr alloys with uniform ligament dimensions and controllable bimetallic ratio. The structural characterization methods demonstrate that the NP-PdCr alloy is comprised of a nanoscaled interconnected network skeleton and hollow channels extending in all three dimensions. Electrocatalytic measurements indicated that the as-made NP-Pd75Cr25 alloy exhibits superior specific and mass activities as well as higher catalytic stability toward oxygen reduction reaction compared with NP-Pd67Cr33, NP-Pd, and commercial Pt/C catalysts. X-ray photoelectron spectroscopy and density functional theory calculations both demonstrate that the weakened Pd-O bond and improved ORR performances depend on the downshifted d-band center of Pd due to the alloying of Pd with Cr (25 at%). It is expected that the as-made NP-PdCr alloy has prospective application as a cathode electrocatalyst in fuel-cell-related technologies with the advantages of superior overall ORR performances, unique structural stability, and easy preparation.

Less Is More: Selective-Atom-Removal-Derived Defective MnOx Catalyst for Efficient Propane Oxidation.

Defect manipulation in metal oxide is of great importance in boosting catalytic performance for propane oxidation. Herein, a selective atom removal strategy was developed to construct a defective manganese oxide catalyst, which involved the partial etching of a Mg dopant in MnOx. The resulting MgMnOx-H catalysts exhibited superior low-temperature catalytic activity (T50 = 185 °C, T90 = 226 °C) with a propane conversion rate of 0.29 µmol·gcat.-1·h-1 for the propane oxidation reaction, which is 4.8 times that of pristine MnOx. Meanwhile, a robust hydrothermal stability was guaranteed at 250 °C for 30 h of reaction time. The comprehensive experimental characterizations revealed that the catalytic performance improvement was closely related to the defective structures including the abundant (metal and oxygen) vacancies, distorted crystals, valence imbalance, etc., which prominently weakened the Mn-O bond and stimulated the mobility of surface lattice oxygen, leading to the elevation in the intrinsic oxidation activity. This work exemplifies the significance of defect engineering for the promotion of the oxidation ability of metal oxide, which will be valuable for the further development of efficient non-noble metal catalysts for propane oxidation.

The resistance-nodulation-division efflux pump EmhABC influences the production of 2,4-diacetylphloroglucinol in Pseudomonas fluorescens 2P24.

The polyketide metabolite 2,4-diacetylphloroglucinol (2,4-DAPG) plays a major role in the biological control of soil-borne plant diseases by Pseudomonas fluorescens 2P24. Two mutants (PM810 and PM820) with increased extracellular accumulation of 2,4-DAPG were isolated using transposon mutagenesis. The disrupted genes in these two mutants shared >80 % identity with the genes of the EmhR-EmhABC resistance-nodulation-division (RND) efflux system of P. fluorescens cLP6a. The deletion of emhA (PM802), emhB (PM803) or emhC (PM804) genes in strain 2P24 increased the extracellular accumulation of 2,4-DAPG, whereas the deletion of the emhR (PM801) gene decreased the biosynthesis of 2,4-DAPG. The promoter assay confirmed the elevated transcription of emhABC in the EmhR disrupted strain (PM801) and an indirect negative regulation of 2,4-DAPG biosynthetic locus transcription by the EmhABC efflux pump. Induction by exogenous 2,4-DAPG led to remarkable differences in transcription of chromosome-borne phlA : : lacZ fusion in PM901 and PM811 (emhA(-)) strains. Additionally, the EmhABC system in strain 2P24 was involved in the resistance to a group of toxic compounds, including ampicillin, chloramphenicol, tetracycline, ethidium bromide and crystal violet. In conclusion, our results suggest that the EmhABC system is an important element that influences the production of antibiotic 2,4-DAPG and enhances resistance to toxic compounds in P. fluorescens 2P24.

Porous Co3O4/CuO composite assembled from nanosheets as high-performance anodes for lithium-ion batteries.

Upon dealloying a carefully designed CoCuAl ternary alloy in NaOH solution at room temperature, a Co3 O4 /CuO nanocomposite with an interconnected porous microstructure assembled by a secondary structure of nanosheets was successfully fabricated. By using the dealloying strategy, the target metals directly grew to form uniform bimetallic oxide nanocomposites. Owing to the unique hierarchical structure and the synergistic effect of both active electrode materials, the Co3 O4 /CuO nanocomposite exhibits much enhanced electrochemical performance with higher capacities and better cycling stability compared to anodes of pure Co3 O4 . Moreover, it performs excellently in terms of cycle reversibility, Coulombic efficiency, and rate capability, at both low or high current rates. With the advantages of unique performance and ease of preparation, the as-made Co3 O4 /CuO nanocomposite demonstrates promising application potential as an advanced anode material for lithium-ion batteries.

Si/Ag composite with bimodal micro-nano porous structure as a high-performance anode for Li-ion batteries.

A one-step dealloying method is employed to conveniently fabricate a bimodal porous (BP) Si/Ag composite in high throughput under mild conditions. Upon dealloying the carefully designed SiAgAl ternary alloy in HCl solution at room temperature, the obtained Si/Ag composite has a uniform bicontinuous porous structure in three dimensions with micro-nano bimodal pore size distribution. Compared with the traditional preparation methods for porous Si and Si-based composites, this dealloying route is easily operated and environmentally benign. More importantly, it is convenient to realize the controllable components and uniform distribution of Si and Ag in the product. Owing to the rich porosity of the unique BP structure and the incorporation of highly conductive Ag, the as-made Si/Ag composite possesses the improved conductivity and alleviated volume changes of the Si network during repeated charging and discharging. As expected, the BP Si/Ag anode exhibits high capacity, excellent cycling reversibility, long cycling life and good rate capability for lithium storage. When the current rate is up to 1 A g(-1), BP Si/Ag can deliver a stable reversible capacity above 1000 mA h g(-1), and exhibits a capacity retention of up to 89.2% against the highest capacity after 200 cycles. With the advantages of unique performance and easy preparation, the BP Si/Ag composite holds great application potential as an advanced anode material for Li-ion batteries.

A Hierarchical Nanoporous PtCu Alloy as an Oxygen-Reduction Reaction Electrocatalyst with High Activity and Durability.

A hierarchical nanoporous (HNP) PtCu alloy was successfully fabricated by two-step dealloying of a well-designed PtCuAl precursor alloy combined with an annealing operation. The as-made PtCu alloy has an interconnected hierarchical network architecture with controllable bimodal ligament/pore distributions obtained by adjusting the annealing temperature and the redealloying time. HNP-PtCu exhibits superior specific and mass activities for the oxygen-reduction reaction (ORR) compared with single-modal nanoporous PtCu and commercial Pt/C catalysts. More importantly, the HNP-PtCu alloy shows much higher structure stability with less loss of the electrochemical surface area of Pt and ORR activity upon long-term potential scans in acid solution. The excellent electrocatalytic performance for ORR makes the HNP-PtCu alloy attractive as efficient cathode electrocatalysts in fuel-cell-related technologies.

Effect of the hfq gene on 2,4-diacetylphloroglucinol production and the PcoI/PcoR quorum-sensing system in Pseudomonas fluorescens 2P24.

Pseudomonas fluorescens 2P24 is an effective biological control agent of a number of soilborne plant diseases caused by pathogenic microorganisms. Among a range of secondary metabolites produced by strain 2P24, the antibiotic 2,4-diacetylphloroglucinol (2,4-DAPG) is the major determinant of its disease-suppressive capacity. In this study, we performed random mutagenesis using mini-Tn5 in order to screen for the transcriptional regulators of the phlA gene, a biosynthase gene responsible for 2,4-DAPG production. The mutant PMphlA23 with significantly decreased phlA gene expression was identified from approximately 10,000 insertion colonies. The protein sequence of the interrupted gene has 84% identity to Hfq, a key regulator important for stress resistance and virulence in Pseudomonas aeruginosa. Genetic inactivation of hfq resulted in decreased expression of phlA and reduced production of 2,4-DAPG. Furthermore, the hfq gene was also required for the expression of pcoI, a synthase gene for the LuxI-type quorum-sensing signaling molecule N-acyl-homoserine lactone. Additionally, the hfq mutation drastically reduced biofilm formation and impaired the colonization ability of strain 2P24 on wheat rhizospheres. Based on these results, we propose that Hfq functions as an important regulatory element in the complex network controlling environmental adaption in P. fluorescens 2P24.