Lithiation Depth Regulation of Silicon Anodes toward Excellent Stability.

Silicon (Si) is an appealing choice of anode for next-generation lithium ion batteries with high energy density, but its dramatic volume expansion makes it a tremendous challenge to achieve acceptable stability. Herein, we demonstrate that no capacity decay is observed during the testing period when the lithiation depth of Si nanoparticles is regulated at 2000 mAh g-1 or below, the fracture of Si anode films is well mitigated under suitable regulation of lithiation depth, and the cycled Si remains particulate without turning flocculent as under full lithiation. In addition, the solid electrolyte interphase (SEI) with a LiF-dominated outer region produced under lithiation regulation could better passivate the Si anodes and prevent further electrolyte decomposition than the mosaic-type SEI formed under full lithiation. Regulating lithiation depth proved to be a feasible solution to the pressing volume issues, and optimization of capacity utilization should be considered as much as materials-level optimization.

Synthesis and Electrochemical Performance of ZnSe Electrospinning Nanofibers as an Anode Material for Lithium Ion and Sodium Ion Batteries.

ZnSe nitrogen-doped carbon composite nanofibers (ZnSe@N-CNFs) were derived as anode materials from selenization of electrospinning nanofibers. Electron microscopy shows that ZnSe nanoparticles are distributed in electrospinning nanofibers after selenization. Electrochemistry tests were carried out and the results show the one-dimensional carbon composite nanofibers reveal a great structural stability and electrochemistry performance by the enhanced synergistic effect with ZnSe. Even at a current density of 2 A g-1, the as-prepared electrodes can still reach up to 701.7 mA h g-1 after 600 cycles in lithium-ion batteries and 368.9 mA h g-1 after 200 cycles in sodium-ion batteries, respectively. ZnSe@N-CNFs with long cycle life and high capacity at high current density implies its promising future for the next generation application of energy storage.

Formation of Mn-Cr mixed oxide nanosheets with enhanced lithium storage properties.

Novel carbon-free Mn2O3/MnCr2O4 hybrid nanosheets are synthesized through thermal decomposition of the facilely co-precipitated Mn-Cr binary hydroxide and a carbonate hybrid precursor. As an anode for lithium-ion batteries, the Mn2O3/MnCr2O4 electrode delivers a wonderful electrochemical performance, i.e., an enhanced stability of 913 mA h g-1 at a current density of 1 A g-1 after 300 cycles, and an excellent rate performance. The excellent electrochemical performance of the Mn2O3/MnCr2O4 electrode can be ascribed to the interconnected nanosheets and porous structure, as well as the possible synergistic effects between Mn and Cr mixed oxides.

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures.

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm-2 and a turnover frequency of 4.1 s-1 at the overpotential of 0.52 V in a near-neutral aqueous solution.

Synergetic inhibition of PCDD/F formation from pentachlorophenol by mixtures of urea and calcium oxide.

Chlorophenols are structurally similar to PCDD/Fs and have been considered as highly potential precursors for PCDD/Fs formation. The suppressing effects of PCDD/F formation from pentachlorophenol (PCP) were investigated on various mass ratios of CaO and urea. The total concentration of 2,3,7,8-PCDD/Fs, mostly dominated by OCDD, was determined to be 48.58-10186ng/mg in inhibitor-reaction systems, being much lower than that in blank reaction system (75654ng/mg). Interestingly, compared with pure CaO and urea reaction system, the concentration and TEQ of formed 2,3,7,8-PCDD/Fs in mixed urea/CaO reaction system were lower, especially with 5-20% urea reaction systems being respectively at decrease by 96.5-99.4% and 99.2-99.7%. The suppression efficiency of TEQ in 5-20% urea reaction systems could be always approximately 100% under 250-350°C. These results suggested that mixed inhibitors, especially 5-20% urea inhibitors, have a synergetic inhibition effect for PCDD/Fs formation from PCP. Mixed inhibitor generated several intermediates, involving CO2, H2O, NH3, Ca(OH)2, CaCO3, HNCO, biuret and ammelide. The complex between PCP and Ca, N-doped species, lower chlorinated phenols and benzenediol, and organic acids were also determined. Synergetic inhibition mechanism may be attributed to accelerated facilitation of acid-base reaction and N doping. The decomposition of PCP itself also contributes to prevent PCDD/Fs formation.

Thermal degradation of octachloronaphthalene over as-prepared Fe(3)O(4) micro/nanomaterial and its hypothesized mechanism.

Decomposition of octachloronaphthalene (CN-75) featuring fully substituted chlorines was investigated over as-prepared Fe3O4 micro/nanomaterial at 300 °C. It conforms to pseudo-first-order kinetics with kobs = 0.10 min(-1) as comparable to that of hexachlorobenzene and decachlorobiphenyl. Analysis of the products indicates that the degradation of CN-75 proceeds via two competitive hydrodechlorination and oxidation pathways. The onset of hydrodechlorination producing lower chlorinated naphthalenes (CNs) is more favored on α-position than ß-position. Higher amounts of CN-73, CN-66/67, CN-52/60, and CN-8/11 isomers were found, while small content difference was detected within the tetrachloronaphthalene and trichloronaphthalene homologues, which might be attributed to lower energy principle and steric effects. The important hydrodechlorination steps, leading to CN-73 ≫ CN-74 in two heptachloronaphthalene isomers contrary to that in technical PCN-mixtures, were specified by calculating the charge of natural bond orbitals in CN-75 and the energy of two heptachloronaphthalene radicals. On the basis of the molecular electrostatic potential of CN-75, the nucleophilic O(2-), and eletrophilic O2(-) and O(-), present on the Fe3O4 surface, might attack the carbon atom and π electron cloud of naphthalene ring, producing naphthol species with Mars-van Krevelen mechanism, and formic and acetic acids.

Synthesis of hierarchical Mg-doped Fe3O4 micro/nano materials for the decomposition of hexachlorobenzene.

An ethylene-glycol (EG) mediated self-assembly process was firstly developed to synthesize micrometer-sized nanostructured Mg-doped Fe3O4 composite oxides to decompose hexachlorobenzene (HCB) at 300°C. The synthesized samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy and inductively coupled plasma optical emission spectrometer. The morphology and composition of the composite oxide precursor were regulated by the molar ratio of the magnesium acetate and ferric nitrate as the reactants. Calcination of the precursor particles, prepared with different molar ratio of the metal salts, under a reducing nitrogen atmosphere, generated three kinds of Mg doped Fe3O4 composite oxide micro/nano materials. Their reactivity toward HCB decomposition was likely influenced by the material morphology and content of Mg dopants. Ball-like MgFe2O4-Fe3O4 composite oxide micro/nano material showed superior HCB dechlorination efficiencies when compared with pure Fe3O4 micro/nano material, prepared under similar experimental conditions, thus highlighting the benefits of doping Mg into Fe3O4 matrices.

Degradation of polychlorinated biphenyls using mesoporous iron-based spinels.

A series of mesoporous iron-based spinel materials were synthesized to degrade polychlorinated biphenyls (PCBs), with CB-209 being used as a model compound. The materials were characterized by X-ray powder diffraction (XRD), pore structure analysis, and X-ray photoelectron spectroscopy (XPS). A comparison of the dechlorination efficiencies (DEs) of the materials revealed that NiFe2O4 had the highest DE, followed by Fe3O4. Newly produced polychlorinated biphenyls, chlorinated benzenes, hydroxyl species and organic acids were detected by gas chromatography-mass spectrometry, high performance liquid chromatography-mass spectrometry and ion chromatograph. Identification of the intermediate products indicates that three degradation pathways, hydrodechlorination, the breakage of CC bridge bond and oxidative reaction, accompanied by one combination reaction, are competitively occurring over the iron-based spinels. The relative amounts of produced three NoCB isomers were illustrated by the CCl BDEs of CB-209 at meta-, para- and ortho-positions, and their energy gap between HOMO and LUMO. The consumption of the reactive oxygen species caused by the transformation of Fe3O4 into Fe2O3 in the Fe3O4 reaction system, and the existence of the highly reactive O2(-) species in the NiFe2O4 reaction system, could provide a reason why the oxidation reaction was more favored over NiFe2O4 than Fe3O4.