One-Step Phase Separation for Core-Shell Carbon@Indium Oxide@Bismuth Microspheres with Enhanced Activity for CO2 Electroreduction to Formate.

It is a substantial challenge to construct electrocatalysts with high activity, good selectivity, and long-term stability for electrocatalytic reduction of carbon dioxide to formic acid. Herein, bismuth and indium species are innovatively integrated into a uniform heterogeneous spherical structure by a neoteric quasi-microemulsion method, and a novel C@In2 O3 @Bi50 core-shell structure is constructed through a subsequent one-step phase separation strategy due to melting point difference and Kirkendall effect with the nano-limiting effect of the carbon structure. This core-shell C@In2 O3 @Bi50 catalyst can selectively reduce CO2 to formate with high selectivity (≈90% faradaic efficiency), large partial current density (24.53 mA cm-2 at -1.36 V), and long-term stability (up to 14.5 h), superior to most of the Bi-based catalysts. The hybrid Bi/In2 O3 interfaces of core-shell C@In2 O3 @Bi will stabilize the key intermediate HCOO* and suppress CO poisoning, benefiting the CO2 RR selectivity and stability, while the internal cavity of core-shell structure will improve the reaction kinetics because of the large specific surface area and the enhancement of ion shuttle and electron transfer. Furthermore, the nano-limited domain effect of outmost carbon prevent active components from oxidation and agglomeration, helpful for stabilizing the catalyst. This work offers valuable insights into core-shell structure engineering to promote practical CO2 conversion technology.

Robust hollow Bowl-like α-Fe2O3 nanostructures with enhanced electrochemical lithium storage performance.

The design and synthesis of hollow-nanostructured transition metal oxide-based anodes is of great importance for long-term operation of lithium ion batteries (LIBs). Herein, a special hollow bowl-like α-Fe2O3 nanostructure is controllably synthesized through a facile hydrothermal technique and exhibits great electrochemical lithium storage performance when used as LIBs anode. Under a facile hydrothermal condition, α-Fe2O3 nanostructures evolve from solid pie-like structure to hollow bowl-like structure and finally α-Fe2O3 nanorings through the regulation of HPO4- derived from ionized Na3PO4·12H2O and Ostwald ripening process. The designed hollow bowl-like α-Fe2O3 nanostructure not only has the merits of hollow structure, which can accelerate the diffusion of lithium ions and electrons, but also shows great mechanical strength to disperse stress when compared to solid pie-like and ring-like α-Fe2O3 nanostructures, which would avoid collapse during charge/discharge process. As a result, the as-synthesized hollow bowl-like α-Fe2O3 nanostructure displays an initial reversible capacity of 1616 mAh g-1 at a current density of 1 A g-1, an excellent cycling performance with a reversible capacity of 1018 mAh g-1 after 500 cycles and an outstanding rate capability (68.1% capacity retention at current densities from 100 to 2000 mA g-1). This work provides not only a novel hollow bowl-like α-Fe2O3 nanostructure with high specific surface area and stable structure as potential electrode materials for energy storage, but also a facile self-templated strategy free of any surfactants and templates for hollow nanostructures.

Highly efficient enzymatic synthesis of an ascorbyl unstaturated fatty acid ester with ecofriendly biomass-derived 2-methyltetrahydrofuran as cosolvent.

Enzymatic synthesis of ascorbyl undecylenate, an unsaturated fatty acid ester of ascorbic acid, was reported with biomass-derived 2-methyltetrahydrofuran (MeTHF) as the cosolvent. Of the immobilized lipases tested, Candida antarctica lipase B (CAL-B) showed the highest activity for enzymatic synthesis of ascorbyl undecylenate. Effect of reaction media on the enzymatic reaction was studied. The cosolvent mixture, t-butanol-MeTHF (1:4, v/v) proved to be the optimal medium, in which not only ascorbic acid had moderate solubility, but also CAL-B showed a high activity, thus addressing the major problem of the solvent conflict for dissolving substrate and keeping satisfactory enzyme activity. In addition, the enzyme was much more stable in MeTHF and t-butanol-MeTHF (1:4) than in previously widely used organic solvents, t-butanol, 2-methyl-2-butanol, and acetone. The much higher initial reaction rate in this cosolvent mixture may be rationalized by the much lower apparent activation energy of this enzymatic reaction (26.6 vs. 38.1-39.1 kJ/mol) and higher enzyme catalytic efficiency (Vmax /Km , 8.4 vs. 1.3-1.4 h(-1) ). Ascorbyl undecylenate was obtained with the yields of 84-89% and 6-regioselectivity of >99% in t-butanol-MeTHF (1:4) at supersaturated substrate concentrations (60 and 100 mM) after 5-8 h.