An active and stable multifunctional catalyst with defective UiO-66 as a support for Pd over the continuous catalytic conversion of acetone and hydrogen.

The one-pot synthesis of methyl isobutyl ketone (MIBK) and methyl isobutyl methanol (MIBC) from acetone and hydrogen is a typical cascade reaction comprised of aldol condensation-dehydration-hydrogenation. Pd loss and aggregation during long term operation are typical problems in industrial application. In this paper, an active and stable catalyst was achieved with defective UiO-66 as a support for Pd, which was synthesized with the ratio 15 : 1 of ZrOCl2·8H2O to ZrCl4 as Zr-precursors. The resultant Pd catalyst remained active for at least 1000 h with a MIBK + MIBC selectivity of 84.87-93.09% and acetone conversion of 45.26-53.22% in a continuous trickle-bed reactor. Besides the increased Brønsted acid amount generated by the defect sites was favorable for the activity, the cavity confinement in the UiO-66 (R = 15 : 1) structure also efficiently prevented Pd loss and aggregation during the long term run. The contrast of the characterization of the fresh and used Pd/UiO-66 (R = 15 : 1) indicated that the deactivation of the catalyst was attributed to carbonaceous accumulation on the catalyst surface, which could be easily regenerated by calcination. This work supplied a new alternative for the design and utilization of industrial catalysts for MIBK and MIBC synthesis.

Synthesis and electrochemical performances of Na3V2(PO4)2F3/C composites as cathode materials for sodium ion batteries.

Na3V2(PO4)2F3 (NVPF) with NASCION (Na superionic conductor) is recognized as a potential cathode material owing to its high theoretical capacity. However, the electronic conductivity of NVPF is much lower than its ionic conductivity, which seriously affects the properties of this material. The carbon layer can be used as the conductive medium to enhance the conductivity of NVPF. In this study, we propose a single-step solid-state reaction method based on mechanical activation with pitch as the carbon source to synthesize NVPF/C composites. The crystallographic structure and morphology of all as-prepared samples were investigated by XRD, Raman spectroscopy, BET measurement, thermal analysis, SEM and TEM. Furthermore, the electrochemical performance and kinetic properties were analyzed by CV, galvanostatic charge-discharge and EIS tests. These tests outcomes demonstrated that the NVPF/C-2 composite with a carbon content of 12.14 wt% showed an excellent rate performance and cycle stability. It presented reversible capacities of 103 and 95 mA h g-1 at 0.2 and 10C, respectively, and an outstanding retention of 91.9% after 500 cycles at 5C. These excellent properties of the NVPF/C-2 composite are attributed to its high ion diffusion coefficient and small charge transfer impedance.