In situ synthesis of silver supported nanoporous iron oxide microbox hybrids from metal-organic frameworks and their catalytic application in p-nitrophenol reduction.

Ag nanoparticles (NPs) are successfully grown in situ on nanoporous Fe2O3 microboxes (Ag/Fe2O3) simply by annealing Prussian blue (PB) in the presence of silver nitrate for the first time. The catalytic activity of the Ag/Fe2O3 microboxes for the reduction of p-nitrophenol (PNP) with NaBH4 is measured by UV-vis spectroscopy. It is found that the composites exhibit bifunctional properties with high magnetization and excellent catalytic activity toward PNP reduction. The high catalytic activity of the catalyst might be attributed to its high surface area and the synergistic effect on the delivery of electrons between Ag NPs and Fe2O3 microboxes. In addition, efficient reduction is observed and found to depend upon the content of Ag in the Ag/Fe2O3 microboxes. The dosage of the catalyst and the reaction temperature were investigated. Furthermore, the catalysts can be easily recycled by applying an external magnetic field while maintaining the catalytic activity without significant decrease even after running six times. The unique properties provide an ideal platform to study various metal/Fe2O3 catalysts which can be potentially applied in a wide variety of fields of catalysis and green chemistry.

Synthesis, crystal structure, electrochemistry and in situ FTIR spectroelectrochemistry of a bisferrocene pyrazole derivative.

One novel bisferrocene pyrazole derivative, bis [2-(5-trifluoromethyl-3-ferrocenyl) pyrazolyl] methane (abbreviated as (3)), was synthesized and fully characterized. A single crystal of (3) was obtained and solved by X-ray diffraction analysis. The bisferrocene derivative exhibits MLCT (metal to ligand charge transfer) and π→π* transitions in the UV-visible range, which have been verified by density functional theory (DFT) calculations. Its electrochemical properties were studied with the aid of cyclic voltammetry (CV), differential pulse voltammetry (DPV) and rapid scan time-resolved Fourier transform infrared spectroscopy (RS-TRS FT-IR) analysis. Furthermore, the electrochemical mechanism was elucidated based on the results from the cyclic voltabsorptometry (CVA) determination technique. (3) apparently shows a single wave in the cyclic voltammetric experiments which indicates there is no intermediate, however, the intermediate of (3) was observed by employing the RS-TRS FT-IR spectroelectrochemistry technique. The detailed investigation brought us safely to the conclusion that the methylene can also act as a linker, leading to electronic communication in either D-π-D and A-π-A systems.