Among lanthanide-based compounds, cerium compounds exhibit a significant role in a variety of research fields due to their distinct tetravalency, high economic feasibility, and high stability of Ce(IV) complexes. Herein, a systematic investigation of crystallographic information, chemical properties, and mechanistic formation of the novel Ce(IV) complex synthesized from cerium(III) nitrate hexahydrate and 2,2′-(methylazanediyl)bis(methylene)bis(4-methylphenol) (MMD) ligand has been explored. According to the analysis of the crystallographic information, the obtained complex crystal consists of the Ce(IV) center coordinated with two nitrate ligands and two bidentate coordinated (N-protonated and O,O-deprotonated) MMD ligands. The fingerprint plots and the Hirshfeld surface analyses suggest that the C–H⋯O and C–H⋯π interactions significantly contribute to the crystal packing. The C–H⋯O and C–H⋯π contacts link the molecules into infinite molecular chains propagating along the [100] and [010] directions. Synchrotron powder X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques have been employed to gain an understanding of the oxidative complexation of Ce(IV)-MMD complex in detail. This finding would provide the possibility to systematically control the synthetic parameters and wisely design the precursor components in order to achieve the desired properties of novel materials for specific applications.
Metal complexes with chelating ligands are known as promising precursors for the synthesis of targeted metal oxides via thermal decomposition pathways. Triethanolamine (TEA) is a versatile ligand possessing a variety of coordination modes to metal ions. Understanding the crystal structure is beneficial for the rational design of the metal complex precursors. Herein, a bis(triethanolamine)nickel (II) dinitrate (named as Ni-TEA) crystal was synthesized and thoroughly investigated. X-ray crystallography revealed that Ni(II) ions adopt a distorted octahedral geometry surrounded by two neutral TEA ligands via two N and four O coordinates. Hirshfeld surface analysis indicated the major contribution of the intermolecular hydrogen-bonding between —OH groups of TEA in the crystal packing. Moreover, several O–H stretching peaks in Fourier transformed infrared spectroscopy (FTIR) spectra emphasizes the various chemical environments of —OH groups due to the formation of the hydrogen-bonding framework. The Density-functional theory (DFT) calculation revealed the electronic properties of the crystal. Furthermore, the Ni-TEA complex is presumably useful for metal oxide synthesis via thermal decomposition at a moderate temperature (380 °C). Cyclic voltammetry indicated the possible oxidative reaction of the Ni-TEA complex at a lower potential than nickel(II) nitrate and TEA ligand, highlighting its promising utility for the synthesis of mixed valence oxides such as spinel structures.
The reduction of unfriendly 4-nitrophenol to make it unimpactful with the environment (4-aminophenol) was carried out using the metastable form of copper ferrite (CuFe5O8) synthesized by the co-precipitation of metal nitrate salts, an efficient method with inexpensive and abundant starting materials. The samples were obtained by calcination at various temperatures ranging from 600 °C to 900 °C. The material characterizations, including X-ray diffraction, N2 adsorption/desorption, scanning electron microscope, X-ray absorption spectroscopy, and ultraviolet–visible spectrometry, were employed to identify the detailed structures and describe their correlations with catalytic activities. The X-ray diffraction and X-ray absorption spectroscopy analyses revealed the presence of mixed CuFe5O8 and copper oxide phases, where the formers are rich in Cu2+, Fe2+, and Fe3+ ions. The electron transfer between Cu2+, Fe2+, and Fe3+ led to the high efficiency of the catalytic reaction of the synthesized copper ferrites. Especially for the sample calcined at 600 °C, the apparent kinetic constant (k) for a reduction of 4-nitrophenol was equal to 0.25 min−1, illustrating nearly 100% conversion of 4-nitrophenol to 4-aminophenol within less than 9 min. Regarding the N2 adsorption/desorption isotherms, the samples calcined at 600 °C have the highest specific Brunauer–Emmett–Teller (BET) surface area (15.93 m2 g−1) among the others in the series, which may imply the most effective catalytic performance investigated herein. The post-catalytic X-ray diffraction investigation indicated the stability of the prepared catalysts. Furthermore, the chemical stability of the prepared catalysts was confirmed by its reusability in five consecutive cycles.
27 April 2022 in Journal of Petroleum Science and Engineering