RESUMEN
Methane is a valuable resource and its valorization is an important challenge in heterogeneous catalysis. Here it is shown that CeO2/CuO composite prepared by ball milling activates methane at a temperature as low as 250 °C. In contrast to conventionally prepared catalysts, the formation of partial oxidation products such as methanol and formaldehyde is also observed. Through an in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and operando Near Edge X-Ray Absorption Fine Structure Spectroscopy (NEXAFS) approach, it can be established that this unusual reactivity can be attributed to the presence of Ce4+/Cu+ interfaces generated through a redox exchange between Ce3+ and Cu2+ atoms facilitated by the mechanical energy supplied during milling. DFT modeling of the electronic properties confirms the existence of a charge transfer mechanism. These results demonstrate the effectiveness and distinctiveness of the mechanical approach in creating unique and resilient interfaces thereby enabling the optimization and refining of CeO2/CuO catalysts in methane activation reactions.
RESUMEN
We describe a synthetic strategy for the preparation of bis-heteroleptic polypyridyl Ru(II) complexes of the type [Ru(L1)2(L2)]2+ (L1 and L2 = diimine ligands) from well-defined Ru(II) precursors. For this purpose, a series of six neutral, anionic, and cationic cis-locked Ru(II)-DMSO complexes (2-7) of the general formula [Y] fac-[RuX(DMSO-S)3(O-O)]n (where O-O is a symmetrical chelating anion: oxalate (ox), malonate (mal), acetylacetonate (acac); X = DMSO-O or Cl-; n = -1/0/+1 depending on the nature and charge of X and O-O; when present, Y = K+ or PF6-) were efficiently prepared from the well-known cis-[RuCl2(DMSO)4] (1). When treated with diimine chelating ligands (L1 = bpy, phen, dpphen), the compounds 2-7 afforded the target [Ru(L1)2(O-O)]0/+ complex together with the undesired (and unexpected) [Ru(L1)3]2+ species. Nevertheless, we found that the formation of [Ru(L1)3]2+can be minimized by carefully adjusting the reaction conditions: in particular, high selectivity toward [Ru(L1)2(O-O)]0/+ and almost complete conversion of the precursor was obtained within minutes, also on a 100-200 mg scale, when the reactions were performed in absolute ethanol at 150 °C in a microwave reactor. Depending on the nature of L1 and concentration, with the oxalate and malonate precursors, the neutral product [Ru(L1)2(O-O)] can precipitate spontaneously from the final mixture, in pure form and acceptable-to-good yields. When spontaneous precipitation of the disubstituted product does not occur, purification from [Ru(L1)3]2+ can be rather easily accomplished by column chromatography or solvent extraction. By comparison, under the same conditions, compound 1 is much less selective, thus demonstrating that locking the geometry of the precursor through the introduction of O-O in the coordination sphere of Ru is a valid strategic approach. By virtue of its proton-sensitive nature, facile and quantitative replacement of O-O in [Ru(L1)2(O-O)]0/+ by L2, selectively affording [Ru(L1)2(L2)]2+, was accomplished in refluxing ethanol in the presence of a slight excess of trifluoroacetic acid or HPF6.