Synthesis Characterization And Optimization Of Fine And Nano Metal Particle Loaded Alumina Catalysts For Co Hydrogenation PDF Download

Metals are dominant catalysts, being used in forms ranging from simple atomically dispersed (single-site) metal complexes to few-atom clusters to nanoparticles to bulk metals. Investigations of atomically dispersed metal complexes are drawing wide attention because their well-defined structures facilitate fundamental understanding of catalysis as well as offering new catalytic properties. In this work, we extend the field of atomically dispersed supported metal catalysts to dinuclear clusters to build a bridge between atomically dispersed metal complexes and few-atom clusters. Thus, the research extends the subject of atomically dispersed supported catalysts to supported metal pair-site catalysts, which have heretofore been little investigated because of their instability, lack of uniformity, and difficulty of precise synthesis. A separate, collaborative project reported on here includes characterization by in-situ X-ray absorption spectroscopy of the structures of single-site supported metals present as promoters in complex catalysts that contain metal nanoparticles for selective hydrogenation of nitroarenes. Iridium and rhodium pair-site catalysts supported on MgO were synthesized and characterized with infrared (IR) and X-ray absorption spectroscopies and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), supported by density functional theory (DFT) calculations done by collaborators. In-situ IR and X-ray absorption near edge structure (XANES) spectra were used to characterize the structural changes of the pair-sites under various treatment conditions, including ligand substitution reactions involving CO and hydrogen. Catalytic properties for ethylene hydrogenation and H-D exchange in the H2 + D2 reaction were tested and compared with those of single-site iridium and rhodium analogues as well as few-atom clusters of these metals supported on MgO. The pair-site catalysts on MgO activated by removal of ligands facilitate H2 dissociation much more rapidly than their single-site analogues and catalyze ethylene hydrogenation one to two orders of magnitude faster than their single-site analogues on MgO. The pair sites are active for ethylene hydrogenation even after being partially poisoned by CO, and, in contrast, the analogous single-site catalysts are fully poisoned. The results provide understanding of the roles of neighboring metal sites and the effects of ligands on pair sites catalysts, opening opportunities for synthesis of stable pairs of various metals on various supports. The benefits of such stable metal pair sites may extend to numerous reactions other than those investigated in this work. The single-site promoters investigated in this work are Sn cations on TiO2 supports that incorporate noble metal nanoparticle catalysts. These catalysts decidedly outperform the comparable unpromoted supported metals for hydrogenation of nitroarenes substituted with various reducible groups. X-ray absorption spectroscopy at the Sn K edge was used to characterize the structural changes in the single-site Sn in the catalysts as influenced by H2 and by nitrobenzene at 353 K and 1 atm. The changes in Sn–O coordination numbers and distances give evidence that the high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface associated with single-site Sn sites that lead to efficient, selective activation of the nitro group (in contrast to the other reducible group) coupled with reaction involving hydrogen atoms activated on the nearby metal nanoparticles.