2,549 research outputs found
Fluorescence quantum yield of visual pigments: evidence for subpicosecond isomerization rates
No full textPicosecond kinetic absorption and fluorescence studies of bovine rhodopsin with a fixed 11-ene
No full textUnveiling the Structure Sensitivity for Direct Conversion of Syngas to C2-Oxygenates with a Multicomponent-Promoted Rh Catalyst
No full textAbstract: Mn and Li promoted Rh catalysts supported on SiO2 with a thin TiO2 layer were synthesized by stepwise incipient wetness impregnation approach. The thin TiO2 layer on the surface of SiO2 was proved to stabilize those small Rh nanoparticles and hinder their agglomeration. The reducibility of Rh on these catalysts depends on Rh particle size as well as the position of manganese oxide, and large Rh nanoparticles with MnO on Rh nanoparticles can be only reduced at an elevated temperature. Catalyst with large Rh particles exhibits a higher CO conversion and higher products selectivity towards long chain hydrocarbons and C2-oxygenates at the expense of decreasing methane formation than a similar catalyst with smaller Rh particles. This was attributed to the synergistic effect of Mn and Li promotion and molar ratio between Rh0 and Rhδ+ sites on the surface of Rh nanoparticles. Moreover, Rh nanoparticles on MnO are proved to be more efficient in promoting hydrogenation of acetaldehyde to ethanol than its counterpart with MnO on Rh nanoparticles. Finally, in order to target high C2-oxygenates selectivity, low reaction temperature together with a low H2/CO ratio in the feed is recommended. Graphic Abstract: [Figure not available: see fulltext.].ChemE/Catalysis EngineeringChemE/O&O groe
Computational Exploration of Rh-III/Rh-V and Rh-III/Rh-I Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes
No full textThe selective rhodium-catalyzed functionalization of arenes is greatly facilitated by oxidizing directing groups that, act both as directing groups and internal oxidants. We report density functional theory (B3LYP and M06) investigations on the mechanism of rhodium(III)-catalyzed redox coupling reaction of N-phenoxyacetamides with alkynes. The results elucidated the role of the internal oxidizing directing group, and the role of Rh-III/Rh-I and Rh-III/Rh-V catalysis of C-H functionalizations. A novel Rh-III/Rh-V-Rh-III cycle successfully rationalizes recent experimental observations by Liu and Lu et al. (Liu, G. Angew. Chem. Int. Ed. 2013, 52, 6033) on the reactions of N-phenoxyacetamides with alkynes in different solvents. Natural Bond Orbital (NBO) analysis confirms the identity of Rhy intermediate in the catalytic cycle.National Natural Science Foundation of China [21133002, 21203004]; Shenzhen Peacock Program [KQTD201103]; National Science Foundation of the USA [CHE-1361104]; National Science Foundation under the CCI Center for Selective C-H Functionalization [CHE-1205646]; National Science Foundation [OCI-1053575]SCI(E)[email protected]; [email protected]
Solvent effects in heterogeneous selective hydrogenation of acetophenone: differences between Rh/C and Rh/Al2O3 catalysts and the superiority of water as a functional solvent
No full textSelective hydrogenation of acetophenone (AP) to 1-phenylethanol (PhE) was investigated over Rh/Al2O3 and Rh/C catalysts in 13 solvents including water and conventional organic solvents. Strong solvent effects on the overall rate of AP conversion were observed in different manners depending on the catalysts used. The conversion obtained is correlated with hydrogen-bond-donation (HBD) capability for Rh/C but with hydrogen-bond-acceptance (HBA) capacity for Rh/Al2O3. The solvent effects should result from interactions between the carbonyl group of AP and the solvent molecules through hydrogen bonding for Rh/C and from those between the solvent molecules and the catalyst surface for Rh/Al2O3 having HBD hydroxyl groups on its surface. Water is the most effective functional solvent in the selective hydrogenation of AP for C and Al2O3-supported Rh catalysts due to its high HBD capability (a) and low HBA capability (beta), respectively. For the hydrogenation with Rh/Al2O3 in water, its large polarity/polarizability index (pi*) may contribute to the high selectivity to PhE
Adverse effects of potassium on NO<sub>x</sub> reduction over Di-Air catalyst (Rh/La-Ce-Zr)
No full textThe influence of potassium in Rh on a lanthium promoted zirconia stablised ceria (CZ) catalysts was studied toward NOxreduction reactivity and selectivity. The results are compared with a Rh/CZ catalyst. The samples were characterised by N2 adsorption, XRD, SEM, ICP, and H2-TPR. The study highlighted the importance of stored NOx regeneration over potassium in determining the overall performance of the Rh/K/CZ catalyst. The NOx stored over Rh/K/CZ in the previous NO gas stream cannot be regenerated sufficiently during the C3H6 gas stream, and stored NOxgradually decreased from one cycle to the next, resulting in deteriorating performance of Rh/K/CZ. Besides, problem of NOx slip, the formation of both NH3 and N2O (selectivities up to 30% for each side product) were observed by the addition of potassium into the Rh/CZ catalyst system, depending on the reaction conditions applied and the severity of the catalyst deactivation.</p
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