4,856 research outputs found
Rh promoted In2O3 as a highly active catalyst for CO2 hydrogenation to methanol
No full textSynthesis of methanol with high selectivity and productivity through hydrogenation of CO2 is highly attractive. This work uses a Rh doped In2O3 catalyst to achieve a high methanol productivity of 1.0 g(MeOH) h(-1) g(cat)(-1) while maintaining the intrinsic high selectivity of pure In2O3. Rh facilitated the dissociation of H-2 leading to creation of oxygen vacancies over the In2O3 surface. In addition, Rh atoms also participated in the activation of CO2 to produce formate species with a low activation barrier as evidenced by DFT calculation. Rh species were atomically dispersed in the In2O3 matrix and were stable during a long term reaction. Under reaction conditions, the surface Rh atoms were reduced and were stabilized by charge transfer from neighbouring In atoms. Our results show that incorporation of atomic Rh species in In2O3 can lead to high methanol productivity by creation of oxygen vacancies as well as Rh centred active sites for CO2 activation
Expression of Plasmodium falciparum genes involved in erythrocyte invasion varies among isolates cultured directly from patients.
No full textPlasmodium falciparum merozoites invade erythrocytes using a range of alternative ligands that includes erythrocyte binding antigenic proteins (EBAs) and reticulocyte binding protein homologues (Rh). Variation in the expression of some of these genes among culture-adapted parasite lines correlates with the use of different erythrocyte receptors. Here, expression profiles of four Rh genes and eba175 are analysed in a sample of 42 isolates cultured from malaria patients in Kenya. The profiles cluster into distinct groups, largely because of very strong negative correlations between the levels of expression of particular gene pairs (Rh1 versus Rh2b, eba175 versus Rh2b, and eba175 versus Rh4), previously associated with alternative invasion pathways in culture-adapted parasite lines. High levels of eba175 are seen in isolates in expression profile group I, and may be associated with sialic acid-dependent invasion. Groups II and III are, respectively, characterized by high levels of Rh2b and Rh4, and are more likely to be associated with sialic acid-independent invasion
Unveiling 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
Anomalous F-electron Hall Effect In The Heavy-fermion System Cetin 5 (t=co, Ir, Or Rh)
No full textThe in-plane Hall coefficient RH(T) of CeRhIn5, CeIrIn5, and CeCoIn5, and their respective nonmagnetic lanthanum analogs are reported in fields up to 90 kOe and at temperatures from 2-325 K. RH(T) is negative, field independent, and dominated by skew scattering above ∼50 K in the Ce compounds. RH(H → 0) becomes increasingly negative below 50 K and varies with temperature in a manner that is inconsistent with skew scattering. Field-dependent measurements show that the low-T anomaly is strongly suppressed when the applied field is increased to 90 kOe. Measurements on LaRhIn5, LaIrIn5, and LaCoIn5 indicate that the same anomalous temperature dependence is present in the Hall coefficient of these nonmagnetic analogs, albeit with a reduced amplitude and no field dependence. Hall angle (θH) measurements find that the ratio ρxx/ρxy). = cot(θH) varies as T2 below 20 K for all three Ce-115 compounds. The Hall angles of the La-115 compounds follow this T dependence as well. 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Mapping Intermediates in Hydrogen Evolution with [Cp*Rh] Catalysts and Carbon Monoxide Release from [Mn(CO)3] Complexes
No full textPentamethylcyclopentadienyl rhodium ([Cp*Rh]) and manganese tricarbonyl ([Mn(CO)3]) complexes represent workhorse families of compounds with key applications in catalytic hydrogen evolution and light-driven carbon monoxide (CO) release, respectively. Investigations with these model molecular systems are motivated by our limited knowledge concerning the fundamental mechanisms involved in storing energy in chemical bonds and releasing carbon monoxide using visible light. In Part I of this dissertation, synthetic, electrochemical, structural, and spectroscopic studies have been applied to map the elementary electron- and proton-transfer steps leading to catalytic dihydrogen evolution. Time-resolved pulse radiolysis and stopped-flow spectroscopic studies reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)]+, followed by tautomerization to form [(η4-Cp*H)Rh(bpy)]+. Spectroscopic monitoring of the second proton transfer event reveals both the hydride and related Cp*H complex are involved in further reactivity and confirm that [(Cp*H)Rh] is not an off-cycle intermediate, but can be an active participant in catalytic H2 evolution. In Part II, synthetic, electrochemical, structural, and spectroscopic studies have been applied to elucidate the redox and electronic properties of a family of monometallic, as well as homo- and hetero-bimetallic complexes, bearing the [Mn(CO)]3 unit. In particular, we have elucidated the early intermediates involved in visible-light-driven speciation of a series of [Mn(CO)3(Rbpy)] complexes bearing 4,4′-disubstituted 2,2′-bipyridyl ligands (Rbpy, R = tBu, H, CF3, NO2). Ultrafast transient absorption spectroscopy measurements with UV-visible monitoring reveals loss of a CO ligand on the femtosecond timescale, followed by solvent coordination on the picosecond timescale. Taken together, the findings described in this dissertation of [Cp*Rh] and [Mn(CO)3] complexes provide a foundation for future investigations that could yield more detailed mechanistic insight into H2 generation and controlled CO release
The response of carbohydrate metabolism to the fluctuation of relative humidity (RH) in the desert soil cyanobacterium Phormidium tenue
No full textThe excreting of exopolysaccharides (EPS) is thought as one of the main protection ways for cyanobacteria in desert algal crusts to survive desiccation. But how cyanobacteria adjust their carbohydrate metabolism to survive this stress is not elucidated. In this study, we treated Phormidium tenue, a cyanobacterium isolated from biological soil crusts with the changes of relative humidity (RH) to simulate different levels of desiccation and investigated its carbohydrate metabolism. It was found that photosynthetic activity (Fv/Fm) and cellular total carbohydrates production decreased significantly at low RH. But the production of EPS, reducing sugar, sucrose and the activity of sucrose phosphate synthase (SPS) increased significantly at low RH and reached maximum at 75% RH. Low RH could also cause the enhanced production of reactive oxygen species (ROS) generation, malondialdehyde (MDA) production and DNA strand breaks. However, when pretreated with exogenous 100 mg/L EPS, Fv/Fm and carbohydrate production were improved significantly, while ROS generation, MDA production and DNA strand breaks decreased significantly at various levels of RH in P tenue. These results indicated that P. tenue in arid regions could enhance desiccation tolerance by adjusting the carbohydrate metabolism to eliminate ROS and decrease oxidative damage. (C) 2011 Elsevier Masson SAS. All rights reserved.The excreting of exopolysaccharides (EPS) is thought as one of the main protection ways for cyanobacteria in desert algal crusts to survive desiccation. But how cyanobacteria adjust their carbohydrate metabolism to survive this stress is not elucidated. In this study, we treated Phormidium tenue, a cyanobacterium isolated from biological soil crusts with the changes of relative humidity (RH) to simulate different levels of desiccation and investigated its carbohydrate metabolism. It was found that photosynthetic activity (Fv/Fm) and cellular total carbohydrates production decreased significantly at low RH. But the production of EPS, reducing sugar, sucrose and the activity of sucrose phosphate synthase (SPS) increased significantly at low RH and reached maximum at 75% RH. Low RH could also cause the enhanced production of reactive oxygen species (ROS) generation, malondialdehyde (MDA) production and DNA strand breaks. However, when pretreated with exogenous 100 mg/L EPS, Fv/Fm and carbohydrate production were improved significantly, while ROS generation, MDA production and DNA strand breaks decreased significantly at various levels of RH in P tenue. These results indicated that P. tenue in arid regions could enhance desiccation tolerance by adjusting the carbohydrate metabolism to eliminate ROS and decrease oxidative damage. (C) 2011 Elsevier Masson SAS. All rights reserved
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