Search Results (4)

Hydrodesulfurization (HDS) is a widely used process currently employed in petroleum refineries to eliminate organosulfur compounds in fuels. The current hydrotreating process struggles to remove organosulfur compounds with a steric hindrance due to the electronic nature of the current catalysts employed. In this work, the effects of adding chelating ligands such as ethylenediaminetetraacetic acid (EDTA), citric acid (CA) and acetic acid (AA) to rhodium (Rh) and active molybdenum (Mo) species for dibenzothiophene (DBT) HDS catalytic activity was evaluated. HDS activities followed the order of RhMo/ɣ-Al₂O₃ (88%) > RhMo-AA/ɣ-Al₂O₃ (73%) > RhMo-CA/ɣ-Al₂O₃ (72%) > RhMo-EDTA/ɣ-Al₂O₃ (68%). The observed trend was attributed to the different chelating ligands with varying electronic properties, thus influencing the metal–support interaction and the favorable reduction of the Mo species. RhMo/ɣ-Al₂O₃ offered the highest HDS activity due to its (i) lower metal–support interaction energy, as observed from the RhMo/ɣ-Al₂O₃ band gap of 3.779 eV and the slight shift toward the lower BE of Mo 3d, (ii) increased Mo-O-Mo species (N_Mo-O-Mo ~1.975) and (iii) better sulfidation of Rh and MoO in RhMo/ɣ-Al₂O₃ compared to the chelated catalysts. The obtained data provides that HDS catalytic activity was mainly driven by the structural nature of the RhMo-based catalyst, which influences the formation of more active sites that can enhance the HDS activity. Full article

PROMETHEUS catalyst, a copper-based polymetallic nano-catalyst has been proven to be suitable for automotive emission control applications. This novel catalyst consists of copper, palladium and rhodium nanoparticles as active phases, impregnated on an inorganic oxide substrate, CeO₂/ZrO₂ (75%, 25%). The aim of PROMETHEUS catalyst’s development is the substitution of a significant amount (85%) of Platinum Group Metals (PGMs) with copper nanoparticles while, at the same time, presenting high catalytic efficiency with respect to the commercial catalysts. In this work, an extensive investigation of the catalytic activity of full scale PROMETHEUS fresh and aged catalyst deposited on ceramic cordierites is presented and discussed. The catalytic activity was tested on an Synthetic Gas Bench (SGB) towards the oxidation of CO and CH₄ and the reduction of NO. The loading of the washcoat was 2 wt% (metal content) on Cu, Pd, Rh with the corresponding metal ratio at 21:7:1. The concentration of the full-scale monolithic catalysts to be 0.032% total PGM loading for meeting Euro III standard and 0.089% for meeting Euro IV to Euro VIb standards. The catalytic activity of all catalysts was tested both in rich-burn (λ = 0.99) and lean-burn conditions (λ = 1.03). Full article

Rh(III)-catalyzed C–H activation features mild reaction conditions, good functional group tolerance, high reaction efficiency, and regioselectivity. Recently, it has attracted tremendous attention and has been employed to synthesize various heterocycles, such as indoles, isoquinolines, isoquinolones, pyrroles, pyridines, and polyheterocycles, which are important privileged structures in biological molecules, natural products, and agrochemicals. In this short review, we attempt to present an overview of recent advances in Rh(III)-mediated C–H bond activation to generate diverse heterocyclic scaffolds with sp³ carbon centers. Full article

Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh₃)₂Rh(CO)Cl. This complex largely draws its stability from the strength of the Rh(I)–CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III). However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction. Full article