Wilkinson's catalyst

Summary

Wilkinson's catalyst is the common name for chloridotris(triphenylphosphine)rhodium(I), a coordination complex of rhodium with the formula [RhCl(PPh3)3], where 'Ph' denotes a phenyl group). It is a red-brown colored solid that is soluble in hydrocarbon solvents such as benzene, and more so in tetrahydrofuran or chlorinated solvents such as dichloromethane. The compound is widely used as a catalyst for hydrogenation of alkenes. It is named after chemist and Nobel laureate Sir Geoffrey Wilkinson, who first popularized its use. Historically, Wilkinson's catalyst has been a paradigm in catalytic studies leading to several advances in the field such as the implementation of some of the first heteronuclear magnetic resonance studies for its structural elucidation in solution (31P), parahydrogen-induced polarization spectroscopy to determine the nature of transient reactive species, or one of the first detailed kinetic investigation by Halpern to elucidate the mechanism. Furthermor

Official source

https://en.wikipedia.org/wiki/Wilkinson's_catalyst

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To curb the severe effects of climate change, our society needs to radically reduce its CO2 footprint. For the heavy-duty sector, where electrification is difficult, alternative fuels can be the solution. Methane-fueled engines have lower energy-specific CO2 emissions than conventional Diesel-fueled engines. Furthermore, they have the potential of becoming carbon-neutral, when combined with bio-methane/synthetic methane. However, oxidation of unburnt methane in the exhaust gas poses a challenge for aftertreatment systems. The aim of this thesis is to investigate the mechanism of methane abatement and to reveal methods to reduce methane and other hazardous gas emissions. The majority of the experiments were conducted directly on an engine test bench, which is rarely seen in studies focusing on catalytic reaction pathways. Initial investigations focused on methane abatement under steady state and Î»-step transitions. Under steady state, the presence of oxygen was identified as a prerequisite for methane conversion. Reacting with oxygen is the only methane conversion pathway. However, after step transition from oxygen excess conditions (slightly lean) to oxygen-poor conditions (slightly rich), high methane conversion was observed under rich conditions with no oxygen available. This high conversion was attributed to steam reforming (SR), which was activated by the step transition. The SR reaction rate decreased over time when staying at rich conditions, until full deactivation. Investigations in the lab-scale model gas reactor confirmed this analysis. In addition, the reason for SR deactivation was identified by DRIFTS measurements as the accumulation of carbonates on the catalytic surface, blocking the active sites. Based on the identified importance of the SR reaction, targeted Î» oscillations across stoichiometry were introduced, in order to repeatably activate SR and achieve sustainable high methane conversion. During the rich parts of the oscillations, methane was converted via SR, while, during lean parts, the carbonates were periodically removed from the catalyst surface. With these oscillations, methane conversion has been significantly improved, in comparison to steady state. In parallel, a numerical model has been developed in order to simulate the catalyst behavior under oscillating conditions. The model provided insights on the reaction pathways and their distribution along the catalyst axis. The catalytic activity of the different Platinum-group metals has been investigated for the identified reactions. Various catalysts of different compositions were tested under cold start, Î» oscillations and quasi-steady state conditions. Both Pt and Pd activated SR reactions, however SR attenuation was faster in Pt catalysts. In lean conditions, Pt exhibited higher methane oxidation. Rh was identified as important for enhancing NOx reduction and lowering NH3 emissions. The combination of all three metals has improved the overall catalyst performances. In the final part of the thesis, a special aftertreatment system was investigated. It combines a Pd/Rh catalyst subject to stoichiometric conditions with a Pt oxidation catalyst subject to lean conditions. In the Pd/Rh catalyst, methane was removed via Î» oscillations. In the Pt catalyst, the remaining CO, H2 and NH3 were oxidized. The setup provided a novel perspective in reducing the overall environmental impacts.

EPFL2022

Chemical and electrochemical promotion of supported rhodium catalyst

Olena Baranova

The chemical and electrochemical promotion of highly dispersed nanofilm Rh catalysts (dispersion: about 10 %, film thickness: 40 nm) has been investigated for the first time. To this end Rh metal was sputter-deposited, either on a purely ionic conductor (8 % Y2O3-stabilized ZrO2) or on a mixed ionic-electronic conductor (TiO2), the latter being a highly dispersed layer of TiO2 (4 µm) deposited on YSZ. These catalysts are designated as Rh/YSZ and Rh/TiO2/YSZ, respectively. It was established analytically that both in the Rh/YSZ and in the Rh/TiO2/YSZ system, the catalyst films have a nanoparticle-size grain structure. The Rh supported on titania is rather porous, exhibiting a higher dispersion and surface area than Rh on YSZ. Both after reduction (H2, T=400 °C) and after oxidation (O2, T=400 °C), Rh supported on TiO2 was found to be in a more highly reduced state than Rh on YSZ. After reducing treatment, the Rh/TiO2/YSZ samples contain a larger amount of weakly bonded oxygen, which can be attributed to oxygen "backspillover" from the TiO2. A major feature of this research was the electrochemical characterization of the oxygen/Rh/solid electrolyte three-phase boundary by steady-state polarization measurements and by impedance spectroscopy. These are powerful techniques for extracting experimental trends and details that are useful for an understanding of the electrochemical promotion principles. It was shown that the exchange current densities at the Rh/solid electrolyte interface are lower on account of the TiO2 layer. The exchange current densities are more than twice lower at Rh/TiO2(4 µm)/YSZ than at Rh/YSZ, demonstrating that the former interface is much more polarizable. The mechanism of oxygen exchange occurring close to equilibrium (O2/O2- couple) was investigated for the first time at Rh catalyst electrodes interfaced with solid electrolyte. The processes of cathodic oxygen reduction and anodic oxygen evolution are not symmetric, but they are similar in the two systems, Rh/YSZ and Rh/TiO2(4 µm)/YSZ. The cathodic process consists of three steps: dissociative adsorption of oxygen at the gas-exposed Rh surface, atomic oxygen diffusion to the electrochemical reaction sites (ERS), and a two-electron transfer to this oxygen on the ERS. The cathodic process is limited by interfacial diffusion of oxygen atoms from the gas-exposed metal surface to the ERS. The anodic process includes two steps: two-electron transfer reaction, which is the rate-determining step, and oxygen desorption to the gas phase. With data obtained from impedance spectroscopy at the equilibrium potential, it was possible to confirm the reaction scheme proposed. It was demonstrated that Rh nanofilm catalysts interfaced with YSZ or TiO2/YSZ can be electrochemically promoted for the reaction of ethylene oxidation. Small anodic currents cause periodic oscillations in catalytic rate and potential of the Rh/YSZ catalyst, while at Rh/TiO2/YSZ they give rise to a stable and reversible rate enhancement by up to a factor 80. The increase in ethylene oxidation rate is up to 2000 times larger than the electrochemical rate, I/2F, of O2- oxidation. The pronounced electrochemical promotion behavior that has been observed is due to the anodically controlled migration of O2- species from the electrolyte to the Rh/gas interface. At the Rh surface, these species destabilize the formation of rhodium surface oxide (Rh2O3). The existence of backspillover oxygen species has been confirmed by impedance measurements under positive applied potential. Another significant result for heterogeneous catalysis is the finding that thick as well as thin films of Rh/TiO2/YSZ catalyst are open to chemical promotion of ethylene oxidation and partial methane oxidation, ie, they offer a higher catalytic activity and stability than the Rh/YSZ catalysts. The modification of catalytic activity observed for Rh/TiO2/YSZ was attributed to either a "long-range" electronic-type SMSI mechanism or to a self-driven electrochemical promotion mechanism. In both cases, the ultimate cause of promotion are different work functions of catalyst and support. Equilibration of the work functions of two solids in contact induces surface charging, a migration of O2- ions to the catalyst/gas interface, and a weakening of the Rh-O chemisorptive bonds. It facilitates reduction of oxidized surface sites. Another important achievement of the present work was that of exploring and confirming the possibilities of current-assisted activation of Rh/TiO2/YSZ catalysts. In partial methane oxidation using close to stoichiometric gas compositions (CH4 : O2 = 2 : 1) at 550 °C, the inactive (oxidized) Rh/TiO2/YSZ catalyst was successfully activated by applied currents, either positive or negative. This phenomenon is an example of "permanent" electrochemical promotion furnishing a permanent rate enhancement ratio of γ = 11. The activation by negative currents is explained in terms of an electrochemical reduction of rhodium surface oxide, while the activation by positive currents can be explained by the mechanism of electrochemical promotion.

EPFL2005

The tetradentate chelate ligand tris[(1-vinylimidazol-2-yl)methyl]amine (10) was synthesized in five steps from commercially available starting materials. Upon reaction with MCl2 (M = Zn, Cu, Ni, Co) in the presence of NH4PF6, the complexes [M(10)Cl]PF6 (M = Zn (11), Cu (12), Co (14)) and [Ni(10)Cl]2(PF6)2 (13) were obtained. The structure of all complexes was determined by single crystal X-ray crystallography. Immobilization of 11 and 12 was achieved by copolymerization with ethyleneglycol dimethacrylate (EGDMA) to obtain P11-Zn and P12-Cu. Immobilized versions of 13 and 14 have been generated by cleavage the metal from P12-Cu and subsequent assembly of MCl2 (M = Ni (P12-Ni), Co (P12-Co)). The supported complexes P11-Zn, P12-Cu, P12-Ni, and P12-Co were found to be efficient catalysts for the hydrolysis of bis(ρ-nitrophenyl)phosphate (BNPP) at 50 °C. At pH 9.5, the heterogeneous catalyst P12-Cu was 56 times more active than the homogeneous catalyst 12. Partitioning effects, which increase the local concentration of BNPP in the polymer, are shown to contribute to the enhanced activity of the immobilized catalyst. The tridentate N,N',N''-chelate ligand tris(1-vinylimidazol-2-yl)phosphine (20) was synthesized from commercially available starting materials. Three immobilized Cu(II) complexes were generated by the following: (a) homopolymerization of 20 and subsequent metalation with CuCl2; (b) copolymerization of 20 with EGDMA and subsequent metalation with CuCl2; or (c) molecular imprinting with the organometallic Mo-complex Mo(η3-C4H7)(CO)2(20) (28) and EGDMA and subsequent replacement of Mo(II) by Cu(II). All three polymeric Cu complexes were found to very efficiently promote the hydrolysis of activated phosphoesters with the relative activity being dependent on the nature of the polymer and the substrate. The complex Fe2O(CH3COO)(10)23 (42) was synthesized and structurally investigated by single crystal X-ray crystallography. After copolymerization with EGDMA and subsequent replacement of Fe(III) by Cu(II), Zn(II) or Mn(III), hydrolysis and oxidation reactions were investigated. A higher activity compared to the corresponding monometallic immobilized complexes was observed. This increase in activity is most likely caused by cooperative effects.

EPFL2006

Chemical and electrochemical promotion of supported rhodium catalyst

Olena Baranova

EPFL2005

EPFL2022

EPFL2006