Oxygen reduction catalyzed by a fluorinated tetraphenylporphyrin free base at liquid/liquid interfaces

The diprotonated form of a fluorinated free base porphyrin, namely 5-(p-aminophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (H(2)FAP), can catalyze the reduction of oxygen by a weak electron donor, namely ferrocene (Fc). At a water/1,2-dichloroethane interface, the interfacial formation of H(4)FAP(2+) is observed by UV-vis spectroscopy and ion-transfer voltammetry, due to the double protonation of H(2)FAP at the imino nitrogen atoms in the tetrapyrrole ring. H(4)FAP(2+) is shown to bind oxygen, and the complex in the organic phase can easily be reduced by Fc to produce hydrogen peroxide as studied by two-phase reactions with the Galvani potential difference between the two phases being controlled by the partition of a common ion. Spectrophotometric measurements performed in 1,2-dichloroethane solutions clearly evidence that reduction of oxygen by Fc catalyzed by H(4)FAP(2+) only occurs in the presence of the tetrakis(pentafluorophenyl)borate (TB-) counteranion in the organic phase. Finally, ab initio computations support the catalytic activation of H(4)FAP(2+) on oxygen.

Electrocatalysis at liquid/liquid interfaces

Raheleh Partovi Nia

This thesis is devoted to the study of oxygen reduction reaction catalysed by porphyrins at the interface between two immiscible electrolyte solutions (ITIES). Electrochemical and spectrophotometric techniques are introduced to these interfaces in order to gather more information about the transfer mechanism. Furthermore, the reduction of oxygen and the oxidation of decamethylferrocene (DMFc) in 1,2-DCE and production of hydrogen peroxide (H2O2) in the aqueous phase, on the basis of the two-phase reaction controlled by a common ion are investigated. Mass spectrometric measurements were carried out for the 1,2-DCE phase before and after two-phase reaction with an aqueous phase containing acid to indicate the stability of DMFc and the DMFc+ over the course of the two-phase reaction. Density function theory (DFT) computations have been performed based on developed a reaction pathway. Catalytic effect of 5,10,15,20-tetraphenylporphyrinatocobalt(II) [Co(tpp)], 2,3,7,8,12,13,17,18-Octaethyl-porphyrin cobalt(II) (CoOEP) and two free-base porphyrins 5,10,15,20-meso-tetraphenylporphyrin (H2TPP) and 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin (H2OEP) have been investigated as a catalyst for a two electron reduction of O2 in presence of an electron donor at various pH values at the polarized water|1,2-DCE interface. Using voltammetry, it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O2. The signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either catalyst, acid or O2. [Co(tpp)] and CoOEP catalysis work like conventional cobalt porphyrins, activating O2 via coordination by the formation of a superoxide structure. The advantages of the present system is that, by controlling the interfacial potential difference, the proton transfer from water to 1,2-DCE can be accurately controlled. Accordingly, the driving force for proton-coupled electron transfer reactions is also effectively harnessed. Assisted proton transfer (APT) reactions were studied across the water|1,2-DCE interface facilitated by two free-base porphyrins such as H2TPP and H2OEP. At a water|1,2-DCE interface, the interfacial formation of di-acid H4TPP2+ and H4OEP2+ are observed by ion-transfer voltammetry and UV-Visible spectroscopy, due to the double protonation of H2TPP and H2OEP at the tertiary nitrogens in the ring. Additionally, "Ionic Partition Diagram" of neutral and ionisable H2TPP compounds is plotted to illustrate the various contributions of H2TPP.

EPFL2010

Etude de la promotion électrochimique de l'oxydation catalytique de l'éthylène sur des oxydes métalliques

The electrochemical promotion of heterogeneous catalytic reactions is a new development which draws the attention of the scientific community as much to fundamental research as to the possible direct applications of this phenomenon in automotive and in industrial catalysis. We have chosen to study the electrochemical promotion of the complete ethylene oxidation on metallic oxides catalysts. The principal oxides which we used has been the iridium oxide (IrO2) and iridium and titanium oxide mixtures (IrO2+TiO2), deposited on yttria-stabilized zirconia (YSZ). We have proved that the electrochemical promotion of ethylene combustion can be applied to these catalysts. Contrary to what was established before, we have demonstrated a certain persistence of activation of the reaction. mainly on the iridium oxide, after the end of polarization. The persistent reaction rate enhancement ratio is a function of the passed electric charge and levels off at a value of approximately 3. The other experimental significant fact for heterogeneous catalysis which has been discovered is the relation between chemical promotion and electrochemical promotion. Applying electrochemical promotion to a IrO2 + TiO2 composite catalyst, the two kinds of promotions have been confronted, since a IrO2 + TiO2 composite catalyst presents a chemical promotion, more precisely a synergy between the two components of the catalyst. The maximal amplitude of the electrochemical promotion of such catalysts has been demonstrated to be strongly reduced in comparison with the one of pure catalysts. As the maximal enhancement factor of the catalytic reaction rate was 12 for pure iridium oxide catalyst, the same factor dropped to less than 2 for a IrO2 + TiO2 composite catalyst. This result has enabled us to affirm that the mechanisms of chemical promotion and electrochemical promotion should involve a common type of surface activating species : a mobile surface spillover oxygen species. The catalyst work function on-line measurement with a Kelvin probe has enabled us to link the reaction rate with the work function change and to link the applied potential with the work function change, for al1 the phases of a transient polarisation experiment. The persistent activation of the catalyst after the end of a polarization has been linked to a persistent change in the work function. A major trend of this research consists in cyclic voltammetry. It is certainly one of the most powerful medium to extract experimental facts which have been useful to understand the electrochemical promotion principles. Due to the small amplitude of the potential which has been used in cyclic voltammetric experiments, the electrolyte-catalyst interface wasn't practically affected by these in situ measurements. By analogy to voltammetric charge formation mechanism in aqueous electrochemistry, we have taken the following chemical capacitance as responsible for the voltammetric charge in our system: IrO2 + δO- ⇄ IrO2+δ + δe- According to this mechanism, the reaction between O- and IrO2 can only occur at the interface between solid electrolyte and catalyst, where contact between the two species exists. In Our system, voltammetric charge has been demonstrated to be proportional to the thickness of the catalyst, proving by this way that the whole surface of the catalyst is in contact with the O- activating species coming from the solid electrolyte. So the implication of a spillover oxygen species during electrochemical promotion has been demonstrated by the way of cyclic voltammetry. The existence of this spillover oxygen species has been also directly proved by thermal desorption experiments under electrochemical promotion conditions. By considering the strong change in the decomposition temperature of the oxide induced by its polarisation, the thermal desorption technique has been used to display the influence of the polarization on the structure of the oxide catalyst itself.

EPFL1999

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