Measurement of oxygen storage capacity in automotive catalysts

There is considerable disagreement in the literature on available oxygen storage capacity, and on the reaction rates associated with the storage process, for three-way automotive catalysts. This paper seeks to address the issue of oxygen storage capacity in a clear and precise manner. The work described involved a detailed investigation of oxygen storage capacity in typical samples of automotive catalysts. The capacity has also been precisely defined and estimates have been made of the specific capacity based on catalyst dimensions. A purpose-built miniature catalyst test rig has been assembled to allow measurement of the capacity and the experimental procedure has been developed to ensure accurate measurement. The measurements from the first series of experiments have been compared with the theoretical calculations and good agreement is seen. A second series of experiments allowed the effect of temperature on oxygen storage capacity to be investigated. This work shows very clearly the large variation of the capacity with temperature.

Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram resulting from widely different diffusion coefficients of oxygen and superoxide

The electrochemical reduction of oxygen in two different room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide ([N-6222][N(Tf)(2)]) was investigated by cyclic voltammetry at a gold microdisk electrode. Chronoamperometric measurements were made to determine the diffusion coefficient, D, and concentration, c, of the electroactive oxygen dissolved in the ionic liquid by fitting experimental transients to the Aoki model. [Aoki, K.; et al. J. Electroanal. Chem. 1981, 122, 19]. A theory and simulation designed for cyclic voltammetry at microdisk electrodes was then employed to determine the diffusion coefficient of the electrogenerated superoxide species, O-2(.-), as well as compute theoretical voltammograms to confirm the values of D and c for neutral oxygen obtained from the transients. As expected, the diffusion coefficient of the superoxide species was found to be smaller than that of the oxygen in both ionic liquids. The diffusion coefficients of O-2 and O-2(.-) in [N-6222][N(Tf)(2)], however, differ by more than a factor of 30 (D-O2 = 1.48 x 10(-10) m(2) s(-1), DO2.- = 4.66 x 10(-12) m(2) s(-1)), whereas they fall within the same order of magnitude in [EMIM][N(Tf)(2)] (D-O2 = 7.3 x 10(-10) m(2) s(-1), DO2.- = 2.7 x 10(-10) m(2) s(-1)). This difference in [N-6222][N(Tf)(2)] causes pronounced asymmetry in the concentration distributions of oxygen and superoxide, resulting in significant differences in the heights of the forward and back peaks in the cyclic voltammograms for the reduction of oxygen. This observation is most likely a result of the higher viscosity of [N-6222][N(Tf)(2)] in comparison to [EMIM][N(Tf)(2)], due to the structural differences in cationic component.

Electroreduction of oxygen in a series of room temperature ionic liquids composed of group 15-centered cations and anions

The electrochemical reduction of oxygen is reported in four room temperature ionic liquids (RTILs) based on quaternary alkyl -onium cations and heavily fluorinated anions in which the central atom is either nitrogen or phosphorus. Data were collected using cyclic voltammetry and potential step chronoamperometry at gold, platinum, and glassy carbon disk electrodes of micrometer dimension under water-free conditions at a controlled temperature. Analysis via fitting, to appropriate theoretical equations was then carried out to obtain kinetic and thermodynamic information pertaining to the electrochemical processes observed. In the quaternary ammonium electrolytes, reduction of oxygen was found to occur reversibly to give stable superoxide, in an analogous manner to that seen in conventional aprotic solvents such as dimethyl sufoxide and acetonitrile. The most significant difference is in the relative rate of diffusion; the diffusion coefficients of oxygen in the RTILs are an order of magnitude lower than in common organic solvents, and for superoxide these values are reduced by a further factor of 10. In the quaternary phosphonium ionic liquids, however, more complex voltammetry is observed, akin to that expected for the reduction of oxygen in acidified organic media. This is shown to be consistent with the occurrence of a proton abstraction reaction between the electrogenerated superoxide and quaternary alkyl phosphonium cations following the initial electron transfer.

The Reduction of Oxygen in Various Room Temperature Ionic Liquids in the Temperature Range 293-318 K: Exploring the Applicability of the Stokes-Einstein Relationship in Room Temperature Ionic Liquids

The voltammetry for the reduction of oxygen at a microdisk electrode is reported in six commonly used RTILs: [C(4)mim][NTf2], [C(4)mpyrr][NTf2], [C(4)dmim][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], and [N-6.2.2.2][NTf2], where [C(4)mim](+) is 1-butyl-3-methylimidazolium, [NTf2](-) is bis(trifluoromethanesulfonyl)imide, [C(4)mpyrr](+) is N-butyl-N-methylpyrrolidinium, [C(4)dmim](+) is 1-butyl-2,3-methylimidazolium, [BF4](-) is tetrafluoroborate, [PF6](-) is hexafluorophosphate, and [N-6.2.2.2](+) is n-hexyltriethylammonium at varying scan rates (50-4000 mV s(-1)) and temperatures (293-318 K). Diffusion coefficients, D, of oxygen are deduced at each temperature from potential-step chronoamperometry, and diffusional activation energies are calculated. Oxygen solubilities are also reported as a function of temperature. In the six ionic liquids, the Stokes-Einstein relationship (D proportional to eta(-1)) was found to apply only very approximately for oxygen. This is considered in relationship to the behavior of other diverse solutes in RTILs.

Cumulative or sequential assessment during hermit crab shell fights: effects of oxygen on decision rules

Agonistic interactions between animals are often settled by the use of repeated signals which advertise the resource-holding potential of the sender. According to the sequential assessment game this repetition increases the accuracy with which receivers may assess the signal, but under the cumulative assessment model the repeated performances accumulate to give a signal of stamina. These models may be distinguished by the temporal pattern of signalling they predict and by the decision rules used by the contestants. Hermit crabs engage in shell fights over possession of the gastropod shells that they inhabit. During these interactions the two roles of signaller and receiver may be examined separately because they are fixed for the duration of the encounter. Attackers rap their shell against that of the defender in a series of bouts whereas defenders remain tightly withdrawn into their shells for the duration of the contest. At the end of a fight the attacker may evict the defender from its shell or decide to give up without first effecting an eviction; the decision for defenders is either to maintain a grip on its shell or to release the shell and allow itself to be evicted. We manipulated fatigue levels separately for attackers and defenders, by varying the oxygen concentration of the water that they are held in prior to fighting, and examined the effects that this has on the likelihood of each decision and on the temporal pattern of rapping. We show that the vigour of rapping and the likelihood of eviction are reduced when the attacker is subjected to low oxygen but that this treatment has no effect on rates of eviction when applied to defenders. We conclude that defenders compare the vigour of rapping with an absolute threshold rather than with a relative threshold when making their decision. The data are compatible with the cumulative assessment model and with the idea that shell rapping signals the stamina of attackers, but do not fit the predictions of the sequential assessment game.

Lack of Oxygen Deactivates Mitochondrial Complex I IMPLICATIONS FOR ISCHEMIC INJURY?

For S-nitrosothiols and peroxynitrite to interfere with the activity of mitochondrial complex I, prior transition of the enzyme from its active (A) to its deactive, dormant (D) state is necessary. We now demonstrate accumulation of the D-form of complex I in human epithelial kidney cells after prolonged hypoxia. Upon reoxygenation after hypoxia there was an initial delay in the return of the respiration rate to normal. This was due to the accumulation of the D-form and its slow, substrate-dependent reconversion to the A-form. Reconversion to the A-form could be prevented by prolonged incubation with endogenously generated NO. We propose that the hypoxic transition from the A-form to the D-form of complex I may be protective, because it would act to reduce the electron burst and the formation of free radicals during reoxygenation. However, this may become an early pathophysiological event when NO-dependent formation of S-nitrosothiols or peroxynitrite structurally modifies complex I in its D-form and impedes its return to the active state. These observations provide a mechanism to account for the severe cell injury that follows hypoxia and reoxygenation when accompanied by NO generation.