O2 reduction at the IFC orbiter fuel cell O2 electrode

O2 reduction Tafel data were obtained for the IFC Orbiter fuel cell O2 electrode (Au-10 percent Pt catalyst) at temperatures between 24 and 81 C. BET measurements gave an electrode surface area of about 2040 sq cm per sq cm of geometric area. The Tafel data could be fitted to three straight line regions. For current densities less than 0.001 A/sq cm, the slope was essentially independent of temperature with a value of about 0.032 V/decade. Above 0.001 A/sq cm, the two regions, designated in the present study as the 0.04 and 0.12 V/decate regions, were temperature dependent. The apparent energies of activation for these two regions were about 9.3 and 6.5 kcal/mol, respectively. Tafel data (1 atmosphere O2) were extrapolated to 120 C for predicting changes in overpotential with increasing temperature. A mechanism is presented for O2 reduction

A study of Na(x)Pt3O4 as an O2 electrode bifunctional electrocatalyst

The present study suggests that polytetrafluoroethylene (PTFE) bonded Na(X)Pt3O4 gas porous diffusion electrodes may be a viable candidate for bifunctional O2 reduction and evolution activity. The electrodes exhibited Tafel slopes of about 0.06 V/decade for both O2 reduction an evolution. For O2 reduction, the 0.06 slope doubled to 0.12 V/decade at larger current densities. Preliminary stability testing at 24 C suggest that the Na(x)Pt3O4 electrodes were relatively stable at reducing and oxidizing potentials typically encountered at the O2 electrodes in a regenerative fuel cell

Oxygen reduction in acid media: influence of the activity of CoNPc(1,2) bilayer deposits in relation to their attachment to the carbon black support and role of surface groups as a function of heat treatment

O2 reduction was investigated using rotating disk electrode and voltammetry techniques on NPcCo(1,2) impregnations deposited onto two kinds of carbon black support. They were selected on the basis of their similar pH and dibuthylphthalate (DBP) adsorption values. Samples were also characterized by IR and X-ray photoelectron spectroscopy techniques. An optimized thermal treatment yielded an improvement in the O2 reducibility and identical activities (with N = 3.8) on both supports. These spectroscopic methods revealed a bilayer structure and suggested the presence of two sorts of site (active and inactive) which differed in their attachment of the substrate via surface groups which were characterized

Alternative outlets for sustaining photosynthetic electron transport during dark-to-light transitions.

Environmental stresses dramatically impact the balance between the production of photosynthetically derived energetic electrons and Calvin-Benson-Bassham cycle (CBBC) activity; an imbalance promotes accumulation of reactive oxygen species and causes cell damage. Hence, photosynthetic organisms have developed several strategies to route electrons toward alternative outlets that allow for storage or harmless dissipation of their energy. In this work, we explore the activities of three essential outlets associated with Chlamydomonas reinhardtii photosynthetic electron transport: (i) reduction of O2 to H2O through flavodiiron proteins (FLVs) and (ii) plastid terminal oxidases (PTOX) and (iii) the synthesis of starch. Real-time measurements of O2 exchange have demonstrated that FLVs immediately engage during dark-to-light transitions, allowing electron transport when the CBBC is not fully activated. Under these conditions, we quantified maximal FLV activity and its overall capacity to direct photosynthetic electrons toward O2 reduction. However, when starch synthesis is compromised, a greater proportion of the electrons is directed toward O2 reduction through both the FLVs and PTOX, suggesting an important role for starch synthesis in priming/regulating CBBC and electron transport. Moreover, partitioning energized electrons between sustainable (starch; energetic electrons are recaptured) and nonsustainable (H2O; energetic electrons are not recaptured) outlets is part of the energy management strategy of photosynthetic organisms that allows them to cope with the fluctuating conditions encountered in nature. Finally, unmasking the repertoire and control of such energetic reactions offers new directions for rational redesign and optimization of photosynthesis to satisfy global demands for food and other resources

Echocardiography combined with cardiopulmonary exercise testing for the prediction of outcome in idiopathic pulmonary arterial hypertension

BACKGROUND: Right ventricular (RV) function is a major determinant of exercise intolerance and outcome in idiopathic pulmonary arterial hypertension (IPAH). The aim of the study was to evaluate the incremental prognostic value of echocardiography of the RV and cardiopulmonary exercise testing (CPET) on long-term prognosis in these patients. METHODS: One hundred-thirty treatment-naïve IPAH patients were enrolled and prospectively followed. Clinical worsening (CW) was defined by a reduction in 6-minute walk distance plus an increase in functional class, or non elective hospitalization for PAH, or death. Baseline evaluation included clinical, hemodynamic, echocardiographic and CPET variables. Cox regression modeling with c-statistic and bootstrapping validation methods were done. RESULTS: During a mean period of 528 ± 304 days, 54 patients experienced CW (53%). Among demographic, clinical and hemodynamic variables at catheterization, functional class and cardiac index were independent predictors of CW (Model-1). With addition of echocardiographic and CPET variables (Model-2), peak O2 pulse (peak VO2/heart rate) and RV fractional area change (RVFAC) independently improved the power of the prognostic model (AUC: 0.81 vs 0.66, respectively; p=0.005). Patients with low RVFAC and low O2 pulse (low RVFAC + low O2 pulse) and high RVFAC+low O2 pulse showed 99.8 and 29.4 increase in the hazard ratio, respectively (relative risk -RR- of 41.1 and 25.3, respectively), compared with high RVFAC+high O2 pulse (p=0.0001). CONCLUSIONS: Echocardiography combined with CPET provides relevant clinical and prognostic information. A combination of low RVFAC and low O2 pulse identifies patients at a particularly high risk of clinical deterioration

Carbon-sulfur bond strength in methanesulfinate and benzenesulfinate ligands directs decomposition of Np(v) and Pu(v) coordination complexes.

Gas-phase coordination complexes of actinyl(v) cations, AnO2+, provide a basis to assess fundamental aspects of actinide chemistry. Electrospray ionization of solutions containing an actinyl cation and sulfonate anion CH3SO2- or C6H5SO2- generated complexes [(AnVO2)(CH3SO2)2]- or [(AnVO2)(C6H5SO2)2]- where An = Np or Pu. Collision induced dissociation resulted in C-S bond cleavage for methanesulfinate to yield [(AnVO2)(CH3SO2)(SO2)]-, whereas hydrolytic ligand elimination occurred for benzenesulfinate to yield [(AnVO2)(C6H5SO2)(OH)]-. These different fragmentation pathways are attributed to a stronger C6H5-SO2-versus CH3-SO2- bond, which was confirmed for both the bare and coordinating sulfinate anions by energies computed using a relativistic multireference perturbative approach (XMS-CASPT2 with spin-orbit coupling). The results demonstrate shutting off a ligand fragmentation channel by increasing the strength of a particular bond, here a sulfinate C-S bond. The [(AnVO2)(CH3SO2)(SO2)]- complexes produced by CID spontaneously react with O2 to eliminate SO2, yielding [(AnO2)(CH3SO2)(O2)]-, a process previously reported for An = U and found here for An = Np and Pu. Computations confirm that the O2/SO2 displacement reactions should be exothermic or thermoneutral for all three An, as was experimentally established. The computations furthermore reveal that the products are superoxides [(AnVO2)(CH3SO2)(O2)]- for An = Np and Pu, but peroxide [(UVIO2)(CH3SO2)(O2)]-. Distinctive reduction of O2- to O22- concomitant with oxidation of U(v) to U(vi) reflects the relatively higher stability of hexavalent uranium versus neptunium and plutonium

On the use of electrochemical techniques to monitor free oxide content in molten fluoride media

The electrochemical behaviour of oxide ions has been studied in fluoride melts(LiF/NaF eutectic) by cyclic voltammetry, square wave voltammetry and chronopotentiometry. The purpose is to determine whether these techniques can be used for titration of free oxide ions (O2-) in molten fluorides released by lithium oxide additions. Cyclic voltammetry is shown to be unsuitable for this purpose due to oxygen bubbling disturbing the oxidation peak, while square wave voltammetry is far more appropriate because the observed signal is a well defined oxidation peak with a height proportional to the oxide content. Thus, the present work is focused on a strategy of oxide ions titration by square wave voltammetry. In addition, this work allows assessing that the electrochemical reduction of oxide ions proceeds by diffusion of these species, and the O2- diffusion coefficient is estimated by chronopotentiometry

Integrated oxygen recovery system

Life Systems has conceptualized an innovative Integrated Oxygen Recovery System (IORS) applicable to advanced mission air revitalization. The IORS provides the capability to electrochemically generate metabolic oxygen (O2) and recover O2 from the space habitat atmosphere via a carbon dioxide (CO2) reduction process within a single assembly. To achieve this capability, the IORS utilizes a Solid Metal Cathode (SMC) water electrolysis unit that simultaneously serves as the Sabatier CO2 reduction reactor. The IORS enables two major life support systems currently baselined in closed loop air revitalization systems to be combined into one smaller, less complex system. This concept reduces fluidic and electrical interface requirements and eliminates a hydrogen (H2) interface. Life Systems is performing an evaluation of the IORS process directed at demonstrating performance and quantifying key physical characteristics including power, weight, and volume. The results of the checkout, shakedown, and initial parametric tests are summarized

Oxygen reduction in acid media on supported iron naphthalocyanine: Effect of isomer configuration and pyrolysis

O2 reduction in H2SO4 medium has been investigated on FeNPc impregnations on Norit BrX by the rotating disk electrode technique. Important differences in activity and stability were found between the 1,2- and 2,3-FeNPc isomers (pyrolysed or not). XPS analyses show, for the most inactive sample, strong demetallation and nitrogen losses. This phenomenon can be attributed to the differences in flexibility between the FeNPc isomers, which influences their stabilization on the substrate