Optimizing oxygen transport through La0.6Sr0.4Co0.2Fe0.8O3-δ hollow fiber by microstructure modification and Ag/Pt catalyst deposition

This work compares the oxygen permeation fluxes of five different La0.6Sr0.4Co0.2Fe0.8O3−δ membranes (e.g. disk, conventional hollow fiber, modified hollow fiber, Ag- or Pt-deposited hollow fiber membranes) to elucidate the dominance of a particular oxygen transport limiting step (e.g., bulk-diffusion or surface reaction) within each of these membranes. At 900 °C and 100 mL min–1 helium gas sweep rate, the oxygen fluxes for disk, conventional hollow fiber, modified hollow fiber, Ag-deposited modified hollow fiber, and Pt-deposited modified hollow fiber membranes are 0.10, 0.33, 0.84, 1.42, and 2.62 mL min–1 cm–2, respectively, denoting enhanced performance in this sequential order. More than 300% enhancement of fluxes is evidenced by modifying the geometry from disk to conventional hollow fiber. This is attributed to the thickness reduction from 1 mm to 0.3 mm, thus implying bulk-diffusion and surface reaction as the jointly limiting transport step for this disk membrane. In contrast to a conventional hollow fiber that has a sandwich cross-sectional structure (e.g. dense center layer sandwiched by two finger-like layers) as well as dense outer and inner circumference surfaces, the modified hollow fiber has only one dense layer in its outer circumference surface with finger-like porous layer extending all the way from outer cross-sectional part to the inner cross-sectional part. This microstructural difference, in turn, provides substantial reduction of membrane thickness and enlarges surface reaction area for modified hollow fiber (relative to conventional hollow fiber), both of which contributes to the reduced bulk-diffusion and surface reaction resistance; evidenced by almost 250% oxygen flux enhancement. To enhance the performance even further, catalyst (e.g., Ag or Pt) deposition on the outer circumference surface of modified hollow fiber can be utilized to reduce its dominating surface reaction resistance. While both catalysts increase the oxygen fluxes, Pt reveals itself as the better candidate relative to Ag due to melting-induced aggregation and growth of Ag at 950 °C.

The significant effect of the phase composition on the oxygen reduction reaction activity of a layered oxide cathode

Layered oxides of Sr4Fe4Co2O13 (SFC2) which contains alternating perovskite oxide octahedral and polyhedral oxide double layers are attractive for their mixed ionic and electronic conducting and oxygen reduction reaction properties. In this work, we used the EDTA–citrate synthesis technique to prepare SFC2 and vary the calcination temperature between 900 and 1100 _C to obtain SFC2, containing different phase content of perovskite (denoted as SFC-P) and (Fe,Co) layered oxide phases (SFC-L). Rietveld refinements show that the SFC-P phase content increased from _39 wt% to _50 wt% and _61 wt% as the calcination temperature increased from 900 _C (SFC2-900) to 1000 _C (SFC2-1000) and 1050 _C (SFC2-1050). At 1100 _C (SFC2-1100), SFC-P became the dominant phase. The oxygen transport properties (e.g. oxygen chemical diffusion coefficient and oxygen permeability), electrical conductivity and oxygen reduction reaction activity is enhanced in the order of SFC2-1000, SFC2-1100 and SFC2-1050. The trend established here therefore negates the hypothesis that the perovskite phase content correlates with the oxygen transport property enhancement. The results suggest instead that there is an optimum composition value (e.g. 61 wt% of SFC-L for SFC2-1050 in this work) on which synergistic effects take place between the SFC-P and SFC-L phase.

Potential of 129Xe NMR spectroscopy of adsorbed xenon for testing the chemical state of the surface of mesoporous carbon materials illustrated by the example of aggregates of diamond and onion-like carbon nanoparticles

The chemical shift in the 129Xe NMR spectrum of adsorbed xenon is very sensitive to the presence of oxygen-containing functional groups on the surface of mesoporous carbon materials. Well-characterized, structurally similar nanodiamond and onion-like carbon samples are considered here as model objects.

Highly stable external short-circuit-assisted oxygen ionic transport membrane reactor for carbon dioxide reduction coupled with methane partial oxidation

A membrane reactor allows for simultaneous separation and reaction, and thus, can play a good role to produce value-added chemicals. In this work, we demonstrated such a membrane reactor based on fluorite oxide samarium-doped ceria (SDC) using an external short-circuit concept for oxygen permeation. The fluorite phase was employed to impart its high structural stability, while its limited electronic conductivity was overcome by the application of an external short circuit to function the SDC membrane for oxygen transport. On one side of the membrane, i.e., feed side, carbon dioxide decomposition into carbon monoxide and oxygen was carried out with the aid of a Pt or Ag catalyst. The resultant oxygen was concurrently depleted on the membrane surface and transported to the other side of the membrane, favorably shifting this equilibrium-limited reaction to the product side. The transported oxygen on the permeate side with the aid of a GdNi/Al2O3 catalyst was then consumed by the reaction with methane to form syngas, i.e., carbon monoxide and hydrogen. As such, the required driving force for gas transport through the membrane can be sustained by coupling two different reactions in one membrane reactor, whose stability to withstand these different gases at high temperatures is attained in this paper. We also examined the effect of the membrane thickness, oxygen ionic transport rate, and CO2 and CH4 flow rates to the membrane reactor performance. More importantly, here, we proved the feasibility of a highly stable membrane reactor based on an external short circuit as evidenced by achieving the constant performance in CO selectivity, CH4 conversion, CO2 conversion, and O2 flux during 100 h of operation and unaltered membrane structure after this operation together with the coking resistance.

Observation of active sites for oxygen reduction reaction on nitrogen-doped multilayer graphene

Active sites and the catalytic mechanism of nitrogen-doped graphene in an oxygen reduction reaction (ORR) have been extensively studied but are still inconclusive, partly due to the lack of an experimental method that can detect the active sites. It is proposed in this report that the active sites on nitrogen-doped graphene can be determined via the examination of its chemical composition change before and after ORR. Synchrotron-based X-ray photoelectron spectroscopy analyses of three nitrogen-doped multilayer graphene samples reveal that oxygen reduction intermediate OH(ads), which should chemically attach to the active sites, remains on the carbon atoms neighboring pyridinic nitrogen after ORR. In addition, a high amount of the OH(ads) attachment after ORR corresponds to a high catalytic efficiency and vice versa. These pinpoint that the carbon atoms close to pyridinic nitrogen are the main active sites among the different nitrogen doping configurations.

Insights into the reversible oxygen reduction reaction in a series of phosphonium-based ionic liquids

New findings supporting the stability of the superoxide ion, O2˙(-), in the presence of the phosphonium cation, [P6,6,6,14](+), are presented. Extended electrochemical investigations of a series of neat phosphonium-based ILs with different anions, including chloride, bis(trifluoromethylsulfonyl)imide and dicyanamide, demonstrate the chemical reversibility of the oxygen reduction process. Quantum chemistry calculations show a short intermolecular distance (r = 3.128 Å) between the superoxide ion and the phosphonium cation. NMR experiments have been performed to assess the degree of long term degradation of [P6,6,6,14](+), in the presence of superoxide and peroxide species, showing no chemically distinct degradation products of importance in reversible air cathodes.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

CO2 laser manufacturing of miniaturised lenses for lab-on-a-chip systems

This article describes the manufacturing and characterisation of plano-convex miniaturised lenses using a CO2 laser engraving process in PMMA substrates. The technique allows for lenses to be fabricated rapidly and in a reproducible manner at depths of over 200 µm and for lens diameters of more than 3 mm. Experimental characterisation of the lens focal lengths shows good correlation with theory. The plano-convex lenses have been successfully embedded into capillary microfluidic systems alongside planar microlenses, allowing for a significant reduction of ancillary optics without a loss of detection sensitivity when performing fluorescence measurements. Such technology provides a significant step forward towards the portability of fluorescence- or luminescence-based systems for biological/chemical analysis.

Oxygen transfer from an intramolecularly coordinated diaryltellurium oxide to acetonitrile. formation and combined AIM and ELI-D analysis of a novel diaryltellurium acetimidate

The reaction of the intramolecularly coordinated diaryltellurium(IV) oxide (8-Me2NC10H6)2TeO with acetonitrile proceeds with oxygen transfer and gives rise to the formation of the novel zwitterionic diaryltelluronium(IV) acetimidate (8-Me2NC 10H6)2TeNC(O)CH3 (1) in 57% yield. Hydrolysis of 1 with hydrochloric acid affords acetamide and the previously known diarylhydroxytelluronium(IV) chloride [(8-Me2NC 10H6)2Te(OH)]Cl. © 2014 American Chemical Society.