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Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and operando Raman spectroscopy were used to study the electrochemical performance and carbon tolerance of SOFCs operating with niobium doped SrTiO 3 (STN) anodes infiltrated with combinations of Ni, Co, and Ce 0.8 Gd 0.2 O 2 (CGO) added to improve catalytic activity. Cell anodes were exposed to fuel feeds of humidified H 2 , pure CH 4 and combinations of CO 2 and CH 4 at an operating temperature of 750 °C. Under pure CH 4 , Raman data show that carbon forms on all anodes containing Ni. In cells with CGO, deposited carbon results in a decreased polarization resistance. This behavior may be due to benefits conferred by CGO to the electrocatalytic activity of triple phase boundaries, presumably through improved oxide ion conductivity and/or due to carbon securing a better electrical connection in the electrodes. Raman spectra from Co-only containing anodes show no sign of carbon deposition. The absence of observable carbon together with low frequency processes observed in the EIS suggest that Co may play a role in oxidizing carbon before measurable amounts accumulate. 

Abstract Material changes in yttrium-doped barium zirconate, BaZr 0.8 Y 0.2 O 3– x , were studied using in situ Raman spectroscopy and ex situ x-ray photoelectron spectroscopy analysis. During in situ Raman analysis, samples were heated to temperatures of 300–600 °C and exposed to both dry and humidified H 2 atmospheres. At the lower temperatures (300–450 °C), a new vibrational peak appears in the Raman spectra during exposure to humidified H 2 . The appearance of this feature is reversible, dependent on previous sample history, and possibly results from new, secondary phase formation or lattice distortion. 

Operando Raman spectroscopy and electrochemical techniques were used to examine carbon deposition on niobium doped SrTiO 3 (STN) based SOFC anodes infiltrated with Ni, Co, Ce 0.9 Gd 0.1 O 2 (CGO) and combinations of these materials. Cells were operated with CH 4 /CO 2 mixtures at 750 °C. Raman data shows that carbon forms on all cells under operating conditions when Ni is present as an infiltrate. Additional experiments performed during cell cool down, and on separate material pellets (not subject to an applied potential), show that chemically labile oxygen available in the CGO infiltrate will preferentially oxidize all deposited surface carbon as temperatures drop below 700 °C. These observations highlight the benefit of CGO as a material in SOFC anodes but more importantly, the value of operando spectroscopic techniques as a tool when evaluating a material's susceptibility to carbon accumulation. Solely relying on ex situ measurements will potentially lead to false conclusions about the studied materials’ ability to resist carbon and improperly inform efforts to develop mechanisms describing electrochemical oxidation and material degradation mechanisms in these high temperature energy conversion devices. 

Resonantly enhanced second harmonic generation (SHG) spectra of Coumarin 152 (C152) adsorbed at the water-silica interface show that C152 experiences a local dielectric environment slightly more polar than that of bulk water. This result stands in contrast to recently reported time-resolved fluorescence experiments and simulations that suggest a alkane-like permittivity for interfacial water at strongly associating, hydrophilic solid surfaces. Taken together, these results imply that while the static electric field across the aqueous-silica interface may be large, restricted water dynamics lead to apparent nonpolar solvation behavior similar to that experienced by solutes in confinement. Resonance-enhanced SHG spectra and time-resolved fluorescence of C152 adsorbed to aqueous-hydrophobic silica surfaces show that when water’s ability to hydrogen bond with the silica surface is eliminated, a solute’s interfacial solvation and corresponding ability to photoisomerize converge to an intermediate limit similar to that experienced in bulk acetone or methanol. While water structure and dynamics at solid-liquid interfaces have received considerable attention, results presented below show how strong solvent-substrate interactions can create conflicting pictures of solute reactivity across buried interfaces. 

Time-resolved fluorescence measurements were used to characterize and quantify solute partitioning into 1,2- dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid vesicles as a function of solute concentration and temperature. The solutes, coumarin 152 (C152) and coumarin 461 (C461), both belong to a family of 7-aminocoumarin dyes that have distinctive fluorescence lifetimes in different solvation environments. The two solutes differ in the 4-position where C152 has a trifluoromethyl group in place of C461’s -CH3 group. In vesicle containing solutions, multiexponential fluorescence decays imply separate solute populations in the aqueous buffer, solvated in the vesicle headgroup region and solvated in the acyl chain bilayer interior, respectively. Fluorescence amplitudes, corrected for differences in radiative rates, are used to calculate absolute partition coefficients and average number of solutes per vesicle as a function of coumarin:lipid ratio and average number of solutes per vesicle. Results show that C152 has an ∼10-fold greater affinity than C461 for lipid bilayers, despite both solutes having similar hydrophobicities as inferred from their log(P) values. Temperature-dependent partitioning data are used to calculate enthalpies and entropies of C152 partitioning as a function of concentration. These values are used to extrapolate to the infinitely dilute limit. Above and below the lipid gel−liquid crystalline temperature, partitioning is exothermic with negative changes in entropy. In the vicinity of the transition temperature, these quantities change sign with ΔHpart becoming endothermic (+70 kJ/mol) and entropically favored (ΔSpart = +240 J/(mol·K)).