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Marchetti, Barbara

Publications and source records attributed to Marchetti, Barbara.

5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Theoretical understanding of stability of the oxygen electrode in a proton-conductor based solid oxide electrolysis cell

The oxygen electrode in a proton-conductor based solid oxide cells is often a triple-conducting material that enables the transport and exchange of electrons (e - ), oxygen ions (O 2- ), and protons (H + ), thus expanding active areas to enhance the oxygen electrode activity. In this work, a theoretical model was developed to understand stability of tri-conducting oxygen electrode by studying chemical potentials of neutral species (i.e., μ o 2 , μ H 2 , and μ H 2 O ) as functions of transport properties, operating parameters, and cell geometry. Our theoretical understanding shows that (1): In a conventional oxygen-ion based solid oxide cell, a high μ o 2 (thus high oxygen partial pressure) exists in the oxygen electrode during the electrolysis mode, which may lead to the formation of cracks at the electrode/electrolyte interface. Further, while in a proton-conductor based solid oxide cell, the μ o 2 is reduced significantly, suppressing the crack formation, and resulting in improved performance stability (2). In a typical proton-conductor based solid oxide electrolyzer, the dependence of μ o 2 on the Faradaic efficiency is negligible. Hence, approaches to block the electronic current can improve the electrolysis efficiency while achieving stability (3). The difference of the μ o 2 (thus p o 2 ) between the oxygen electrode and gas phase can be reduced by using higher ionic conducting components and improving electrode kinetics, which lead to further improvement of electrode stability.

08 HYDROGEN↗
DOE OSTI2022

Call attention to using DRT and EIS to quantify the contributions of solid oxide cell components to the total impedance

The contributions of anode and cathode processes to solid oxide fuel cell (SOFC) impedance were studied using electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT). Specifically, the role of gas composition at both anode and cathode was explored in a systematic study aimed at deconvoluting, identifying and quantifying the contributions of different anode and cathode processes. Further, five distinct relaxation time distributions were observed in the DRT spectra; although the peaks were ascribed to diffusion and charge transfer processes at the electrodes, it was found that both electrodes contributed to various peaks at the same time. Moreover, it was found that two distinctive operating conditions could return equivalent DRT spectra. While DRT analysis allows to obtain useful information regarding cell performance, extra consideration is needed when assessing and quantifying anodic and cathodic resistances within the SOFC.

08 HYDROGEN↗
DOE OSTI2022

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH 2 OO, CH 3 CHOO, (CH 3 ) 2 COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH 2 OO and (CH 3 ) 2 COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1 ππ* state, and how this varies with CI, with conformer and with excitation wavelength. Furthermore, the later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗