利用NIRTI在SOFC阳极上观察空间非均相化学

Elias D Pomeroy, Daniel Steinhurst, Stanislav Tsoi, John David Kirtley, Bryan Eigenbrodt, Jeffrey Owrutsky, William A Maza, Robert A. Walker
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摘要

对于使用含碳燃料的固体氧化物燃料电池(sofc)来说,碳形成仍然是主要的降解机制。采用近红外热成像(NIRTI)、傅里叶变换红外发射光谱(FTIRES)、时间电流/时间电位测定(CA/CP)和质谱(MS)研究了o2 (g)和h2o (g)电化学气化和重整对碳(C)诱导降解的修复机制。碳的去除遵循一个循序渐进的机制,首先将表面碳氧化为CO (g),然后氧化为CO 2(g)。CO (g)氧化需要一个催化表面来形成CO 2, CO 2在通过反向Boudouard化学去除C中起着关键作用。NIRTI揭示了空间上的非均相化学,并表明了表面氧的特定作用。这些物种形成于解离吸附和通过电解质的非法拉第氧化物通量,以及由于高o2利用率而发生的o2运输限制过程。与o2相比,电化学氧化和蒸汽对C的去除在空间上是均匀的,部分原因在于它们各自的活性表面物质,以及它们各自的传输限制。在o2 - C的去除下,尽管有电化学结果,但它似乎不完全。这些实验阐明了SOFC阳极上C的修复机制,并强调了在操作条件下研究SOFC的空间分辨技术的必要性。
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Spatially Heterogeneous Chemistry Observed using NIRTI on SOFC Anodes
Carbon formation remains the primary degradation mechanism for solid oxide fuel cells (SOFCs) operating on carbonaceous fuels. The mechanisms for the remediation of carbon (C) induced degradation via electrochemical gasification and reforming using O 2(g) and H 2 O (g) was studied using Near Infrared Thermal Imaging (NIRTI), Fourier Transform Infrared Emission Spectroscopy (FTIRES), chronoamperometry/chronopotentiometry (CA/CP), and mass spectrometry (MS). Carbon removal follows a stepwise mechanism, first oxidizing surface carbon to CO (g) , and subsequently to CO 2(g) . CO (g) oxidation requires a catalytic surface to form CO 2 which plays a key role in removing C via the reverse Boudouard chemistry. NIRTI reveals spatially heterogenous chemistry and suggests a specific role of surface oxygen species. These species form from dissociative adsorption and non-faradaic oxide flux through the electrolyte, as well as O 2 transport limited processes occurring due to high O 2 utilization. C removal from electrochemical oxidation and steam spatially homogeneous compared to O 2 , due in part to the respective active surface species, and their respective transport limitations. Under O 2 C removal is appears incomplete, despite electrochemical results. These experiments clarify the mechanisms responsible for remediation of C on SOFC anodes and highlight the need of spatially resolved techniques to study SOFCs under operating conditions.
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