a b s t r a c tPerformance degradation during startup and shutdown is considered an important issue affecting the durability and lifetime of proton exchange membrane fuel cells (PEMFCs). Due to the high potentials experienced by the cathode during startup and shutdown, the conventional carbon support for the cathode catalyst is prone to oxidation by reacting with oxygen or water. This paper presents an overview of the causes and consequences of performance degradation after frequent startup-shutdown cycles. Mitigation strategies are also summarized, including the use of novel catalyst supports and the application of system strategies to prevent performance degradation in PEMFCs. It is found from the literature review that improvements in catalyst supports to prevent oxidation come at the expense of high cost, and the novel supports developed to date are not sufficient to completely prevent carbon oxidation in fuel cell engines. System strategies, including potential control and reaction gas control, have been developed and applied in fuel cell engines to alleviate or even avoid performance decay. This review aims to provide a clear understanding of the mechanisms related to degradation behaviors during the startup and shutdown processes, thereby helping fuel cell material or system developers in their efforts to prevent performance degradation and prolong the lifetime of PEMFCs.Crown
Single atom catalysts (SACs) have shown high activity and selectivity in a growing number of chemical reactions. Many efforts aimed at unveiling the structure− property relationships underpinning these activities and developing synthesis methods for obtaining SACs with the desired structures are hindered by the paucity of experimental methods capable of probing the attributes of local structure, electronic properties, and interaction with supportfeatures that comprise key descriptors of their activity. In this work, we describe a combination of experimental and theoretical approaches that include photon and electron spectroscopy, scattering, and imaging methods, linked by density functional theory calculations, for providing detailed and comprehensive information on the atomic structure and electronic properties of SACs. This characterization toolbox is demonstrated here using a model single atom Pt/CeO 2 catalyst prepared via a sol−gelbased synthesis method. Isolated Pt atoms together with extra oxygen atoms passivate the (100) surface of nanosized ceria. A detailed picture of the local structure of Pt nearest environment emerges from this work involving the bonding of isolated Pt 2+ ions at the hollow sites of perturbed (100) surface planes of the CeO 2 support, as well as a substantial (and heretofore unrecognized) strain within the CeO 2 lattice in the immediate vicinity of the Pt centers. The detailed information on structural attributes provided by our approach is the key for understanding and improving the properties of SACs.
MgCo2O4, CoCr2O4, and Co2TiO4 were selected, where only Co3+ in the center of octahedron (Oh), Co2+ in the center of tetrahedron (Td), and Co2+ in the center of Oh, can be active sites for the oxygen evolution reaction (OER). Co3+(Oh) sites are the best geometrical configuration for OER. Co2+(Oh) sites exhibit better activity than Co2+(Td). Calculations demonstrate the conversion of O* into OOH* is the rate‐determining step for Co3+(Oh) and Co2+(Td). For Co2+(Oh), it is thermodynamically favorable for the formation of OOH* but difficult for the desorption of O2. Co3+(Oh) needs to increase the lowest Gibbs free energy over Co2+(Oh) and Co2+(Td), which contributes to the best activity. The coexistence of Co3+(Oh) and Co2+(Td) in Co3O4 can promote the formation of OOH* and decrease the free‐energy barrier. This work screens out the optimal geometrical configuration of cobalt cations for OER and gives a valuable principle to design efficient electrocatalysts.
Phytophthora root and stem rot of soybean caused by the oomycete Phytophthora sojae, is a destructive disease worldwide. Ethylene response factors (ERFs) play important roles in regulating plant biotic and abiotic stress tolerance. In this study, a new ERF gene, GmERF113, was isolated from the highly resistant soybean ‘Suinong 10.’ Sequence analysis suggested that the protein encoded by GmERF113 contained a conserved AP2/ERF domain of 58 amino acid and belonged to the B-4 subgroup of the ERF subfamily. Expression of GmERF113 was significantly induced by P. sojae, ethylene, and methyl jasmonate. GmERF113 protein localized to the nucleus when transiently expressed in Arabidopsis protoplasts, could bind to the GCC-box, and acted as a transcription activator. In addition, a region of the full-length GmERF113, GmERF113-II, interacted with a basic helix-loop-helix transcription factor (GmbHLH) in yeast cells. Full-length GmERF113 also interacted with GmbHLH in planta. GmERF113-overexpressing transgenic plants in susceptible cultivar ‘Dongnong 50’ soybean exhibited increased resistance to P. sojae and positively regulated the expression of the pathogenesis-related genes, PR1 and PR10-1. These results indicate that GmERF113 may play a crucial role in the defense of soybean against P. sojae infection.
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