Design of active and stable Pt-based nanoscale electrocatalysts for the oxygen reduction reaction (ORR) will be the key to improving the efficiency of fuel cells that are needed to deliver reliable, affordable and environmentally friendly energy. Here, by exploring the ORR on Pt single crystals, cubo-octahedral (polyhedral) Pt NPs with different sizes (ranging from 2 to 7 nm), and 7-8 nm Pt NPs with different shapes (cubo-octahedral vs. cube vs. octahedral), we presented surface science approach capable of rationalizing, and ultimately understanding, fundamental relationships between stability of Pt NPs and activity of the ORR in acidic media. By exploring the potential induced dissolution/re-deposition of Pt between 0.05 and 1.3 V, we found that concomitant variations in morphology of Pt(111) and Pt(100) lead to narrowing differences in activity between Pt single crystal surfaces. We also found that regardless of an initial size or shape, NPs are metastable and easily evolve to thermodynamically equilibrated shape and size with very similar activity for the ORR. We concluded that while initially clearly observed, the particle size and shape effects diminish as the particles age to the point that it may appear that the ORR depends neither on the particle size nor particle shape. IntroductionThe last two decades have witnessed remarkable progress in our ability to chemically synthesize metal nanoparticles (NPs) ranging in size from 1 to 10 nm with unique electrocatalytic properties. 1-4 Because the electronic properties of metal NPs in this size range are not unique, 5 (electro)catalyst research with such materials has focused on the variations in the reaction rate or selectivity with characteristic dimensions of metallic catalysts. While Boronin and co-workers 6 pioneered this approach to understand the "crystalline size effect" in heterogeneous catalysis, Kinoshita 7 and others 8,9 used this tactic to understand the "particle size effect" in electrocatalysis. There is no simple ideal structure that will model all the aspects of NP catalysts, particularly in the configuration that are used in electrolytic cells. However, if one considers the equilibrium shape of a face-centered cubic (fcc) metal NP such as a cubooctahedron, consisting of (111) and (100) facets bounded by edge atom rows that are like the topmost rows in the (110) surface, single-crystal surfaces may serve as a reasonable model for
An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potential limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+ , and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+ . Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x . The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.
Patients who suffer from subarachnoid hemorrhage (SAH) usually have long-term neurological impairments. Endogenous neurogenesis might play a potential role in functional recovery after SAH; however, the underlying neurogenesis mechanism is still unclear. We assessed the extent of neurogenesis in the subventricular zone (SVZ) to better understand the neurogenesis mechanism after SAH. We performed a rat model of SAH to examine the extent of neurogenesis in the SVZ and assessed functional effects of the neurotrophic factors in the cerebrospinal fluid (CSF) on neural stem cells (NSCs) after SAH. In this study, the proliferation, differentiation, and migratory capacities of NSCs in the SVZ were significantly increased on days 5 and 7 post SAH. Furthermore, treatment of cultured rat fetal NSCs with the CSF collected from rats on days 5 and 7 post SAH enhanced their proliferation, differentiation, and migration. Enzyme-linked immunosorbent assay (ELISA) of the CSF detected a marked increase in the concentration of brain-derived neurotrophic factor (BDNF). Treating the cultured NSCs with recombinant BDNF (at the same concentration as that in the CSF) or with CSF from SAH rats, directly, stimulated proliferation, differentiation, and migration to a similar extent. BDNF expression was upregulated in the SVZ of rats on days 5 and 7 post SAH, and BDNF release occurred from NSCs, astrocytes, and microglia in the SVZ. These results indicate that SAH triggers the expression of BDNF, which promotes the proliferation, differentiation, and migration of NSCs in the SVZ after SAH.
As the battery industry shifts toward high Ni content cathodes, such as LiNi0.8Mn0.1Co0.1O2 [NMC811], a complete understanding of the degradation mechanisms of NMC811 under extreme fast charging (XFC) (XFC, ≤10–15 min charging) conditions is needed. Such comprehensive understanding would identify the most critical materials gaps that need to be addressed for enabling XFC long‐life cells for electric vehicles. This study maps out the key aging mechanisms for NMC811 cycled at different XFC conditions (between 1C and 9C) for up to 1000 cycles. To acquire a fundamental understanding of utilization and degradation, cells are evaluated using a range of electrochemical techniques, and multimodal and multiscale microscopy techniques to quantify chemical, structural, and crystallographic degradation as a function of cycling conditions for the NMC cathode. When comparing NMC811 to NMC532, it is observed that NMC811 has a greater subsurface crystallographic degradation and displays a similar magnitude of subparticle cracking. However, the NMC811 maintains superior performance despite those advanced degradations. The superior cycle life performance is attributed to the NMC811 particles having radially oriented grains and improved transport properties. NMC811 shows between 4.6× and 3.15× reduction in capacity fade than NMC532 for charging rates between 4C (e.g., 15‐min charging) and 6C (10‐min charging).
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