Surface functional groups constitute major electroactive components in pyrogenic carbon. However, the electrochemical properties of pyrogenic carbon matrices and the kinetic preference of functional groups or carbon matrices for electron transfer remain unknown. Here we show that environmentally relevant pyrogenic carbon with average H/C and O/C ratios of less than 0.35 and 0.09 can directly transfer electrons more than three times faster than the charging and discharging cycles of surface functional groups and have a 1.5 V potential range for biogeochemical reactions that invoke electron transfer processes. Surface functional groups contribute to the overall electron flux of pyrogenic carbon to a lesser extent with greater pyrolysis temperature due to lower charging and discharging capacities, although the charging and discharging kinetics remain unchanged. This study could spur the development of a new generation of biogeochemical electron flux models that focus on the bacteria–carbon–mineral conductive network.

Maintaining high performance after extensive use remains a key challenge for low-Pt proton exchange membrane fuel cells for transportation applications. Strategically improving catalyst durability requires better understanding of the relationship between degradation mechanisms and catalyst structure. To investigate the effects of the carbon support morphology, we compare the electrochemical performance and durability of membrane electrode assemblies (MEAs) using Pt and PtCo x catalysts with a range of porous, solid, and intermediate carbon supports (HSC, Vulcan, and acetylene black). We find that electrochemical surface area (ECSA) retention after a catalyst-targeted durability test tends to improve with increasing support porosity. Using electron microscopy, we investigate microstructural changes in the catalysts and reveal the underlying degradation mechanisms in MEA specimens. Pt migration to the membrane and catalyst coarsening, measured microscopically, together were quantitatively consistent with the ECSA loss, indicating that these were the only two significant degradation pathways. Changes in catalyst particle size, morphology, and PtCo core-shell structure indicate that Ostwald ripening is a significant coarsening mechanism for catalysts on all carbons, while particle coalescence is only significant on the more solid carbon supports. Porous carbon supports thus appear to protect against particle coalescence, providing an effective strategy for mitigating catalyst coarsening.

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Atomic vibrations control all thermally activated processes in materials including ionic, atomic and electron diffusion, heat transport, phase transformations and surface chemical reactions. The jump frequency characterizing thermally activated processes is of great practical importance and is determined by the local phonon and molecular vibrational modes of the system. Atomic and molecular heterogeneities and defects such as vacancies, interstitials, dislocations and grain boundaries often regulate kinetic pathways and are associated with vibrational modes which are substantially different from bulk modes. High spatial resolution vibrational spectroscopy is required to probe these defect modes.Recent developments in aberration corrected, monochromated, scanning transmission electron microscopy (STEM) have enabled nanoscale probing of vibrational modes via electron energy-loss spectroscopy (EELS) 1,2 . Nanoscale vibrational spectroscopy is already impacting a wide range of important scientific problems such as measurement of surface and bulk vibrational excitations in MgO nanocubes 3 , probing hyperbolic phonon polaritons in nanoflakes of hBN 4 , measuring temperature in nanometer-sized areas with 1°K precision 5,6 and determining phonon dispersion in nanoparticles 7 . The delocalized nature of certain vibrational signals allows damagefree nanoscale detection for a variety of organic and inorganic material-systems 8-11 . This progress has been impressive, however, to date there have been no experimental methods to spectroscopically probe individual vibrational modes in materials with atomic resolution. Theoretical treatments have explored the question of spatial resolution 12,13 with some treatments suggesting that atomic resolution vibrational EELS should be possible [14][15][16] . Here we demonstrate atomic resolution vibrational spectroscopy in STEM for signals predominantly excited by impact scattering. The resulting order of magnitude advance in spatial resolution will

A series of experiments is presented that establishes for the first time the role of some of the key design parameters of porous carbons including surface area, pore volume, and pore size on battery performance. A series of hierarchical porous carbons is used as a model system with an open, 3D, interconnected porous framework and highly controlled porosity. Specifically, carbons with surface areas ranging from ≈500–2800 m2 g−1, pore volume from ≈0.6–5 cm3 g−1, and pore size from micropores (≈1 nm) to large mesopores (≈30 nm) are synthesized and tested. At high sulfur loadings (≈80 wt% S), pore volume is more important than surface area with respect to sulfur utilization. Mesopore size, in the range tested, does not affect the sulfur utilization. No relationship between porosity and long‐term cycle life is observed. All systems fail after 200–300 cycles, which is likely due to the consumption of the LiNO3 additive over cycling. Moreover, cryo‐scanning transmission electron microscopy imaging of these carbon–sulfur composites combined with X‐ray diffraction (XRD) provides further insights into the effect of initial sulfur distribution on sulfur utilization while also revealing the inadequacy of the indirect characterization techniques alone in reliably predicting distribution of sulfur within porous carbon matrices.

The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo–mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo–organic interfaces in contrast to exclusively organo–mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo–organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo–mineral interface, 88% (72–92%) and 33% (16–53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo–organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.

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The ideals underlying education are essentially similar to those underlying democracy, suggesting that schools should embody principles of democracy for students as part of a sound education. Changes in social conditions make this requirement even more important today. School practices, however, are far from democratic in most cases, even though the arguments against democratic practices are not strong. The article concludes with suggestions for democratic practices in working with students.