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The incorporation of relatively minor impurity metals onto metal (oxy)hydroxides can strongly impact solubility. In complex highly alkaline multicomponent radioactive tank wastes such as those at the Hanford Nuclear Reservation, tests indicate that the surface area-normalized dissolution rate of boehmite (γ-AlOOH) nanomaterials is at least an order of magnitude lower than that predicted for the pure phase. Here, we examine the dissolution kinetics of boehmite coated by adsorbed Cr(III), which adheres at saturation coverages as sparse chemisorbed monolayer clusters. Using 40 nm boehmite nanoplates as a model system, temperature-dependent dissolution rates of pure versus Cr(III)-adsorbed boehmite showed that the initial rate for the latter is consistently several times lower, with an apparent activation energy 16 kJ·mol -1 higher. Although the surface coverage is only around 50%, solution analysis coupled to multimethod solids characterization reveal a phyicochemical armoring effect by adsorbed Cr(III) that substantially reduces the number of dissolution-active sites on particle surfaces. Such findings could help improve kinetics models of boehmite and/or metal ion adsorbed boehmite nanomaterials, ultimately providing a stronger foundation for the development of more robust complex radioactive liquid waste processing strategies.

Development of inexpensive sulfur-free catalysts for selective hydrogenolysis of the C-O bond in phenolics ( i.e. , selective removal of oxygen without aromatic ring saturation) under liquid-phase conditions is highly challenging. Here, we report an efficient approach to engineer earth-abundant Fe catalysts with a graphene overlayer and alkali metal ( i.e. , Cs), which produces arenes with 100% selectivity from liquid-phase hydrodeoxygenation (HDO) of phenolics with high durability. In particular, we report that a thin (a few layers) surface graphene overlayer can be engineered on metallic Fe particles (G@Fe) by a controlled surface reaction of a carbonaceous compound, which prevents the iron surface from oxidation by hydroxyls or water produced during HDO reaction. More importantly, further tailoring the surface electronic properties of G@Fe with the addition of cesium, creating a Cs-G@Fe composite catalyst in contrast to a deactivated Cs@Fe one, promotes the selective C-O bond cleavage by inhibiting the tautomerization, a pathway that is very facile under liquid-phase conditions. The current study could open a general approach to rational design of highly efficient catalysts for HDO of phenolics., (This journal is © The Royal Society of Chemistry 2020.)

The amine-rich surfaces of pyrolyzed human solid waste (py-HSW) can be "primed" or "regenerated" with carbon dioxide (CO 2 ) to enhance their adsorption of ammonia (NH 3 ) for use as a soil amendment. To better understand the mechanism by which CO 2 exposure facilitates NH 3 adsorption to py-HSW, we artificially enriched a model sorbent, pyrolyzed, oxidized wood (py-ox wood) with amine functional groups through exposure to NH 3 . We then exposed these N-enriched materials to CO 2 and then resorbed NH 3 . The high heat of CO 2 adsorption ( Q st ) on py-HSW, 49 kJ mol -1 , at low surface coverage, 0.4 mmol CO 2 g -1 , showed that the naturally occurring N compounds in py-HSW have a high affinity for CO 2 . The Q st of CO 2 on py-ox wood also increased after exposure to NH 3 , reaching 50 kJ mol -1 at 0.7 mmol CO 2 g -1 , demonstrating that the incorporation of N-rich functional groups by NH 3 adsorption is favorable for CO 2 uptake. Adsorption kinetics of py-ox wood revealed continued, albeit diminishing NH 3 uptake after each CO 2 treatment, averaging 5.9 mmol NH 3 g -1 for the first NH 3 exposure event and 3.5 and 2.9 mmol NH 3 g -1 for the second and third; the electrophilic character of CO 2 serves as a Lewis acid, enhancing surface affinity for NH 3 uptake. Furthermore, penetration of 15 NH 3 and 13 CO 2 measured by NanoSIMS reached over 7 μm deep into both materials, explaining the large NH 3 capture. We expected similar NH 3 uptake in py-HSW sorbed with CO 2 and py-ox wood because both materials, py-HSW and py-ox wood sorbed with NH 3 , had similar N contents and similarly high CO 2 uptake. Yet NH 3 sorption in py-HSW was unexpectedly low, apparently from potassium (K) bicarbonate precipitation, reducing interactions between NH 3 and sorbed CO 2 ; 2-fold greater surface K in py-HSW was detected after exposure to CO 2 and NH 3 than before gas exposure. We show that amine-rich pyrolyzed waste materials have high CO 2 affinity, which facilitates NH 3 uptake. However, high ash contents as found in py-HSW hinder this mechanism., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Intrinsic properties of a compound (e.g., electronic structure, crystallographic structure, optical and magnetic properties) define notably its chemical and physical behavior. In the case of nanomaterials, these fundamental properties depend on the occurrence of quantum mechanical size effects and on the considerable increase of the surface to bulk ratio. Here, we explore the size dependence of both crystal and electronic properties of CeO 2 nanoparticles (NPs) with different sizes by state-of-the art spectroscopic techniques. X-ray diffraction, X-ray photoelectron spectroscopy, and high-energy resolution fluorescence-detection hard X-ray absorption near-edge structure (HERFD-XANES) spectroscopy demonstrate that the as-synthesized NPs crystallize in the fluorite structure and they are predominantly composed of Ce IV ions. The strong dependence of the lattice parameter with the NPs size was attributed to the presence of adsorbed species at the NPs surface thanks to Fourier transform infrared spectroscopy and thermogravimetric analysis measurements. In addition, the size dependence of the t 2g states in the Ce L III XANES spectra was experimentally observed by HERFD-XANES and confirmed by theoretical calculations.

The rhizosphere is arguably the most complex microbial habitat on Earth, comprising an integrated network of plant roots, soil and a highly diverse microbial community (the rhizosphere microbiome). Understanding, predicting and controlling plant-microbe interactions in the rhizosphere will allow us to harness the plant microbiome as a means to increase or restore plant ecosystem productivity, improve plant responses to a wide range of environmental perturbations, and mitigate the effects of climate change by designing ecosystems for long-term soil carbon storage. To this end, it is imperative to develop new molecular approaches with high spatial resolution to capture interactions at the plant-microbe, microbe-microbe, and plant-plant interfaces. In this work, we designed an imaging sample holder that allows integrated surface imaging tools to map the same locations of a plant root-microbe interface with submicron lateral resolutions, providing novel in vivo analysis of root-microbe interactions. Specifically, confocal fluorescence microscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were used for the first time for the correlative imaging of the Brachypodium distachyon root and its interaction with Pseudomonas SW25, a typical plant growth-promoting soil bacterium. Imaging data suggest that the root surface is inhomogeneous and that the interaction between Pseudomonas and Brachypodium roots was confined to only a few spots along the sampled root segments and that the bacterial attachment spots were enriched in Na- and S-related and high-mass organic species. We conclude that the attachment of the Pseudomonas cells to the root surface is outcompeted by strong root-soil mineral interactions but facilitated by the formation of extracellular polymeric substances (EPS).

Lithium metal has the lowest standard electrochemical redox potential and very high theoretical specific capacity, making it the ultimate anode material for rechargeable batteries. However, its application in batteries has been impeded by the formation of Li whiskers, which consume the electrolyte, deplete active Li and may lead to short-circuit of the battery. Tackling these issues successfully is dependent on acquiring sufficient understanding of the formation mechanisms and growth of Li whiskers under the mechanical constraints of a separator. Here, by coupling an atomic force microscopy cantilever into a solid open-cell set-up in environmental transmission electron microscopy, we directly capture the nucleation and growth behaviour of Li whiskers under elastic constraint. We show that Li deposition is initiated by a sluggish nucleation of a single crystalline Li particle, with no preferential growth directions. Remarkably, we find that retarded surface transport of Li plays a decisive role in the subsequent deposition morphology. We then explore the validity of these findings in practical cells using a series of carbonate-poisoned ether-based electrolytes. Finally, we show that Li whiskers can yield, buckle, kink or stop growing under certain elastic constraints.

The development of advanced functional nanomaterials for selective adsorption in complex chemical environments requires partner studies of binding mechanisms. Motivated by observations of selective Cr(III) adsorption on boehmite nanoplates (γ-AlOOH) in highly caustic multicomponent solutions of nuclear tank waste, here we unravel the adsorption mechanism in molecular detail. We examined Cr(III) adsorption to synthetic boehmite nanoplates in sodium hydroxide solutions up to 3 M, using a combination of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), scanning/transmission electron microscopy (S/TEM), electron energy loss spectroscopy (EELS), high-resolution atomic force microscopy (HR-AFM), time-of-fight secondary ion mass spectrometry (ToF-SIMS), Cr K-edge X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS), and electron paramagnetic resonance (EPR). Adsorption isotherms and kinetics were successfully fit to Langmuir and pseudo-second-order kinetic models, respectively, consistent with monotonic uptake of Cr(OH) 4 - monomers until saturation coverage of approximately half the aluminum surface site density. High resolution AFM revealed monolayer cluster self-assembly on the (010) basal surfaces with increasing Cr(III) loading, possessing a structural motif similar to guyanaite (β-CrOOH), stabilized by corner-sharing Cr-O-Cr bonds and attached to the surface with edge-sharing Cr-O-Al bonds. The selective uptake appears related to short-range surface templating effects, with bridging metal connections likely enabled by hydroxyl anion ligand exchange reactions at the surface. Such a cluster formation mechanism, which stops short of more laterally extensive heteroepitaxy, could be a metal uptake discrimination mechanism more prevalent than currently recognized.

Aqueous rechargeable zinc-manganese dioxide batteries show great promise for large-scale energy storage due to their use of environmentally friendly, abundant, and rechargeable Zn metal anodes and MnO 2 cathodes. In the literature various intercalation and conversion reaction mechanisms in MnO 2 have been reported, but it is not clear how these mechanisms can be simultaneously manipulated to improve the charge storage and transport properties. A systematical study to understand the charge storage mechanisms in a layered δ-MnO 2 cathode is reported. An electrolyte-dependent reaction mechanism in δ-MnO 2 is identified. Nondiffusion controlled Zn 2+ intercalation in bulky δ-MnO 2 and control of H + conversion reaction pathways over a wide C-rate charge-discharge range facilitate high rate performance of the δ-MnO 2 cathode without sacrificing the energy density in optimal electrolytes. The Zn-δ-MnO 2 system delivers a discharge capacity of 136.9 mAh g -1 at 20 C and capacity retention of 93% over 4000 cycles with this joint charge storage mechanism. This study opens a new gateway for the design of high-rate electrode materials by manipulating the effective redox reactions in electrode materials for rechargeable batteries., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electrolyte generally dictates the working temperature range of lithium-ion batteries (LIBs), thus developing a new class of electrolytes (primarily functional additives) in LIBs for wide temperature applications will be quite essential for further development of LIBs for the electric vehicle market. In this study, we develop new functional electrolytes containing multiple additives to enable the LIBs to perform well in a wide temperature range from -40 to 60 °C. Importantly, those cells based on the above optimized electrolytes have been proven to behave significantly enhanced discharging performance at -40 °C, the long-term cycling stability at 25 °C (more than 85% of capacity retention after 1000 cycles at 1C/1C rates in 1 Ah pouch cells), as well as the obviously improved cycling stability at 60 °C. These remarkable cell performances originate from the highly conductive, uniform, and compact passivating films formed on both anode and cathode surfaces by the synergistic effects of the multiple additives. Our finding on the synergistic benefits originating from a certain additive combination in the optimized electrolytes would favorably widen the working temperature range of future high-performance LIBs.

A simple and rapid process of ReO 4 - (as a surrogate of TcO 4 - ) removal from aqueous solutions based on the electrically switched ion exchange (ESIX) method has been demonstrated in this work. Activated carbon-Polypyrrole (AC-PPy) was synthesized from activated carbon and pyrrole by electrodeposition method which was served as an electrically switched ion exchanger for ReO 4 - removal. The characterization results show that the AC-PPy composite exhibited an excellent loading capacity and a high stability for ions uptake and release. Chronoamperometric studies show that the ESIX treatment could be completed within 60 s, demonstrating the rapid uptake and release of ions. Uptake and release of ReO 4 - was verified by electrochemical quartz crystal microbalance with dissipation shift (EQCMD) studies. By modulating the electrochemical potential of the AC-PPy, the uptake and release of ReO 4 - ions can be controlled. Similar trends of uptake and release of ReO 4 - were observed in cyclic voltammetry (-0.4 to 0.8 V) for five cycles with the EQCMD. X-ray photoelectron spectroscopy (XPS) confirmed the process of ReO 4 - removal in the AC-PPy composite. Conclusively, the smart material shows excellent efficiency and selectivity for the removal of ReO 4 - from aqueous solutions.

Over the past three decades, the widespread utility and applicability of X-ray photoelectron spectroscopy (XPS) in research and applications has made it the most popular and widely used method of surface analysis. Associated with this increased use has been an increase in the number of new or inexperienced users which has led to erroneous uses and misapplications of the method. This article is the first in a series of guides assembled by a committee of experienced XPS practitioners that are intended to assist inexperienced users by providing information about good practices in the use of XPS. This first guide outlines steps appropriate for determining whether XPS is capable of obtaining the desired information, identifies issues relevant to planning, conducting and reporting an XPS measurement, and identifies sources of practical information for conducting XPS measurements. Many of the topics and questions addressed in this article also apply to other surface-analysis techniques.

Here, Cr(VI) effects on Tc-immobilization by Fe(OH) 2 (s) are investigated while assessing Fe(OH) 2 (s) as a potential treatment method for Hanford low-activity waste destined for vitrification. Batch studies using simulated low-activity waste indicate that Tc(VII) and Cr(VI) removal is contingent on reduction to Tc(IV) and Cr(III). Furthermore, complete removal of both Cr and Tc depends on the amount of Fe(OH) 2 (s) present, where complete Cr and Tc removal requires more Fe(OH) 2 (s) (∼200 g/L of simulant), than removing Cr alone (∼50 g/L of simulant). XRD analysis suggests that Fe(OH) 2 (s) reaction and transformation in the simulant produces mostly goethite (α-FeOOH), where Fe(OH) 2 (s) transformation to goethite rather than magnetite is likely due to the simulant chemistry, which includes high levels of nitrite and other constituents. Once reduced, a fraction of Cr(III) and Tc(IV) substitute for octahedral Fe(III) within the goethite crystal lattice as supported by XPS, XANES, and/or EXAFS results. The remaining Cr(III) forms oxide and/or hydroxide phases, whereas Tc(IV) not fully incorporated into goethite persists as either adsorbed or partially incorporated Tc(IV)-oxide species. As such, to fully incorporate Tc(IV) into the goethite crystal structure, additional Fe(OH) 2 (s) (>200 g/L of simulant) may be required.

Aluminum-bearing minerals show different hydrogen evolution and dissolution properties when subjected to radiation, but the complicated sequence of events following interaction with high-energy radiation is not understood. To gain insight into the possible mechanisms of hydrogen production in nanoparticulate minerals, we study the electronic response and determine the bandgap energies of three common aluminum-bearing minerals with varying hydrogen content: gibbsite (Al(OH) 3 ), boehmite (AlOOH), and alumina (Al 2 O 3 ) using electron energy loss spectroscopy, X-ray photoelectron spectroscopy, and first-principles electronic structure calculations employing hybrid density functionals. We find that the amount of hydrogen has only a small effect on the number and spectrum of photoexcitations in this class of materials. Electronic structure calculations demonstrate that low energy electrons are isotropically mobile, while holes in the valence band are likely constrained to move in layers. Furthermore, holes in the valence band of boehmite are found to be significantly more mobile than those in gibbsite, suggesting that the differences in radiolytic and dissolution behavior are related to hole transport.

The long-term cycling performance, rate capability, and voltage stability of lithium (Li) metal batteries with LiNi 0.76 Mn 0.14 Co 0.10 O 2 (NMC76) cathodes is greatly enhanced by lithium bis(oxalato)borate (LiBOB) additive in the LiPF 6 -based electrolyte. With 2 % LiBOB in the electrolyte, a Li∥NMC76 cell is able to achieve a high capacity retention of 96.8 % after 200 cycles at C/3 rate (1 C=200 mA g -1 ), which is the best result reported for a Ni-rich NMC cathode coupled with Li metal anode. The significantly enhanced electrochemical performance can be ascribed to the stabilization of both the NMC76 cathode/electrolyte and Li-metal-anode/electrolyte interfaces. The LiBOB-containing electrolyte not only facilitates the formation of a more compact solid-electrolyte interphase on the Li metal surface, it also forms a enhanced cathode electrolyte interface layer, which efficiently prevents the corrosion of the cathode interface and mitigates the formation of the disordered rock-salt phase after cycling. The fundamental findings of this work highlight the importance of recognizing the dual effects of electrolyte additives in simultaneously stabilizing both cathode and anode interfaces, so as to enhance the long-term cycle life of high-energy-density battery systems., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Understanding fundamental Tc chemistry is important to both the remediation of nuclear waste and the reprocessing of nuclear fuel; however, current knowledge of the electronic structure and spectral signatures of low-valent Tc compounds significantly lags behind the remainder of the d-block elements. In particular, identification and treatment of Tc speciation in legacy nuclear waste is challenging due to the lack of reference data especially for Tc compounds in the less common oxidation states (I-VI). In an effort to establish a spectroscopic library corresponding to the relevant conditions of extremely high ionic strength typical for the legacy nuclear waste, compounds with the general formula of [ fac-Tc(CO) 3 (OH 2 ) 3- n (OH) n ] 1- n (where n = 0-3) were examined by a range of spectroscopic techniques including 99 Tc/ 13 C NMR, IR, XPS, and XAS. In the series of monomeric aqua species, stepwise hydrolysis results in the increase of the Tc metal center electron density and corresponding progressive decrease of the Tc-C bond distances, Tc electron binding energies, and carbonyl stretching frequencies in the order [ fac-Tc(CO) 3 (OH 2 ) 3 ] + > [ fac-Tc(CO) 3 (OH 2 ) 2 (OH)] > [ fac-Tc(CO) 3 (OH 2 )(OH) 2 ] - . These results correlate with established trends of the 99 Tc upfield chemical shift and carbonyl 13 C downfield chemical shift. The lone exception is [ fac-Tc(CO) 3 (OH)] 4 which exhibits a comparatively low electron density at the metal center attributed to the μ 3 -bridging nature of the - OH ligands causing less σ-donation and no π-donation. This work also reports the first observations of these compounds by XPS and [ fac-Tc(CO) 3 Cl 3 ] 2- by XAS. The unique and distinguishable spectral features of the aqua [ fac-Tc(CO) 3 ] + complexes lay the foundation for their identification in the complex aqueous matrixes.

In nature, specific biomolecules interacting with mineral precursors are responsible for the precise production of nanostructured inorganic materials that exhibit complex morphologies and superior performance. Despite advances in developing biomimetic approaches, the design rules for creating sequence-defined molecules that lead to the synthesis of inorganic nanomaterials with predictable complex morphologies are unknown. Herein we report the design of sequence-defined peptoids for controlled synthesis of highly branched plasmonic gold particles. By engineering peptoid sequences and investigating the resulting particle formation mechanisms, we develop a rule of thumb for designing peptoids that predictively enabled the morphological evolution from spherical to coral-shaped nanoparticles. Through a combination of hyperspectral UV-Vis extinction microscopy and three-photon photoemission electron microscopy, we demonstrate that the individual coral-shaped gold nanoparticles exhibit a plasmonic enhancement as high as 10 5 -fold. This research significantly advances our ultimate vision of predictive bio-inspired materials synthesis using sequence-defined synthetic molecules that mimic proteins and peptides.

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Herein, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation of neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.

Rechargeable lithium-metal batteries (LMBs) are regarded as the "holy grail" of energy-storage systems, but the electrolytes that are highly stable with both a lithium-metal anode and high-voltage cathodes still remain a great challenge. Here a novel "localized high-concentration electrolyte" (HCE; 1.2 m lithium bis(fluorosulfonyl)imide in a mixture of dimethyl carbonate/bis(2,2,2-trifluoroethyl) ether (1:2 by mol)) is reported that enables dendrite-free cycling of lithium-metal anodes with high Coulombic efficiency (99.5%) and excellent capacity retention (>80% after 700 cycles) of Li||LiNi 1/3 Mn 1/3 Co 1/3 O 2 batteries. Unlike the HCEs reported before, the electrolyte reported in this work exhibits low concentration, low cost, low viscosity, improved conductivity, and good wettability that make LMBs closer to practical applications. The fundamental concept of "localized HCEs" developed in this work can also be applied to other battery systems, sensors, supercapacitors, and other electrochemical systems., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Olivines are divalent orthosilicates with important geologic, biological, and industrial significance and are typically comprised of mixtures of Mg 2+ and Fe 2+ ranging from forsterite (Mg 2 SiO 4 ) to fayalite (Fe 2 SiO 4 ). Investigating the role of Fe(II) in olivine reactivity requires the ability to synthesize olivines that are nanometer-sized, have different percentages of Mg 2+ and Fe 2+ , and have good bulk and surface purity. This article demonstrates a new method for synthesizing nanosized fayalite and Mg-Fe mixture olivines.First, carbonaceous precursors are generated from sucrose, PVA, colloidal silica, Mg 2+ , and Fe 3+ . Second, these precursors are calcined in air to burn carbon and create mixtures of Fe(III)-oxides, forsterite, and SiO 2 . Finally, calcination in reducing CO-CO 2 gas buffer leads to Fe(II)-rich olivines. XRD, Mössbauer, and IR analyses verify good bulk purity and composition. XPS indicates that surface iron is in its reduced Fe(II) form, and surface Si is consistent with olivine. SEM shows particle sizes predominately between 50 and 450 nm, and BET surface areas are 2.8-4.2 m 2 /g. STEM HAADF analysis demonstrates even distributions of Mg and Fe among the available M1 and M2 sites of the olivine crystals. These nanosized Fe(II)-rich olivines are suitable for laboratory studies with in situ probes that require mineral samples with high reactivity at short timescales., (Copyright © 2018 Elsevier Inc. All rights reserved.)

As one of the alternatives to replace precious metal catalysts, transition-metal-nitrogen-carbon (M-N-C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M-N-C catalysts can achieve good electrochemical performances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. In this work, metal-organic frameworks derived porous single-atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further posttreatment. Combining the X-ray absorption near-edge spectroscopy and electrochemical measurements, the SAEs have been identified with superior oxygen reduction reaction (ORR) activity and stability compared with Pt/C catalysts in alkaline condition. More impressively, the SAEs also show excellent ORR electrocatalytic performance in both acid and neutral media. This study of nonprecious catalysts provides new insights on nanoengineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The effects of lithium imide and lithium orthoborate dual-salt electrolytes of different salt chemistries in carbonate solvents on the cycling stability of lithium (Li) metal batteries are systematically and comparatively investigated. Two imide salts (LiTFSI and LiFSI) and two orthoborate salts (LiBOB and LiDFOB) are chosen for this study and compared with the conventional LiPF 6 salt. Density functional theory calculations indicate that the chemical and electrochemical stabilities rank in the following order: LiTFSI-LiBOB > LiTFSI-LiDFOB > LiFSI-LiDFOB > LiFSI-LiBOB. The experimental cycling stability of the Li metal batteries with the electrolytes ranks in the following order: LiTFSI-LiBOB > LiTFSI-LiDFOB > LiFSI-LiDFOB > LiPF 6 > LiFSI-LiBOB, which is in well accordance with the calculation results. The LiTFSI-LiBOB can effectively protect the Al substrate and form a more robust surface film on Li metal anode, while the LiFSI-LiBOB results in serious corrosion to the stainless steel cell case and a thicker and looser surface film on Li anode. The key findings of this work emphasize that the salt chemistry is critically important for enhancing the interfacial stability of Li metal anode and should be carefully manipulated in the development of high-performance Li metal batteries.

In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film is prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance with maximum specific capacitance of 670 F cm -3 (134 mF cm -2 ), due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as-prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder-free electrode effectively reduce electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provide a high specific surface area to improve electron transport, enhancing rapid ion transport, and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/microsize electronic devices., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To improve fuel efficiency, advanced combustion engines are being designed to minimize the amount of heat wasted in the exhaust. Hence, future generations of catalysts must perform at temperatures that are 100°C lower than current exhaust-treatment catalysts. Achieving low-temperature activity, while surviving the harsh conditions encountered at high engine loads, remains a formidable challenge. In this study, we demonstrate how atomically dispersed ionic platinum (Pt 2+ ) on ceria (CeO 2 ), which is already thermally stable, can be activated via steam treatment (at 750°C) to simultaneously achieve the goals of low-temperature carbon monoxide (CO) oxidation activity while providing outstanding hydrothermal stability. A new type of active site is created on CeO 2 in the vicinity of Pt 2+ , which provides the improved reactivity. These active sites are stable up to 800°C in oxidizing environments., (Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

The development of highly active and cost-efficient electrocatalysts for the oxygen reduction reaction (ORR) is of great importance in a wide range of clean energy devices, including fuel cells and metal-air batteries. Herein, the simultaneous formation of Co 9 S 8 and N,S-codoped carbon with high ORR catalytic activity was achieved in an efficient strategy with a dual templates system. First, Co(OH) 2 nanosheets and tetraethyl orthosilicate were utilized to direct the formation of two-dimensional carbon precursors, which were then dispersed into thiourea solution. After subsequent pyrolysis and template removal, N,S-codoped porous carbon-sheet-confined Co 9 S 8 catalysts (Co 9 S 8 /NSC) were obtained. Owing to the morphological and compositional advantages as well as the synergistic effects, the resultant Co 9 S 8 /NSC catalysts with a modified doping level and pyrolysis degree exhibit superior ORR catalytic activity and long-term stability compared with the state-of-the-art Pt/C catalysts in alkaline media. Remarkably, the as-prepared carbon composites also reveal exceptional tolerance of methanol, indicating their potential applications in fuel cells.

The conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Rational design of high active and robust nonprecious metal catalysts with excellent catalytic efficiency in oxygen evolution reaction (OER) is extremely vital for making the water splitting process more energy efficient and economical. Among these noble metal-free catalysts, transition-metal-based nanomaterials are considered as one of the most promising OER catalysts due to their relatively low-cost intrinsic activities, high abundance, and diversity in terms of structure and morphology. Herein, a facile sugar-blowing technique and low-temperature phosphorization are reported to generate 3D self-supported metal involved carbon nanostructures, which are termed as Co 2 P@Co/nitrogen-doped carbon (Co 2 P@Co/N-C). By capitalizing on the 3D porous nanostructures with high surface area, homogeneously dispersed active sites, the intimate interaction between active sites, and 3D N-doped carbon, the resultant Co 2 P@Co/N-C exhibits satisfying OER performance superior to CoO@Co/N-C, delivering 10 mA cm -2 at overpotential of 0.32 V. It is worth noting that in contrast to the substantial current density loss of RuO 2 , Co 2 P@Co/N-C shows much enhanced catalytic activity during the stability test and a 1.8-fold increase in current density is observed after stability test. Furthermore, the obtained Co 2 P@Co/N-C can also be served as an excellent nonprecious metal catalyst for methanol and glucose electrooxidation in alkaline media, further extending their potential applications., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Technetium (Tc) remains a priority remediation concern due to persistent challenges, including mobilization due to rapid reoxidation of immobilized Tc, and competing comingled contaminants, e.g., Cr(VI), that inhibit Tc(VII) reduction and incorporation into stable mineral phases. Here Fe(OH) 2 (s) is investigated as a comprehensive solution for overcoming these challenges, by serving as both the reductant, (Fe(II)), and the immobilization agent to form Tc-incorporated magnetite (Fe 3 O 4 ). Trace metal analysis suggests removal of Tc(VII) and Cr(VI) from solution occurs simultaneously; however, complete removal and reduction of Cr(VI) is achieved earlier than the removal/reduction of comingled Tc(VII). Bulk oxidation state analysis of the final magnetite solid phase by XANES shows that the majority of Tc is Tc(IV), which is corroborated by XPS measurements. Furthermore, EXAFS results show successful, albeit partial, Tc(IV) incorporation into magnetite octahedral sites. Cr XPS analysis indicates reduction to Cr(III) and the formation of a Cr-incorporated spinel, Cr 2 O 3 , and Cr(OH) 3 phases. Spinel (modeled as Fe 3 O 4 ), goethite (α-FeOOH), and feroxyhyte (δ-FeOOH) are detected in all reacted final solid phase samples analyzed by XRD. Incorporation of Tc(IV) has little effect on the spinel lattice structure. Reaction of Fe(OH) 2 (s) in the presence of Cr(III) results in the formation of a spinel phase that is a solid solution between magnetite (Fe 3 O 4 ) and chromite (FeCr 2 O 4 ).

The development of active, durable, and low-cost catalysts to replace noble metal-based materials is highly desirable to promote the sluggish oxygen reduction reaction in fuel cells. Herein, nitrogen and fluorine-codoped three-dimensional carbon nanowire aerogels, composed of interconnected carbon nanowires, were synthesized for the first time by a hydrothermal carbonization process. Owing to their porous nanostructures and heteroatom-doping, the as-prepared carbon nanowire aerogels, with optimized composition, present excellent electrocatalytic activity that is comparable to commercial Pt/C. Remarkably, the aerogels also exhibit superior stability and methanol tolerance. This synthesis procedure paves a new way to design novel heteroatom-doped catalysts., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solid-electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li- and Na-ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li- or Na-based electrolyte, and that ionic transport can be kinetically controlled. Selective Li- and Na-based SEI membranes are produced using Li- or Na-based electrolytes, respectively. The Na-based SEI allows easy transport of Li ions, while the Li-based SEI shuts off Na-ion transport. Na-ion storage can be manipulated by tuning the SEI layer with film-forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g -1 ; ≈ 1/10 of the normal capacity (250 mAh g -1 ). Unusual selective/preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion-selective conductors using electrochemical approaches., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2 O 3 and HY zeolite., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Self-assembled M-N-doped carbon nanotube aerogels with single-atom catalyst feature are for the first time reported through one-step hydrothermal route and subsequent facile annealing treatment. By taking advantage of the porous nanostructures, 1D nanotubes as well as single-atom catalyst feature, the resultant Fe-N-doped carbon nanotube aerogels exhibit excellent oxygen reduction reaction electrocatalytic performance even better than commercial Pt/C in alkaline solution., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Instability of carbon-based oxygen electrodes and incomplete decomposition of Li 2 CO 3 during charge process are critical barriers for rechargeable Li-O 2 batteries. Here we report the complete decomposition of Li 2 CO 3 in Li-O 2 batteries using the ultrafine iridium-decorated boron carbide (Ir/B 4 C) nanocomposite as a noncarbon based oxygen electrode. The systematic investigation on charging the Li 2 CO 3 preloaded Ir/B 4 C electrode in an ether-based electrolyte demonstrates that the Ir/B 4 C electrode can decompose Li 2 CO 3 with an efficiency close to 100% at a voltage below 4.37 V. In contrast, the bare B 4 C without Ir electrocatalyst can only decompose 4.7% of the preloaded Li 2 CO 3 . Theoretical analysis indicates that the high efficiency decomposition of Li 2 CO 3 can be attributed to the synergistic effects of Ir and B 4 C. Ir has a high affinity for oxygen species, which could lower the energy barrier for electrochemical oxidation of Li 2 CO 3 . B 4 C exhibits much higher chemical and electrochemical stability than carbon-based electrodes and high catalytic activity for Li-O 2 reactions. A Li-O 2 battery using Ir/B 4 C as the oxygen electrode material shows highly enhanced cycling stability than those using the bare B 4 C oxygen electrode. Further development of these stable oxygen-electrodes could accelerate practical applications of Li-O 2 batteries.

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated from the electrochemical oxidation are energetically unstable and readily undergo a deprotonation reaction that generates protons and promotes the dissolution of Al 3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.

Dendritic nanostructures are capturing increasing attention in electrocatalysis owing to their unique structural features and low density. Herein, we report for the first time, bromide ion mediated synthesis of low Pt-content PdCuPt ternary nanodendrites via galvanic replacement reaction between a Pt precursor and a PdCu template in aqueous solution. The experimental results show that the ternary PdCuPt nanodendrites present enhanced electrocatalytic performance for oxygen reduction reaction in acid solution compared with commercial Pt/C as well as some state-of-the-art catalysts. In detail, the mass activity of the PdCuPt catalyst with optimized composition is 1.73 A mg Pt -1 at 0.85 V vs. RHE, which is 14 times higher than that of a commercial Pt/C catalyst. Moreover, the long-term stability test demonstrates its better durability in acid solution. After 5k cycles, there is still 70% electrochemical surface area maintained. This method provides an efficient method to synthesize trimetallic alloys with controllable composition and specific structure for oxygen reduction reaction.

Rational design and construction of Pt-based porous nanostructures with large mesopores have triggered significant considerations because of their high surface area and more efficient mass transport. Hydrochloric acid-induced kinetically controlled reduction of metal precursors in the presence of soft template F-127 and hard template tellurium nanowires has been successfully demonstrated to construct one-dimensional hierarchical porous PtCu alloy nanostructures with large mesopores. Moreover, the electrochemical experiments demonstrated that the PtCu hierarchically porous nanostructures synthesized under optimized conditions exhibit enhanced electrocatalytic performance for oxygen reduction reaction in acid media.

Heating a mixture of uranyl(vi) nitrate and tantalum(v) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3 O 10 . The honey colored to yellow brown crystals of UTa 3 O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6 ] 7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6 ] 7- octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2 ] + , with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3 O 10 from Ta 2 O 5 , β-U 3 O 7 , and U 3 O 8 has been determined to be 13.1 ± 18.1 kJ mol -1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa 3 O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3 O 10 compounds.

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) inter-laboratory study on the measurement of the shell thickness and chemistry of nanoparticle coatings. Peptide-coated gold particles were supplied to laboratories in two forms: a colloidal suspension in pure water and; particles dried onto a silicon wafer. Participants prepared and analyzed these samples using either X-ray photoelectron spectroscopy (XPS) or low energy ion scattering (LEIS). Careful data analysis revealed some significant sources of discrepancy, particularly for XPS. Degradation during transportation, storage or sample preparation resulted in a variability in thickness of 53 %. The calculation method chosen by XPS participants contributed a variability of 67 %. However, variability of 12 % was achieved for the samples deposited using a single method and by choosing photoelectron peaks that were not adversely affected by instrumental transmission effects. The study identified a need for more consistency in instrumental transmission functions and relative sensitivity factors, since this contributed a variability of 33 %. The results from the LEIS participants were more consistent, with variability of less than 10 % in thickness and this is mostly due to a common method of data analysis. The calculation was performed using a model developed for uniform, flat films and some participants employed a correction factor to account for the sample geometry, which appears warranted based upon a simulation of LEIS data from one of the participants and comparison to the XPS results.

Three water adsorption-desorption mechanisms are common in inorganic materials: chemisorption, which can lead to the modification of the first coordination sphere; simple adsorption, which is reversible; and condensation, which is irreversible. Regardless of the sorption mechanism, all known materials exhibit an isotherm in which the quantity of water adsorbed increases with an increase in relative humidity. Here, we show that carbon-based rods can adsorb water at low humidity and spontaneously expel about half of the adsorbed water when the relative humidity exceeds a 50-80% threshold. The water expulsion is reversible, and is attributed to the interfacial forces between the confined rod surfaces. At wide rod spacings, a monolayer of water can form on the surface of the carbon-based rods, which subsequently leads to condensation in the confined space between adjacent rods. As the relative humidity increases, adjacent rods (confining surfaces) in the bundles are drawn closer together via capillary forces. At high relative humidity, and once the size of the confining surfaces has decreased to a critical length, a surface-induced evaporation phenomenon known as solvent cavitation occurs and water that had condensed inside the confined area is released as a vapour.

Nitrous acid (HONO) accumulates in the nocturnal boundary layer where it is an important source of daytime hydroxyl radicals. Although there is clear evidence for the involvement of heterogeneous reactions of NO2 on surfaces as a source of HONO, mechanisms remain poorly understood. We used coated-wall flow tube measurements of NO2 reactivity on environmentally relevant surfaces (Fe (hydr)oxides, clay minerals, and soil from Arizona and the Saharan Desert) and detailed mineralogical characterization of substrates to show that reduction of NO2 by Fe-bearing minerals in soil can be a more important source of HONO than the putative NO2 hydrolysis mechanism. The magnitude of NO2-to-HONO conversion depends on the amount of Fe(2+) present in substrates and soil surface acidity. Studies examining the dependence of HONO flux on substrate pH revealed that HONO is formed at soil pH < 5 from the reaction between NO2 and Fe(2+)(aq) present in thin films of water coating the surface, whereas in the range of pH 5-8 HONO stems from reaction of NO2 with structural iron or surface complexed Fe(2+) followed by protonation of nitrite via surface Fe-OH2(+) groups. Reduction of NO2 on ubiquitous Fe-bearing minerals in soil may explain HONO accumulation in the nocturnal boundary layer and the enhanced [HONO]/[NO2] ratios observed during dust storms in urban areas.

A redox-active metal-organic composite material shows improved and selective O2 adsorption over N2 with respect to individual components (MIL-101 and ferrocene). The O2 sensitivity of the composite material arises due to the formation of maghemite nanoparticles with the pore of the metal-organic framework material., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly dispersed discrete redox-active cluster anions (50 ng of pure ∼0.75 nm size molybdenum polyoxometalate (POM) anions on 25 μg (∼0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft landing (SL). Electron microscopy provides atomically resolved images of a uniform distribution of individual POM species soft landed directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.

Spectral modeling of photoelectrons can serve as a valuable tool when combined with X-ray photoelectron spectroscopy (XPS) analysis. Herein, a new version of the NIST Simulation of Electron Spectra for Surface Analysis (SESSA 2.0) software, capable of directly simulating spherical multilayer NPs, was applied to model citrate stabilized Au/Ag-core/shell nanoparticles (NPs). The NPs were characterized using XPS and scanning transmission electron microscopy (STEM) to determine the composition and morphology of the NPs. The Au/Ag-core/shell NPs were observed to be polydispersed in size, nonspherical, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis, SESSA spectral modeling indicated that washed Au/Ag-core-shell NPs were stabilized with a 0.8 nm layer of sodium citrate and a 0.05 nm (one wash) or 0.025 nm (two wash) layer of adventitious hydrocarbon, but did not fully account for the observed XPS signal from the Au-core. This was addressed by a series of simulations and normalizations to account for contributions of NP nonsphericity and off-centered Au-cores. Both of these nonuniformities reduce the effective Ag-shell thickness, which effect the Au-core photoelectron intensity. The off-centered cores had the greatest impact for the particles in this study. When the contributions from the geometrical nonuniformities are included in the simulations, the SESSA generated elemental compositions that matched the XPS elemental compositions. This work demonstrates how spectral modeling software such as SESSA, when combined with experimental XPS and STEM measurements, advances the ability to quantitatively assess overlayer thicknesses for multilayer core-shell NPs and deal with complex, nonideal geometrical properties.

Although pentavalent uranium can exist in aqueous solution, its presence in the solid state is uncommon. Metal monouranates, MgUO4, CrUO4 and FeUO4 were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and (57)Fe-Mössbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. The presence of U(5+) has been solidly confirmed in CrUO4 and FeUO4, which are thermodynamically stable compounds, and the origin and stability of U(5+) in the system was elaborated by DFT. The structural and thermodynamic behaviour of U(5+) elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.

The effects of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite∥LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs(+) additive. The synergistic effects of Cs(+) additive and appropriate amount of PC enable the formation of a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li(+) ions and allows fast Li(+) ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite∥NCA full cells under a wide temperature range. The fundamental findings also shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.

The development of highly efficient catalysts is critical for the practical application of lithium-oxygen (Li-O2) batteries. Nanosheet-assembled ZnCo2O4 (ZCO) microspheres and thin films grown in situ on single-walled carbon nanotube (ZCO/SWCNT) composites as high-performance air electrode materials for Li-O2 batteries are reported. The in situ grown ZCO/SWCNT electrodes delivered high discharge capacities, decreased the onset of the oxygen evolution reaction by 0.9 V during the charging process, and led to longer cycling stability. These results indicate that in situ grown ZCO/SWCNT composites can be used as highly efficient air electrode materials for oxygen reduction and evolution reactions. The enhanced catalytic activity displayed by the uniformly dispersed ZCO catalyst on nanostructured electrodes is expected to inspire further development of other catalyzed electrodes for Li-O2 batteries and other applications., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite the potential advantages it brings, such as wider liquid range and lower cost, propylene carbonate (PC) is seldom used in lithium-ion batteries because of its sustained cointercalation into the graphene structure and the eventual graphite exfoliation. Here, we report that cesium cation (Cs(+)) directs the formation of solid electrolyte interphase on graphite anode in PC-rich electrolytes through its preferential solvation by ethylene carbonate (EC) and the subsequent higher reduction potential of the complex cation. Effective suppression of PC-decomposition and graphite-exfoliation is achieved by adjusting the EC/PC ratio in electrolytes to allow a reductive decomposition of Cs(+)-(EC)m (1 ≤ m ≤ 2) complex preceding that of Li(+)-(PC)n (3 ≤ n ≤ 5). Such Cs(+)-directed interphase is stable, ultrathin, and compact, leading to significant improvement in battery performances. In a broader context, the accurate tailoring of interphasial chemistry by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions that once were elusive to control.

Widespread use of silver nanoparticles raises questions of environmental and biological impact. Many synthesis approaches are used to produce pure silver and silver-shell gold-core particles optimized for specific applications. Since both nanoparticles and silver dissolved from the particles may impact the biological response, it is important to understand the physicochemical characteristics along with the biological impact of nanoparticles produced by different processes. The authors have examined the structure, dissolution, and impact of particle exposure to macrophage cells of two 20 nm silver particles synthesized in different ways, which have different internal structures. The structures were examined by electron microscopy and dissolution measured in Rosewell Park Memorial Institute media with 10% fetal bovine serum. Cytotoxicity and oxidative stress were used to measure biological impact on RAW 264.7 macrophage cells. The particles were polycrystalline, but 20 nm particles grown on gold seed particles had smaller crystallite size with many high-energy grain boundaries and defects, and an apparent higher solubility than 20 nm pure silver particles. Greater oxidative stress and cytotoxicity were observed for 20 nm particles containing the Au core than for 20 nm pure silver particles. A simple dissolution model described the time variation of particle size and dissolved silver for particle loadings larger than 9 μg/ml for the 24-h period characteristic of many in-vitro studies.

Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex.