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Lithium nickel oxide (LNO) is an attractive positive electrode active material for lithium ion batteries (LIBs) due to its high reversible specific capacity and absence of cobalt. Nevertheless, it is prone to structural instabilities that lead to rapid capacity fading, safety concerns and shows in average a lower voltage than mixtures with cobalt, limiting its applicability to date. Herein this study introduces the sulfur‐based electrolyte additive, benzo[d][1,3,2]dioxathiole 2,2‐dioxide (DTDPh), to stabilize the LNO electrode and study its effects on interphase compositions by means of complementary electrochemical and spectroscopic techniques. Obtained results demonstrate an improved galvanostatic cycling performance in terms of cycle life and achievable specific discharge capacity that significantly outperform the common film‐forming additive vinylene carbonate (VC). The cycle life is increased from 102 to 147 cycles compared to the baseline electrolyte and the accumulated discharge energy until end of life is increased by 45%. This study furthermore provides strong evidence of a significant cross‐talk and negative interplay between DTDPh and VC when both are present in the electrolyte formulation. Mechanistic consideration based on density functional theory (DFT) calculations suggest the formation of mobile poly(VC) species, which is supported by the results of post mortem analysis of the resulting interphases. [ABSTRACT FROM AUTHOR]

We investigated the effects of X‐ray beam damage during X‐ray photoelectron spectroscopy measurement on LiNiO2 electrodes. The degree of damage induced by lab‐based and synchrotron X‐ray radiation has been compared between pristine and cycled electrodes, highlighting the role of positive solid electrode–electrolyte interphase to protect the cycled LiNiO2 surface from beam damage. The possible steps to avoid or at least reduce the beam‐induced effects are outlined. [ABSTRACT FROM AUTHOR]

Addressing the oxidation state of functional materials such as transition metal oxides is a current critical challenge and requires new methodologies to characterize their electronic structure within surface to bulk resolution at the nanometer scale. One approach to this issue is the combination of co‐localized soft and hard X‐ray photoelectron spectroscopies for a non‐destructive depth profiling. In this work, we demonstrate the capability to characterize the oxidation state of cobalt in LiCoO2 thin films, a model electrode material in the Li‐ion battery field, within the first 15 nm. The capability of the methodology to address the surface evolution of the cobalt oxidation state is tested through a proof of concept surface modification introduced by Ar‐ion sputtering. To address the cobalt local electronic structure at different depths from the extreme surface, we exploited Auger‐free Hard X‐ray photoelectron spectroscopy (HAXPES) spectra to fit the Co 2p core‐level features in the X‐ray photoelectron spectroscopy (XPS) spectra. This approach may pave the way for a better understanding of the surface electronic structure changes in transition metal oxides driven by their applications in a broad range of technologies. [ABSTRACT FROM AUTHOR]

Using Si as anode materials for Li-ion batteries remain challenging due to its morphological evolution and SEI modification upon cycling. The present work aims at developing a composite consisting of carbon-coated Si nanoparticles (Si@C NPs) intimately embedded in a three-dimensional (3D) graphene hydrogel (GHG) architecture to stabilize Si inside LiB electrodes. Instead of simply mixing both components, the novelty of the synthesis procedure lies in the in situ hydrothermal process, which was shown to successfully yield graphene oxide reduction, 3D graphene assembly production, and homogeneous distribution of Si@C NPs in the GHG matrix. Electrochemical characterizations in half-cells, on electrodes not containing additional conductive additive, revealed the importance of the protective C shell to achieve high specific capacity (up to 2200 mAh.g−1), along with good stability (200 cycles with an average Ceff > 99%). These performances are far superior to that of electrodes made with non-C-coated Si NPs or prepared by mixing both components. These observations highlight the synergetic effects of C shell on Si NPs, and of the single-step in situ preparation that enables the yield of a Si@C-GHG hybrid composite with physicochemical, structural, and morphological properties promoting sample conductivity and Li-ion diffusion pathways. [ABSTRACT FROM AUTHOR]

Lithium metal electrodes have been submitted to a long-term storage in contact with carbonated-based electrolyte at different temperatures, with the aim of gaining more understanding on the impact of aging conditions on the lithium metal surface. To do so, the evolution of lithium surface∣electrolyte interface has been monitored via electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy and FE-SEM techniques, to correlate the change of the interface properties with the chemical and morphological modifications at the electrode’s surface. After this aging, lithium electrodes were galvanostatically cycled in symmetric Li∣Li coin cell configuration at 10, 25 and 45 °C. Through this approach, a better cycling stability was observed in those cells stored at 45 °C, which can be ascribed to the more compact lithium electrodeposition than that observed in the rest of cells previously aged at lower temperatures. These results indicate that calendar at high temperature condition benefits lithium electrode performance, which can be attributed to a homogeneous passivation of the metal surface with fluorine and/or phosphate-based compounds, following XPS measurements, which can improve the behaviour of the solid electrolyte interface. [ABSTRACT FROM AUTHOR]

The timely arrival of novel materials plays a key role in bringing advances to society, as the pace at which major technological breakthroughs take place is usually dictated by the discovery rate at which novel materials are identified within chemical space. High‐throughput experimentation and computation strategy, now widely considered as a watershed in accelerating the discovery and optimization of novel materials in virtually every field, enables simultaneous screening, synthesis and characterization of large arrays of different material classes toward identification of the lead candidates for given system and targeted application. However, the ability to acquire data, through the continued advancement of automation platforms and workflows especially in the field of battery research and development, often outpaces the ability to optimally leverage obtained data for improved decision‐making. Closing this gap inevitably calls for adapted algorithms, development of reliable predictive models and enhanced integration with machine learning, deep learning, and artificial intelligence. This Review aims to highlight state‐of‐the‐art achievements along with an assessment of current and future challenges as well as resulting perspectives toward accelerated development of advanced battery electrolytes and their interfaces. [ABSTRACT FROM AUTHOR]

Driven by the continuous search for improving performances, understanding the phenomena at the electrode/electrolyte interfaces has become an overriding factor for the success of sustainable and efficient battery technologies for mobile and stationary applications. Toward this goal, rapid advances have been made regarding simulations/modeling techniques and characterization approaches, including high‐throughput electrochemical measurements coupled with spectroscopies. Focusing on Li‐ion batteries, current developments are analyzed in the field as well as future challenges in order to gain a full description of interfacial processes across multiple length/timescales; from charge transfer to migration/diffusion properties and interphases formation, up to and including their stability over the entire battery lifetime. For such complex and interrelated phenomena, developing a unified workflow intimately combining the ensemble of these techniques will be critical to unlocking their full investigative potential. For this paradigm shift in battery design to become reality, it necessitates the implementation of research standards and protocols, underlining the importance of a concerted approach across the community. With this in mind, major collaborative initiatives gathering complementary strengths and skills will be fundamental if societal and environmental imperatives in this domain are to be met. [ABSTRACT FROM AUTHOR]

Lithium-rich disordered rocksalt Li2TiS3 offers large discharge capacities (>350 mAh·g−1) and can be considered a promising cathode material for high-energy lithium-ion battery applications. However, the quick fading of the specific capacity results in a poor cycle life of the system, especially when liquid electrolyte-based batteries are used. Our efforts to solve the cycling stability problem resulted in the discovery of new high-energy selenium-substituted materials (Li2TiSexS3−x), which were prepared using a wet mechanochemistry process. X-ray diffraction analysis confirmed that all compositions were obtained in cation-disordered rocksalt phase and that the lattice parameters were expanded by selenium substitution. Substituted materials delivered large reversible capacities, with smaller average potentials, and their cycling stability was superior compared to Li2TiS3 upon cycling at a rate of C/10 between 3.0–1.6 V vs. Li+/Li. [ABSTRACT FROM AUTHOR]

Carbon black (CB) filled elastomers are structurally complex materials that offer unique properties at different length scales. They have tremendous potential applications in a number of fields including the automotive and aerospace industries and for designing innovative smart materials such as artificial muscles but their applications remain limited primarily due to inadequate understanding of their unique mechanical properties. Here, using the Berkovich technique to probe the surface mechanical properties at different scales the nanoindentation response of a series of composites made by homogeneously dispersed CB nanoparticles inside a semicrystalline copolymer matrix has been explored. While the measured loading part of the force–displacement curves is well described by Meyer's empirical power relation, the inverted methodology (IM) approach to deal with the unloading part has been considered and its outcome has been compared with that obtained from the standard Oliver–Pharr's method. The results were consistent with the observed increase of hardness when the applied displacement decreases for all composite samples over a large range of CB volume fraction. Zhang and Xu's model is demonstrated to produce experimentally consistent explanation of this indentation size effect. X‐ray photoelectron spectroscopy (XPS) spectra also show composition gradients with depth up to 100 nm. Furthermore, the effect of CB content, surface features, and length scale‐dependent deformation on the hardness–displacement behavior have been considered. These findings highlight the possibility of attaining a diverse set of mechanical properties by a better understanding of the nanoindentation response of CB filled elastomers which can be useful for material selection and design improvements in a number of practical applications. [ABSTRACT FROM AUTHOR]

A novel well-defined precatalyst for ammonia-selective catalytic reduction of NOx (NH3-SCR), namely, [W(≡CtBu)(CH2tBu)3]/CeO2, was prepared by surface organometallic chemistry and then characterized. Due to the high dispersion of the active phase, this catalyst showed excellent activity after calcination at 500 °C, described by up to 99% conversion of NOx, high N2 selectivity, broad operation temperature window (225–500 °C), and extremely high durability for the selective catalytic reduction of NOx with NH3. [ABSTRACT FROM AUTHOR]

The dependence of the induced morphological layer variations on the processing conditions and parameters during injection molding of polymers is analyzed through a robust numerical framework of the complete microinjection molding cycle. Predicted temperature, heat transfer and viscous dissipation, spherulite diameters, and shear rates provide sufficient clarifications to develop a deeper understanding of the complex evolution of the induced thicknesses of layers. The evolution of the structure of polyoxymethylene (POM) under strong strain rates and high thermal gradients is investigated while flowing along an expanding flow configuration composed of three steps of increasing thickness. High and low mold temperatures and injection velocity levels are tested according to the design of the experiment method (DOE). Morphological development in each zone was examined to provide the induced crystalline layer thickness in the longitudinal as well as the transverse directions using polarized light microscopy (PLM). The thickness of the layers strongly depends on the local thickness of the stepped‐part and on the abrupt dimensional changes. The variation of bulk tensile properties obtained by dynamic mechanical analysis (DMA) is related to the thermomechanical history experienced by the melt. [ABSTRACT FROM AUTHOR]

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe3)2}] with KC8, or [Co(IPr){N(SiMe3)2}2] with mes*PH2, mes* = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe3)2}] with excess KC8 in toluene gave the heteronuclear ‘inverse-sandwich’ Fe–K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre. [ABSTRACT FROM AUTHOR]

Copper/copper oxide (Cu/Cu2O) electrodes are known to display interesting electrocatalytic performances for the reduction of CO2, and thus, deserve further investigation for optimization. Here, we show that the addition of nitrogen- based organic additives greatly improves the activity of these electrodes (higher current densities, greater selectivity, and higher faradaic yields). The best effector is found to be tetramethyl cyclam. For example, electrolysis at -2.0 V versus Fc+/Fc in CO2-saturated DMF/H2O (99:1, v/v) in the presence of this effector results in formic acid with almost 90% faradaic yield. SEM and XPS analysis of the electrode surface reveals that the organic additive promotes the formation of active Cu0 nanoparticles from Cu2O during electrolysis. This simple approach provides a straightforward strategy toward the optimization of Cu/Cu2O electrodes. [ABSTRACT FROM AUTHOR]

To achieve high-mobility and high-reliability oxide thin film transistors (TFTs), ZnON has been investigated following an anion control strategy based on the substitution of oxygen with nitrogen in ZnO. However, as nitrogen possesses, compared to oxygen, a low reactivity with Zn, the chemical composition of ZnON changes easily, causing in turn a degradation of both the performance and the stability. Here, we have solved the issues of long-time stability and composition nonuniformity while maintaining a high channel mobility by adopting the argon plasma process, which can delay the reaction of oxygen with Zn-O-N; as a result, owing to the formation of very fine nano-crystalline structure in stable glassy phase without changes in the chemical composition, the material properties and stability under e-radiation have significantly improved. In particular, the channel mobility of the ZnON TFTs extracted from the pulsed IV method was measured to be 138 cm²/V s. [ABSTRACT FROM AUTHOR]

We present versatile ZnOxNy applicable to a wide range of imaging/display devices. A well-optimized ZnOxNy material exhibits high mobility exceeding 100 cm2/Vs, bandgap of 1.3 eV and nanocrystalline microstructure with multiphase. Accordingly, the performance of ZnOxNy-based device can be adjustable to meet the requisite of future electronic/photonic device elements. [ABSTRACT FROM AUTHOR]

Carbon serves as one of the best coating materials for the cathode in lithium ion batteries. This is because it can solve two main problems, which are surface deterioration and poor electrical conductivity. However, the conventional carbon coating procedures and, chemical carbonization processes, are especially difficult to implement for the oxide cathode, which could thereby deteriorate the oxide structure. We prepared a new dry 100 nm-thick homogeneous multi-walled carbon nanotube (MWCNT) coating on the high-capacity oxide cathode material, Li1.17Ni0.17Co0.1Mn0.56O2, by applying shear stress without breaking down the crystal structure or morphology of the cathode. The electronic conductivity of the carbon composite with the coated sample is 170 mS cm−1, which is over 40 times as much as the conductivity of the pristine cathode containing the same amount of carbon. In addition, at a high current condition of 2450 mA g−1, a specific capacity of 103 mA h g−1 is observed even with 3 percent of the carbon (in weight) constituting the coated MWCNT. The unconventionally improved performances are explained by the suppression of the electronic resistance and surface charge transfer resistance by electrochemical analyses. [ABSTRACT FROM AUTHOR]

5-Hydroxy-1H-indazole (HI) is investigated as an effective film-forming additive for an over-lithiated layered oxide (OLO) positive electrode. The protective film that is generated by oxidative decomposition of the additive (HI) prior to the carbonate electrolyte is thin and less resistive. As a result, a full cell comprised of OLO/graphite in the HI-added electrolyte gives a better cycling performance. [ABSTRACT FROM AUTHOR]

A novel well-defined precatalyst for ammonia-selective catalytic reduction of NOx (NH3-SCR), namely, [W(≡CtBu)(CH2tBu)3]/CeO2, was prepared by surface organometallic chemistry and then characterized. Due to the high dispersion of the active phase, this catalyst showed excellent activity after calcination at 500 °C, described by up to 99% conversion of NOx, high N2 selectivity, broad operation temperature window (225–500 °C), and extremely high durability for the selective catalytic reduction of NOx with NH3. [ABSTRACT FROM AUTHOR]

Controlling the stoichiometry of supported bimetallic nanoparticles is essential in many catalytic reactions, notably selective CO 2 hydrogenation. Thus, a new strategy to ensure the preferred stoichiometry (1:1) of supported bimetallic PdZn nanoparticles is presented, involving the deposition of a heterobimetallic precursor, [PdZn(μ-OOCMe) 4 ] 2 on a CeZrO x support. After calcination and reduction, the material contained mainly a PdZn alloy, as revealed by powder XRD and XAFS, and further supported by XPS, TEM-EDX, elemental analysis and in-situ IR at low temperature using CO as probe molecule. Moreover, a minor phase of oxidized Zn was determined by XAFS. This PdZn/CeZrOx reduced catalyst was combined with SAPO-34 to form a tandem catalytic system for CO 2 conversion to hydrocarbons. This system could readily convert CO 2 and H 2 at high temperature (380 °C) into hydrocarbons with a conversion of 24% and high relative selectivity in light hydrocarbons (C2–C3: 82%) with virtually no deactivation of the catalyst after 16 h on stream. Controlled experiments were performed with Pd/CeZrOx and Zn/CeZrOx in order to gain supplementary insights on this system: Pd/CeZrOx gave only methane and Zn/CeZrOx gave mainly CO under the same conditions. The latter clearly shows that the control of the formation of PdZn phase has great impact for the selective production of hydrocarbons. [Display omitted] • Development of PdZn supported on CeO 2 , ZrO 2 and CeZrOx for the conversion of CO 2 to methanol. • Catalyst PdZn/CeZrOx presents highly dispersed bimetallic PdZn nanoparticles with 1:1 ratio. • CO 2 conversion to light hydrocarbons is studied over tandem catalysts comprising PdZn supported on oxide and SAPO-34. • PdZn/CeZrOx/SAPO-34 catalysts present high CO 2 conversion and selectivity in light hydrocabons. [ABSTRACT FROM AUTHOR]

We have evaluated as-grown MoS2 crystals, epitaxially grown on a monocrystalline sapphire by chemical vapor deposition (CVD), with direct electronic band-structure measurements by energy-filtered k-space photoelectron emission microscopy performed with a conventional laboratory vacuum ultraviolet He I light source under off-normal illumination. The valence states of the epitaxial MoS2 were mapped in momentum space down to 7 eV below the Fermi level. Despite the high nucleation density within the imaged area, the CVD MoS2 possesses an electronic structure similar to the free-standing monolayer MoS2 single crystal, and it exhibits hole effective masses of 2.41±0.05m0, and 0.81±0.05m0, respectively, at Γ and K high-symmetry points that are consistent with the van der Waals epitaxial growth mechanism. This demonstrates the excellent ability of the MoS2 CVD on sapphire to yield a highly aligned growth of well-stitched grains through epitaxial registry with a strongly preferred crystallographic orientation. [ABSTRACT FROM AUTHOR]

Lithium-rich disordered rocksalt Li2TiS3 offers large discharge capacities (>350 mAh·g−1) and can be considered a promising cathode material for high-energy lithium-ion battery applications. However, the quick fading of the specific capacity results in a poor cycle life of the system, especially when liquid electrolyte-based batteries are used. Our efforts to solve the cycling stability problem resulted in the discovery of new high-energy selenium-substituted materials (Li2TiSexS3−x), which were prepared using a wet mechanochemistry process. X-ray diffraction analysis confirmed that all compositions were obtained in cation-disordered rocksalt phase and that the lattice parameters were expanded by selenium substitution. Substituted materials delivered large reversible capacities, with smaller average potentials, and their cycling stability was superior compared to Li2TiS3 upon cycling at a rate of C/10 between 3.0−1.6 V vs. Li+/Li.

With the goal to improve their photostability, InP-based QDs are passivated with three types of inorganic shells, namely (i) a gradient ZnSe x S 1-x shell, (ii) an additional ZnS shell on top of the gradient shell with two different thicknesses (core/shell/shell, CSS), (iii) an alumina coating on top of ZnS. All three systems have photoluminescence quantum yields (PLQY) > 50% and similar PL decay times (64-67 ns). To assess their photostability they are incorporated into a transparent poly (methyl methacrylate) (PMMA) matrix and exposed to continuous irradiation with simulated sunlight in a climate chamber. The alumina coated core/shell system exhibits the highest stability in terms of PLQY retention as well as the lowest shift of the PL maximum and lowest increase of the PL linewidth, followed by the CSS QDs and finally the gradient shell system. By means of XPS studies we identify the degradation of the ZnS outer layer and concomitant oxidation of the emissive InZnP core as the main origins of degradation in the gradient structure. These modifications do not occur in the case of the alumina-capped sample, which exhibits excellent chemical stability. The gradient shell and CSS systems could be transferred to the aqueous phase using surface ligand exchange with penicillamine. Cytotoxicity studies on human primary keratinocytes revealed that exposure for 24 h to 6.25-100 nM of QDs did not affect cell viability. However, a trend toward reduced cell proliferation is observed for higher concentrations of gradient shell and CSS QDs with a thin ZnS shell, while CSS QDs with a thicker ZnS shell do not exhibit any impact.

The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. Because ionic liquids can be easily obtained with chosen molecular structures and tuneable physicochemical properties, they can be use as media to optimize the exfoliation of graphite. The understanding of the interactions involved between graphite and various chemical functions in the solvent ions will be helpful to find liquids capable of dissociating and stabilizing important quantities of large graphene layers. After a step of sonication, as a mechanical precursor, samples of suspended exfoliated graphene in different ionic liquids have been characterized experimentally in terms of flake size, number of layers, total concentration and purity of the exfoliated material. Nine different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate anions have been tested. UV-vis, Raman and X-ray photoelectron in addition to high resolution transmission electron and atomic force microscopy have been selected to characterize suspended exfoliated graphene in ionic liquids. The number of layers in the flakes exfoliated, the size and concentration depend of the structure of the ionic liquid selected. In order to obtain large flake sizes, ionic liquids with bis(trifluoromethylsulfonyl)imide anions and a cation with an alkyl chain of medium length should be selected. Smaller cation and anion favors the exfoliation of graphene. The exfoliation caused the formation of C-H bonds and the oxidation of the graphitic surface.

High content nitrogen, sulfur and phosphorus heteroatoms assembled in tree-like dendrimers (DG n ) are confined within the galleries of two-dimensional graphene oxide (GO). The presence of the ternary diethyl- N -ethyl-ammonium groups on the dendrimer peripheries ensures the exfoliation of graphene sheets thereby affording interfacially bridged, three-dimensional heteroatom-enriched graphene-based hybrid nanostructures (DG n -GO). Dendrimer generation (from 1 to 4) that reflects the bulkiness of these conceived nano-trees impacts increasingly the degree of dispersion-exfoliation and sheet desordering. The long-term stability of these aqueous suspensions associated with their handling flexibility allows uniform accommodation of the resulting hybrid materials as flame-retardants in bioplastics., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Whereas the integration of silver nanowires in functional devices has reached a fair level of maturity, the integration of copper nanowires still remains difficult, mainly due to the intrinsic instability of copper nanowires in ambient conditions. In this paper, copper nanowire based transparent electrodes with good performances (33 Ω sq -1 associated with 88% transparency) were obtained, and their degradation in different conditions was monitored, in particular by electrical measurements, transmission electron microscopy, x-ray photoelectron spectrometry and Auger electron spectroscopy. Several routes to stabilize the random networks of copper nanowires were evaluated. Encapsulation through laminated barrier film with optical clear adhesive and atmospheric pressure spatial atomic layer deposition were found to be efficient and were used for the fabrication of transparent film heaters.

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe 3 ) 2 }] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally M I complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe 3 ) 2 }] with KC 8 , or [Co(IPr){N(SiMe 3 ) 2 } 2 ] with mes*PH 2 , mes* = 2,4,6-tBu 3 C 6 H 2 . The magnetism of 3 and 4 implies Co II and Fe II centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe 3 ) 2 }] with excess KC 8 in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η 6 -toluene sandwiched between one Fe 0 and one K + centre.

Copper/copper oxide (Cu/Cu 2 O) electrodes are known to display interesting electrocatalytic performances for the reduction of CO 2 , and thus, deserve further investigation for optimization. Here, we show that the addition of nitrogen-based organic additives greatly improves the activity of these electrodes (higher current densities, greater selectivity, and higher faradaic yields). The best effector is found to be tetramethyl cyclam. For example, electrolysis at -2.0 V versus Fc + /Fc in CO 2 -saturated DMF/H 2 O (99:1, v/v) in the presence of this effector results in formic acid with almost 90 % faradaic yield. SEM and XPS analysis of the electrode surface reveals that the organic additive promotes the formation of active Cu 0 nanoparticles from Cu 2 O during electrolysis. This simple approach provides a straightforward strategy toward the optimization of Cu/Cu 2 O electrodes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The purpose of this article is to report a new method for the surface functionalization of commercially available gas diffusion layers (GDLs) by the electrochemical reduction of diazonium salt containing hydrophobic functional groups. The method results in superhydrophobic GDLs, over a large area, without pore blocking. An X-ray photoelectron spectroscopy study based on core level spectra and chemical mapping has demonstrated the successful grafting route, resulting in a homogeneous distribution of the covalently bonded hydrophobic molecules on the surface of the GDL fibers. The result was corroborated by contact angle measurement, showing similar hydrophobicity between the grafted and PTFE-modified GDLs. The electrochemically modified GDLs were tested in proton exchange membrane fuel cells under automotive, wet, and dry conditions and demonstrated improved performance over traditional GDLs.

The use of mild oxidants in chemical vapor deposition (CVD) reactions has proven enormously useful. This was also true for the CVD growth of carbon nanotubes. As yet though, the use of mild oxidants in the CVD of graphene has remained unexplored. Here we explore the use of CO2 as a mild oxidant during the growth of graphene over Ni with CH4 as the feedstock. Both our experimental and theoretical findings provide in-depth insight into the growth mechanisms and point to the mild oxidants playing multiple roles. Mild oxidants lead to the formation of a suboxide in the Ni, which suppresses the bulk diffusion of C species suggesting a surface growth mechanism. Moreover, the formation of a suboxide leads to enhanced catalytic activity at the substrate surface, which allows reduced synthesis temperatures, even as low as 700 °C. Even at these low temperatures, the quality of the graphene is exceedingly high as indicated by a negligible D mode in the Raman spectra. These findings suggest the use of mild oxidants in the CVD fabrication as a whole could have a positive impact.

We examined the ultrafast dynamics of photocarriers in nanocrystalline ZnOxNy thin films as a function of compositional variation using femtosecond differential transmittance spectroscopy. The relaxation dynamics of photogenerated carriers and electronic structures are strongly dependent on nitrogen concentration. Photocarriers of ZnOxNy films relax on two different time scales. Ultrafast relaxation over several picoseconds is observed for all chemical compositions. However, ZnO and oxygen-rich phases show slow relaxation (longer than several nanoseconds), whereas photocarriers of films with high nitrogen concentrations relax completely on subnanosecond time scales. These relaxation features may provide a persistent photocurrent-free and prompt photoresponsivity for ZnOxNy with high nitrogen concentrations, as opposed to ZnO for display applications.