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Hydrogen spillover is a catalytic process that occurs by surface reaction and subsequent diffusion to reversibly provide a massive amount of hydrogen dopants in correlated oxides, but the mechanism at the surface of correlated oxides with metal catalyst are not well understood. Here we show that a significant amount of oxygen is released from the surface of correlated VO2 films during hydrogen spillover, contrary to the well-established observation of the formation of hydrogen interstitials in the bulk part of VO2 films. By using ambient-pressure X-ray photoelectron spectroscopy, we prove that the formation of surface oxygen vacancies is a consequence of a favorable reaction for the generation of weakly adsorbed H2O from surface O atoms that have low coordination and weak binding strength. Our results reveal the importance of in situ characterization to prove the dynamic change during redox reaction and present an opportunity to control intrinsic defects at the surface.

As the channel lengths of electronic devices are scaled down to the nanometer range, the conventional methods to evaluate charge-carrier mobility approach a technical limit that is imposed by interfering effects of the electrode and forcing field. In this study, we demonstrate that electron spectroscopy provides additional (yet hidden) information on unipolar charge transport, which is free from conventional problems. We demonstrate that the estimated effective diffusion current through the target sample allows the measurement that is precise enough (10−4 cm2/V s) to obtain the mobility of electrons μelectron and holes μhole in nanolength organic channels. Using this method, we show how μelectron and μhole are correlated with the local structural order of poly(3-hexylthiophene) at the nanoscale. This method enables in situ charge-resolved observations of μelectron and μhole by eliminating the need for electrode and forcing field and will help to expand our understanding of charge conduction in nanoscale materials. [ABSTRACT FROM AUTHOR]

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. However, the FeO2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate-adsorbate interactions may impact reactivity. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.

Controlling the number of oxygen vacancies (Vos) in metal‐oxide nanoparticles (MO NPs; TiO2, SnO2, and CeO2) using Li‐ions has been shown to endow MO NPs with improved photocatalytic and electrocatalytic properties. Increasing the number of Vos in nanostructures provides a foundation for efficient multi‐use catalyst designs that facilitate biomass oxidation reactions and improve electrocatalytic activity. Herein, the trends in the properties of MO‐based catalysts are investigated with varying amounts of Vos achieved by Li‐ion deposition. The controlled introduction of Vos into MO NPs tunes the band structures and surface chemistry, leading to enhanced activities of the NPs as photocatalysts for the selective oxidation of 2,5‐hydroxymethylfurfural and as electrocatalysts for acidic hydrogen evolution. It is believed that Li‐ion deposition in the MO matrix provides a novel approach for optimizing oxide‐based catalyst defect engineering, thereby enabling more efficient biomass conversion and water splitting. These findings contribute significantly to the field of multi‐purpose catalysis and are expected to inspire new catalyst designs for a more sustainable future. The results provide a pathway for the facile and efficient engineering of surface defect structures on catalytic metal oxide NPs toward designing high‐performance photocatalysts. [ABSTRACT FROM AUTHOR]

Graphene‐based magnetic materials exhibit novel properties and promising applications in the development of next‐generation spintronic devices. Modern synthesis techniques have paved the way to design precisely the local environments of metal atoms anchored onto a nitrogen‐doped graphene matrix. Herein, it is demonstrated that grafting cobalt (Co) into the graphene lattice induces robust and stable room‐temperature ferromagnetism. These comprehensive experiments and first‐principles calculations unambiguously identify that the mechanism for this unusual ferromagnetism is π‐d orbital hybridization between Co dxz and graphene pz orbitals. Here, it is found that the magnetic interactions of Co–carbon ions are mediated by the spin‐polarized graphene pz orbitals, and room temperature ferromagnetism can be stabilized by electron doping. It is also found that the electronic structure near the Fermi level, which sets the nature of spin polarization of graphene pz bands, strongly depends on the local environment of the Co moiety. This is the crucial, previously missing, ingredient that enables control of the magnetism. Overall, these observations unambiguously reveal that engineering the atomic structure of metal‐embedded graphene lattices through careful d to p orbital interactions opens a new window of opportunities for developing graphene‐based spintronics devices. [ABSTRACT FROM AUTHOR]

Although anionic-redox-based layered oxide materials have attracted great attention as promising cathodes for Na-ion batteries because of their high practical capacities, they suffer from undesirable structural degradation, resulting in the poor electrochemical behavior. Moreover, the occurrence of stable anionic-redox reaction without the use of expensive elements such as Li, Co, and Ni is considered one of the most important issues for high-energy and low-cost Na-ion batteries. Herein, using first-principles calculation and various experimental techniques, we investigate the combination of vacancy (□) and Ti4+ cations in the transition-metal sites to enable outstanding anionic-redox-based electrochemical performance in the Na-ion battery system. The presence of vacancies in the P2-type Na0.56[Ti0.1Mn0.76□0.14]O2 structure suppresses the large structural change such as the P2–OP4 phase transition, and Ti4+ cations in the structure result in selectively oxidized oxygen ions with structural stabilization during Na+ deintercalation in the high-voltage region. The high structural stability of P2-type Na0.56[Ti0.1Mn0.76□0.14]O2 enables not only the high specific capacity of 224.92 mAh g−1 at 13 mA g−1 (1C = 264.1 mA g−1) with an average potential of ∼2.62 V (vs Na+/Na) but also excellent cycle performance with a capacity retention of ∼80.38% after 200 cycles at 52 mA g−1 with high coulombic efficiencies above 99%. Although there are some issues such as low Na contents in the as-prepared state, these findings suggest potential strategies to stabilize the anionic-redox reaction and structure in layered-oxide cathodes for high-energy and low-cost Na-ion batteries. [ABSTRACT FROM AUTHOR]

Carbon hydrogasification is the slowest reaction among all carbon‐involved small‐molecule transformations. Here, we demonstrate a mechanochemical method that results in both a faster reaction rate and a new synthesis route. The reaction rate was dramatically enhanced by up to 4 orders of magnitude compared to the traditional thermal method. Simultaneously, the reaction exhibited very high selectivity (99.8 % CH4, versus 80 % under thermal conditions) with a cobalt catalyst. Our study demonstrated that this extreme increase in reaction rate originates from the continuous activation of reactive carbon species via mechanochemistry. The high selectivity is intimately related to the activation at low temperature, at which higher hydrocarbons are difficult to form. This work is expected to advance studies of carbon hydrogasification, and other solid‐gas reactions. [ABSTRACT FROM AUTHOR]

It has recently been observed that benzoic acid strongly reacts with OH group on the silicon surface. Here, by defining the area in which OH group is adsorbed on the Si surface, the selective adsorption of benzoic acid species was attempted. The patterned OH/Si surface was prepared by irradiating the zeroth order beam from the bending magnet of the synchrotron facility through the gold mesh placed in front of the OH/Si sample. For discerning the selectively adsorbed molecule by x-ray photoelectron emission microscopy (X-PEEM) at N k edge, 4-nitrobenzoic acid was utilized instead of benzoic acid. Near edge x-ray absorption fine structure spectra at carbon and oxygen k edges were in good accord with the previous results obtained from the benzoic acid system. The X-PEEM images around N k edge clearly showed that the molecules adsorb only on the area in which OH groups remain. [ABSTRACT FROM AUTHOR]

Abstract: The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in material stability and the ability to catalyze reactions. The local change in valence and formation of surface adsorbates affect the oxide electronic structure and chemical reactivity, yet are challenging to probe experimentally. In this paper a detailed study of the oxidation and reduction of Cr in the perovskite oxide family of La(1–x)SrxCrO3 using ambient pressure X‐ray photoelectron spectroscopy is presented. The incorporation of Sr increases the propensity to oxidize at the surface, leading to the presence of Cr4+ and Cr6+ principally confined to the top unit cell when in equilibrium with O2 gas. These acidic sites are readily reduced to Cr3+ in equilibrium with H2O vapor, and the resultant amount of hydroxyls formed from the dissociation of H2O is directly proportional to the density of surface sites formerly oxidized. The quantification of the redox stability of La(1–x)SrxCrO3 and the relationship between the extent of oxidation, reduction, and hydroxylation with Sr yield important insight into the surface functionality during electrochemical applications. [ABSTRACT FROM AUTHOR]

Sporadic catalytic decomposition because of the presence of Au grains is a significant issue to be clarified in electronic devices. Here, we report the inhomogeneous dissociation of native silicon oxide depending on the electronic structure of Au grains using scanning photoelectron microscopy. Upon annealing, the oxygen atoms dissociated from native SiOx layer out-diffuses in non-uniform manner, resulting in oxidize the Au layer. Valence band spectra showed that the spit-orbit splitting, directly related to the coordination number, differs from site to site. Scanning photoelectron microscopy images show that dissociated SiOx coincides with the regions where low-coordinated Au resides. These results imply that Au with low coordination number activated the dissociation of SiOx and open new pathway to remove undesirable oxide layer at relatively low temperature. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

We show a set-up of poly(4,4′-aminotriphenylene hexafluoroisopropylidenediphthalimide) (6F-TPA PI)/Al sample in which holes are injected by photoelectron emission process instead of direct charge carrier injection via metal electrode. In this process, an irreversible electrical phase transition of 6F-TPA PI is found in contrast to the Al/6F-TPA PI/Al structure, leading to a write-once-read-many behavior. The photoelectron spectroscopy results measured before and after the switching process revealed that the irreversible electrical phase transition of 6F-TPA PI is attributed to the chemical modification of the carbonyl group in phthalimide moiety. [ABSTRACT FROM AUTHOR]

The roles of metal nanoparticles (NPs) decorated on carbon nanotubes (CNTs) in the enhancement of field emission properties were investigated by measuring the work functions (WF), densities of state (DOS), turn-on fields, current densities, and sizes of NPs. RuO2 was deposited on CNTs and reduced to Ru by annealing at elevated temperatures. The WF decreased during reduction, and integrated DOS increased after the formation of Ru NPs. Consequently, the turn-on field showed strong correlation with the WF, and the shape of the Ru NPs had a more significant impact on current density than the WF and DOS. [ABSTRACT FROM AUTHOR]

Impressive optical properties of graphene have been attracting the interest of researchers, and, recently, the photovoltaic effects of a heterojunction structure embedded with few layer graphene (FLG) have been demonstrated. Here, we show the direct dependence of open-circuit voltage (Voc) on numbers of graphene layers. After unavoidably adsorbed contaminants were removed from the FLGs, by means of in situ annealing, prepared by layer-by-layer transfer of the chemically grown graphene layer, the work functions of FLGs showed a sequential increase as the graphene layers increase, despite of random interlayer-stacking, resulting in the modulation of photovoltaic behaviors of FLGs/Si interfaces. [ABSTRACT FROM AUTHOR]

Abstract: Water is one of the obstacles for prolonged life-time of organic based field-effect-transistors (OFETs). Here, we show how H2O molecules adsorb and affect pentacene crystal by using photoelectron spectroscopic methods. Diffusion into the crystal is accompanied with accumulation of H2O onto the crystal. Valence band, core level, and X-ray absorption spectra show that H2O molecules physisorb on the pentacene surface via oxygen, resulting in the increase of the hole-injection barrier. The diffused molecules results in the deteriorated crystallinity, and they reflect the weakening inter-molecular interactions of pentacene crystal. [Copyright &y& Elsevier]

The characteristic feature of metal contacts with gold on organics is deterioration of the organic crystals during the contact formation. The unveiled key challenge is to probe dynamic details of the microscopic evolution of the organic crystal when the atomic Au is introduced. Here, we report how the collapse of the pentacene crystal is initiated even by a few Au atoms. Our results indicate that the gentle decoupling of intra and intermolecular π-π interactions causes the localization of the lowest unoccupied molecular orbital as well as the removal of cohesive forces between molecules, leading to the subsequent crystal collapse. [ABSTRACT FROM AUTHOR]