Although it is being successfully implemented for exploration of the genome, discovery science has eluded the functional neuroimaging community. The core challenge remains the development of common paradigms for interrogating the myriad functional systems in the brain without the constraints of a priori hypotheses. Resting-state functional MRI (R-fMRI) constitutes a candidate approach capable of addressing this challenge. Imaging the brain during rest reveals large-amplitude spontaneous low-frequency (<0.1 Hz) fluctuations in the fMRI signal that are temporally correlated across functionally related areas. Referred to as functional connectivity, these correlations yield detailed maps of complex neural systems, collectively constituting an individual's "functional connectome." Reproducibility across datasets and individuals suggests the functional connectome has a common architecture, yet each individual's functional connectome exhibits unique features, with stable, meaningful interindividual differences in connectivity patterns and strengths. Comprehensive mapping of the functional connectome, and its subsequent exploitation to discern genetic influences and brain-behavior relationships, will require multicenter collaborative datasets. Here we initiate this endeavor by gathering R-fMRI data from 1,414 volunteers collected independently at 35 international centers. We demonstrate a universal architecture of positive and negative functional connections, as well as consistent loci of inter-individual variability. Age and sex emerged as significant determinants. These results demonstrate that independent R-fMRI datasets can be aggregated and shared. Highthroughput R-fMRI can provide quantitative phenotypes for molecular genetic studies and biomarkers of developmental and pathological processes in the brain. To initiate discovery science of brain function, the 1000 Functional Connectomes Project dataset is freely accessible at www.nitrc.org/projects/fcon_1000/.

Hybrid metal nanoparticles can allow separate reaction steps to occur in close proximity at different metal sites and accelerate catalysis. We synthesized iron-nickel hydroxide-platinum (transition metal-OH-Pt) nanoparticles with diameters below 5 nanometers and showed that they are highly efficient for carbon monoxide (CO) oxidation catalysis at room temperature. We characterized the composition and structure of the transition metal-OH-Pt interface and showed that Ni(2+) plays a key role in stabilizing the interface against dehydration. Density functional theory and isotope-labeling experiments revealed that the OH groups at the Fe(3+)-OH-Pt interfaces readily react with CO adsorbed nearby to directly yield carbon dioxide (CO2) and simultaneously produce coordinatively unsaturated Fe sites for O2 activation. The oxide-supported PtFeNi nanocatalyst rapidly and fully removed CO from humid air without decay in activity for 1 month.

Graphitic overlayers on metals have commonly been considered as inhibitors for surface reactions due to their chemical inertness and physical blockage of surface active sites. In this work, however, we find that surface reactions, for instance, CO adsorption/desorption and CO oxidation, can take place on Pt(111) surface covered by monolayer graphene sheets. Surface science measurements combined with density functional calculations show that the graphene overlayer weakens the strong interaction between CO and Pt and, consequently, facilitates the CO oxidation with lower apparent activation energy. These results suggest that interfaces between graphitic overlayers and metal surfaces act as 2D confined nanoreactors, in which catalytic reactions are promoted. The finding contrasts with the conventional knowledge that graphitic carbon poisons a catalyst surface but opens up an avenue to enhance catalytic performance through coating of metal catalysts with controlled graphitic covers.arbonaceous deposits such as carbidic carbon and graphitic carbon often form on transition metal (TM) surfaces in catalytic processes involving carbon-containing reactants (1). It has been shown that carbidic species can be involved in some hydrogenation reactions, which are attributed to the observed high reaction activity (2-5). In contrast, graphitic carbon deposited on TM is conventionally considered as catalyst poison due to its chemical inertness and physical blockage of surface active sites (6-8). It has been generally assumed that formation of graphitic carbon on metal catalysts should be avoided before and during catalytic reactions (9, 10). Nevertheless, for decades, extensive research efforts have been made to use surface carbon layers formed on TMs and to understand their role in catalytic reactions (11)(12)(13)(14), which, however, have been impeded by complexity of the ill-defined carbon structures. Graphene, as a simple form of graphitic deposit, has been grown on many late TM surfaces via catalytic cracking of carbon-containing gases (15)(16)(17)(18)(19)(20). Surface science studies on the well-defined graphene/metal surfaces have shown that gaseous molecules such as CO, O 2 , and H 2 O can be readily intercalated under the graphene overlayers (21-27). Defects in graphene including island edges (22,23,(28)(29)(30), domain boundaries (26,31,32), and wrinkles (33) provide channels for molecule diffusion into the graphene/metal interfaces. These new results raise the intriguing possibility that the space between graphene overlayers and metal substrates can act as a 2D container for reactions. The distance between the graphene overlayers and the metal surfaces typically falls in the subnanometer range (19,20), and molecules trapped inside interact directly with both the graphene cover and the metal substrate. Catalytic reactions, if occurring, are strongly confined in the 2D space, and extraordinary catalytic performance may be expected due to the confinement effect. In the present work, graphene/Pt(111) [Gr/Pt(111)] was used ...

Ceria (CeO) has recently been found to be a promising catalyst in the selective hydrogenation of alkynes to alkenes. This reaction occurs primarily on highly dispersed metal catalysts, but rarely on oxide surfaces. The origin of the outstanding activity and selectivity observed on CeO remains unclear. In this work, we show that one key aspect of the hydrogenation reaction-the interaction of hydrogen with the oxide-depends strongly on the presence of O vacancies within CeO. Through infrared reflection absorption spectroscopy on well-ordered CeO(111) thin films and density functional theory (DFT) calculations, we show that the preferred heterolytic dissociation of molecular hydrogen on CeO(111) requires H pressures in the mbar regime. Hydrogen depth profiling with nuclear reaction analysis indicates that H species stay on the surface of stoichiometric CeO(111) films, whereas H incorporates as a volatile species into the volume of partially reduced CeO(111) thin films (x ∼ 1.8-1.9). Complementary DFT calculations demonstrate that oxygen vacancies facilitate H incorporation below the surface and that they are the key to the stabilization of hydridic H species in the volume of reduced ceria.

In heterogeneous catalysis molecule-metal interaction is often modulated through structural modifications at the surface or under the surface of the metal catalyst. Here, we suggest an alternative way toward this modulation by placing a two-dimensional (2D) cover on the metal surface. As an illustration, CO adsorption on Pt(111) surface has been studied under 2D hexagonal boron nitride (h-BN) overlayer. Dynamic imaging data from surface electron microscopy and in situ surface spectroscopic results under near ambient pressure conditions confirm that CO molecules readily intercalate monolayer h-BN sheets on Pt(111) in CO atmosphere but desorb from the h-BN/Pt(111) interface even around room temperature in ultrahigh vacuum. The interaction of CO with Pt has been strongly weakened due to the confinement effect of the h-BN cover, and consequently, CO oxidation at the h-BN/Pt(111) interface was enhanced thanks to the alleviated CO poisoning effect.

Room temperature adsorption of carbon dioxide (CO) on monocrystalline CaO(001) thin films grown on a Mo(001) substrate was studied by infrared reflection-absorption spectroscopy (IRAS) and quantum chemical calculations. For comparison, CO adsorption was examined on poorly ordered, nanoparticulate CaO films prepared on Ru(0001). For both systems, CO readily adsorbs on the clean CaO surface. However, additional bands were observable on the CaO/Ru(0001) films compared with CaO/Mo(001), because the stricter IRAS surface selection rules do not apply to adsorption on the disordered thin films grown on Ru(0001). Spectral evolution with increasing exposure of the IRA bands suggested the presence of several adsorption sites which are consecutively populated by CO. Density functional calculations showed that CO adsorption occurs as monodentate surface carbonate (CO) species at monatomic step sites and other low-coordinated sites, followed by formation of carbonates on terraces, which dominate at increasing CO exposure. To explain the coverage-dependent IRAS results, we propose CO surface islanding from the onset, most likely in the form of pairs and other chain-like species, which were calculated as thermodynamically favorable. The calculated adsorption energy for isolated CO on the terrace sites (184 ± 10 kJ mol) is larger than the adsorption energy obtained by temperature programmed desorption (∼120-140 kJ mol) and heat of adsorption taken from microcalorimetry measurements at low coverage (∼125 kJ mol). However, the calculated adsorption energies become less favorable when carbonate chains intersect on CaO terraces, forming kinks. Furthermore, our assignments of the initial stages of CO adsorption are consistent with the observed coverage effect on the CO adsorption energy measured by microcalorimetry and the IRAS results.

Abstract. We studied CO oxidation on FeO(111) films on Pt(111) at sub-monolayer oxide coverages at ultra-high vacuum (UHV) and near-atmospheric pressure conditions. The FeO (111) bilayer islands are inert towards CO2 formation. In contrast, the FeO2-x trilayer structure shows substantial CO2 production that reaches a maximum at(~40%) coverage at both, UHV and realistic, pressure conditions. The results provide compelling evidence that the FeO2-x/Pt (111) interface is the most active in CO oxidation. Although FeO2-x boundaries possesses weakly bound oxygen species, strong binding of CO to Pt favors the reaction at the FeO2-x/Pt interface as compared to the FeO2-x/FeO one, thus giving a rationale to the reactivity enhancement observed in systems exposing metal/oxide boundaries. In addition, oxygen diffusion from the interior of an FeO2-x island to the active edge sites may be effective for the oxygen replenishment in the CO oxidation catalytic cycle.

Lithium–sulfur (Li–S) batteries are considered as one of the most promising next‐generation rechargeable batteries owing to their high energy density and cost‐effectiveness. However, the sluggish kinetics of the sulfur reduction reaction process, which is so far insufficiently explored, still impedes its practical application. Metal–organic frameworks (MOFs) are widely investigated as a sulfur immobilizer, but the interactions and catalytic activity of lithium polysulfides (LiPs) on metal nodes are weak due to the presence of organic ligands. Herein, a strategy to design quasi‐MOF nanospheres, which contain a transition‐state structure between the MOF and the metal oxide via controlled ligand exchange strategy, to serve as sulfur electrocatalyst, is presented. The quasi‐MOF not only inherits the porous structure of the MOF, but also exposes abundant metal nodes to act as active sites, rendering strong LiPs absorbability. The reversible deligandation/ligandation of the quasi‐MOF and its impact on the durability of the catalyst over the course of the electrochemical process is acknowledged, which confers a remarkable catalytic activity. Attributed to these structural advantages, the quasi‐MOF delivers a decent discharge capacity and low capacity‐fading rate over long‐term cycling. This work not only offers insight into the rational design of quasi‐MOF‐based composites but also provides guidance for application in Li–S batteries.