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Water is the only available fossil-free source of hydrogen. Splitting water electrochemically is among the most used techniques, however, it accounts for only 4% of global hydrogen production. One of the reasons is the high cost and low performance of catalysts promoting the oxygen evolution reaction (OER). Here, we report a highly efficient catalyst in acid, that is, solid-solution Ru‒Ir nanosized-coral (RuIr-NC) consisting of 3 nm-thick sheets with only 6 at.% Ir. Among OER catalysts, RuIr-NC shows the highest intrinsic activity and stability. A home-made overall water splitting cell using RuIr-NC as both electrodes can reach 10 mA cm −2 geo at 1.485 V for 120 h without noticeable degradation, which outperforms known cells. Operando spectroscopy and atomic-resolution electron microscopy indicate that the high-performance results from the ability of the preferentially exposed {0001} facets to resist the formation of dissolvable metal oxides and to transform ephemeral Ru into a long-lived catalyst. Ru is one of the most active metals for oxygen evolution reaction, but it quickly dissolves in acidic electrolyte particularly in nanosized form. Here, the authors show that coral-like solid-solution Ru‒Ir consisting of 3 nm-thick sheets with only 6 at% Ir is a long-lived catalyst with high activity.

We have investigated the structural, optical band gap, and electrical properties of (Fe 2 O 3 ) 0.5 x :(NiO) 1 − 0.5 x ( x  = 0.3, 0.4, 0.5, 0.6 and 0.7) epitaxial thin films grown on an atomically smooth substrate at room temperature. With increasing Fe 2 O 3 content, the rock-salt structure of the thin films transformed to a spinel structure above x  = 0.6. In terms of the local structure, the increased ratio of Fe 2+ ions to Fe 3+ ions indicates that the octahedral sites of FeO were continuously transformed into distorted octahedral and tetrahedral sites. On the other hand, the NiO matrix was not affected by the local structure change. Chemical composition of Fe 2 O 3 :NiO affected the crystal structure, the electrical conductivity and the optical band gap of direct transition (3.35 to 2.99 eV).

Cuprous oxide (Cu2O) homojunction thin films on Ti substrates were fabricated by an electrochemical deposition in which a p-Cu2O layer was deposited on an n-Cu2O layer by carefully controlled bath conditions. It was found that the open-circuit voltage of the homojunction solar cell was significantly influenced by the pH of the lactate bath. The variation of the pH was used to achieve the best possible crystal orientation for homojunctions. The crystallinity and morphology of the products were characterized by X-ray diffraction (XRD), high-energy x-ray diffraction (HEXRD), and scanning electron microscopy (SEM). The current density voltage (J-V) analysis showed that the sulfur treatment and annealing enhanced the photocurrent by ten-fold compared to the untreated and unannealed homojunction solar cell. X-ray photoelectron spectroscopy (XPS) studies confirmed that the sulfur treatment eliminated the surface CuO and formed a thin layer of CuS, which was very useful to make the front Ohmic contact. Transient measurements confirmed that the p-type Cu2O layer, which was subjected to sulfur treatment, significantly reduced the recombination, thus enhancing the efficiency of the solar cell. The best sulfur treated annealed Ti/n-Cu2O/p-Cu2O/Au solar cell produced an energy conversion efficiency of 2.64% with an open-circuit voltage of 490 mV and a short circuit current density of 12.8 mA cm−2 under AM 1.5 illumination.

Hybrid materials composed of metal nanoparticles and metal-organic frameworks have attracted attention for various applications because of the synergistic functionality between their constituent materials. Interfacial interaction is expected however the mechanism remains ambiguous. Here we report the valence bands of palladium nanocubes covered by copper(II) 1, 3, 5-benzenetricarboxylate (HKUST-1), denoted as Pd@HKUST-1,  and the charge transfer from the palladium nanocubes to HKUST-1 at the Pd/HKUST-1 interface is investigated quantitatively. Interfacial density of states are different from those of internal constituents and imply that the Cu–O group in HKUST-1 acts as a charge accepter. The role of Cu–O group in charge transfer behaviour is also observed experimentally. Finally, we reveal the charge transfer mechanism from the Pd 4 d bands to the Cu 3 d (4 sp ) – O 2 p hybridization bands of HKUST-1 at the Pd/HKUST-1 interface, which explains the enhanced hydrogen storage capacity in Pd@HKUST-1. Transition metal nanoparticle-MOF systems have promising hydrogen storage properties but the nature of the interfacial interaction remains ambiguous. Here, the authors use computational and spectroscopic methods to investigate the electronic structure and charge transfer processes in a palladium nanocube-MOF system.

The fabrication of porous coordination frameworks in thin-film forms has been investigated intensively with a view to using their structural response to external stimuli and guests for potential nanotechnological applications, for example as membranes for gas separation. Here we report a coordination framework that exhibits a dynamic guest-sorption behaviour in a nanometre-sized thin-film form (16 nm thick), yet shows no guest uptake in the bulk. Highly oriented crystalline thin films of this coordination framework—which consists of interdigitated two-dimensional layers of {Fe(py) 2 [Pt(CN) 4 ]} (py, pyridine)—were fabricated through liquid-phase layer-by-layer synthesis. The resulting thin film exhibited a clear guest uptake with a structural transformation of the gate-opening type as characterized by in situ X-ray diffraction. Increasing the film's thickness markedly suppressed this behaviour. We envisage that such a crystal-downsizing effect may be observed with other coordination frameworks, and may be of use to develop functional materials, for example, for switching or sensing devices. The sorption properties of a metal–organic framework (MOF) typically depend on its structure. Now, a MOF that consists of interdigitated layers has been prepared that does not take up guests in its bulk or thick-film form, yet does so—with a dynamic gate-opening behaviour—in thin-film form.

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

The previously published version of this Article contained an error in Fig. 1. In panel c, the thickness of the HKUST-1 layer (3 nm) was incorrectly labelled. This error has been corrected in both the PDF and HTML versions of the Article.

We have investigated the structural, optical band gap, and electrical properties of (Fe O ) :(NiO) (x = 0.3, 0.4, 0.5, 0.6 and 0.7) epitaxial thin films grown on an atomically smooth substrate at room temperature. With increasing Fe O content, the rock-salt structure of the thin films transformed to a spinel structure above x = 0.6. In terms of the local structure, the increased ratio of Fe ions to Fe ions indicates that the octahedral sites of FeO were continuously transformed into distorted octahedral and tetrahedral sites. On the other hand, the NiO matrix was not affected by the local structure change. Chemical composition of Fe O :NiO affected the crystal structure, the electrical conductivity and the optical band gap of direct transition (3.35 to 2.99 eV).

To reveal the origin of the CO oxidation activity of Ruthenium nanoparticles (Ru NPs), we structurally characterized Ru NPs through Rietveld refinement analysis of high-energy X-ray diffraction data. For hexagonal close-packed (hcp) Ru NPs, the CO oxidation activity decreased with decreasing domain surface area. However, for face-centered cubic (fcc) Ru NPs, the CO oxidation activity became stronger with decreasing domain surface area. In comparing fcc Ru NPs with hcp Ru NPs, we found that the hcp Ru NPs of approximately 2 nm, which had a smaller domain surface area and smaller atomic displacement, showed a higher catalytic activity than that of fcc Ru NPs of the same size. In contrast, fcc Ru NPs larger than 3.5 nm, which had a larger domain surface area, lattice distortion and larger atomic displacement, exhibited higher catalytic activity than that of hcp Ru NPs of the same size. In addition, the fcc Ru NPs had larger atomic displacements than hcp Ru NPs for diameters ranging from 2.2 to 5.4 nm. Enhancement of the CO oxidation activity in fcc Ru NPs may be caused by an increase in imperfections due to lattice distortions of close-packed planes and static atomic displacements.

Bimetallic Pd 1− x Pt x solid-solution nanoparticles (NPs) display charging/discharging of hydrogen gas, which has relevance for fuel cell technologies; however, the constituent elements are immiscible in the bulk phase. We examined these material systems using high-energy synchrotron X-ray diffraction, X-ray absorption fine structure and hard X-ray photoelectron spectroscopy techniques. Recent studies have demonstrated the hydrogen storage properties and catalytic activities of Pd-Pt alloys; however, comprehensive details of their structural and electronic functionality at the atomic scale have yet to be reported. Three-dimensional atomic-scale structure results obtained from the pair distribution function (PDF) and reverse Monte Carlo (RMC) methods suggest the formation of a highly disordered structure with a high cavity-volume-fraction for low-Pt content NPs. The NP conduction band features, as extracted from X-ray absorption near-edge spectra at the Pd and Pt L III -edge, suggest that the Pd conduction band is filled by Pt valence electrons. This behaviour is consistent with observations of the hydrogen storage capacity of these NPs. The broadening of the valence band width and the down-shift of the d -band centre away from the Fermi level upon Pt substitution also provided evidence for enhanced stability of the hydride (Δ H ) features of the Pd 1− x Pt x solid-solution NPs with a Pt content of 8-21 atomic percent.