Snowflake relocated Cu2O electrocatalyst on an Ag backbone template for the production of liquid C2+ chemicals from CO2.

In this study, we performed the CO2 reduction reaction (CO2RR) using a structural composite catalyst of cuprous oxide (Cu2O) and silver (Ag) that was simultaneously electrodeposited. While the underneath Ag electrodeposits maintained their spiky backbone structures even after the CO2RR, the Cu2O deposits were reduced to Cu(111) and relocated on the backbone template. The structural changes in Cu2O to Cu increase the active area of the Cu-Ag interface, resulting in a remarkable production rate of 125.01 µmol h-1 of liquid C2+ chemicals via the stabilization of the C-C coupling of the key intermediate species of acetaldehyde. This study provides new insights into designing a bimetallic catalyst for producing sustainable C2+ products from CO2 without any selectivity towards the production of methane.

Development of hard x-ray photoelectron spectroscopy using synchrotron radiation x-ray up to 30 keV.

Hard X-ray photoelectron spectroscopy (HAXPES) is a powerful tool for investigating the chemical and electronic states of bulk and buried interfaces non-destructively due to its large probing depth. To obtain a much larger probing depth and measure deeper regions than conventional HAXPES, we have developed a high-energy HAXPES (HE-HAXPES) system excited by photon energies up to 30 keV. This system is achieved by combining an applied bias voltage on the sample with a conventional hemispherical electron energy analyzer. By utilizing this system, we successfully observed a Si 1s peak from the bulk-Si substrate underneath the 110-nm-thick SiO2 film at a photon energy of 30 keV. Moreover, the system found that the asymmetrical spectral shape of the Si substrate signal originated from the electronic state, which is upward band bending formed at the interface between the SiO2 film and Si substrate. The HE-HAXPES system, excited by photon energy up to 30 keV, could be a very useful tool to yield genuine insights into the chemical and electronic states in deeply buried regions.

Continuous-Flow Chemical Synthesis for Sub-2 nm Ultra-Multielement Alloy Nanoparticles Consisting of Group IV to XV Elements.

Multielement alloy nanoparticles have attracted much attention due to their attractive catalytic properties derived from the multiple interactions of adjacent multielement atoms. However, mixing multiple elements in ultrasmall nanoparticles from a wide range of elements on the periodic table is still challenging because the elements have different properties and miscibility. Herein, we developed a benchtop 4-way flow reactor for chemical synthesis of ultra-multielement alloy (UMEA) nanoparticles composed of d-block and p-block elements. BiCoCuFeGaInIrNiPdPtRhRuSbSnTi 15-element alloy nanoparticles composed of group IV to XV elements were synthesized by sequential injection of metal precursors using the reactor. This methodology realized the formation of UMEA nanoparticles at low temperature (66 °C), resulting in a 1.9 nm ultrasmall average particle size. The UMEA nanoparticles have high durability and activity for electrochemical alcohol oxidation reactions and high tolerance to CO poisoning. These results suggest that the multiple interactions of UMEA efficiently promote the multistep alcohol oxidation reaction.

Near-UV light emitting diode with on-chip photocatalysts for purification applications.

A new design for light-emitting diodes (LEDs) with on-chip photocatalysts is presented for purification applications. An array of disk-shaped TiO2, with a diameter of several hundred nanometers, combined with SiO2 pedestals was fabricated directly on the surface of an InGaN-based near-ultraviolet (UV) LED using a dry etching process. The high refractive-index contrast at the boundary and the circular shape can effectively confine the near-UV light generated from the LED through multiple internal reflections inside the TiO2 nanodisks. Such a feature results in the enhancement of light absorption by the photocatalytic TiO2. The degradation of the organic dye malachite green was monitored as a model photocatalytic reaction. The proposed structure of LEDs with TiO2/SiO2 nanodisk/pedestal array exhibited a photocatalytic activity that was three times higher than the activity of LEDs with a TiO2 planar layer. The integration of photocatalytic materials with near-UV LEDs in a single system is promising for various purification applications, such as sterilization and disinfection.

Compositional dependence of structures and hydrogen evolution reaction activity of platinum-group-metal quinary RuRhPdIrPt alloy nanoparticles.

Platinum-group-metal quinary RuRhPdIrPt alloy nanoparticles were synthesised with compositions slightly away from equimolar, and their crystal and electronic structures were investigated. Their lattice constant changed linearly with composition, while the d-band centre changed nonlinearly. Their catalytic activities for the hydrogen evolution reaction were not correlated with their d-band centre.

Noble-Metal High-Entropy-Alloy Nanoparticles: Atomic-Level Insight into the Electronic Structure.

The compositional space of high-entropy-alloy nanoparticles (HEA NPs) significantly expands the diversity of the materials library. Every atom in HEA NPs has a different elemental coordination environment, which requires knowledge of the local electronic structure at an atomic level. However, such structure has not been disclosed experimentally or theoretically. We synthesized HEA NPs composed of all eight noble-metal-group elements (NM-HEA) for the first time. Their electronic structure was revealed by hard X-ray photoelectron spectroscopy and density function theory calculations with NP models. The NM-HEA NPs have a lower degeneracy in energy level compared with the monometallic NPs, which is a common feature of HEA NPs. The local density of states (LDOS) of every surface atom was first revealed. Some atoms of the same constituent element in HEA NPs have different LDOS profiles, whereas atoms of other elements have similar LDOS profiles. In other words, one atom in HEA loses its elemental identity and it may be possible to create an ideal LDOS by adjusting the neighboring atoms. The tendency of the electronic structure change was shown by supervised learning. The NM-HEA NPs showed 10.8-times higher intrinsic activity for hydrogen evolution reaction than commercial Pt/C, which is one of the best catalysts.

Phase Control of Solid-Solution Nanoparticles beyond the Phase Diagram for Enhanced Catalytic Properties.

The crystal structure, which intrinsically affects the properties of solids, is determined by the constituent elements and composition of solids. Therefore, it cannot be easily controlled beyond the phase diagram because of thermodynamic limitations. Here, we demonstrate the first example of controlling the crystal structures of a solid-solution nanoparticle (NP) entirely without changing its composition and size. We synthesized face-centered cubic (fcc) or hexagonal close-packed (hcp) structured Pd x Ru1-x NPs (x = 0.4, 0.5, and 0.6), although they cannot be synthesized as bulk materials. Crystal-structure control greatly improves the catalytic properties; that is, the hcp-Pd x Ru1-x NPs exceed their fcc counterparts toward the oxygen evolution reaction (OER) in corrosive acid. These NPs only require an overpotential (η) of 200 mV at 10 mA cm-2, can maintain the activity for more than 20 h, greatly outperforming the fcc-Pd0.4Ru0.6 NPs (η = 280 mV, 9 min), and are among the most efficient OER catalysts reported. Synchrotron X-ray-based spectroscopy, atomic-resolution electron microscopy, and density functional theory (DFT) calculations suggest that the enhanced OER performance of hcp-PdRu originates from the high stability against oxidative dissolution.

Total x-ray scattering setup for crystalline particles at SPring-8 BL15XU NIMS beamline.

We report a total x-ray scattering (TXS) system for structural analysis of crystalline particle materials at the BL15XU NIMS beamline of SPring-8 in Japan. To achieve a high angular resolution over a high Q region up to 25 Å-1, the TXS system was capable of measuring to 120° at an x-ray energy of 29.02 keV with five CdTe pin detectors. The sample alignment and measuring system were controlled by LabView software. The x-ray pair distribution function (PDF) results for Ni bulk powder and Pt and AgRh nanoparticles were successfully simulated by the PDFgui program. In addition, Rietveld refinement results were also obtained from x-ray diffraction patterns, reflecting long-range order in the Pt nanoparticles. We expect that this TXS system may be useful for understanding structural information of crystalline nanoparticles, including amorphous features at their surface region.

Chemical and Electronic Investigation of Buried NiO1-δ, PCBM, and PTAA/MAPbI3-xClx Interfaces Using Hard X-ray Photoelectron Spectroscopy and Transmission Electron Microscopy.

Identification and profiling of molecular fragments generated over the lifespan of halide perovskite solar cells are needed to overcome the stability issues associated with these devices. Herein, we report the characterization of buried CH3NH3PbI3-xClx (HaP)-transport layer (TL) interfaces. By using hard X-ray photoelectron spectroscopy in conjunction with transmission electron microscopy, we reveal that the chemical decomposition of HaP is TL-dependent. With NiO1-δ, phenyl-C61-butyric acid methyl ester (PCBM), or poly(bis(4-phenyl) (2,4,6-trimethylphenyl)amine) (PTAA) as TLs, probing depth analysis shows that the degradation takes place at the interface (HaP/TL) rather than the HaP bulk area. From core-level data analysis, we identified iodine migration toward the PCBM- and PTAA-TLs. Unexpected diffusion of nitrogen inside NiO1-δ-TL was also found for the HaP/NiO1-δ sample. With a HaP/PCBM junction, HaP is dissociated to PbI2, whereas HaP/PTAA contact favored the formation of CH3I. The low stability of HaP solar cells in the PTAA-TL system is attributed to the formation of CH3I and iodide ion vacancies. Improved stability observed with NiO1-δ-TL is related to weak dissociation of stoichiometric HaP. Here, we provide a new insight to further distinguish different mechanisms of degradation to improve the long-term stability and performance of HaP solar cells.

Correction: On the electronic structure and hydrogen evolution reaction activity of platinum group metal-based high-entropy-alloy nanoparticles.

[This corrects the article DOI: 10.1039/D0SC02351E.].

Mechanism of Hydrogen Storage and Structural Transformation in Bimetallic Pd-Pt Nanoparticles.

The hydrogen storage capacity of Pd nanoparticles (NPs) decreases as the particles become smaller; however, this reduced capacity is ameliorated by addition of Pt. In the present work, the hydrogen storage mechanism and structural transformations of core (Pd)-shell (Pt) (CS) and solid-solution (SS) NPs during hydrogen absorption and desorption (PHAD) processes are investigated. In situ X-ray absorption spectroscopy measurements were performed to study the evolution of electronic and local structures around Pd and Pt during PHAD. Under ambient conditions, Pd and Pt have distinct local structures. The Pd atomic pairs are more strained in CS NPs than in SS NPs. A similar behavior has been seen in CS NPs after PHAD. The Pd K-edge extended X-ray absorption fine structure data indicate that in CS and SS NPs a substantial fraction of the signal derives from Pd-Pd atomic pairs, indicating that Pd clusters remain present even after PHAD. PHAD causes a rearrangement of the interfacial structure, which becomes homogeneously distributed. The higher coverage of active bimetallic sites results in a higher observed hydrogen storage capacity in the SS phase.

Highly Stable and Active Solid-Solution-Alloy Three-Way Catalyst by Utilizing Configurational-Entropy Effect.

Since 1970, people have been making every endeavor to reduce toxic emissions from automobiles. After the development of a three-way catalyst (TWC) that concurrently converts three harmful gases, carbon monoxide (CO), hydrocarbons (HCs), and nitrogen oxides (NOx ), Rh became an essential element in automobile technology because only Rh works efficiently for catalytic NOx reduction. However, due to the sharp price spike in 2007, numerous efforts have been made to replace Rh in TWCs. Nevertheless, Rh remains irreplaceable, and now, the price of Rh is increasing significantly again. Here, it is demonstrated that PdRuM ternary solid-solution alloy nanoparticles (NPs) exhibit highly durable and active TWC performance, which will result in a significant reduction in catalyst cost compared to Rh. This work provides insights into the design of highly durable and efficient functional alloy NPs, guiding how to best take advantage of the configurational entropy in addition to the mixing enthalpy.

Efficient overall water splitting in acid with anisotropic metal nanosheets.

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-2geo 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.

Crystalline to amorphous transformation in solid-solution alloy nanoparticles induced by boron doping.

We synthesized a palladium-ruthenium-boron (Pd-Ru-B) solid-solution ternary alloy. Elemental mappings confirmed successful alloying of B with Pd-Ru body without changing the particle sizes, demonstrating the first discovery of this ternary alloy. Pair distribution function analysis revealed a drastic decrease in atomic correlation in Pd-Ru nanoparticles by B doping. This result gives the first example of structural transformation from crystalline to amorphous in solid-solution alloy nanoparticles induced by the doping of light elements.

Correlation between structural phase transition and surface chemical properties of thin film SrRuO3/SrTiO3 (001).

The correlation between the structural phase transition (SPT) and oxygen vacancy in SrRuO3 (SRO) thin films was investigated by in situ X-ray diffraction (XRD) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In situ XRD shows that the SPT occurs from a monoclinic SRO phase to a tetragonal SRO phase near ∼200 °C, regardless of the pressure environment. On the other hand, significant core level shifts in both the Ru and Sr photoemission spectra are found under ultrahigh vacuum, but not under the oxygen pressure environment. The directions and behavior of the core level shift of Ru and Sr are attributed to the formation of oxygen vacancy across the SPT temperature of SRO. The analysis of in situ XRD and AP-XPS results provides an evidence for the formation of metastable surface oxide possibly due to the migration of internal oxygen atoms across the SPT temperature, indicating the close relationship between oxygen vacancy and SPT in SRO thin films.

On the electronic structure and hydrogen evolution reaction activity of platinum group metal-based high-entropy-alloy nanoparticles.

We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H2SO4 and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.

Surface morphology smoothing of a 2 inch-diameter GaN homoepitaxial layer observed by X-ray diffraction topography.

We investigated the surface morphology changes in a 2 inch-diameter, c-plane, free-standing GaN wafer using X-ray diffraction topography in a grazing-incidence geometry. We observed a decrease in the peak intensity and increase in the full width at half maximum of the GaN 112̄4 Bragg peak after the deposition of a homoepitaxial layer on the same GaN wafer. However, the lattice plane bending angles did not change after homoepitaxial layer deposition. Distorted-wave Born approximation calculations near the total external reflection condition revealed a decrease in the X-ray incidence angle of the 112̄4 Bragg peak after the homoepitaxial layer deposition. The decrease in both X-ray penetration and incidence angle induced broader and weaker diffraction peaks from the surface instead of the bulk GaN.

Hydrogen absorption and desorption on Rh nanoparticles revealed by in situ dispersive X-ray absorption fine structure spectroscopy.

To unveil the origin of the hydrogen-storage properties of rhodium nanoparticles (Rh NPs), we investigated the dynamical structural change of Rh NPs using in situ dispersive X-ray absorption fine structure spectroscopy (XAFS). The variation of the Rh-Rh interatomic distance and Debye-Waller factor of Rh NPs with a size of 4.0 and 10.5 nm during hydrogen absorption and desorption suggested that they have a different mechanism for hydrogen absorption, which is that the hydrogen absorption on the inner site has a greater contribution than that on a surface for Rh 4.0 nm. In the case of Rh 10.5 nm, it is opposed to Rh 4.0 nm. This study demonstrates a powerful in situ XAFS method for observing small local structural changes of metal nanoparticles and its importance for understanding of the hydrogen-absorption properties of Rh NPs with an interesting hydrogenation mechanism.

Discovery of face-centred cubic Os nanoparticles.

We succeeded in controlling the crystal structure of osmium (Os) nanoparticles (NPs). Although Os adopts only a hexagonal close-packed (hcp) structure in the bulk state, a face-centred cubic (fcc) Os was synthesized by a chemical reduction method using an Os acetylacetonate complex as a precursor.

Time-resolved X-ray diffraction system for study of Pb(Zr, Ti)O3 films under a temporal electric field at BL15XU, SPring-8.

We report on the use of a time-resolved X-ray diffraction system to study a piezoelectric material under a temporal electric field at the BL15XU NIMS beamline, at SPring-8 in Japan. By synchronizing focused X-rays onto a device under an applied electric field with a two-dimensional detector and measurements performed with respect to the synchrotron clock signal, we successfully observed shifts of the 222 Bragg peak of 750-nm-thick Pb(Zr, Ti)O3 films near time zero under a unipolar rectangular wave at 24 V. We expect that this system might be useful for understanding the piezoresponse, lattice dynamics, and domain switching dynamics of functional oxide thin films.