First synthesis of RuSn solid-solution alloy nanoparticles and their enhanced hydrogen evolution reaction activity.

Solid-solution alloys based on platinum group metals and p-block metals have attracted much attention due to their promising potential as materials with a continuously fine-tunable electronic structure. Here, we report on the first synthesis of novel solid-solution RuSn alloy nanoparticles (NPs) by electrochemical cyclic voltammetry sweeping of RuSn@SnOx NPs. High-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy maps confirmed the random and homogeneous distribution of Ru and Sn elements in the alloy NPs. Compared with monometallic Ru NPs, the RuSn alloy NPs showed improved hydrogen evolution reaction (HER) performance. The overpotentials of Ru0.94Sn0.06 NPs/C and Ru0.87Sn0.13 NPs/C to achieve a current density of 10 mA cm-2 were 43.41 and 33.19 mV, respectively, which are lower than those of monometallic Ru NPs/C (53.53 mV) and commercial Pt NPs/C (55.77 mV). The valence-band structures of the NPs investigated by hard X-ray photoelectron spectroscopy demonstrated that the d-band centre of RuSn NPs shifted downward compared with that of Ru NPs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure analyses indicated that in the RuSn alloy NPs, charge transfer occurs from Sn to Ru, which was considered to result in a downward shift of the d-band centre in RuSn NPs and to regulate the adsorption energy of intermediate Hads effectively, and thus enable the RuSn solid-solution alloy NPs to exhibit excellent HER catalytic properties.

Phase control of solid-solution RuIn nanoparticles and their catalytic properties.

The properties of solids could be largely affected by their crystal structures. We achieved, for the first time, the phase control of solid-solution RuIn nanoparticles (NPs) from face-centred cubic (fcc) to hexagonal close-packed (hcp) crystal structures by hydrogen heat treatment. The effect of the crystal structure of RuIn alloy NPs on the catalytic performance in the hydrogen evolution reaction (HER) was also investigated. In the hcp RuIn NPs, enhanced HER catalytic performance was observed compared to the fcc RuIn NPs and monometallic Ru NPs. The intrinsic electronic structures of the NPs were investigated by valence-band X-ray photoelectron spectroscopy (VB-XPS). The d-band centre of hcp RuIn NPs obtained from VB-XPS was deeper than that of fcc RuIn NPs and monometallic Ru NPs, which is considered to enable the hcp RuIn NPs to exhibit enhanced HER catalytic performance.

B2-structured indium-platinum group metal high-entropy intermetallic nanoparticles.

We first report the synthesis of B2-structured indium-platinum group metal high-entropy intermetallic nanoparticles (In-PGM HEI NPs). The synthesis was achieved by a wet-chemistry method and subsequent heat treatment. The crystal structure of these NPs is unique in the coexistence of completely orderly arranged indium and disorderly arranged PGMs.

Chemical Synthesis, Characterization, and Properties of Multi-Element Nanoparticles.

Multi-element nanoparticles (NPs) consisting of five or more elements have been increasingly studied in the past five years. Their emergence is taking materials science one step further because they exhibit superior properties to those of conventional NPs in a range of respects, including catalysis. This Review focuses on the recent progress in multi-element NPs regarding synthesis, especially with regard to chemical synthesis, characterization, and properties. We begin with a brief introduction of multi-element NPs and an overview of their synthesis methods. Then, we present representative examples of multi-element alloy NPs and ceramic NPs, including oxide NPs prepared by chemical syntheses. This Review intends to provide useful insights into the chemical methods that are used to synthesize multi-element NPs, and includes a discussion on the possibilities arising from their use in new functional materials.

Nanoparticle/metal-organic framework hybrid catalysts: elucidating the role of the MOF.

Hybrid materials of metal-organic frameworks (MOFs) and nanoparticles (NPs) have attracted significant attention because of the wide variety of attractive properties derived from the two components. In the last decade, the development of synthesis techniques for NP/MOF composites was particularly significant. In the field of catalysis in particular, various synergistic effects that make the composites attractive catalysts have been reported. However, the role of MOFs in the composite catalysts is still not well understood and is being elucidated. In this feature article, we focus on recent progress in NP/MOF composite catalysts, concentrating on the analysis of the interaction between NPs and MOFs and the reaction mechanisms, together with the synthetic techniques used for NP/MOF hybrid materials.

Systematic Tuning of the Magnetic Properties in Mixed-Metal MOF-74.

Recently, mixed-metal metal-organic frameworks (MOFs) have been attracting much attention in various fields. In this study, we have systematically investigated the magnetic properties of CoxNi1-x-MOF-74 [Co2xNi2(1-x)(dhtp), where H4dhtp = 2,5-dihydroxyterephthalic acid] with two different kinds of metals (Co and Ni) across the composition range 0 ≤ x ≤ 1. Bimetallic CoxNi1-x-MOF-74 (x = 0.752, 0.458, and 0.233) were successfully synthesized and confirmed to have homogeneous metal distributions. Weak ferromagnetic (canted antiferromagnetic) behavior was exhibited, while homometallic Co-MOF-74 and Ni-MOF-74 are antiferromagnetic. We also investigated the effects of C2H4 sorption on the magnetic properties and found that C2H4-adsorbed Co0.5Ni0.5-MOF-74 exhibited a change in the interchain magnetic interaction.

Fabrication of Integrated Copper-Based Nanoparticles/Amorphous Metal-Organic Framework by a Facile Spray-Drying Method: Highly Enhanced CO2 Hydrogenation Activity for Methanol Synthesis.

We report on Cu/amUiO-66, a composite made of Cu nanoparticles (NPs) and amorphous [Zr6 O4 (OH)4 (BDC)6 ] (amUiO-66, BDC=1,4-benzenedicarboxylate), and Cu-ZnO/amUiO-66 made of Cu-ZnO nanocomposites and amUiO-66. Both structures were obtained via a spray-drying method and characterized using high-resolution transmission electron microscopy, energy dispersive spectra, powder X-ray diffraction and extended X-ray absorption fine structure. The catalytic activity of Cu/amUiO-66 for CO2 hydrogenation to methanol was 3-fold that of Cu/crystalline UiO-66. Moreover, Cu-ZnO/amUiO-66 enhanced the methanol production rate by 1.5-fold compared with Cu/amUiO-66 and 2.5-fold compared with γ-Al2 O3 -supported Cu-ZnO nanocomposites (Cu-ZnO/γ-Al2 O3 ) as the representative hydrogenation catalyst. The high catalytic performance was investigated using in situ Fourier transform IR spectra. This is a first report of a catalyst comprising metal NPs and an amorphous metal-organic framework in a gas-phase reaction.

Ni@onion-like carbon and Co@amorphous carbon: control of carbon structures by metal ion species in MOFs.

We first report the facile synthesis of metal-carbon composites consisting of metal nanoparticles (NPs) and different types of carbon species: onion-like and amorphous carbon, Ni@onion-like carbon and Co@amorphous carbon. By simply changing the metal species in an isostructural metal-organic framework, thermal decompositions of MOF-74 directly afforded different types of metal NPs and carbon composites, which exhibited good electrical conductivity. In particular, the Ni@onion-like carbon, having a well-ordered carbon structure, had high electrical conductivity (σ = 5.3 Ω-1 cm-1 at 295 K), explained by a modified model of the Efros-Shklovskii variable range hopping.

Local Geometry and Electronic Properties of Nickel Nanoparticles Prepared via Thermal Decomposition of Ni-MOF-74.

Metal-organic frameworks (MOFs) provide highly selective catalytic activity because of their porous crystalline structure. There is particular interest in metal nanoparticle-MOF composites (MNP@MOF) that could take advantage of synergistic effects for enhanced catalytic properties. We present an investigation into the local geometry and electronic properties of thermally decomposed Ni-MOF-74 calcined at different temperatures and time durations. Pair distribution function analysis using high-energy X-ray diffraction reveals the formation of fcc-Ni nanoparticles with a mixture of MOF phase in samples heated at 623 K for 12 h. Elevating the calcination temperature and lengthening the time duration assisted complete precipitation of Ni nanoparticles in the MOF matrix. Local structures and valence states were investigated using X-ray absorption fine structure spectroscopy. Evidence of ligand-to-metal charge transfer and gradual reduction of Ni2+ is apparent for those samples heated above 623 K for 12 h. In addition, the Ni lattice was found to be slightly compressed as a result of surface stresses in the nanosized particles or surface ligand environment. Electronic structure investigation using hard X-ray photoelectron spectroscopy shows a significant narrowing of the valence band and a decrease in the d-band center (toward the Fermi level) when the heating temperature is increased, thus suggesting promising catalytic properties for NiNP@MOF composite.

Recognition of 1,3-Butadiene by a Porous Coordination Polymer.

The separation of 1,3-butadiene from C4 hydrocarbon mixtures is imperative for the production of synthetic rubbers, and there is a need for a more economical separation method, such as a pressure swing adsorption process. With regard to adsorbents that enable C4 gas separation, [Zn(NO2 ip)(dpe)]n (SD-65; NO2 ip=5-nitroisophthalate, dpe=1,2-di(4-pyridyl)ethylene) is a promising porous material because of its structural flexibility and restricted voids, which provide unique guest-responsive accommodation. The 1,3-butadiene-selective sorption profile of SD-65 was elucidated by adsorption isotherms, in situ PXRD, and SSNMR studies and was further investigated by multigas separation and adsorption-desorption-cycle experiments for its application to separation technology.

Hybrid materials of Ni NP@MOF prepared by a simple synthetic method.

We demonstrate a novel, simple synthetic method for metal (Ni) NPs in a MOF using the partial thermal decomposition of nickel(II) 2,5-dihydroxyterephthalate (Ni-MOF-74). The Ni NPs inside the Ni-MOF-74 are several nanometers in size, and the size can be precisely controlled by the heating conditions.