New Triclinic Perovskite-Type Oxide Ba5CaFe4O12 for Low-Temperature Operated Chemical Looping Air Separation.

We present the discovery of Ba5CaFe4O12, a new iron-based oxide with remarkable properties as a low-temperature driven oxygen storage material (OSM). OSMs, which exhibit selective and rapid oxygen intake and release capabilities, have attracted considerable attention in chemical looping technologies. Specifically, chemical looping air separation (CLAS) has the potential to revolutionize oxygen production as it is one of the most crucial industrial gases. However, the challenge lies in utilizing OSMs for energy-efficient CLAS at lower temperatures. Ba5CaFe4O12, a cost-competitive material, possesses an unprecedented 5-fold perovskite-type A5B5O15-δ structure, where both Fe and Ca occupy the B sites. This distinctive structure enables excellent oxygen intake/release properties below 400 °C. This oxide demonstrates the theoretical daily oxygen production rate of 2.41 mO23 kgOSM-1 at 370 °C, surpassing the performance of the previously reported material, Sr0.76Ca0.24FeO3-δ (0.81 mO23 kgOSM-1 at 550 °C). This discovery holds great potential for reducing costs and enhancing the energy efficiency in CLAS.

Synthesis and Characterization of the Orthorhombic Sn3 O4 Polymorph.

An unexplored tin oxide crystal phase (Sn3 O4 ) was experimentally synthesized via a facile hydrothermal method. After tuning the often-neglected parameters for the hydrothermal synthesis, namely the degree of filling of the precursor solution and the gas composition in the reactor head space, an unreported X-ray diffraction pattern was discovered. Through various characterization studies, such as Rietveld analysis, energy dispersive X-ray spectroscopy, and first-principles calculations, this novel material was characterized as orthorhombic mixed-valence tin oxide with the composition SnII 2 SnIV O4 . This orthorhombic tin oxide is a new polymorph of Sn3 O4 , which differs from the reported conventional monoclinic structure. Computational and experimental analyses showed that orthorhombic Sn3 O4 has a smaller band gap (2.0 eV), enabling greater absorption of visible light. This study is expected to improve the accuracy of hydrothermal synthesis and aid the discovery of new oxide materials.

Tunable Oxygen Intake/Release Characteristics of Brownmillerite-Type Ca2AlMnO5+δ Involving Atomic Defect Formations.

The oxygen intake/release characteristics were systematically studied for Ca2AlMnO5+δ samples synthesized under precisely controlled oxygen pressures. Both the oxygen storage capacity (OSC) and operating temperature were systematically lowered as the oxygen pressure in the firing atmosphere increased. Notably, the sample fired under a 1% O2 atmosphere exhibited sufficiently large OSC and superior oxygen intake/release kinetics to the pristine sample synthesized in an anaerobic condition. The high-angle annular dark-field scanning TEM observation revealed that the samples contain defects in their atomic arrangement when fired in oxygen-rich atmospheres. This result indicates that the oxygen intake/release characteristics of Ca2AlMnO5+δ are sensitive to the synthesis condition and widely tunable even without chemical substitutions.

Unusual chirality transfer from silica to metallic nanoparticles with formation of distorted atomic array in crystal lattice structure.

Transfer of chirality from chiral organic molecules to metallic nanoparticles (NPs) is a very attractive field of research and some unique approaches to obtaining chiral metallic NPs have been developed. However, to date, there has been no report in the literature that the chiral information of silica can be transferred into metallic NPs. In this work, a new chirality transfer system to metallic NPs from chiral silica has been achieved. The chiral transfer was performed by simple two steps: (1) trapping metal cations of silver (Ag) and gold (Au) in chiral silica of nano fibrous bundles embedding poly(ethyleneimine) inside and (2) thermoreducing the metal ions into metallic NPs. The metallic NPs of Au and Ag grown around a silica frame, using a thermo-reduction (calcination) process, showed a spherical shape with a size of about 30 nm. Interestingly, the metallic NPs detached or isolated from the silica via crushing and/or hydrolysis of the silica showed remarkable circular dichroism activity in their plasmon absorption band with an exciton coupling feature. Using an atomic resolution scanning transmission protocol, it was found that the chiral metallic NPs have a definite distortion in the atomic array in their crystal lattice structures. In comparison, achiral metallic NPs, which were prepared using a similar method around achiral silica bundles, showed a precisely ordered atomic line without distortion.

Nanophase-separated Ni3Nb as an automobile exhaust catalyst.

Catalytic remediation of automobile exhaust has relied on precious metals (PMs) including platinum (Pt). Herein, we report that an intermetallic phase of Ni and niobium (Nb) (i.e., Ni3Nb) exhibits a significantly higher activity than that of Pt for the remediation of the most toxic gas in exhaust (i.e., nitrogen monoxide (NO)) in the presence of carbon monoxide (CO). When subjected to the exhaust-remediation atmosphere, Ni3Nb spontaneously evolves into a catalytically active nanophase-separated structure consisting of filamentous Ni networks (thickness < 10 nm) that are incorporated in a niobium oxide matrix (i.e., NbO x (x < 5/2)). The exposure of the filamentous Ni promotes NO dissociation, CO oxidation and N2 generation, and the NbO x matrix absorbs excessive nitrogen adatoms to retain the active Ni0 sites at the metal/oxide interface. Furthermore, the NbO x matrix immobilizes the filamentous Ni at elevated temperatures to produce long-term and stable catalytic performance over hundreds of hours.

Insights into the dominant factors of porous gold for CO oxidation.

Three different porous Au catalysts that exhibit high catalytic activity for CO oxidation were prepared by the leaching of Al from an intermetallic compound, Al2Au, with 10 wt. %-NaOH, HNO3, or HCl aqueous solutions. The catalysts were investigated using Brunauer-Emmett-Teller measurements, synchrotron X-ray powder diffraction, hard X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy (TEM). Broad diffraction peaks generated during the leaching process correlated with high activity for all the porous Au catalysts. CO oxidation catalyzed by porous Au leached with NaOH and HNO3 is considered to be dominated by different mechanisms at low (< 320 K) and high (> 370 K) temperatures. Activity in the low-temperature region is mainly attributed to the perimeter interface between residual Al species (AlOx) and porous Au, whereas activity in the high-temperature region results from a high density of lattice defects such as twins and dislocations, which were evident from diffraction peak broadening and were observed with high-resolution TEM in the porous Au leached with NaOH. It is proposed that atoms located at lattice defects on the surfaces of porous Au are the active sites for catalytic reactions.

Tailoring the surface-oxygen defects of a tin dioxide support towards an enhanced electrocatalytic performance of platinum nanoparticles.

Tin-dioxide nanofacets (SnO2 NFs) are crystal-engineered so that oxygen defects on the maximal {113} surface are long-range ordered to give rise to a non-occupied defect band (DB) in the bandgap. SnO2 NFs-supported platinum-nanoparticles exhibit an enhanced ethanol-electrooxidation activity due to the promoted charge-transport via the DB at the metal-semiconductor interface.

Correlation between the surface electronic structure and CO-oxidation activity of Pt alloys.

The surface electronic structure and CO-oxidation activity of Pt and Pt alloys, Pt3T (T = Ti, Hf, Ta, Pt), were investigated. At temperatures below 538 K, the CO-oxidation activities of Pt and Pt3T increased in the order Pt < Pt3Ti < Pt3hHf < Pt3Ta. The center-of-gravity of the Pt d-band (the d-band center) of Pt and Pt3T was theoretically calculated to follow the trend Pt3Ti < Pt3Ta < Pt3Hf < Pt. The CO-oxidation activity showed a volcano-type dependence on the d-band center, where Pt3Ta exhibited a maximum in activity. Theoretical calculations demonstrated that the adsorption energy of CO on the catalyst surface monotonically decreases with the lowering of the d-band center because of diminished hybridization of the surface d-band and the lowest-unoccupied molecular orbital (LUMO) of CO. The observed volcano-type correlation between the d-band center and the CO oxidation activity is rationalized in terms of the CO adsorption energy, which counterbalances the surface coverage by CO and the rate of CO oxidation.

Visible-light photodecomposition of acetaldehyde by TiO2-coated gold nanocages: plasmon-mediated hot electron transport via defect states.

Skeletal gold nanocages (Au NCs) are synthesized and coated with TiO2 layers (TiO2-Au NCs). The TiO2-Au NCs exhibit enhanced photodecomposition activity toward acetaldehyde under visible light (>400 nm) illumination because hot electrons are generated over the Au NCs by local surface plasmon resonance (LSPR) and efficiently transported across the metal/semiconductor interface via the defect states of TiO2.

Stimulation of electro-oxidation catalysis by bulk-structural transformation in intermetallic ZrPt3 nanoparticles.

Although compositional tuning of metal nanoparticles (NPs) has been extensively investigated, possible control of the catalytic performance through bulk-structure tuning is surprisingly overlooked. Here we report that the bulk structure of intermetallic ZrPt3 NPs can be engineered by controlled annealing and their catalytic performance is significantly enhanced as the result of bulk-structural transformation. Chemical reduction of organometallic precursors yielded the desired ZrPt3 NPs with a cubic FCC-type structure (c-ZrPt3 NPs). The c-ZrPt3 NPs were then transformed to a different phase of ZrPt3 with a hexagonal structure (h-ZrPt3 NPs) by annealing at temperatures between 900 and 1000 °C. The h-ZrPt3 NPs exhibited higher catalytic activity and long-term stability than either the c-ZrPt3 NPs or commercial Pt/C NPs toward the electro-oxidation of ethanol. Theoretical calculations have elucidated that the enhanced activity of the h-ZrPt3 NPs is attributed to the increased surface energy, whereas the stability of the catalyst is retained by the lowered bulk-free-energy.

Low-temperature remediation of NO catalyzed by interleaved CuO nanoplates.

A copper(II)-oxide-based exhaust catalyst exhibits better activity than Pt- and Rh-nanoparticle catalysts in NO remediation at 175 °C. Following theoretical design, the CuO catalyst is rationally prepared; CuO nanoplates bearing a maximized amount of the active {001} facet are arranged in interleaved layers. A field test using a commercial gasoline engine demonstrates the ability of the catalyst to remove NO from the exhaust of small vehicles.

Synthesis and electrocatalytic performance of atomically ordered nickel carbide (Ni3C) nanoparticles.

Atomically ordered nickel carbide, Ni3C, was synthesized by reduction of nickel cyclopentadienyl (NiCp2) with sodium naphthalide to form Ni clusters coordinated by Cp (Ni-Cp clusters). Ni-Cp clusters were thermally decomposed to Ni3C nanoparticles smaller than 10 nm. The Ni3C nanoparticles showed better performance than Ni nanoparticles and Au nanoparticles in the electrooxidation of sodium borohydride.

Interleaved mesoporous copper for the anode catalysis in direct ammonium borane fuel cells.

Mesoporous materials with tailored microstructures are of increasing importance in practical applications particularly for energy generation and/or storage. Here we report a mesoporous copper material (MS-Cu) can be prepared in a hierarchical microstructure and exhibit high catalytic performance for the half-cell reaction of direct ammonium borane (NH3BH3) fuel cells (DABFs). Hierarchical copper oxide (CuO) nanoplates (CuO Npls) were first synthesized in a hydrothermal condition. CuO Npls were then reduced at room temperature using water solution of sodium borohydride (NaBH4) to yield the desired mesoporous copper material, MS-Cu, consisting of interleaved nanoplates with a high density of mesopores. The surface of MS-Cu comprised high-index facets, whereas a macroporous copper material (MC-Cu), which was prepared from CuO Npls at elevated temperatures in a hydrogen stream, was surrounded by low-index facets with a low density of active sites. MS-Cu exhibited a lower onset potential and improved durability for the electro-oxidation of NH3BH3 than MC-Cu or copper particles because of the catalytically active mesopores on the interleaved nanoplates.

Photocatalytic water splitting under visible light by mixed-valence Sn(3)O(4).

A mixed-valence tin oxide, (Sn(2+))2(Sn(4+))O4, was synthesized via a hydrothermal route. The Sn3O4 material consisted of highly crystalline {110} flexes. The Sn3O4 material, when pure platinum (Pt) was used as a co-catalyst, significantly catalyzed water-splitting in aqueous solution under illumination of visible light (λ > 400 nm), whereas neither Sn(2+)O nor Sn(4+)O2 was active toward the reaction. Theoretical calculations have demonstrated that the co-existence of Sn(2+) and Sn(4+) in Sn3O4 leads to a desirable band structure for photocatalytic hydrogen evolution from water solution. Sn3O4 has great potential as an abundant, cheap, and environmentally benign solar-energy conversion catalyst.

Activation of Al-Cu-Fe quasicrystalline surface: fabrication of a fine nanocomposite layer with high catalytic performance.

A fine layered nanocomposite with a total thickness of about 200 nm was formed on the surface of an Al63Cu25Fe12 quasicrystal (QC). The nanocomposite was found to exhibit high catalytic performance for steam reforming of methanol. The nanocomposite was formed by a self-assembly process, by leaching the Al-Cu-Fe QC using a 5 wt% Na2CO3 aqueous solution followed by calcination in air at 873 K. The quasiperiodic nature of theQC played an important role in the formation of such a structure. Its high catalytic activity originated from the presence of highly dispersed copper and iron species, which also suppressed the sintering of nanoparticles.

Specimen preparation of porous Au for transmission electron microscopy using cryo ion-milling.

Porous Au specimens suitable for transmission electron microscopic investigations were prepared by the Ar ion-milling equipped with a cryo-system. The cryo technique enabled the preparation of an artifact-free specimen, avoiding the deposition of Au particles induced by ion-milling. This result demonstrates that cooling is necessary for defect-free preparation of the specimens.