Exploration of heterogeneous catalyst for molecular hydrogen ortho-para conversion.

Molecular hydrogen (H2) ortho-para conversion (O/P conversion) proceeds slowly at low temperatures accompanying a heat release. Thus, catalysts for accelerating this conversion rate are highly demanded in terms of the storage and utilization of liquid H2. The catalysts for this purpose are experimentally screened by examining a broad range of materials covering magnetic, non-magnetic, metallic, and nonmetallic oxides. The primary conclusions obtained are summarized below. (1) active materials are required to be non-metallic and to bear the cations with ionic radii smaller than the bond length of H2. (2) Metallic materials have almost no activity irrespective of with or without magnetism (3) The activity of materials belonging to (1) is largely enhanced when the constituting cation has a magnetic moment. In addition, there is a class of materials for which the activity is distinctly enhanced just upon substitution by the foreign ions.

Ammonia Cracking Catalyzed by Ni Nanoparticles Confined in the Framework of CeO2 Support.

For the extraction of hydrogen from ammonia at low temperatures, we investigated Ni-based catalysts fabricated by the thermal decomposition of RNi5 intermetallics (R = Ce or Y). The interconnected microstructure formed via phase separation between the Ni catalyst and the resulting oxide support was observed to evolve via low-temperature thermal decomposition of RNi5. The resulting Ni/CeO2 nanocomposite exhibited superior catalytic activity of ∼25% at 400 °C for NH3 cracking. The high catalytic activity was attributed to the interlocking of Ni nanoparticles with the CeO2 framework. The growth of Ni nanoparticles was prevented by this interconnected microstructure, in which the Ni nanoparticles incorporated nitrogen owing to the size effect, whereas Ni does not commonly form nitrides. To the best of our knowledge, this is a unique example of a microstructure that enhances catalytic NH3 cracking.

Unique Conduction Band Minimum of Semiconductors Possessing a Zincblende-Type Framework.

Tetrahedral semiconductors such as Si adopt a diamond-type crystal structure with low packing density arising from open cavities in the crystallographic space. By taking LiAlGe as an example, we propose a zincblende-type framework as a platform for semiconductors possessing electroactive cavities. LiAlGe adopts a half-Heusler-type crystal structure including an ordered diamond-type sublattice (zincblende-type) (AlGe) and is an indirect semiconductor with a band gap of ∼0.1 eV. The conduction band minimum (CBM) is uniquely located at the cavity space surrounded by four cations (Al4) in real space. The bond ionicity and cation (Al) p orbitals located around the Fermi energy are requisite for the CBM to float in the cavity space. DFT calculations indicate the conversion of the semiconductor to a semimetallic electride under a pressure of ∼8 GPa, which is accompanied by band gap collapse due to electron transfer from valence band maximum to the cavity space. The high-pressure electride of LiAlGe formed under a very small critical pressure is derived from the presence of inherent crystallographic cavities having deep orbital levels energetically. This finding suggests the possible utilization of electroactive cavity spaces in tetrahedral semiconductors, which are widely used in modern electronic devices.

Superior catalytic performance of intermetallic CaPt2 nanoparticles supported on titanium group oxides in hydrogenation of ketones to alcohols.

Intermetallic CaPt2 nanoparticles, supported on titanium group oxides, were prepared using a molten salt method with CaH2 as both the reducing agent and the calcium source. The nanoparticles exhibited superior catalytic activity compared to a commercial Pt/C catalyst in the hydrogenation of ketones to alcohols, which could be promoted by electron-rich Pt sites in CaPt2.

Chemical route to prepare nickel supported on intermetallic Ti6Si7Ni16 nanoparticles catalyzing CO methanation.

In this study, ternary intermetallic nickel silicide, Ti6Si7Ni16, nanoparticles with a high surface area of 37.5 m2 g-1 were chemically prepared from SiO2-impregnated oxide precursors, which were reduced at as low as 600 °C by a CaH2 reducing agent in molten LiCl, resulting in the formation of single-phase Ti6Si7Ni16 with a nanosized morphology. The intermetallic Ti6Si7Ni16 phase in the nanoparticles was stabilized in air by surface passive oxide layers of TiOx-SiOy, which facilitated the handling of the nanoparticles. Considering our previous successful work of preparing single-phase LaNi2Si2 (39.3 m2 g-1) and YNi2Si2 (27.0 m2 g-1) nanoparticles in a similar manner, the proposed chemical method showed to be a versatile approach in preparing ternary silicide nanoparticles. In this study, we applied the obtained Ti6Si7Ni16 nanoparticles as catalyst supports in CO methanation. The supported nickel catalyst showed an activation energy of 56 kJ mol-1, which is half as low as that of common TiO2-supported nickel catalysts. Also, Ni/Ti6Si7Ni16 provided the lower activation energy more than any previous Ni-based catalyst. Since the measured work function of Ti6Si7Ni16 (4.5 eV) was lower than that of nickel (5.15 eV), it was suggested that the Ti6Si7Ni16 support can accelerate the rate-determining step of C-O bond dissociation in CO methanation due to its good electron donation capacity.

A View on Formation Gap in Transition Metal Hydrides and Its Collapse.

Late transition metals (LTMs) do not form hydrides under conventional experimental conditions except for palladium (Pd). The incorporation of a small amount of metal with low electronegativity converts LTMs into hydrogen (H) storage intermetallics (IMs) such as LaNi5. We examined the critical property of the H absorbing ability of LTMs and found that the lattice softness of Pd is a unique parameter for H insertion. This idea is applicable to H storage IMs. Indeed, negatively charged LTM ions, such as Niδ- in LaNi5, play a crucial role in hydrogenation. These ions cause lattice softening, which renders H solution possible. As a result, we propose that lattice softness can be an effective criterion for the development of new H storage IMs.

Origin of Metallic Nature of Na3N.

Among inorganic clathrates, the inner cavity space rarely affects the electronic structure of the framework. We report that the anti-ReO3-type compound Na3N has a metallic nature irrespective of the stoichiometric chemical composition of simple representative elements and that this unusual nature originates from the collapse of the bandgap owing to the presence of a crystallographic cavity. We synthesized Na3N by the plasma-assisted nitridation of alkali metals, and diffuse reflectance measurements indicated a metallic nature. The introduction of nitrogen into the Na metal induced the formation of both the Na+ ion and the crystallographic cavity. The former increased the density of the lattice of Na+ ions to form a wide Na 3s conduction band. The latter interacted with the Na 3s band to enhance the bandwidth, resulting in the collapse of the bandgap. Na3N is a unique nitride, which possesses an electronically active cavity space.

Twinning by Merohedry and Thermal Expansion of Zeolitic Clathrasil Deca-dodecasil 3R.

Rhombohedral crystal particles of zeolitic clathrasil deca-dodecasil 3R (DDR), hydrothermally synthesized from a mixture consisting of fumed silica, water, and 1-adamantanamine, were characterized by single-crystal and powder X-ray diffractometry as a function of temperature and pole figure analysis. The crystallite was bounded by six equivalent {101̅1} faces and exhibited twin-free appearance, whereas the structure was resolved with the binary twin by merohedry, defined by the twin point group 3̅2'/m'1, consisting of two twin domains with nearly equal volume fractions. This twinning modifies the positions of O atoms in the Si-O-Si framework while preserving the positions of Si atoms that define the topology of polyhedral cages. This type of twinning therefore does not disrupt the microporous channels via the 8-membered rings of the 19-hedral cages and little disturbs the adsorption and permeation of gas molecules in DDR. The cell volume of DDR increased monotonically with an increase in temperature up to ∼673 K accompanied by an elongation perpendicular to the [0001] axis and a shrinkage along the [0001] axis. Above ∼673 K, the cell volume decreased with temperature. These positive and negative volume expansion coefficients observed in this study were roughly one-half and one-third of the values currently available.

On the Origin of the Negative Thermal Expansion Behavior of YCu.

Among the intermetallics and alloys, YCu is an unusual material because it displays negative thermal expansion without spin ordering. The mechanism behind this behavior that is caused by the structural phase transition of YCu has yet to be fully understood. To gain insight into this mechanism, we experimentally examined the crystal structure of the low-temperature phase of YCu and discuss the origin of the phase transition with the aid of thermodynamics calculations. The result shows that the high-temperature (cubic CsCl-type) to low-temperature (orthorhombic FeB-type) structural phase transition is driven by the rearrangement of three covalent bonds, namely, Y-Cu, Y-Y, and Cu-Cu, which compete for the bonding energy and phonon entropy. At low temperatures, the mixing of Y and Cu does not take place easily because of the weak attractive force between these atoms expected from the small negative mixing enthalpy. This causes all three interactions to take part in the bonding, and Y and Cu are segregated to form an FeB-type structure, which is stabilized by internal energy. At higher temperatures, Cu ions are bound loosely with Y ions due to the large Y-Cu distance (3.01 Å), which results in large vibration entropy and stabilizes a CsCl-type crystal structure. In addition, the CsCl-type structure is reinforced by the Y-Y interaction between next-nearest neighbors, resulting in a smaller unit cell volume. The crystal structure has the simple cubic framework of Y containing Cu ions bound loosely at the cavity sites. The calculated frequency of the Y-like phonon modes is much higher than that of the Cu-like modes, indicating the presence of Y-Y covalent interactions in the CsCl-type phase.

Implementation and Evaluation of a Wide-Range Human-Sensing System Based on Cooperating Multiple Range Image Sensors.

A museum is an important place for science education for children. The learning method in the museum is reading exhibits and explanations. Museums are investing efforts to quantify interests using questionnaires and sensors to improve their exhibitions and explanations. Therefore, even in places where many people gather, such as in museums, it is necessary to quantify people's interest by sensing behavior of multiple people. However, this has not yet been realized. We aim to quantify the interest by sensing a wide range of human behavior for multiple people by coordinating multiple noncontact sensors. When coordinating multiple sensors, the coordinates and the time of each sensor differ. To solve these problems, coordinates were transformed using a simultaneous transformation matrix and time synchronization was performed using unified time. The effectiveness of this proposal was verified through experimental evaluation. Furthermore, we evaluated the actual museum content. In this paper, we describe the proposed method and the results of the evaluation experiment.

Zeolitic Intermetallics: LnNiSi (Ln = La-Nd).

LnNiSi (Ln = La-Nd) comprising a three-dimensional NiSi framework has electrons in the crystallographic cavity space. In the temperature region 473-773 K, it accepts the insertion/de-insertion of hydrogen topotactically without a change in unitcell volume. The insertion of hydrogens into the cavity space is accompanied by a redox reaction with the orbitals of atoms constituting the cavity wall. Having small work functions, such intermetallic electrides exhibit metallic electrical and magnetic properties. Owing to a high electron-donating power and reversible exchange between hydrogen and the electrons, Ru5wt%-loaded LaNiSi powder worked as an efficient catalyst for ammonia synthesis under ambient pressure.

Transformation of the Chromium Coordination Environment in LaCrAsO Induced by Hydride Doping: Formation of La2Cr2As2OyHx.

We report the synthesis of La2Cr2As2OyHx (0.1 < y < 1.6) oxyhydride solid solutions using a solid-state reaction under high pressure with a solid-state hydrogen source and exhibit an example of how H- doping can also promote structural changes: H- doping in LaCrAsO results in the formation of La2Cr2As2OyHx with the La2Fe2Se2O3-type layered structure. Remarkably, this transformation includes a change of the coordination number of Cr from 4 to 6, with the some of the H- being accommodated in new sites within the CrAs layers. In this way, H- not only serves as a conventional electron dopant by the substitution of O2- but also makes new bonds to the transition metals.

Cubic Fluorite-Type CaH2 with a Small Bandgap.

A cubic variant of CaH2 adopting a fluorite-type crystal structure was synthesized by cationic substitution with La or Y, yielding the first alkaline earth hydride-based with fluorite-type framework. The material has a bandgap of ∼2.5 eV (greenish yellow in color), which is much smaller than that of orthorhombic PbCl2-type CaH2 (4.4 eV) and is, in fact, the smallest among alkaline or alkaline earth metal hydrides reported to date. Analysis of the density functional theory band structure of cubic-CaH2 indicates that its conduction band minimum is formed mainly by the interaction between the Ca 3d eg orbitals around the crystallographic cavity defined by cubes of H- ions. The use of such cavities in the creation of low-lying conduction band minima by semiconductors is extremely rare, and has similarities to inorganic electrides.

The Unique Electronic Structure of Mg2 Si: Shaping the Conduction Bands of Semiconductors with Multicenter Bonding.

The electronic structures of the antifluorite-type compound Mg2 Si is described in which a sublattice of short cation-cation contacts creates a very low conduction band minimum. Since Mg2 Si shows n-type conductivity without intentional carrier doping, the present result indicates that the cage defined by the cations plays critical roles in carrier transport similar to those of inorganic electrides, such as 12 CaO⋅7 Al2 O3 :e- and Ca2 N. A distinct difference in the location of conduction band minimum between Mg2 Si and the isostructural phase Na2 S is explained in terms of factors such as the differing interaction strengths of the Si/S 3s orbitals with the cation levels, with the more core-like character of the S 3s leading to a relatively low conduction band energy at the Γ point. Based on these results and previous research on electrides, approaches can be devised to control the energy levels of cation sublattices in semiconductors.

Hydride-Based Electride Material, LnH2 (Ln = La, Ce, or Y).

In view of the strong electron-donating nature of H(-) and extensive vacancy formation in metals by hydrogen insertion, a series of LnH2+x (Ln = La, Ce, or Y) compounds with fluorite-type structures were verified to be the first hydride-based electride, where itinerant electrons populating the cage are surrounded by H(-) anions. The electron transfer into the cage probably originates from Ln-cage covalent interaction. To the best of our knowledge, anion-rich electrides are extremely rare, and a key requirement for their formation is that the cage site is not occupied by lone pair electrons of the adjacent ions. In the case of LnH2, the cage site is surrounded by eight H(-) anions with isotopic electronic character caused by the lack of mixing of H p-orbital character. Notably, Ru-loaded LnH2+x electride powders synthesized by hydrogen embrittlement (Ln = La or Ce) were found to work as efficient catalysts for ammonia synthesis at ambient pressure, without showing serious signs of hydrogen poisoning. There are several possible origins of the observed high catalytic activity in the hydride promotors: the small work function of LnH2+x derived from the covalent interaction between Ln cation and the H(-) σ donor, and the formation of Ln nitride during catalytic reaction.

Six-axis orthodontic force and moment sensing system for dentist technique training.

The purpose of this study is to develop a sensing system device that measures three-axis orthodontic forces and three-axis orthodontic moments for dentist training. The developed sensing system is composed of six-axis force sensors, action sticks, sliders, and tooth models. The developed system also simulates various types of tooth row shape patterns in orthodontic operations, and measures a 14 × 6 axis orthodontic force and moment from tooth models simultaneously. The average force and moment error per loaded axis were 2.06 % and 2.00 %, respectively.

Dental plaque assessment lifelogging system using commercial camera for oral healthcare.

We present a system for estimating the dental plaque adhesion area using a commercial camera image for oral healthcare via management of the intraoral environment. In recent years, several studies have reported on the relationship between a general disease and a periodontal disease. Such studies mention that normalization of the intraoral environment by tooth brushing is the most important treatment in preventive dentistry. However, evaluation of individual tooth brushing skill is difficult. Some devices for automatically measuring the quantity of dental plaque have already been proposed for the teaching tool of tooth brushing. However, these devices have certain limitations, such as large size, requirement to fix the head position, and limited applicability in daily life. In this study, we propose a method for calculating the dental plaque adhesion area using a commercial camera and an intraoral camera. We also propose an evaluation method for the quantity of adhered dental plaque for replacing the Plaque Control Record (PCR). The relationship between PCR of the front teeth and that of all teeth was investigated by using the proposed method. The experimental results show that the proposed method can estimate the PCR of all teeth from the information of the front tooth. This method is not dependent on a particular camera system, and is applicable with many types of cameras, including smartphones. Therefore, it will be a useful tool in daily use for routine and sustainable management of the intraoral environment.

Measurement of the passive stiffness of ankle joint in 3 DOF using stewart platform type ankle foot device.

This paper presents a method to measure the passive stiffness of an ankle joint in three degrees of freedom (DOF) under two motion speeds (1 Hz and 5 degree/s) using a developed Stewart platform-type device. The developed device can reproduce input motions of the foot in 6 DOF by controlling six pneumatic linear motion actuators. We used the device to measure the passive stiffness of an ankle joint undergoing three kinds of motion, namely dorsi-plantar flexion, inversion-eversion, and adduction-abduction. The measured values of the passive stiffness of the ankle joint in dorsiflexion that we obtained agreed well with that obtained in a previous study, indicating that the developed device is useful for measuring the passive stiffness of ankle joint. In addition, the developed device can be used to measure the stiffness in inversion-eversion and adduction-abduction motions as well, parameters that have never been measured. The results we obtained demonstrated certain interesting features as we varied both the direction and pace of motion (e.g., there were significant differences in the stiffness not only between adduction and abduction during the faster pace, but also between these and the other motions).

Support system for pathologists and researchers.

AIMS: In Japan, cancer is the most prevalent cause of death; the number of patients suffering from cancer is increasing. Hence, there is an increased burden on pathologists to make diagnoses. To reduce pathologists' burden, researchers have developed methods of auto-pathological diagnosis. However, virtual slides, which are created when glass slides are digitally scanned, saved in a unique format, and it is difficult for researchers to work on the virtual slides for developing their own image processing method. This paper presents the support system for pathologists and researchers who use auto-pathological diagnosis (P-SSD). Main purpose of P-SSD was to support both of pathologists and researchers. P-SSD consists of several sub-functions that make it easy not only for pathologists to screen pathological images, double-check their diagnoses, and reduce unimportant image data but also for researchers to develop and apply their original image-processing techniques to pathological images. METHODS: We originally developed P-SSD to support both pathologists and researchers developing auto-pathological diagnoses systems. Current version of P-SSD consists of five main functions as follows: (i) Loading virtual slides, (ii) making a supervised database, (iii) learning image features, (iv) detecting cancerous areas, (v) displaying results of detection. RESULTS: P-SSD reduces computer memory size random access memory utilization and the processing time required to divide the virtual slides into the smaller-size images compared with other similar software. The maximum observed reduction in computer memory size and reduction in processing time is 97% and 99.94%, respectively. CONCLUSIONS: Unlike other vendor-developed software, P-SSD has interoperability and is capable of handling virtual slides in several formats. Therefore, P-SSD can support both of pathologists and researchers, and has many potential applications in both pathological diagnosis and research area.

Evaluation of venous return in lower limb by passive ankle exercise performed by PHARAD.

This paper presents evaluation of venous return, i.e., blood flow volume of vein (BF), in the lower limb after passive exercise performed by our developed "parallel link type human ankle rehabilitation assistive device (PHARAD)". The PHARAD can perform complex passive exercises (plantar flexion/dorsiflexion, inversion/eversion, adduction/abduction, and combination of these motions) by reproducing input motions of a foot plate that is attached to a sole of foot. The passive exercise can be performed for not only rehabilitation but also prevention of deep vein thrombosis (DVT). In this study, we measured the concentration of Total hemoglobin (Total-Hb) using multi-channel near infra-red spectroscopy (NIRS)-based tissue oximeters and calculated a gradient of Total-Hb during a venous occlusion. We defined the gradient as BF and evaluated BF after 3 min passive exercise performed by the PHARAD comparing to BF of resting. Seven healthy young adult people were recruited for the experiment and we assessed passive exercise, active exercise, and walking. Experimental results show that BF after the passive exercises significantly increases compare to BF of resting and this indicates that passive exercises performed by the PHARAD increases BF and has a potential to prevent DVT.