Dynamic in situ observation of automotive catalysts for emission control using X-ray absorption fine structure

Two main pivotal subjects of research in automotive catalysts were studied by modern X-ray absorption analysis techniques. One is oxygen storage/release behaviour, and the other is sintering inhibition of Pt particles. First, three types of CeO₂–ZrO₂ (Ce:Zr = 1:1 molar ratio) compounds with different oxygen storage/release capacities and different structural properties were prepared, and the valence change of Ce as a function of temperature during oxygen release/storage processes was investigated. The reduction of surface Ce mainly occurred in the range 100–170 °C, and the reduction of bulk Ce progressed at high temperatures of 170 °C and above. The Ce reduction behaviour depended not only on the homogeneity of the Ce and Zr for bulk reduction at high temperatures but also on the particle size of the CeO₂–ZrO₂ samples for surface reduction at low temperatures. Secondly, sintering inhibition of Pt in Pt/Al₂O₃, Pt/MgO and Pt/ceria-based catalysts after 800 °C ageing in air was studied. We found that the Pt–O–M (M = Mg, Ce) bond acted as an anchor and inhibited the sintering of Pt particles on MgO or ceria-based oxide. Especially, it was noteworthy that the Pt–O–Ce⁴⁺ bond on the ceria-based support breaks easily through the reduction of Ce (Ce⁴⁺ → Ce³⁺) during the usual stoichiometric and reducing conditions.     

Control of biped walking robot for human living environment

This paper introduces biped robot adaptation to human living environment from viewpoints of battery operation time extension and environmental recognition. These issues are important when robots actually work at home. First, in order to extend battery operation time, we propose energy-saving bipedal locomotion gait. The problem is formulated as an optimal control problem, which is conventionally hard to solve when a target system is complicated. In this paper, partial derivatives appeared in optimal control problem are implicitly represented by using automatic differentiation technique. This approach enables complicated optimal control problem solvable. In combination with receding horizon control, its computation cost is also reduced. Second, we introduce the biped walk tracking based on the camera image mounted on the walking robot, and the visual servoing by the posture change for the purpose of the target image tracking in the camera frame. We propose a new control law to track the rotated target object using the characteristic of the walking, which considered the interference between translational motion and rotational motion. The decoupling is realized by simulations and experiments. As a result, the walking robot tracked the translated and rotated target object without a practical issue. Copyright © 2009 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Nanocube Superlattices of Cesium Lead Bromide Perovskites and Pressure‐Induced Phase Transformations at Atomic and Mesoscale Levels

Lead halide perovskites are promising materials for a range of applications owing to their unique crystal structure and optoelectronic properties. Understanding the relationship between the atomic/mesostructures and the associated properties of perovskite materials is crucial to their application performances. Herein, the detailed pressure processing of CsPbBr₃ perovskite nanocube superlattices (NC‐SLs) is reported for the first time. By using in situ synchrotron‐based small/wide angle X‐ray scattering and photoluminescence (PL) probes, the NC‐SL structural transformations are correlated at both atomic and mesoscale levels with the band‐gap evolution through a pressure cycle of 0 ? 17.5 GPa. After the pressurization, the individual CsPbBr₃ NCs fuse into 2D nanoplatelets (NPLs) with a uniform thickness. The pressure‐synthesized perovskite NPLs exhibit a single cubic crystal structure, a 1.6‐fold enhanced photoluminescence quantum yield, and a longer emission lifetime than the starting NCs. This study demonstrates that pressure processing can serve as a novel approach for the rapid conversion of lead halide perovskites into structures with enhanced properties.     

Preparation of Cu(In,Ga)(S,Se)2 thin films by sequential evaporation and annealing in sulfur atmosphere

Cu(In,Ga)(S,Se)₂ thin films with high Ga/III ratio (around 0.8) were prepared by sequential evaporation from CuGaSe₂, CuInSe₂, In₂Se₃ and Ga₂Se₃ compounds and then annealing in H₂S gas atmosphere. The annealing temperature was varied from 400 to 500 °C. These samples were characterized by means of XRF, EPMA, XRD and SEM. The S/(S+Se) mole ratio in the thin films increased with increase in the annealing temperature, keeping the Cu, In and Ga contents nearly constant. The open circuit voltage increased and the short circuit current density decreased with increase in the annealing temperature. The best solar cell using Cu(In,Ga)(S,Se)₂ thin film with Ga/(In+Ga)=0.79 and S/(S+Se)=0.11 annealed at 400 °C demonstrated V_oc=535 mV, I_sc=13.3 mA/cm², FF=0.61 and efficiency=4.34% without AR-coating.     

Preparation of Carbon-Doped TiO2 Nanopowder Synthesized by Droplet Injection of Solution Precursor in a DC-RF Hybrid Plasma Flow System

Carbon-doped titanium dioxide nanopowder has received much attention because of its higher photocatalytic performance, which is practically activated not only by UV, but also by visible light irradiation. In the present study, C-TiO₂ nanopowder was synthesized by droplet injection of solution precursor in a DC-RF hybrid plasma flow system, resulting in higher photocatalytic performance even under visible light irradiation. In-flight C-TiO₂ nanoparticles reacted with the high concentration of carbon in plasma flow and were then deposited on the surfaces of two quartz tubes in the upstream and downstream regions of this system. The collected C-TiO₂ nanopowder contained anatase-rutile mixed-phase TiO₂ and TiC, the contents of which depended on the location of the powder collection, the temperature, and the duration of plasma treatment. Highly functional C-TiO₂ nanopowder collected in the downstream region exhibited a higher degradation rate of methylene blue than that of single-phase anatase TiO₂, even under visible light irradiation, in spite of being TiC.     

Synthesis of Polypeptide-Polyether Conjugates from an Activated Urethane Derivative of γ-Benzyl-L-glutamate as a Monomer

N-(4-Nitrophenoxycarbonyl)-γ-benzyl-L-glutamate (1) was heated at 60 °C in N,N-dimethylacetoamide (DMAc) in the presence of p-(tert-butyl)phenylmethylamine (2) to afford poly(γ-benzyl-L-glutamate) in high yield. ¹H NMR analysis of the obtained polymer revealed that the p-(tert-butyl)phenylmethyl group was successfully introduced into the polymer chain end. Under the same conditions, polycondensations of 1 in the presence of poly(ethylene glycol)s having amino terminals were performed. Both of the components were consumed quantitatively to afford the corresponding block copolymers having poly(γ-benzyl-L-glutamate) and poly(ethylene glycol) segments. The molecular weights of the copolymers were controlled by the feed ratio [1]₀/[amino group in the macroinitiator]₀. Electronic Supplementary Material  The online version of this article at contains supplementary material, which is available to authorized users.     

Simplified protocol for detection of protein-ligand interactions via surface-enhanced resonance Raman scattering and surface-enhanced fluorescence

A simple and effective protocol for detections of protein-protein and protein-small molecule interactions has been developed. After interactions between proteins and their corresponding ligands, we employed colloidal silver staining for producing active substrates for surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). Tetramethylrhodamine isothiocyanate (TRITC) and Atto610 were used for both Raman and fluorescent probes. We detected interactions between human IgG and TRITC-anti-human IgG, and those between avidin and Atto610-biotin by surface-enhanced resonance Raman scattering (SERRS) and SEF. The detection limits of the proposed SERRS-based method are comparable to those of the proposed SEF-based one, 0.9 pg/mL for anti-human IgG and 0.1 pg/mL for biotin. This protocol exploits several advantages of simplicity over other SERS and SEF-based related methods because of the protein staining-based strategy for silver nanoparticle assembling, high sensitivity from SERRS and SEF, and high stability in photostability comparing to fluorescence-based protein detections. Therefore, the proposed method for detection of protein-ligand interactions has great potential in high-sensitivity and high-throughput chip-based protein function determination.     

pH-dependent network formation of quantum dots and fluorescent quenching by Au nanoparticle embedding

A simple approach to the creation of colloidal assemblies is in high demand for the development of functional devices. Here, we present the preparation of CdTe-QD (quantum dot) networks in as little as 1 day simply by pH modification without the use of oxidants. The QD network was tractable in water and casting from a droplet produced a porous networked film on both hydrophobic and hydrophilic solid substrates. Further, we found that citrate-protected gold nanoparticles (AuNPs, d = 5 nm) could be incorporated into the QD networks to afford a QD/Au composite network, and that the fluorescence from the QDs was largely decreased by the addition of a small proportion of AuNPs (QD:AuNP = 99.4:0.6), probably due to the efficient charge transfer through the network. These data indicate that our method is suitable for application to the creation of metal/QD hybrid materials that can be integrated into wet-based processes.