Reticular Imine-linked Coordination Polymers Based on Paddlewheel Diruthenium/Dirhodium Nodes: Synthesis and Metal-site Dependent Photocatalytic Reduction of CO2.

The paddlewheel-type dimetal core ([M2]) is a ubiquitous motif in the nodes in coordination polymers (CPs) and metal-organic frameworks (MOFs). However, their preparation has relied on ligand-substitution-labile metal ions owing to challenges associated with crystallization. Consequently, examples featuring ligand-substitution-inert metal ions, such as Ru or Rh, are scarce. This study presents the synthesis of novel reticular imine-linked CPs incorporating the paddlewheel-type diruthenium(II, II) ([Ru2II,II]; 1-Ru) or dirhodium(II, II) ([Rh2II,II]; 1-Rh) subunits. The synthetic approach involved a Schiff base dehydration condensation reaction between p-formylbenzoate-bridged [Ru2II,II] or [Rh2II,II] precursors (i.e., CHO-Ru and CHO-Rh, respectively) and 2,5-dimethyl-1,4-phenylenediamine in a 1:2 ratio. The catalytic activities of 1-Ru and 1-Rh for the photochemical reduction of CO2 in a heterogeneous system depended on the metal site. The 1-Rusystem exhibited exceptional selectivity, generating 3.0 ´ 104 mmol g-1 of CO after 24 h of irradiation, whereas the 1-Rhsystem generated a lower amount of CO (3.2 ´ 103 mmol g-1). The catalytic activity of 1-Ru ranked with that of all relevant catalytic systems. This study paves the way for the exploration of [Ru2II,II]- or [Rh2II,II]-based polymers with open metal site-dependent functional properties.

Microstructures and Interface Magnetic Moments in Mn2VAl/Fe Layered Films Showing Exchange Bias.

Heusler alloys are a material class exhibiting various magnetic properties, including antiferromagnetism. A typical application of antiferromagnets is exchange bias that is a shift of the magnetization curve observed in a layered structure consisting of antiferromagnetic and ferromagnetic films. In this study, a layered sample consisting of a Heusler alloy, Mn2VAl and a ferromagnet, Fe, is selected as a material system exhibiting exchange bias. Although the fully ordered Mn2VAl is known as a ferrimagnet, with an optimum fabrication condition for the Mn2VAl layer, the Mn2VAl/Fe layered structure exhibits exchange bias. The appearance of the antiferromagnetic property in the Mn2VAl is remarkable; however, the details have been unclear. To clarify the microscopic aspects on the crystal structures and magnetic moments around the Mn2VAl/Fe interface, cross-sectional scanning transmission electron microscope (STEM) observation, and synchrotron soft X-ray magnetic circular dichroism (XMCD) measurements were employed. The high-angle annular dark-field STEM images demonstrated clusters of Mn2VAl with the L21 phase distributed only around the interface to the Fe layer in the sample showing the exchange bias. Furthermore, antiferromagnetic coupling between the Mn- and Fe-moments were observed in element-specific hysteresis loops measured using the XMCD. The locally ordered L21 phase and antiferromagnetic Mn-moments in the Mn2VAl were suggested as important factors for the exchange bias.

Beating Thermal Coarsening in Nanoporous Materials via High-Entropy Design.

Controlling the feature sizes of 3D bicontinuous nanoporous (3DNP) materials is essential for their advanced applications in catalysis, sensing, energy systems, etc., requiring high specific surface area. However, the intrinsic coarsening of nanoporous materials naturally reduces their surface energy leading to the deterioration of physical properties over time, even at ambient temperatures. A novel 3DNP material beating the universal relationship of thermal coarsening is reported via high-entropy alloy (HEA) design. In newly developed TiVNbMoTa 3DNP HEAs, the nanoporous structure is constructed by very fine nanoscale ligaments of a solid-solution phase due to enhanced phase stability by maximizing the configuration entropy and suppressed surface diffusion. The smallest size of 3DNP HEA synthesized at 873 K is about 10 nm, which is one order of magnitude smaller than that of conventional porous materials. More importantly, the yield strength of ligament in 3DNP HEA approaches its theoretical strength of G/2π of the corresponding HEA alloy even after thermal exposure. This finding signifies the key benefit of high-entropy design in nanoporous materials-exceptional stability of size-related physical properties. This high-entropy strategy should thus open new opportunities for developing ultrastable nanomaterials against its environment.

Evaluation of spatial and temporal resolution on in situ annealing aberration-corrected transmission electron microscopy with proportional-integral-differential controller.

The in situ annealing observation in transmission electron microscope (TEM) is one of the effective methods for imaging thermally induced microstructural changes. For applying this dynamical characterization to bulk samples fabricated by ion-milling, electro-polishing or focused ion beam (FIB) mill, it is generally needed to use a heating-pot type system. We here report an initial trial to improve the spatial and temporal resolution during the in-situ annealing observation of bulk samples using a spherical aberration corrected (AC) TEM with a new thermal control unit. The information limit of 1.5 Å and the point resolution of 2.0 Å are achieved under isothermal annealing at 350°C, which is the same resolution at room temperature, and it is affected strongly of sample drift by the temperature variation. The sample is heated at a heating rate of +1.0°C/s, the drift distance observed by a TV readout speed CCD camera is less than 2.0 Å/s.

Atomic and nanoscale imaging of a cellulose nanofiber and Pd nanoparticles composite using lower-voltage high-resolution TEM.

We have examined the advanced application of transmission electron microscopy (TEM) for the structural characterization of a composite of cellulose nanofiber (CNF) and palladium (Pd) nanoparticles. In the present study, we focused on electron-irradiation damage and optimization of high-resolution TEM imaging of the composite. The investigation indicates that the CNF breaks even under low-electron-dose conditions at an acceleration voltage of 200 kV. We then applied lower-voltage TEM at 60 kV using a spherical aberration corrector and a monochromator, in order to reduce electron-irradiation damage and improve the spatial resolution. The TEM observation achieved high-resolution imaging and revealed the existence of small Pd nanoparticles, around 2 nm in diameter, supported on the CNF. It is considered that the use of a monochromator in combination with spherical aberration correction contributed to the atomic and nanoscale imaging of the composite, owing to the improvement of the information limit under a lower-acceleration voltage.

The demonstration of significant ferroelectricity in epitaxial Y-doped HfO2 film.

Ferroelectricity and Curie temperature are demonstrated for epitaxial Y-doped HfO2 film grown on (110) yttrium oxide-stabilized zirconium oxide (YSZ) single crystal using Sn-doped In2O3 (ITO) as bottom electrodes. The XRD measurements for epitaxial film enabled us to investigate its detailed crystal structure including orientations of the film. The ferroelectricity was confirmed by electric displacement filed - electric filed hysteresis measurement, which revealed saturated polarization of 16 µC/cm(2). Estimated spontaneous polarization based on the obtained saturation polarization and the crystal structure analysis was 45 µC/cm(2). This value is the first experimental estimations of the spontaneous polarization and is in good agreement with the theoretical value from first principle calculation. Curie temperature was also estimated to be about 450 °C. This study strongly suggests that the HfO2-based materials are promising for various ferroelectric applications because of their comparable ferroelectric properties including polarization and Curie temperature to conventional ferroelectric materials together with the reported excellent scalability in thickness and compatibility with practical manufacturing processes.

Thermally stable dielectric responses in uniaxially (001)-oriented CaBi4Ti4O15 nanofilms grown on a Ca2Nb3O10- nanosheet seed layer.

To realize a high-temperature capacitor, uniaxially (001)-oriented CaBi4Ti4O15 films with various film thicknesses were prepared on (100)cSrRuO3/Ca2Nb3O10(-) nanosheet/glass substrates. As the film thickness decreases to 50 nm, the out-of-plane lattice parameters decrease while the in-plane lattice ones increase due to the in-plane tensile strain. However, the relative dielectric constant (εr) at room temperature exhibits a negligible degradation as the film thickness decreases to 50 nm, suggesting that εr of (001)-oriented CaBi4Ti4O15 is less sensitive to the residual strain. The capacitance density increases monotonously with decreasing film thickness, reaching a value of 4.5 µF/cm(2) for a 50-nm-thick nanofilm, and is stable against temperature changes from room temperature to 400 °C irrespective of film thickness. This behaviour differs from that of the widely investigated perovskite-structured dielectrics. These results show that (001)-oriented CaBi4Ti4O15 films derived using Ca2Nb3O10(-) nanosheets as seed layers can be made candidates for high-temperature capacitor applications by a small change in the dielectric properties against film thickness and temperature variations.

Three-Dimensional Imaging of Dislocations in a Ti-35mass%Nb Alloy by Electron Tomography.

We have studied three-dimensional (3D) configurations of dislocations in the ß phase of a Ti-35mass%Nb alloy by means of single-axis tilt tomography using bright-field scanning transmission electron microscopy (BF-STEM). To visualize dislocations, the hh0 systematic reflections were excited throughout tilt-series acquisition with the maximum tilt angle of 70°. Dislocations in the ß grains were clearly reconstructed by the weighted back-projection algorithm. The slip planes of the dislocations were deduced by rotating the reconstructed volumes with the aid of selected area electron diffraction patterns. It was found that BF-STEM images with relatively low contrasts, taken along low-order zone axes, are capable to reproduce and preserve the quality of reconstructed image of dislocations. We also found that tilt angles as low as 40° are practically acceptable to visualize 3D configurations of dislocations, while there exists limitation in resolution due to the existence of a large missing wedge.

Polymers of 2-methacryloyloxyethyl phosphorylcholine truly work as cell membrane mimic?

We have prepared several types of polymers derived from 2-methacryloyloxyethyl phosphorylcholine (MPC) to evaluate whether polymers of MPC work as cell membrane mimic or not. We firstly applied capturing test of target proteins of 4-carboxybenzenesulfonamide (Sul) or ibuprofen (Ibu) as a probe. As the results, the rather hydrophilic polymers based on MPC were able to suppress non-specific binding proteins as expected. Additionally, some of the MPC based polymeric surface was able to capture greater amount of carbonic anhydrase II than those of other polymers, when Sul was utilized as probe. In contrary, all the polymers having PC groups and Ibu probe were unable to capture Cyclooxygenase-1 (COX-1), its target protein. These results suggested that the position of PC groups realized hydrophilic polymer surface, while MPC based polymer was not able to supply the suitable environment for COX-1 to interact with Ibu.

Diffraction contrast analysis of 90° and 180° ferroelectric domain structures of PbTiO3 thin films.

The ferroelectric domain structure of a PbTiO3 thin film on (100) SrTiO3 has been investigated by transmission electron microscopy (TEM). Two types of a-domain were found: one extended through the film to the surface and another comprised small a-domains confined within the film. Dark-field TEM (DFTEM) observation revealed that 180° domains formed near the substrate and stopped their growth 100 nm away from the substrate. The DFTEM observation also revealed that 90° domain boundaries had head-to-tail structures. To confirm the polarization direction obtained by experiments, diffracted intensities under a two-beam condition were simulated using the extended Darwin-Howie-Whelan equations. On the basis of the obtained results, a ferroelectric domain structure model of PbTiO3 thin films on SrTiO3 is proposed.

Configuration and local elastic interaction of ferroelectric domains and misfit dislocation in PbTiO3/SrTiO3 epitaxial thin films.

We have studied the strain field around the 90° domains and misfit dislocations in PbTiO3/SrTiO3 (001) epitaxial thin films, at the nanoscale, using the geometric phase analysis (GPA) combined with high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark field--scanning transmission electron microscopy (HAADF-STEM). The films typically contain a combination of a/c-mixed domains and misfit dislocations. The PbTiO3 layer was composed from the two types of the a-domain (90° domain): a typical a/c-mixed domain configuration where a-domains are 20-30 nm wide and nano sized domains with a width of about 3 nm. In the latter case, the nano sized a-domain does not contact the film/substrate interface; it remains far from the interface and stems from the misfit dislocation. Strain maps obtained from the GPA of HRTEM images show the elastic interaction between the a-domain and the dislocations. The normal strain field and lattice rotation match each other between them. Strain maps reveal that the a-domain nucleation takes place at the misfit dislocation. The lattice rotation around the misfit dislocation triggers the nucleation of the a-domain; the normal strains around the misfit dislocation relax the residual strain in a-domain; then, the a-domain growth takes place, accompanying the introduction of the additional dislocation perpendicular to the misfit dislocation and the dissociation of the dislocations into two pairs of partial dislocations with an APB, which is the bottom boundary of the a-domain. The novel mechanism of the nucleation and growth of 90° domain in PbTiO3/SrTiO3 epitaxial system has been proposed based on above the results.

Direct observation of a surface induced disordering process in magnetic nanoparticles.

We present experimental evidence of surface induced disordering at magnetic FeCoPd nanoparticles during the L1(0)-A1 phase transition using high-resolution aberration-corrected electron microscopy and strain mapping. In situ electron diffraction studies show a narrow temperature range of fully ordered L1(0) structure. The order-disorder transition is size dependent and induces strong lattice deformation in outer part of the nanocrystals. The formation of unusually large strain of 20% is discussed in terms of core-shell structure formation with surface disordered layer and ordered core.

HAADF-STEM study on the early stage of precipitation in aged Al-Ag alloys.

We report on the structure of Ag precipitates in aged Al-Ag alloys using transmission electron microscopy and high-angle annular detector darkfield scanning transmission electron microscopy (HAADF-STEM). Irregularly shaped small Ag particles of 1-2 nm dominate the alloy annealed at 140 degrees C for 10 h. These particles are present also within large precipitates (10-50 nm), which are often characterized by their {100} and {110} facets. In addition, atomic-resolution HAADF-STEM images revealed that Ag atoms tend to form {111} planar clusters, which criss-cross a colony of the irregularly shaped small Ag precipitates.