Molecular Characteristics of Catalytic Nitrogen Removal from Coal Tar Pitch over γ-Alumina-Supported NiMo and CoMo Catalysts.

The removal of nitrogen from coal tar pitch (CTP) through the hydrodenitrogenation (HDN) of CTP and its molecular behavior were evaluated in the presence of NiMo/γ-alumina and CoMo/γ-alumina catalysts. Fourier transform ion cyclotron resonance mass spectrometry with atmospheric pressure photoionization was used to analyze the complicated chemical classes and species of CTP and the treated products at the molecular level. Nitrogen species were qualitatively analyzed before and after hydrotreatment. A single-stage hydrotreatment with an HDN catalyst resulted in a high sulfur removal performance (85.6-94.7%) but a low nitrogen removal performance (26.8-29.2%). Based on relative abundance analyses of nitrogen and binary nitrogen species, CcHh-NnSs was the most challenging species to remove during HDN treatment. Furthermore, prior hydrodesulfurization was combined with HDN treatment, and the dual hydrotreatments yielded a significantly improved nitrogen removal performance (46.4-48.7%).

Hydrogel Ionic Diodes toward Harvesting Ultralow-Frequency Mechanical Energy.

Energy harvesting from human motion is regarded as a promising protocol for powering portable electronics, biomedical devices, and smart objects of the Internet of things. However, state-of-the-art mechanical-energy-harvesting devices generally operate at frequencies (>10 Hz) well beyond human activity frequencies. Here, a hydrogel ionic diode formed by the layered structures of anionic and cationic ionomers in hydrogels is presented. As confirmed by finite element analysis, the underlying mechanism of the hydrogel ionic diode involves the formation of the depletion region by mobile cations and anions and the subsequent increase of the built-in potential across the depletion region in response to mechanical pressure. Owing to the enhanced ionic rectification ratio by the embedded carbon nanotube and silver nanowire electrodes, the hydrogel ionic diode exhibits a power density of ≈5 mW cm-2 and a charge density of ≈4 mC cm-2 at 0.01 Hz, outperforming the current energy-harvesting devices by several orders of magnitude. The applications of the self-powered hydrogel ionic diode to tactile sensing, pressure imaging, and touchpads are demonstrated, with sensing limitation is as low as 0.01 kPa. This work is expected to open up new opportunities for ionic-current-based ionotronics in electronics and energy devices.

A vacancy-driven phase transition in MoX2 (X: S, Se and Te) nanoscrolls.

Atomically thin MoX2 (MoS2, MoSe2 and MoTe2) exhibits semiconducting, metallic, and semi-metallic properties associated with different polymorphic phases such as 2H, 1T and distorted 1T (1T'), respectively. The phase transitions from 2H to 1T for TMDs have been reported, but the mechanism for the formation and fraction control of 1T and 1T' phases in phase transition processes has never been reported because the 1T and 1T' phases are very unstable even at room temperature. To solve the problem of the thermal instability in the 1T and 1T' phases and investigate the mechanism, we design and synthesize nanoscrolls of MoX2 which have two key attributes, bending strain for phase transition and van der Waals forces as the self-stabilizing energy for thermal stability at high temperature and then investigate the mechanism of phase transition in the synthesized nanoscrolls by an increase in temperature. It turns out that the phase transition of the 2H to the 1T phase is driven by the transition metal Mo vacancy in the XY plane and that of the 1T to the 1T' phase is induced by the chalcogen X vacancy in the Z plane. In addition, each phase itself and fractions of the 2H, 1T and 1T' phases in nanoscrolls can be freely controlled by inducing vacancies of transition metal and chalcogen with increasing temperature.

Fast Hydrolysis Polyesters with a Rigid Cyclic Diol from Camphor.

2,2:3,3-Bis(4'-hydroxymethylethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane, abbreviated as CaG, is a compound obtained by transforming a ketone group to a ketal group with camphorquinone and glycerol. The CaG diol has a complex and rigid structure and two primary hydroxyl groups. A polyester series was synthesized with the CaG diol, ethylene glycol, and dimethyl terephthalate. The polyesters exhibited adequate thermal stability up to nearly 330 °C and had a high Tg, which steadily increased from 78 to 129 °C as the content of CaG increased. A high proportion of the CaG moiety led to an amorphous region that is susceptible to hydrolysis and promoted degradation of the polyester in acidic conditions. Depending on the proportion of CaG in the polymer, the hydrolytic degradation of the polyesters was adjustable.

Highly efficient hydrogen evolution reaction by strain and phase engineering in composites of Pt and MoS2 nano-scrolls.

The phase transition through local strain engineering is an exciting avenue for controlling electronic, magnetic properties and catalyst activity of materials but complex phenomenon in nanoscience. Herein, we demonstrate the first combinations of bending strain and 2H/1T phase transition by rolling up MoS2 sheets for improving catalytic activity in relatively inert basal plane surfaces and promoting electron transfer from the less-conducting 2H MoS2 sheets to the electrodes. Furthermore, we generate various MoS2@Pt nanoparticle hybrids nanomaterials and especially MoS2@Pt scrolls containing the coverage of Pt NPs (8.3 wt%) have a high catalytic activity (39 mV per decade). The rolled up MoS2@Pt sheets with bending strain (2.4%) provide an intra-layer plane gliding that allows the transversal displacement of an S plane from the 2H to the 1T phases (28%). This unique combination also allows us to maximize the intrinsic HER activity among molybdenum-sulfide based catalysts.

Evolution of magnetism by rolling up hexagonal boron nitride nanosheets tailored with superparamagnetic nanoparticles.

Controlling tunable properties by rolling up two dimensional nanomaterials is an exciting avenue for tailoring the electronic and magnetic properties of materials at the nanoscale. We demonstrate the tailoring of a magnetic nanocomposite through hybridization with magnetic nanomaterials using hexagonal boron nitride (h-BN) templates as an effective way to evolve magnetism for the first time. Boron nitride nanosheets exhibited their typical diamagnetism, but rolled-up boron nitride sheets (called nanoscrolls) clearly have para-magnetism in the case of magnetic susceptibility. Additionally, the Fe3O4 NP sample shows a maximum ZFC curve at about 103 K, which indicates well dispersed superparamagnetic nanoparticles. The ZFC curve for the h-BN-Fe3O4 NP scrolls exhibited an apparent rounded maximum blocking temperature at 192 K compared to the Fe3O4 NPs, leading to a dramatic increase in TB. These magnetic nanoscroll derivatives are remarkable materials and should be suitable for high-performance composites and nano-, medical- and electromechanical-devices.

Highly thermal-stable paramagnetism by rolling up MoS2 nanosheets.

Controlling phase transitions through local strain engineering is an exciting avenue for tailoring the electronic and magnetic properties of materials at the nanoscale. Herein, we demonstrate a tunable semiconducting to metallic phase transition of two-dimensional transition metal dichalcogenides using strain engineering through rolled up MoS2 sheets (named as MoS2 scrolls). A phase incorporated structure for MoS2 nanoscrolls containing the maximum concentration of 1T phase (∼58%) with high thermal stability up to 473 K can be produced by a gliding-rolling process for the S plane. These phase transitions are irreversible by virtue of the van der Waals interaction between the layers of the nanoscrolls, which is relatively stronger than the bending strain. A high concentration of the 1T phase can tune the bandgap through temperature, and also the magnetic property from nonmagnetic to paramagnetic MoS2. This study, which is able to control phase transitions by strain engineering in the field of 2D materials, proves an exciting avenue for tailoring the novel functional properties of low-dimensional materials.

Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system.

Inhibition of blood vessel formation by a chondrocyte-derived extracellular matrix.

In this study, the chondrocyte-derived extracellular matrix (CECM) was evaluated for its activity to inhibit vessel invasion in vitro and in vivo. Human umbilical vein endothelial cells (HUVECs) and rabbit chondrocytes were plated on a bio-membrane made of CECM or human amniotic membrane (HAM). The adhesion, proliferation, and tube formation activity of HUVECs and chondrocytes were examined. The CECM and HAM powders were then mixed individually in Matrigel and injected subcutaneously into nude mice to examine vessel invasion in vivo after 1 week. Finally, a rabbit model of corneal neovascularization (NV) was induced by 3-point sutures in the upper cornea, and CECM and HAM membranes were implanted onto the corneal surface at day 5 after suture injury. The rabbits were sacrificed at 7 days after transplantation and the histopathological analysis was performed. The adhesion and proliferation of HUVECs were more efficient on the HAM than on the CECM membrane. However, chondrocytes on each membrane showed an opposite result being more efficient on the CECM membrane. The vessel invasion in vivo also occurred more deeply and intensively in Matrigel containing HAM than in the one containing CECM. In the rabbit NV model, CECM efficiently inhibited the neovessels formation and histological remodeling in the injured cornea. In summary, our findings suggest that CECM, an integral cartilage ECM composite, shows an inhibitory effect on vessel invasion both in vitro and in vivo, and could be a useful tool in a variety of biological and therapeutic applications including the prevention of neovascularization after cornea injury.

The chondrogenic differentiation of mesenchymal stem cells on an extracellular matrix scaffold derived from porcine chondrocytes.

Extracellular matrix (ECM) materials have diverse physiological functions by themselves and can also act as reservoirs of cytokines and growth factors, so that they can affect the cell phenotype, attachment, migration and proliferation of cells. In this study, an ECM scaffold derived from porcine cartilage was evaluated for whether it can support and maintain chondrogenesis of rabbit mesenchymal stem cells (rMSCs) in vitro and in the nude mouse model in vivo. The porcine ECM scaffold was compared to a polyglycolic acid (PGA) scaffold and an MSC pellet as a control group. In an in vitro environment until 4 weeks, the ECM scaffold evoked chondrogenic differentiation of rMSCs earlier and produced more cartilaginous tissues than the PGA scaffold. Next, rMSCs in each scaffold were preconditioned with chondrogenic media in vitro for 1 week and implanted in the backs of nude mice for 6 weeks. The initially formed cartilaginous tissues turned into bone matrix with time centripetally from the outside of the region as observed by Safranin-O and von Kossa stains. This phenomenon progressed much more rapidly in the PGA group than in the ECM group. In the ECM group, the chondrogenic phenotypes of rMSCs were also maintained longer than in the PGA group. The loss of chondrogenic phenotypes was accompanied by the calcification of matrix, and hypertrophic changes by immunohistochemistry for osteocalcin and collagen type I and X. Blood vessel invasion took place more deeply and intensively in the PGA group. These results suggest that the ECM scaffold not only strongly supports chondrogenic differentiation of rMSCs, but also helps maintain its phenotype in vivo. We speculate that the ECM scaffold provides rMSCs with a favorable, native cartilage-like environment and therefore can be a promising tool for cartilage tissue engineering.

Novel imaging analysis system to measure the spatial dimension of engineered tissue construct.

The measurement of the spatial dimensions of tissue-engineered constructs is very important for their clinical applications. In this study, a novel method to measure the volume of tissue-engineered constructs was developed using iterative mathematical computations. The method measures and analyzes three-dimensional (3D) parameters of a construct to estimate its actual volume using a sequence of software-based mathematical algorithms. The mathematical algorithm is composed of two stages: the shape extraction and the determination of volume. The shape extraction utilized 3D images of a construct: length, width, and thickness, captured by a high-quality camera with charge coupled device. The surface of the 3D images was then divided into fine sections. The area of each section was measured and combined to obtain the total surface area. The 3D volume of the target construct was then mathematically obtained using its total surface area and thickness. The accuracy of the measurement method was verified by comparing the results with those obtained from the hydrostatic weighing method (Korea Research Institute of Standards and Science [KRISS], Korea). The mean difference in volume between two methods was 0.0313 +/- 0.0003% (n = 5, P = 0.523) with no significant statistical difference. In conclusion, our image-based spatial measurement system is a reliable and easy method to obtain an accurate 3D volume of a tissue-engineered construct.