Nickel-Tin Nanoalloy Supported ZnO Catalysts from Mixed-Metal Zeolitic Imidazolate Frameworks for Selective Conversion of Glycerol to 1,2-Propanediol.

The successful synthesis of finely tuned Ni1.5 Sn nanoalloy phases containing ZnO catalyst with a small particle size (6.7 nm) from a mixed-metal zeolitic imidazolate framework (MM-ZIF) is investigated. The catalyst was evaluated for the efficient production of 1,2-propanediol (1,2-PDO) from crude glycerol and comprehensively characterized using several analytical techniques. Among the catalysts, 3Ni1Sn/ZnO (Ni/Sn=3/1) showed the best catalytic performance and produced the highest yield (94.2 %) of 1,2-PDO at ~100 % conversion of glycerol; it also showed low apparent activation energy (15.4 kJ/mol) and excellent stability. The results demonstrated that the synergy between Ni-Sn alloy, finely dispersed Ni metallic sites, and the Lewis acidity of SnOx species-loaded ZnO played a pivotal role in the high activity and selectivity of the catalyst. The confirmation of acetol intermediate and theoretical calculations verify the Ni1.5 Sn phases provide the least energetic pathway for the formation of 1,2-PDO selectively. The reusability of solvent for successive ZIF synthesis, along with the excellent recyclability of the ZIF-derived catalyst, enables an overall sustainable process. We believe that the present synthetic protocol that uses MM-ZIF for the conversion of various biomass-derived platform chemicals into valuable products can be applied to various nanoalloy preparations.

Market weight, slaughter age, and yield grade to determine economic carcass traits and primal cuts yield of Hanwoo beef.

This study was conducted to evaluate the relationship among market weight, slaughter age, yield grade, and primal cut yield in Hanwoo. A total of 403 Hanwoo (Korean native cattle) was assessed for carcass traits such as carcass cold weight, backfat thickness, ribeye area, dressing percentage, yield index, and marbling score. The production yield of the individual major primal cuts of Hanwoo beef was also measured. Carcass cold weight, ribeye area, and backfat thickness, which affect meat quality increased with increased market weight (p < 0.05). The production yield of the ten major primal cuts also increased with increased market weight (p < 0.05). In terms of slaughter age, carcass cold weight, ribeye area, and backfat thickness all increased from 25 months to 28-29 months, and the production yield of all prime cuts also increased with increasing slaughter age. According to the meat yield grade, carcass cold weight and backfat thickness increased from grade A to grade C, although the ribeye area was not affected. The combined findings of the study suggest that slaughtering Hanwoo at the weight of 651-700 kg and 701-750 and age of 28.23 and 29.83 months could be desirable to achieve the best quality and quantity grade of Hanwoo beef. However, the positive correlation of carcass cold weight and backfat thickness, and the negative correlation of the yield index according to primal cuts yield indicated that it is necessary to couple the slaughtering management of cattle with improved genetic and breeding method of Hanwoo to increase the production yield of the major prime cuts of Hanwoo beef.

Hand Gesture Recognition Using Single Patchable Six-Axis Inertial Measurement Unit via Recurrent Neural Networks.

Recording human gestures from a wearable sensor produces valuable information to implement control gestures or in healthcare services. The wearable sensor is required to be small and easily worn. Advances in miniaturized sensor and materials research produces patchable inertial measurement units (IMUs). In this paper, a hand gesture recognition system using a single patchable six-axis IMU attached at the wrist via recurrent neural networks (RNN) is presented. The IMU comprises IC-based electronic components on a stretchable, adhesive substrate with serpentine-structured interconnections. The proposed patchable IMU with soft form-factors can be worn in close contact with the human body, comfortably adapting to skin deformations. Thus, signal distortion (i.e., motion artifacts) produced for vibration during the motion is minimized. Also, our patchable IMU has a wireless communication (i.e., Bluetooth) module to continuously send the sensed signals to any processing device. Our hand gesture recognition system was evaluated, attaching the proposed patchable six-axis IMU on the right wrist of five people to recognize three hand gestures using two models based on recurrent neural nets. The RNN-based models are trained and validated using a public database. The preliminary results show that our proposed patchable IMU have potential to continuously monitor people's motions in remote settings for applications in mobile health, human-computer interaction, and control gestures recognition.

Mechanistic and microkinetic study of non-oxidative methane coupling on a single-atom iron catalyst.

Non-oxidative methane coupling has promising economic potential, but the catalytic and radical reactions become complicated at high temperatures. Here, we investigate the mechanism of non-oxidative methane coupling on an iron single-atom catalyst using density functional theory, and evaluate the catalytic performance under various reaction conditions using microkinetic modelling and experiments. Under typical reaction conditions (1300 K and 1 bar), C-C coupling and subsequent dehydrogenation to produce ethylene shows comparable energetics between the gas-phase and catalytic pathways. However, the microkinetic analysis reveals that the iron single-atom catalyst converted methane to mainly CH3 and H2 at reaction temperatures above 1300 K, and acetylene production is dominant over ethylene production. The sensitivity analysis suggests that increasing the C2 hydrocarbon yield by optimising the reaction conditions is limited. The experimental results obtained at 1293 K are consistent with the theoretical estimation that acetylene is the main C2 product over the iron single-atom catalyst.

Linear α-olefin production with Na-promoted Fe-Zn catalysts via Fischer-Tropsch synthesis.

The production of linear alpha-olefins (α-olefins) is a practical way to increase the economic potential of the Fischer-Tropsch synthesis (FTS) because of their importance as chemical intermediates. Our study aimed to optimize Na-promoted Fe1Zn1.2O x catalysts such that they selectively converted syngas to linear α-olefins via FTS at 340 °C and 2.0 MPa. The Fe1Zn1.2O x catalysts were calcined at different temperatures from 350 to 700 °C before Na anchoring. The increase in the size of the ZnFe2O4 crystals comprising the catalyst had a negative effect on the reducibility of Fe oxides and the particle size of Fe5C2 during the reaction. The Na species in the catalyst restrained the reduction of Fe1Zn1.2O x but facilitated the formation of Fe5C2. When pure Fe1Zn1.2O x was calcined at 400 °C, the corresponding catalyst (i.e., Na0.2/Fe1Zn1.2O x (400)) exhibited higher catalytic activity and stability than the other catalysts for a 50 h reaction. Compared to the other catalysts, Na0.2/Fe1Zn1.2O x (400) enabled a higher number of active Fe carbides (Fe5C2) to intimately interact with the Na species, even though the catalyst had a lower total surface basicity based on surface area. The Na0.2/Fe1Zn1.2O x (400) showed a maximum hydrocarbon yield of 49.7% with a maximum olefin selectivity of 61.3% in the C1-C32 range. Examination of the reaction product mixture revealed that the Na0.2/Fe1Zn1.2O x catalysts converted α-olefins to branched paraffins (13.9-19.5%) via a series of isomerization, skeletal isomerization, and hydrogenation reactions. The Na0.2/Fe1Zn1.2O x (400) catalyst had a relatively low consumption rate of internal olefins compared to other catalysts, resulting in the lowest selectivity for branched paraffins. The Na0.2/Fe1Zn1.2O x (400) showed a maximum α-olefin yield (26.6%) in the range C2-C32, which was 27.9-50.0% higher than that of other catalysts. The α-olefin selectivity in the C5-C12 range for the Na0.2/Fe1Zn1.2O x (400) was 37.5% relative to the total α-olefins.

Hydrogen Production by Steam Reforming of Liquefied Natural Gas (LNG) Over Nickel-Phosphorus-Alumina Xerogel Catalyst Prepared by a Carbon-Templating Epoxide-Driven Sol-Gel Method.

A nickel-phosphorus-alumina xerogel catalyst was prepared by a carbon-templating epoxide-driven sol-gel method (denoted as CNPA catalyst), and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel-phosphorus-alumina xerogel catalyst was also prepared by a similar method in the absence of carbon template (denoted as NPA catalyst). The effect of carbon template addition on the physicochemical properties and catalytic activities of the catalysts in the steam reforming of LNG was investigated. Both CNPA and NPA catalysts showed excellent textural properties with well-developed mesoporous structure. However, CNPA catalyst retained a more reducible nickel aluminate phase than NPA catalyst. XRD analysis of the reduced CNPA and NPA catalysts revealed that nickel sintering on the CNPA catalyst was suppressed compared to that on the NPA catalyst. From H2-TPD and CH4-TPD measurements of the reduced CNPA and NPA catalysts, it was also revealed that CNPA catalyst with large amount of hydrogen uptake and strong hydrogen-binding sites showed larger amount of methane adsorption than NPA catalyst. In the hydrogen production by steam reforming of LNG, CNPA catalyst with large methane adsorption capacity showed a better catalytic activity than NPA catalyst.

Direct Synthesis of Diphenyl Carbonate from Phenol and Carbon Dioxide Over Ti-Salen-Based Catalysts.

Various metal-salen catalysts were prepared for use in the direct synthesis of diphenyl carbonate (DPC) from phenol and carbon dioxide. We found that metal-salen complexes containing titanium as central metal species retained suitable Lewis acid property for the reaction. It was revealed that the catalytic activity of Ti-salen complexes could be controlled by introducing appropriate substituents into salen ligand. Insertion of phosphonium salts into para-position of aromatic aldehyde of salen ligand enhanced solubility of the catalyst in the methanol-phenol solution, and tert-butyl substituent in the salen ligand induced selective formation of DPC due to steric effect. In addition, introduction of various bridging groups into salen ligand caused change in electronic property of central metal atom. Among the catalysts tested, Ti-(t-butyl)salphen(PPh3)Cl showed the best catalytic performance at 100 °C and 60 bar. The catalytic system utilizing Ti-(t-butyl)salphen(PPh3)Cl catalyst was then optimized by conducting the reaction at various reaction temperatures and pressures.

Unusual solvent-dependent photophysical and self-assembly properties of NO2 substituted T-shaped phenazines.

This paper investigates the importance of substituent placement when designing low-molecular mass π-organogelators. The electron-deficient NO2 substituent was systematically added to novel T-shaped phenazines to examine electronic as well as assembly properties. This T-shaped molecular platform promotes selective electronic tuning, which can be theoretically analyzed by examining the system's frontier molecular orbitals. Electronic properties were characterized by UV-vis spectroscopy and cyclic voltammetry, and comparisons were made based on number and placement of the NO2 group. Computational chemistry (B3LYP/6-31G*) was employed for geometry optimizations, and to generate molecular orbital diagrams for all systems. The most noticeable influence of NO2 position was found for two molecules with four NO2 groups placed at different locations about the molecule (T-34dNT and T-35dNT). A 0.13 eV difference in ELUMO was observed while EHOMO was not significantly impacted by this change only in NO2 placement. Interestingly and unexpectedly, the photophysical properties and solvent-dependent gelation properties were considerably different for T-34dNT and T-35dNT. T-34dNT exhibited a unique fluorescence (FL) solvatochromism, with FL intensity and maxima dependent on solvent polarity. This result is indicative of intramolecular charge transfer. In addition, long tailing at the solid-state absorption of T-34dNT suggests the presence of intermolecular charge transfer. The gelation of T-34dNT produced chromism ranging from red to orange to yellow when the solvents changed from acetonitrile to ethyl acetate to cyclohexane, respectively. T-35dNT gels in these solvents did not exhibit any of the same properties. Xerogel morphology characterizations were carried out using three different solvents for both T-34dNT and T-35dNT. In the case of T-34dNT, striking differences in the morphology were detected by field-emission scanning electron microscopy (FE-SEM). We conclude that numbers of substituents are not the only consideration in effective molecular design for organogelators, but that substituent position plays a critical role in certain fundamental properties of these systems.

High temperature carbon dioxide capture on nano-structured MgO-Al2O3 and CaO-Al2O3 adsorbents: an experimental and theoretical study.

Nano-structured alkaline-earth metal oxide adsorbents (denoted as MgO-Al2O3 and CaO-Al2O3) were prepared by an epoxide-driven one-pot sol-gel method, and they were applied to the dynamic and static CO2 adsorption. For comparison, a nano-structured aluminum oxide adsorbent (denoted as Al2O3) was also prepared by a similar method. MgO-Al2O3 adsorbent exhibited a well-developed mesopore structure through the formation of MgAl2O4 spinel phase, whereas CaO-Al2O3 adsorbent was composed of nano-sized CaO and CaAl2O4, resulting in a pore plugging. It was revealed that total basicity increased in the order of Al2O3 (0.11 mmol-CO2/g) < MgO-Al2O3 (0.37 mmol-CO2/g) < CaO-Al2O3, (1.21 mmol-CO2/g), which is in concurrent with adsorption energy obtained from DFT calculations. However, it was found that both basicity and base strength of the adsorbents played an important role in determining the CO2 adsorptive performance at different operating temperature. Among the adsorbents tested, MgO-Al2O3, which mostly retained medium basic sites, exhibited a best CO2 adsorptive performance at 200 degrees C. Furthermore, the experimental results are well supported by theoretical estimation, suggesting a useful design method of adsorbents for facile and regenerative adsorption in the applications of CO2 capture.