Functionally Antagonistic Hybrid Electrode with Hollow Tubular Graphene Mesh and Nitrogen‐Doped Crumpled Graphene for High‐Performance Ionic Soft Actuators

Ionic soft actuators, which exhibit large mechanical deformations under low electrical stimuli, are attracting attention in recent years with the advent of soft and wearable electronics. However, a key challenge for making high‐performance ionic soft actuators with large bending deformation and fast actuation speed is to develop a stretchable and flexible electrode having high electrical conductivity and electrochemical capacitance. Here, a functionally antagonistic hybrid electrode with hollow tubular graphene meshes and nitrogen‐doped crumpled graphene is newly reported for superior ionic soft actuators. Three‐dimensional network of hollow tubular graphene mesh provides high electrical conductivity and mechanically resilient functionality on whole electrode domain. On the contrary, nitrogen‐doped wrinkled graphene supplies ultrahigh capacitance and stretchability, which are indispensably required for improving electrochemical activity in ionic soft actuators. Present results show that the functionally antagonistic hybrid electrode greatly enhances the actuation performances of ionic soft actuators, resulting in much larger bending deformation up to 620%, ten times faster rise time and much lower phase delay in a broad range of input frequencies. This outstanding enhancement mostly attributes to exceptional properties and synergistic effects between hollow tubular graphene mesh and nitrogen‐doped crumpled graphene, which have functionally antagonistic roles in charge transfer and charge injection, respectively.     

Determining the Dielectric Constants of Organic Photovoltaic Materials Using Impedance Spectroscopy

The photovoltaic and electrical properties of organic semiconductors are characterized by their low dielectric constant, which leads to the formation of polarons and Frenkel excitons. The low dielectric constant of organic semiconductors has been suggested to be significantly influential in geminate and bimolecular recombination losses in organic photovoltaics (OPVs). However, despite the critical attention that the dielectric constant has received in literature discussions, there has not yet been a thorough study of the dielectric constant in common organic semiconductors and how it changes when blended. In fact, there have been some inconsistent and contradictory reports on such dielectric constants, making it difficult to identify trends. Herein, at first a detailed explanation of a specific methodology to determine the dielectric constant in OPV materials with impedance spectroscopy is provided, including guidelines for possible experimental pitfalls. Using this methodology, the analysis for the dielectric constant of 17 common neat organic semiconductors is carried out. Furthermore, the relationship between the dielectric constant and blend morphology are studied and determined. It is found that the dielectric constant of a blend system can be very accurately predicted solely based on the dielectric constants of the neat materials, scaled by their respective weight ratios in the blend film.     

Strength improvement and purification of Yb2Si2O7‐SiC nanocomposites by surface oxidation treatment

A two‐step processing was developed to prepare Yb₂Si₂O₇‐SiC nanocomposites. Yb₂Si₂O₇‐Yb₂SiO₅‐SiC composites were first fabricated by a solid‐state reaction/hot‐pressing method. The composites were then annealed at 1250°C in air for 2 hours to activate the oxidation of SiC, which effectively transformed the Yb₂SiO₅ into Yb₂Si₂O₇. The surface cracks purposely induced can be fully healed during the oxidation treatment. The treated composites have improved flexural strength compared to their pristine composites. The mechanism for crack healing and silicate transformation have been proposed and discussed in detail.     

Insight into adsorption mechanism of cationic dye onto agricultural residues-derived hydrochars: Negligible role of <Emphasis Type="Italic">π-π</Emphasis> interaction

Hydrochars derived from golden shower pod (GSH), coconut shell (CCH), and orange peel (OPH) were synthesized and applied to remove methylene green (MG5). The results indicated that the hydrochars possessed low specific surface areas (6.65-14.7m²/g), but abundant oxygen functionalities (1.69-2.12mmol/g). The hydrochars exhibited cellular and spherical morphologies. Adsorption was strongly dependent on the solution pH (2-10) and ionic strength (0-0.5M NaCl). Equilibrium can be quickly established in the kinetic study (60-120 min). The maximum Langmuir adsorption capacities at 30 °C followed the order GSH (59.6mg/g)>CCH (32.7mg/g)>OPH (15.6mg/g)> commercial glucose-prepared hydrochar (12.6mg/g). The dye adsorption efficiency was determined by the concentrations of oxygen-containing functionalities on the hydrochar surface. The adsorption process occurred spontaneously (? ΔG^o) and exothermically (?ΔH^o). Desorption studies confirmed the reversible adsorption process. Oxygenation of the hydrochar surface through a hydrothermal process with acrylic acid contributed to increasing MG5 adsorption and identifying the negligible role of π-π interaction to the adsorption process. The analysis of Fourier transform infrared spectrometry demonstrated that the aromatic C=C peak did not significantly decrease in intensity or shift toward higher/lower wavenumbers after adsorption, which further confirms the insignificant contribution of π-π interaction. Electrostatic attraction played a major role in adsorption mechanisms, while minor contributions were accounted for hydrogen bonding and n-π interactions. The primary adsorption mechanisms of MG5 onto hydrochar were similar to biosorbent, but dissimilar to biochar and activated carbon (i.e., π-π interaction and pore filling).     

X-ray absorption spectroscopies of Mg-Al-Ni hydrotalcite like compound for explaining the generation of surface acid sites

Hydrotalcite-like compound containing metal cations such as Mg²⁺, Al³⁺ and Ni²⁺ was characterized using Ni K-edge EXAFS and in situ Ni K-edge XANES techniques for clarifying its bonding environment around Ni²⁺ sites and structure changes during calcination from room temperature to 550 °C, respectively. At the fixed molar ratio of Mg/Ni/Al of 2/1/1, the results obtained from EXAFS analysis showed a slight blue shift before and after the calcination at 550 °C and a reduction in white line peak; the best fits of the two samples revealed tiny change in coordination number about 7 for Ni-O path but considerable difference for Ni-Mg(Al) path from about 4.5 to 9.5, confirming a modification from brucite like to mixed oxide structure. On the other hand, bond distances of the Ni-O and Ni-Mg paths nearly fixed at about 2.06 Å to 3.0 Å reflected stability of the cationic bond order on each plane, but partial collapse and decomposition of the interlayer formed by water molecules and anion CO ₃ ^2? after the calcination. Linear combination fit extracted from the in situ Ni K-edge XANES also confirmed the changes along with the calcination such as slow and fast decreases of brucite fraction at 150 °C and 330 °C, respectively, in corresponding to the mixed oxide fraction increases. The achieved bonding structures were also applied to explain acid-base occurrence of the hydrotalcite-like material, especially the acid sites generated by different static charges along with the bonds. The explanation was illustrated by NH₃-TPD method.     

Investigation of waste heat recovery system at supercritical conditions with vehicle drive cycles

Waste heat recovery (WHR) for internal combustion engines in vehicles using Organic Rankine cycle (ORC) has been a promising technology. The operation of the ORC WHR system in supercritical conditions has a potential to generate more power output and thermal efficiency compared with the conventional subcritical conditions. However, in supercritical conditions, the heat transfer process in the evaporator, the key component of the ORC WHR system, becomes unpredictable as the thermo-physical properties of the working fluid change with the temperature. Furthermore, the transient heat source from the vehicle’s exhaust makes the operation of the WHR system difficult. We investigated the performance of the ORC WHR system at supercritical conditions with engine’s exhaust data from real city and highway drive cycles. The effects of operating variables, such as refrigerant flow rates, evaporator and condenser pressure, and evaporator outlet temperature, on the performance indicators of the WHR system in supercritical conditions were examined. Simulation of operating parameters and the boundary of the WHR system are also included in this paper.

     

Optimization of site investigation program for improved statistical characterization of geotechnical property based on random field theory

This paper presents a framework for optimization of site investigation program, within which the robustness of the site investigation program and the investigation effort are optimized. A site investigation program is judged robust if the derived statistics of the geotechnical property of interest are robust against the uncertainties caused by limited data availability and test error. In this study, a Markov chain Monte Carlo simulation-based Bayesian inference approach was used to characterize the statistics of the intended geotechnical property. The robustness of the site investigation program was formulated as a byproduct of the Bayesian inference of the geotechnical property statistics. The proposed framework for optimization of the site investigation program was implemented as a bi-objective optimization problem that considers both robustness and investigation effort. The concepts of Pareto Front and knee point were employed to aid in making an informed decision regarding selection of site investigation program. The effectiveness and significance of the proposed framework were demonstrated through a simulation study.     

Highly Efficient Deep‐Blue Electrophosphorescent Pt(II) Compounds with Non‐Distorted Flat Geometry: Tetradentate versus Macrocyclic Chelate Ligands

A new class of deep blue electrophosphorescent Pt(II) emitters have been designed and synthesized. This new class of deep blue Pt(II) emitters employ tetradentate and macrocyclic chelate chromophores to constrain the Pt(II) molecules in a non‐distorted flat geometry in both the ground state and the excited state. The new deep blue emitters do not produce excimer emission, with emission quantum efficiency as high as 95% in 10% doped PMMA (poly(methyl methacrylate) films, and excellent UV stability, compared to the corresponding bidentate Pt(II) emitters. The macrocyclic tetradentate chelate Pt(II) compounds are the first examples of fully sterically constrained deep blue Pt(II) emitters that do not display structural distortion and have a higher thermal stability and a higher emission quantum efficiency than the corresponding non‐macrocyclic tetradentate Pt(II) analogues. A computational study supports that the macrocylic Pt(II) compounds are structurally more stable than the tetradentate Pt(II) molecules. Bright and efficient deep blue electrophosphorescent devices using a macrocyclic Pt(II) emitter have been successfully fabricated with a maximum brightness of 10 680 cd m^?2, maximum external quantum efficiency of 15.4% (at 490 cd m^?2), and Commission Internationale de L'Eclairage (1931) coordinates (x + y ) of less than or near 0.30, respectively.     

Monomolecular and Bimolecular Recombination of Electron–Hole Pairs at the Interface of a Bilayer Organic Solar Cell

While it has been argued that field‐dependent geminate pair recombination (GR) is important, this process is often disregarded when analyzing the recombination kinetics in bulk heterojunction organic solar cells (OSCs). To differentiate between the contributions of GR and nongeminate recombination (NGR) the authors study bilayer OSCs using either a PCDTBT‐type polymer layer with a thickness from 14 to 66 nm or a 60 nm thick p‐DTS(FBTTh₂)₂ layer as donor material and C₆₀ as acceptor. The authors measure JV‐characteristics as a function of intensity and charge‐extraction‐by‐linearly‐increasing‐voltage‐type hole mobilities. The experiments have been complemented by Monte Carlo simulations. The authors find that fill factor (FF) decreases with increasing donor layer thickness (L_p) even at the lowest light intensities where geminate recombination dominates. The authors interpret this in terms of thickness dependent back diffusion of holes toward their siblings at the donor–acceptor interface that are already beyond the Langevin capture sphere rather than to charge accumulation at the donor–acceptor interface. This effect is absent in the p‐DTS(FBTTh₂)₂ diode in which the hole mobility is by two orders of magnitude higher. At higher light intensities, NGR occurs as evidenced by the evolution of s‐shape of the JV‐curves and the concomitant additional decrease of the FF with increasing layer thickness.