Thiol-Functionalized Covalent Organic Frameworks as Thermal History Indictor for Temperature and Time History Monitoring

Various products, including foods and pharmaceuticals, are sensitive to temperature fluctuations. Thus, temperature monitoring during production, transportation, and storage is critical. Facile indicators are required to monitor temperature conditions via color changes in real time. This study aimed to prepare and apply thiol-functionalized covalent organic frameworks (COFs) as a novel indicator for monitoring thermal history and temperature abuse. The COFs underwent obvious color changes from bright yellow to purple after exposure to different temperatures for varying durations. The reaction kinetics are analyzed under isothermal conditions, which reveal that the order of reaction rates is k_−20°C < k_4°C < k_20°C < k_35°C < k_55°C. The activation energy (E_a) of the COFs is calculated using the Arrhenius equation as 50.71 kJ moL⁻¹. The COFs are capable of sensitive color changes and offer a broad temperature tracking range, thereby demonstrating their application potential for the monitoring of temperature and time exposure history during production, transportation, and storage. This excellent performance thermal history indicator also shows promise for expanding the application field of COFs.     

Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

A novel utilized method of tar derived from biomass gasification for fabricating binder-free all-solid-state hybrid supercapacitors

As an industrial pollutant, tar derived from biomass gasification is used as the precursor for fabricating a novel carbon-metal hydroxides composite electrode. A slurry (the mixture of tar, KOH and melamine) is daubed uniformly onto the nickel foam, which is directly carbonized to form NPC@LDH electrode material. This electrode is further coated with NiCo-LDH nanosheets using an electrodeposition method to form NF@NPC@LDH. The newly made NF@NPC@LDH electrode exhibits a high specific capacity of 9.6 F cm⁻² at a current density of 2 mA cm⁻² and good rate performance (55.3% retention). Furthermore, a hybrid NF@NPC@LDH//NF@PC all-solid-state supercapacitor is fabricated, and the device exhibits high energy density of 1.28 mWh cm⁻³ at a power density of 8.04 mW cm⁻³, low resistance and good cycling stability.     

11B and 15N solid state NMR investigation of a boron nitride preceramic polymer prepared by ammonolysis of borazine

A poly(aminoborazine), precursor for hexagonal boron nitride (h-BN) obtained by reaction of borazine B₃N₃H₆ with ammonia, and its pyrolysis derivatives have been extensively characterised by ¹⁵N and ¹¹B MAS NMR. The various B and N sites have been identified according to their first neighbouring atoms, as well as to the second ones in the case of ¹⁵N, and have also been quantified. This study demonstrates that a suitable choice of NMR techniques together with the use of isotopic enrichment can lead to a large improvement in spectral resolution, which allows a better understanding of such complex BN preceramic polymer structures and permits to follow the polymer-to-ceramic transformation.     

Deformation behaviour of iron-doped alumina

Compressive creep tests in air were carried out on 1 cat.% Fe-doped alumina at a temperature T=1400 °C. Iron doping affected the plastic deformation by different ways in relation with Fe²⁺ cations population. Fe²⁺ cations sped up the deformation rates. FeAl₂O₄ spinel precipitates were identified and they were found (i) to interact with alumina grain boundaries (ii) to limit the grain growth within a range of strain. The Fe²⁺ cations underwent oxidation and this resulted in the dissolution of the some precipitates and in the decrease of deformation rates. It was suggested that deformation sped up this evolution through mass transport and that time was not a dominating parameter.     

Synthesis and electrochemical properties of layered Li[Ni0.333Co0.333Mn0.293Al0.04]O2−zFz cathode materials prepared by the sol–gel method

The cathode-active materials, layered Li[Ni_0.333Co_0.333Mn_0.293Al_0.04]O_2−zF_z (0 ≤ z ≤ 0.1), were synthesized from a sol–gel precursor at 900 °C in air. The influence of Al–F co-substitution on the structural and electrochemical properties of the as-prepared samples was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and electrochemical experiments. The results showed that Li[Ni_0.333Co_0.333Mn_0.293Al_0.04]O_2−zF_z has a typical hexagonal structure with a single phase, the particle sizes of the samples tended to increase with increasing fluorine content. It has been found that Li[Ni_0.333Co_0.333Mn_0.293Al_0.04]O_1.95F_0.05 showed an improved cathodic behavior and discharge capacity retention compared to the undoped samples in the voltage range of 3.0–4.3 V. The electrodes prepared from Li[Ni_0.333Co_0.333Mn_0.293Al_0.04]O_1.95F_0.05 delivered an initial discharge capacity of 158 mAh⁻¹ g and an initial coulombic efficiency is 91.3%, and the capacity retention at the 20th cycle was 94.9%. Though the F-doped samples had lower initial capacities, they showed better cycle performances compared with F-free samples. Therefore, this is a promising material for a lithium-ion battery.     

An efficient face segmentation algorithm based on binary partition tree

This paper presents an efficient face segmentation algorithm based on binary partition tree. Skin-like regions are first obtained by integrating the results of pixel classification and watershed segmentation. Facial features are extracted by the techniques of valley detection and entropic thresholding, and are used to refine the skin-like regions. In order to segment the facial regions from the skin-like regions, a novel region merging algorithm is proposed by considering the impact of the common border ratio between adjacent regions, and the binary partition tree is used to represent the whole region merging process. Then the facial likeness of each node in the binary partition tree is evaluated using a set of fuzzy membership functions devised for a number of facial primitives of geometrical, elliptical and facial features. Finally, an efficient algorithm of node selecting in the binary partition tree is proposed for the final face segmentation, which can exactly segment the faces without any underlying assumption. The performance of the proposed face segmentation algorithm is demonstrated by experimental results carried out on a variety of images in different scenarios.     

Ultra-Stretchable Monofilament Flexible Sensor with Low Hysteresis and Linearity based on MWCNTs/Ecoflex Composite Materials

Wearable human–computer interaction equipment is a common technology, which can improve the comfort, convenience, and safety of the human body, and also can monitor human health. The flexible and wearable tensile sensor can be conveniently installed on clothes or directly connected to the body. This provides a convenient, timely, and portable solution for the detection of human motion. Therefore, wearable electronic equipment is gaining more attention. In this paper, a highly stretchable, flexible, and sensitive strain sensor which is based on multi-walled carbon nanotubes/Ecoflex nanocomposites is reported. A monofilament tensile sensor obtains good linearity (10.77%), low hysteresis (1.63%), good stability (6000 cycles under 100% strain), and ultra-high strain range (ε = 1300%). This ultra-stretchable sensor has potential applications in human motion monitoring, medical rehabilitation, health monitoring, human–computer interaction, and soft robots.     

A moving horizon approach to input design for closed loop identification

The identification of high fidelity models is a critical element in the implementation of high performance model predictive control (MPC) applications in the industry. These controllers can vary in size with input–ouput dimensions ranging from 5 × 10 to 50 × 100. Identifying models of this scale accurately is a time consuming and demanding exercise. We present a novel approach wherein an information rich test signal is generated in closed loop by maximizing the MPC objective, as opposed to minimization that is done in the standard controller. We show that the proposed input design approach is similar to T-optimal (trace optimal) experiment design method. Our approach automatically accounts for the input and output constraints and is implemented in a moving horizon manner. It is demonstrated through simulation examples on both well and ill-conditioned processes.     

Controllable Fabrication of Co3−xMnxO4 with Tunable External Co3+/Co2+ Ratio for Promoted Oxygen Reduction Reaction

Co_3?xMn_xO₄ is a bimetal oxide with excellent electrochemical activity in alkaline solution, has been regarded as a promising alternative in the field of ion-air batteries and proton exchange membrane fuel cell (PEMFC). Herein, we report a simple solvothermal-calcination method to fabricate Co_3?xMn_xO₄ with tunable external Co³⁺/Co²⁺ and Mn³⁺/Mn²⁺ ratio. The tunable ratio of element valence in the bimetal results in a higher exposure of active center for oxygen redox reaction (ORR), and thus lead to a better ORR activity, which was confirmed by X-ray photoelectron spectroscopy characterizations and electrochemical measurements. Specially, Co_1.8Mn_1.2O₄ with a Co³⁺/Co²⁺ ratio of 2.08 showed an overpotential of 0.37 V at benchmark ORR current density of 3 mA/cm² in 0.1 M KOH, which is lower than that of pure oxide (Mn₃O₄ 0.53 V and Co3O4 0.56 V). In addition, the as prepared Co_1.8Mn_1.2O₄ exhibited a positive half-wave potential (0.83 V vs RHE) due to their more active sites, promotes charge transfer, adsorption and desorption of oxygen species. This work provides a strategy for the design and fabrication of earth-abundant, low-cost electrocatalysts for PEMFC in practical applications.

Graphic Abstract

Co_3?xMn_xO₄ was fabricated by tuning external Co³⁺/Co²⁺ and Mn³⁺/Mn²⁺ ratio, and the activity initially shows a positive correlation with the ration of Co³⁺/Co²⁺ in Co_3?xMn_xO₄.