Density functional theory study of the copper phthalocyanine based metal−organic frameworks as the highly active electrocatalysts for the oxygen reduction

Recently, the copper phthalocyanine based 2D conjugated MOFs have been demonstrated that it can efficiently catalyze the oxygen reduction reaction (ORR) experimentally. Herein, the inherent properties and ORR mechanism of PcCu-O₈-M (M = Fe, Co, Ni, Cu) containing two potential active sites (M–O₄ and Cu–N₄ sites) are investigated by density functional theory methods. The binding energy of oxygen-containing intermediates on PcCu-O₈-M indicates that the binding strength of 1OOH, 1O, and 1OH at the M–O₄ site is more moderate than that at the Cu–N₄ site. For all studied sites, their potential-determining steps are the step of O₂ → 1OOH except for the Ni–O₄ site of PcCu-O₈-Ni (1OH → H₂O). Among all sites of PcCu-O₈-M, the Fe–O₄ and Co–O₄ sites have excellent ORR activity with the overpotentials of 0.46 and 0.49 V, respectively, and the Cu–N₄ site of PcCu-O₈-Co possesses the relatively high ORR activity with the overpotential of 0.79 V. It can be concluded that compared with the Cu–N₄ site, the M–O₄ site plays major role for each PcCu-O₈-M during the ORR process. Moreover, the charge analysis of PcCu-O₈-Co suggests that the ORR activities of the Co–O₄ and Cu–N₄ sites are mainly originated from metal atoms (Co atom and Cu atom) as well as the O and N atoms (O and N-1) coordinated with metal atoms. In addition, PcCu-O₈-Co has high poisoning-tolerance ability to NO, NH₃, CO, SO₂, and H₂S.     

Catalytical enhancement on hydrogen production from LiAlH4 by Fe–Fe2O3 addition

Hydrogen storage technology plays an important role on the development of hydrogen fuel cell and lithium aluminum hydride is a powerful candidate for solid-state hydrogen storage materials. However, the high stability and slow dehydrogenation kinetics of LiAlH₄ hinder its application. In this paper, the two-step thermal decomposition properties of LiAlH₄ with and without Fe–Fe₂O₃ catalysts are investigated. According to the master plots, the model of mample power law (Pn) and nucleation and growth (An) are the optimal mechanism functions for the two-step decomposition of LiAlH₄, respectively. After doping catalysts, the activation energies decrease significantly. The theoretical and optimized kinetic method are consistent with each other on activation energy. And the latter can also yield other kinetic parameters for a more comprehensive kinetic modelling of LiAlH₄ decomposition. Furthermore, Fe–Al₂O₃ and Fe–Al intermetallics generated during dehydrogenation might significantly improve the hydrogen release properties of LiAlH₄.     

An experimental study to validate optimum distance between metal hydride tanks with staggered arrangement for effective thermal management

Thermal control is crucial in enhancing the life cycle of metal hydride tanks, which necessitates considering several critical parameters. In addition, a suitable arrangement of a metal hydride bank plays a significant role in transferring the heat efficiently. We have already studied the existence of an optimal distance in theory and proved that the maximized heat transfer rate is a function of the geometric arrangement. In this study, which is the second step of our previous work, we aim to experimentally validate the possible ideal distance in optimized metal hydride array by taking into account the results of our previous study. The experiments are carried out at a triple metal hydride bank with a forced convection system and the effects of optimum distance on the heat transfer performance of the metal hydride bank are analyzed with the staggered arrays in order to validate the results of numerical calculations for staggered metal hydride bank with the pitch-to-diameter ratio of 0.06 and 0.07 at the Reynolds number of 6000 and 12,000, respectively. The results obtained at the end of the experiments are as follows; i) metal hydride storage tanks are strongly affected by the array geometry for maximum heat transfer, especially for small pitch arrays at high Reynolds numbers; ii) the experimental findings are compared with the theoretical models and validated; iii) the overall efficiency of fuel cell-metal hydride system could potentially be increased by simple geometrical arrangements.     

Active disturbance rejection control of metal hydride hydrogen storage

Metal hydride (MH) hydrogen storage is used in both mobile and stationary applications. MH tanks can connect directly to high-pressure electrolyzers for on-demand charging, saving compression costs. To prevent high hydrogen pressure during charging, hydrogen generation needs to be controlled with consideration for unknown disturbances and time-varying dynamics. This work presents a robust control system to determine the appropriate mass flow rate of hydrogen, which the water electrolyzer should produce, to maintain the gaseous hydrogen pressure in the tank for the hydriding reaction. A control-oriented model is developed for MH hydrogen storage for control system design purposes. A proportional-integral (PI) and an active disturbance rejection control (ADRC) feedback controllers are investigated, and their performance is compared. Simulation results show that both the PI and ADRC controllers can reject both noises from the output measurements and unknown disturbances associated with the heat exchanger. ADRC excels in eliminating disturbances produced by the input mass flow rate, maintaining the pressure of the tank at the charging pressure with little oscillations. Additionally, the parameters estimated by the ADRC's extended state observer was used to predict the state-of-charge (SOC) of the MH.     

矿井钻孔测井分析仪在云冈矿上覆采空区积水探放中的应用

通过分析云冈矿12号层410盘区81010回采工作面上覆采空区情况,发现上覆3号层、7号层采空区中均存在积水,为消除该水患对回采工作的影响,须先行探放。文章结合81010回采工作面探放水实践,介绍了YCJ90/360矿用钻孔测井分析仪对钻孔轨迹的指导意义,以及测井技术对成孔准确性和可靠性的保障作用,证明其对采空区探放水钻孔施工具有必不可少的保障作用。     

Switching between negative and positive electrorheological effect of g-C3N4 by copper ions doping

Investigation of pristine g-C₃N₄ and copper ions doped g-C₃N₄ as dispersed phases in silicone-oil based electrorheological (ER) fluids is reported for the first time. Pristine g-C₃N₄ was prepared via standard thermal polycondensation of urea. Introduction of Cu ions into g-C₃N₄ polymeric network was performed by treatment of pristine powder by a solution containing tetraammoniumdiaquacopper(II) complex ions followed by annealing. The structure and properties of products were revealed with the aid of XRD, FTIR, UV–Vis and XPS, and complemented by SEM investigation of morphology, pycnometry, BET analysis, and conductivity measurements. The response of prepared ER fluids to an external electric field was examined by rheometry and the effects visualized with optical microscopy. While ER fluids based on g-C₃N₄ exhibited negative ER effect (decrease in viscosity when the field is switched-on), ER fluids based on a g-C₃N₄/Cu-doped analogue exhibited positive ER effect. Dielectric spectroscopy using Havriliak-Negami model revealed that introduction of the dopant almost doubled the dielectric relaxation strength while the relaxation time was halved. The ability of g-C₃N₄/Cu as a candidate for further studies necessary to increase the ER effect was demonstrated. Thereto, described modification of g-C₃N₄ by copper ions shall be applicable also for other metals forming ammonia complexes.     

Histidine as a key modulator of molecular self-assembly: Peptide-based supramolecular materials inspired by biological systems

Histidine, a versatile proteinogenic amino acid, plays a broad range of roles in all living organisms and behaves as a key mediator of the interactions of biomolecules with inorganic constituents. The self-assembly of histidine-rich peptides and proteins is critical in biology, as the histidine unit is both a multifunctional regulator and an ideal motif for the construction of complex biological structures. In particular, non-covalent interactions between the imidazole ring and other molecular building blocks and metal ions are routinely employed to generate these complexes. Therefore, this strategy can be duplicated in an artificial context to create sophisticated bioactive materials. In this review, we first highlight a clear perspective of the bio-inspired design strategies which can replicate the hierarchical structure of biological systems allowing the engineering of the supramolecular self-assembly of histidine-functionalized peptides. We further summarize advancements in the field of peptide supramolecular structures incorporating histidine residues in the peptide backbone to generate organized functional supramolecular biomaterials with customizable features. We also discuss significant advances and future prospects in supramolecular self-assembly of histidine-functionalized peptides, as well as provide an overview of advanced techniques for the fabrication of histidine-based biomaterials for bio-nanotechnology, optoelectronic engineering, and biomedicine. Overall, artificial supramolecular materials based on histidine functionalized peptides, motivated by the intriguing properties discovered in natural proteins, bear the potential to boost the creation of sustainable bio-inspired materials.     

An overview of reactive hydride composite (RHC) for solid-state hydrogen storage materials

Hydrogen storage using the metal hydrides and complex hydrides is the most convenient method because it is safe, enables high hydrogen capacity and requires optimum operating condition. Metal hydrides and complex hydrides offer high gravimetric capacity that allows storage of large amounts of hydrogen. However, the high operating temperature and low reversibility hindered the practical implementation of the metal hydrides and complex hydrides. An approach of combining two or more hydrides, which are called reactive hydride composites (RHCs), was introduced to improve the performance of the metal hydrides and complex hydrides. The RHC system approach has significantly enhanced the hydrogen storage performance of the metal hydrides and complex hydrides by modifying the thermodynamics of the composite system through the metathesis reaction that occurred between the hydrides, hence enhancing the kinetic and reversibility performance of the composite system. In this paper, the overview of the RHC system was presented in detail. The challenges and perspectives of the RHC system are also discussed. This is the first review report on the RHC system for solid-state hydrogen storage.     

Multiscale insights into hydrogen charging behavior in metal hydride reactor packed with porous ZrCo particles

The primary purpose of this work is to develop a novel model for comprehensively investigating the hydrogen storage performance under the framework of diffusion of hydrogen atoms through hydride layer. The proposed model is constructed upon perfectly mathematical-physical equations, by taking into account complicated multi-scale and multi-physics coupling actions. Importantly, three-dimensional numerical simulations are performed to explore the coupling effects of micro diffusion, mesoscopic permeation, and macroscopic fluid flow. An analytical approach accounting for the characteristics of reaction bed, particle, and crystal grain is presented as well. In addition, a parametric analysis is conducted to reveal that the hydride particle dimension, particle porosity, grain size, and diffusion coefficient of reacted layer have a significant effect on overall hydrogen storage performance, highlighting that grain size and hydrogen diffusion coefficient are vital factors that need to be considered for material preparation and design.     

Effects of post-lift-off annealing conditions on contact oxidation of Ti–Au top-contacts in In-Sn–Zn–O TFT

Thin film transistors (TFT) with an indium based mixed oxide semiconductor are investigated for titanium–gold top-contacts. It is noticed that upon post annealing, in order to remove chemical residuals from top-contact lift-off steps, oxidation of titanium occurs depending on the annealing conditions. Mobility of the TFT is strongly affected by contact oxidation arising from this post lift-off annealing process. Oxidation of the top-contact is facilitated by adsorbed surface oxygen or out-diffusing oxygen from the semiconductor depending on the post lift-off annealing conditions. A passivation layer that binds effectively to surface vacancies and removes adsorbed oxygen species from the semiconductor surface is demonstrated. The combinations of this passivation layer with relatively low temperature and short post lift-off annealing in an oxygen deficient environment result in significantly reduced contact oxidation and subsequently better transistor performance. Contact resistance as low as 90 Ω cm and mobility as high as 5.3 cm²/V s are obtained for solution processed mixed metal oxide semiconductor in top-contact geometry.