Construction of hierarchically porous metal-organic framework particle by a facile MOF-template strategy

Increasing the mass diffusion efficiency is a major challenge in the realm of metal-organic frameworks (MOFs). Construction of hierarchically porous, typically microporous MOF adsorbents or catalysts is crucial for enhancing both mass transfer and molecular accessibility. Many strategies have been proposed for the synthesis of hierarchically porous MOFs (HP-MOFs), with some striking results. In this paper, we proposed a facile and versatile strategy, termed the MOF-Template strategy, for fabricating hierarchical pores in MOF particle. The highly controlled crystalline sizes and morphologies of the unstable Cu-MOFs Cu₃(BTC)₂ and Cu(Qc)₂ have been exploited in their utilization as sacrificial agents by uniformly dispersing them during the shaping process of ZIF-8. Through a facile treatment with alkaline solution, tunable mesopores and macropores could be easily introduced in the shaped ZIF-8 spheres. This strategy could effectively improve the adsorption kinetics and separation productivity of MOF materials while maintaining high mechanical stability, offering promising prospects for industrial application.     

涉氢环境机械部件的摩擦学研究现状

氢气作为一种清洁、高效、可持续的二次能源,在未来我国终端能源体系占比至少10%,以氢能作为汽车和飞机动力学系统燃料的研究成为热点. 机械运动部件表界面与氢介质将发生复杂的物理化学反应,影响着机械运动接触面的摩擦学行为,使役过程中氢致疲劳、磨损及腐蚀失效行为,严重制约着机械动力部件运行稳定性、可靠性和安全性. 本文中重点调研了国际上氢气气氛环境下机械运动部件材料的摩擦磨损行为研究进展,总结了氢气环境下聚合物基、陶瓷基、金属基及低维度固体颗粒材料的摩擦磨损行为及其损伤失效演变规律,进一步阐述了摩擦工况下氢气和其他气体介质共存与使役材料的摩擦学行为之间的关联性. 从摩擦学角度提出了抑制氢致损伤的可行性关键技术及防护材料,并对未来涉氢机械部件服役安全性的科学问题进行了展望.      

Traction–separation laws and stick–slip shear phenomenon of interfaces between cellulose nanocrystals

Cellulose nanocrystals (CNCs) are one of nature's most abundant structural material building blocks and possess outstanding mechanical properties including a tensile modulus comparable to Kevlar. It remains challenging to upscale these properties in CNC neat films and nanocomposites due to the difficulty of characterizing interfacial bonding between CNCs that governs stress transfer under deformation. Here we present new analyses based on atomistic simulations of shear and tensile failure of the interfaces between Iβ CNCs, providing new insight into factors governing the mechanical behavior of hierarchical nanocellulose materials. We compare the two most relevant crystal interfaces and find that hydrogen bonded surfaces have greater tensile strength compared to the surfaces governed by weaker interactions. On the contrary, shearing simulations reveal that friction between the atomic interfaces depends not only on surface energy but also the energy landscape along the shear direction. While being a weaker interface, the intersheet plane exhibits greater energy barriers to shear. The molecular roughness of this interface, characterized by a greater energy barrier, exhibits stick–slip deformation behavior as opposed to a more continuous sliding and rebonding mechanism observed for the interfaces with hydrogen bonds. Analytical models to describe the energy landscapes are developed using energy scaling relations for van der Waals surfaces in combination with a modification of the Prandtl–Tomlinson model for atomic friction. Our simulations pave the way for tailoring hierarchical CNC materials by taking a similar approach to techniques employed for describing metals, where mechanical properties can be tuned through a deeper understanding of grain boundary physics and nanoscale interfaces.     

High-Throughput Screening of Metal-Organic Frameworks for the Impure Hydrogen Storage Supplying to a Fuel Cell Vehicle

Transport in Porous Media - Metal-organic frameworks (MOFs), as typical porous materials, have been widely used for gas storage. However, impurities usually coexist in the stored gas, which will...     

In-situ constructing visible light CdS/Cd-MOF photocatalyst with enhanced photodegradation of methylene blue

Based on high specific surface area, high porosity of metal-organic frameworks (MOFs) and excellent visible light response of CdS, the CdS/Cd-MOF nanocomposites were constructed by in-situ sulfurization to form CdS using Cd-MOF as precursor and the CdS loading was controlled by the dose of thioacetamide. Under the irradiation of simulated sunlight, the degradation rate of methylene blue (MB) by 10 mg MOF/CdS-6 (mass ratio of MOF to thioacetamide is 6:1) was 91.9% in 100 min, which was higher than that of pure Cd-MOF (62.3%) and pure CdS (67.5%). This is attributed to the larger specific surface area of the composite catalysts, which provides more active sites. Meanwhile, the loading of CdS obviously broadens the light response range of Cd-MOF and improves the utilization of visible light. The Mott-Schottky model experiment shows that the formed type-II heterojunction between Cd-MOF and CdS can effectively inhibit the recombination of photogenerated electrons and holes. Meanwhile, the photocurrent intensity of MOF/CdS-6 is 8 times and 2.5 times of that of pure Cd-MOF and CdS. In addition, MOF/CdS-6 showed good photocatalytic performance after five cycles, showing excellent stability and reusability.     

Thermal energy storage： Challenges and the role of particle technology

Thermal energy is at the heart of the whole energy chain providing a main linkage between the primary and secondary energy sources. Thermal energy storage （TES） has a pivotal role to play in the energy chain and hence in future low carbon economy. However, a competitive TES technology requires a number of scientific and technological challenges to be addressed including TES materials, TES components and devices, and integration of TES devices with energy networks and associated dynamic optimization. This paper provides a perspective of TES technology with a focus on TES materials challenges using molten salts based phase change materials for medium and high temperature applications. Two key challenges for the molten salt based TES materials are chemical incompatibility and low thermal conductivity. The use of composite materials provides an avenue to meeting the challenges. Such composite materials consist of a phase change material, a structural supporting material, and a thermal conductivity enhancement material. The properties of the supporting material could determine the dispersion of the thermal con- ductivity enhancement material in the salt. A right combination of the salt, the structural supporting material, and the thermal conductivity enhancement material could give a hierarchical structure that is able to encapsulate the molten salt and give a substantial enhancement in the thermal conductivity. Understanding of the structure-property relationships for the composite is essential for the formulation design and fabrication of the composite materials. Linking materials properties to the system level performance is recommended as a key future direction of research.     

Thermal energy storage: Challenges and the role of particle technology

Thermal energy is at the heart of the whole energy chain providing a main linkage between the primary and secondary energy sources. Thermal energy storage (TES) has a pivotal role to play in the energy chain and hence in future low carbon economy. However, a competitive TES technology requires a number of scientific and technological challenges to be addressed including TES materials, TES components and devices, and integration of TES devices with energy networks and associated dynamic optimization. This paper provides a perspective of TES technology with a focus on TES materials challenges using molten salts based phase change materials for medium and high temperature applications. Two key challenges for the molten salt based TES materials are chemical incompatibility and low thermal conductivity. The use of composite materials provides an avenue to meeting the challenges. Such composite materials consist of a phase change material, a structural supporting material, and a thermal conductivity enhancement material. The properties of the supporting material could determine the dispersion of the thermal conductivity enhancement material in the salt. A right combination of the salt, the structural supporting material, and the thermal conductivity enhancement material could give a hierarchical structure that is able to encapsulate the molten salt and give a substantial enhancement in the thermal conductivity. Understanding of the structure–property relationships for the composite is essential for the formulation design and fabrication of the composite materials. Linking materials properties to the system level performance is recommended as a key future direction of research.     

活性材料冲击释能行为研究进展

活性材料是一种具备释能特性的新型材料,其在冲击导致的高压/高温作用下可以发生化学反应,释放大量的化学能,因此在破片、聚能破甲战斗部等军事领域有广泛的应用潜力。为了实现对活性材料释能过程的设计与控制,推进活性材料武器化应用进程,就必须解答活性材料冲击释能行为中所包含的一系列复杂的力-热-化耦合问题。近40年来,对活性材料的冲击释能行为已开展了大量研究,本文在此基础上系统梳理了活性材料的冲击诱发化学反应机理、动力学以及相关效应的研究现状,重点关注活性材料的冲击释能实验表征技术、冲击诱发化学反应理论模型以及考虑力-热-化耦合的冲击压缩数值模拟方法等3方面的研究进展。总结认为,对活性材料冲击释能行为的研究已经具有一定的积淀,但目前对实验中超快化学反应行为的实时诊断研究还缺乏更加丰富、精细、直观的表征与探索,相关理论与数值模拟研究尚未建立能够完整描述活性材料冲击释能行为的力-热-化理论模型,缺乏能够从宏观尺度描述冲击释能行为的有效方法。因此,超快化学反应实验表征技术、宏观角度的力-热-化机理与模型建立及其数值模拟应用以及具备可调性能的活性材料制备新工艺3方面研究内容将是推进活性材料未来军事化应用的重点关注对象。     

A theory for grain boundaries with strain-gradient plasticity

In this work, the effect of the material microstructural interface between two materials (i.e., grain boundary in polycrystalls) is adopted into a thermodynamic-based higher order strain gradient plasticity framework. The developed grain boundary flow rule accounts for the energy storage at the grain boundary due to the dislocation pile up as well as energy dissipation caused by the dislocation transfer through the grain boundary. The theory is developed based on the decomposition of the thermodynamic conjugate forces into energetic and dissipative counterparts which provides the constitutive equations to have both energetic and dissipative gradient length scales for the grain and grain boundary. The numerical solution for the proposed framework is also presented here within the finite element context. The material parameters of the gradient framework are also calibrated using an extensive set of micro-scale experimental measurements of thin metal films over a wide range of size and temperature of the samples.     

材料高温力学性能理论表征方法研究进展

随着科学技术的迅猛发展,材料在高温领域的应用越来越广泛。然而高温下材料的力学性能和常温相比有很大差异,材料的高温力学性能研究和表征已成为当前的研究热点。论文文对材料在高温下力学行为理论表征方法研究的最新进展进行了总结和回顾。着重介绍了近年来高温陶瓷材料的断裂强度、金属材料的屈服强度、弹性模量与本构关系的温度相关性理论表征方法的研究进展。最后,总结已有研究工作的特点和不足之处,对材料高温力学性能理论表征方法的后续研究进行了展望,就进一步研究提供建议。     

Composites graphite/sel pour le stockage d'énergie à haute température : étude des effets du graphite et de la microstructure des composites sur les propriétés de changement de phase des sels

Thermal energy storage at high temperature is an efficient way for energy saving in the industrial sector, as well as a key component for power generation based on renewable energy resources. Thermal energy storage technology based on phase change materials (mainly salts) has been identified to meet the requirements of investment costs and compactness. However, the low thermal conductivity of salts (1 W/m/K) could be a limiting factor concerning power. To overcome such a drawback, new materials combining salts with graphite have been developed. Nevertheless, it is important to verify that no degradation of the salts storage properties is induced by their thermal conductivity enhancement. In this Note, the effects of the graphite and the composites graphite/salt microstructure on the phase change properties of salts are analysed. To cite this article: J. Lopez et al., C. R. Mecanique 336 (2008).     

Mechanics of hydrogen storage in carbon nanotubes

A continuum mechanics model is established for hydrogen storage in single- and multi-wall carbon nanotubes (CNTs) and the bundle of single-wall CNTs. The model accounts for the deformation of CNTs, and van der Waals interactions among hydrogen molecules and between hydrogen and carbon atoms. The analytical expressions of hydrogen storage (number of hydrogen molecules per unit volume) in CNTs are obtained, and are validated by atomistic simulations. CNTs are categorized as tiny, small, medium and large CNTs; tiny CNTs cannot achieve the goals of hydrogen storage (62 kg/m³ and 6.5 wt% of hydrogen set by the US Department of Energy) without fracture; small CNTs are strained during hydrogen storage; medium CNTs can achieve the above goals without the strain and do not self collapse; and large CNTs may self collapse upon the release of hydrogen.     

Characterization and modification of waste magnesium chip utilized as an Mg-rich intermetallic composite

In this study,the characterization and modification of waste magnesium chips（WMCs）,which were produced by plastic molding in a gold manufacturing factory and are used as Mg-rich intermetallic composites in storing hydrogen,were discussed in detail.WMCs were analyzed using X-ray diffraction（XRD）,X-ray fluorescence（XRF） spectroscopy,differential scanning calorimetry（DSC）,scanning electron microscopy（SEM）,and Brunauer-Emmett-Teller（BET） analysis to characterize the materials’ structural properties.Mechanical milling,organic treatment,and inorganic salt addition were carried out to modify the WMCs’ surface to prepare Mg-rich intermetallic composites for storing hydrogen.The modified samples were analyzed using high-pressure volumetric analyses to calculate their hydrogen storage capacity.The authors conclude that modified WMC was promising as an Mg-rich intermetallic composite that was suitable for use in hydrogen storage with a 4.59 wt%capacity at 320 C under a hydrogen pressure of 60 bar.     

Multi‐material incompressible flow simulation using the moment‐of‐fluid method

This paper compares the numerical performance of the moment‐of‐fluid (MOF) interface reconstruction technique with Youngs, LVIRA, power diagram (PD), and Swartz interface reconstruction techniques in the context of a volume‐of‐fluid (VOF) based finite element projection method for the numerical simulation of variable‐density incompressible viscous flows. In pure advection tests with multiple materials MOF shows dramatic improvements in accuracy compared with the other methods. In incompressible flows where density differences determine the flow evolution, all the methods perform similarly for two material flows on structured grids. On unstructured grids, the second‐order MOF, LVIRA, and Swartz methods perform similarly and show improvement over the first‐order Youngs' and PD methods. For flow simulations with more than two materials, MOF shows increased accuracy in interface positions on coarse meshes. In most cases, the convergence and accuracy of the computed flow solution was not strongly affected by interface reconstruction method. Published in 2009 by John Wiley & Sons, Ltd.     

Engineering models for synthetic microvascular materials with interphase mass,momentum and energy transfer

New materials are being developed that consist of a solid matrix with pores or vessels through which a functional fluid phase may pass. The fluid can provide expanded functionality such as healing and remodeling, damage disclosure, enhanced heat transfer, and controlled deformation, stiffness and damping. This paper presents a class of engineering models for synthetic microvascular materials that have fluid passages much smaller than a characteristic structural length such as panel thickness. The materials are idealized as two-phase continua with a solid phase and a fluid phase occupying every volume. The model permits the solid and fluid phases to exchange mass, momentum and energy. Balance equations and the entropy inequality for general mixtures are taken from existing continuum mixture theory. These are augmented with certain definite types of solid–fluid interactions in order to enable adequately general, but workable, engineering analysis. The thermomechanical characteristics of this restricted class of materials are delineated. By demanding that the law of increase of entropy be satisfied for all processes, much is deduced about the acceptable forms of constitutive equations and internal state variable evolution equations. The paper concludes with a study of the uniaxial tension behavior of an idealized vascular material.     

On separation of energies in viscoelasticity

Separation of the storaged and dissipated energies in viscoelastic deformation is considered. This is a key problem for the construction of viscoelastic minimum rinciples and for the micromechanics of heterogeneous materials with memory. The notion of the viscoelastic free energy functional is discussed, thermodynamic admissibility conditions are established. An engineering analysis is realized through the method of harmonic strain regimes, influence of the loss and the storage moduli on the dissipation rate is studied. For the Volterra-Frechet integral expansion approach, necessary conditions on the general form of a free energy viscoelastic functional are formulated. The obtained results are used to examine the thermodynamic validity of certain classic viscoelastic models, like that of Staverman-Schwarzl. Through the spectral method, this energy representation is shown to correspond to a generalized Maxwell model.     

Analytical approximation for solidification processes in PCM storage with internal fins: imposed heat flux

Uses of thermal energy storage systems have expanded notably in recent decades. In thermal energy systems, internal heat transfer enhancement techniques such as fins are often used because of the low thermal conductivity of the phase change materials (PCMs). In this paper, solidification of a PCM is studied in a rectangular storage with horizontal internal plate fins and an imposed constant heat flux on the vertical walls. A simplified analytical solution is presented and its results are compared to those for a numerical approach based on an enthalpy method. The fraction of solidified PCM in storage is calculated with the derived analytical model which determines how much of the storage is solidified after a certain time. The results show that the analytical model satisfactorily estimates the solid–liquid interface and the temperature distribution for the fin, which are useful in the design of PCM-based thermal energy storage or cooling systems.     

Design of layered-stacking graphene assemblies as advanced electrodes for supercapacitors

Graphene is a competitive electrode material for supercapacitors due to its unique two-dimensional structure, large surface area, high conductivity, and good physicochemical stability. However, random agglomeration and restacking of graphene sheets result in a reduced surface area and a loose structure with low density, which severely restricts the application for high gravimetric/volumetric energy density devices. Rational design of the layered-stacking structure of graphene assemblies can effectively prevent the restacking of graphene sheets, construct efficient ion transport channels, and improve spatial utilization, demonstrating the huge potential for developing advanced electrode materials. Herein, from the aspect of improving the electrochemical kinetics through designing efficient electron and ion transport paths, we first highlight the advantages of layered-stacking graphene assemblies, describe some common routes for preparing graphene building units, and then summarize the novel methods to design layered-stacking structures. A comprehensive review of the typical structure including nanocarbon pillared graphene, porous graphene blocks, and graphene ribbon films is provided with a focus on the mechanisms behind the performance improvements. Finally, critical challenges and some general ideas for future development are proposed, which may open up new opportunities for material chemistry and device innovation.     

周期性蜂窝材料微极等效模型及其微观应力的一种快速算法

将周期性蜂窝材料等效为具有非局部本构的微极连续介质,以解释实验中出现的尺度效应和边界层效应.在评论相关的多种不同方法(能量法、体积平均的均匀化法等)之后,提出了一种基于位移连续和单胞力平衡的推导微极等效本构参数的新方法.以正方形单胞制成的结构为例,在不同的结构与单胞尺寸比下,考虑承受集中点载荷、均布轴力和均布剪力三种载荷工况,比较了离散完全计算、经典连续介质等效和不同微极连续体等效本构的计算结果,建议了较好的微极本构参数值.数值模拟表明,集中点载荷和剪切载荷作用时,在加载点附近和边界部分,微极等效可以显著提高计算精度.最后,给出了一种映射算法,可以根据微极等效连续体分析的结果,快速计算出对应微观单胞构件的应力,以开有圆孔的方板应力集中为例,验证并考察了所提快速算法的有效性和计算精度.