Massive Anisotropic Thermal Expansion and Thermo‐Responsive Breathing in Metal–Organic Frameworks Modulated by Linker Functionalization

Functionalized metal–organic frameworks (fu‐MOFs) of general formula [Zn₂(fu‐L)₂dabco]_n show unprecedentedly large uniaxial positive and negative thermal expansion (fu‐L = alkoxy functionalized 1,4‐benzenedicarboxylate, dabco = 1,4‐diazabicyclo[2.2.2]octane). The magnitude of the volumetric thermal expansion is more comparable to property of liquid water rather than any crystalline solid‐state material. The alkoxy side chains of fu‐L are connected to the framework skeleton but nevertheless exhibit large conformational flexibility. Thermally induced motion of these side chains induces extremely large anisotropic framework expansion and eventually triggers reversible solid state phase transitions to drastically expanded structures. The thermo‐responsive properties of these hybrid solid–liquid materials are precisely controlled by the choice and combination of fu‐Ls and depend on functional moieties and chain lengths. In principle, this combinatorial approach allows for a targeted design of extreme thermo‐mechanical properties of MOFs addressing the regime between crystalline solid matter and the liquid state.     

负热膨胀材料及其在激光熔覆中的应用

激光熔覆是一种典型的表面改性技术,已得到了广泛的应用。在激光熔覆快速冷凝过程中容易产生热应力,进而产生变形,严重时会产生裂纹、失效等缺陷。负膨胀材料是指在一定温度范围内材料体积出现热缩冷涨行为的材料,和热胀冷缩材料正好相反,负膨胀材料的发现为解决材料在受热时出现膨胀变形和失效提供了处理方法。正确的使用负膨胀材料可以抑制激光熔覆加工中的裂纹和热应力集中等缺陷,提高熔覆层的机械性能,产生热膨胀可控的材料甚至零膨胀材料。本文分析了激光熔覆中裂纹产生的机理,对负膨胀材料的种类及负膨胀的原理进行了总结,对每种负膨胀材料产生负膨胀行为的条件进行了对比和分析,负膨胀材料的膨胀系数和产生负膨胀行为的温度区间会影响在激光熔覆过程中的使用。重点对国内外已经实验验证的负膨胀材料在激光熔覆中的应用进行了总结概括,提出负膨胀材料在激光熔覆中存在的一些普遍规律,以及现阶段负膨胀材料在激光熔覆应用中的不足,对负膨胀材料在激光熔覆中的应用进行概括和展望。     

Smart Metal–Organic Frameworks with Reversible Luminescence/Magnetic Switch Behavior for HCl Vapor Detection

Smart luminescent metal–organic frameworks (MOFs) demonstrate promising performance in the detection of toxic gases. The incorporation of twisted or rotary organic ligands with aggregation-induced emission (AIE) characteristics can provide further opportunities in designing such smart MOFs with new topologies and stimuli-responsive behaviors. Herein, novel AIE MOFs are reported with reversible luminescence or a magnetic switch for HCl vapor detection. The twisted conformation of tetrakis(4-carboxyphenyl)ethylene (TCPE) ligand leads to the unique [M⁺–L–M⁻–L–M]_∞ (M = metal clusters, L = ligand) configuration for ZnMOF and CoMOF. Different from conventional MOFs with [M–L]_∞ topology, ZnMOF and CoMOF exhibit a blue-to-yellow greenish fluorescence transition and a ferrimagnetic-to-antiferromagnetic switch behavior, respectively, upon recognition of HCl vapor. The adsorbed HCl molecules rather than coordinated ones are determined to be the main reason, and such luminescence and magnetic switch can be induced in a reversible manner via HCl vapor adsorption/desorption processes with high reliability. This work of AIE MOFs with twisted and rotary ligands shall pave new avenue in design of smart MOFs with new topologies and stimuli-responsive behavior for real-time sensing and detection applications.     

Laser metal interaction in vacuum

We investigate the processes by which energy is exchanged when a laser pulse is incident on a metal surface, originally in vacuum. The thermal state of the metal is determined by numerical solution of the nonlinear heat transfer equations. A method is described for extrapolating data on material thermal properties which are usually given at lower temperatures. Results are compared with the predictions of a steady-state calculation. Kinetic equations describing the growth of a plasma in the ablated vapor are formulated to describe effects of importance in the early stages of the plasma evolution process, when strong longitudinal spatial gradients cause thermal diffusion effects to dominate hydrodynamic expansion. Numerical studies of these equations indicate several distinct periods, during each of which a different physical mechanism takes on primary importance. Features of the numerical results pertaining to the propagation of the discharge front are deduced from an analytic model of the breakdown process.     

Analytical Solutions to Estimate the Temperature Sensitivity of Arrayed Waveguide Gratings With Stress Plates

Controlling thermal stress is a promising way to reduce the temperature instability of arrayed waveguide gratings (AWGs). A simple method to apply thermal stress is to attach stress plates on the arrayed waveguides. In this paper, a general analytical method to study the temperature sensitivity of the central wavelength in modified AWGs with stress plates is developed. The complete analysis shows that the temperature sensitivity can be controlled effectively by tuning the material parameters and the thickness of the stress plates. To obtain athermal AWGs, a stress plate with large positive thermal expansion coefficient and small Young's modulus should be attached on the bottom of the arrayed waveguides. The material with large negative thermal expansion coefficient suggests another potential scheme.      

Mechanical Loss of HTS Coils Reinforced With Negative Thermal Expansion Fiber Materials

High-$T_ c$superconducting (HTS) coils with various types of reinforcement are investigated with respect to the reduction of mechanical loss. The total AC loss of the coils is measured under an external DC magnetic field at liquid nitrogen temperature, the reduction of the mechanical loss components are estimated. Tensioned stainless-steel tape is found to be the most effective for reducing the mechanical loss by improving the rigidity of the entire winding. The mechanical loss of the HTS coils is reduced by reinforcement with a bobbin of negative thermal expansion material, although the hoop stress caused by radial expansion of the bobbin is absorbed by a small number of winding turns. Bobbins of negative thermal expansion material are therefore unsuitable for pancake-type coils or multilayer windings, but can be expected to realize substantial reductions in mechanical loss for single-layer windings or thin solenoids.     

材料性能参数与板料激光弯曲成形角度的相关性研究

板料激光弯曲成形是一种柔性、无模成形新工艺，它通过激光扫描金属板料所导致的非均匀热应力使板料产生塑性变形。材料的性能参数(包括力学性能与热物理性能)对激光弯曲成形的影响很大，通过三维热机耦合有限元仿真研究了材料性能参数与板料激光弯曲角度之间的相关性，研究表明，小弹性模量、低屈服强度的材料容易产生大的弯曲变形。热膨胀系数与弯曲角度之间成正比关系，当热膨胀系数趋于零时，弯曲角度也趋于零。小的热传导系数有利于形成大的温度梯度，从而使板料产生大的弯曲变形；比热越小，加热区内材料的温升越大，使板料容易弯曲变形。     

Synthesis and Functionalization of Oriented Metal–Organic‐Framework Nanosheets: Toward a Series of 2D Catalysts

Synthesis of metal–organic frameworks (MOFs) is based on coordination‐driven self‐assembly of metal ions and organic ligands. However, to date, it remains difficult to adjust the coordination behaviors of MOFs and then control geometric shapes of nanostructures; especially their morphologies in 1D nanofibers or 2D nanosheets have seldom been explored. Here, a facile route at room temperature and ambient pressure is reported for the preparation of copper‐based MOFs with low‐dimensional shapes (i.e., nanofibers, nanorods, nanosheets, and nanocuboids), via thermodynamic and kinetic controls over the anisotropic growth. Importantly, the as‐prepared 2D MOF nanosheets with monocrystalline nature (100% exposed {010} facets) provide a material platform to the fabrication of 2D supported metal nanocatalysts. First, the MOF nanosheets can serve as a self‐templating solid precursor to prepare different CuO and CuO‐Cu₂O nanocomposites, or even Cu metals via thermolysis or reduction under controlled atmospheres. Upon their formation, second, ultrafine noble metal nanoparticles (e.g., Au, Ag, Pt, Pd, Au_0.4Pt_0.6, Au_0.4Pd_0.6, and Au_0.3Pt_0.3Pd_0.4) can be exclusively anchored on the external surfaces of the MOF nanosheets. To show their open accessibility, catalytic activities of the derived catalysts have been evaluated using CO₂ hydrogenation and 4‐nitrophenol reduction in gas phase and liquid phase, respectively.     

Ultrafast Melting of Metal–Organic Frameworks for Advanced Nanophotonics

The conversion of metal–organic frameworks (MOFs) into derivatives with a well‐defined shape and composition is considered a reliable way to produce efficient catalysts and energy capacitors at the nanometer scale. Yet, approaches based on conventional melting of MOFs provide the derivatives such as amorphous carbon, metal oxides, or metallic nanoclusters with an appropriate morphology. Here ultrafast melting of MOFs is utilized by femtosecond laser pulses to produce a new generation of derivatives with complex morphology and enhanced nonlinear optical response. It is revealed that such a nonequilibrium process allows conversion of interpenetrated 3D MOFs comprising flexible ligands into well‐organized spheres with a metal oxide dendrite core and amorphous organic shell. The ability to produce such derivatives with a complex morphology is directly dependent on the electronic structure, crystal density, ligand flexibility, and morphology of initial MOFs. An enhanced second harmonic generation and three‐photon luminescence are also demonstrated due to the resonant interaction of 100–1000 nm spherical derivatives with light. The results obtained are in the favor of new approaches for melting special types of MOFs for nonlinear nanophotonics.     

Visible Light Triggered CO2 Liberation from Silver Nanocrystals Incorporated Metal–Organic Frameworks

Widespread deployment of metal–organic frameworks (MOFs) for CO₂ capture remains challenging due to the great energy‐penalty associated with their regeneration. To overcome this challenge, a new type of photodynamic carbon capture material synthesized by incorporating Ag nanocrystals with UiO‐66 (Ag/UiO‐66) framework is presented. Upon the irradiation of visible light, Ag nanocrystals within the composites serve as “nanoheaters” to convert photon energy into thermal energy locally. Driven by such light‐induced localized heat (LLH), the adsorbed CO₂ within MOFs is remotely released. The CO₂ desorption capacity of such Ag/UiO‐66 composites can be readily regulated by control over their Ag contents and the applied light intensity. Up to 90.5% of CO₂ desorption is achieved under the investigated conditions. Distinct from the traditional light‐responsive MOFs for gas trigger release, currently developed LLH‐driven CO₂ release method not only offers a promising solution to the heat‐insulating nature of MOFs, but also demonstrates a potentially low energy method to remotely regenerate MOF adsorbents given the utilization of naturally abundant visible light as efficient stimulus.     

Preconcentration of Nitroalkanes with Archetype Metal–Organic Frameworks (MOFs) as Concept for a Sensitive Sensing of Explosives in the Gas Phase

Thermal desorption based enrichment is a general concept that can enhance any detection system's sensitivity and selectivity. Given their large interior surface area and chemical versatility, archetype metal–organic frameworks (MOFs) are selected for preconcentration of explosives and their precursors occurring in low concentrations, and are compared to the state‐of‐the‐art sorbent Tenax TA . Applying inverse gas chromatography (iGC), this study shows that several archetype MOFs, namely HKUST‐1 and MIL‐53 , surpass Tenax regarding their specific retention volume for nitromethane, a typical ingredient in improvised explosives. Using linear hydrocarbons as reference probe molecules, the dispersive surface energy is determined for all MOFs along with the specific contribution of the nitro group for HKUST‐1 and ZIF‐8 . Trends from pulse‐chromatographic iGC‐investigations are mostly followed in breakthrough and thermal desorption experiments using a 1000 ppm nitromethane source. In these experiments, HKUST‐1 proves the peak substance, with enrichment factors being 109‐fold higher than for Tenax , followed by MIL‐53 . In case of HKUST‐1 , this factor is successfully reproduced for a 1 ppm concentration scenario. This shows that archetype MOFs can be suitable or even superior candidates for a sensitive sensing of nitroalkane explosives from the gas phase by a concept of preconcentration.     

Laser-Assisted Printing of Electrodes Using Metal–Organic Frameworks for Micro-Supercapacitors

Direct laser scribing, an advanced printing technique, has been recently developed to enable the carbonization of carbonaceous precursors in a rapid, precise, and cost-effective manner. Herein, it is reported that metal−organic frameworks (MOFs) can be converted into patterned derived carbon with desired structural features using a CO₂ infrared laser system. Metal species in MOFs play a key role in the morphology, porous structure, and crystallinity of the resulting laser-induced products by studying six representative MOFs. Diverse features such as ordered porous structure and continuous network microstructure can be obtained in the laser-induced MOF-derived carbon, which is influenced by the melting and boiling points of metals and their magnetic and catalytic behaviors. Furthermore, a core–shell structured composite (MOF-199@ZIF-67) has been designed and prepared for the fabrication of 12-interdigital electrodes derived from the composite by laser-assisted printing. The as-obtained electrodes with highly porous and hierarchical structure show an enhanced specific capacitance for micro-supercapacitors (MSCs). This work provides a complementary heat treatment method to produce MOF-derived carbon nanomaterials with desired structural features and patterns for MSCs and micro-device-related applications.     

Post-Synthetic Modification of Metal–Organic Frameworks Toward Applications

Post-synthetic modification (PSM) of metal–organic framework (MOF) compounds is a useful technique for preparing new MOFs that can exhibit or enhance many of the properties of the parent MOFs. PSM can be carried out by a number of approaches such as modifying the linker (ligand) and/or metal node, and adsorption/exchange of guest species. The surface environment of the MOF can be modified to increase structural stability as well as introducing desired properties. There is considerable scope in widening the applications of the MOF with compatible metal or ligand employing the PSM. This review focuses on the recent developments of modified materials through PSM, which augers well for the chemical modification and functionalization of MOFs. In this review, different types of PSM methods are presented in an orderly manner, and the diverse applications of resultant frameworks are described and discussed.     

金属PTC陶瓷复合材料结构及其导电机理

研究了金属ＰＴＣ陶瓷复合材料的电学性能和其材料组分。结果表明，掺入金属的ＰＴＣ陶瓷材料经氮气中烧结，然后在空气中进行热处理，材料表面形成高势垒层，金属ＰＴＣ陶瓷复合材料的室温电阻较ＰＴＣ的陶瓷高。样品之中存在大量不同类型的极化，在低温时样品电阻较高，温度增加后，大量各种类型离子极化出现，在变价金属铁的变价导电作用下，削弱表面势垒，使金属ＰＴＣ陶瓷复合材料电阻降低，表现出ＮＴＣ现象。在电场作用下，正负电荷、晶粒畸变和空位缺陷等产生空间电荷极化使金属ＰＴＣ陶瓷复合材料有较高介电常数。介电损耗（ｔｇδ）频谱和介电δ温度谱上都出现一个介电峰，其主要原因是跃迁极化，金属阳离子由一个位置跃迁到另一个位置，在介电损耗所对应的频率和温度时出现跃迁极化率最大     

材料性能参数对板料激光弯曲成形的影响

板料激光变曲成形是通过激光扫描金属板料所导致的非均匀热应力使板料产生塑性变形,材料的性能参数（包括材料的力学性能与热物理性能）对激光弯曲成形的影响很大。本文在实验的基础上,建立了符合实际的三维热机耦合有限元分析模型,对板料激光弯曲成形过程进行了数值仿真,研究了材料性能参数,如弹性模量、屈服强度、热膨胀系数、比热及热传导系数等对成形的影响规律。     

Thermo-mechanical stresses in copper interconnects - A modeling analysis

This study focuses on numerical modeling of thermo-mechanical stresses in copper interconnects. The three-dimensional analyses utilize a two-level metal structure connected by a via. Attention is devoted to the effects of the incorporation of polymer-based low-k dielectric material. Deformation is generated by thermal strain mismatches during cooling from an elevated temperature, as well as from cyclic thermal excursions. The thin barrier layers encasing the copper are also included in the models. Plastic deformation in the metal is taken into consideration in the analysis. The stress and deformation fields are examined in detail. It is found that the incorporation of low-k dielectric in place of traditional oxide-based dielectric significantly reduces the triaxial tensile stresses in copper but enhances plastic deformation, particularly in the via and its vicinity. The generation of shear stresses at the interface regions is also assessed. A parametric analysis is conducted to elucidate the individual influences of the thermal expansion and elastic properties of the dielectric material. Salient features having direct implications in device reliability are highlighted and discussed.     

Preparation and Characterization of Bi-metallic and Tri-metallic Metal Organic Frameworks Based on Trimesic Acid and Co(II), Ni(II), and Cu(II) Ions

Trimesic acid-M1(II):M2(II) (M1,2(II)=M(II)=Co(II), Ni(II) and Cu(II)) bi-metallic or tri-metallic organic frameworks (MOFs) were synthesized by the reaction of trimesic acid (H3BTC) ligand with the corresponding MCl₂nH₂O aqueous solutions. Here, bi- and tri-metallic MOF preparations were demonstrated by using H3BTC as an organic linker, with dual metal ion mixtures at different mole ratios such as Co(II):Ni(II), Ni(II):Cu(II), and Cu(II):Co(II) as metal ion sources in the synthesis of bi-metallic MOFs, and the triple metal ion mixture of Co(II):Ni(II):Cu(II) as the metal ion source in the synthesis of tri-metallic MOFs. The bi- or tri-metallic MOFs were characterized via the Brunauer–Emmett–Teller method, thermogravimetric analyzer (TGA), and magnetic susceptibility measurements with the Gouy method, FT-IR spectroscopy, and electronic spectral studies. The results revealed that the H3BTC MOFs have octahedral and distorted octahedral arrangement around the metal ions, and the d–d transition was not observed in the complex. It was further found that all the prepared MOFs contain water molecules confirmed by Fourier transform infrared (FT-IR) and TGA analyses. The FT-IR spectra of the MOF complexes were characterized by the appearance of a broad band in the region of 3454–3300 cm^?1 due to the ν(-OH) of the coordinated water; therefore, the location of the two water molecules was assumed to be inside the complex structure. Remarkably, the synthesized bi-metallic MOFs had unique and distinct colors depending on the amounts of metal ions used in the feed, implying that these bi-metallic MOFs with tunable M1(II) and M2(II) ratios offer great potential in the design of color-coded materials for use as sensors.     

Void Engineering in Metal–Organic Frameworks via Synergistic Etching and Surface Functionalization

The rational design and engineering of metal–organic framework (MOF) crystals with hollow features has been used for various applications. Here, a top‐down strategy is established to construct hollow MOFs via synergistic etching and surface functionalization by using phenolic acid. The macrosized cavities are created inside various types of MOFs without destroying the parent crystalline framework, as evidenced by electron microscopy and X‐ray diffraction. The modified MOFs are simultaneously coated by metal–phenolic films. This coating endows the MOFs with the additional functionality of responding to near infrared irradiation to produce heat for potential photothermal therapy applications.     

多普勒效应与激光外差技术复合检测金属线膨胀系数

物体的热膨胀性质反映了材料本身的属性,通常将固体受热后在一维方向上长度的变化称为线膨胀。测量材料的线膨胀系数,不仅对新材料的研制具有重要意义,而且也是选用材料的重要指标之一。将激光外差技术与多普勒效应深度融合,提出一种多光束激光外差测量金属线膨胀系数的新方法,即利用多普勒振镜把待测参数信息调制到多光束激光外差信号的频率差中,信号解调后可以同时获取多个待测参数信息,对多个待测参数加权平均,从而可以精确得到待测样品长度随温度的变化量,最终提高待测样品线膨胀系数的测量精度。基于该方法,对不同温度情况下金属棒线膨胀系数进行了仿真研究,结果表明该方法测量金属棒线膨胀系数的相对误差为0.1%。与传统测量方法相比,测量精度提高了一个数量级。     

Sublimation‐Vapor Phase Pseudomorphic Transformation of Template‐Directed MOFs for Efficient Oxygen Evolution Reaction

Using vapor phase transformation to synthesize template‐directed metal–organic frameworks (MOFs) shows great promise as an approach to avoid the shortcomings of solution‐based strategies. However, among current research, either the products are confined to zeolitic imidazolate frameworks or the conversion technologies are limited to complex processes such as chemical vapor deposition. Here, a well‐designed sublimation‐vapor phase pseudomorphic transformation method is reported to fabricate vertically aligned nanosheet arrays of NiFe‐based MOFs with a uniform and controlled thickness, derived from NiFe‐layered double hydroxides. Benefiting from the optimized morphology and the high intrinsic activity originating from the synergistic coupling effect of NiFe metal clusters, the as‐prepared MOF electrocatalyst displays a superior oxygen evolution reaction performance, requiring an overpotential of 318 mV at 50 mA cm^?2 with a Tafel slope of only 47 mV dec^?1. Furthermore, a string of metal oxide‐MOFs are obtained, demonstrating the universality of this strategy. By observing the different stages of transformation, the transformation and growth mechanism of MOF crystals is unveiled for the first time. These findings may inspire the exploration and preparation of more species of MOFs, further broadening their application areas.