The complexation of silicon with carbon materials is considered an effective method for using silicon as an anode material for lithium-ion batteries. In the present study, carbon frameworks with a 3D porous structure were fabricated using metal–organic frameworks (MOFs), which have been drawing significant attention as a promising material in a wide range of applications. Subsequently, the fabricated carbon frameworks were subjected to CVD to obtain silicon-carbon complexes. These siliconcarbon complexes with a 3D porous structure exhibited excellent rate capability because they provided sufficient paths for Li-ion diffusion while facilitating contact with the electrolyte. In addition, unoccupied space within the silicon complex, combined with the stable structure of the carbon framework, allowed the volume expansion of silicon and the resultant stress to be more effectively accommodated, thereby reducing electrode expansion. The major findings of the present study demonstrate the applicability of MOF-based carbon frameworks as a material for silicon complex anodes.
유기 전구체와 금속 이온, 또는 금속-옥소 클로스터 간의 규칙적 배열을 통한 종의 다양성을 장점으로 하는 금속- 유기 골격체(Metal-Organic Frameworks, MOFs)는 에너지 사용량이 높은 상변화 기반 분리공정을 대체할 수 있는 에너지 효율 적인 막 기반 분리 기술의 개발 가능성을 열어주었다. 이에 최근 10년 동안 다결정 MOFs 분리막 합성 기술에서 상당한 진전 이 있었지만, 매우 제한된 종류의 MOFs만이 활용되고 있다. 이러한 기술 개발의 정체는 다결정 분리막의 비 선택적인 확산 경로인 결정 사이 결함(intercrystalline defects)에 대한 명확한 해결법이 없기 때문이다. 후처리 성능 제어기술(postsynthetic modifications, PSMs)은 기존 분리막을 플랫폼으로 활용하고 이를 물리적 그리고/혹은 화학적으로 처리함을 통해 분리 특성 을 개선 혹은 변경하는 기술을 말한다. PSMs 기술은 특정 분리막을 개발하는 데 있어서 새로운 MOFs를 설계하거나 막 합성 기술을 개발하지 않아도 된다는 장점이 있어서 다결정 MOF 분리막의 다양성을 제공하기 위한 새로 부상하는 전략으로 평가 된다. 본 총설에서는 PSMs 기술을 7개의 세부기술((1) 공유결합법, (2) 결정간 결함 플러깅법, (3) 결정 내부 결함 치유법, (4) 기공내 기능성 소재 함침법, (5) 기공 경화법, (6) 전구체 치환법 및 (7) 비정질화법)로 분류하고, 각 세부기술의 연구 동향 및 도전과제 그리고 향후 연구 방향에 대해 논의하고자 한다.
We have prepared MIL-101/graphene oxide (GO) composites with various mixing molar ratio of Fe-containing metal– organic frameworks (MOFs) against GO. When synthesizing MOFs, it was possible to synthesize uniform crystal powders using hydrothermal method. MIL-101 consists of a terephthalic acid (TPA) ligand, with the central metal composed of Fe, which was the working electrode material for supercapacitors. Field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis had been done to ascertain microstructures and morphologies of the composites. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge measurements were performed to analyze the electrochemical properties of the composite electrodes in 6 M KOH electrolyte. By controlling the metal ligand mole ratio against GO, we prepared a changed MOF structure and a different composite morphology, which could be studied as one of the promising optimized electrode materials for supercapacitors.
Metal–organic frameworks (MOFs) are widely used as supports for single-atom catalysts (SACs) owing to their high specific surface area, porosity, and ordered metal–ligand structure. Their activity can be increased by increasing the number of electrochemically accessible active sites via the formation of atomically dispersed metal catalysts (M–Nx) that coordinate with nitrogen atoms on the MOF. Herein, we introduce the relationship between the size of the MOF as a starting material and the catalytic activity for the oxygen reduction reaction in alkaline media. The morphology and features of the MOFs are critically dependent on their size. Remarkably, cage-like MOFs below 33 nm are converted into collapsed structures and are connected between each MOF, even carbon fiber- or tube-like features, after carbonization. SACs derived from medium-sized MOFs exhibit excellent activity and are comparable to commercial Pt/C catalysts owing to their porous structure. Therefore, we believed that controlling the size of MOFs containing active atoms is an effective method of modulating the morphological properties of the support and even the number of active sites that are closely related to the activity.
The magnetocaloric effect (MCE), which is the reversible temperature change of magnetic materials due to an applied magnetic field, occurs largely in the vicinity of the magnetic phase transition temperature. This phenomenon can be used to induce magnetic refrigeration, a viable, energy-efficient solid-state cooling technology. Recently, Metal-organic frameworks (MOFs), due to their structural diversity of tunable crystalline pore structure and chemical functionality, have been studied as good candidates for magnetic refrigeration materials in the cryogenic region. In cryogenic cooling applications, MCE using MOF can have great potential, and is even considered comparable to conventional lanthanum alloys and magnetic nanoparticles. Owing to the presence of large internal pores, however, MOF also exhibits the drawback of low magnetic density. To overcome this problem, therefore, recent reports in literature that achieve high magnetic entropy change using a dense structure formation and ligand tuning are introduced.
We developed a facile methodology for fabricating a free-standing mixed-matrix membrane (MMM) containing covalently incorporated vinyl-functionalized UiO-66-CH=CH2 particles up to 60 wt% by utilizing thiol-ene photopolymerization. FTIR, TGA, SEM, EDX, and XRD strongly supported the fact that the desired MMM containing well-dispersed UiO-66-CH=CH2 particles was successfully produced by C–S bond formation. The MMM was highly flexible and showed improved mechanical properties compared to the pristine polymeric membrane, indicating that the covalently immobilized UiO-66-CH=CH2 particles were homogeneously distributed in the polymer matrix. Gas permeability across the MMM was significantly enhanced compared with the pristine polymeric membrane as diffusion of the gas molecules was facilitated in the porous space of the MOF.
Nitrogen is a serious contaminant in natural gas because it decreases the energy density. The natural gas specification in South Korea requires a N2 content of less than 1 mol%. Thus, cost-effective N2 removal technology from natural gas is necessary, but until now the only option has been energy-intensive processes, e.g., cryogenic distillation. Using porous materials for the removal process would be beneficial for an efficient separation of CH4/N2 mixtures, but this still remains one of the challenges in modern separation technology due to the very similar size of the components. Among various porous materials, metal-organic frameworks (MOFs) present a promising candidate for the potential CH4/N2 separation material due to their unique structural flexibility. A MIL-53(Al), the most well-known flexible metal-organic framework, creates dynamic changes with closed pore (cp) transitions to open pores (ops), also called the ‘breathing’ phenomenon. We demonstrate the separation performance of CH4/N2 mixtures of MIL-53(Al) and its derivative MIL-53-NH2. The CH4/N2 selectivity of MIL- 53-NH2 is higher than pristine MIL-53(Al), suggesting a stronger CH4 interaction with NH2.