Hydrogen Storage in Metal-Organic Frameworks

Recent decades have witnessed the explosive emergence of metal organic frameworks (MOFs) as functional ultrahigh surface area materials. Categorized as an intriguing class of hybrid materials, MOFs exhibit infinite crystalline lattices with inorganic vertices and molecular-scale organic linkers. Fortunately, the large internal surface areas and overall pore volumes, adjustable pore sizes, ultralow densities, and tunable framework–adsorbate interaction by ligand functionalization and metal choice, enable MOFs to be promising materials for wide applications. In particular, these remarkable properties render MOFs potential hydrogen storage materials. By virtue of their exceptionally high surface areas, unparalleled tenability and structural diversity, MOFs have become a hotspot of research within the scientific community. This paper reviews the different methods used for the synthesis of MOFs, the relationship between structural features and hydrogen adsorption, the strategies for hydrogen uptake improvement as well as the molecular simulation.     

Tuning the topology and functionality of metal-organic frameworks by ligand design

Metal-organic frameworks (MOFs)-highly crystalline hybrid materials that combine metal ions with rigid organic ligands-have emerged as an important class of porous materials. The organic ligands add flexibility and diversity to the chemical structures and functions of these materials. In this Account, we summarize our laboratory's experience in tuning the topology and functionality of MOFs by ligand design. These investigations have led to new materials with interesting properties. By using a ligand that can adopt different symmetry conformations through free internal bond rotation, we have obtained two MOFs that are supramolecular stereoisomers of each other at different reaction temperatures. In another case, where the dimerized ligands function as a D(3)-Piedfort unit spacer, we achieve chiral (10,3)-a networks. In the design of MOF-based materials for hydrogen and methane storage, we focused on increasing the gas affinity of frameworks by using ligands with different geometries to control the pore size and effectively introduce unsaturated metal centers (UMCs) into the framework. Framework interpenetration in PCN-6 (PCN stands for porous coordination network) can lead to higher hydrogen uptake. Because of the proper alignment of the UMCs, PCN-12 holds the record for uptake of hydrogen at 77 K/760 Torr. In the case of methane storage, PCN-14 with anthracene-derived ligand achieves breakthrough storage capacity, at a level 28% higher than the U.S. Department of Energy target. Selective gas adsorption requires a pore size comparable to that of the target gas molecules; therefore, we use bulky ligands and network interpenetration to reduce the pore size. In addition, with the help of an amphiphilic ligand, we were able to use temperature to continuously change pore size in a 2D layer MOF. Adding charge to an organic ligand can also stabilize frameworks. By ionizing the amine group within mesoMOF-1, the resulting electronic repulsion keeps the network from collapsing, giving rise to the first case of mesoporous MOF that demonstrates the type IV isotherm. We use dendritic hexacarboxylate ligands to synthesize an isoreticular series of MOFs with (3,24)-connected network topology. The cuboctahedral cages serve as building blocks that narrow the opening of the mesocavities into microwindows and stabilize these MOFs. The resulting materials have exceptionally high surface areas and hydrogen uptake capacities. Despite the many achievements in MOF development, there is still ample opportunity for further exploration. We will be continuing our efforts and look forward to contributing to this blossoming field in the next decade.     

Metal Organic Frameworks as Solid Acid Catalysts for Acetalization of Aldehydes with Methanol

Room temperature acetalization of aldehydes with methanol has been carried out using metal organic frameworks (MOFs) as solid heterogeneous catalysts. Of the MOFs tested, a copper‐containing MOF [Cu₃(BTC)₂] (BTC=1,3,5‐benzenetricarboxylate) showed better catalytic activity than an iron‐containing MOF [Fe(BTC)] and an aluminium containing MOF [Al₂(BDC)₃] (BDC=1,4‐benzenedicarboxylate). The protocol was validated for a series of aromatic and aliphatic aldehydes and used to protect various aldehydes into commercially important acetals in good yields without the need of water removal. In addition, the reusability and heterogeneity of this catalytic system was demonstrated. The structural stability of MOF was further studied by characterization with powder X‐ray diffraction, Brunauer–Emmett–Teller surface area measurements and Fourier‐transformed infrared spectroscopic analysis of a deactivated catalyst used to convert a large amount of benzaldehyde. The performance of copper MOF as acetalization catalyst compares favourably with those of other conventional homogeneous and heterogeneous catalysts such as zinc chloride, zeolite and clay.     

锆基金属有机骨架材料用于氨吸附性能的研究

近年来,金属有机骨架材料（MOF）在气体吸附和储存领域得到了迅速发展,但由于结构的不稳定性,其在强腐蚀性气体氨（NH₃）的吸附方面并不令人满意。考虑到NH₃是唯一的无碳排放的氢能源载体,开发高效的储氨技术来载氢是有效的降低二氧化碳排放的手段。利用MOF材料具有的高比表面积和结构多样的特性,在NH₃的吸附和储存方面具有广阔的应用前景。而NH₃具有孤对电子,会攻击金属与配体之间形成的配位键,使MOF材料的结构遭到破坏。锆基金属有机骨架材料是公认结构稳定性较好的MOF材料,但其是否能胜任干燥NH₃及含水条件下的稳定性仍未深入考察,由此需探究该系列材料在NH₃吸附领域的适用性。在此,通过实验和计算模拟研究锆基系列的金属有机骨架UiO-66、NU-1000、MOF-801和 MOF-808的结构特征、稳定性和NH₃吸附性能。结果表明,UiO-66、NU-1000和MOF-808在纯NH₃环境下的稳定性较好,并且显示出高吸附量且可循环的氨吸附性能（13.04、6.38、9.65 mmol/g）。受限于水和氨对结构的协同破坏作用,NU-1000和MOF-801的结构均不能维持,而UiO-66和MOF-808的结构非常稳定,无论在干燥NH₃环境及含水NH₃环境下均能胜任而应用于NH₃吸附和储存。     

QSAR model for ethylene polymerisation catalysed by supported bis(imino)pyridine iron complexes

We present a quantitative structure–activity relationship study performed over a set of bis(imino)pyridine iron catalyst used for olefin polymerisation. The experimental results were previously obtained by our research group. The structural variability of this catalyst set is mainly focused on the substituents of the aryl rings. We managed to find a statistically robust model which correlates the experimentally determined polymer's molecular weight with the steric and electrostatic fields. As a result the main contribution comes from the steric contribution which amounts up to 75% of the model. The predictive capability of the model was successfully probed with a test set of catalyst reported in the literature by other research group.     

Emerging Synthetic Methods and Applications of MOF-Based Gels in Supercapacitors,Water Treatment,Catalysis, Adsorption,and Energy Storage

Metal–organic frameworks (MOFs), which are synthesized through the self-assembly of organic ligands and inorganic metals, have drawn considerable research interest owing to their unique properties and attractive structures. Many studies on various MOF derivatives, such as MOFs and cellulose aerogels, hydrogel composite materials, and bimetallic-centered MOF materials, have provided the potential for wide application of MOFs. However, MOFs mostly exist in the form of powder particles, which are difficult to form. In addition, MOFs have problems with structural instability. MOF-based gels can overcome this problem. MOF-based gels also have significant advantages in secondary processing. In this review, synthetic methods for MOF-based gels, particularly the synergistic effect with other materials, are introduced. The applications of MOF-based hydrogels and aerogels in supercapacitors, water treatment, catalysis, adsorption, and energy storage are also discussed.     

High‐throughput and comprehensive prediction of H2 adsorption in metal‐organic frameworks under various conditions

High‐throughput prediction of H₂ adsorption in metal‐organic framework (MOF) materials has been extended from a few specific conditions to the whole T, p space. The prediction is based on a classical density functional theory and has been implemented over 712 MOFs in 441 different conditions covering a wide range. Some testing materials show excellent behavior at low temperatures and obvious improvement at high temperatures compared to conventional MOFs. The structures of the best MOFs at high and low temperatures are totally different. Linear and nonlinear correlations between the two Langmuir parameters have been found at high and low temperatures, respectively. According to the analysis of the excess uptake, we found that the saturated pressure increases along with temperature in the low temperature region but decreases in the high temperature region. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2951–2957, 2015     

Encapsulation and controlled release of fragrances from functionalized porous metal–organic frameworks

In the fragrance and perfume industry, the encapsulation and controlled release of fragrance is important to appeal to consumers and promote the quality of products. Here, we demonstrate that porous metal–organic frameworks (MOFs) can effectively encapsulate and release fragrant molecules in a controlled manner. The incorporation of functional groups into MOFs can improve the adsorption and release behavior of fragrant molecules. We find that polar ester-type fragrances exhibit higher adsorption on polar hydroxyl-functionalized MOF [UiO-66-(OH)₂] than on nonpolar MOF (UiO-66), while nonpolar terpenoid-type fragrances show no adsorption difference between these two MOFs. The release profiles show that UiO-66-(OH)₂ can prolong the release of polar fragrances compared with nonpolar fragrances. Both the experimental results and computer molecular modeling demonstrate that the hydroxyl groups in UiO-66-(OH)₂ can form strong hydrogen binding with different ester fragrances. The releasing kinetics indicates that pore diffusion is the rate-limiting step of fragrance release from MOFs. © 2018 American Institute of Chemical Engineers AIChE J, 65: 491–499, 2019     

金属有机框架材料吸附分离水中铀的应用

金属有机框架材料（metal-organic frameworks,MOFs）具有极高的比表面积和孔隙率,结构可设计调控,但在水相吸附分离方面存在水稳定和选择吸附性较差、分离困难、合成与再生成本偏高等问题。针对MOFs的缺陷,可以通过有目的的功能化改性从而提升其对目标污染物的吸附性能。本文介绍了MOFs的结构优势,分析了水稳定性的影响因素和判断手段,简述了具有代表性的高水稳定性MOFs材料的特性;根据MOFs改性方法的分类回顾了MOFs及改性MOFs在去除水相中放射性铀的应用;基于不同分析技术探讨了MOFs与铀酰离子的吸附机理;提出推动MOFs在吸附铀方面规模化应用发展的核心是合成高稳定性MOFs,通过改性提高MOFs的选择吸附性能和再生性以及深入研究吸附机理。     

Computational screening of porous carbons,zeolites, and metal organic frameworks for desulfurization and decarburization of biogas,natural gas,and flue gas

Eighteen kinds of porous materials from carbons, zeolites, and metal organic frameworks (MOFs) have been extensively investigated for desulfurization and decarburization of the biogas, natural gas, and flue gas by using a molecular modeling approach. By considering not only the selectivity but also capacity, Na‐5A, zeolite‐like MOF (zMOF), and Na‐13X, MIL‐47 are screened as the most promising candidates for removal of sulfide in the CH₄? CO₂? H₂S and N₂? CO₂? SO₂ systems, respectively. However, for simultaneous removal of sulfide and CO₂, the best candidates are zMOF for the natural gas and biogas (i.e., CH₄? CO₂? H₂S system) and MOF‐74‐Zn for the flue gas (i.e., N₂? CO₂? SO₂ system). Moreover, the regeneration ability of the recommended adsorbents is further assessed by studying the effect of temperature on adsorption. It is found that compared to the zMOF and MIL‐47 MOFs, the Na‐5A and Na‐13X zeolites are not easily regenerated due to the difficulty in desorption of sulfide at high temperature, which results from the stronger adsorbent–adsorbate interactions in zeolites. The effect of sulfide concentration on the adsorption properties of the recommended adsorbents is also explored. We observe that the zMOF and MIL‐47 are also superior to the Na‐5A and Na‐13X for desulfurization of gas mixtures containing high sulfide concentration. This is because MOFs with larger pore volume lead to a greater sulfide uptake. The effects of porosity, framework density, pore volume, and accessible surface area on the separation performance are analyzed. The optimum porosity is about 0.5–0.6, to meet the requirements of both high selectivity and uptake. It is expected this work provides a useful guidance for the practical applications of desulfurization and decarburization. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2928–2942, 2013     

CO2/CH4 and CH4/N2 separation on isomeric metal organic frameworks☆

Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH_4 and N_2 adsorption properties of the two isomeric MOFs were investigated from 263 K to 298 K at0.1 MPa.The results showed that the 2D MOF exhibited a higher selectivity for CO_2 from CO_2/CH_4 and CH_4from CH_4/N_2 compared to the 3D MOF,even though it possessed a lower surface area and pore volume.The higher adsorption heats of gases on the 2D MOF inferred the strong adsorption potential energy in the layered MOFs.Dynamic separation experiments using CO_2/CH_4 and CH_4/N_2 mixtures on the two MOFs proved that the2 D MOF had a longer elution time than the 3D MOF as well as better separation abilities.     

Research on synthesis and application of metal-organic frame composites in supercapacitors

Electrode material is a key component of supercapacitors (SCs). As a porous material, metal-organic frameworks (MOFs) have attracted much attention in the field of SCs electrode materials due to their high specific surface area, controllable structure, and adjustable pore size. The low conductivity and stability of MOFs are still the main challenges in practical applications. MOF composite materials are a type of composite materials composed of MOFs and one or more different materials. They can effectively combine the advantages of MOFs with the advantages of other functional materials, such as excellent electrical conductivity and unique electrochemical properties. Therefore, MOF composite materials can achieve high reversible capacity and excellent cycle performance, overcome the shortcomings of MOFs materials, and have broad application prospects in the field of SCs electrode materials. According to the dimensional classification of the materials combined with MOFs, they can be divided into four types of composite materials: 0D, 1D, 2D, and 3D MOFs. The composition and synthesis methods of these four types of composite materials are reviewed. The application of MOF composite materials in the field of SCs is systematically introduced. Furthermore, its development prospects are prospected.     

用于发光温度传感的金属有机框架材料

金属有机框架(Metal organic frameworks,MOFs)由于其显著的结构多样性和可调的发光性能,为制备不同种类的发光传感器提供了良好契机。近年来,利用发光MOFs探测温度传感技术受到了人们的广泛关注。结合对发光测温的描述后,总结了发光型MOF温度计的最新研究进展,重点介绍了双发射型MOF在温度传感领域中的广泛应用。     

金属有机框架复合材料在超级电容器中的合成及应用研究

电极材料是超级电容器（SCs）的关键部件,金属有机框架（MOFs）作为一种多孔材料,由于其具有比表面积大、结构可控、孔径可调等优点在SCs电极材料领域得到诸多关注,而MOFs的低导电性和稳定性仍然是实际应用中的主要挑战。MOF复合材料是一类由MOFs与一种或多种不同材料组成的复合材料,它可以有效地结合MOFs和其他功能材料的优势,例如优良的导电性和独特的电化学性质等。因此,MOF复合材料可以实现高可逆容量和优良的循环性能,克服MOFs材料的缺点,在超级电容器电极材料领域具有广阔的应用前景。根据与MOFs复合的材料维度分类,可分为0D、1D、2D和3D MOFs四类复合材料,重点综述了这四类复合材料的组成及合成方法,并系统介绍了MOF复合材料的SCs应用,对其发展前景进行展望。     

Spillover enhanced hydrogen storage in Pt-doped MOF/graphene oxide composite produced via an impregnation method

Pt-doped MOF/graphene oxide (GO) composites were synthesized via a colloidal Pt nanoparticle (NP) incipient-wetness impregnation method for the first time. The composites Pt@HKUST-1/GO and Pt@ZIF-8/GO were characterized by X-ray diffraction, electron microscopy and gas adsorption. The hydrogen uptakes of both composites at 298 K and 860 mm Hg were enhanced by a factor of 3.6 or 4.1 compared to MOFs, although Pt NPs were obviously aggregated throughout MOF/GO networks. This significant enhancement is mainly attributed to the combination of high porosities of MOF/GO supports and hydrogen spillover mechanism, in which Pt NPs and MOF/GO act as dissociation source and receptor, respectively.     

Potential Therapeutic Effects of Mg/HCOOH Metal Organic Framework on Relieving Osteoarthritis

This study was designed to explore the potential therapeutic effects of Mg-based metal organic frameworks (MOFs) in osteoarthritis (OA) and to broaden the application field of MOFs. Mg/HCOOH−MOF was introduced and characterized by using SEM, XRD, TGA, and FTIR. ICP-MS results proved that Mg/HCOOH−MOF is stable in various physiological media and can maintain the release of Mg²⁺ ions for a long time. In vitro experiments were carried out to evaluate its potential application in attenuating OA. Mg/HCOOH−MOF was successfully synthesized, and results of MTT assays showed that it is biocompatible and can promote cell proliferation. qPCR results suggested that it can significantly regulate the expression of OCN, Axin2, iNOS and IL-1β, which indicated its activity in anti-inflammation and bone protection. We believe that Mg/HCOOH−MOF could benefit OA therapy.     

A porous mixed-valent iron MOF exhibiting the acs net: Synthesis, characterization and sorption behavior of Fe3O(F4BDC)3(H2O)3·(DMF)3.5

A new mixed-valent iron MOF, formulated as Fe₃O(F₄BDC)₃(H₂O)₃·(DMF)_3.5 (1), has been synthesized by using a perfluorinated linear dicarboxylate to link trigonal prismatic Fe₃(μ³-O)(O₂C–)₆ clusters. The structure refinement based on single crystal X-ray diffraction data collected from 1 reveals the material exhibits the acs topology with large channels along the crystallographic c-axis. Due to the presence of fluorine atoms the organic link, 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate (F₄BDC), has a 63° torsion angle between the carboxylate and aromatic planes, resulting in larger channels compared to those in the isoreticular material MOF-235. While few iron-based MOFs have demonstrated porosity, nitrogen and hydrogen sorption experiments carried out at 77 K proved the porosity of outgassed 1, which has a Langmuir surface are of 635 m²/g and a gravimetric capacity of 0.9 wt% of hydrogen at 1 bar.     

构筑手性金属有机骨架的方法及其在不对称催化中的应用

手性金属有机骨架(MOF)具有独特的结构、不对称催化和手性拆分等性能,引起了催化学者的极大重视.系统地介绍了国内外有关手性MOF的合成方法,即:①非手性物质在晶体生长过程中自组装;②使用手性化合物来诱导合成;③通过手性有机基团与金属离子配位将手性成分嵌入金属有机骨架;④表面修饰的方法,第3种方法是最常用的合成手性MOF的方法.重点阐述了近年来手性MOF在不对称催化领域的最新研究成果,希望能为手性MOF研究者设计、合成更优良的手性MOF催化剂提供参考.未来手性MOF催化的主要目标在于合成性能更加高效、稳定的新型手性MOF催化剂,并应用于大规模工业生产中,在温和条件下实现较高的转化数和对映体选择性.     

Poly(L‐lactic acid) metal organic framework composites: optical,thermal and mechanical properties

Biodegradable composites based on poly(L ‐lactic acid) (PLLA) and metal organic frameworks (MOFs) were developed. PLLA without and with the addition of 1, 3 and 5 wt% MOFs was melt compounded in a microextruder. The optical, physical, thermal, mechanical and thermomechanical properties of the composites were evaluated. The Fourier transform infrared, ultraviolet and colorimetric studies showed selected absorption at particular wavelengths due to the presence of copper and benzene belonging to the MOFs. The dynamic mechanical analysis results revealed that the heat deflection temperature, storage modulus and loss modulus of the PLLA–MOF composites did not significantly change compared with the neat PLLA samples. However, a significant decrease in the brittleness of the PLLA–MOF composite was found as evidenced by an increase of 15% in Izod impact strength and 170% in elongation at break. Overall, the brittleness of the PLLA–MOF composite sample decreased as the amount of MOF in the PLLA increased. Copyright © 2011 Society of Chemical Industry