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Mesoporous Metal Organic Framework

Zhengyun Wang, Ting Liu, Yang Yu, Muhammad Asif, Ning Xu, Fei Xiao, Hongfang Liu
The emergence of metal-organic frameworks (MOFs) has sparked intensive attention and opened up the possibility of "crystal engineering." However, low conductivity, slow diffusion of guest molecules, as well as powder forms always hinder the development of MOF application, especially for biosensors and bioelectronics. Herein, a coffee ring-inspired strategy toward oriented self-assembly of a biomimetic MOF film following Murray's law is proposed, which can effectively reduce the transfer resistance...
October 18, 2018: Small
Effrosyni Gkaniatsou, Clemence Sicard, Rémy Ricoux, Linda Benahmed, Flavien Bourdreux, Qi Zhang, Christian Serre, Jean-Pierre Mahy, Nathalie Steunou
Microperoxidase-8, a small, peroxidase-type enzyme was successfully immobilized into nanoparticles of the mesoporous and ultra-stable MIL-101(Cr). The immobilized enzyme retained fully its catalytic activity and exhibited enhanced resistance to acidic conditions. The biocatalyst was reusable and showed a long-term stability. By exploiting the properties of the MOF's framework, we demonstrated, for the first time, that the MOF matrix could act in synergy with the enzyme (Microperoxidase-8) and enhance selectivity the oxidation reaction of dyes...
October 11, 2018: Angewandte Chemie
Mahdiyeh Rashki Ghaleno, Mansour Ghaffari-Moghaddam, Mostafa Khajeh, Ali Reza Oveisi, Mousa Bohlooli
A bioinspired iron(III)porphyrinic Zr-MOF, PCN-222(Fe), was modified by post-synthetic cluster metalation with iron(III) chloride, as a cheap, earth-abundant, and environmentally friendly metal precursor, towards formation a new multifunctional MOF, namely Fe@PCN-222(Fe). The MOF consists of bimetallic (Zr-oxo-Fe) nodes linked by Fe(III)porphyrin struts. The cluster metalation and pre-activation treatment of PCN-222(Fe) were performed cooperatively using the FeCl3 . The respective MOF was characterized through various techniques, such as FT-IR, PXRD, ICP-AES, BET surface area, SEM, UV-Vis DRS, TGA/DSC, PL, and XPS analyses...
September 29, 2018: Journal of Colloid and Interface Science
Yuanyuan Liu, Pramila Ghimire, Mietek Jaroniec
The development of novel porous materials for CO2 capture and storage has received increasing attention due to the global warming problem. The aim of this work was to develop novel composites by merging Cu-BTC framework and porous carbon materials, including ordered mesoporous non-activated carbon (OMC), ordered mesoporous activated carbon (AC), and nitrogen-containing microporous carbon (NC) as efficient adsorbents for CO2 capture. The morphology, porosity and surface area of the parent materials and composites were fully characterized...
September 25, 2018: Journal of Colloid and Interface Science
Xin Leng, Xiaoxv Dong, Wenping Wang, Na Sai, Chunjing Yang, Longtai You, Hongliang Huang, Xingbin Yin, Jian Ni
Sustained-release preparation is a hot spot in antitumor drug research, where the first task is to select suitable drug carriers. Research has revealed that carboxylic acid iron metal⁻organic frameworks (MOFs), constructed from iron (Fe) ions and terephthalic acid, are nontoxic and biocompatible. Due to the breathing effect, the skeleton of this mesoporous material is flexible and can reversibly adapt its pore size through drug adsorption. Therefore, we chose one kind of Fe-MOF, MIL-53(Fe), as a carrier for the anticancer drug oridonin (Ori)...
September 28, 2018: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
Jie Wu, Mengjia Liu, Hongwei Hou
Converting light hydrocarbons, such as methane, ethane, propane, and cyclohexane into value-added chemicals and fuel products by direct C-H functionalization is an attractive method in the petrochemical industry. Emerging as a relatively new class of porous solid materials, metal-organic frameworks (MOFs) are appealing as single-site heterogeneous catalysts or catalyst supports for C-H bond activation. In contrast to the traditional microporous and mesoporous materials, MOFs feature high porosity, versatile structural and functional tunability, and molecular level characterization of the structures for the study of structure-property relationships...
September 27, 2018: Chemistry: a European Journal
Ying Yang, Dehong Zeng, Senjie Yang, Lin Gu, Baijun Liu, Shijie Hao
Core-shell structured carbon nanofiber@metal oxide is one of the most promising hybrid electrodes as supercapacitors, in which the pseudocapacitive metal oxides can be fully exerted and stabilized on the carbonaceous scaffolds. However, facile fabrication of mesoporous carbon nanofibers and integration of them with metal oxides are challenging. Herein, we report a new type of mesoporous carbon nanofibers (MCNs), derived from zinc-trimesic acid fibers, acting as the scaffolds to anchor nickel cobaltite (NiCo2 O4 ) nanosheets after surface O-functionalization...
September 12, 2018: Journal of Colloid and Interface Science
Lian Xia, Lijie Liu, Yanan Dou, Lan Guo, Guoliang Li, Zhiwei Sun, Jinmao You
Owing to the big molecular sizes of polycyclic aromatic hydrocarbons, adsorption of them using microporous sorbents leaded to low adsorption capacity. Here, to increase extraction capacity and detection sensitivity of polycyclic aromatic hydrocarbons, a highly efficient dispersive micro solid phase extraction method was developed based on a stable mesoporous metal-organic framework named Jilin University China 48. Jilin University China 48 is a super hybrid with large 1D hexagonal nanotube-like channels of 24...
September 19, 2018: Journal of Separation Science
X Unamuno, E Imbuluzqueta, F Salles, P Horcajada, M J Blanco-Prieto
Due to their high porosity and versatile composition and structure, nanoscaled Metal-Organic Frameworks (nanoMOFs) have been recently proposed as novel drug delivery systems, and have been demonstrated to have important capacities and potential for controlled release of different active ingredients. Gentamicin (GM; a broad spectrum aminoglycoside antibiotic indicated in bacterial septicemia therapy) has great therapeutic interest, but the associated bioavailability and toxicity drawbacks accompanying high doses and repeated administration of this free drug make its encapsulation inside new nanocarriers necessary...
September 1, 2018: European Journal of Pharmaceutics and Biopharmaceutics
Ines M Hönicke, Irena Senkovska, Volodymyr Bon, Igor A Baburin, Nadine Bönisch, Silvia Raschke, Jack D Evans, Stefan Kaskel
A new mesoporous metal-organic framework (MOF; DUT-60) was conceptually designed in silico using Zn4 O6+ nodes, ditopic and tritopic linkers to explore the stability limits of framework architectures with ultrahigh porosity. The robust ith-d topology of DUT-60 provides an average bulk and shear modulus (4.97 GPa and 0.50 GPa, respectively) for this ultra-porous framework, a key prerequisite to suppress pore collapse during desolvation. Subsequently, a cluster precursor approach, resulting in minimal side product formation in the solvothermal synthesis, was used to produce DUT-60, a new crystalline framework with the highest recorded accessible pore volume (5...
October 15, 2018: Angewandte Chemie
Dongmei Wang, Jian Zhang, Guanghua Li, Jiaqi Yuan, Jiantang Li, Qisheng Huo, Yunling Liu
Despite many advances in the design and assembly of mesoporous metal-organic frameworks (meso-MOFs), it is still a challenge to obtain the desired structure. Here, we utilized an effective cluster cooperative assembly strategy by introducing SO4 2- ions as chelating binding sites to construct a novel mesoporous MOF, [Cu8 (SO4 )(TBA)6 (OH)2 ( N,N-dimethylacetamide (DMA))4 ]·12DMA·12CH3 OH [JLU-MOF51, H2 TBA = 4-(1 H-tetrazol-5-yl)-benzoic acid]. Remarkably, the cooperative assembly of the infrequent hexanuclear [Cu6 SO4 (OH)2 ] cluster and the classical paddlewheel [Cu2 (CO2 )4 ] via linear hetero-N, O donor ligand results in an open three-dimensional framework, which possesses one-dimensional nanometer tube channels with the diameter of 24 and 28 Å...
September 19, 2018: ACS Applied Materials & Interfaces
Wei Meng, Yongfei Zeng, Zibin Liang, Wenhan Guo, Chenxu Zhi, Yingxiao Wu, Ruiqin Zhong, Chong Qu, Ruqiang Zou
Three Co-based isostructural MOF-74-III materials with expanded pores are synthesized, with varied extent of fused-benzene rings onto sidechain of same-length ligands to finely tune the pore sizes as 2.6, 2.4 and 2.2 nm. Gas sorption results for these highly mesoporous materials show that alternately arranged fused-benzene rings on one side of the ligand could serve as extra anchoring sites for CO2 molecules with π-π interactions, conspicuously enhancing CO2 uptake and CO2/CH4 and CO2/N2 selectivity; while more steric hindrance effect towards open Co(II) sites were imposed by ligands flanked with fused-benzene rings on both sides, compromising such extra-sites enhancement...
August 20, 2018: ChemSusChem
Yingxiang Ye, Shimin Chen, Liangji Chen, Jitao Huang, Zhenlin Ma, Ziyin Li, Zizhu Yao, Jindan Zhang, Zhangjing Zhang, Shengchang Xiang
Although supramolecular isomerism in metal-organic frameworks (MOFs) would offer a favorable platform for in-depth exploring their structure-property relationship, the design and synthesis of the isomers are still rather a challenging aspect of crystal engineering. Here, a pair of supramolecular isomers of Co(II)-based MOFs (FJU-88 and FJU-89) can be directionally fabricated by rational tuning the additives. In spite of the fact that the isomers have the similar Co3 secondary building units and organic linkers, they adopt distinct networks with acs and snw topologies, respectively, which derive from the conformational flexibility of the organic ligands...
September 12, 2018: ACS Applied Materials & Interfaces
Chung-Wei Kung, Ana E Platero-Prats, Riki J Drout, Junmo Kang, Timothy C Wang, Cornelius O Audu, Mark C Hersam, Karena W Chapman, Omar K Farha, Joseph T Hupp
A representative mesoporous metal-organic-framework (MOF) material, NU-1000, has been rendered electronically conductive via a robust inorganic approach that permits retention of MOF crystallinity and porosity. The approach is based on condensed-phase grafting of molecular tin species onto the MOF nodes via irreversible reaction with hydroxyl and aqua ligands presented at the node surface, a self-limiting process termed solvothermal installation (of metal ions) in MOFs (SIM, a solution-phase analog of atomic layer deposition in MOFs)...
September 12, 2018: ACS Applied Materials & Interfaces
Dingxin Liu, Dianting Zou, Haolin Zhu, Jianyong Zhang
Metal-organic frameworks (MOFs) have attracted much attention over the past two decades due to their highly promising applications not only in the fields of gas storage, separation, catalysis, drug delivery, and sensors, but also in relatively new fields such as electric, magnetic, and optical materials resulting from their extremely high surface areas, open channels and large pore cavities compared with traditional porous materials like carbon and inorganic zeolites. Particularly, MOFs involving pores within the mesoscopic scale possess unique textural properties, leading to a series of research in the design and applications of mesoporous MOFs...
September 2018: Small
Yana Liu, Cheng Zhang, Chen Xu, Caixue Lin, Keke Sun, Jie Wang, Xueli Chen, Ling Li, Andrew K Whittaker, Hai-Bing Xu
Using a facile one-step hydrothermal method, a series of metal-organic frameworks containing Gd/Tm (Gd/Tm-MOFs) were prepared successfully. Through the mutual activation of Gd3+ and Tm3+, Gd/Tm-MOFs showed unexpected excellent up-conversion luminescence (UCL) and a superior positive magnetic resonance image (MRI). Using doxorubicin hydrochloride (DOX) as a drug model, the feasibility of Gd/Tm-MOFs as a multifunctional drug carrier was demonstrated. Through modifying Gd/Tm-MOFs with uniform mesoporous silica (mSiO2) shells and folic acid (FA), the drug loading was improved up to 41...
August 14, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Biswa Nath Bhadra, Sung Hwa Jhung
A series of metal-organic framework-74s (MOF-74s), composed of two different metallic species (Zn/Ni or Zn/Mn in various compositions), were synthesized, and Ni or MnO-doped carbonaceous materials were first prepared by pyrolysis of the MOFs under an inert environment for catalytic applications. These MOF-derived nanomaterials (MDNMs), obtained by pyrolysis of MOF-74s, were characterized thoroughly to understand their phase, porosity, particle size, dispersion, and composition. With increasing Zn content in the bimetallic MOF-74s, the porosity of the MDNMs increased but the size and content of Ni or MnO in the MDNMs decreased monotonously...
August 9, 2018: Nanoscale
Hong Yu, Khang Ngoc Dinh, Yuanmiao Sun, Haosen Fan, Yonghui Wang, Yao Jing, Shuzhou Li, Madhavi Srinivasan, Qingyu Yan
Novel nitrogen-doped porous molybdenum carbide (α-MoC1-x and β-Mo2C) architectures were prepared using Mo-based metal-organic frameworks (MOFs) as the precursor. The synthesized molybdenum carbides consist of numerous nanocrystals organized into micro-sized rods with interpenetrating mesoporous-channels and macroporous-tunnels along the axial direction. When employed as the cathode catalyst for Li-O2 batteries, this dual pore configuration offers abundant active sites for the electrochemical reaction and many nucleation sites for the discharge product of Li2O2; hence, decent performances were obtained...
August 9, 2018: Nanoscale
Qiang Wang, Xu-Sheng Wang, Chun-Hui Chen, Xue Yang, Yuan-Biao Huang, Rong Cao
Highly dispersed ultrafine defective Pt nanoparticles (NPs) encapsulated in the mesopores of MIL-101 were successfully achieved for the first time through a facile chemical dealloying approach. PtCo alloy NPs inside the mesoporous MIL-101 were firstly formed via a double-solvent method and the Co species were subsequently selectively etched by diluted nitric acid to achieve the defective Pt NPs. Compared with PtCo alloy NPs, the as-prepared defective Pt NPs showed an improved catalytic activity towards the hydrogenation of nitroarenes under mild conditions...
August 7, 2018: Chemical Communications: Chem Comm
Seo-Yul Kim, Tae-Ung Yoon, Jo Hong Kang, Ah-Reum Kim, Tea-Hoon Kim, Seung-Ik Kim, Wanje Park, Ki Chul Kim, Youn-Sang Bae
Olefin/paraffin separation is an important and challenging issue because the two molecules have similar physicochemical properties. Although a couple of olefin adsorbents have been developed by introducing inorganic nanoparticles into metal-organic frameworks (MOFs), there has been no study on the development of an olefin adsorbent by introducing a certain organic functional group into a MOF. In this study, we posited that azo compounds could offer olefin/paraffin selectivity. We have revealed using first-principles calculations that the simplest aromatic azo compound (azobenzene, Azob) has an unusual propylene/propane selectivity due to special electrostatic interactions between Azob and propylene molecules...
August 15, 2018: ACS Applied Materials & Interfaces
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