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Mesoporous Metal Organic Framework

Xiaodong Zhang, Yang Yang, Xutian Lv, Yuxin Wang, Ning Liu, Dan Chen, Lifeng Cui
In this work, micro-mesoporous UiO-66 was successfully prepared with P123 (EO20 PO70 EO20 ) as structure-directing agent by a simple solvothermal method. Adsorption/desorption kinetics of gaseous toluene over pristine UiO-66 and micro-mesoporous UiO-66 were investigated by breakthrough experiments, toluene vapor adsorption isotherm measurements and temperature programmed desorption (TPD) experiments. The interactions between toluene and UiO-66 samples were assessed through the Henry's law constant (KH ) and the isosteric adsorption heat (ΔHads )...
November 26, 2018: Journal of Hazardous Materials
Dongdong Xu, Hao Lv, Ben Liu
Metal nanoparticles (NPs) exhibit desired activities in various catalytic reactions. However, the aggregation and sintering of metal NPs usually cause the loss of catalytic performance in practical reaction processes. Encapsulation of catalytically active metal NPs on/within a high-surface-area inorganic support partially resolve such concerns. Microporous zeolites, owing to their rigid frameworks and porous structural features, have been considered as one of ideal inorganic supports. Metal NPs can be easily encapsulated and stabilized within zeolitic frameworks to prevent unwished aggregation during the catalysis...
2018: Frontiers in Chemistry
Xin-Yue Lou, Yu-Peng Li, Ying-Wei Yang
Supramolecular nanovalves are an emerging class of important elements that are functionalized on the surfaces of inorganic or hybrid nanocarriers in the constructions of smart cargo delivery systems. Taking advantage of the pseudorotaxane structure via host-guest complexation and the dynamic nature of supramolecular interactions, macrocyclic arene-based supramolecular nanovalves have shown great promise in the applications of drug delivery and controlled release. Careful selection of diverse external stimuli, such as pH variations, temperature changes, redox, enzymes, light irradiation and competitive binding, can activate the opening and closing of the nanovalves by altering the supramolecular structure or binding affinities...
November 20, 2018: Biotechnology Journal
Qi Liu, Yinyin Song, Yanhang Ma, Yi Zhou, Hengjiang Cong, Chao Wang, Jorryn Wu, Gaoli Hu, Michael O'Keeffe, Hexiang Deng
We report the design and synthesis of two metal-organic frameworks (MOFs) with permanent porosity, MOF-818 and MOF-919, us-ing a small di-topic organic linker, 1H-pyrazole-4-carboxylic acid (H2PyC), 0.4 nm in length. Three mesoporous cages of unprecedent-ed polyhedra are identified in these MOFs, wuh cage in MOF-818, yys and liu cages in MOF-919, with the diameter of 3.8, 4.9 and 6.0 nm, respectively. The di-topic H2PyC linker functions as the edge in the structure, while two types of metal-containing second building units (SBUs) function as the vertices...
November 19, 2018: Journal of the American Chemical Society
Hong Zhao, Guiqin Yu, Man Yuan, Jin Yang, Dan Xu, Zhengping Dong
The fabrication of stable porous organic polymers (POPs) with heteroatoms that can firmly anchor noble metal nanoparticles (NPs) is a challenging and significant task for heterogeneous catalysis. In the current work, we used piperazine and cyanuric chloride as precursors and successfully fabricated a PC-POP material. Then, through the impregnation method and subsequently the reduction method, ultrafine Pt NPs were confined in the PC-POP with a high dispersion. The Pt NP active sites are accessible due to the uniform mesopores of the PC-POP that facilitate diffusion and mass transfer...
December 7, 2018: Nanoscale
Fanchen Meng, Suoying Zhang, Lu Ma, Weina Zhang, Matthew Li, Tianpin Wu, Hang Li, Tao Zhang, Xiaohua Lu, Fengwei Huo, Jun Lu
Nanoparticles@metal-organic frameworks (MOFs) composites have attracted considerable attention in recent years due to the prominent selective catalytic activity. However, it is highly desirable to develop a simple and universal way to settle the trade-off between the catalytic efficiency and selectivity. Herein, by employing the thermal instability of inherent defects, hierarchically porous Pt@UiO-66-NH2 , Pt@UiO-66, Pt@ZIF-8, and Au@ZIF-8 are successfully constructed after annealing at an appropriate temperature, respectively...
October 10, 2018: Advanced Materials
Shinji Inagaki
Periodic mesoporous organosilicas (PMOs), synthesized via surfactant-directed self-assembly of a polysilylated organic precursor (R[Si(OR')3 ]n ; n≥2, R: organic group), are promising candidates such as catalysts and adsorbents, and for use in optical and electrical devices, owing to their high surface area, well-defined nanoporous structure, and highly functional organosilica framework. Their framework functionality can be widely tuned by selecting appropriate organic groups and controlling their arrangement...
2018: Enzymes
Vincent Guillerm, Heng Xu, Jorge Albalad, Inhar Imaz, Daniel Maspoch
Herein we report a novel, ozone-based method for postsynthetic generation of mesoporosity in metal-organic frameworks (MOFs). By carefully selecting mixed-ligand Zr-fcu-MOFs based on organic ligand pairs in which one ligand has ozone-cleavable olefin bonds and the other ligand is ozone-resistant, we were able to selectively break the cleavable ligand via ozonolysis to trigger fusion of micropores into mesopores within the MOF framework. This solid-gas phase method is performed at room-temperature, and, depending on the cleavable ligand used, the resultant ligand-fragments can be removed from the ozonated MOF by either washing or sublimation...
October 26, 2018: Journal of the American Chemical Society
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...
November 2018: Small
Effrosyni Gkaniatsou, Clémence Sicard, Rémy Ricoux, Linda Benahmed, Flavien Bourdreux, Qi Zhang, Christian Serre, Jean-Pierre Mahy, Nathalie Steunou
Microperoxidase-8, a small, peroxidase-type enzyme was immobilized into nanoparticles of the mesoporous and ultra-stable metal-organic framework (MOF) MIL-101(Cr). The immobilized enzyme fully retained 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...
February 1, 2019: 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...
February 1, 2019: 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...
January 15, 2019: 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 to 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 CoII sites were imposed by ligands flanked with fused benzene rings on both sides, compromising such extra-sites enhancement...
August 20, 2018: ChemSusChem
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