共查询到20条相似文献,搜索用时 15 毫秒
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Hyeonbin Ha Youngik Kim Dopil Kim Jihyun Lee Yoodae Song Suyeon Kim Prof. Dr. Myung Hwan Park Prof. Dr. Youngjo Kim Hyungjun Kim Prof. Minyoung Yoon Prof. Dr. Min Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14414-14420
The effect of metal on the degree of flexibility upon evacuation of metal–organic frameworks (MOFs) has been revealed with positional control of the organic functionalities. Although Co-, Cu-, and Zn-based DMOFs (DMOF = DABCO MOF, DABCO = 1,4-diazabicyclo[2.2.2]octane) with ortho-ligands (2,3-NH2Cl) have frameworks that are inflexible upon evacuation, MOFs with para-ligands (2,5-NH2Cl) showed different N2 uptake amounts after evacuation by metal exchange. Considering that the structural analyses were not fully sufficiently different to explain the drastic changes in N2 adsorption after evacuation, quantum chemical simulation was explored. A new index (η) was defined to quantify the regularity around the metal based on differences in the oxygen-metal-oxygen angles. Within 2,5-NH2Cl, the η value becomes larger as the metal are varied from Co to Zn. A large η value means that the structures around the metal center are less ordered. These results can be used to explain flexibility changes upon evacuation by altering the metal cation in this regioisomeric system. 相似文献
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Hongfeng Li Peng Wu Yawen Xiao Meng Shao Yu Shen Yun Fan Huanhuan Chen Ruijie Xie Wenlei Zhang Prof. Sheng Li Prof. Jiansheng Wu Prof. Yu Fu Prof. Bing Zheng Prof. Weina Zhang Prof. Fengwei Huo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4793-4799
Metal–organic frameworks (MOFs) are promising materials with fascinating properties. Their widespread applications are sometimes hindered by the intrinsic instability of frameworks. However, this instability of MOFs can also be exploited for useful purposes. Herein, we report the use of MOFs as metal ion precursors for constructing functional nanocomposites by utilizing the instability of MOFs. The heterogeneous growth process of nanostructures on substrates involves the release of metal ions, nucleation on substrates, and formation of a covering structure. Specifically, the synthesized CoS with carbon nanotubes as substrates display enhanced performance in a lithium-ion battery. Such strategy not only presents a new way for exploiting the instability of MOFs but also supplies a prospect for designing versatile functional nanocomposites. 相似文献
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Xuan Gong Yufei Shu Zhuo Jiang Lingxiang Lu Xiaohui Xu Chao Wang Prof. Hexiang Deng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5364-5369
Discoveries of the accurate spatial arrangement of active sites in biological systems and cooperation between them for high catalytic efficiency are two major events in biology. However, precise tuning of these aspects is largely missing in the design of artificial catalysts. Here, a series of metal–organic frameworks (MOFs) were used, not only to overcome the limit of distance between active sites in bio-systems, but also to unveil the critical role of this distance for efficient catalysis. A linear correlation was established between photocatalytic activity and the reciprocal of inter active-site distance; a smaller distance led to higher activity. Vacancies created at selected crystallographic positions of MOFs promoted their photocatalytic efficiency. MOF-525-J33 with 15.6 Å inter active-site distance and 33 % vacancies exhibited unprecedented high turnover frequency of 29.5 h−1 in visible-light-driven acceptorless dehydrogenation of tetrahydroquinoline at room temperature. 相似文献
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William R. Webb Matthew E. Potter Daniel J. Stewart Stuart J. Elliott Pier J. A. Sazio Zhongxing Zhang He-Kuan Luo Jinghua Teng Liling Zhang Chiara Ivaldi Ivana Miletto Enrica Gianotti Prof. Robert Raja 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13606-13610
The grafting of imidazole species onto coordinatively unsaturated sites within metal–organic framework MIL-101(Cr) enables enhanced CO2 capture in close proximity to catalytic sites. The subsequent combination of CO2 and epoxide binding sites, as shown through theoretical findings, significantly improves the rate of cyclic carbonate formation, producing a highly active CO2 utilization catalyst. An array of spectroscopic investigations, in combination with theoretical calculations reveal the nature of the active sites and associated catalytic mechanism which validates the careful design of the hybrid MIL-101(Cr). 相似文献
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Paula G. Saiz Naroa Iglesias Bárbara González Navarrete Maibelin Rosales Yurieth Marcela Quintero Ander Reizabal Dr. Joseba Orive Dr. Arkaitz Fidalgo Marijuan Dr. Edurne S. Larrea Dr. Ana Catarina Lopes Prof. Luis Lezama Dr. Andreina García Prof. Senentxu Lanceros-Mendez Prof. María Isabel Arriortua Dr. Roberto Fernández de Luis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(61):13861-13872
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Dr. Xue Feng Lu Prof. Bao Yu Xia Prof. Shuang-Quan Zang Prof. Xiong Wen Lou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4662-4678
In view of the clean and sustainable energy, metal–organic frameworks (MOFs) based materials, including pristine MOFs, MOF composites, and their derivatives are emerging as unique electrocatalysts for oxygen reduction reaction (ORR). Thanks to their tunable compositions and diverse structures, efficient MOF-based materials provide new opportunities to accelerate the sluggish ORR at the cathode in fuel cells and metal–air batteries. This Minireview first provides some introduction of ORR and MOFs, followed by the classification of MOF-based electrocatalysts towards ORR. Recent breakthroughs in engineering MOF-based ORR electrocatalysts are highlighted with an emphasis on synthesis strategy, component, morphology, structure, electrocatalytic performance, and reaction mechanism. Finally, some current challenges and future perspectives for MOF-based ORR electrocatalysts are also discussed. 相似文献
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Feng-Dong Wang Bin-Cheng Wang Biao-Biao Hao Prof. Chen-Xi Zhang Prof. Qing-Lun Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(21):e202103732
Metal–organic frameworks (MOFs), as a porous frame material, exhibit considerable electrical conductivity. In recent decades, research on the proton conductivity of MOFs has made gratifying progress. In this review, the designable guest molecules encapsulated into MOFs are summarized and generalized into four types in terms of promoting proton conductive performance, and then recent progress in the promotion of proton conductivity by MOFs encapsulating guest molecules is discussed. The existing challenges and prospects for the development of this strategy for promoting MOFs’ proton conductivity are also listed. 相似文献
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Yi-Xiang Shi Huan-Huan Chen Prof. Wen-Hua Zhang Gregory S. Day Prof. Jian-Ping Lang Prof. Hong-Cai Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8543-8549
The photoinduced dynamic behavior of flexible materials has received considerable attention for potential applications, such as in data storage or as smart optical devices and molecular mechanical actuators. Until now, precisely controlling expansion and contraction with light has remained a challenge. Unraveling the detailed mechanisms of photoinduced structural transformations remains a critical step necessary to understand the molecular architecture necessary for the design of sensitive photomechanical actuators. Herein, a two-dimensional flexible metal–organic framework [Zn2(bdc)2(3-CH3-spy)2]⋅H2O ( Zn2-1 ; H2bdc=1,4-benzenedicaboxylic acid; 3-CH3-spy=3-methylstyrylpyridine) with a positive volumetric thermal expansion coefficient of +78.78×10−6 K−1 is reported. Upon light irradiation at different wavelengths, the MOF underwent a [2+2] cycloaddition, which afforded a family of isomeric, three-dimensional MOFs ( Zn2-2 n , n=a–d) in a single-crystal-to-single-crystal (SCSC) manner. An unprecedented phenomenon, that is, photoinduced nonlinear contraction (PINC), was observed during this conversion. The PINC is caused by conformational changes in the 3-CH3-spy and bdc2− ligands, the bending of metal–ligand bonds, and the local distortion of the paddle-wheel SBUs. The formation of a “wrinkle morphology” on the crystal surface after the photoreaction was observed by AFM. This PINC behavior can broaden the studies on materials expansion and offer a photodriven approach for the future design of supersensitive photomechanical actuators. 相似文献
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Anh N. Hong Diana Luong Mohammed Alghamdi Wei-Cheng Liao Weiyi Zhang Emily Kusumoputro Yichong Chen Prof. P. Alex Greaney Prof. Yongtao Cui Prof. Jing Shi Prof. Xianhui Bu Prof. Boniface P. T. Fokwa Prof. Pingyun Feng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(52):e202201576
Two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn2+ with a stronger Lewis acidic Co2+, leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials. 相似文献
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Dr. Xiao-Gang Wang Lei Xu Min-Jie Li Prof. Dr. Xian-Zheng Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18234-18242
Multi-component MOFs contain multiple sets of unique and hierarchical pores, with different functions for different applications, distributed in their inter-linked domains. Herein, we report the construction of a class of precisely aligned flexible-on-rigid hybrid-phase MOFs with a unique rods-on-octahedron morphology. We demonstrated that hybrid-phase MOFs can be constructed based on two prerequisites: the partially matched topology at the interface of the two frameworks, and the structural flexibility of MOFs with acs topology, which can compensate for the differences in lattice parameters. Furthermore, we achieved domain selective loading of multiple guest molecules into the hybrid-phase MOF, as observed by scanning transmission electron microscopy–energy-dispersive X-ray spectrometry elemental mapping. Most importantly, we successfully applied the constructed hybrid-phase MOF to develop a dual-drug delivery system with controllable loading ratio and release kinetics. 相似文献
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Marcel Schulz Nele Marquardt Malte Schäfer Dawid Peter Warwas Saskia Zailskas Dr. Andreas Schaate 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(59):13598-13608
In a systematic investigation, the synthesis of metal–organic frameworks (MOFs) with MIL-140 structure was studied. The precursors of this family of MOFs are the same as for the formation of the well-known UiO-type MOFs although the synthesis temperature for MIL-140 is significantly higher. This study is focused on the formation of Zr-based MIL-140 MOFs with terephthalic acid (H2bdc), biphenyl-4,4′-dicarboxylic acid (H2bpdc), and 4,4′-stilbenedicarboxylic acid (H2sdc) and the introduction of synthesis field diagrams to discover parameters for phase-pure products. In this context, a MIL-140 network with H2sdc as linker molecule is first reported. Additionally, an important aspect is the reduction of the synthesis temperature to make MIL-140 MOFs more accessible even though linkers with a more delicate nature are used. The solvothermal syntheses were conducted in highly concentrated reaction mixtures whereby a targeted synthesis to yield the MIL-140 phase is possible. Furthermore, the effect of the often-used modulator approach is examined for these systems. Finally, the characteristics of the synthesized MOFs are compared with physisorption measurements, thermogravimetric analyses, and scanning electron microscopy. 相似文献
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Dr. Megan J. Neufeld Dr. Alec Lutzke Prof. Guillem Pratx Prof. Conroy Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3229-3237
X-ray radiation is commonly employed in clinical practice for diagnostic and therapeutic applications. Over the past decade, developments in nanotechnology have led to the use of high-Z elements as the basis for innovative new treatment platforms that enhance the clinical efficacy of X-ray radiation. Nanoscale metal–frameworks (nMOFs) are coordination networks containing organic ligands that have attracted attention as therapeutic platforms in oncology and other areas of medicine. In cancer therapy, X-ray activated, high-Z nMOFs have demonstrated potential as radiosensitizers that increase local radiation dose deposition and generation of reactive oxygen species (ROS). This minireview summarizes current research on high-Z nMOFs in cancer theranostics and discusses factors that may influence future clinical application. 相似文献
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Zhongchao Jin Dr. Xiaorong Zhu Dr. Ningning Wang Prof. Dr. Yafei Li Prof. Dr. Huangxian Ju Prof. Dr. Jianping Lei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10532-10536
Metal–organic frameworks (MOFs) have limited applications in electrochemistry owing to their poor conductivity. Now, an electroactive MOF (E-MOF) is designed as a highly crystallized electrochemiluminescence (ECL) emitter in aqueous medium. The E-MOF contains mixed ligands of hydroquinone and phenanthroline as oxidative and reductive couples, respectively. E-MOFs demonstrate excellent performance with surface state model in both co-reactant and annihilation ECL in aqueous medium. Compared with the individual components, E-MOFs significantly improve the ECL emission due to the framework structure. The self-enhanced ECL emission with high stability is realized by the accumulation of MOF cation radicals via pre-reduction electrolysis. The self-enhanced mechanism is theoretically identified by DFT. The mixed-ligand E-MOFs provide a proof of concept using molecular crystalline materials as new ECL emitters for fundamental mechanism studies. 相似文献
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Prof. Qi Lei Yaqian Sun Junda Huang Wei Liu Xiaolong Zhan Wenxiang Yin Sishi Guo Dr. Anna Sinelshchikova Prof. C. Jeffrey Brinker Prof. Zhiyuan He Prof. Jimin Guo Prof. Stefan Wuttke Prof. Wei Zhu 《Angewandte Chemie (International ed. in English)》2023,62(22):e202217374
To increase the red blood cell (RBC) cryopreservation efficiency by metal–organic frameworks (MOFs), a dimensional reduction approach has been proposed. Namely, 3D MOF nanoparticles are progressively reduced to 2D ultra-thin metal–organic layers (MOLs). We found that 2D MOLs are beneficial for enhanced interactions of the interfacial hydrogen-bonded water network and increased utilization of inner ordered structures, due to the higher surface-to-volume ratio. Specifically, a series of hafnium (Hf)-based 2D MOLs with different thicknesses (monolayer to stacked multilayers) and densities of hydrogen bonding sites have been synthesized. Both ice recrystallization inhibition activity (IRI) and RBCs cryopreservation assay confirm the pronounced better IRI activity and excellent cell recovery efficiency (up to ≈63 % at a very low concentration of 0.7 mg mL−1) of thin-layered Hf-MOLs compared to their 3D counterparts, thereby verifying the dimensional reduction strategy to improved cryoprotectant behaviors. 相似文献
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Dr. Lun Shu Dr. Yuan Peng Hongling Song Chenyu Zhu Prof. Weishen Yang 《Angewandte Chemie (International ed. in English)》2023,62(49):e202315057
Metal–organic frameworks (MOFs) are considered ideal membrane candidates for energy-efficient separations. However, the MOF membrane amount to date is only a drop in the bucket compared to the material collections. The fabrication of an arbitrary MOF membrane exhibiting inherent separation capacity of the material remains a long-standing challenge. Herein, we report a MOF modular customization strategy by employing four MOFs with diverse structures and physicochemical properties and achieving innovative defect-free membranes for efficient separation validation. Each membrane fully displays the separation potential according to the MOF pore/channel microenvironment, and consequently, an intriguing H2/CO2 separation performance sequence is achieved (separation factor of 1656–5.4, H2 permeance of 964–2745 gas permeation unit). Taking advantage of this strategy, separation performance can be manipulated by a non-destructive modification separately towards the MOF module. This work establishes a universal full-chain demonstration for membrane fabrication-separation validation-microstructure modification and opens an avenue for exclusive customization of membranes for important separations. 相似文献
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Dr. Jun Heuk Park Dr. Jan Paczesny Namhun Kim Prof. Bartosz A. Grzybowski 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10387-10391
When components of a metal–organic framework (MOF) and a crystal growth modulator diffuse through a gel medium, they can form arrays of regularly-spaced precipitation bands containing MOF crystals of different morphologies. With time, slow variations in the local concentrations of the growth modulator cause the crystals to change their shapes, ultimately resulting in unusual concave microcrystallites not available via solution-based methods. The reaction–diffusion and periodic precipitation phenomena 1) extend to various types of MOFs and also MOPs (metal–organic polyhedra), and 2) can be multiplexed to realize within one gel multiple growth conditions, in effect leading to various crystalline phases or polycrystalline formations. 相似文献
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Jialuo Li Shuai Yuan Jun-Sheng Qin Jiandong Pang Peng Zhang Yingmu Zhang Yanyan Huang Hannah F. Drake Wenshe R. Liu Prof. Dr. Hong-Cai Zhou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9405-9409
The controlled synthesis of multicomponent metal–organic frameworks (MOFs) allows for the precise placement of multiple cooperative functional groups within a framework, leading to emergent synergistic effects. Herein, we demonstrate that turn-on fluorescence sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. An anthracene-based fluorescent linker and a hemicyanine-containing CN−-responsive linker were sequentially installed into the lattice of PCN-700. The selective binding of CN− to hemicyanine inhibited the energy transfer between the two moieties, resulting in a fluorescence turn-on effect. Taking advantage of the high tunability of the MOF platform, the ratio between anthracene and the hemicyanine moiety could be fine-tuned in order to maximize the sensitivity of the overall framework. The optimized MOF-sensor had a CN−-detection limit of 0.05 μm , which is much lower than traditional CN− fluorescent sensors (about 0.2 μm ). 相似文献
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Mohamed E. A. Safy Dr. Muhamed Amin Dr. Rana R. Haikal Basma Elshazly Junjun Wang Dr. Yuemin Wang Prof. Christof Wöll Prof. Mohamed H. Alkordi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(31):7109-7117
A comprehensive model to describe the water stability of prototypical metal–organic frameworks (MOFs) is derived by combining different types of theoretical and experimental approaches. The results provide an insight into the early stages of water-triggered destabilization of MOFs and allow detailed pathways to be proposed for the degradation of different MOFs under aqueous conditions. The essential elements of the approach are computing the pKa values of coordinated water molecules and geometry relaxations. Variable-temperature and pH infrared spectroscopy techniques are used to corroborate the main findings. The model developed herein helps to explain stability limits observed for several prototypical MOFs, including MOF-5, HKUST-1, UiO-66, and MIL-101-Cr, in aqueous solutions, and thus, provides an insight into the possible degradation pathways in acidic and basic environments. The formation of a metal hydroxide through the autoprotolysis of metal-coordinated water molecules and the strength of carboxylate–metal interactions are suggested to be two key players that govern stability in basic and acidic media, respectively. The methodology presented herein can effectively guide future efforts, which are especially significant for in silico screening, for developing novel MOFs with enhanced aqueous stability. 相似文献
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Jin Liu Xingyu Liu Qi Liu Jing Cao Xinheng Lv Prof. Shaoru Wang Prof. Tian Tian Prof. Xiang Zhou Prof. Hexiang Deng 《Angewandte Chemie (International ed. in English)》2023,62(42):e202302649
A metal–organic framework (MOF) with mespores (2 to 50 nm) allows the inclusion of large biomolecules, such as nucleic acids. However, chemical reaction on the nucleic acids, to further regulate their bioactivity, is yet to be demonstrated within MOF pores. Here, we report the deprotection of carbonate protected RNA molecules (21 to 102 nt) to restore their original activity using a MOF as a heterogeneous catalyst. Two MOFs, MOF-626 and MOF-636 are designed and synthesized, with mesopores of 2.2 and 2.8 nm, respectively, carrying isolated metal sites (Ni, Co, Cu, Pd, Rh and Ru). The pores favor the entrance of RNA, while the metal sites catalyze C−O bond cleavage at the carbonate group. Complete conversion of RNA is achieved by Pd-MOF-626, 90 times more efficiently than Pd(NO3)2. MOF crystals are also removable from the aqueous reaction media, leaving a negligible metal footprint, 3.9 ppb, only 1/55 of that using homogeneous Pd catalysts. These features make MOF potentially suited for bioorthogonal chemistry. 相似文献