共查询到20条相似文献,搜索用时 15 毫秒
1.
Laurens D. B. Mandemaker Miguel Rivera-Torrente Guusje Delen Dr. Jan P. Hofmann Dr. Matthias Lorenz Dr. Alex Belianinov Prof. Dr. Bert M. Weckhuysen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):691-698
Metal–organic frameworks (MOFs) are a promising class of materials for many applications, due to their high chemical tunability and superb porosity. By growing MOFs as (thin-)films, additional properties and potential applications become available. Here, copper (II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal–organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in “nanowebs”, that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm ) was determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varying the rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that rotation speeds ≥2000 rpm (with precursors in a water/ethanol solution) generate the catena-triaqua-μ-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H2O)3 coordination polymer. X-ray photoelectron spectroscopy (XPS) highlighted the strong decrease in number of (defective) Cu+ sites, as the nanowebs mainly consist of coordinated Cu2+ Lewis acid sites (LAS) and organic linker–linker, for example, hydrogen-bonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of α-pinene oxide. The higher number of LAS (≥3000 rpm), result in higher campholenic aldehyde selectivity reaching up to 87.7 %. Furthermore, the strength of a combined micro- and spectroscopic approach in understanding the nature of MOF thin-films in a spatially resolved manner is highlighted. 相似文献
2.
Prof. Hanzhou Liu Haoming Qin Dr. Nannan Shen Siqi Yan Prof. Yaxing Wang Dr. Xuemiao Yin Prof. Xinjian Chen Chao Zhang Prof. Xing Dai Prof. Ruhong Zhou Prof. Xiaoping Ouyang Prof. Zhifang Chai Prof. Shuao Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15321-15326
Radio-photoluminescence (RPL) materials display a distinct radiation-induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal-ion-doped inorganic materials. Here we document the RPL of a metal–organic framework (MOF) for the first time: X-ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X-ray attenuator. These radicals afford new emission features in both UV-excited and X-ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF-based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated. 相似文献
3.
Xiaoyu Song Xinyue Wang Yusen Li Chengzhi Zheng Bowen Zhang Prof. Chong-an Di Dr. Feng Li Dr. Chao Jin Prof. Wenbo Mi Prof. Long Chen Prof. Wenping Hu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1134-1139
2D conductive metal–organic frameworks (2D c-MOFs) feature promising applications as chemiresistive sensors, electrode materials, electrocatalysts, and electronic devices. However, exploration of the spin-polarized transport in this emerging materials and development of the relevant spintronics have not yet been implemented. In this work, layer-by-layer assembly was applied to fabricate highly crystalline and oriented thin films of a 2D c-MOF, Cu3(HHTP)2, (HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene), with tunable thicknesses on the La0.67Sr0.33MnO3 (LSMO) ferromagnetic electrode. The magnetoresistance (MR) of the LSMO/Cu3(HHTP)2/Co organic spin valves (OSVs) reaches up to 25 % at 10 K. The MR can be retained with good film thickness adaptability varied from 30 to 100 nm and also at high temperatures (up to 200 K). This work demonstrates the first potential applications of 2D c-MOFs in spintronics. 相似文献
4.
Dr. Bastian Rühle Dr. Erika Virmani Dr. Hanna Engelke Dr. Florian M. Hinterholzinger Dr. Tobias von Zons Birte Brosent Prof. Dr. Thomas Bein Prof. Dr. Adelheid Godt Dr. Stefan Wuttke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(25):6349-6354
The synthesis and characterization of a chemiluminescent metal–organic framework with high porosity is reported. It consists of Zr6O6(OH)4 nodes connected by 4,4′-(anthracene-9,10-diyl)dibenzoate as the linker and luminophore. It shows the topology known for UiO-66 and is therefore denoted PAP-UiO. The MOF was not only obtained as bulk material but also as a thin film. Exposure of PAP-UiO as bulk or film to a mixture of bis-(2,4,6-trichlorophenyl) oxalate, hydrogen peroxide, and sodium salicylate in a mixture of dimethyl and dibutyl phthalate evoked strong and long lasting chemiluminescence of the PAP-UiO crystals. Time dependent fluorescence spectroscopy on bulk PAP-UiO and, for comparison, on dimethyl 4,4′-(anthracene-9,10-diyl)dibenzoate provided evidence that the chemiluminescence originates from luminophores being part of the PAP-UiO, including the luminophores inside the crystals. 相似文献
5.
Dr. Prantik Mondal Zachary Neuschuler Dr. Dipendu Mandal Ritchie E. Hernandez Prof. Seth M. Cohen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(9):e202317062
Postsynthetic modification (PSM) of metal–organic frameworks (MOFs) provides access to functional materials and advanced porous solid engineering. Herein, we report the reversible PSM of a multivariate isoreticular MOF by applying dynamic furan-maleimide Diels–Alder (DA) chemistry. The key step involves incorporating a furan group into the MOF via “click” PSM, which can then undergo repeated cycles of modification and de-modification with maleimides. The structural integrity, crystallinity, and porosity of the furan-appended MOF remained intact even after three consecutive PSM/de-modification cycles using three different functionalized maleimides. 相似文献
6.
7.
Dr. Amandine Cadiau Nikita Kolobov Dr. Sivaranjani Srinivasan Dr. Maarten G. Goesten Dr. Henrik Haspel Dr. Anastasiya V. Bavykina Dr. Mohamed R. Tchalala Dr. Partha Maity Dr. Andrey Goryachev Artem S. Poryvaev Prof. Dr. Mohamed Eddaoudi Dr. Matvey V. Fedin Prof. Dr. Omar F. Mohammed Prof. Dr. Jorge Gascon 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13570-13574
The one-step synthesis and characterization of a new and robust titanium-based metal–organic framework, ACM-1 , is reported. In this structure, which is based on infinite Ti−O chains and 4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge-separation lifetimes. The suitable energies for band gap and conduction band minimum (CBM) offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates. 相似文献
8.
Debanjan Chakraborty Shyamapada Nandi Rahul Maity Dr. Radha Kishan Motkuri Dr. Kee Sung Han Sean Collins Dr. Paul Humble Dr. James C. Hayes Prof. Tom K. Woo Dr. Ramanathan Vaidhyanathan Dr. Praveen K. Thallapally 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12544-12548
Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO2. Further 129Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement. 相似文献
9.
Andrzej Gładysiak Dr. Tu N. Nguyen Dr. Mariana Spodaryk Dr. Jung-Hoon Lee Prof. Dr. Jeffrey B. Neaton Prof. Dr. Andreas Züttel Dr. Kyriakos C. Stylianou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):501-506
A pyrene-based metal-organic framework (MOF) SION-8 captured iodine (I2) vapor with a capacity of 460 and 250 mg g−1MOF at room temperature and 75 °C, respectively. Single-crystal X-ray diffraction analysis and van-der-Waals-corrected density functional theory calculations confirmed the presence of I2 molecules within the pores of SION-8 and their interaction with the pyrene-based ligands. The I2–pyrene interactions in the I2-loaded SION-8 led to a 104-fold increase of its electrical conductivity compared to the bare SION-8 . Upon adsorption, ≥95 % of I2 molecules were incarcerated and could not be washed out, signifying the potential of SION-8 towards the permanent capture of radioactive I2 at room temperature. 相似文献
10.
Craig A. Peeples Ahmet Çetinkaya Patrik Tholen Dr. Franz-Josef Schmitt Prof. Dr. Yunus Zorlu Kai Bin Yu Prof. Dr. Ozgur Yazaydin Prof. Dr. Jens Beckmann Prof. Dr. Gabriel Hanna Prof. Dr. Gündoğ Yücesan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104041
Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal–organic framework (MOF) with the composition Cu3(H5-MTPPA)2 ⋅ 2 NMP (H8-MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m2/g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin-dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta-gap for the trigonal bipyramidal copper atoms is 3.72 eV. 相似文献
11.
Huiye Zhong Wei-Shang Lo Tiantian Man Benjamin P. Williams Dan Li Dr. Sheng-Yu Chen Prof. Dr. Hao Pei Prof. Dr. Li Li Prof. Dr. Chia-Kuang Tsung 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12931-12935
DNAzymes are a promising class of bioinspired catalyst; however, their structural instability limits their potential. Herein, a method to stabilize DNAzymes by encapsulating them in a metal–organic framework (MOF) host is reported. This biomimetic mineralization process makes DNAzymes active under a wider range of conditions. The concept is demonstrated by encapsulating hemin-G-quadruplex (Hemin-G4) into zeolitic imidazolate framework-90 (ZIF-90), which indeed increases the DNAzyme's structural stability. The stabilized DNAzymes show activities in the presence of Exonuclease I, organic solvents, or high temperature. Owing to its elevated stability and heterogeneous nature, it is possible to perform catalysis under continuous-flow conditions, and the DNAzyme can be reactivated in situ by introducing K+. Moreover, it is found that the encapsulated DNAzyme maintains its high enantiomer selectivity, demonstrated by the sulfoxidation of thioanisole to (S)-methyl phenyl sulfoxide. This concept of stabilizing DNAzymes expands their potential application in chemical industry. 相似文献
12.
Dr. M. Menaf Ayhan Ceyda Bayraktar Kai Bin Yu Dr. Gabriel Hanna Dr. A. Ozgur Yazaydin Dr. Yunus Zorlu Dr. Gündoğ Yücesan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14813-14816
A one-dimensional nanotubular metal–organic framework (MOF) [Ni(Cu-H4TPPA)]⋅2 (CH3)2NH2+ (H8TPPA=5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H8TPPA is reported. The structure of this MOF, known as GTUB-4 , was solved by using single-crystal X-ray diffraction and its geometric accessible surface area was calculated to be 1102 m2 g−1, making it the phosphonate MOF with the highest reported surface area. Due to the extended conjugation of its porphyrin core, GTUB-4 possesses narrow indirect and direct bandgaps (1.9 eV and 2.16 eV, respectively) in the semiconductor regime. Thermogravimetric analysis suggests that GTUB-4 is thermally stable up to 400 °C. Owing to its high surface area, low bandgap, and high thermal stability, GTUB-4 could find applications as electrodes in supercapacitors. 相似文献
13.
Julia G. Knapp Dr. Xijun Wang Dr. Andrew S. Rosen Xingjie Wang Dr. Xinyi Gong Dr. Matthew Schneider Dr. Tatyana Elkin Dr. Kent O. Kirlikovali Dr. Melissa Fairley Dr. Matthew D. Krzyaniak Prof. Michael R. Wasielewski Prof. Nathan C. Gianneschi Prof. Randall Q. Snurr Prof. Omar K. Farha 《Angewandte Chemie (International ed. in English)》2023,62(29):e202305526
The interactions between uranium and non-innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium-based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self-assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non-innocent linkers. We report the synthesis of the MOF NU-1700 , assembled from U4+-paddlewheel nodes and catecholate-based linkers. We propose this highly unusual structure, which contains two U4+ ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X-ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations. 相似文献
14.
Xiao-Lan Liu Wen-Wen Fan Zhi-Xiang Lu Yu Qin Shao-Xiong Yang Yuan Li Yan-Xiong Liu Li-Yan Zheng Qiu-E Cao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(22):5787-5792
Over the last decade, the controllable reversible phase transition of functional materials has received growing interest as it shows unique suitability for various technological applications. Although many metal–organic frameworks (MOFs) possess a lamellar structure, the reversible structural transformation of MOFs between their three-dimensional (3D) phase and two-dimensional (2D) phase remains a largely unexplored area. Herein, we report for the first time a europium MOF with unprecedented reversible morphology in different solvents at room temperature. This europium MOF displayed a 3D nanorod morphology in organic solvent and a 2D nanobelt architecture in water. As a proof of concept for potential applications of this reversible-phase-transition MOF, we were able to use a delamination recovery method to load dye molecules that previously could not be loaded into europium MOFs. 相似文献
15.
Dr. Soichiro Nakatsuka Yusuke Watanabe Yoshinobu Kamakura Prof. Satoshi Horike Prof. Daisuke Tanaka Prof. Takuji Hatakeyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1451-1455
A triphosphaazatriangulene (H3L) was synthesized through an intramolecular triple phospha-Friedel–Crafts reaction. The H3L triangulene contains three phosphinate groups and an extended π-conjugated framework, which enables the stimuli-responsive reversible transformation of [Cu(HL)(DMSO)⋅(MeOH)]n, a 3D-MOF that exhibits reversible sorption characteristics, into (H3L⋅0.5 [Cu2(OH)4⋅6 H2O] ⋅4 H2O), a 1D-columnar assembled proton-conducting material. The hydrophilic nature of the latter resulted in a proton conductivity of 5.5×10−3 S cm−1 at 95 % relative humidity and 60 °C. 相似文献
16.
Chen Tan Michelle C. Lee Mohammad Arshadi Morteza Azizi Alireza Abbaspourrad 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9593-9600
Processing metal–organic frameworks (MOFs) into hierarchical macroscopic materials can greatly extend their practical applications. However, current strategies suffer from severe aggregation of MOFs and limited tuning of the hierarchical porous network. Now, a strategy is presented that can simultaneously tune the MOF loading, composition, spatial distribution, and confinement within various bio-originated macroscopic supports, as well as control the accessibility, robustness, and formability of the support itself. This method enables the good dispersion of individual MOF nanoparticles on a spiderweb-like network within each macrovoid even at high loadings (up to 86 wt %), ensuring the foam pores are highly accessible for excellent adsorption and catalytic capacity. Additionally, this approach allows the direct pre-incorporation of other functional components into the framework. This strategy provides precise control over the properties of both the hierarchical support and MOF. 相似文献
17.
Dr. Yong Peng Dr. Soheila Sanati Prof. Ali Morsali Prof. Hermenegildo García 《Angewandte Chemie (International ed. in English)》2023,62(9):e202214707
Transition metal complexes are well-known homogeneous electrocatalysts. In this regard, metal–organic frameworks (MOFs) can be considered as an ensemble of transition metal complexes ordered in a periodic arrangement. In addition, MOFs have several additional positive structural features that make them suitable for electrocatalysis, including large surface area, high porosity, and high content of accessible transition metal with exchangeable coordination positions. The present review describes the current state in the use of MOFs as electrocatalysts, both as host of electroactive guests and their direct electrocatalytic activity, particularly in the case of bimetallic MOFs. The field of MOF-derived materials is purposely not covered, focusing on the direct use of MOFs or its composites as electrocatalysts. Special attention has been paid to present strategies to overcome their poor electrical conductivity and limited stability. 相似文献
18.
Hongde An Jie Song Ting Wang Nannan Xiao Prof. Zhenjie Zhang Prof. Peng Cheng Prof. Shengqian Ma Prof. He Huang Prof. Yao Chen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(38):16907-16912
An enzyme formulation using customized enzyme activators (metal ions) to directly construct metal–organic frameworks (MOFs) as enzyme protective carriers is presented. These MOF carriers can also serve as the disintegrating agents to simultaneously release enzymes and their activators during biocatalysis with boosted activities. This highly efficient enzyme preparation combines enzyme immobilization (enhanced stability, easy operation) and homogeneous biocatalysis (fast diffusion, high activity). The MOF serves as an ion pump that continuously provides metal ion activators that greatly promote the enzymatic activities (up to 251 %). This MOF–enzyme composite demonstrated an excellent protective effect against various perturbation environments. A mechanistic investigation revealed that the spontaneous activator/enzyme release and ion pumping enable enzymes to sufficiently interact with their activators owing to the proximity effects, leading to a boost in biocatalytic performance. 相似文献
19.
Daniel Josef Bell Monika Wiese Ariel Augusto Schönberger Matthias Wessling 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16181-16187
Metal–organic frameworks (MOFs) are suitable enzyme immobilization matrices. Reported here is the in situ biomineralization of glucose oxidase (GOD) into MOF crystals (ZIF-8) by interfacial crystallization. This method is effective for the selective coating of porous polyethersulfone microfiltration hollow fibers on the shell side in a straightforward one-step process. MOF layers with a thickness of 8 μm were synthesized, and fluorescence microscopy and a colorimetric protein assay revealed the successful inclusion of GOD into the ZIF-8 layer with an enzyme concentration of 29±3 μg cm−2. Enzymatic activity tests revealed that 50 % of the enzyme activity is preserved. Continuous enzymatic reactions, by the permeation of β-d -glucose through the GOD@ZIF-8 membranes, showed a 50 % increased activity compared to batch experiments, emphasizing the importance of the convective transport of educts and products to and from the enzymatic active centers. 相似文献
20.
De Ao Zibo Yang Zhihua Qiao Yuxiu Sun Zhengqing Zhang Michael D. Guiver Chongli Zhong 《Angewandte Chemie (International ed. in English)》2023,62(28):e202304535
Metal–organic framework (MOF) glass is an easy to process and self-supported amorphous material that is suitable for fabricating gas separation membranes. However, MOF glasses, such as ZIF-62 and ZIF-4 have low porosity, which makes it difficult to obtain membranes with high permeance. Here, a self-supported MOF crystal–glass composite (CGC) membrane was prepared by melt quenching a mixture of ZIF-62 as the membrane matrix and ZIF-8 as the filler. The conversion of ZIF-62 from crystal to glass and the simultaneous partial melting of ZIF-8 facilitated by the melt state of ZIF-62 make the CGC membrane monolithic, eliminating non-selective grain boundaries and improving selectivity. The thickness of CGC membrane can be adjusted to fabricate a membrane without the need of a support substrate. CGC membranes exhibit a C2H6 permeance of 41 569 gas permeation units (GPU) and a C2H6/C2H4 selectivity of 7.16. The CGC membrane has abundant pores from the glassy state of ZIF-62 and the crystalline ZIF-8, which enables high gas permeance. ZIF-8 has preferential adsorption for C2H6 and promotes C2H6 transport in the membrane, and thus the GCG membrane exhibits ultrahigh C2H6 permeance and good C2H6/C2H4 selectivity. 相似文献