共查询到20条相似文献,搜索用时 15 毫秒
1.
Jin‐Yue Zeng Xiao‐Shuang Wang Yong‐Dan Qi Yun Yu Xuan Zeng Xian‐Zheng Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5748-5752
Polycyclic aromatic derivatives can trap 1O2 to form endoperoxides (EPOs) for O2 storage and as sources of reactive oxygen species. However, these materials suffer from structural amorphism, which limit both practical applications and fundamental studies on their structural optimization for O2 capture and release. Metal–organic frameworks (MOFs) offer advantages in O2 binding, such as clear structure–performance relationships and precise controllability. Herein, we report the reversible binding of O2 is realized via the chemical transformation between anthracene‐based and the corresponding EPO‐based MOF. It is shown that anthracene‐based MOF, the framework featuring linkers with polycyclic aromatic structure, can rapidly trap 1O2 to form EPOs and can be restored upon UV irradiation or heating to release O2. Furthermore, we confirm that photosensitizer‐incorporated anthracene‐based MOF are promising candidates for reversible O2 carriers controlled by switching Vis/UV irradiation. 相似文献
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Diego Mateo Andrea Santiago‐Portillo Josep Albero Sergio Navaln Mercedes Alvaro Hermenegildo García 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):18007-18012
Prolonged (weeks) UV/Vis irradiation under Ar of UiO‐66(Zr), UiO66 Zr‐NO2, MIL101 Fe, MIL125 Ti‐NH2, MIL101 Cr and MIL101 Cr(Pt) shows that these MOFs undergo photodecarboxylation of benzenedicarboxylate (BDC) linker in a significant percentage depending on the structure and composition of the material. Routine characterization techniques such as XRD, UV/Vis spectroscopy and TGA fail to detect changes in the material, although porosity and surface area change upon irradiation of powders. In contrast to BCD‐containing MOFs, zeolitic imidazolate ZIF‐8 does not evolve CO2 or any other gas upon irradiation. 相似文献
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Ning Li Jiang Liu Jing‐Jing Liu Long‐Zhang Dong Zhi‐Feng Xin Yun‐Lei Teng Ya‐Qian Lan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(16):5280-5285
Visible‐light driven photoconversion of CO2 into energy carriers is highly important to the natural carbon balance and sustainable development. Demonstrated here is the adenine‐dependent CO2 photoreduction performance in green biomimetic metal–organic frameworks. Photocatalytic results indicate that AD‐MOF‐2 exhibited a very high HCOOH production rate of 443.2 μmol g?1 h?1 in pure aqueous solution, and is more than two times higher than that of AD‐MOF‐1 (179.0 μmol g?1h?1) in acetonitrile solution. Significantly, experimental and theoretical evidence reveal that the CO2 photoreduction reaction mainly takes place at the aromatic nitrogen atom of adenine molecules through a unique o‐amino‐assisted activation rather than at the metal center. This work not only serves as an important case study for the development of green biomimetic photocatalysts used for artificial photosynthesis, but also proposes a new catalytic strategy for efficient CO2 photoconversion. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(33):9889-9893
Metal–organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass‐transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet‐based membranes remain as great challenges. A modified soft‐physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub‐10 nm‐thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H2/CO2 separation performance, with a separation factor of up to 166 and H2 permeance of up to 8×10−7 mol m−2 s−1 Pa−1 at elevated testing temperatures owing to a well‐defined size‐exclusion effect. This nanosheet‐based membrane holds great promise as the next generation of ultrapermeable gas separation membrane. 相似文献
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Sibo Wang Wangshu Yao Jinliang Lin Zhengxin Ding Xinchen Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(4):1052-1056
Metal–organic frameworks (MOFs) have shown great promise for CO2 capture and storage. However, the operation of chemical redox functions of framework substances and organic CO2‐trapping entities which are spatially linked together to catalyze CO2 conversion has had much less attention. Reported herein is a cobalt‐containing zeolitic imidazolate framework (Co‐ZIF‐9) which serves as a robust MOF cocatalyst to reduce CO2 by cooperating with a ruthenium‐based photosensitizer. The catalytic turnover number of Co‐ZIF‐9 was about 450 within 2.5 hours under mild reaction conditions, while still keeping its original reactivity during prolonged operation. 相似文献
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Shan‐Shan Wang Long Jiao Yunyang Qian Wen‐Chao Hu Gui‐Yin Xu Chen Wang Hai‐Long Jiang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10823-10827
Efficient hydrogen evolution via electrocatalytic water splitting holds great promise in modern energy devices. Herein, we demonstrate that the localized surface plasmon resonance (LSPR) excitation of Au nanorods (NRs) dramatically improves the electrocatalytic hydrogen evolution activity of CoFe‐metal–organic framework nanosheets (CoFe‐MOFNs), leading to a more than 4‐fold increase of current density at ?0.236 V (vs. RHE) for Au/CoFe‐MOFNs composite under light irradiation versus in dark. Mechanistic investigations reveal that the hydrogen evolution enhancement can be largely attributed to the injection of hot electrons from AuNRs to CoFe‐MOFNs, raising the Fermi level of CoFe‐MOFNs, facilitating the reduction of H2O and affording decreased activation energy for HER. This study highlights the superiority of plasmonic excitation on improving electrocatalytic efficiency of MOFs and provides a novel avenue towards the design of highly efficient water‐splitting systems under light irradiation. 相似文献
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Kai Chen Chuan‐De Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8203-8207
Metal‐organic frameworks (MOFs) are an emerging class of porous materials with attractive properties, however, their practical applications are heavily hindered by their fragile nature. We report herein an effective strategy to transform fragile coordination bonds in MOFs into stable covalent organic bonds under mild annealing decarboxylative coupling reaction conditions, which results in highly stable organic framework materials. This strategy successfully endows intrinsic framework skeletons, porosity and properties of the parent MOFs in the daughter organic framework materials, which exhibit excellent chemical stability under harsh catalytic conditions. Therefore, this work opens a new avenue to synthesize stable organic framework materials derived from MOFs for applications in different fields. 相似文献
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Wei Zhang Wenqian Chen Xiaoli Zhao Qi Dang Yucen Li Tianyu Shen Fengchang Wu Liang Tang Hu Jiang Ming Hu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(22):7509-7512
Harvesting energy directly in oceans by electrochemical devices is essential for driving underwater appliances such as underwater vehicles or detectors. Owing to the extreme undersea environment, it is important but difficult to use the devices with both a high energy density and power density simultaneously. Inspired by marine organisms that have switchable energy extraction modes (aerobic respiration for long‐term living or anaerobic respiration to provide instantaneously high output power for fast movement), an auto‐switchable dual‐mode seawater energy extraction system is presented to provide high energy density and power density both by initiatively choosing different solutes in seawater as electron acceptors. With assistance from metal–organic frameworks, this device had a theoretical energy density of 3960 Wh kg?1, and a high practical power density of 100±4 mW cm?2 with exceptional stability and low cost, making practical applications in seawater to be possible. 相似文献
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Lauren N. McHugh Angela Terracina Paul S. Wheatley Gianpiero Buscarino Martin W. Smith Russell E. Morris 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):11873-11877
Metal–organic frameworks (MOFs) are a class of porous materials that show promise in the removal of toxic industrial chemicals (TICs) from contaminated airstreams, though their development for this application has so far been hindered by issues of water stability and the wide availability and low cost of traditionally used activated carbons. Here a series of three MOF‐activated carbon composite materials with different MOF to carbon ratios are prepared by growing STAM‐17‐OEt crystals inside the commercially available BPL activated carbon. The composite materials display excellent water stability and increased uptake of ammonia gas when compared to unimpregnated carbon. Such properties make these composites very promising in the fields of air purification and personal protective equipment. 相似文献
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Jingru Luo Yang Li Haochuan Zhang Ailun Wang Wei‐Shang Lo Qi Dong Nicholas Wong Christopher Povinelli Yucai Shao Sumanth Chereddy Stephanie Wunder Udayan Mohanty Chia‐Kuang Tsung Dunwei Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(43):15457-15461
The incompatibility between the anode and the cathode chemistry limits the used of Mg as an anode. This issue may be addressed by separating the anolyte and the catholyte with a membrane that only allows for Mg2+ transport. Mg‐MOF‐74 thin films were used as the separator for this purpose. It was shown to meet the needs of low‐resistance, selective Mg2+ transport. The uniform MOF thin films supported on Au substrate with thicknesses down to ca. 202 nm showed an intrinsic resistance as low as 6.4 Ω cm2, with the normalized room‐temperature ionic conductivity of ca. 3.17×10?6 S cm?1. When synthesized directly onto a porous anodized aluminum oxide (AAO) support, the resulting films were used as a standalone membrane to permit stable, low‐overpotential Mg striping and plating for over 100 cycles at a current density of 0.05 mA cm?2. The film was effective in blocking solvent molecules and counterions from crossing over for extended period of time. 相似文献
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Xing Ma Li Wang Qun Zhang Hai‐Long Jiang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(35):12303-12307
Defect engineering is a versatile approach to modulate band and electronic structures as well as materials performance. Herein, metal–organic frameworks (MOFs) featuring controlled structural defects, namely UiO‐66‐NH2‐X (X represents the molar equivalents of the modulator, acetic acid, with respect to the linker in synthesis), were synthesized to systematically investigate the effect of structural defects on photocatalytic properties. Remarkably, structural defects in MOFs are able to switch on the photocatalysis. The photocatalytic H2 production rate presents a volcano‐type trend with increasing structural defects, where Pt@UiO‐66‐NH2‐100 exhibits the highest activity. Ultrafast transient absorption spectroscopy unveils that UiO‐66‐NH2‐100 with moderate structural defects possesses the fastest relaxation kinetics and the highest charge separation efficiency, while excessive defects retard the relaxation and reduce charge separation efficiency. 相似文献
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Chengdong Peng Xueling Song Jinlin Yin Guiyang Zhang Honghan Fei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7900-7904
The secondary building units in metal–organic frameworks (MOFs) are commonly well‐defined metal–oxo clusters or chains with very limited structural strain. Herein, the structurally deformable haloplumbate units that are often observed in organolead halide perovskites have been successfully incorporated into MOFs. The resultant materials are a rare class of isoreticular MOFs exhibiting large Stokes‐shifted broadband white‐light emission, which is probably induced by self‐trapped excitons from electron–phonon coupling in the deformable, zigzag [Pb2X3]+ (X=Cl, Br, or I) chains. In contrast, MOFs with highly symmetric, robust haloplumbate chains only exhibit narrow UV–blue photoemission. The designed MOF‐based intrinsic white‐light photoemitters have a number of advantages over hybrid inorganic–organic perovskites in terms of stability and tunability, including moisture resistance, facile functionalization of photoactive moieties onto the organic linkers, introduction of luminescent guests. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(2):593-596
The incorporation of metal–organic frameworks (MOFs) into membrane‐shaped architectures is of great importance for practical applications. The currently synthesized MOF‐based membranes show many disadvantages, such as poor compatibility, low dispersity, and instability, which severely limit their utility. Herein, we present a general, facile, and robust approach for the synthesis of MOF‐based composite membranes through the in situ growth of MOF plates in the channels of anodized aluminum oxide (AAO) membranes. After being used as catalysis reactors, they exhibit high catalytic performance and stability in the Knoevenagel condensation reaction. The high catalytic performance might be attributed to the intrinsic structure of MOF‐based composite membranes, which can remove the products from the reaction zone quickly, and prevent the aggregation and loss of catalysts during reaction and recycling process. 相似文献
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Yao Jiang Peng Tan Shi‐Chao Qi Xiao‐Qin Liu Jia‐Hui Yan Fan Fan Lin‐Bing Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(20):6672-6676
Photoresponsive metal–organic frameworks (PMOFs) are of interest for tailorable CO2 adsorption. However, modulation of CO2 adsorption on PMOFs is based on steric hindrance or structural change owing to weak interactions between CO2 and active sites. It is challenging to fabricate PMOFs with strong but tailorable sites for CO2 adsorption. Now, the construction of PMOFs with target‐specific (strong) active sites is achieved by introducing tetraethylenepentamine into azobenzene‐functionalized MOFs for tailorable CO2 adsorption. Amines are specific active sites for CO2, contributing to capture CO2 selectively. Cis/trans isomerization of azobenzene motifs trigged by UV/Vis light adjusts the electrostatic potential of amines significantly, leading to exposure/shelter of amines and modulation of CO2 adsorption on strong active sites. This system enables us to design adsorption processes for CO2 capture from mixtures, which is impossible to realize by traditional PMOFs. 相似文献
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Yang Yang Xiaodong Sun Guanqun Han Xi Liu Xiangyu Zhang Yongfang Sun Min Zhang Zhi Cao Yujie Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10754-10759
The sluggish hydrogen oxidation reaction (HOR) under alkaline conditions has hindered the commercialization of hydroxide‐exchange membrane hydrogen fuel cells. A low‐cost Ni/NiO/C catalyst with abundant Ni/NiO interfacial sites was developed as a competent HOR electrocatalyst in alkaline media. Ni/NiO/C exhibits an HOR activity one order of magnitude higher than that of its parent Ni/C counterpart. Moreover, Ni/NiO/C also shows better stability and CO tolerance than commercial Pt/C in alkaline media, which renders it a very promising HOR electrocatalyst for hydrogen fuel cell applications. Density functional theory (DFT) calculations were also performed to shed light on the enhanced HOR performance of Ni/NiO/C; the DFT results indicate that both hydrogen and hydroxide achieve optimal binding energies at the Ni/NiO interface, resulting from the balanced electronic and oxophilic effects at the Ni/NiO interface. 相似文献
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Shuo Dou Jiajia Song Shibo Xi Yonghua Du Jiong Wang Zhen‐Feng Huang Zhichuan J. Xu Xin Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(12):4081-4085
Electrochemical CO2 reduction relies on the availability of highly efficient and selective catalysts. Herein, we report a general strategy to boost the activity of metal–organic frameworks (MOFs) towards CO2 reduction via ligand doping. A strong electron‐donating molecule of 1,10‐phenanthroline was doped into Zn‐based MOFs of zeolitic imidazolate framework‐8 (ZIF‐8) as CO2 reduction electrocatalyst. Experimental and theoretical evidences reveal that the electron‐donating nature of phenanthroline enables a charge transfer, which induces adjacent active sites at the sp2 C atoms in the imidazole ligand possessing more electrons, and facilitates the generation of *COOH, hence leading to improved activity and Faradaic efficiency towards CO production. 相似文献
20.
Huimin Wang Yuqi Chen Hong Wang Xiaoqing Liu Xiang Zhou Fuan Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(22):7458-7462
DNAzymes have been recognized as potent therapeutic agents for gene therapy, while their inefficient intracellular delivery and insufficient cofactor supply precludes their practical biological applications. Metal–organic frameworks (MOFs) have emerged as promising drug carriers without in‐depth consideration of their disassembled ingredients. Herein, we report a self‐sufficient MOF‐based chlorin e6‐modified DNAzyme (Ce6‐DNAzyme) therapeutic nanosystem for combined gene therapy and photodynamic therapy (PDT). The ZIF‐8 nanoparticles (NPs) could efficiently deliver the therapeutic DNAzyme without degradation into cancer cells. The pH‐responsive ZIF‐8 NPs disassemble with the concomitant release of the guest DNAzyme payloads and the host Zn2+ ions that serve, respectively, as messenger RNA‐targeting agent and required DNAzyme cofactors for activating gene therapy. The auxiliary photosensitizer Ce6 could produce reactive oxygen species (ROS) and provide a fluorescence signal for the imaging‐guided gene therapy/PDT. 相似文献