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Interest in mesoporous materials (IUPAC definition: pore size 2–50 nm) has developed dramatically over the last few years, not least because the pore structure of these materials provides an extremely large surface area within a relatively small volume of material. This makes the materials suitable, for example, for catalysis, chemical sensors, and molecular separation.
The following is a selection of recent articles in this field from Angewandte Chemie, Chemistry—A European Journal, Advanced Materials, Advanced Functional Materials, and the European Journal of Inorganic Chemistry.
Olesia Kozachuk, Kira Khaletskaya, Markus Halbherr, Angélique Bétard, Mikhail Meilikhov, Rüdiger W. Seidel, Bettina Jee, Andreas Pöppl, Roland A. Fischer
Microporous Mixed-Metal Layer-Pillared [Zn1–xCux(bdc)(dabco)0.5] MOFs: Preparation and Characterization [Full Paper]
Alessandro Agostini, Laura Mondragón, Carmen Coll, Elena Aznar, M. Dolores Marcos, Ramón Martínez-Máñez, Félix Sancenón, Juan Soto, Enrique Pérez-Payá, Pedro Amorós
Dual Enzyme-Triggered Controlled Release on Capped Nanometric Silica Mesoporous Supports [Communication]
Please release me: Mesoporous silica nanoparticles capped with bulky organic moieties containing amide and urea linkages were able to release their cargo upon addition of amidase and urease. Amidase induced an immediate, yet not complete, release of the cargo. On the other hand, urease allowed a near total cargo release that was delayed in time (see graph).
ChemistryOpen, February 17, 2012, DOI: 10.1002/open.201200003
Yurdanur Türker, Cüneyt Karakaya, Ömer Dag
Fabrication of Mesoporous Metal Chalcogenide Nanoflake Silica Thin Films and Spongy Mesoporous CdS and CdSe [Full Paper]
A new approach for the fabrication of mesoporous metal chalcogenide silica thin films and their conversion into mesoporous metal chalcogenides has been demonstrated. The metal precursors have been incorporated into the pore walls through salt-assisted self-assembly process that produces homogenous metal oxide coatings over the pore walls of the mesoporous silica thin films (see figure).
Chem. Eur. J., February 16, 2012, DOI: 10.1002/chem.201102643
Hao Zhou, Yuanyuan Qu, Yibin Bu, Xinliang Li, Chunlei Kong, Qiao Ma, Qiang Zhang, Xuwang Zhang, Jiti Zhou
Molecular-Simulation-Assisted Immobilization and Catalytic Performance of C-C Hydrolase MfphA on SBA-15 Mesoporous Silica [Full Paper]
The right strategy: A molecular simulation approach based on homology modeling and electrostatic potential calculations has been proposed to assist the immobilization process of a C-C hydrolase MfphA onto a mesoporous silicate (see figure). The theoretical molecule size, isoelectric point, and immobilization site were first predicted and then verified by adsorption kinetics and catalytic activity assays. The stability, activity, and reusability of the immobilized enzyme are also investigated.
ChemPlusChem, February 16, 2012, DOI: 10.1002/cplu.201100041
Nadine Menzel, Erik Ortel, Ralph Kraehnert, Peter Strasser
Electrocatalysis Using Porous Nanostructured Materials [Minireview]
Great potential from the nanoscale: Important synthetic routes for porous nanostructured electrocatalysts (see picture) are discussed and applications of them as catalysts showing how catalyst performance benefits from the nanostructure are also described.
ChemPhysChem, February 14, 2012, DOI: 10.1002/cphc.201100984
Kohei Miyata, Tadashi Ohba, Atsushi Kobayashi, Masako Kato, Takayuki Nakanishi, Koji Fushimi, Yasuchika Hasegawa
Thermostable Organo-phosphor: Low-Vibrational Coordination Polymers That Exhibit Different Intermolecular Interactions [Communication]
Novel thermostable organo-phosphor compounds composed of coordination polymers are reported. Tight-binding structures with intermolecular interactions of the coordination polymer induce both thermostability (decomposition point >300 °C) and high emission quantum yield (ΦLn=83 %). Their structures (see picture), thermogravimetric analyses, and remarkable photophysical properties are presented for the first time.
ChemPlusChem, February 14, 2012, DOI: 10.1002/cplu.201200002
Jiao Zhao, Mingrun Li, Junliang Sun, Leifeng Liu, Panpan Su, Qihua Yang, Can Li
Metal-Oxide Nanoparticles with Desired Morphology Inherited from Coordination-Polymer Precursors [Communication]
The “escape-by-crafty-scheme” strategy is an efficient approach to prepare metal-oxide nanomaterials with desirable morphology and crystal planes inherited from coordination-polymer nanoparticle precursors, which can be designed and finely tuned by soft chemical assembly of metal ions and organic ligands at the molecular level (see scheme; ptcda=perylene-3,4,9,10-tetracarboxylic dianhydride).
Chem. Eur. J., February 13, 2012, DOI: 10.1002/chem.201103415
Zhen-an Qiao, Suree S. Brown, Jamie Adcock, Gabriel M. Veith, J. Chris Bauer, E. Andrew Payzant, Raymond R. Unocic, Sheng Dai
A Topotactic Synthetic Methodology for Highly Fluorine-Doped Mesoporous Metal Oxides [Communication]
F tactic: Highly fluorine-doped mesoporous metal oxides (up to 40 at %) were synthesized by topotactic fluorination synthesis with mesoporous metal oxides starting materials and fluorine as the fluorination agent. The surface areas, pore sizes, pore volumes, and F atomic concentrations of these materials could be adjusted over a wide range by varying the fluorination time and temperature.
Angew. Chem. Int. Ed., February 6, 2012, DOI: 10.1002/anie.201107812
Feng Li, Brittany Dever, Hongquan Zhang, Xing-Fang Li, X. Chris Le
Mesoporous Materials in Peptidome Analysis [Highlight]
Peptide profiles: The use of mesoporous materials, such as ordered mesoporous carbon, improves the efficiency and selectivity of peptide extraction for profiling complicated samples. Controling the pore size of such mesoporous materials during synthesis allows specific molecular weight cut-offs to be introduced, which can eliminate a large number of interfering entities, such as serum proteins.
Angew. Chem. Int. Ed., February 3, 2012, DOI: 10.1002/anie.201107849
Zhen-Zhong Lu, Rui Zhang, Zhao-Rui Pan, Yi-Zhi Li, Zi-Jian Guo, He-Gen Zheng
Metal–Organic Frameworks Constructed from Versatile [WS4Cux]x−2 Units: Micropores in Highly Interpenetrated Systems [Full Paper]
![Metal–Organic Frameworks Constructed from Versatile [WS4Cux]x−2 Units: Micropores in Highly Interpenetrated Systems](http://www.wiley-vch.de/util/hottopics/img/chem201101963.gif "Metal–Organic Frameworks Constructed from Versatile [WS4Cux]x−2 Units: Micropores in Highly Interpenetrated Systems")
Versatile SBUs: [WS4Cux]x−2 units show different geometries and connectivities when used as secondary building units (SBUs) for constructing metal–organic frameworks (MOFs; see figure). Temperature and ligand are more important parameters for the synthesis of new [WS4Cux]x−2-based MOFs than the ratio of [NH4]2WS4 to CuI salt.
Chem. Eur. J., February 3, 2012, DOI: 10.1002/chem.201101963
Huai-Ping Cong, Xiao-Chen Ren, Hong-Bin Yao, Ping Wang, Helmut Cölfen, Shu-Hong Yu
Synthesis and Optical Properties of Mesoporous β-Co(OH)2/Brilliant Blue G (G250) Hybrid Hierarchical Structures [Communication]
New mesoporous β-Co(OH)2/brilliant blue G (G250) hybrid hierarchical structures constructed by thin mesocrystal nanosheets can be synthesized by a one-step refluxing process under the synergistic effect of CTAB and G250 (see Figure). This approach opens up an avenue to access new novel inorganic/dye hybrid materials with hierarchical structures for pigment and electrocatalytic application.
Yu Chen, Yu Gao, Hangrong Chen, Deping Zeng, Yaping Li, Yuanyi Zheng, Faqi Li, Xiufeng Ji, Xia Wang, Feng Chen, Qianjun He, Linlin Zhang, Jianlin Shi
Engineering Inorganic Nanoemulsions/Nanoliposomes by Fluoride-Silica Chemistry for Efficient Delivery/Co-Delivery of Hydrophobic Agents [Full Paper]
A simple and efficient drug-formulation protocol is developed to solve the delivery problem of hydrophobic agents. The protocol uses inorganic mesoporous silica nanocapsules as a promising alternative to traditional organic emulsions and liposomes while preserving the advantages of inorganic materials. This is demonstrated by delivery of drugs for cancer chemotherapy and surgery as well as the co-delivery of molecules for enhanced chemotherapy of drug-resistant cancer.
Adv. Funct. Mater., February 2, 2012, DOI: 10.1002/adfm.201102052
Hongjing Wang, Masataka Imura, Yoshihiro Nemoto, Sang-Eon Park, Yusuke Yamauchi
Synthesis of Olive-Shaped Mesoporous Platinum Nanoparticles (MPNs) with a Hard-Templating Method Using Mesoporous Silica (SBA-15) [Full Paper]
Antipasti, anyone? Well-ordered olive-shaped mesoporous Pt nanoparticles (see picture) can be prepared by using two-dimensional (2D) hexagonal mesoporous silica (SBA-15) as a hard template. The average particle sizes are controllable in the range of 150 nm to 230 nm by changing the deposition time.
Chem. Asian J., February 1, 2012, DOI: 10.1002/asia.201100949
Shuangbing Han, Thomas M. Hermans, Patrick E. Fuller, Yanhu Wei, Bartosz A. Grzybowski
Transport into Metal–Organic Frameworks from Solution Is Not Purely Diffusive [Communication]
Chemistry in motion: A combination of confocal microscopy (see picture) and reaction-diffusion modeling provided a powerful toolkit with which solution transport into metal–organic framework crystals was studied. Commonly used pure diffusion models are insufficient to describe this process and, instead, it is necessary to account for the interactions of the guest molecules and the MOF scaffold.
Angew. Chem. Int. Ed., February 1, 2012, DOI: 10.1002/anie.201108492
John A. McLeod, Ernst Z. Kurmaev, Peter V. Sushko, Teak D. Boyko, Igor A. Levitsky, Alexander Moewes
Selective Response of Mesoporous Silicon to Adsorbants with Nitro Groups [Full Paper]
Compound-selective changes in the electronic structure of mesoporous silicon have been observed upon adsorption of nitro-based explosive molecules. This selective response is demonstrated by probing the adsorption of two nitro-based molecular explosives (trinitrotoluene and cyclotrimethylenetrinitramine) and a nonexplosive nitro-based aromatic molecule (nitrotoluene) on mesoporous silicon by using soft X-ray spectroscopy (see figure).
Chem. Eur. J., January 30, 2012, DOI: 10.1002/chem.201102084
Xiaojiao Kang, Ziyong Cheng, Dongmei Yang, Ping'an Ma, Mengmeng Shang, Chong Peng, Yunlu Dai, Jun Lin
Design and Synthesis of Multifunctional Drug Carriers Based on Luminescent Rattle-Type Mesoporous Silica Microspheres with a Thermosensitive Hydrogel as a Controlled Switch [Full Paper]
Hydrogel-modified luminescent rattle-type mesoporous silica microspheres are prepared. The composites have good compatibility and can act as a magnetic resonance (MR) contrast agent because of the Gd3+ ions. The drug release behavior is regulared via a change in temperature.
Adv. Funct. Mater., January 30, 2012, DOI: 10.1002/adfm.201102746
Tewodros Asefa
Chiral Nematic Mesoporous Carbons from Self-Assembled Nanocrystalline Cellulose [Highlight]
C-ing cellulose in a new light: The self-assembly of nanocrystalline cellulose (NCC) with tetraalkoxysilane produces a chiral nematic NCC–silica composite material, which upon carbonization, and then etching of the silica with dilute base solution produces a novel high surface area chiral nematic mesoporous carbon (see picture).
Angew. Chem. Int. Ed., January 24, 2012, DOI: 10.1002/anie.201107332
Zhaogang Teng, Gengfeng Zheng, Yuqian Dou, Wei Li, Chung-Yuan Mou, Xuehua Zhang, Abdullah M. Asiri, Dongyuan Zhao
Highly Ordered Mesoporous Silica Films with Perpendicular Mesochannels by a Simple Stöber-Solution Growth Approach [Communication]
A simple solution: In the simple approach to silica films with perpendicular mesochannels presented herein, the substrate is immersed into a Stöber solution in which the silica precursors are hydrolyzed, cross-linked by an ammonia catalyst, and assembled with a surfactant on the substrate to form hexagonal mesostructures perpendicular to the substrate surface.
Angew. Chem. Int. Ed., January 24, 2012, DOI: 10.1002/anie.201108748
Ali Coskun, Mohamad Hmadeh, Gokhan Barin, Felipe Gándara, Qiaowei Li, Eunwoo Choi, Nathan L. Strutt, David B. Cordes, Alexandra M. Z. Slawin, J. Fraser Stoddart, Jean-Pierre Sauvage, Omar M. Yaghi
Metal–Organic Frameworks Incorporating Copper-Complexed Rotaxanes [Communication]
MOFs on the move: A copper-coordinated [2]pseudorotaxanate which reacts with zinc nitrate to form threefold interpenetrated networks retains most of its solution-state chemistry, including its ability to undergo electronic switching of some of the copper(I) ions under redox control.
Angew. Chem. Int. Ed., January 20, 2012, DOI: 10.1002/anie.201107873
Hongwei Yang, Abdullah M. Khan, Youzhu Yuan, Shik Chi Tsang
Mesoporous Silicon Nitride for Reversible CO2 Capture [Communication]
A good catch of CO2! It is demonstrated for the first time that a high-surface-area, inorganic-based mesoporous silicon nitride prepared through a precipitation–sublimation route shows a high, reversible CO2 uptake over a wide temperature range (298–423 K) with a moderate heat of adsorption. Our data render the thermally stable material a new contender for practical CO2 capture.
Chem. Asian J., January 13, 2012, DOI: 10.1002/asia.201100615
Eric L. Spitler, John W. Colson, Fernando J. Uribe-Romo, Arthur R. Woll, Marissa R. Giovino, Abraham Saldivar, William R. Dichtel
Lattice Expansion of Highly Oriented 2D Phthalocyanine Covalent Organic Framework Films [Communication]
Expanding into application: Covalent organic framework (COF) films are ideally suited for vertical charge transport and serve as precursors of ordered heterojunctions. Their pores, however, were previously too small to accommodate continuous networks of complementary electron acceptors. Four phthalocyanine COFs with increased pore size well into the mesoporous regime are now described (see example).
Angew. Chem. Int. Ed., January 3, 2012, DOI: 10.1002/anie.201107070
Jeonghun Kim, Chokkalingam Anand, Siddulu N. Talapaneni, Jungmok You, Salem S. Aldeyab, Eunkyoung Kim, Ajayan Vinu
Catalytic Polymerization of Anthracene in a Recyclable SBA-15 Reactor with High Iron Content by a Friedel–Crafts Alkylation [Communication]
Ironing it out: A FeSBA-15 catalyst with a high iron content as well as a large pore diameter has been synthesized and used for the production of soluble poly(methylene anthracene) (PMAn, see scheme). The catalyst is stable, active, reusable, and affords a high yield of high molecular weight PMAn. The properties of the PMAns obtained can be controlled by tuning the specific surface area, pore diameter, pore volume, and Fe content of the catalysts.
Angew. Chem. Int. Ed., January 2, 2012, DOI: 10.1002/anie.201107145
Ying-Ya Liu, Karen Leus, Maciej Grzywa, David Weinberger, Katrien Strubbe, Henk Vrielinck, Rik Van Deun, Dirk Volkmer, Veronique Van Speybroeck, Pascal Van Der Voort
Synthesis, Structural Characterization, and Catalytic Performance of a Vanadium-Based Metal–Organic Framework (COMOC-3) [Full Paper]
Stefan K. Henninger, Felix Jeremias, Harry Kummer, Christoph Janiak
MOFs for Use in Adsorption Heat Pump Processes [Microreview]
Xiu-Zhen Lin, Zhong-Yong Yuan
Synthesis of Mesoporous Zirconium Organophosphonate Solid-Acid Catalysts [Short Communication]
Junjie Xie, Huibin Qiu, Shunai Che
Handedness Inversion of Chiral Amphiphilic Molecular Assemblies Evidenced by Supramolecular Chiral Imprinting in Mesoporous Silica Assemblies [Full Paper]
Twisted helical ribbons with lamellar bilayer structures were obtained by self-assembly of chiral amphiphilic molecules in water (left-handed) and water/ethanol (right-handed). The handedness inversion of these chiral amphiphilic molecular assemblies was investigated by supramolecular chiral imprinting in mesoporous silica replicas (see figure).
Merwen Aouadi, Giulia Fornasieri, Valérie Briois, Pierrick Durand, Anne Bleuzen
Chemistry of Cobalt(II) Confined in the Pores of Ordered Silica Monoliths: From the Formation of the Monolith to the CoFe Prussian Blue Analogue Nanocomposite [Full Paper]
Under Co-ntrol: Synthesis of CoFe Prussian blue analogue (PBA)/silica nanocomposites is fully controlled by the Co species (see figure). Investigation of the local environment and electronic structure of Co showed a rich chemistry at each step of the formation process. Understanding the reactivity of the Co species is mandatory to fully control the PBA chemistry within the silica mesopores.
Weijun Fang, Jing Yang, Jiawei Gong, Nanfeng Zheng
Photo- and pH-Triggered Release of Anticancer Drugs from Mesoporous Silica-Coated Pd@Ag Nanoparticles [Full Paper]
Based on mesoporous silica-coated Pd@Ag nanoparticles, a smart drug delivery system with anticancer drugs coordinated inside the mesopores is designed and developed. The release of the loaded anticancer drugs is triggered by pH and near infrared (NIR) light irradiation.
Jianan Liu, Wenbo Bu, Shengjian Zhang, Feng Chen, Huaiyong Xing, Limin Pan, Liangping Zhou, Weijun Peng, Jianlin Shi
Controlled Synthesis of Uniform and Monodisperse Upconversion Core/Mesoporous Silica Shell Nanocomposites for Bimodal Imaging [Full Paper]
Movin' on up: Uniform and monodisperse upconversion core/mesoporous silica shell structured nanocomposites of sub-50 nm diameter were successfully synthesized (see figure). Multifunctional bioapplications of the synthesized nanocomposite particles for simultaneous magnetic resonance and upconversion fluorescence imaging are presented.
Alexandra Inayat, Isabel Knoke, Erdmann Spiecker, Wilhelm Schwieger
Assemblies of Mesoporous FAU-Type Zeolite Nanosheets [Communication]
Holey sheets: Nanosheet assemblies of FAU-type zeolite X with intracrystalline mesopores are prepared (see picture). This material is synthesized by soft-templating and combines micro, meso, and macropores in a hierarchically interconnected manner.
Ramanathan Vaidhyanathan, Simon S. Iremonger, George K. H. Shimizu, Peter G. Boyd, Saman Alavi, Tom K. Woo
Competition and Cooperativity in Carbon Dioxide Sorption by Amine-Functionalized Metal–Organic Frameworks [Communication]
Molecular insights into the roles of amine functionalization and cooperative CO2 interactions into enhancing (and diminishing) CO2 binding by metal-organic frameworks are shown both experimentally and computationally. Contrary to popular thinking, higher amination decreases CO2 binding in this system. This loss is compensated by cooperativity between CO2 triads that enhances binding by over 7 kJ mol−1.
Youn-Sang Bae, Chang Yeon Lee, Ki Chul Kim, Omar K. Farha, Peter Nickias, Joseph T. Hupp, SonBinh T. Nguyen, Randall Q. Snurr
High Propene/Propane Selectivity in Isostructural Metal–Organic Frameworks with High Densities of Open Metal Sites [Communication]
Two go in, one comes out: A series of isostructural M-MOF-74 materials (M=Co, Mn, and Mg) with high densities of open metal sites have been examined for the selective adsorption of propene over propane. Co-MOF-74 exhibits the highest thermodynamic C3H6/C3H8 selectivity (ca. 45) reported for any MOF to date.
Yuanbiao Huang, Shuiying Gao, Tianfu Liu, Jian Lü, Xi Lin, Hongfang Li, Rong Cao
Palladium Nanoparticles Supported on Mixed-Linker Metal–Organic Frameworks as Highly Active Catalysts for Heck Reactions [Full Paper]
Like a MOF to a flame: A facile ion-exchange approach for the preparation of palladium nanoparticle (Pd NP) catalysts supported on amine-functionalized, mixed-linker metal–organic frameworks based on MIL-53(Al) has been developed. These well-dispersed Pd NPs drastically enhance N2 adsorption and show high activity and selectivity for Heck reactions (see scheme). The Pd NPs catalysts exhibit high stability and can be easily recovered and reused.
Weigang Lu, Daqiang Yuan, Trevor A. Makal, Jian-Rong Li, Hong-Cai Zhou
A Highly Porous and Robust (3,3,4)-Connected Metal–Organic Framework Assembled with a 90° Bridging-Angle Embedded Octacarboxylate Ligand [Communication]
Picky cage: A dicopper(II)-paddle-wheel-based metal–organic framework (PCN-80, see picture) with a rare (3,3,4)-connected topology has been synthesized by using a unique octatopic ligand featuring 90° bridging-angle dicarboxylate moieties. PCN-80 has Brunauer-Emmett-Teller (BET) and Langmuir surface areas of 3850 and 4150 m2 g−1, respectively. It exhibits high gas-uptake capacity for H2 and large adsorption selectivity of CO2 over N2.
Yabing He, Zhangjing Zhang, Shengchang Xiang, Hui Wu, Frank R. Fronczek, Wei Zhou, Rajamani Krishna, Michael O'Keeffe, Banglin Chen
High Separation Capacity and Selectivity of C2 Hydrocarbons over Methane within a Microporous Metal–Organic Framework at Room Temperature [Communication]
A separation story! A microporous metal–organic framework (UTSA-34) of non-interpenetrated binodal (4,6)-connected ybh network with interconnected cages of about 12.8 Å has been realised to exhibit highly selective separation of C2 hydrocarbons from methane with a separation capacity of 3.0 mol kg−1 and selectivity of 35 at room temperature (see figure).
Jian-Ke Sun, Qing-Xia Yao, Yu-Yang Tian, Lei Wu, Guang-Shan Zhu, Rui-Ping Chen, Jie Zhang
Borromean-Entanglement-Driven Assembly of Porous Molecular Architectures with Anion-Modified Pore Space [Full Paper]
You're a Borromeanie: Borromean-entangled porous frameworks (an example is shown here) that can accommodate different kinds of anions with various sizes, shapes, and locations demonstrate the superstability of Borromean linkages and their potential in constructing porous frameworks with tunable pore environments.
Minoru Waki, Norihiro Mizoshita, Yoshifumi Maegawa, Takeru Hasegawa, Takao Tani, Toyoshi Shimada, Shinji Inagaki
Enhanced Fluorescence Detection of Metal Ions Using Light-Harvesting Mesoporous Organosilica [Full Paper]
Fluorescence chemosensors: Periodic mesoporous organosilica with a fluorescent 2,2'-bipyridine receptor attached in the mesochannels showed enhanced fluorescence quenching or band shift upon the addition of a low concentration of metal ions (Cu2+, Zn2+, etc.) because of the unique light-harvesting property of the mesoporous organosilica (see figure).
Sebastian C. Junggeburth, Katharina Schwinghammer, Kulpreet S. Virdi, Christina Scheu, Bettina V. Lotsch
Towards Mesostructured Zinc Imidazolate Frameworks [Full Paper]
The structural analogy between microporous ZIFs and zeolites has been demonstrated to also hold for mesostructured silica materials on the one hand, and mesostructured imidazolate frameworks (MIFs) on the other (see figure). Comprehensive characterization of the obtained MIF materials gives evidence of a lamellar hybrid structure composed of bromine-terminated zinc imidazolate chains, which are sandwiched by cationic surfactant layers.
You-Kyong Seo, Ji Woong Yoon, Ji Sun Lee, Young Kyu Hwang, Chul-Ho Jun, Jong-San Chang, Stefan Wuttke, Philippe Bazin, Alexandre Vimont, Marco Daturi, Sandrine Bourrelly, Philip L. Llewellyn, Patricia Horcajada, Christian Serre, Gérard Férey
Energy-Efficient Dehumidification over Hierachically Porous Metal–Organic Frameworks as Advanced Water Adsorbents [Communication]
Hierarchically porous metal–organic frameworks with mesoporous cages are demonstrated to behave as promising water adsorbents in energy-efficient dehumidification. Their low temperature desorption properties for water with huge sorption uptakes are essential for various water sorption applications including desiccant dehumidification and fresh water production.
Baiyan Li, Zhijuan Zhang, Yi Li, Kexin Yao, Yihan Zhu, Zhiyong Deng, Fen Yang, Xiaojing Zhou, Guanghua Li, Haohan Wu, Nour Nijem, Yves J. Chabal, Zhiping Lai, Yu Han, Zhan Shi, Shouhua Feng, Jing Li
Enhanced Binding Affinity, Remarkable Selectivity, and High Capacity of CO2 by Dual Functionalization of a rht-Type Metal–Organic Framework [Communication]
Open and friendly: The smallest member of the rht-type metal–organic frameworks (MOFs, see picture) constructed by a hexacarboxylate ligand with a nitrogen-rich imino triazine backbone shows a significantly enhanced gas binding affinity relative to all other isoreticular rht-type MOFs. The high adsorption capacity and remarkable selectivity of CO2 are attributed to the high density of open metal and Lewis basic sites in the framework.
Jesús Ferrando-Soria, Rafael Ruiz-García, Joan Cano, Salah-Eddine Stiriba, Julia Vallejo, Isabel Castro, Miguel Julve, Francesc Lloret, Pedro Amorós, Jorge Pasán, Catalina Ruiz-Pérez, Yves Journaux, Emilio Pardo
Reversible Solvatomagnetic Switching in a Spongelike Manganese(II)–Copper(II) 3D Open Framework with a Pillared Square/Octagonal Layer Architecture [Full Paper]
Molecular magnetic sponges: A new oxamato-based mixed-metal–organic framework (shown here) reversibly switches from a crystalline hydrated phase with long-range ferromagnetic ordering at a critical temperature (Tc) of 22.5 K to an amorphous dehydrated phase at Tc=2.3 K. The dehydration/rehydration process is accompanied by large changes in crystal volume (ca. 45 %) and color.
Faysal Benaskar, Volker Engels, Evgeny V. Rebrov, Narendra G. Patil, Jan Meuldijk, Peter C. Thüne, Pieter C. M. M. Magusin, Brahim Mezari, Volker Hessel, Lumbertus A. Hulshof, Emiel J. M. Hensen, Andrew E. H. Wheatley, Jaap C. Schouten
New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions [Full Paper]
Copper catalysts captured: The Ullmann-type C-O cross-coupling of potassium phenolate and 4-chloropyridine was successfully carried out by applying copper nanoparticles supported on both non-porous and mesoporous titania (see figure).
Hua Zhang, Huan Wang, You Xu, Sifei Zhuo, Yifu Yu, Bin Zhang
Conversion of Sb2Te3 Hexagonal Nanoplates into Three-Dimensional Porous Single-Crystal-Like Network-Structured Te Plates Using Oxygen and Tartaric Acid [Communication]
Pore genius: Sb2Te3 hexagonal nanoplates can be transformed into 3D porous network-structured Te plates by the dissolution of Sb3+ ions induced by tartaric acid (TA), the O2-assisted oxidation of Te2− ions to Te0, and a subsequent Ostwald ripening process (see picture). These Te plates can be adopted as templates for the synthesis of 3D porous nanothread-based (or nanotube-based) metal and metal telluride nanoplates.
Miroslav Rubeš, Lukáš Grajciar, Ota Bludský, Andrew D. Wiersum, Philip L. Llewellyn, Petr Nachtigall
Combined Theoretical and Experimental Investigation of CO Adsorption on Coordinatively Unsaturated Sites in CuBTC MOF [Article]
In the frame: The adsorption enthalpy of CO in metal–organic framework CuBTC material is investigated. The reliability of various methods for the description of CO interaction with the Cu2+ site in CuBTC is discussed based on experimental results and accurate coupled-cluster calculations of the paddle wheel (see picture).
Sachin M. Chavan, Greig C. Shearer, Eric Bloch, Silvia Bordiga
Acetylene Adsorption on CPO-27-M Metal–Organic Frameworks (M=Fe, Co and Ni) [Communication]
MOFs as acetylene adsorbents: The adsorption of acetylene on the isostructural metal–organic frameworks CPO-27-M (where M=Fe, Co and Ni) is studied by FTIR, UV/Vis spectroscopy, and calorimetric isotherm measurements. The results show that M–O pairs act as the adsorption sites in these materials and that the Ni analogue is the strongest acetylene adsorbent of the series.
Andreas Schaate, Simon Dühnen, Georg Platz, Sebastian Lilienthal, Andreas M. Schneider, Peter Behrens
A Novel Zr-Based Porous Coordination Polymer Containing Azobenzenedicarboxylate as a Linker [Full Paper]
A new Zr porous coordination polymer with azobenzenedicarboxylate linkers was prepared by using a modulated synthetic approach. Without a modulator (benzoic acid), no crystalline products were formed. The material is thermally stable in air up to 400 °C and exhibits a large specific surface area (3000 m2 g–1).
Daniel L. Reger, Agota Debreczeni, Mark D. Smith
Homochiral, Supramolecular Frameworks Built from a Zinc(II) Tetramer or Cadmium(II) Dimer Containing Enantiopure Carboxylate Ligands Functionalized with a Strong π···π Stacking Synthon [Full Paper]
The ligand (S)-2-(1,8-naphthalimido)propanoate (Lala–) forms a tetrameric zinc(II) complex, [Zn4(Lala)6(OH)2(MeOH)4], in which strong π···π stacking interactions of the 1,8-naphthalimide groups organize the tetramers into a 3D, homochiral supramolecular framework supported exclusively by noncovalent forces. The ligand also forms the acentric dimeric cadmium(II) complex, [Cd2(Lala)4(DMF)3(MeOH)].
Nazmul Abedin Khan, Sung Hwa Jhung
Remarkable Adsorption Capacity of CuCl2-Loaded Porous Vanadium Benzenedicarboxylate for Benzothiophene [Communication]
A molecular sieve: A metal–organic framework (MOF) MIL-47 loaded with CuCl2 shows the highest adsorption capacity for benzothiophene because of the presence of CuI ions derived from CuII ions and porous MIL-47. The CuI ions were obtained by reduction of CuII with VIII ions in MIL-47. The modified MOF could be successfully used for the desulfurization of a liquid fuel (see picture).
Norihiro Mizoshita, Takao Tani, Hiroshi Shinokubo, Shinji Inagaki
Mesoporous Organosilica Hybrids Consisting of Silica-Wrapped π–π Stacking Columns [Communication]
A new class of periodic mesoporous organosilica (PMO) materials with a columnar π-stacking arrangement of the framework organic groups has been prepared from disklike precursors with hydrophobic perylene bisimide (PBI) cores (see picture). The PBI-bridged PMOs exhibit exciton coupling and efficient formation of mobile radical spins by electron doping within the pore walls.
Zhangxiong Wu, Wei Li, Paul A. Webley, Dongyuan Zhao
General and Controllable Synthesis of Novel Mesoporous Magnetic Iron Oxide@Carbon Encapsulates for Efficient Arsenic Removal [Communication]
A facile ammonia-atmosphere pre-hydrolysis post-synthetic route that can uniformly and selectively deposit Fe2O3 nanoparticles in the predefined mesopores (5.6 nm) of a bimodal (2.3, 5.6 nm) mesoporous carbon matrix is demonstrated (see figure). The mesoporous magnetic Fe2O3@C encapsulates show excellent performance for arsenic capture with remarkable adsorption capacity, fast uptake rate, easy magnetic separation, and good cyclic stability.
Ming Hu, Shuhei Furukawa, Ryo Ohtani, Hiroaki Sukegawa, Yoshihiro Nemoto, Julien Reboul, Susumu Kitagawa, Yusuke Yamauchi
Synthesis of Prussian Blue Nanoparticles with a Hollow Interior by Controlled Chemical Etching [Communication]
A facile route has been found to prepare Prussian blue (PB) hollow particles with a cubic shape (see picture). With PB mesocrystals used as a starting material, hollow interiors were created through controlled chemical etching in the presence of poly(vinylpyrrolidone). The hollow cavities and particle sizes could be tuned by changing the synthetic conditions, and the original PB crystallinity was preserved even after formation of interior hollows.
Nikola Ž. Knežević, Igor I. Slowing, Victor S.-Y. Lin
Tuning the Release of Anticancer Drugs from Magnetic Iron Oxide/Mesoporous Silica Core/Shell Nanoparticles [Full Paper]
A series of core/shell magnetic mesoporous silica nanoparticle (MMSN) materials were prepared. The loading and release of anticancer drugs, 9-aminoacridine (9AA) and camptothecin (CPT), as well as cytotoxic activity of drug loaded materials, is influenced by the presence of phenylethyl functionalization inside the MMSN mesopores (see figure). An externally applied magnetic field accelerates the drug release from the materials.
Ji Ha Lee, Sunwoo Kang, Justyn Jaworski, Ki-Young Kwon, Moo Lyong Seo, Jin Yong Lee, Jong Hwa Jung
Fluorescent Composite Hydrogels of Metal–Organic Frameworks and Functionalized Graphene Oxide [Communication]
GO MOFs! Azobenzoic acid functionalized graphene (A-GO) can act as a structure-directing template that influences hydrogel formation together with metal–organic frameworks (MOFs). Zn2+ MOFs of pyridine derivatives work as framework linkers between the A-GO sheets (MOF–A-GO, see figure). MOF–A-GO exhibits a strong fluorescence enhancement upon gel formation. In addition, MOF–A-GO selectively recognizes trinitrotoluene.
Matthias J. Beier, Wolfgang Kleist, Michael T. Wharmby, Reinhard Kissner, Bertram Kimmerle, Paul A. Wright, Jan-Dierk Grunwaldt, Alfons Baiker
Aerobic Epoxidation of Olefins Catalyzed by the Cobalt-Based Metal–Organic Framework STA-12(Co) [Full Paper]
Aim for the STAs: The metal–organic framework catalyst STA-12(Co) showed remarkable activity in the aerobic epoxidation of E-stilbene in DMF (see figure) and could be efficiently recycled. High selectivity (80–90 %) for stilbene oxide was observed. The induction period of the reaction could be reduced by styrene/stilbene co-epoxidation. Detailed parameter studies combined with spectroscopic investigations were performed to obtain an initial insight into the reaction mechanism.
Xufang F. Qian, Bin Li, Yuanyuan Y. Hu, Guoxing X. Niu, D. Yahong H. Zhang, Renchao C. Che, Yi Tang, Dangsheng S. Su, Abdullah M. Asiri, Dongyuan Y. Zhao
Exploring Meso-/Microporous Composite Molecular Sieves with Core–Shell Structures [Full Paper]
Esprit de core: Meso-/microporous core–shell composite molecular sieves with hierarchical pore structures (see figure), from opened mesopore channels (2.4–3.0 nm) to accessible micropores (≈0.51 nm), and graded acidity distributions, from weakly acidic mesopores to accessible strongly acidic ZSM-5 cores, have been synthesized.
Carlos Bartual-Murgui, Lionel Salmon, Amal Akou, Norma A. Ortega-Villar, Helena J. Shepherd, M. Carmen Muñoz, Gábor Molnár, José Antonio Real, Azzedine Bousseksou
Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann-like Metal–Organic Frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni) [Full Paper]
![Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann-like Metal–Organic Frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni)](http://www.wiley-vch.de/util/hottopics/img/chem201102357.gif "Synergetic Effect of Host–Guest Chemistry and Spin Crossover in 3D Hofmann-like Metal–Organic Frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni)")
It's what's inside that counts: 3D Hofmann-like clathrate metal–organic frameworks {Fe(bpac)[M(CN)4]}·H2O· x (bpac) (M=Pt, Pd, Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin crossover at room temperature with significant hysteresis loops (up to 68 K) are reported. Their physical properties are closely related to the stoichiometry of the samples and in particular to the nature and the amount of guest molecules (see figure).
Pradip Pachfule, Yifei Chen, Jianwen Jiang, Rahul Banerjee
Fluorinated Metal–Organic Frameworks: Advantageous for Higher H2 and CO2 Adsorption or Not? [Full Paper]
Fluorine or not? The synthesis, structure, and gas adsorption properties of three new metal–organic frameworks (MOFs) designed from isonicotinic acid (INA) and 3-fluoroisonicotinic acid (FINA) along with CoII as the metal center are studied (see scheme). The effect of the partial introduction of fluorine atoms into the framework on H2 uptake by the isostructural MOFs Co-INA-1 and Co-FINA-1 is analyzed experimentally and computationally.
Kohsuke Mori, Kentaro Watanabe, Kojirou Fuku, Hiromi Yamashita
Photoluminescence Emission and Photoinduced Hydrogen Production Driven by PtII Pyridyl Complexes Anchored onto Mesoporous Silica [Communication]
Photocatalytic H2 evolution: The anchored PtII terpyridine complexes, which are closely situated to each other within the mesoporous channels, exhibit unique photoluminescence properties and behave as single-component bifunctional photocatalysts that enable both visible-light sensitization and H2 evolution without the need for an additional electron relay (see figure).
Christian Argyo, Valentina Cauda, Hanna Engelke, Joachim Rädler, Gregor Bein, Thomas Bein
Heparin-Coated Colloidal Mesoporous Silica Nanoparticles Efficiently Bind to Antithrombin as an Anticoagulant Drug-Delivery System [Communication]
Blood ties: A novel nanoscale, injectable drug-delivery system that combines heparin, which prevents blood clotting, with multifunctional core-shell colloidal mesoporous silica nanoparticles has been designed (see figure). The anticoagulant and biocompatible properties of heparin together with the highly porous features of the nanoparticles lead to an efficient multifunctional drug-delivery system that can itself act as an anticoagulant and allows for incorporation of biologically active molecules as deliverable cargo.
Tia Jacobs, Michaele J. Hardie
Construction of Metal–Organic Frameworks: Versatile Behaviour of a Ligand Containing Mono- and Bidentate Coordination Sites [Full Paper]
soc it and see: Trischelate and monochelate metal complexes of a decorated 2,2'-bipyridine ligand are effective structural nodes or building units for the construction of three- or two-dimensional coordination polymer materials. The three-dimensional structure has a highly unusual {44·62}3{46·89}2 soc topology, which can also be described as vertex-sharing stella octangula prisms with large channels and cavities.
Angela Datcu, Nans Roques, Véronique Jubera, Daniel Maspoch, Xavier Fontrodona, Klaus Wurst, Inhar Imaz, Georges Mouchaham, Jean-Pascal Sutter, Concepció Rovira, Jaume Veciana
Three-Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals [Full Paper]
A rare find: MOFs that combine a fairly rare (6,3) connectivity and large 1D channels were obtained by reacting LnIII ions (Ln=Tb, Gd, Eu) with open- or closed-shell perchlorinated triphenylmethyl (PTM) ligands (see picture). Tb and Eu compounds based on the diamagnetic ligand show metal-centered luminescence. In radical-based complexes, {Ln-Radical; Ln=Tb, Gd} the interactions were found to be ferromagnetic.
Yong Wang, Xinchen Wang, Markus Antonietti
Polymeric Graphitic Carbon Nitride as a Heterogeneous Organocatalyst: From Photochemistry to Multipurpose Catalysis to Sustainable Chemistry [Review]
Multipurpose catalyst: Graphitic carbon nitride (g-C3N4; see SEM image) is an effective (photo)catalyst for a whole series of reactions. This Review describes the synthesis of g-C3N4, how the band positions and bandgaps can be varied by copolymerization and doping and how changes in the solid-state structure can improve heterogeneous organocatalyst effectiveness.
Prakash Kanoo, Ashta Chandra Ghosh, Soumya T. Cyriac, Tapas Kumar Maji
A Metal–Organic Framework with Highly Polar Pore Surfaces: Selective CO2 Adsorption and Guest-Dependent On/Off Emission Properties [Full Paper]
Polar pore club: A new 3D microporous metal–organic framework with pore surfaces decorated with open ZnII sites and pendant hydroxyl groups from a dihydroxyterphthalate (H2dht) linker has been synthesised (see figure). It shows highly selective adsorption of CO2 gas at 195 K and exhibits guest induced on/off emission.
Ilke Muylaert, Jan Musschoot, Karen Leus, Jolien Dendooven, Christophe Detavernier, Pascal Van Der Voort
Atomic Layer Deposition of Titanium and Vanadium Oxide on Mesoporous Silica and Phenol/Formaldehyde Resins – the Effect of the Support on the Liquid Phase Epoxidation of Cyclohexene [Full Paper]
Supported titanium and vanadium oxide catalysts have been synthesised by atomic layer deposition. The influence of the support type (mesoporous silica vs. mesoporous phenolic resin) on the catalytic activity has been investigated. The support–oxygen–metal bond is assumed to be critical for catalytic behaviour.
Madhab C. Das, Shengchang Xiang, Zhangjing Zhang, Banglin Chen
Functional Mixed Metal–Organic Frameworks with Metalloligands [Minireview]
Metal mixer: A novel metalloligand approach allows the rational immobilization of a variety of functional sites in mixed metal–organic frameworks (M'MOFs). This Minireview highlights some important functional M'MOFs with metalloligands for gas storage and separation, enantioselective separation, heterogeneous asymmetric catalysis, sensing, drug delivery, and biomedical imaging.
Mark D. Allendorf, Adam Schwartzberg, Vitalie Stavila, A. Alec Talin
A Roadmap to Implementing Metal–Organic Frameworks in Electronic Devices: Challenges and Critical Directions [Concept]
MOFs in electronics: Research focused on using metal–organic frameworks (MOFs) as components of electronic devices is in its infancy. New fabrication methods are required to take advantage of their unique properties and extend their use to the realm of electronic circuitry. A high-level roadmap for device-related MOF research is proposed, the objective of which is to stimulate thinking within the MOF community concerning the development of these materials for applications including sensing, photonics, and microelectronics.
Thomas Hügle, Monika Hartl, Dieter Lentz
The Route to a Feasible Hydrogen-Storage Material: MOFs versus Ammonia Borane [Review]
Future fuels: Since molecular hydrogen is not suited as a car fuel for a variety of reasons, immense efforts have been undertaken to develop hydrogen storage materials that will meet the car manufacturers' requirements. In this critical review, we compare the achievements and shortcomings of the two most promising approaches for storing hydrogen: chemical storage in ammonia borane and physisorption in metal–organic frameworks (see picture).
Barbara Platschek, Andreas Keilbach, Thomas Bein
Mesoporous Structures Confined in Anodic Alumina Membranes [Review]
Nanoporous membranes with ordered morphology are of interest for potential applications in various fields of nanoscience, including the templated synthesis of oriented nanowires, or the controlled separation and release of molecules. This review focuses on the synthesis strategies, mesophase evolution mechanisms and potential applications of mesoporous materials (e.g., silica, titania, and carbon) confined within anodic alumina membranes (AAM).
K. Travis Holman
Molecule-Constructed Microporous Materials: Long under Our Noses, Increasingly on Our Tongues, and Now in Our Bellies [Highlight]
Emerging roles for MOFs: Crystalline microporous materials constructed from molecular components have been known for over four decades, and are increasingly utilized in the context of materials design. Recent developments in the field of metal–organic frameworks (MOFs) further highlight the roles of design and serendipity at the crossroads of emerging applications for this family of materials, from robust dynamics to food science.
Cedric Boissiere, David Grosso, Alexandra Chaumonnot, Lionel Nicole, Clement Sanchez
Aerosol Route to Functional Nanostructured Inorganic and Hybrid Porous Materials [Review]
A wind of change is blowing in the field of innovative advanced porous materials. The combination of aerosol processing with sol–gel chemistry, self-assembly and multiple templating allows the designed construction of hierarchically structured porous inorganic or hybrid materials with multiscale texturation. The available materials span a very large collection of structures and chemical compositions and impact various applications domains such as catalysis, sensing, photonic and microelectronic devices, nanoionics and energy, functional coatings, biomaterials, multifunctional therapeutic carriers, and microfluidics...
Michael Hirscher
Hydrogen Storage by Cryoadsorption in Ultrahigh-Porosity Metal–Organic Frameworks [Highlight]
Take it to the limit: Ultrahigh-porosity metal–organic frameworks (MOFs) with extremely high specific surface areas show very high hydrogen uptake by physisorption at low temperatures. The total hydrogen storage capacity of MOF-210 through cryoadsorption exceeds even that of complex hydrides.
© Wiley-VCH 2011.
RSS feed![Microporous Mixed-Metal Layer-Pillared [Zn1–xCux(bdc)(dabco)0.5] MOFs: Preparation and Characterization](http://www.wiley-vch.de/util/hottopics/img/ejic201101295.jpg "Microporous Mixed-Metal Layer-Pillared [Zn1–xCux(bdc)(dabco)0.5] MOFs: Preparation and Characterization")
