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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.
Xiaoxia Zhou, Hangrong Chen, Yan Zhu, Yudian Song, Yu Chen, Yongxia Wang, Yun Gong, Guobin Zhang, Zhu Shu, Xiangzhi Cui, Jinjin Zhao, Jianlin Shi
Dual-Mesoporous ZSM-5 Zeolite with Highly b-Axis-Oriented Large Mesopore Channels for the Production of Benzoin Ethyl Ether [Full Paper]
An aggregation–assembly process was developed for the synthesis of dual-mesoporous zeolite ZSM-5 with b-axis-aligned larger mesopores and smaller wormlike mesopores by using nonionic copolymer F127 and cationic surfactant CTAB as co-templates (see figure). It shows excellent catalytic performance in the condensation of benzaldehyde with ethanol due to the free access of bulky reactants provided by the dual-mesoporous structure, especially the b-axis-oriented large mesopores, and the large number of active sites and strong acidity offered by the zeolite framework.
Zilong Zhao, Hongmin Meng, Nannan Wang, Michael J. Donovan, Ting Fu, Mingxu You, Zhuo Chen, Xiaobing Zhang, Weihong Tan
A Controlled-Release Nanocarrier with Tumor Extracellular pH Value Driven Targeting and Translocation for Drug Delivery [Communication]
This pHLIP is no flop: Functionalizing mesoporous silica nanoparticles (MSNs) with pHLIPss peptide provides a controlled-release nanoparticle drug delivery system targeting the acidic tumor microenvironment. At low pH values, pHLIPss inserts into the cell membrane and translocates carriers into cells, where the cargo is released by the cleavage of the pHLIPss disulfide bonds (see scheme).
Angew. Chem. Int. Ed., Jun 11, 2013, DOI: 10.1002/anie.201302557
Ayyakkalai Balamurugan, Arvind Kumar Gupta, Ramamoorthy Boomishankar, Mundlapudi Lakshmipathi Reddy, Manickam Jayakannan
Heavy Atom Effect Driven Organic Phosphors and Their Luminescent Lanthanide Metal–Organic Frameworks [Full Paper]
Heavyweight glowing: The heavy atom effect is employed to engineer the excited-state energy levels in luminescent lanthanide metal–organic frameworks (MOFs) by coupling two independent energy-transfer photophysical process: enhancing the electronic population in the excited triplet state through intersystem crossing and ligand-to-metal energy transfer (LMET; see picture).
Li-Li Yu, Jun-Jie Zhu, Jing-Tai Zhao
Three-Dimensional Network Mesoporous Nanostructured α-Manganese Dioxide with High Supercapacitive Performance: Facile, Environmental and Large-Scale Synthesis [Full Paper]
Three-dimensional network mesoporous nanostructured α-MnO2 with a high specific surface area and narrow pore size distribution has been fabricated in high yields without a template at room temperature.
Eur. J. Inorg. Chem., Jun 10, 2013, DOI: 10.1002/ejic.201300265
Krishanu Sarkar, Yolanda Salinas, Inmaculada Campos, Ramón Martínez-Máñez, María D. Marcos, Félix Sancenón, Pedro Amorós
Organic–Inorganic Hybrid Mesoporous Materials as Regenerable Sensing Systems for the Recognition of Nitroaromatic Explosives [Full Paper]
All in the family: A family of mesoporous materials functionalised with fluorophores (pyrene, dansyl and fluorescein) have been prepared, characterised and used for the fluorogenic recognition of nitroaromatic explosives (see red hexagons in figure). The emission of the pyrene and dansyl functionalised materials was quenched upon the addition of picric acid or 2,4,6-trinitrophenylmethylnitramine, hence easy detection was possible.
Pei-Zhou Li, Yanli Zhao
Nitrogen-Rich Porous Adsorbents for CO2 Capture and Storage [Focus Review]
Ways to get (N)-rich: The construction of physical and chemical adsorbents for CO2 capture and sequestration (CCS) is a vital technology on the way towards a sustainable low-carbon future. Nitrogen-rich porous materials including amine-functionalized porous silica, nitrogen-rich porous carbons, nitrogen-rich metal-organic frameworks, and nitrogen-rich porous organic polymers have been emerging as cost-effective and energy-efficient adsorbents for CCS. This review highlights recent progress in the fabrication and application of nitrogen-rich porous materials for CCS.
Xiangfen Jiang, Norihiro Suzuki, Bishnu Prasad Bastakoti, Wei-Jung Chen, Yu-Tzu Huang, Yusuke Yamauchi
Controlled Synthesis of Well-Ordered Mesoporous Titania Films with Large Mesopores Templated by Spherical PS-b-PEO Micelles [Short Communication]
Both large-sized mesopores and long-range ordering are realized in titania thin films by precisely controlling the properties of the precursor solution. The mesostructural domains successfully extend up to the micrometer scale, which, to the best of our knowledge, has never been seen in previous reports.
Eur. J. Inorg. Chem., Jun 05, 2013, DOI: 10.1002/ejic.201300221
Stan C. Davis, Vonda C. Sheppard, Gousia Begum, Ye Cai, Yunnan Fang, John D. Berrigan, Nils Kröger, Kenneth H. Sandhage
Rapid Flow-Through Biocatalysis with High Surface Area, Enzyme-Loaded Carbon and Gold-Bearing Diatom Frustule Replicas [Full Paper]
Electrically conductive microparticles possessing the hollow, hierarchically-porous architectures of diatom frustules can be attractive as enzyme supports. Freestanding, high-specific-surface-area carbon and gold-bearing frustule replicas (generated via shape-preserving conversion of diatom silica) functionalized with a high loading of glucose oxidase (GOx) exhibit rates of flow-through catalysis more than 80% greater than for GOx-bearing carbon black and gold nanoparticles.
Adv. Funct. Mater., Jun 05, 2013, DOI: 10.1002/adfm.201203758
Kojirou Fuku, Ryunosuke Hayashi, Shuhei Takakura, Takashi Kamegawa, Kohsuke Mori, Hiromi Yamashita
The Synthesis of Size- and Color-Controlled Silver Nanoparticles by Using Microwave Heating and their Enhanced Catalytic Activity by Localized Surface Plasmon Resonance [Communication]
Silver nanoparticles (Ag NPs) of various colors were synthesized within the mesopore structure of SBA-15 by using microwave-assisted alcohol reduction. The charge density is partially localized on the surface of these Ag NPs owing to localized surface plasmon resonance. This charge localization results in them having enhanced catalytic activity under visible light irradiation compared to Ag NPs obtained by thermal processes.
Angew. Chem. Int. Ed., Jun 05, 2013, DOI: 10.1002/anie.201301652
Bo Liu, Min Tu, Denise Zacher, Roland A. Fischer
Multi Variant Surface Mounted Metal–Organic Frameworks [Full Paper]
Cüneyt Karakaya, Yurdanur Türker, Ömer Dag
Molten-Salt-Assisted Self-Assembly (MASA)-Synthesis of Mesoporous Metal Titanate-Titania, Metal Sulfide-Titania, and Metal Selenide-Titania Thin Films [Full Paper]
High quality mesoporous metal titanate thin films are synthesized using a molten-phase-assisted self-assembly (MASA) method. The metal salts are used as a non-volatile solvent in the new assembly process. The films are converted into mesoporous titania-metal chalcogenides (TiO2-CdS, TiO2-CdSe, and TiO2-ZnSe) under H2S or H2Se at room temperature and may find applications in solar cells, catalysis, photocatalysis, electronics, and optoelectronics.
Adv. Funct. Mater., Jun 03, 2013, DOI: 10.1002/adfm.201202716
Ji Bong Joo, Ilkeun Lee, Michael Dahl, Geon Dae Moon, Francisco Zaera, Yadong Yin
Controllable Synthesis of Mesoporous TiO2 Hollow Shells: Toward an Efficient Photocatalyst [Full Paper]
A simple yet effective method is developed for the synthesis of hollow mesoporous TiO2 nanoshells with well-controlled crystallinity and phase. It is now convenient to optimize their structures for enhanced performance in photocatalysis.
Adv. Funct. Mater., Jun 03, 2013, DOI: 10.1002/adfm.201300255
Changshin Jo, Jongkook Hwang, Hannah Song, Anh Ha Dao, Yong-Tae Kim, Sang Hyup Lee, Seok Won Hong, Songhun Yoon, Jinwoo Lee
Block-Copolymer-Assisted One-Pot Synthesis of Ordered Mesoporous WO3−x/Carbon Nanocomposites as High-Rate-Performance Electrodes for Pseudocapacitors [Full Paper]
An ordered mesoporous tungsten-oxide/carbon (m-WO3−x-C-s) nanocomposite is synthesized using a block-copolymer-assisted one-pot self-assembly method. As a pseudocapacitor electrode, m-WO3−x-C-s exhibits a high average volumetric capacitance of 340 F cm−3 and a gravimetric capacitance of 103 F g−1. The amorphous carbon in the m-WO3−x-C-s decreases the internal resistance of m-WO3−x-C-s electrode by facilitating electric conduction.
Adv. Funct. Mater., Jun 03, 2013, DOI: 10.1002/adfm.201202682
Lei Liao, Jie Zhu, Xiaojun Bian, Lina Zhu, Micheál D. Scanlon, Hubert H. Girault, Baohong Liu
MoS2 Formed on Mesoporous Graphene as a Highly Active Catalyst for Hydrogen Evolution [Full Paper]
A highly active electrocatalyst of MoS2/MGF, where the MoS2 nanoparticles are formed uniformly on mesoporous graphene foams (MGF) via a facile solvothermal approach, is reported. The MoS2/MGF nanocomposites exhibit the high hydrogen evolution reaction activity with a low overpotential and large cathodic currents arising from MGF's high surface area, abundant mesopores, and highly conductive skeleton of graphene.
Adv. Funct. Mater., Jun 03, 2013, DOI: 10.1002/adfm.201300318
Binod Nepal, Siddhartha Das
Sustained Water Oxidation by a Catalyst Cage-Isolated in a Metal–Organic Framework [Communication]
Keep ’em separated: Pores of a MOF were used to isolate a highly reactive water-oxidation catalyst (MnIII(μ-O)2MnIV; spheres in picture). The resulting construct shows highly sustained water oxidation, with minimized intermolecular degradative side-reactions. This system provides a simple path to extend the lifetime of reactive catalysts without compromising their molecular definition and reactivity.
Angew. Chem. Int. Ed., May 31, 2013, DOI: 10.1002/anie.201301327
Thangavelu Palaniselvam, Bishnu P. Biswal, Rahul Banerjee, Sreekumar Kurungot
Zeolitic Imidazolate Framework (ZIF)-Derived, Hollow-Core, Nitrogen-Doped Carbon Nanostructures for Oxygen-Reduction Reactions in PEFCs [Full Paper]
Rabbit-proof FeNC: Fe-N-doped porous carbon (FeNC) materials were prepared by annealing [Fe(Phen)3]2+ that was embedded in ZIFs (ZIF-68, ZIF-69, and ZIF-70) and electrochemically examined for their activity in oxygen-reduction reactions (see figure).
Yichao Lin, Chunlong Kong, Liang Chen
Facile Synthesis of Aluminum-Based Metal–Organic Frameworks with Different Morphologies and Structures through an OH−-Assisted Method [Full Paper]
Taken with a pinch of salt: Metal–organic frameworks (MOFs) with different structures and morphologies were synthesized by tuning the OH− ion content in the synthesis solution. MIL-96 crystals with dodecahedral and hexagonal columnar shapes, and nanorod-shaped MIL-110 were obtained (see picture).
Aman Kaur, Tomislav Pintauer
Copper(I)–Cyanide Frameworks through Thermal or Photodecomposition of the Free Radical Diazo Initiator AIBN [Short Communication]
Thermal or photodecomposition of 2,2'-azobis(2-methylpropionitrile) (AIBN) is used as a source of cyanide anions in the synthesis of copper(I)–cyanide frameworks. The reported methodology utilizes the direct reduction of CuII(aa)(NN)X (aa = deprotonated amino acid, NN = bidentate nitrogen-based ligand, X = Cl or Br) complexes by AIBN/ascorbic acid to yield six novel coordination networks.
Eur. J. Inorg. Chem., May 17, 2013, DOI: 10.1002/ejic.201300495
Fang Pu, Xia Liu, Xinjian Yang, Zhen Liu, Jinsong Ren, Shu Wang, Xiaogang Qu
Versatile Fluorescent Conjugated Polyelectrolyte-Capped Mesoporous Silica Nanoparticles for Controlled Drug Delivery and Imaging [Full Paper]
Luminescent cap: The properties of a fluorescent conjugated polyelectrolyte and mesoporous silica nanoparticles have been combined to prepare a pH-controlled drug delivery and cellular imaging system by using a simple and general method (see scheme). The fluorescent conjugated polyelectrolyte was used as both the capping agent and the imaging probe with low cytotoxicity. It is a promising candidate for simultaneous diagnostics and therapeutics.
Jiwei Cui, Robert De Rose, James P. Best, Angus P. R. Johnston, Sheilajen Alcantara, Kang Liang, Georgina K. Such, Stephen J. Kent, Frank Caruso
Mechanically Tunable, Self-Adjuvanting Nanoengineered Polypeptide Particles [Communication]
DNA-loaded polypeptide particles are prepared via templated assembly of mesoporous silica for the delivery of adjuvants. The elasticity and cargo-loading capacity of the obtained particles can be tuned by the amount of cross-linker used to stabilize the polypeptide particles. The use of polypeptide particles as biocarriers provides a promising method for vaccine delivery.
Min Zhang, Keyou Yan, Wei Han, Shihe Yang
One-pot Synthesis of Mesoporous TiO2 from Self-Assembled Sol Particles and Its Application as Mesoscopic Photoanodes of Dye-Sensitized Solar Cells [Full Paper]
Highly crystalline mesoporous TiO2 was synthesized by a one-pot strategy that combines advantages of the Stöber, surfactant-templated, and hydrothermal methods (see figure; ACAC=acetyl acetone, IPA=isopropanol, TIP=titanium isopropoxide). The resulting photoanodes showed much higher efficiency because of extended electron lifetime related to the mesoporous structure confinement effect and accelerated electron transport.
Ilknur Erucar, Gamze Yilmaz, Seda Keskin
Recent Advances in Metal–Organic Framework-Based Mixed Matrix Membranes [Focus Review]
Trapped in the matrix: Metal–organic frameworks (MOFs) have been recently used as filler particles in mixed matrix membranes (MMMs), and significant improvements have been reported for gas selectivity and gas permeability in these MOF-based membranes (see figure). This review covers the opportunities and challenges of MOF-based MMMs in gas-separation applications.
Yanmin Bing, Na Xu, Wei Shi, Ke Liu, Peng Cheng
Two Lanthanide(III)-Copper(II) Organic Frameworks Based on {OLn6} Clusters that Exhibited a Large Magnetocaloric Effect and Slow Relaxation of the Magnetization [Full Paper]
Penny Ln: Two lanthanide(III)-copper(II) organic frameworks based on {OLn6} clusters were synthesized. Isotropic Gd-Cu showed a large magnetocaloric effect while anisotropic Dy-Cu exhibited slow relaxation of the magnetization at low temperatures.
Gang Ye, Yuxiao Leng, Feifei Bai, Jichao Wei, Jianchen Wang, Jing Chen
Site-Selective Functionalization of Periodic Mesoporous Organosilica (PMO) with Macrocyclic Host for Specific and Reversible Recognition of Heavy Metal [Full Paper]
Playing the host: A novel class of macrocyclic-host-functionalized periodic mesoporous organosilica (PMO) materials with excellent and reversible recognition of PbII was developed and upgraded by a site-selective post-modification method (see figure).
Yu Chen, Hangrong Chen, Jianlin Shi
In Vivo Bio-Safety Evaluations and Diagnostic/Therapeutic Applications of Chemically Designed Mesoporous Silica Nanoparticles [Review]
Significant progress in nano-biotechnology has promoted the biomedical evaluation and diagnostic/therapeutic applications of mesoporous silica nanoparticles (MSNs) from extensive in vitro research towards preliminary in vivo evaluation. This comprehensive review highlights the recent progresses in the chemical design and engineering of MSN-based biomaterials for in vivo biomedical applications.
Pablo Cubillas, Michael W. Anderson, Martin P. Attfield
Materials Discovery and Crystal Growth of Zeolite A Type Zeolitic–Imidazolate Frameworks Revealed by Atomic Force Microscopy [Full Paper]
Surface inspired: A new zeolitic–imidazolate framework that has the zeolite A framework topology and contains relatively inexpensive organic linkers has been grown on the structure-directing surface of ZIF-76 ([Zn(imidazolate)1.5(5-chlorobenzimidazolate)0.5]) crystals (see figure). Structural aspects, crystal growth mechanisms and possible surface terminations of both materials are revealed using in situ atomic force microscopy. The work exemplifies the use of this methodology to discover new MOFs with desirable frameworks.
Kohei Miyata, Yuji Konno, Takayuki Nakanishi, Atsushi Kobayashi, Masako Kato, Koji Fushimi, Yasuchika Hasegawa
Chameleon Luminophore for Sensing Temperatures: Control of Metal-to-Metal and Energy Back Transfer in Lanthanide Coordination Polymers [Communication]
A chameleon luminophore: A temperature-sensing material is reported that has a high thermostability (see picture). The material is composed of color-changing luminescent coordination polymers containing EuIII and TbIII ions. The coordination polymer exhibits a high emission quantum yield Φ of 40 % at room temperature and a temperature-sensing ability over a wide range of 200–500 K.
Konrad Hindelang, Alexander Kronast, Sergei I. Vagin, Bernhard Rieger
Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups [Full Paper]
One MOF, many modifications: The postsynthetic transformation of C=C double bonds is a versatile synthetic strategy for the introduction of functional groups in metal–organic frameworks (MOFs). A zinc-based, olefin-tagged MOF was applied to develop epoxidation, dihydroxylation, hydroboration, and thiol–ene click reactions as new postsynthetic modifications (PSM). The discussed PSMs are high yielding, maintaining the crystallinity and porosity of the frameworks (see scheme).
Yu Chen, Pengfei Xu, Hangrong Chen, Yongsheng Li, Wenbo Bu, Zhu Shu, Yaping Li, Jiamin Zhang, Lingxia Zhang, Limin Pan, Xiangzhi Cui, Zile Hua, Jin Wang, Linlin Zhang, Jianlin Shi
Colloidal HPMO Nanoparticles: Silica-Etching Chemistry Tailoring, Topological Transformation, and Nano-Biomedical Applications [Communication]
Hybridization produces the better: Colloidal hollow periodic mesoporous organosilica nanoparticles (HPMO NPs) with tunable compositions and highly hybridized nanostructures are successfully synthesized by a simple, easily scale-up but versatile silica-etching chemistry (alkaline or HF etching) for their applications in nano-fabrication and nano-medicine.
Reynaldo Villalonga, Paula Díez, Alfredo Sánchez, Elena Aznar, Ramón Martínez-Máñez, José M. Pingarrón
Enzyme-Controlled Sensing–Actuating Nanomachine Based on Janus Au–Mesoporous Silica Nanoparticles [Full Paper]
Janus-nanoparticle-based nanomachine: An integrated sensing–actuating nanomachine based on Janus Au–mesoporous silica nanoparticles can be prepared using a Pickering emulsion technique. Gatelike scaffolding is used for enzyme-controlled cargo release (see figure).
Maarten Goesten, Eli Stavitski, Evgeny A. Pidko, Canan Gücüyener, Bart Boshuizen, Steven N. Ehrlich, Emiel J. M. Hensen, Freek Kapteijn, Jorge Gascon
The Molecular Pathway to ZIF-7 Microrods Revealed by In Situ Time-Resolved Small- and Wide-Angle X-Ray Scattering, Quick-Scanning Extended X-Ray Absorption Spectroscopy, and DFT Calculations [Full Paper]
X-ray marks the spot: In situ time-resolved small- and wide-angle X-ray scattering and quick-scanning extended X-ray absorption spectroscopy was used to study the crystallization of the metal–organic framework ZIF-7. These studies along with density functional theory calculation show that the self-assembly mechanism is rather complex (see figure).
Yan-Jing Gu, Bing Yan
Lanthanide-Functionalized SBA-15 Mesoporous Hybrids – Ultraviolet-Visible Excitation and Visible–NIR Emission [Full Paper]
Ln3+ (Eu3+, Nd3+, Yb3+) organic–inorganic mesoporous hybrid materials are prepared. The hybrids contain lanthanide complexes covalently grafted to 2-methyl-9-hydroxyphenalenone (MHPO) functionalized ordered mesoporous SBA-15 and with 1,10-phenanthroline as a second ligand. The materials exhibit the characteristic visible (Eu3+) and near-infrared (NIR) luminescence (Nd+ and Yb3+) of lanthanides.
You Xu, Huan Wang, Rongjiao Zhu, Cuibo Liu, Xuan Wu, Bin Zhang
Conversion of CuO Nanoplates into Porous Hybrid Cu2O/Polypyrrole Nanoflakes through a Pyrrole-Induced Reductive Transformation Reaction [Full Paper]
Flaking out: Porous hybrid Cu2O/polypyrrole nanoflakes were synthesized through reductive transformation of CuO nanoplates in the presence of pyrrole. The as-prepared porous hybrid nanostructures exhibited efficient catalytic activity and high stability towards an oxygen reduction reaction in alkaline solution.
Hao Yu, Changjiang Shen, Zhonggang Wang
Micro- and Mesoporous Polycyanurate Networks Based on Triangular Units [Full Paper]
Three sides to the story: Microporous and mesoporous polycyanurate networks were synthesized by means of thermal self-cyclotrimerization from two triangular cyanate resin monomers, 1,3,5-tri(4-cyanatophenyl)benzene and 1,3,5-tricyanatobenzene, respectively (see scheme). The adsorptions of CO2, H2, benzene, n-hexane, and water vapors were investigated.
Jun Nakazawa, Tomoaki Hori, T. Daniel P. Stack, Shiro Hikichi
Alkane Oxidation by an Immobilized Nickel Complex Catalyst: Structural and Reactivity Differences Induced by Surface-Ligand Density on Mesoporous Silica [Full Paper]
Going nowhere fast: An immobilized SBA*-L-x/Ni complex was prepared with various ligand loadings and used in the oxidation of cyclohexane. The importance of site-density control for the development of immobilized catalysts has been demonstrated.
Madhappan Santha Moorthy, Mi-Ju Kim, Jae-Ho Bae, Sung Soo Park, Nagappan Saravanan, Sun-Hee Kim, Chang-Sik Ha
Multifunctional Periodic Mesoporous Organosilicas for Biomolecule Recognition, Biomedical Applications in Cancer Therapy, and Metal Adsorption [Full Paper]
A multifunctional mesoporous silica hybrid is presented, in which the receptor site plays a key role in nucleobase recognition, pH-induced delivery of anticancer agents, and as a metal binding site for Cu2+ ions. The pyridine-containing material selectively recognizes thymidine, is an effective potential drug-carrier system in cancer therapy, and is an efficient adsorbent for Cu2+ removal.
Tianyu Yang, Jian Liu, Yao Zheng, Michael J. Monteiro, Shi Zhang Qiao
Facile Fabrication of Core–Shell-Structured Ag@Carbon and Mesoporous Yolk–Shell-Structured Ag@Carbon@Silica by an Extended Stöber Method [Communication]
Layer upon layer: A facile extended Stöber method has been developed for the synthesis of diverse metal–carbon spheres, which includes core–shell-structured Ag@carbon, rattle-type Ag,AgBr@meso-SiO2, and yolk–shell-structured Ag@carbon@meso-SiO2 (see figure).
Ziwei Tang, Xiaowei Chen, Hao Chen, Limin Wu, Xuebin Yu
Metal-Free Catalysis of Ammonia–Borane Dehydrogenation/Regeneration for a Highly Efficient and Facilely Recyclable Hydrogen-Storage Material [Communication]
As easy as ABC: Mesoporous graphitic carbon nitride (MGCN; g-C3N4) is utilized to support ammonia borane (AB) on the basis of its accessible nanoporous structure and basic properties. A high loading of uniformly dispersed AB nanoparticles into the MGCN is possible giving greatly enhanced H2 generation from AB, and facile regeneration cycles by a hydrazine hydrogenation process, even at room temperature.
Sheng Chen, Jingjing Duan, Yonghong Tang, Shi Zhang Qiao
Hybrid Hydrogels of Porous Graphene and Nickel Hydroxide as Advanced Supercapacitor Materials [Full Paper]
Inside out: In-plane and out-of-plane pores were introduced into a graphene–Ni(OH)2 hybrid hydrogel system (see figure), which facilitated kinetics of processes occurring in electrodes, leading to excellent electrochemical properties with a combination of a high charge storage capacitance, a fast rate capability and a stable cycling performance.
Thomas D. Bennett, Paul J. Saines, David A. Keen, Jin-Chong Tan, Anthony K. Cheetham
Ball-Milling-Induced Amorphization of Zeolitic Imidazolate Frameworks (ZIFs) for the Irreversible Trapping of Iodine [Full Paper]
Having a ball: The I2-sorption and -retention properties of several zeolitic imidazolate frameworks have been characterised. The topologically identical ZIF-8 ([Zn(mIm)2]; mIm=2-methylimidazolate) and ZIF-mnIm ([Zn(mnIm)2]; mnIm=4-methyl-5-nitroimidazolate) display similar sorption abilities, though strikingly different guest-retention behaviour (see figure). Upon facile amorphisation by ball milling, the guest retention is greatly enhanced.
Mingyan Ma, Heshmat Noei, Bernd Mienert, Johanna Niesel, Eckhard Bill, Martin Muhler, Roland A. Fischer, Yuemin Wang, Ulrich Schatzschneider, Nils Metzler-Nolte
Iron Metal–Organic Frameworks MIL-88B and NH2-MIL-88B for the Loading and Delivery of the Gasotransmitter Carbon Monoxide [Full Paper]
Send and deliver: Spindle-shaped crystals of MIL-88B-Fe with a length of about 2 μm and a diameter of 1 μm and needle-shaped crystals of NH2-MIL-88B-Fe with a length of about 1.5 μm and a diameter of 300 nm were produced with uniform size and excellent crystallinity (see picture). These materials show good biocompatibility and have potential pharmacological and therapeutic applications as carriers and delivery vehicles for the gasotransmitter CO.
Jing Wei, Dandan Zhou, Zhenkun Sun, Yonghui Deng, Yongyao Xia, Dongyuan Zhao
A Controllable Synthesis of Rich Nitrogen-Doped Ordered Mesoporous Carbon for CO2 Capture and Supercapacitors [Full Paper]
A facile and controllable synthesis method for producing ordered mesoporous carbon with high surface area and high nitrogen content is demonstrated. The approach uses soluble resol and dicyandiamide as the carbon and nitrogen source, respectively, and Pluronic F127 copolymer as a soft template via a solvent evaporation-induced self-assembly process.
Na Li, Zhengze Yu, Wei Pan, Yaoyao Han, Tingting Zhang, Bo Tang
A Near-Infrared Light-Triggered Nanocarrier with Reversible DNA Valves for Intracellular Controlled Release [Full Paper]
A novel near-infrared light-triggered nanocarrier is developed based on mesoporous silica-coated gold nanorods with reversible DNA valves. The release amount of the cargo molecules can be controlled precisely by adjusting the irradiation time and the laser on-off cycles. The controlled release can be accomplished in living cells. Moreover, the therapeutic effect toward cancer cells can also be regulated.
Jun Wang, Hai-xia Zhong, Yu-ling Qin, Xin-bo Zhang
An Efficient Three-Dimensional Oxygen Evolution Electrode [Communication]
Oxygen evolution: A 3D nickel foam/porous carbon/anodized nickel electrode was designed for the oxygen evolution reaction (see picture). The conductive porous carbon membrane, which is derived from a zeolite imidazolate framework, plays a key role as an interlayer to both protect the inner instable Ni foam and support the outermost oxygen-evolving Ni catalyst layer.
Hao-Yiang Wu, Fa-Kuen Shieh, Hsien-Ming Kao, Yi-Wen Chen, Juti Rani Deka, Shih-Hsiang Liao, Kevin C.-W. Wu
Synthesis, Bifunctionalization, and Remarkable Adsorption Performance of Benzene-Bridged Periodic Mesoporous Organosilicas Functionalized with High Loadings of Carboxylic Acids [Full Paper]
Functionalization matters! Highly ordered benzene-bridged periodic mesoporous silicas with extremely high loadings (up to 80 mol %) of COOH groups have been synthesized and used as adsorbents for the removal of methylene blue (MB) and the delivery of an anticancer drug, doxorubicin (DOX). These materials exhibited high adsorption capacities, rapid adsorption rates for methylene blue removal, and an excellent loading/release profile for doxorubicin.
Zhao Jin, Feng Wang, Feng Wang, Junxin Wang, Jimmy C. Yu, Jianfang Wang
Metal Nanocrystal-Embedded Hollow Mesoporous TiO2 and ZrO2 Microspheres Prepared with Polystyrene Nanospheres as Carriers and Templates [Full Paper]
Polystyrene nanospheres are employed simultaneously as the template for creating hollow interiors and as the carrier for bringing noble metal nanocrystals in mesoporous metal oxide microspheres. The preparation relies on aerosol spray-assisted assembly. The Pd nanocube-embedded hollow mesoporous ZrO2 microspheres exhibit much better catalytic performances than a commercial Pd/C catalyst.
Jung Tae Park, Jacob H. Prosser, Sung Hoon Ahn, Sang Jin Kim, Jong Hak Kim, Daeyeon Lee
Enhancing the Performance of Solid-State Dye-Sensitized Solar Cells Using a Mesoporous Interfacial Titania Layer with a Bragg Stack [Full Paper]
A heterostructured photoanode based on mesoporous titania layer with a Bragg stack results in high efficiency dye-sensitized solar cells (6.6% for solid electrolyte). The efficiency improvements are due to improved light collection, decreased interfacial resistance at electrode/electrolyte, and excellent electrolyte infiltration.
Hubert Chevreau, Thomas Devic, Fabrice Salles, Guillaume Maurin, Norbert Stock, Christian Serre
Mixed-Linker Hybrid Superpolyhedra for the Production of a Series of Large-Pore Iron(III) Carboxylate Metal–Organic Frameworks [Communication]
It's all in the mix! Metal–organic frameworks (MOFs) were constructed from iron(III) trimers and mixtures of di- and tricarboxylate linkers. The dicarboxylate linker determined the size and shape of the pores in one series of materials with an interwoven structure and also enabled the introduction of different functionalities. Another mesoporous iron(III) MOF based on hybrid supertetrahedra had an extended β-cristobalite structure (see picture).
Hao Wang, Weiting Yang, Zhong-Ming Sun
Mixed-Ligand Zn-MOFs for Highly Luminescent Sensing of Nitro Compounds [Full Paper]
Don't lose trace: Three ZnII metal–organic frameworks (Zn-MOFs) based on mixed ligands have been synthesized by a hydrothermal method. Compounds 1 and 2 are 3-dimensional frameworks, and 3 is a layered structure. Changes in the luminescence of the three Zn-MOFs dispersed in different solvents allow for the detection of trace amounts of nitro compounds through a fluorescence quenching mechanism.
Jinsuo Gao, Xueying Zhang, Yan Yang, Jun Ke, Xinyong Li, Yaobin Zhang, Feng Tan, Jingwen Chen, Xie Quan
Surface-Passivated SBA-15-Supported Gold Nanoparticles: Highly Improved Catalytic Activity and Selectivity toward Hydrophobic Substrates [Full Paper]
Passive aggressive: Surface-passivated SBA-15-supported gold nanoparticles that were almost superhydrophobic, with a contact angle of 144°, were prepared by surface passivation. The catalytic activity of this catalyst was more than 14-times that of non-passivated SBA-15 for the reduction of nitrobenzene. This method is a general method for the preparation of surface-passivated catalysts.
Sneha R. Bajpe, Eric Breynaert, Ana Martin-Calvo, Danilo Mustafa, Sofia Calero, Christine E. A. Kirschhock, Johan A. Martens
COK-16: A Cation-Exchanging Metal–Organic Framework Hybrid [Communication]
X-ray spectroscopy: Substoichiometric encapsulation of polyoxometalate ions into a metal–organic framework results in a fully functional cation exchanger with accessible porosity. Cu2+ cations compensating the charge of [PW12O40]3− in the as-synthesized material can be exchanged with cations such as Na+ and Eu3+. When exchanged with Eu3+, the material appears bright red under UV irradiation (see figure).
Nicolas Bibent, Thibault Charpentier, Sabine Devautour-Vinot, Ahmad Mehdi, Philippe Gaveau, François Henn, Gilles Silly
Solid-State NMR Spectroscopic Studies of Propylphosphonic Acid Functionalized SBA-15 Mesoporous Silica: Characterization of Hydrogen-Bonding Interactions [Full Paper]
Solid-state NMR spectroscopy was used to describe the local structure of the functional groups and to characterize hydrogen-bonding interactions in propylphosphonic acid functionalized mesoporous silica SBA-15. An original 31P–1H–1H–31P correlation experiment highlighted the presence of hydrogen bonding between adjoining phosphonic acid groups.
Prasannan Karthika, Hamed Ataee-Esfahani, Hongjing Wang, Malar Auxilia Francis, Hideki Abe, Natarajan Rajalakshmi, Kaveripatnam S. Dhathathreyan, Dakshinamoorthy Arivuoli, Yusuke Yamauchi
Synthesis of Mesoporous Pt–Ru Alloy Particles with Uniform Sizes by Sophisticated Hard-Templating Method [Communication]
Team work: Mesoporous Pt–Ru alloy particles with uniform sizes are synthesized by controlled chemical reduction with ascorbic acid using mesoporous silica as a hard template. Elemental mapping shows uniform distribution of Pt and Ru particles. The electrochemical activity and stability of the alloys towards methanol oxidation much higher than that of mesoporous Pt and commercial Pt catalyst.
Mohamed B. Zakaria, Norihiro Suzuki, Nagy L. Torad, Mikiya Matsuura, Kazuhiko Maekawa, Hirofumi Tanabe, Yusuke Yamauchi
Preparation of Mesoporous Titania Thin Films with Well-Crystallized Frameworks by Using Thermally Stable Triblock Copolymers [Full Paper]
Mesoporous titania (TiO2) thin films are prepared by a spin-coating method using new laboratory-made polystyrene-block-polybutadiene-block-polystyrene-based triblock copolymers in which the polystyrene block is functionalized with hydrophilic sulfonic groups.
Sichao Xu, Yunxia Zhang, Shuan Wang, Junmin Xu, Hualin Ding, Guanghai Li
Structure-Enhanced Photocatalytic Removal of CrVI by a TiO2 Superstructure with Ultrathin Rutile Nanorods and Abundant {110} Faces [Full Paper]
An urchin-like rutile superstructure of TiO2 with abundant {110} faces has excellent photocatalytic activity and can remove CrVI ions from solution. Two-step purification of plating wastewater with the TiO2 superstructures can almost eliminate CrVI (from 1075 to 0.011 ppm).
Natalia Candu, Mădălina Tudorache, Mihaela Florea, Elena Ilyes, Florin Vasiliu, Ionel Mercioniu, Simona M. Coman, Ionel Haiduc, Marius Andruh, Vasile I. Pârvulescu
Postsynthetic Modification of a Metal–Organic Framework (MOF) Structure for Enantioselective Catalytic Epoxidation [Full Paper]
Transformed and ready for action! Postsynthetic modification of [Cu2(mand)2(hmt)] (mand=mandelic acid, hmt=hexamethylenetetramine) results in an effective catalyst (see picture) for the enantioselective epoxidation of trans-methyl cinnamate to provide methyl (2R,3S)-phenylglycidate with a high ee value at room temperature.
Rupali Deshmukh, Ulrich Schubert
Synthesis of CuO and Cu3N Nanoparticles in and on Hollow Silica Spheres [Full Paper]
Depending on the copper precursors and the templating method, CuO nanoparticles in or on hollow (mesoporous) silica spheres were obtained. The CuO nanoparticles were converted into Cu3N by nitridation with ammonia.
Miguel Cortijo, Santiago Herrero, Reyes Jiménez-Aparicio, Josefina Perles, José L. Priego, M. José Torralvo, Javier Torroba
Hybrid Polyfunctional Systems Based on Nickel(II) Isonicotinate [Full Paper]
Several metal–organic frameworks of nickel(II) were obtained from [Ni(OH2)4(4-pyc)2] (1) (4-pyc = 4-pyridinecarboxylate): two polymorphs of [Ni(4-pyc)2]n (2a and 2b) and [Ni5(OH2)3(4-pyc)10]n (3). A detailed comparative structural analysis was performed. Compounds 1 and 3 were transformed into 2a by heating, and 2a and 2b are a rare case of coordination framework isomers.
Yangyang Liu, Jian-Rong Li, Wolfgang M. Verdegaal, Tian-Fu Liu, Hong-Cai Zhou
Isostructural Metal–Organic Frameworks Assembled from Functionalized Diisophthalate Ligands through a Ligand-Truncation Strategy [Full Paper]
Gas station: Four isostructural metal–organic frameworks have been synthesized from functionalized ligands through a ligand-truncation strategy (see figure). The frameworks adopt a new topology. They are good adsorbent materials for both CO2 capture and H2 storage.
Rob Ameloot, Michael Aubrey, Brian M. Wiers, Ana P. Gómora-Figueroa, Shrayesh N. Patel, Nitash P. Balsara, Jeffrey R. Long
Ionic Conductivity in the Metal–Organic Framework UiO-66 by Dehydration and Insertion of Lithium tert-Butoxide [Communication]
Shields up! Post-synthetic modification of the secondary building units in the metal–organic framework UiO-66 (Zr6O4(OH)4(O2CR)12) by dehydration and subsequent grafting of LiOtBu (see picture, green) yields a solid Li+ electrolyte with a conductivity of 1.8×10−5 S cm−1 at 293 K. As the grafting leads to screening of the anionic charge, the activation energy for ionic conduction is significantly lower than when Li+ is introduced through deprotonation.
Jie Yang, Liang Zhou, Jun Zhang, Jin Zou, Zhiguo Yuan, Chengzhong Yu
Confinement of Chemisorbed Phosphates in a Controlled Nanospace with Three-Dimensional Mesostructures [Full Paper]
Captivating! The confinement of chemisorbed phosphates in three-dimensional cubic mesoporous materials with adjustable structural parameters has been investigated (see figure). By using advanced electron tomography techniques, the relationship between the growth of chemisorbed phosphates, the overall phosphate-adsorption performance and mesostructure parameters are revealed.
Feng Sun, Zheng Yin, Que-Qiao Wang, Di Sun, Ming-Hua Zeng, Mohamedally Kurmoo
Tandem Postsynthetic Modification of a Metal–Organic Framework by Thermal Elimination and Subsequent Bromination: Effects on Absorption Properties and Photoluminescence [Communication]
Inside and outside: Two consecutive postsynthetic modifications, first an elimination reaction in the channels and then bromination at the surface, were realized in a new hybrid metal–organic framework. The dramatic effects of the different groups in the channels and at the surface were studied using gas sorption and the loading/release of solvent and iodine.
Sam C. K. Hau, Thomas C. W. Mak
Systematic Investigation of Silver–Carbon Bonding in Coordination Frameworks with Aryl Ligands That Contain Ethynyl and Ethenyl Substituents [Full Paper]
Hi ho silver lining: A structural investigation of silver(I) trifluoroacetates with aromatic ligands that were functionalized with terminal and internal ethynyl groups and a vinyl substituent was performed. AgL·6 AgCF3CO2· H2O· MeOH (HL=1-{[4-(prop-2-ynyloxy)-3-vinylphenyl]ethynyl}naphthalene) is the first example that contained all four principal types of AgI-C bonding (Ag-ethynide, Ag-ethynyl, Ag-ethenyl, and Ag-aromatic).
Clément Falaise, Christophe Volkringer, Jean-François Vigier, Natacha Henry, Arnaud Beaurain, Thierry Loiseau
Three-Dimensional MOF-Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U6O8) [Full Paper]
In the open: Open frameworks of uranium(IV) compounds have been synthesized solvothermally by using dicarboxylate ligands in N,N-dimethylformamide. MOF-type structures are built up from the connection of hexanuclear [U6O4(OH)4(H2O)6] units in a fcc fashion by the ditopic ligands. This generates a 3D open framework (see figure) with octahedral and tetrahedral cavities, similar to Zr-based UiO-66/67 phases.
Li-Chiang Lin, Jihan Kim, Xueqian Kong, Eric Scott, Thomas M. McDonald, Jeffrey R. Long, Jeffrey A. Reimer, Berend Smit
Understanding CO2 Dynamics in Metal–Organic Frameworks with Open Metal Sites [Communication]
Hopping along: Metal–organic frameworks such as Mg-MOF-74 possess open metal sites that interact strongly with CO2. Molecular simulations reveal detailed CO2 dynamics (hops between metal sites and localized fluctuations), which can be used to accurately explain the experimentally measured 13C NMR chemical shift anisotropy pattern.
Jianan Liu, Wenbo Bu, Limin Pan, Jianlin Shi
NIR-Triggered Anticancer Drug Delivery by Upconverting Nanoparticles with Integrated Azobenzene-Modified Mesoporous Silica [Communication]
Photomediated drug release: Silica-coated upconverting nanoparticles with mesopores modified by azobenzene molecules were synthesized. The azobenzene molecules make possible the release of the anticancer drug doxorubicin from the pore network of the mesoporous silica outer layer by irradiation with near-infrared (NIR) laser light. The release is regulated by the trans–cis photoisomerization of the azobenzene molecules (see picture).
Youhei Numata, Surya Prakash Singh, Ashraful Islam, Munetaka Iwamura, Atsushi Imai, Koichi Nozaki, Liyuan Han
Enhanced Light-Harvesting Capability of a Panchromatic Ru(II) Sensitizer Based on π-Extended Terpyridine with a 4-Methylstylryl Group for Dye-Sensitized Solar Cells [Full Paper]
Moderate electron-donating substituents are important for enhancement of the light harvesting capability of Ru(II) sensitizers. Substitution of a terpyridyl ligand with a 4-methylstyryl group increases the molecular absorption coefficient from the UV to the NIR region compared with black dye owing to the wider lowest unoccupied molecular orbital (LUMO) distributed over the terpyridyl and extended π-conjugation. The intense absorption gives a high JSC of 23.07 mA cm−2, and a resulting overall conversion efficiency of 11.1%.
Yifeng Shi, Chunxiu Hua, Bin Li, Xiangpeng Fang, Chaohua Yao, Yichi Zhang, Yong-Sheng Hu, Zhaoxiang Wang, Liquan Chen, Dongyuan Zhao, Galen D. Stucky
Highly Ordered Mesoporous Crystalline MoSe2 Material with Efficient Visible-Light-Driven Photocatalytic Activity and Enhanced Lithium Storage Performance [Full Paper]
Ordered mesoporous crystalline MoSe2 is synthesized using mesoporous silica as a hard template via a nanocasting strategy. It shows a strong light absorption throughout the entire visible wavelength region and has remarkable photocatalytic activity for the degradation of rhodamine B under visible light irradiation. The synthesized mesoporous MoSe2 has a reversible lithium storage capacity of 630 mAh g−1 and better rate performance than the analogously synthesized mesoporous MoS2.
Dalong Yang, Tongxiang Fan, Di Zhang, Jun Zhu, Yun Wang, Bin Du, Yaxian Yan
Biotemplated Hierarchical Porous Material: The Positively Charged Leaf [Full Paper]
Leaf shield: A hierarchical porous, positively charged material was synthesized from a leaf biotemplate (see graphic). The final product inherited the advantages of a positively charged property, hierarchical porous structure and sterilization effect. The product, like a leaf shield, could be used to protect against bacteria.
Jun Xu, Victor V. Terskikh, Yining Huang
Resolving Multiple Non-equivalent Metal Sites in Magnesium-Containing Metal–Organic Frameworks by Natural Abundance 25Mg Solid-State NMR Spectroscopy [Communication]
In a spin: Directly differentiating multiple Mg sites in Mg-containing MOFs by 25Mg solid-state NMR spectroscopy is very challenging at natural abundance. By performing 25Mg two-dimensional triple-quantum magic-angle spinning solid-state NMR experiments at a magnetic field of 21.1 T at natural abundance, four non-equivalent Mg sites with very similar local environments in α-Mg3(HCOO)6 were unambiguously resolved (see figure).
Norihiro Suzuki, Mohamed B. Zakaria, Nagy L. Torad, Kevin C.-W. Wu, Yoshihiro Nemoto, Masataka Imura, Minoru Osada, Yusuke Yamauchi
Synthesis of Highly Strained Mesostructured SrTiO3/BaTiO3 Composite Films with Robust Ferroelectricity [Communication]
A new class of highly stable ferroelectric material, that is, a mesostructured SrTiO3/BaTiO3 composite film, obtained by a surfactant-templated sol–gel method is reported. Due to the concave surface geometry and abundant hetero-interface between SrTiO3 (ST) and BaTiO3 (BT) phases, a large number of strains can be created in the composite film, thereby leading to dramatic enhancement of ferroelectric property (see scheme).
Susanna Mandic, Merinda R. Healey, Jan M. Gotthardt, Kerwyn G. Alley, Robert W. Gable, Chris Ritchie, Colette Boskovic
A Polyoxometalate-Based Coordination Polymer with the Diamondoid Topology [Short Communication]
The polyoxometalate-based 3D coordination polymer [ε-PMo12O37(OH)3{La(H2O)3}4(L)]·28H2O [H4L = tetrakis(4-carboxyphenyl)silane] was readily synthesized from two pseudotetrahedral building blocks and exhibits a diamondoid network topology.
Chuanyong Zhang, Sibing Wang, Hongjing Huo, Zhibin Huang, Yi Li, Baozong Li, Yonggang Yang
Preparation of Helical Mesoporous Tantalum Oxide Nanotubes through a Sol–Gel Transcription Approach [Communication]
The TaO of nanotubes: Single-handed helical Ta2O5 nanotubes with mesopores in the walls were prepared using the self-assemblies of the low-molecular-weight gelators as the templates. The handedness of the Ta2O5 nanotubes was controlled by organic self-assemblies.
Hui Liu, Yonggang Zhao, Zhijuan Zhang, Nour Nijem, Yves J. Chabal, Xiangfang Peng, Heping Zeng, Jing Li
Ligand Functionalization and Its Effect on CO2 Adsorption in Microporous Metal–Organic Frameworks [Full Paper]
One up, one down: Functionalization of metal–organic framework structures by a methyl group leads to two opposing and competitive effects on CO2 adsorption: enhanced CO2 affinity and reduced porosity.
Xiaoyu Liu, Li Wang, Xuena Yin, Rudan Huang
Assembly of Hybrid Materials Based on a Lanthanide–Organic Framework and a Keggin-Type [PMo12–xVxO40](3+x)– (x = 1, 2) Cluster [Full Paper]
– (x = 1, 2) Cluster](http://www.wiley-vch.de/util/hottopics/img/ejic201201275.jpg "Assembly of Hybrid Materials Based on a Lanthanide–Organic Framework and a Keggin-Type [PMo12–xVxO40](3+x)– (x = 1, 2) Cluster")
A series of polyoxometalate-based hybrid compounds, [Ln4(pdc)4(H2O)16][PMo11VO40]·2H2O (1–5) and [Ln4(pdc)4(H2O)16][HPMo10V2O40]·H2O (6, 7) (Ln = La, Ce, Pr, Nd, Sm for 1–5 and Ln = La and Ce for 6 and 7; H2pdc = pyridine-2,6-dicarboxylic acid), were synthesized and characterized. Moreover, photoluminescent properties, electrochemical properties, and catalytic properties were investigated.
Daniela Carta, Salvatore Bullita, Maria F. Casula, Alberto Casu, Andrea Falqui, Anna Corrias
Cubic Mesoporous Silica (SBA-16) Prepared Using Butanol as the Co-Surfactant: A General Matrix for the Preparation of FeCo-SiO2 Nanocomposites [Full Paper]
The host with the most: The picture shows the three-dimensional image reconstruction of a nanocomposite based on mesoporous SBA-16 silica as obtained by electron tomography. Evidence is provided that FeCo nanocrystals are located inside the highly ordered interconnected mesostructure with cubic symmetry
Masahiro Egi, Koji Sugiyama, Moriaki Saneto, Ryosuke Hanada, Katsuya Kato, Shuji Akai
A Mesoporous-Silica-Immobilized Oxovanadium Cocatalyst for the Lipase-Catalyzed Dynamic Kinetic Resolution of Racemic Alcohols [Communication]
V for resolution: A new oxovanadium catalyst (V-MPS; see scheme) immobilized in the pores of mesoporous silica has been developed. The combined use of V-MPS and lipases achieved the dynamic kinetic resolution of a wide range of racemic alcohols (1 or 2) to produce optically active esters 3 in high chemical and optical yields. The paired catalysts retained high catalytic activity when reused up to six times.
Estela Climent, Delia Gröninger, Mandy Hecht, M. Astrid Walter, Ramón Martínez-Máñez, Michael G. Weller, Félix Sancenón, Pedro Amorós, Knut Rurack
Selective, Sensitive, and Rapid Analysis with Lateral-Flow Assays Based on Antibody-Gated Dye-Delivery Systems: The Example of Triacetone Triperoxide [Communication]
Set them free: Brightly fluorescent indicators that are loaded into mesoporous silica nanoparticle carriers, capped with bulky antibodies, are released into the lateral flow of a test strip upon analyte arrival. Integration of the system into a rapid, simple flow test with fluorescence readout is applied for the selective and sensitive determination of the presence of triacetone triperoxide (TATP) as a prototype small-molecule analyte (see figure).
Liangcan He, Yong Liu, Jingzhu Liu, Yansong Xiong, Jianzhong Zheng, Yaling Liu, Zhiyong Tang
Core–Shell Noble-Metal@Metal-Organic-Framework Nanoparticles with Highly Selective Sensing Property [Communication]
Of cores! Core–shell Au@metal-organic-framework-5 (MOF-5) nanoparticles (NPs), in which a single Au NP core is coated with a uniform MOF-5 shell, were prepared by a facile one-pot method. The diameter of the Au NP core and the thickness of the MOF-5 shell are easily tuned by controlling the reaction conditions. These nanoparticles are selective sensors of CO2 in gas mixtures.
Richelle Lyndon, Kristina Konstas, Bradley P. Ladewig, Peter D. Southon, Prof Cameron J. Kepert, Matthew R. Hill
Dynamic Photo-Switching in Metal–Organic Frameworks as a Route to Low-Energy Carbon Dioxide Capture and Release [Communication]
Like wringing out a sponge, a metal–organic framework loaded with structure-changing light-responsive groups can squeeze out captured CO2. Because of the groups being structurally integral, there is oscillation between native and excited states. Pairing with CO2 capture from coal-based power generation could reduce the parasitic energy load of adsorbent regeneration.
Yunxin Liu, Jianxin Shi, Qing Peng, Yadong Li
CuO Quantum-Dot-Sensitized Mesoporous ZnO for Visible-Light Photocatalysis [Full Paper]
Into the light! Ultraviolet mesoporous (MP) ZnO photocatalysts can be extended into the visible-light region (see figure) through coupling to CuO quantum dots (QDs). Theoretical analysis demonstrates that the quantum size effect plays a key role in the photoactivity of CuO/ZnO composites.
Huanhuan Li, Wei Shi, Kaina Zhao, Zheng Niu, Huimin Li, Peng Cheng
Highly Selective Sorption and Luminescent Sensing of Small Molecules Demonstrated in a Multifunctional Lanthanide Microporous Metal–Organic Framework Containing 1D Honeycomb-Type Channels [Full Paper]
Honeytrap: A robust microporous lanthanide metal–organic framework with 1D honeycomb-type channels is reported (see figure). Excellent adsorption capabilities for N2, H2, and CO2 and significant selective sorption of CO2 over N2 and CO2 over CH4 were observed. The guest-dependent luminescent behavior indicates the potential for sensing small-molecule pollutants such as benzene and acetone.
Xi-Sen Wang, Matthew Chrzanowski, Lukasz Wojtas, Yu-Sheng Chen, Shengqian Ma
Formation of a Metalloporphyrin-Based Nanoreactor by Postsynthetic Metal–Ion Exchange of a Polyhedral-Cage Containing a Metal–Metalloporphyrin Framework [Communication]
A change for the better: Exchange of CdII in the catalytically inactive framework MMPF-5 (see scheme) with CoII afforded a metalloporphyrin-based nanoreactor, MMPF-5(Co). This framework, consisting of small cubicuboctahedral cages, demonstrated interesting performances in the catalytic epoxidation of trans-stilbene with tBuOOH.
Minyoung Yoon, Kyungwon Suh, Srinivasan Natarajan, Kimoon Kim
Proton Conduction in Metal–Organic Frameworks and Related Modularly Built Porous Solids [Minireview]
Pores and protons: Development of new types of proton-conducting materials is important in fuel-cell technology. Newly developed proton-conducting materials formed from modularly built porous solids, including coordination polymers (CPs) or metal–organic frameworks (MOFs) are discussed (see scheme).
Jia Liu, Juan Peng, Shuai Shen, Qianru Jin, Can Li, Qihua Yang
Enzyme Entrapped in Polymer-Modified Nanopores: The Effects of Macromolecular Crowding and Surface Hydrophobicity [Full Paper]
Entrapment: The effects of macromolecular crowding and surface hydrophobicity on the properties of an immobilized enzyme were explored by accommodating lipase into a series of mesoporous silicas that contained various amounts of inert poly(methacrylate) (PMA) covalently anchored inside the nanopores.
Chengzhou Zhu, Shaojun Guo, Shaojun Dong
Rapid, General Synthesis of PdPt Bimetallic Alloy Nanosponges and Their Enhanced Catalytic Performance for Ethanol/Methanol Electrooxidation in an Alkaline Medium [Full Paper]
Soak it up: A rapid and general strategy is demonstrated for the preparation of novel three-dimensional PdPt bimetallic alloy nanosponges (see figure) that exhibit greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium.
Chao Qi, Ying-Jie Zhu, Xin-Yu Zhao, Bing-Qiang Lu, Qi-Li Tang, Jing Zhao, Feng Chen
Highly Stable Amorphous Calcium Phosphate Porous Nanospheres: Microwave-Assisted Rapid Synthesis Using ATP as Phosphorus Source and Stabilizer, and Their Application in Anticancer Drug Delivery [Full Paper]
Stabilized nanospheres: Highly stable amorphous calcium phosphate (ACP) porous nanospheres with an average pore diameter of about 10 nm have been synthesized by using a microwave-assisted hydrothermal method with adenosine 5'-triphosphate disodium salt (ATP) as the phosphorus source and stabilizer (see scheme). The as-prepared ACP porous nanospheres show a high ability to damage tumor cells after loading docetaxel, thus, are promising for application in anticancer drug delivery.
David N. Bunck, William R. Dichtel
Mixed Linker Strategies for Organic Framework Functionalization [Concept]
Providing a framework: Framework materials have attracted intense interest for gas storage, separations, catalysis, and other applications as a consequence of their periodicity, high specific surface area, and rational synthesis. Cocrystallizing multiple monomers with identical linking chemistry represents an emerging route to functionalized materials. This Concept Article highlights three strategies for framework functionalization that employ comonomers with identical, expanded, or reduced linking geometries.
Wei Wei, Chao Yu, Qingfei Zhao, Guisheng Li, Ying Wan
Improvement of the Visible-Light Photocatalytic Performance of TiO2 by Carbon Mesostructures [Full Paper]
Mesostructure photocatalysis: A mesoporous carbon–titania composite showed excellent adsorption–catalysis cycles in the elimination of azo dyes (see figure). The mesostructure, which incorporates mesopores, carbon-pore walls, and carbon-doped anatase nanoparticles formed by interaction between carbon and titania and immobilized within the framework, is responsible for the improved photocatalytic performance and reusability.
Wei Li, Dongyuan Zhao
Extension of the Stöber Method to Construct Mesoporous SiO2 and TiO2 Shells for Uniform Multifunctional Core–Shell Structures [Research News]
The Stöber method is a well-known and versatile process for synthesizing silica spheres with controllable particle size, narrow size distribution, smooth surface, and porosity. This contribution highlights recent advances on the extension of the Stöber method to construct mesoporous SiO2 and TiO2 shells for uniform multifunctional core–shell nanostructures.
Chang Woo Kim, Minhyuk Kang, Bongjin Moon, Jinheung Kim, Young Soo Kang
Manganese-Doped Highly Ordered Mesoporous Silicate with High Efficiency for Oxidation Suppression [Full Paper]
Kiss me silicate: Hexagonally close-packed mesoporous SiO2 with completely opened pores was doped with Mn ions (see figure) by using an ultrasound-assisted technique. This material was tested for the preservation of organic antioxidizing agents, such as ascorbic acid (vitamin C). The possibility of incorporating several hetero-elemental guest clusters into these mesoporous composite particles makes them highly attractive for multifunctional applications.
Jasmin Geserick, Sarah Meyer, Michael Puchberger, Silvia Pabisch, Herwig Peterlik, Ole Bethge, Emmerich Bertagnolli, Ulrich Schubert
Porous Silica-Based Mixed Oxides with Basic Organic Sites [Full Paper]
Porous, organically modified silica-based mixed oxides were prepared by sol-gel processing of organotrialkoxysilanes with bridging amono groups and metal chlorides. Materials with ordered porosity and uniform mesopores were obtained with metal proportions up to about 20 %.
Alfonso García Márquez, Aude Demessence, Ana Eva Platero-Prats, Daniela Heurtaux, Patricia Horcajada, Christian Serre, Jong-San Chang, Gérard Férey, Victor Antonio de la Peña-O'Shea, Cédric Boissière, David Grosso, Clément Sanchez
Green Microwave Synthesis of MIL-100(Al, Cr, Fe) Nanoparticles for Thin-Film Elaboration [Full Paper]
The syntheses of nanoparticles of mesoporous MIL-100(Al, Cr, or Fe) metal–organic frameworks were performed by a microwave-assisted solvothermal route with green solvents. Stable colloidal solutions of iron and chromium MIL-100 nanoparticles were obtained and used to prepare high optical quality thin films by dip coating. Their porosity was investigated by environmental ellipsometric porosimetry.
Samir El Hankari, Peter Hesemann
Guanidinium vs. Ammonium Surfactants in Soft-Templating Approaches: Nanostructured Silica and Zwitterionic i-Silica from Complementary Precursor–Surfactant Ion Pairs [Full Paper]
We compared ammonium and guanidinium surfactants as structure-directing agents in soft templating syntheses of nanostructured and hybrid-silica-based ionic substructures (i-silicas). Nanostructured i-silicas exist due to specific carboxylate precursor/guanidinium surfactant interactions. Results suggest that nanostructured silica hybrid materials can be obtained from complementary precursor–surfactant pairs.
Taissire Benamor, Julien Miesh, Gaëtan Montégut, Habiba Nouali, Claire Marichal, Bénédicte Lebeau
Post-Synthesis Grafting of Fluoropropyl Groups on SBA-15 Type Ordered Mesoporous Silica [Full Paper]
To prepare more hydrophobic SBA-15 materials, (3,3,3-trifluoropropyl)dimethylchlorosilane was used as a grafting agent. The initial content and the accessibility of silanol groups in the material were found to be the key factors for efficient grafting.
Simona Mihai, Justine Dauthier, Yann Le Duc, Abdelsalam El Mansouri, Ahmad Mehdi, Mihail Barboiu
Dynamic Constitutional Hybrid Materials – Confined Guanosine Ribbons within Mesoporous Silica [Full Paper]
“Dynamic convergence” between directional supramolecular self-assembled guanosine ribbons (G-ribbons) and inorganic silica mesoporous scaffolds leads to self-organized hybrid materials in which G-ribbons are strongly stabilized.
Xiaodan Huang, Kun Qian, Jie Yang, Jun Zhang, Li Li, Chengzhong Yu, Dongyuan Zhao
Functional Nanoporous Graphene Foams with Controlled Pore Sizes [Communication]
A simple hydrophobic-affinity-derived assembly approach to pack graphene sheets into a nanoporous foam structure has been developed. Nanoporous graphene foams with the highest pore volume and large surface area are obtained. The pore diameter of the graphene foams can be finely adjusted from the mesopore to the macropore range by employing spherical templates with different sizes.
Paolo Falcaro, Shuhei Furukawa
Doping Light Emitters into Metal–Organic Frameworks [Highlight]
Space division with red cubes: Doping metal–organic frameworks with another metal component gives a further opportunity to tune their properties. Recent work successfully introduced europium into the inorganic nodes of frameworks. Although the doping element does not affect the framework topology, highly improved emissive performance was measured thanks to the intrinsic red emission of europium.
Hao Jiang, Jan Ma, Chunzhong Li
Mesoporous Carbon Incorporated Metal Oxide Nanomaterials as Supercapacitor Electrodes [Research News]
This Research News article aims to review recent progress in the development of mesoporous carbon-incorporated metal oxide nanomaterials, in particular metal oxide nanoparticles confined in ordered mesoporous carbon and 1D metal oxides coated with a layer of mesoporous carbon for high-performance supercapacitor applications.
Patrick Bottke, Yu Ren, Peter G. Bruce, Martin Wilkening
Ex situ NMR Measurements of Li Dynamics in TiO2 Anodes with an Ordered Hierarchical Pore Structure [Poster]
Michael J. Sailor, Ji-Ho Park
Hybrid Nanoparticles for Detection and Treatment of Cancer [Review]
Hybrid nanoparticles (consisting of more than one type of nanostructure) for the detection and treatment of cancer are reviewed. Functional nanocomponents such as metal nanoparticles, magnetic nanocrystals, or quantum dots can be placed either on the surface of a structural nanocomponent (“barge”) or into its inner space (“tanker”). The structural components are classified based on the therapeutic function they deliver.
Xiangfen Jiang, Norihiro Suzuki, Bishnu Prasad Bastakoti, Kevin C.-W. Wu, Yusuke Yamauchi
Synthesis of Continuous Mesoporous Alumina Films with Large-Sized Cage-Type Mesopores by Using Diblock Copolymers [Full Paper]
I'm fixing a hole: Mesoporous alumina films with large cage-type mesopores (see picture) were prepared by using commercially available diblock copolymer (PS-b-PEO) and economic inorganic salt (AlCl3) as aluminum source. Pore size and connectivity can be controlled by adjusting the solvent system and the amount of polymer used.
Christian Serre
Superhydrophobicity in Highly Fluorinated Porous Metal–Organic Frameworks [Highlight]
A new job: Highly fluorinated porous MOFs (see picture) that exhibit a superior hydrophobic character can possibly find an application as new superhydrophobic adsorbents in aqueous-phase separation processes.
Stefan K. Henninger, Felix Jeremias, Harry Kummer, Christoph Janiak
MOFs for Use in Adsorption Heat Pump Processes [Microreview]
This review introduces metal–organic frameworks (MOFs) as a promising new class of microporous materials for use in adsorption heat transformation applications. The water adsorption characteristics of several MOFs are summarized, including heat of adsorption and cycle stability, which show the tremendous potential of MOFs in thermally driven heat pumps.
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.
Jovana Zečević, Cedric J. Gommes, Heiner Friedrich, Petra E. de Jongh, Krijn P. de Jong
Mesoporosity of Zeolite Y: Quantitative Three-Dimensional Study by Image Analysis of Electron Tomograms [Communication]
Quantitative insight into the three-dimensional morphology of complex zeolite Y mesopore networks was achieved by combining electron tomography and image processing. Properties could be studied that are not measurable by other techniques, such as the size distribution of the intact microporous domains. This has great relevance in descriptions of the molecular diffusion through zeolite crystals and, hence, catalytic activity and selectivity.
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.
Fangqiong Tang, Linlin Li, Dong Chen
Mesoporous Silica Nanoparticles: Synthesis, Biocompatibility and Drug Delivery [Review]
Mesoporous silica nanoparticles (MSNs) are drawing growing attention for their biomedical applications. With unique mesoporous structure, high surface area and low toxicity, MSNs exhibit super performance as versatile drug delivery systems especially for cancer therapy. This review focuses on recent progresses of synthesis strategies, biocompatibility research and drug delivery application of MSNs.
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.
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).
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).
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.
© Wiley-VCH 2011.
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