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Mesoporous Materials

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.

Recent Articles

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Visible Light Triggered CO2 Liberation from Silver Nanocrystals Incorporated Metal–Organic Frameworks

Visible Light Triggered CO2 Liberation from Silver Nanocrystals Incorporated Metal–Organic Frameworks

A new type of photodynamic carbon capture material with up to 90.5% of CO2 desorption capacity is synthesized via integration of silver nanocrystals with UiO-66 metal–organic frameworks. Such a highly efficient CO2 desorption is driven by the naturally abundant visible light, confirming a promising alternative to low energy regeneration of gas adsorbents.

[Full Paper]
Haiqing Li, Matthew R. Hill, Christian Doblin, Seng Lim, Anita J. Hill, Paolo Falcaro
Adv. Funct. Mater., May 23, 2016, DOI: 10.1002/adfm.201600827. Read article

Co–templating Synthesis of Bimodal Mesoporous Silica for Potential Drug Carrier

Co–templating Synthesis of Bimodal Mesoporous Silica for Potential Drug Carrier

Bimodal mesoporous silica is prepared by co-templating method using PEO-b-PLA and F127. The pore size distribution of the mesoporous silica is bimodal can be divided between the larger pores, originating from PEO-b-PLA, and the smaller pores, originating from F127. We are able to ascertain that the F127 produces the smaller pores, and acts as a swelling agent in the formation of the larger pores. This novel material is further successfully employed as a drug-carrier for doxorubicin in ambient conditions.

[Full Paper]
Wei C. Chu, Dong R. Peng, Bishnu P. Bastakoti, Malay Pramanik, Victor Malgras, Tansir Ahamad, Saad M. Alshehri, Yusuke Yamauchi, Shiao W. Kuo
ChemistrySelect, May 20, 2016, DOI: 10.1002/slct.201600406. Read article

Nanofabrication of a Solid-State, Mesoporous Nanoparticle Composite for Efficient Photocatalytic Hydrogen Generation

Nanofabrication of a Solid‐State, Mesoporous Nanoparticle Composite for Efficient Photocatalytic Hydrogen Generation

Making room: An assembly of nearly monodispersed Al3+-doped SiO2 nanoparticles (20–30 nm) that display interparticle mesospaces has been found to be suitable for incorporating Pt nanoparticles and an organic photocatalyst (2-phenyl-4-(1-naphthyl)quinolinium ion), which act as an efficient composite catalyst for photocatalytic H2 evolution (see figure).

[Communication]
Yusuke Yamada, Hideyuki Tadokoro, Masood Naqshbandi, John Canning, Maxwell J. Crossley, Tomoyoshi Suenobu, Shunichi Fukuzumi
ChemPlusChem, May 20, 2016, DOI: 10.1002/cplu.201600148. Read article

Thermo and Gas Dual-Responsive Behaviors of An Expanded UiO-66 Type Porous Coordination Polymer

By using a modified solvothermal reaction using benzoic acid as an additive, the fcu-type framework [Zr6O4(OH)4(edba)6] (H2edba = 4,4'-(ethyne-1,2-diyl)dibenzoic acid), an expanded version of UiO-66 based on 1,4-benzenedicarboxylate, was synthesized as high-quality single crystals, which can retain single-crystallinity after solvent exchange and degas treatments. In situ variable temperature single-crystal X-ray diffraction measurements showed that the guest-free framework exhibits a remarkably large isotropic negative thermal expansion (alpha = −11.0 × 10-6 K-1, beta = −33.8 × 10-6 K-1), as a result of the transverse vibrational bending of the long organic ligand. By virtue of the relatively large  conjugation system of the organic ligand, [Zr6O4(OH)4(edba)6] also exhitis bright blue luminescence, which can be efficiently quenched by gaseous O2 (Ksv = 2.4 bar−1).

[Full Paper]
Hao-Long Zhou, Jie Bai, Jia-Wen Ye, Zong-Wen Mo, Wei-Xiong Zhang, Jie-Peng Zhang, Xiao-Ming Chen
ChemPlusChem, May 20, 2016, DOI: 10.1002/cplu.201600145. Read article

Metal-Organic Frameworks Help Conducting Polymers Optimize the Efficiency of the Oxygen Reduction Reaction in Neutral Solutions

Metal‐Organic Frameworks Help Conducting Polymers Optimize the Efficiency of the Oxygen Reduction Reaction in Neutral Solutions

The anchoring of an electro-inactive metal-organic framework (ZIF-8 MOF) layer on a conducting polymer-modified electrode enhances its electrocatalytic efficiency toward the oxygen reduction reaction in neutral solutions by a selective uptake and preconcentration of oxygen in the ZIF-8 microporous matrix that ultimately acts as an oxygen reservoir in intimate contact with the electroactive material.

[Communication]
Matías Rafti, Waldemar A. Marmisollé, Omar Azzaroni
Adv. Mater. Interfaces, May 20, 2016, DOI: 10.1002/admi.201600047. Read article

3D Macro-Mesoporous TiO2-Graphene Oxide (GO) Composite with Enhanced Catalytic Performance in the Epoxidation of Styrene and its Derivatives

3D Macro‐Mesoporous TiO2‐Graphene Oxide (GO) Composite with Enhanced Catalytic Performance in the Epoxidation of Styrene and its Derivatives

An ordered macro-mesoporous titania composites with graphene oxide (TiO2-GO) was synthetized through a confinement self-assembly method. Compared with the pure mesoporous titania (TiO2), TiO2-GO had a superior catalytic activity for styrene and its derivatives.

[Full Paper]
Gang Bian, Pingping Jiang, Hui Zhao, Kelei Jiang, Ling Hu, Yuming Dong, Weijie Zhang
ChemistrySelect, May 19, 2016, DOI: 10.1002/slct.201600387. Read article

Low Cytotoxic Metal-Organic Frameworks as Temperature-responsive Drug Carriers

Two Zn-based porous metal-organic frameworks, ZJU-64 and ZJU-64-CH3 sharing the same crystal structure, have been synthesized from zinc ions, biomolecular linker adenine and carboxylates-based ligands, resulting in three-dimensional frameworks with one-dimensional channels (around 1.6 nm × 1.9 nm). The material ZJU-64 and ZJU-64-CH3 exhibit low-toxic natures by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay and microscopy photos indicating their potential applications for human health care. The anticancer drug methotrexate (MTX) is successfully loaded into MOFs via a simple impregnation method and the drug payloads reach to about 13.45 wt% and 10.63 wt% for ZJU-64 and ZJU-64-CH3, respectively. Sustainable drug release behaviors of MTX from MTX-loaded ZJU-64 and MTX-loaded ZJU-64-CH3 for several days are detected. The temperature-responsive deliveries of ZJU-64 and ZJU-64-CH3 reveal hyperthermia can control the drug release and open up a new treatment which combines drug therapy and thermal therapy to kill more cancer cells with less side effects, revealing the practical values of ZJU-64 and ZJU-64-CH3 as "smart" drug carriers with more therapeutic efficacy.

[Full Paper]
Wenxin Lin, Quan Hu, Jiancan Yu, Ke Jiang, Yanyu Yang, Shengchang Xiang, Yuanjing Cui, Yu Yang, Zhiyu Wang, Guodong Qian
ChemPlusChem, May 19, 2016, DOI: 10.1002/cplu.201600142. Read article

Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells

We demonstrated that the oxygen reduction reaction (ORR) activity over the catalysts derived from pyrolyzed cobalt zeolitic imidazolate frameworks depends strongly on the imidazole ligand structure and cobalt content. The activity and durability of these catalysts were tested in the proton exchange membrane fuel cell for the first time. The membrane electrode assembly containing a catalyst derived from Co/Zn bimetallic ZIF at cathode achieved an open circuit voltage of 0.93 V, a current density of 28 mA cm-2 at 0.8 ViR-free and a peak power density of 374 mW cm-2.

[Communication]
Lina Chong, Gabriel A. Goenaga, Kia Williams, Heather M. Barkholtz, Lauren R. Grabstanowicz, Alex B. Papandrew, Radwan Elzein, Rudiger Schlaf, Thomas A. Zawodzinski Jr., Jianxin Zou, Shengqian Ma, Di-Jia Liu
ChemElectroChem, May 19, 2016, DOI: 10.1002/celc.201600163. Read article

A 2-Fold Interpenetrated Metal-Organic Framework with High Performance in Selective Separation of C2H2/CH4

A 2-fold interpenetrated metal-organic framework, PMOF-3, composed of four kinds of polyhedrons exhibits a highest selectivity of 157 for C2H2/CH4 separation at 296 K and 1 atm owning to the synergistic effect of the open metal sites, C≡C triple bonds, and microporous structure.

[Full Paper]
Osamah Alduhaish, Hailong Wang, Bin Li, Tong-Liang Hu, Hadi Arman, Khalid Alfooty, Banglin Chen
ChemPlusChem, May 18, 2016, DOI: 10.1002/cplu.201600194. Read article

The Road to MOF-Related Functional Materials and Beyond: Desire, Design, Decoration, and Development

The Road to MOF‐Related Functional Materials and Beyond: Desire, Design, Decoration, and Development

Metal-organic frameworks (MOFs), usually self-assembled by metal ions or clusters and organic ligands, are porous materials with the characteristics of designable and tunable structures and topologies. Suitable postsynthetic methods via metal ions, organic linkers, or the cavities of the frameworks, could result in new materials with superior properties to the precursors, in aspects of catalysis, gas storage, and so on; thus, intentions to affect the future of mankind can be foreseen.

[Personal Account]
Junying Chen, Yingwei Li
The Chemical Record, May 17, 2016, DOI: 10.1002/tcr.201500304. Read article

Facile Synthesis of Yolk–Shell-Structured Triple-Hybridized Periodic Mesoporous Organosilica Nanoparticles for Biomedicine

Facile Synthesis of Yolk–Shell‐Structured Triple‐Hybridized Periodic Mesoporous Organosilica Nanoparticles for Biomedicine

Yolk–shell-structured periodic mesoporous organosilica (PMO) nanoparticles simultaneously incorporated with ethane-, thioether-, and benzene-bridged moieties are successfully synthesized for the first time. The PMO nanoparticles have uniform and controllable diameter, large surface area, accessible mesochannels, large pore volume, and excellent biocompatibility. By using the incorporated organic groups, fluorescence imaging probes and stimuli-responsive drug carriers are successfully prepared.

[Full Paper]
Zhaogang Teng, Junjie Zhang, Wei Li, Yuanyi Zheng, Xiaodan Su, Yuxia Tang, Meng Dang, Ying Tian, Lihui Yuwen, Lixing Weng, Guangming Lu, Lianhui Wang
Small, May 17, 2016, DOI: 10.1002/smll.201600616. Read article

Metal–Metalloporphyrin Framework Modified with Flexible tert-Butyl Groups for Selective Gas Adsorption

Metal–Metalloporphyrin Framework Modified with Flexible tert‐Butyl Groups for Selective Gas Adsorption

Alkyl groups as gatekeepers: A porous metal metalloporphyrin–organic framework has been constructed based on a custom-designed porphyrin ligand featuring pendant tert-butyl groups. This material demonstrates interesting selective gas adsorption behavior.

[Communication]
Weijie Zhang, Lukasz Wojtas, Briana Aguila, Pingping Jiang, Shengqian Ma
ChemPlusChem, May 17, 2016, DOI: 10.1002/cplu.201600158. Read article

Investigation of the Co-Dependence of Morphology and Fluorescence Lifetime in a Metal-Organic Framework

Investigation of the Co‐Dependence of Morphology and Fluorescence Lifetime in a Metal‐Organic Framework

A novel approach to elucidate the structural, functional, and morphological properties of (in)organic materials using correlative fluorescence lifetime image microscopy and scanning electron microscopy is presented. Using this method, a correlation between the morphology and the fluorescence lifetime in a metal-organic framework (MOF) is shown. Additionally, two quenching mechanisms of fluorescein in this MOF are identified and quantified.

[Full Paper]
Waldemar Schrimpf, Giulia Ossato, Patrick Hirschle, Stefan Wuttke, Don C. Lamb
Small, May 12, 2016, DOI: 10.1002/smll.201600619. Read article

A Bifunctional Metal-organic Framework: Striking CO2 Selective Sorption Features with Guest-Induced Luminescence Tuning Behaviour

CO2-selective adsorption properties and phenolic guest-induced photoluminescence tuning features of a phenanthroline-functionalized Cd(II) aminoterepthalate [Cd(NH2-bdc)(phen)]n (NH2-bdc= 2-aminobenzenedicarboxylic acid, phen = 1,10-phenanthroline) metal-organic framework (MOF) is reported. The inherently guest-free, rigid amine-rich framework exhibits substantial CO2-selective adsorption traits at ambient temperatures (both at 273 and 298 K) over other flue gases like N2, CH4, O2, Ar and H2, with high isosteric heat of adsorption at zero coverage (ΔHads ~ 34 KJmol-1). Moreover, the rationally infused fluorescent phenanthroline moiety renders the MOF with excellent photoluminescence signature, letting it act as a phenolic guest-induced luminescence tuning marker. This marks the first report of manifesting distinct fluorescence responses to differentially functionalized phenolic analytes, in the domain of coordination polymer materials.

[Communication]
Soumya Mukherjee, Aamod V. Desai, Yogeshwar D. More, Arif I. Inamdar, Sujit K. Ghosh
ChemPlusChem, May 12, 2016, DOI: 10.1002/cplu.201600138. Read article

Enhanced Ligand-based Luminescence in Metal-Organic Framework Sensor

Metal-Organic Frameworks are appealing hybrid solids which attract continuously growing interest. Their advantageous application in sensing device is demonstrated here. Especially the use of a short-pulse laser excitation of luminescent Metal-Organic Framework is reported for the first time to favor the ligand-based emission. The designed MOF-based system achieves in vitro H2S dosing by turn-on fluorescence with unprecedented sensitivity. The Al-MIL-101-based sensor detects sulfide produced by living cells and sulfide-releasing molecules in physiological media with a constant accuracy at sub-micromolar level. The reported sensitivity allows addressing medical applications and opens new perspectives in the design of new point-of-care testing devices. The detailed relationship between photoluminescence mechanisms and chemical modification of the MOF upon sensing is also reported.

[Full Paper]
Alexandre Legrand, Anton Pastushenko, Vladimir Lysenko, Alain Geloen, Elsjealessandra Quadrelli, Jérôme Canivet, David Farrusseng
ChemNanoMat, May 11, 2016, DOI: 10.1002/cnma.201600124. Read article

Graphene-Wrapped Graphitic Carbon Hollow Spheres: Bioinspired Synthesis and Applications in Batteries and Supercapacitors

Graphene‐Wrapped Graphitic Carbon Hollow Spheres: Bioinspired Synthesis and Applications in Batteries and Supercapacitors

Complete package: Graphene-wrapped graphitic hollow carbon spheres can be prepared by a facile, bioinspired double-coating method. These structures show favorable properties for the construction of advanced energy-storage devices, such as rechargeable lithium/sodium batteries and supercapacitors.

[Full Paper]
Lei Song, Sen Xin, Da-Wei Xu, Hui-Qin Li, Huai-Ping Cong, Shu-Hong Yu
ChemNanoMat, May 11, 2016, DOI: 10.1002/cnma.201600079. Read article

Dopamine-Directed In-Situ and One-Step Synthesis of Au@Ag Core-Shell Nanoparticles Confined in Metal-Organic Framework for Synergistic Catalysis

We report a facile and general approach to formation of bimetallic core-shell Au@Ag nanoparticles (NPs) immobilized in metal-organic frameworks (MOFs) via one-step synthetic route at room temperature. Dopamine (DA) is used as a moderate reductant, which can bind to negatively charged groups of MOFs through electrostatic interaction and subsequently Au@Ag core-shell NPs are formed by in-situ reduction of the bimetallic Au and Ag precursors step-by-step spontaneously without the pre-synthesized seeds. The as-formed Au@Ag core-shell NPs confined in MOFs exhibit excellent catalytic activity for the model reaction of the reduction of 4-nitrophenol (4-NPh) by NaBH4 to 4-aminophenol (4-APh) due to the synergistic effect with a high stability after cycles.

[Communication]
Pengcheng Huang, Wenjie Ma, Ping Yu, Lanqun Mao
Chem. Asian J., May 11, 2016, DOI: 10.1002/asia.201600469. Read article

Microporous Ln-MOFs with multiple 1D channels: tunable colors, white light emission and luminescent sensing for Fe(II) and Fe(III)

A new series of isostructural lanthanide-based metal-organic frameworks, [H3O][HN(CH3)3]2[Ln3L6] [Ln = Gd (1), Eu(2), and Tb (3), H2L = 1,3-benzenedicarboxylic acid] was prepared under solvothermal conditions. Single-crystal X-ray diffraction studies reveal that these compounds are 3D microporous frameworks with 1D channels distributed in four different directions. In the 1D channels are located with protonated water molecules and trimethylammonium cations, which can be partially exchanged with different metal ions. Notably, they do not contain any solvent molecules as the coordination sphere of Ln3+ ion is fully occupied by chelating and bridging carboxylate oxygen atoms. Tunable colors and white light emission can be achieved by encapsulating different molar ratios of Eu3+ and Tb3+ ions in the Gd framework through cation-exchange. In addition, the Eu framework can act as a sensitive and selective luminescence sensor for both Fe2+ and Fe3+.

[Full Paper]
Zhong-Yuan Zhou, Yun-Hu Han, Xiu-Shuang Xing, Shaowu Du
ChemPlusChem, May 09, 2016, DOI: 10.1002/cplu.201600141. Read article

Synthesis of Nitrogen-Doped Porous Carbon Nanocubes as a Catalyst Support for Methanol Oxidation

Synthesis of Nitrogen‐Doped Porous Carbon Nanocubes as a Catalyst Support for Methanol Oxidation

The cube root: Nitrogen-doped porous carbon nanocubes (PFCs) with a high surface area (465.8 m2 g−1) are successfully synthesized as a support for Pt nanoparticles. The Pt nanoparticles/nitrogen-doped porous carbon nanocubes catalyst (Pt/PFC-800) exhibits excellent electrocatalytic activity (11.36 mA cm−2) and electrochemical stability for the electro-oxidation of methanol. PB=Prussian blue, (P)FA=(poly)(furfuryl alcohol).

[Communication]
Yan Liang, Jing Wei, Xinyi Zhang, Jin Zhang, San Ping Jiang, Huanting Wang
ChemCatChem, May 09, 2016, DOI: 10.1002/cctc.201501402. Read article

Increasing CO2/N2 Selectivity with Higher Surface Density of Pyridinic Lewis Basic Sites in Porous Carbon Derived from a Pyridyl-Ligand Based MOF

The development of functional porous carbon with high CO2/N2 selectivity is of great importance for CO2 capture. In this paper, a type of porous carbon with doped pyridinic sites (termed as MOFCs) was prepared from the carbonization of a pyridyl-ligand based MOF. Four MOFCs derived from different carbonizing temperatures were prepared. Structural study reveals high contents of pyridinic-N groups and nearly the same pore size distributions for these MOFCs. Gas sorption studies reveal outstanding CO2 uptakes at low pressures and room temperatures. Owing to the high content of pyridinic-N groups, the CO2/N2 selectivity on these MOFCs exhibits CO2/N2 selectivities of about 40 ~ 50, which are among the top values in carbon materials. Further correlation studies demonstrate that the CO2/N2 selectivities show a positive linear relationship with the surface density of pyridinic-N groups, thus validating the synergistic effect of the doped pyridinic-N groups on CO2 adsorption selectivity.

[Full Paper]
Liangjun Li, Ying Wang, Xin Gu, Qipeng Yang, Xuebo Zhao
Chem. Asian J., May 04, 2016, DOI: 10.1002/asia.201600427. Read article

Metal-Derived Mesoporous Structure of a Carbon Nanofiber Electrocatalyst for Improved Oxygen Evolution Reaction in Alkaline Water Electrolysis

Metal‐Derived Mesoporous Structure of a Carbon Nanofiber Electrocatalyst for Improved Oxygen Evolution Reaction in Alkaline Water Electrolysis

Cheaper catalysts: The lowest overpotential value of the oxygen evolution reaction with cost-effective carbon nanofiber (CNF) electrocatalysts is reported. This can be attributed to the homogeneous placement of active species in the metal-derived mesoporous structure.

[Article]
Xianghua An, Dongyoon Shin, Jaehoon Jeong, Jaeyoung Lee
ChemElectroChem, May 02, 2016, DOI: 10.1002/celc.201600072. Read article

Metal-organic frameworks based chemical sensors

Metal-organic frameworks (MOFs) as chemical sensors have developed rapidly in recent years. There have been plenty of papers concerning this field and the interest is still growing. The reason is the specific merits of MOFs can be utilized to enhance sensitivity and selectivity by various energy / charge transfers occurring among different ligands, ligand and metal centers such as from ligand to metal centers or metal center to ligand, as well as from MOF skeletons to guest species, etc.. This review intends to update the recent progress of various applications with different MOF-based sensors on the basis of their luminescent and electrochemical responses towards small molecules, gas molecules, ions (cation and anion), pH, humidity, temperature, as well as biomolecules. The MOF-based sensor based on different mechanism including luminescent response of "turn-on" and "turn-off" as well as electrochemical response was concluded and discussed. We expect this article to be a retrieve database for MOFs sensor through the examples and analyses as much as possible.

[Review]
Hai-Long Jiang, Fei-Yan Yi, Dongxiao Chen, Meng-Ke Wu, Lei Han
ChemPlusChem, April 28, 2016, DOI: 10.1002/cplu.201600137. Read article

The Modulation of Gas Sorption Properties via Cation Exchange Within an Anionic Metal-Organic Framework

A novel 3D anionic metal-organic framework (MOF) of (Me2NH2)4[Ni8(PTCA)4(μ3-OH)4(H2O)4](DMF)5(H2O)13 has been synthesized, in which Me2NH2+ can be exchanged by Li+ ion. The results of gas sorption measurements indicate that both desolvated MOFs before and after Li+ exchange show a highly selective adsorption for CO2 over CH4 and N2 gases, and the Li+ ion exchanged MOF exhibits enhanced CO2, CH4 and H2 storage.

[Full Paper]
Yong-Liang Huang, Long Jiang, Tongbu Lu
ChemPlusChem, April 28, 2016, DOI: 10.1002/cplu.201600121. Read article

Assembling metal-organic frameworks in ionic liquids and supercritical CO2

Ionic liquids (ILs) and supercritical carbon dioxide (scCO2) are both considered as green solvents with tunable properties. Recently, the study on the synthesis of metal-organic frameworks (MOFs) in the presence of ILs and scCO2 has become a burgeoning direction in chemistry and material science. ILs have shown to be ideal media for the synthesis of a variety of MOFs due to their peculiar properties including the ability to dissolve a wide range of organic and inorganic compounds and flexible designability. scCO2 has adjustable solvent power and excellent mass transfer characteristics that offer the opportunity to replace organic solvents for MOFs activation, MOF aerogel synthesis, and MOFs construction. More interestingly, the simultaneous utilization of IL and scCO2 can combine the advantages of the two liquids, which provide novel routes for the fabrication of MOF structures. This review describes the advances of MOFs synthesis in ILs, scCO2 and IL/scCO2 systems.

[Focus Review]
Jianling Zhang, Bingxing Zhang, Buxing Han
Chem. Asian J., April 28, 2016, DOI: 10.1002/asia.201600323. Read article

Metal-Organic Framework-Templated Polyelectrolyte Nanocapsules for the Encapsulation and Delivery of Small Molecule-Polymer Conjugates

In this work, a strategy to explore nanoscale metal-organic frameworks (nano-MOFs) as templates for the layer-by-layer (LbL) assembly of polyelectrolytes was developed. As small-molecule drugs or imaging agents cannot be efficiently encapsulated by polyelectrolyte nanocapsules, two promising and biocompatible polymers (i.e., comb-shaped polyethylene glycol (PEG) and hyperbranched polyglycerol-based PEG) were exploited for the conjugation of model drugs and imaging agents, which were then encapsulated into the nano-MOF-templated nanocapsules. Moreover, we systemically explored the release kinetics of the encapsulated conjugates, and examined how the encapsulation and/or release processes can be controlled by varying the composition and architectures of the polymers. We envision that our nano-MOFs-templated nanocapsules, through combining with small molecule-polymer conjugates, would represent a new type of delivery systems which might open new opportunities for biomedicine applications.

[Full Paper]
Chuanliu Wu, Shuo Liu, Jianbin Chen, Xiaojia Bao, Tao Li, Yunyang Ling, Chunxiang Li, Yibing Zhao
Chem. Asian J., April 28, 2016, DOI: 10.1002/asia.201600250. Read article

Anionic Metal–Organic Framework for Selective Dye Removal and CO2 Fixation

Anionic Metal–Organic Framework for Selective Dye Removal and CO2 Fixation

A microporous Zn-based anionic metal–organic framework (MOF) is synthesized with triangular 4,4',4″-(pyridine-2,4,6-triyl)tribenzoic acid; it features open channels and proves to be a good capturing agent for cationic dyes. In addition, the Zn-MOF demonstrates excellent catalytic activity for CO2 fixation by cycloaddition reaction with epoxides.

[Communication]
Sanjay Kumar, Gaurav Verma, Wen-Yang Gao, Zheng Niu, Lukasz Wojtas, Shengqian Ma
Eur. J. Inorg. Chem., April 27, 2016, DOI: 10.1002/ejic.201600218. Read article.

Carbon Cathodes in Rechargeable Lithium–Oxygen Batteries Based on Double-Lithium-Salt Electrolytes

Carbon Cathodes in Rechargeable Lithium–Oxygen Batteries Based on Double‐Lithium‐Salt Electrolytes

Plenty of carbs, lots of salt: Four different carbon materials (multiwalled carbon nanotubes (MWCNTs), CMK-3, graphene nanosheets (GNSs), and Ketjen Black (KB)) are studied as cathodes for lithium–oxygen (Li–O2) batteries, using a double lithium salt (LiNO3–LiTFSI/DMSO) as electrolyte. The Li–O2 cell using MWCNTs as electrode exhibits not only good cycling stability but also good rate performance.

[Communication]
Eunjoo Yoo, Haoshen Zhou
ChemSusChem, April 27, 2016, DOI: 10.1002/cssc.201600177. Read article

A Threefold Interpenetrated Pillared-Layer Metal–Organic Framework for Selective Separation of C2H2/CH4 and CO2/CH4

A Threefold Interpenetrated Pillared‐Layer Metal–Organic Framework for Selective Separation of C2H2/CH4 and CO2/CH4

Trapped wind: A new threefold interpenetrated pillared-layer microporous metal–organic framework, [Zn2(cca)2(4-bpdb)]n(DMF)2n (UTSA-85) (H2cca= 4-carboxycinnamic acid, 4-bpdb=1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, and DMF=N,N-dimethylformamide), is described. The desolvated framework, UTSA-85 a, exhibits high selectivity for C2H2/CH4 separation as a result of the microporous structure and functional azine-groups decorating the pore channels (see figure).

[Full Paper]
Osamah Alduhaish, Hailong Wang, Bin Li, Hadi D. Arman, Vladimir Nesterov, Khalid Alfooty, Banglin Chen
ChemPlusChem, April 27, 2016, DOI: 10.1002/cplu.201600088. Read article

Solution-Based Chemical Process for Synthesis of Highly Active Li2S/Carbon Nanocomposite for Lithium-Sulfur Batteries

Solution‐Based Chemical Process for Synthesis of Highly Active Li2S/Carbon Nanocomposite for Lithium‐Sulfur Batteries

Filling the gaps: Disproportionation of a Li2S6 polysulfide solution in the presence of porous carbon yields a composite with a homogeneous Li2S distribution with small Li2S particle size and good contact with the carbon surface. The composite is promising for application in high-energy-density long-cycle-life lithium-sulfur batteries.

[Communication]
Patrick Strubel, Holger Althues, Stefan Kaskel
ChemNanoMat, April 27, 2016, DOI: 10.1002/cnma.201600067. Read article

Fe3O4@MIL-101 – A Selective and Regenerable Adsorbent for the Removal of As Species from Water

Fe3O4@MIL-101 – A Selective and Regenerable Adsorbent for the Removal of As Species from Water

MIL-101(Cr) serves as a host for the in situ synthesis of Fe3O4 nanoparticles. The resulting material shows excellent affinity towards AsIII and AsV species in water. Ca2+, Mg2+, and phosphate ions as well as natural organic matter do not affect the removal efficiency or selectivity. The structural integrity of the host is maintained during the adsorption and desorption process.

[Full Paper]
Karel Folens, Karen Leus, Nina Ricci Nicomel, Maria Meledina, Stuart Turner, Gustaaf Van Tendeloo, Gijs Du Laing, Pascal Van Der Voort
Eur. J. Inorg. Chem., April 21, 2016, DOI: 10.1002/ejic.201600160. Read article.

Carboxylate–Hydrazone Mixed-Linker Metal–Organic Frameworks: Synthesis, Structure, and Selective Gas Adsorption

Carboxylate–Hydrazone Mixed-Linker Metal–Organic Frameworks: Synthesis, Structure, and Selective Gas Adsorption

Two metal–organic frameworks incorporating carboxylate and acylhydrazone moieties are constructed from 4-pyridinecarbaldehyde isonicotinoyl hydrazone (PCIH) and linear dicarboxylate [dcx = 1,4-benzene- (BDC) or 4,4'-biphenyldicarboxylate (BPDC)]. Interpenetrated pillar-layered [Zn2(dcx)2(PCIH)2] frameworks selectively adsorb CO2 over N2.

[Full Paper]
Kornel Roztocki, Irena Senkovska, Stefan Kaskel, Dariusz Matoga
Eur. J. Inorg. Chem., April 21, 2016, DOI: 10.1002/ejic.201600134. Read article.

A Promising White-Light-Emitting Material Constructed from Encapsulating Eu3+/Tb3+ Hybrid Ions into a Robust Microporous Metal–Organic Framework

A Promising White-Light-Emitting Material Constructed from Encapsulating Eu3+/Tb3+ Hybrid Ions into a Robust Microporous Metal–Organic Framework

A fascinating {[Zn(H2thca)0.5(tib)]·5H2O}n [H6thca = p-terphenyl-3,3',3″,5,5',5″-hexacarboxylic acid; tib = 1,3,5-tris(imidazolyl)benzene] metal–organic framework with a permanently porous structure and containing uncoordinated carboxyl groups within the pores is obtained. It emits blue light and can serve as a host for several guest Ln3+ cations; thus, it can exhibit broadband white emission by simple postmodification methods.

[Full Paper]
Xuechuan Gao, Siyuan Chang, Houting Liu, Zhiliang Liu
Eur. J. Inorg. Chem., April 21, 2016, DOI: 10.1002/ejic.201501431. Read article.

Kagóme Cobalt(II)-Organic Layers as Robust Scaffolds for Highly Efficient Photocatalytic Oxygen Evolution

Kagóme Cobalt(II)‐Organic Layers as Robust Scaffolds for Highly Efficient Photocatalytic Oxygen Evolution

Water splitting: Two assembled cobalt(II)-carboxylate layers that bear bridging OH ligands are explored as water oxidation catalysts for photocatalytic O2 production. Their activities towards H2O oxidation are assessed by monitoring the in situ O2 concentration versus time in the reaction medium by utilizing a Clark-type oxygen electrode under photochemical conditions.

[Full Paper]
Jiaheng Xu, Zhi Wang, Wenguang Yu, Di Sun, Qing Zhang, Chen-Ho Tung, Wenguang Wang
ChemSusChem, April 21, 2016, DOI: 10.1002/cssc.201600101. Read article

Synthesis, Characterization, and Luminescence Modulation of a Metal–Organic Framework Based on a Cyclotriphosphazene-Functionalized Multicarboxylate Ligand

Synthesis, Characterization, and Luminescence Modulation of a Metal–Organic Framework Based on a Cyclotriphosphazene‐Functionalized Multicarboxylate Ligand

Pack it in! An anionic three-dimensional metal–organic framework based on a novel cyclotriphosphazene-functionalized multicarboxylate exhibits luminescence response to different metal ions (see figure).

[Full Paper]
Yajing Ling, Huiming Liu, Jingjing Jiao, Yunlong Feng, Yabing He
ChemPlusChem, April 21, 2016, DOI: 10.1002/cplu.201600129. Read article

High Catalytic Performance of MIL-101-Immobilized NiRu Alloy Nanoparticles towards the Hydrolytic Dehydrogenation of Ammonia Borane

High Catalytic Performance of MIL-101-Immobilized NiRu Alloy Nanoparticles towards the Hydrolytic Dehydrogenation of Ammonia Borane

Ultrafine NiRu alloy nanoparticles are successfully immobilized in the pores of MIL-101 by the double-solvent method combined with the overwhelming reduction approach. The immobilized nanoparticles show high catalytic performance towards the hydrolytic dehydrogenation of ammonia borane.

[Communication]
Sandipan Roy, Pradip Pachfule, Qiang Xu
Eur. J. Inorg. Chem., April 19, 2016, DOI: 10.1002/ejic.201600180. Read article.

Catalytic Fast Pyrolysis of Lignin over High-Surface-Area Mesoporous Aluminosilicates: Effect of Porosity and Acidity

Catalytic Fast Pyrolysis of Lignin over High‐Surface‐Area Mesoporous Aluminosilicates: Effect of Porosity and Acidity

Im-pore-tance of space: The relationship between product distribution of catalytic fast pyrolysis and pore size, particle size, acid sites, mesoporosity, and pore connectivity is complex. Unlike zeolites, that show clear correlation between acidity and deoxygenation selectivity, such a relationship is harder to establish for mesoporous alumino- silicates with different pore structures. Thus we could identify key characteristics for a good lignin CFP catalyst.

[Full Paper]
Victoria B. F. Custodis, Stamatia A. Karakoulia, Kostas S. Triantafyllidis, Jeroen A. van Bokhoven
ChemSusChem, April 15, 2016, DOI: 10.1002/cssc.201600105. Read article

Ligand Functionalization in Metal–Organic Frameworks for Enhanced Carbon Dioxide Adsorption

Ligand Functionalization in Metal–Organic Frameworks for Enhanced Carbon Dioxide Adsorption

CO2 clean up: Ligand functionalization often leads to enhanced CO2–MOF (MOF=metal–organic framework) interactions, at the cost of a decrease in porosity. The overall adsorption capacity will increase when interactions dominate.

[Personal Account]
Hao Wang, Junjie Peng, Jing Li
The Chemical Record, April 13, 2016, DOI: 10.1002/tcr.201500307. Read article

Liquid-Phase Epitaxially Grown Metal–Organic Framework Thin Films for Efficient Tandem Catalysis Through Site-Isolation of Catalytic Centers

Liquid‐Phase Epitaxially Grown Metal–Organic Framework Thin Films for Efficient Tandem Catalysis Through Site‐Isolation of Catalytic Centers

Tandem catalysis: A tandem epoxidation/CO2 insertion is shown in a metal–organic framework, composed of two Mn-porphyrin units, which catalyze the epoxidation of an olefin substrate, and a Zn-porphyrin, which catalyzes the epoxide-opening reaction (see figure). A film of this MOF constructed in layer-by-layer fashion is more catalytically active than the bulk prepared crystalline MOF.

[Communication]
M. Hassan Beyzavi, Nicolaas A. Vermeulen, Kainan Zhang, Monica So, Chung-Wei Kung, Joseph T. Hupp, Omar K. Farha
ChemPlusChem, April 13, 2016, DOI: 10.1002/cplu.201600046. Read article

Shuttle-like Porous Carbon Rods from Carbonized Metal–Organic Frameworks for High-Performance Capacitive Deionization

Shuttle‐like Porous Carbon Rods from Carbonized Metal–Organic Frameworks for High‐Performance Capacitive Deionization

Shuttle bus: Shuttle-like porous carbon rods are prepared through a high-temperature pyrolysis step and a subsequent etching step by using rod-like metal–organic frameworks, MIL-88 (Fe), as a precursor for the first time. When applied as capacitive deionization electrodes, they show an ultrahigh electrosorption capacity of 16.2 mg g−1, which is one of the highest values achieved under similar experimental conditions.

[Article]
Xingtao Xu, Jinliang Li, Miao Wang, Yong Liu, Ting Lu, Likun Pan
ChemElectroChem, April 06, 2016, DOI: 10.1002/celc.201600051. Read article

A Rhenium-Functionalized Metal–Organic Framework as a Single-Site Catalyst for Photochemical Reduction of Carbon Dioxide

A Rhenium-Functionalized Metal–Organic Framework as a Single-Site Catalyst for Photochemical Reduction of Carbon Dioxide

A (bpy)Re(CO)3Cl-containing metal–organic framework (MOF) acts as an effective single-site catalyst to photochemically reduce carbon dioxide to carbon monoxide and formate. Mechanistic insights into the monomolecular pathway of the photocatalytic CO2 reduction have been obtained without interference from bimolecular pathways, thanks to site-isolation of the catalytic centers in MOFs.

[Communication]
Ruiyun Huang, Yu Peng, Cheng Wang, Zhan Shi, Wenbin Lin
Eur. J. Inorg. Chem., April 5, 2016, DOI: 10.1002/ejic.201600064. Read article.

Two Six-Connected MOFs with Distinct Architecture: Synthesis, Structure, Adsorption, and Magnetic Properties

Two Six‐Connected MOFs with Distinct Architecture: Synthesis, Structure, Adsorption, and Magnetic Properties

Well connected: Two unusual six-connected metal–organic frameworks were constructed by assembling CoII ions, 5-(4-pyridyl)tetrazole and formate ions. With slight modulation of the coordination environment of the trinuclear cobalt cluster, the two complexes take on completely distinct structures (see figure). One of the complexes strongly interacts with CO2 and might potentially serve as an adsorption material.

[Full Paper]
Guo-Jian Ren, Song-De Han, Yan-Qing Liu, Tong-Liang Hu, Xian-He Bu
ChemPlusChem, April 01, 2016, DOI: 10.1002/cplu.201600092. Read article

A Highly Sensitive Luminescent Dye@MOF Composite for Probing Different Volatile Organic Compounds

A Highly Sensitive Luminescent Dye@MOF Composite for Probing Different Volatile Organic Compounds

Metal–organic framework sensor: We report an interesting layered coordination network based on the derivative of the natural amino acid l-phenylalanine and zinc ions, which can embed Rhodamine B dye to result in a luminescent sensor of Rho@MOF composite, which can detect different volatile organic compounds with clearly differentiable and unique luminescence readouts by tuning the ligand-to-dye energy transfer (see figure).

[Full Paper]
Jun-Ping Zheng, Sha Ou, Min Zhao, Chuan-De Wu
ChemPlusChem, March 24, 2016, DOI: 10.1002/cplu.201600057. Read article

SALE-Ing a MOF-Based “Ship of Theseus.” Sequential Building-Block Replacement for Complete Reformulation of a Pillared-Paddlewheel Metal-Organic Framework

SALE-Ing a MOF-Based “Ship of Theseus.” Sequential Building-Block Replacement for Complete Reformulation of a Pillared-Paddlewheel Metal-Organic Framework

Text for Table of Contents: Interchange of a non-interpenetrating Zn based pillared-paddlewheel MOF into an entirely different Ni-based pillared-paddlewheel MOF has been achieved through the combination of solvent assisted linker exchange and transmetalation.

[Communication]
Yan Xu, Nicolaas A. Vermeulen, Yangyang Liu, Joseph T. Hupp, Omar K. Farha
Eur. J. Inorg. Chem., March 18, 2016, DOI: 10.1002/ejic.201600069. Read article.

Three Cluster Organic Frameworks Constructed from Tetranuclear Cluster Units: Structure and Properties

Three Cluster Organic Frameworks Constructed from Tetranuclear Cluster Units: Structure and Properties

Rare connections: Three isostructural cluster organic 3D metal–organic frameworks (MOFs) are constructed by combining a semirigid multi-carboxylic acid with tetranuclear metal–hydroxy–carboxyl clusters (see figure). Manganese and cobalt MOFs showed significant antiferromagnetic interactions between intracluster metal ions, whereas the cadmium MOF reveals strong blue photoluminescence.

[Full Paper]
Ge Liu, Dong Xie, Rui Li, Lei Hou, Wen-Yan Zhang, Yao-Yu Wang
ChemPlusChem, March 11, 2016, DOI: 10.1002/cplu.201600025. Read article

Switchable Room-Temperature Ferroelectric Behavior, Selective Sorption and Solvent-Exchange Studies of [H3O][Co2(dat)(sdba)2]⋅H2sdba⋅5 H2O

Switchable Room‐Temperature Ferroelectric Behavior, Selective Sorption and Solvent‐Exchange Studies of [H3O][Co2(dat)(sdba)2]⋅H2sdba⋅5 H2O

Complex behavior: The compound [H3O][Co2(dat)(sdba)2]H2sdba5 H2O (dat=3,5-diamino-1,2,4-triazole; H2sdba=4,4′-sulfonyldibenzoic acid) is ferroelectric at room temperature, exhibits polarization switching behavior upon dehydration and subsequent rehydration, and undergoes a solvent-mediated single-crystal-to-single-crystal transformation. Gas sorption studies on the dehydrated compound indicate the selective adsorption of CO2 over CH4 at 195 K.

[Full Paper]
Saurav Bhattacharya, Somnath Pal, Srinivasan Natarajan
ChemPlusChem, March 01, 2016, DOI: 10.1002/cplu.201500564. Read article

A Boiling-Water-Stable, Tunable White-Emitting Metal–Organic Framework from Soft-Imprint Synthesis

A Boiling-Water-Stable, Tunable White-Emitting Metal–Organic Framework from Soft-Imprint Synthesis

White light/white heat: A porous metal–organic framework, inspired by conceptually crosscutting the molecular imprint of polymers and the template of zeolites, emits white light in boiling water. The MOF incorporates an effective hard-and-soft divide, in which the EuIII–carboxylate framework holds up the primary grid, whereas the imbedded soft CuI block, like a template, can be dislodged (e.g., by reacting with H2S) from the surrounding sulfur donors while the host net remains intact.

[Communication]
Jun He, Jian Huang, Yonghe He, Peng Cao, Matthias Zeller, Allen D. Hunter, Zhengtao Xu
Chem. Eur. J., January 8, 2016, DOI: 10.1002/chem.201504941. Read article.

Coated/Sandwiched rGO/CoSx Composites Derived from Metal–Organic Frameworks/GO as Advanced Anode Materials for Lithium-Ion Batteries

Coated/Sandwiched rGO/CoSx Composites Derived from Metal–Organic Frameworks/GO as Advanced Anode Materials for Lithium-Ion Batteries

High-performance anode materials: Composites made of reduced graphene oxide (rGO)-coated or sandwiched CoSx are constructed through facile thermal sulfurization of a metal–organic framework/GO precursor, and used as high-performance anode materials for lithium-ion batteries (see scheme).

[Full Paper]
Dongming Yin, Gang Huang, Feifei Zhang, Yuling Qin, Zhaolin Na, Yaoming Wu, Limin Wang
Chem. Eur. J., January 8, 2016, DOI: 10.1002/chem.201504399. Read article.

Origin of the Ability of α-Fe2O3 Mesopores to Activate C-H Bonds in Methane

Origin of the Ability of α-Fe2O3 Mesopores to Activate C-H Bonds in Methane

Origin of the activation: The inner surface structures of the pore wall in mesoporous α-Fe2O3 are mainly comprised of turbostratic ribbons and K crystal faces. They show excellent catalytic performance for methane activation, during which the C-H bonds are converted into C-O bonds in an O2 atmosphere at 140 °C (see figure).

[Full Paper]
Bing Dong, Zhen Han, Yongbo Zhang, Youyi Yu, Aiguo Kong, Yongkui Shan
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201503183. Read article.

A Highly Energetic N-Rich Metal–Organic Framework as a New High-Energy-Density Material

A Highly Energetic N-Rich Metal–Organic Framework as a New High-Energy-Density Material

High-energy MOF: Metal–organic framework [Cu3(MA)2(N3)3] (MA=melamine) was synthesized hydrothermally as gray crystals (see figure). The structural analysis revealed the existence of unusual multiwalled tubular channels and interwoven single and double helices. Its standard molar enthalpy of formation of 1788.73 kJ mol−1 is the highest among previously reported MOF-based energetic materials, and the calculated detonation properties showed that it can be used as a promising explosive.

[Full Paper]
Huabin Zhang , Mingjian Zhang , Ping Lin , Victor Malgras, Jing Tang , Saad M. Alshehri, Yusuke Yamauchi , Shaowu Du, Jian Zhang
Chem. Eur. J., December 10, 2015, DOI: 10.1002/chem.201503561. Read article.

A Post-Synthetically Modified MOF for Selective and Sensitive Aqueous-Phase Detection of Highly Toxic Cyanide Ions

A Post-Synthetically Modified MOF for Selective and Sensitive Aqueous-Phase Detection of Highly Toxic Cyanide Ions

Going hunting! Selective and sensitive detection of toxic cyanide (CN) by a post-synthetically altered metal–organic framework (MOF) has been achieved (see scheme). The aqueous-phase sensing and very low detection limit, the essential prerequisites for an effective sensory material, has been fulfilled by the MOF. Moreover, the present detection level meets the standard set by the World Health Organization (WHO) for the permissible limit of cyanide concentration in drinking water.

[Communication]
Avishek Karmakar, Naveen Kumar, Partha Samanta, Aamod V. Desai, Sujit K. Ghosh
Chem. Eur. J., December 10, 2015, DOI: 10.1002/chem.201503323. Read article.

Metal–Organic Frameworks Containing Missing-Linker Defects Leading to High Hydroxide-Ion Conductivity

Metal–Organic Frameworks Containing Missing-Linker Defects Leading to High Hydroxide-Ion Conductivity

The missing link: The deliberate introduction of defects on fcu frameworks by KOH/EtOH, leading to missing-linker defects and metal cluster basification, is responsible for a boosting of the ion conductivity and depletion of activation energy.

[Full Paper]
Carmen Montoro, Pilar Ocón, Félix Zamora, Jorge A. R. Navarro
Chem. Eur. J., December 8, 2015, DOI: 10.1002/chem.201503951. Read article.

Direct Assembly of Mesoporous Silica Functionalized with Polypeptides for Efficient Dye Adsorption

Direct Assembly of Mesoporous Silica Functionalized with Polypeptides for Efficient Dye Adsorption

An inside job: A polypeptide-functionalized mesoporous silica template is fabricated from a biodegradable poly(ethylene oxide-b-ε-caprolactone) (PEO-b-PCL) diblock copolymer and a poly(tyrosine) (PTyr) biopolymer as a template. Treatment of the silica system by selective solvent extraction removed the block copolymer, while retaining the polypeptide inside the mesostructured silica matrix (see figure).

[Full Paper]
Yi-Syuan Lu, Bishnu Prasad Bastakoti, Malay Pramanik, Victor Malgras, Yusuke Yamauchi, Shiao-Wei Kuo
Chem. Eur. J., December 2, 2015, DOI: 10.1002/chem.201503679. Read article.

Selective Heterogeneous C-H Activation/Halogenation Reactions Catalyzed by Pd@MOF Nanocomposites

Selective Heterogeneous C-H Activation/Halogenation Reactions Catalyzed by Pd@MOF Nanocomposites

A directed heterogeneous C-H activation/halogenation reaction catalyzed by readily synthesized Pd@MOF nanocatalysts was developed (see scheme). The heterogeneous Pd catalysts used were a novel and environmentally benign Fe-based metal–organic framework (MOF) (Pd@MIL-88B-NH2(Fe)) and the previously developed Pd@MIL-101-NH2(Cr). Very high conversions and selectivities were achieved under very mild reaction conditions and in short reaction times.

[Full Paper]
Vlad Pascanu, Fabian Carson, Marta Vico Solano, Jie Su, Xiaodong Zou, Magnus J. Johansson, Belén Martín-Matute
Chem. Eur. J., October 20, 2015, DOI: 10.1002/chem.201502918. Read article.

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