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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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Direct synthesis of an Iridium(III)-bipyridine-Metal-Organic Framework as heterogeneous catalyst for aerobic alcohol oxidation

[Full Paper]
Sara Abednatanzi, Parviz Gohari Derakhshandeh, Alireza Abbasi, Pascal van der Voort, Karen Leus
ChemCatChem, September 26, 2016, DOI: 10.1002/cctc.201600985. Read article

Size Effects of Platinum Nanoparticles in the Photocatalytic Hydrogen Production Over 3D Mesoporous Networks of CdS and Pt Nanojunctions

Size Effects of Platinum Nanoparticles in the Photocatalytic Hydrogen Production Over 3D Mesoporous Networks of CdS and Pt Nanojunctions

3D mesoporous architectures of CdS and Pt nanocrystals are demonstrated as highly effective catalysts for the hydrogen evolution reaction (HER). Photocatalytic measurements coupled with spectroscopic studies suggest that deposition of ultrasmall Pt nanoparticles enhances the HER activity because of variations in the band-edge positions and electron donor density of CdS nanocrystals.

[Full Paper]
Ioannis Vamvasakis, Bin Liu, Gerasimos S. Armatas
Adv. Funct. Mater., September 26, 2016, DOI: 10.1002/adfm.201603292. Read article

Palladium(II)@Zirconium-Based Mixed-Linker Metal–Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross-Coupling Reactions

Palladium(II)@Zirconium‐Based Mixed‐Linker Metal–Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross‐Coupling Reactions

In the mix: It is possible to control the density of the introduced active centers by adjusting the feed ratio of the linkers that contain functional groups during the synthesis of metal–organic frameworks. The prepared heterogeneous Pd catalysts are very efficient for Suzuki and Heck cross-coupling reactions with a very low Pd loading and could be recycled in at least 10 cycles.

[Full Paper]
Rong Sun, Bing Liu, Bo-Geng Li, Suyun Jie
ChemCatChem, September 22, 2016, DOI: 10.1002/cctc.201600774. Read article

Electrochemical Impedance Spectroscopy at Well Controlled dc Bias for Nanoporous Platinum Microelectrode in Embryo Brain

Nanoporous Pt with extremely small (1-2 nm) and uniform nanopores, L2-ePt, was electrochemically investigated in embryo brain. For comparison study under precise control of electrochemical potential, we constituted an electrochemical cell beneath the embryo surface by introducing a flat and a nanoporous Pt twisted wires around which a Ag/AgCl wound. L2-ePt and flat Pt in the brain were compared with each other by conventional voltammetry and electrochemical impedance spectroscopy at the dc bias, which was carefully selected to minimize faradaic interference. The electrochemical behavior at L2-ePt implanted in embryo brain is immune to severe passivation and closer to an ideal capacitor than flat Pt. Lower electrode impedance of L2-ePt leads to less potential drop at the interface between the electrode and the extracellular solution, protecting the implanted system from unwanted faradaic reactions. Various aspects including the low electrode impedance and electrochemical stability of L2-ePt in the embryo brain suggest L2-ePt as a promising electrode material for effectively stimulating distant neuronal cells and recording local field potential signals.

[Article]
Beom Jin Kim, Yang-Rae Kim, Minjee Seo, Eun Joong Kim, Joohee Jeon, Taek Dong Chung
ChemElectroChem, September 21, 2016, DOI: 10.1002/celc.201600404. Read article

Ultra-Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

Ultra‐Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

Skewering nerve agents: Conformal metal–organic framework (MOF) kebab structures decorated on nanofibers that can degrade chemical warfare agents within minutes are described. These MOF–nanofiber composites show excellent reactivity towards both simulant and nerve agent soman (GD).

[Communication]
Junjie Zhao, Dennis T. Lee, Robert W. Yaga, Morgan G. Hall, Heather F. Barton, Ian R. Woodward, Christopher J. Oldham, Howard J. Walls, Gregory W. Peterson, Gregory N. Parsons
Angew. Chem. Int. Ed., September 21, 2016, DOI: 10.1002/anie.201606656. Read article

An O2 Self-Sufficient Biomimetic Nanoplatform for Highly Specific and Efficient Photodynamic Therapy

An O2 Self‐Sufficient Biomimetic Nanoplatform for Highly Specific and Efficient Photodynamic Therapy

An O2 self-sufficient cell-like biomimetic nanoplatform based on zeolitic imidazolate framework (ZIF-8) is developed for effective photodynamic therapy (PDT). In vitro and in vivo investigations confirm that this cell-like PDT agent possesses immune escape, homologous targeting, and O2 self-sufficient capabilities for highly specific PDT against hypoxic tumor cells.

[Full Paper]
Hong Cheng, Jing-Yi Zhu, Shi-Ying Li, Jin-Yue Zeng, Qi Lei, Ke-Wei Chen, Chi Zhang, Xian-Zheng Zhang
Adv. Funct. Mater., September 20, 2016, DOI: 10.1002/adfm.201603212. Read article

Template-based synthesis of a formate metal-organic framework/activated carbon fibre composite for high-performance methane adsorptive separation

Simultaneous improvement in adsorption selectivity and capacity for single adsorbents is challenging but counting for much in adsorptive separations. To this end, a formate metal-organic framework and activated carbon fibre composite was synthesized in our work by a simple two-step process, involving homogeneous precipitation of a MOF precursor on an activated carbon fiber, and subsequent template replication. The resultant core-shell composite, ACF@[Ni3(HCOO)6], exhibited optimized adsorption performance both in selectivity and capacity for the separation of CH4/N2 to most of state-of-the-art adsorbents.

[Communication]
Xiaowei Liu, Jiangliang Hu, Tianjun Sun, Ya Guo, Thomas Bennett, Xinyu Ren, Shudong Wang
Chem. Asian J., September 19, 2016, DOI: 10.1002/asia.201601134. Read article

Enhanced Adsorption Efficiency through Materials Design for Direct Air Capture over Supported Polyethylenimine

Enhanced Adsorption Efficiency through Materials Design for Direct Air Capture over Supported Polyethylenimine

Catch CO2 if you can: Supported polyethylenimine (PEI) adsorbents with unprecedented amine efficiencies are obtained for the capture of CO2 from air through molecular-scale design. A uniform layer of cetyltrimethylammonium (CTMA+) cations over the internal surface of the silica support plays a key role in the distribution of PEI throughout the extra-large pore channels and, thus, promotes CO2 interactions with amine groups.

[Full Paper]
Abdelhamid Sayari, Qing Liu, Prashant Mishra
ChemSusChem, September 15, 2016, DOI: 10.1002/cssc.201600834. Read article

Alignment under Magnetic Field of Mixed Fe2O3/SiO2 Colloidal Mesoporous Particles Induced by Shape Anisotropy

Alignment under Magnetic Field of Mixed Fe2O3/SiO2 Colloidal Mesoporous Particles Induced by Shape Anisotropy

Fe2O3/SiO2 colloidal mesoporous particles with high shape anisotropy are promising building blocks to achieve macroscopically oriented nanocomposites. When dispersed in a solvent, these particles can be easily oriented under magnetic field. Two polymorphs of iron oxide can be stabilized, the superparamagnetic γ phase and the rarest multiferroic ε phase, opening new perspectives for nanocomposites with anisotropic magnetic properties.

[Full Paper]
Jheng-Guang Li, Giulia Fornasieri, Anne Bleuzen, Martí Gich, Alexandre Gloter, Frédéric Bouquet, Marianne Impéror-Clerc
Small, September 14, 2016, DOI: 10.1002/smll.201602272. Read article

Surfactant-Free Palladium Nanoparticles Encapsulated in ZIF-8 Hollow Nanospheres for Size-Selective Catalysis in Liquid-Phase Solution

Surfactant‐Free Palladium Nanoparticles Encapsulated in ZIF‐8 Hollow Nanospheres for Size‐Selective Catalysis in Liquid‐Phase Solution

Size matters: The encapsulation of surfactant-free Pd nanoparticles in ZIF-8 hollow nanospheres is achieved. Pd@ZIF-8 hollow nanospheres show excellent size-selective catalysis properties in the liquid-phase hydrogenation of olefins. As a result of the uniform pore size of the ZIF-8 shell, the catalyst shows high activity for the hydrogenation of 1-hexene but very low activity for larger molecules such as cis-cyclooctene and trans-stilbene.

[Communication]
Xiaoshi Wang, Mingyu Li, Changyan Cao, Chang Liu, Jian Liu, Yanan Zhu, Sidi Zhang, Weiguo Song
ChemCatChem, September 14, 2016, DOI: 10.1002/cctc.201600846. Read article

Steady-State, Scalable Production of Mesoporous Rutile and Brookite Particles and Their Use in Energy Conversion and Storage Cells

Steady‐State, Scalable Production of Mesoporous Rutile and Brookite Particles and Their Use in Energy Conversion and Storage Cells

A continuously stirred tank reactor (CSTR) was employed to synthesize TiO2 nanoparticles. Tuning the aqueous TiCl4 concentration and consequently the solution pH gives rutile aggregates with a cauliflower-like morphology and an internal structure of self-assembled nanoneedles (>0.5 M) or planar brookite nanoplatelets (0.1 M). The mesoporous rutile particles have excellent light scattering properties and the brookite nanoplatelets exhibit stable Li-ion intercalation functionality.

[Full Paper]
Amrita Yasin, Fuqiang Guo, Micah J. Sussman, Raynald Gauvin, George P. Demopoulos
ChemNanoMat, September 13, 2016, DOI: 10.1002/cnma.201600185. Read article

Iron-Based Metal-Organic Frameworks (MOF) as Photocatalysts for Radical and Cationic Polymerizations under Near UV and Visible LEDs (385–405 nm)

Iron‐Based Metal‐Organic Frameworks (MOF) as Photocatalysts for Radical and Cationic Polymerizations under Near UV and Visible LEDs (385–405 nm)

Highly porous iron(III)-based metal-organic frameworks (MOFs) can be used as photocatalysts for polymerization reactions. This provides the possibility of designing MOF/polymer composite materials with enhanced mechanical properties through the in situ incorporation of the MOF structure during the photopolymerization process.

[Full Paper]
Jing Zhang, Frederic Dumur, Patricia Horcajada, Carine Livage, Pu Xiao, Jean Pierre Fouassier, Didier Gigmes, Jacques Lalevée
Macromol. Chem. Phys., September 12, 2016, DOI: 10.1002/macp.201600352. Read article

MOF Derived Nonstoichiometric NixCo3−xO4−y Nanocage for Superior Electrocatalytic Oxygen Evolution

MOF Derived Nonstoichiometric NixCo3−xO4−y Nanocage for Superior Electrocatalytic Oxygen Evolution

The nonhomogeneous surface charge distribution and high electrochemical surface area of nonstoichiometric NixCo3–xO4–y three dimensional nanocages results in improved electrocatalytic oxygen evolution activity compared to Co3O4. This is due to the synergetic effect of porosity, nonstoichiometry and rich redox centers in NixCo3−xO4−y The efficient catalytic activity for NixCo3−xO4−y is supported by higher turnover frequency and lower apparent activation energy.

[Full Paper]
Rajini P. Antony, Ashis K. Satpati, Kaustava Bhattacharyya, Bhagawantrao N. Jagatap
Adv. Mater. Interfaces, September 12, 2016, DOI: 10.1002/admi.201600632. Read article

A Highly Stable Nonhysteretic {Cu2(tebpz) MOF+water} Molecular Spring

A Highly Stable Nonhysteretic {Cu2(tebpz) MOF+water} Molecular Spring

Spring loaded: A molecular spring (MS) system formed by a highly hydrophobic metal–organic framework (MOF) and water (see figure) with exceptional stability, efficiency, and operating pressure is reported. This is the first MS having such a combination of properties and the first nonhysteretic MOF-based heterogeneous lyophobic system. Mechanical and thermal characteristics of the MS are presented.

[Communication]
Yaroslav Grosu, Mian Li, Yun-Lei Peng, Dong Luo, Dan Li, Abdessamad Faik, Jean-Marie Nedelec, Jean-Pierre Grolier
ChemPhysChem, September 09, 2016, DOI: 10.1002/cphc.201600567. Read article

Creating Accessible Active Sites in Hierarchical MFI Zeolites for Low-Temperature Acid Catalysis

Creating Accessible Active Sites in Hierarchical MFI Zeolites for Low‐Temperature Acid Catalysis

Pore sorting: Hierarchically-porous architectures of H-ZSM-5 with different Si/Al ratios are highly active and selective for low-temperature acid catalysis. This architecture is introduced by a versatile desilication strategy, and the nature, strength, and the accessibility of the acid sites is elucidated by a variety of physico-chemical characterization tools.

[Full Paper]
Andrea Erigoni, Stephanie H. Newland, Geo Paul, Leonardo Marchese, Robert Raja, Enrica Gianotti
ChemCatChem, September 09, 2016, DOI: 10.1002/cctc.201600729. Read article

Ethylene Epoxidation with Nitrous Oxide over Fe-BTC Metal-Organic Frameworks: A DFT Study

The epoxidation of ethylene with N2O over the metal-organic framework Fe-BTC (BTC = 1,3,5-benzentricarboxylate) has been investigated by means of density functional calculations. Two reaction paths for the production of ethylene oxide and of acetaldehyde were systematically considered in order to assess the efficiency of Fe-BTC for the selective formation of ethylene oxide. The reaction starts with the decomposition of N2O to form an active surface oxygen on the Fe site of Fe-BTC which subsequently reacts with an ethylene molecule, forming an ethyleneoxy intermediates. This intermediate can then either be selectively transformed via 1,2 hydride shift into the undesired product acetaldehyde or into the desired product ethylene oxide by way of ring closure of the intermediate. The ethylene oxide production requires an activation energy of 5.1 kcal/mol, which is only about one third than the activation energy for the acetaldehyde formation (14.3 kcal/mol). The predicted reaction rate constants for the formation of ethylene oxide in the relevant temperature range are about 2-4 orders of magnitude higher than the ones for the acetaldehyde. Altogether, the results suggest that Fe-BTC is a good candidate catalyst for the epoxidation of ethylene by molecular N2O.

[Article]
Thana Maihom, Saowapak Choomwattana, Sippakorn Wannakao, Michael Probst, Jumras Limtrakul
ChemPhysChem, September 08, 2016, DOI: 10.1002/cphc.201600836. Read article

Neon-Bearing Ammonium Metal Formates: Formation and Behaviour under Pressure

Neon‐Bearing Ammonium Metal Formates: Formation and Behaviour under Pressure

Neon inclusion: The closed porosity of ammonium metal formates becomes accessible for inclusion of neon upon application of pressure. Using the same pressure conditions, argon cannot enter in the ammonium metal formate structures.

[Communication]
Ines E. Collings, Elena Bykova, Maxim Bykov, Sylvain Petitgirard, Michael Hanfland, Damian Paliwoda, Leonid Dubrovinsky, Natalia Dubrovinskaia
ChemPhysChem, September 06, 2016, DOI: 10.1002/cphc.201600854. Read article

A Novel Three-Dimensional Copper(II) 1,2-Ethylenediphosphonate Framework with Channel-like Voids

A Novel Three‐Dimensional Copper(II) 1,2‐Ethylenediphosphonate Framework with Channel‐like Voids

[Article]
Roberto Köferstein, Michael Arnold, Christian Robl
Z. anorg. allg. Chem., September 05, 2016, DOI: 10.1002/zaac.201600248. Read article

Nanoreactor Based on Macroporous Single Crystals of Metal-Organic Framework

Nanoreactor Based on Macroporous Single Crystals of Metal‐Organic Framework

Au@ZIF-8 nanoreactor with yolkshell nanostructure is synthesized via a sacrificial template approach. The Au@ZIF-8 nanoreactor features single-crystalline metal-organic framework shell with intrinsic monodisperse micropores and introduced macropores, tunable reactor units integrated in each ZIF-8 shell, and large voids in between Au NPs and ZIF-8 shell, which therefore results in its excellent performances toward the catalytic aerobic oxidation of alcohols.

[Full Paper]
Shuhai Wang, Yanan Fan, Jun Teng, Yan-Zhong Fan, Ji-Jun Jiang, Hai-Ping Wang, Hansjörg Grützmacher, Dawei Wang, Cheng-Yong Su
Small, September 04, 2016, DOI: 10.1002/smll.201601873. Read article

Incorporation of Alkylamine into Metal–Organic Frameworks through a Brønsted Acid–Base Reaction for CO2 Capture

Incorporation of Alkylamine into Metal–Organic Frameworks through a Brønsted Acid–Base Reaction for CO2 Capture

Amino-MOF on demand: A Brønsted acid–base reaction based method was employed to incorporate alkylamine into metal–organic frameworks for CO2 capture. The alkylamine molecules are fixed through the electrostatic interaction between sulfonate groups and ammonium groups, which are generated from the proton transfer between sulfonic acid groups and amine groups.

[Full Paper]
Hao Li, Kecheng Wang, Dawei Feng, Ying-Pin Chen, Wolfgang Verdegaal, Hong-Cai Zhou
ChemSusChem, September 01, 2016, DOI: 10.1002/cssc.201600768. Read article

Elucidation of Surface Species through in Situ FTIR Spectroscopy of Carbon Dioxide Adsorption on Amine-Grafted SBA-15

Elucidation of Surface Species through in Situ FTIR Spectroscopy of Carbon Dioxide Adsorption on Amine‐Grafted SBA‐15

Surface species revealed: The formation of CO2 surface species on amine-grafted SBA-15 is observed through in situ FTIR spectroscopy. The results show that the structures of carbamate and carbamic acid species are different between primary and secondary amines, whereas only a small concentration of bicarbonate ions is observed on tertiary amines under ostensibly dry conditions.

[Full Paper]
Guo Shiou Foo, Jason J. Lee, Chia-Hsin Chen, Sophia E. Hayes, Carsten Sievers, Christopher W. Jones
ChemSusChem, August 30, 2016, DOI: 10.1002/cssc.201600809. Read article

Fe/W Co-Doped BiVO4 Photoanodes with a Metal–Organic Framework Cocatalyst for Improved Photoelectrochemical Stability and Activity

Fe/W Co‐Doped BiVO4 Photoanodes with a Metal–Organic Framework Cocatalyst for Improved Photoelectrochemical Stability and Activity

It does it all: The photoelectrochemical stability issue of BiVO4 was successfully resolved by Fe-doping, which can synergize with other means to further improve the PEC activity of BiVO4. Here, a nanoporous Fe/W co-doped BiVO4 photoelectrode modified with a metal–organic framework (MOF) cocatalyst is introduced to further promote the PEC stability and activity.

[Full Paper]
Zhengbo Jiao, Jingjing Zheng, Chenchen Feng, Zeli Wang, Xuesen Wang, Gongxuan Lu, Yingpu Bi
ChemSusChem, August 30, 2016, DOI: 10.1002/cssc.201600761. Read article

Photocatalytic decontamination of wastewater containing organic dyes by metal-organic frameworks and their derivatives

[Minireview]
Zhibin Wu, Xingzhong Yuan, Jin Zhang, Hou Wang, Longbo Jiang, Guangming Zeng
ChemCatChem, August 30, 2016, DOI: 10.1002/cctc.201600808. Read article

Copper-Based Metal–Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols

Copper‐Based Metal–Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols

Closing the loop: Metal–organic porous materials are effective electrocatalysts for the continuous electrochemical conversion of CO2 to alcohols, a process that could promote the transition to a low-carbon economy. The modularity of these systems yields many opportunities for further performance improvements and opens new directions in electrocatalysis.

[Full Paper]
Jonathan Albo, Daniel Vallejo, Garikoitz Beobide, Oscar Castillo, Pedro Castaño, Angel Irabien
ChemSusChem, August 25, 2016, DOI: 10.1002/cssc.201600693. Read article

Highly Crystalline Mesoporous Silicon Spheres for Efficient Visible Photocatalytic Hydrogen Evolution

Highly Crystalline Mesoporous Silicon Spheres for Efficient Visible Photocatalytic Hydrogen Evolution

Highly crystalline mesoporous silicon spheres are developed through a modified salt-assisted aerosol synthesis, and overcome the limitation of particulate silicon in photocatalytic H2 evolution. The developed silicon structures exhibit high efficiency in visible-light-driven H2 production from water, which can otherwise be virtually impossible to attain by counterpart materials.

[Communication]
Hongguang Song, Dong Liu, Jia Yang, Lei Wang, Hangxun Xu, Yujie Xiong
ChemNanoMat, August 24, 2016, DOI: 10.1002/cnma.201600203. Read article

High Energy Density Materials Incorporating 4,5-Bis(dinitromethyl)-Furoxanate and 4,5-Bis(dinitromethyl)-3-Oxy-Furoxanate

High Energy Density Materials Incorporating 4,5‐Bis(dinitromethyl)‐Furoxanate and 4,5‐Bis(dinitromethyl)‐3‐Oxy‐Furoxanate

Energetic MOFs: 3-Oxy-furoxanate was immobilized in a heterometallic energetic metal–organic framework. Two furoxan-based MOFs were synthesized and their energetic performance evaluated (see figure).

[Communication]
Lianjie Zhai, Xiaoni Qu, Bozhou Wang, Fuqiang Bi, Sanping Chen, Xuezhong Fan, Gang Xie, Qing Wei, Shengli Gao
ChemPlusChem, July 29, 2016, DOI: 10.1002/cplu.201600287. Read article

Amide-CO2 Interaction Induced Gate-Opening Behavior for CO2 Adsorption in 2-Fold Interpenetrating Framework

Amide‐CO2 Interaction Induced Gate‐Opening Behavior for CO2 Adsorption in 2‐Fold Interpenetrating Framework

A flexible amide-containing metal-organic framework is comprised of a 2-fold interpenetrating network with amide groups exposed in the channels. The regular arrangement of the amide groups provided significant amide-CO2 and possible amide-CO2-CO2 cooperative effects that enhanced the adsorption of CO2 molecules. Significantly, the findings show that the amide-CO2 interactions induced gate-opening behavior.

[Full Paper]
Cheng-Hua Lee , Hung-Yu Huang , Jey-Jau Lee, Chia-Yuan Huang, Ya-Chuan Kao, Gene-Hsiang Lee, Shie-Ming Peng , Jyh-Chiang Jiang, Ito Chao, Kuang-Lieh Lu
ChemistrySelect, July 26, 2016, DOI: 10.1002/slct.201600345. Read article

Cover Picture: A New Paddlewheel-Type Dirhodium-Based Metal-Organic Framework with Deprotonated 2,6-Bis(2-benzimidazolyl)pyridine (ChemistrySelect 11/2016)

Cover Picture: A New Paddlewheel‐Type Dirhodium‐Based Metal‐Organic Framework with Deprotonated 2,6‐Bis(2‐benzimidazolyl)pyridine (ChemistrySelect 11/2016)

The cover picture shows an artist's representation of the porous metal-organic framework (MOF) constructed from paddlewheel-type dirhodium tetracetate and 2,6-bis(2-benzimidazolyl)pyridine and an intermediate complex in the middle of formation of the MOF. This MOF shows the color-changing behavior from orange-red to yellow-brown depending on the structural decomposition due to the removal of guest solvents from the pores of MOF. The decomposed MOF is easily recovered to the porous MOF by soaking in ethanol. More information can be found in the Full Paper by Yusuke Kataoka, Natsumi Yano, et al. (DOI: 10.1002/slct.201600617).

[Cover Picture]
Natsumi Yano, Yusuke Kataoka, Hidekazu Tanaka, Tatsuya Kawamoto, Makoto Handa
ChemistrySelect, June 30, 2016, DOI: 10.1002/slct.201600725. Read article

A New Paddlewheel-Type Dirhodium-Based Metal-Organic Framework with Deprotonated 2,6-Bis(2-benzimidazolyl)pyridine

A New Paddlewheel‐Type Dirhodium‐Based Metal‐Organic Framework with Deprotonated 2,6‐Bis(2‐benzimidazolyl)pyridine

Two different crystals, orange-red chips (1) and purple blocks (2), are obtained via the solvothermal reaction of [Rh2(OAc)4(H2O)2] (OAc=acetate) and 2,6-bis(2-benzimidazolyl)pyridine (bzimpy2H) in EtOH. Single crystal X-ray diffraction analyses revealed that complex 1 forms a porous two-dimensional framework constructed from [Rh2(OAc)4] and [Rh(bzimpyH)(bzimpy)], whereas complex 2 forms a bis-bzimpy2H-adducted discrete complex, [Rh2(OAc)4(bzimpy2H)2]. Complex 2 shows the color-changing behavior due to the presence of the guest solvents in the pores.

[Full Paper]
Natsumi Yano, Yusuke Kataoka, Hidekazu Tanaka, Tatsuya Kawamoto, Makoto Handa
ChemistrySelect, June 30, 2016, DOI: 10.1002/slct.201600617. Read article

Dopamine-Directed In-Situ and One-Step Synthesis of Au@Ag Core–Shell Nanoparticles Immobilized to a Metal–Organic Framework for Synergistic Catalysis

Dopamine‐Directed In‐Situ and One‐Step Synthesis of Au@Ag Core–Shell Nanoparticles Immobilized to a Metal–Organic Framework for Synergistic Catalysis

There′s a synergy: Bimetallic core–shell Au@Ag NPs were immobilized in MOFs via one-step synthetic route at room temperature by using dopamine (DA) as a moderate reductant to reduce the bimetallic precursors step-by-step spontaneously. The as-formed Au@Ag/MOF composites show a striking synergistic effect for heterogeneous catalysis.

[Communication]
Pengcheng Huang, Wenjie Ma, Ping Yu, Lanqun Mao
Chem. Asian J., June 02, 2016, DOI: 10.1002/asia.201600469. Read article

Assembling Metal–Organic Frameworks in Ionic Liquids and Supercritical CO2

Assembling Metal–Organic Frameworks in Ionic Liquids and Supercritical CO2

Being green: Ionic liquids (ILs) and supercritical carbon dioxide (scCO2) are considered to be green solvents with tunable properties. They have been shown to be ideal media for the synthesis of a variety of metal–organic frameworks (MOFs) with desirable structures and properties (see figure). This review describes advances in MOF synthesis in ILs, scCO2, and IL/scCO2 systems.

[Focus Review]
Bingxing Zhang, Jianling Zhang, Buxing Han
Chem. Asian J., May 24, 2016, DOI: 10.1002/asia.201600323. 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.

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.

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.

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.

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.

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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