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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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Ag-Nanoparticle-Anchored rGO-Coated MIL-88B(Fe) Hybrids as Robust Electrocatalysts for the Highly Efficient Oxygen Evolution Reaction at Neutral pH

Ag‐Nanoparticle‐Anchored rGO‐Coated MIL‐88B(Fe) Hybrids as Robust Electrocatalysts for the Highly Efficient Oxygen Evolution Reaction at Neutral pH

Extended cat.lifetime: A robust water oxidation catalyst, a Ag-nanoparticle-anchored rGO-coated MIL-88B(Fe) hybrid, exhibits remarkable oxygen evolution activity at neutral pH. The designed electrolyzer shows sustained water oxidation with a high current density (1 mA cm−2) at very low overpotential (ca. 395 mV) and an extended lifetime, maintaining the catalyst integrity.

[Article]
Dewan Azharul Islam, Koushik Barman, Sk Jasimuddin, Himadri Acharya
ChemElectroChem, September 25, 2017, https://doi.org/10.1002/celc.201700883 Read article

Conformal Coating of Co/N-Doped Carbon Layers into Mesoporous Silica for Highly Efficient Catalytic Dehydrogenation–Hydrogenation Tandem Reactions

Conformal Coating of Co/N‐Doped Carbon Layers into Mesoporous Silica for Highly Efficient Catalytic Dehydrogenation–Hydrogenation Tandem Reactions

Co-nanocluster-intercalated N-doped carbon layers are conformally coated into mesoporous silicas. The features of ultrasmall Co nanoclusters, including strong N coordination, suitable pore size, and high water dispersibility, make them excellent for tandem catalytic hydrogenation of nitrobenzene and dehydrogenation of NaBH4 with well-matched reaction kinetics, 100% conversion and selectivity, high turnover frequencies, excellent stability, and magnetic recyclability.

[Communication]
Zhujun Zhang, Xiangru Wei, Yan Yao, Zhi Chen, Aijian Zhang, Wei Li, Winston Duo Wu, Zhangxiong Wu, Xiao Dong Chen, Dongyuan Zhao
Small, September 22, 2017, https://doi.org/10.1002/smll.201702243 Read article

In-Situ Fabrication of MOF-Derived Co−Co Layered Double Hydroxide Hollow Nanocages/Graphene Composite: A Novel Electrode Material with Superior Electrochemical Performance

In‐Situ Fabrication of MOF‐Derived Co−Co Layered Double Hydroxide Hollow Nanocages/Graphene Composite: A Novel Electrode Material with Superior Electrochemical Performance

Layer cake: A metal–organic framework derived Co−Co LDH/graphene composite was successfully synthesized through facile co-precipitation method followed by chemical etching. The special hollow nanocages structure of Co−Co LDH combined with high conductivity of graphene nanosheets endowed the material with superior electrochemical performance. Moreover, an asymmetric supercapacitor based on the composite and active carbon exhibit outstanding electrochemical properties ascribed to the co-effect of graphene and Co−Co LDH.

[Full Paper]
Xue Bai, Jingyuan Liu, Qi Liu, Rongrong Chen, Xiaoyan Jing, Bin Li, Jun Wang
Chem. Eur. J., September 22, 2017, https://doi.org/10.1002/chem.201702676 Read article

H2S-Activable MOF Nanoparticle Photosensitizer for Effective Photodynamic Therapy against Cancer with Controllable Singlet-Oxygen Release

H2S‐Activable MOF Nanoparticle Photosensitizer for Effective Photodynamic Therapy against Cancer with Controllable Singlet‐Oxygen Release

Selective cancer treatment: A mixed-metal metal–organic framework nanoparticle photosensitizer has been activated by a H2S-signaling molecule in a specific tumor microenvironment for photodynamic therapy of cancer using controllable singlet-oxygen release. The effective removal of tumors in vivo confirms the satisfactory treatment effect of the photosensitizer.

[Communication]
Yu Ma, Xiangyuan Li, Aijie Li, Peng Yang, Caiyun Zhang, Bo Tang
Angew. Chem. Int. Ed., September 22, 2017, https://doi.org/10.1002/anie.201708005 Read article

Mesoporous Semimetallic Conductors: Structural and Electronic Properties of Cobalt Phosphide Systems

Mesoporous Semimetallic Conductors: Structural and Electronic Properties of Cobalt Phosphide Systems

Phosphorization of ordered mesoporous cobalt oxide generates mesoporous cobalt phosphide. Its electrical conductivity is 37 times higher than that of nonporous CoP, and it displays semimetallic behavior with a negligibly small activation energy of 26 meV at temperatures below 296 K. These properties were attributed to the coexistence of nanocrystalline Co2P phases.

[Communication]
Malay Pramanik, Satoshi Tominaka, Zhong-Li Wang, Toshiaki Takei, Yusuke Yamauchi
Angew. Chem. Int. Ed., September 22, 2017, https://doi.org/10.1002/anie.201707878 Read article

Sustainable Separations of C4-Hydrocarbons by Using Microporous Materials

Sustainable Separations of C4‐Hydrocarbons by Using Microporous Materials

Break the flow: Alkane/alkene separations are probably the most cost-intensive separations today. This review discusses the principles and advantages of adsorptive separation by using zeolites and metal–organic frameworks. Both experimental and theoretical studies are outlined to highlight the challenges and opportunities in C4 separation, with a focus on the separation mechanisms and structure–selectivity correlations.

[Review]
Mascha Gehre, Zhiyong Guo, Gadi Rothenberg, Stefania Tanase
ChemSusChem, September 18, 2017, https://doi.org/10.1002/cssc.201700657 Read article

Kinetic-Controlled Formation of Bimetallic Metal–Organic Framework Hybrid Structures

Kinetic‐Controlled Formation of Bimetallic Metal–Organic Framework Hybrid Structures

Metal–organic framework (MOF) hybrids: Bimetallic MOF hybrids are synthesized in a well-designed manner based on kinetic studies monitored by in situ optical turbidity methods. Distinct growth behaviors of two isostructural monometallic MOFs are first revealed. Bimetallic MOFs with either solid-solution or core–shell nanostructure are further constructed in a kinetic-directed manner, while kinetic-blocked nanostructures are not acquired.

[Full Paper]
Wenhan Guo, Wei Xia, Kunting Cai, Yingxiao Wu, Bin Qiu, Zibin Liang, Chong Qu, Ruqiang Zou
Small, September 14, 2017, https://doi.org/10.1002/smll.201702049 Read article

Immobilizing Organic-Based Molecular Switches into Metal–Organic Frameworks: A Promising Strategy for Switching in Solid State

Immobilizing Organic‐Based Molecular Switches into Metal–Organic Frameworks: A Promising Strategy for Switching in Solid State

Transferring organic-based molecular switches (OMS) from solution into the solid state has remained a big challenge. A promising way to circumvent this issue is harboring the functional OMS within the robust and porous environment of metal–organic frameworks (MOFs) as organic components. This feature article summarizes the recent research progress of OMS-based MOFs, including their switching behaviors and applications.

[Feature Article]
Bo Gui, Yi Meng, Yang Xie, Ke Du, Andrew C.-H. Sue, Cheng Wang
Macromol. Rapid Commun., September 14, 2017, https://doi.org/10.1002/marc.201700388 Read article

Highly Efficient Sorption of Methyl Orange by a Metal–Organic Resin–Alginic Acid Composite

Highly Efficient Sorption of Methyl Orange by a Metal–Organic Resin–Alginic Acid Composite

Waste not, want not: The composite anion-exchange material MOR-1–HA (see structure) showed an exceptional sorption capacity for methyl orange (MO). For the first time, an ion-exchange column containing a metal–organic sorbent was demonstrated to be highly efficient for the removal of dyes from wastewater.

[Full Paper]
Anastasia D. Pournara, Sofia Rapti, Euaggelia Skliri, Gerasimos S. Armatas, Athanassios C. Tsipis, Manolis J. Manos
ChemPlusChem, September 14, 2017, https://doi.org/10.1002/cplu.201700278 Read article

Selective One-Pot Two-Step C−C Bond Formation using Metal–Organic Frameworks with Mild Basicity as Heterogeneous Catalysts

Selective One‐Pot Two‐Step C−C Bond Formation using Metal–Organic Frameworks with Mild Basicity as Heterogeneous Catalysts

Two steps forward… Copper-exchanged metal–organic frameworks (MOFs) show tunable basicity, activity, and selectivity in C−C bond-forming reactions. Herein, these MOFs are used as selective heterogeneous catalysts for the one-pot, two-step (Henry reaction/Michael-type addition) synthesis of neuroactive pharmaceutical intermediates starting from nitromethane and benzaldehyde.

[Communication]
Francisco G. Cirujano, Elena López-Maya, Marleny Rodríguez-Albelo, Elisa Barea, Jorge A. R. Navarro, Dirk E. De Vos
ChemCatChem, September 14, 2017, https://doi.org/10.1002/cctc.201700784 Read article

Performance of MOF-Derived Spinel Type NixCo3-xO4-y Nanocages in Efficient Methanol Electro-Oxidation

Performance of MOF‐Derived Spinel Type NixCo3‐xO4‐y Nanocages in Efficient Methanol Electro‐Oxidation

I want MOR: Excellent MOR activity is observed in MOF-derived NixCo3-xO4-y, which is compared to Co3O4 and found to be superior.

[Article]
Rajini P. Antony, Ashis K. Satpati, Bhagawantrao N. Jagatap
ChemElectroChem, September 12, 2017, https://doi.org/10.1002/celc.201700832 Read article

Photocatalytic Overall Water Splitting over MIL-125(Ti) upon CoPi and Pt Co-catalyst Deposition

Photocatalytic Overall Water Splitting over MIL‐125(Ti) upon CoPi and Pt Co‐catalyst Deposition

Time to split: Photocatalytic overall water splitting is realized by taking advantage of the semiconductive and porous properties of MIL-125(Ti). CoPi and Pt are deposited into MIL-125(Ti) in two steps, and the as-prepared MIL-125(Ti)-CoPi-Pt produces stoichiometric H2 and O2 evolution from pure water with no external bias. The co-catalysts CoPi and Pt not only act as reactive sites for oxygen and hydrogen evolution, respectively, but also decrease the overpotential of O2 and H2 evolution from water and improve the photogenerated charge separation efficiency.

[Communication]
Yang An, Benyan Xu, Yuanyuan Liu, Zeyan Wang, Peng Wang, Ying Dai, Xiaoyan Qin, Xiaoyang Zhang, Baibiao Huang
ChemistryOpen, September 07, 2017, https://doi.org/10.1002/open.201700100 Read article

Sensitive Photoacoustic IR Spectroscopy for the Characterization of Amino/Azido Mixed-Linker Metal–Organic Frameworks

Sensitive Photoacoustic IR Spectroscopy for the Characterization of Amino/Azido Mixed‐Linker Metal–Organic Frameworks

Photoacoustic Fourier-transform IR spectroscopy makes it possible to determine the organic composition of mixed-linker metal–organic frameworks (MOFs). The sound produced upon IR irradiation enables the discrimination of azido and amino linkers in three different MOF platforms with a sensitivity that is two orders of magnitude higher than that achieved using classic IR analysis.

[Communication]
Jerome Canivet, Vladimir Lysenko, Jaakko Lehtinen, Alexandre Legrand, Florian M. Wisser, Elsje Alessandra Quadrelli, David Farrusseng
ChemPhysChem, September 07, 2017, https://doi.org/10.1002/cphc.201700663 Read article

Single Cell Fabrication Towards the Realistic Evaluation of a CNT-Strung ZIF-Derived Electrocatalyst as a Cathode Material in Alkaline Fuel Cells and Metal−Air Batteries

Single Cell Fabrication Towards the Realistic Evaluation of a CNT‐Strung ZIF‐Derived Electrocatalyst as a Cathode Material in Alkaline Fuel Cells and Metal−Air Batteries

Keeping it real: A maximum power density of 296 and 60 mW/cm2 in single cell zinc-air battery and anion exchange membrane fuel cell systems, respectively, establishes the CoNC-900 electrocatalyst to have practical proficiency as a cathode electrocatalyst for real-world energy applications.

[Article]
Harshitha Barike Aiyappa, Siddheshwar N. Bhange, Vijitha P. Sivasankaran, Sreekumar Kurungot
ChemElectroChem, September 07, 2017, https://doi.org/10.1002/celc.201700562 Read article

Metal-organic Frameworks (MOFs) as Functional Supramolecular Architectures for Anion Recognition and Sensing

Metal‐organic Frameworks (MOFs) as Functional Supramolecular Architectures for Anion Recognition and Sensing

Metal-organic frameworks (MOFs) have experienced a tremendous growth during last few decades as porous crystalline molecular materials. The comprehensive effect of structural diversity, tunability and high surface area makes MOFs suitable for multifarious applications. MOFs can act as potential receptors toward various target components including ionic species, small molecules, solvents, explosives etc. Anion recognition remains important phenomena considering many chemical and biological processes. Ligand designing, incorporation of appropriate function groups and post-synthetic modifications are key strategies in MOFs for selective recognition and scavenging of environmentally toxic and detrimental anions (i. e. cyanide, oxo-anions etc.). The main focus of this personal account is on our research towards development and potential applications of MOFs with special emphasis on selective and sensitive anion sensing.

[Personal Account]
Tarak Nath Mandal, Avishek Karmakar, Shivani Sharma, Sujit K. Ghosh
Chem. Rec., September 06, 2017, https://doi.org/10.1002/tcr.201700033 Read article

Silica-Modified Electrodes for Electrochemical Detection of Malachite Green

Silica‐Modified Electrodes for Electrochemical Detection of Malachite Green

[Full Paper]
Ana Maria Sacara, Valentina Nairi, Andrea Salis, Graziella Liana Turdean, Liana Maria Muresan
Electroanalysis, September 06, 2017, https://doi.org/10.1002/elan.201700400 Read article

A Zinc(II) Porous Metal–Organic Framework and Its Morphologically Controlled Catalytic Properties in the Knoevenagel Condensation Reaction

A Zinc(II) Porous Metal–Organic Framework and Its Morphologically Controlled Catalytic Properties in the Knoevenagel Condensation Reaction

Get in shape: Zinc metal–organic framework (MOF) microcrystals with different morphologies were synthesized through coordination modulation and solvent-dependent methods and their catalytic performance in Knoevenagel condensation was studied (see figure). The catalytic properties of the MOF microcrystals is highly depended on the morphology.

[Full Paper]
Jiajia Wang, Xiaoxiao Wang, Haitao Xu, Xi Zhao, Zhizhong Zheng, Zhen-liang Xu
ChemPlusChem, September 06, 2017, https://doi.org/10.1002/cplu.201700327 Read article

Nitrogen-Doped Porous Carbon Matrix Derived from Metal-Organic Framework-Supported Pt Nanoparticles with Enhanced Oxygen Reduction Activity

Nitrogen‐Doped Porous Carbon Matrix Derived from Metal‐Organic Framework‐Supported Pt Nanoparticles with Enhanced Oxygen Reduction Activity

Hard to resist: A porous nitrogen-doped carbon matrix of NH2-MIL-101-C, derived from the NH2-MIL-101 precursor, is applied as a corrosion-resistant support matrix for the targeted growth of Pt nanoparticles. The oxygen reduction reaction activity in basic medium is subsequently explored, and the enhanced mass activity and specific activity of the catalyst relative to the commercial Pt/C catalyst gives promise for practical alkaline fuel cell applications.

[Article]
Wenling Gu, Changshuai Shang, Jing Li, Erkang Wang
ChemElectroChem, September 06, 2017, https://doi.org/10.1002/celc.201700632 Read article

Mesoporous Ceria-Supported Gold Catalysts Self-Assembled from Monodispersed Ceria Nanoparticles and Nanocubes: A Study of the Crystal Plane Effect for the Low-Temperature Water Gas Shift Reaction

Mesoporous Ceria‐Supported Gold Catalysts Self‐Assembled from Monodispersed Ceria Nanoparticles and Nanocubes: A Study of the Crystal Plane Effect for the Low‐Temperature Water Gas Shift Reaction

Leaving on a crystal plane: We compare the water gas shift reaction activity over Au/CeO2 catalysts assembled by CeO2 nanocrystals with different naked crystal planes to illustrate the nanoscale crystal plane effect of the CeO2 {1 0 0} and {1 1 1} crystal planes.

[Full Paper]
Yeheng He, Sanya Du, Jianwei Li, Runduo Zhang, Xin Liang, Biaohua Chen
ChemCatChem, September 05, 2017, https://doi.org/10.1002/cctc.201700645 Read article

Voltammetric Determination of Captopril on a Glassy Carbon Electrode Modified with Copper Metal-Organic Framework

Voltammetric Determination of Captopril on a Glassy Carbon Electrode Modified with Copper Metal‐Organic Framework

[Full Paper]
Wellyton Silva Vasconcelos, Gilvaldo Gentil da Silva, Severino Alves Junior, Janaína Versiani dos Anjos, Madalena Carneiro da Cunha Areias
Electroanalysis, September 04, 2017, https://doi.org/10.1002/elan.201700384 Read article

Cobalt Phosphide Coupled with Heteroatom-Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long-Life Rechargeable Zinc–Air Batteries

Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long‐Life Rechargeable Zinc–Air Batteries

High-performance rechargeable zinc–air batteries (ZABs) are demonstrated with air electrodes consisting of 1D, cobalt phosphide supported onto N-,S-,P-codoped carbon hybrid catalysts. The presence of a high content of cobalt phosphite and its in situ conversion to cobalt oxide during ZAB operation minimizes the decomposition of carbon even at high current densities over a long period of time, resulting in low overpotentials for the discharge–charge cycles without compromising the performance of the ZABs.

[Full Paper]
Sung Hoon Ahn, Arumugam Manthiram
Small, September 01, 2017, https://doi.org/10.1002/smll.201702068 Read article

Zinc Imidazolate Metal–Organic Frameworks (ZIF-8) for Electrochemical Reduction of CO2 to CO

Zinc Imidazolate Metal–Organic Frameworks (ZIF‐8) for Electrochemical Reduction of CO2 to CO

Zeolitic imidazolate frameworks (ZIF-8) are synthesized using various zinc sources in aqueous solution. These materials are effective catalysts for electrochemical reduction of CO2, with CO as the major product. The roles of the electrolyte and Zn nodes are investigated in detail.

[Communication]
Yulin Wang, Pengfei Hou, Zhuo Wang, Peng Kang
ChemPhysChem, August 16, 2017, https://doi.org/10.1002/cphc.201700716 Read article

Molecular Mechanism of Swing Effect in Zeolitic Imidazolate Framework ZIF-8: Continuous Deformation upon Adsorption

Molecular Mechanism of Swing Effect in Zeolitic Imidazolate Framework ZIF‐8: Continuous Deformation upon Adsorption

The flexibility of zeolitic imidazolate framework ZIF-8 and its “swing” effect are investigated by first-principles molecular dynamics.

[Article]
François-Xavier Coudert
ChemPhysChem, August 04, 2017, https://doi.org/10.1002/cphc.201700463 Read article

Two New Fluorogenic Aptasensors Based on Capped Mesoporous Silica Nanoparticles to Detect Ochratoxin A

Two New Fluorogenic Aptasensors Based on Capped Mesoporous Silica Nanoparticles to Detect Ochratoxin A

Pop the cap: Two new fluorogenic aptasensors based on capped mesoporous silica nanoparticles for the detection of ochratoxin A (OTA) are prepared. The presence of OTA induces displacement of the aptamer from the solid surface, opens the pores, and selectively releases dye (see figure). These new capped nanomaterials allow accurate determination of OTA in realistic wheat samples and may allow the development of a simple test for the detection of OTA in food samples.

[Full Paper]
Àngela Ribes, Sara Santiago-Felipe, Andrea Bernardos, M. Dolores Marcos, Teresa Pardo, Félix Sancenón, Ramón Martínez-Máñez, Elena Aznar
ChemistryOpen, August 02, 2017, https://doi.org/10.1002/open.201700106 Read article

Stimuli-Responsive Metal-Organic Frameworks with Photoswitchable Azobenzene Side Groups

Stimuli‐Responsive Metal‐Organic Frameworks with Photoswitchable Azobenzene Side Groups

Metal-organic frameworks (MOFs) are nanoporous, crystalline hybrid materials that enable remote control over their key properties by incorporating linker molecules with photoswitchable azobenzene side groups. The applications of these stimuli-responsive nanoporous solids range from switching the adsorption capacity of various gases over remote-controlled release of guest molecules to continuously tunable membrane separation of molecular mixtures.

[Review]
Anemar Bruno Kanj, Kai Müller, Lars Heinke
Macromol. Rapid Commun., July 31, 2017, https://doi.org/10.1002/marc.201700239 Read article

CO2 Cycloaddition to Epoxides by using M-DABCO Metal–Organic Frameworks and the Influence of the Synthetic Method on Catalytic Reactivity

CO2 Cycloaddition to Epoxides by using M‐DABCO Metal–Organic Frameworks and the Influence of the Synthetic Method on Catalytic Reactivity

The route matters: A series of M2(BDC)2(DABCO) (M=Zn, Co, Ni, Cu; BDC=1,4-benzene dicarboxylate; DABCO=1,4-diazabicyclo[2.2.2]octane) metal–organic frameworks (M-DABCO) are prepared by using a solvothermal route, and their activity in the cycloaddition of CO2 to epoxides is investigated. The most active catalyst, Zn-DABCO, is also prepared by using a spray-drying method and the physicochemical properties of both types of Zn-DABCO are compared.

[Full Paper]
Bibimaryam Mousavi, Somboon Chaemchuen, Behrooz Moosavi, Kui Zhou, Mekhman Yusubov, Francis Verpoort
ChemistryOpen, July 20, 2017, https://doi.org/10.1002/open.201700060 Read article

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