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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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Serendipitous Observation of Liquid-Phase Size Selectivity inside a Mesoporous Silica Nanoreactor in the Reaction of Chromene with Formic Acid

Serendipitous Observation of Liquid‐Phase Size Selectivity inside a Mesoporous Silica Nanoreactor in the Reaction of Chromene with Formic Acid

Shape up: Unprecedented product shape selectivity in the hydrolysis/decarboxylation reaction sequences of chromene with formic acid within MCM-41 as nanoreactor in the liquid phase affords enol lactones and δ-keto acids.

[Full Paper]
Paramita Das, Suman Ray, Piyali Bhanja, Asim Bhaumik, Chhanda Mukhopadhyay
ChemCatChem, March 15, 2018, https://doi.org/10.1002/cctc.201701975 Read article

Thermal Transition of Bimetallic Metal–Phenolic Networks to Biomass-Derived Hierarchically Porous Nanofibers

Thermal Transition of Bimetallic Metal–Phenolic Networks to Biomass‐Derived Hierarchically Porous Nanofibers

Waste nothing: A bimetallic metal–phenolic network was used to convert collagen fibers from leather industry waste to functional hierarchically porous nanofibers.

[Communication]
Gao Xiao, Wei Chen, Fan Tian, Joseph J. Richardson, Blaise L. Tardy, Minghua Liu, Neel S. Joshi, Junling Guo
Chem. Asian J., March 15, 2018, https://doi.org/10.1002/asia.201800284 Read article

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

A buffer strategy boosts the aqueous stability of a MOF over a broad range of pH values. The local buffer environment resulting from the weak acid–base pairs (green/blue bars on right of picture) of the custom-designed organic ligand also greatly facilitates the performance of MOF in chemical fixation of carbon dioxide under ambient conditions.

[Communication]
Hongming He, Qi Sun, Wenyang Gao, Jason A. Perman, Fuxing Sun, Guangshan Zhu, Briana Aguila, Katherine Forrest, Brian Space, Shengqian Ma
Angew. Chem. Int. Ed., March 15, 2018, https://doi.org/10.1002/anie.201801122 Read article

Ultrathin 2D Zirconium Metal–Organic Framework Nanosheets: Preparation and Application in Photocatalysis

Ultrathin 2D Zirconium Metal–Organic Framework Nanosheets: Preparation and Application in Photocatalysis

Ultrathin zirconium-porphyrinic metal–organic framework (MOF) nanosheets with thickness down to 1.5 nm are synthesized through a pseudo-assembly–disassembly strategy. Owing to the their unique properties originating from their ultrathin thickness and highly accessible active sites, the as-prepared ultrathin nanosheets exhibit far superior photocatalysis performance compared with the corresponding bulk MOF.

[Communication]
Ting He, Bing Ni, Simin Zhang, Yue Gong, Haiqing Wang, Lin Gu, Jing Zhuang, Wenping Hu, Xun Wang
Small, March 13, 2018, https://doi.org/10.1002/smll.201703929 Read article

Enhanced Li Storage Stability Induced by Locating Sn in Metal–Organic Frameworks

Enhanced Li Storage Stability Induced by Locating Sn in Metal–Organic Frameworks

Tin can: By locating elemental Sn in an open anionic framework, the particle cracking arising from huge volume expansion of Sn-based anode materials during lithiation/delithiation is alleviated, and the cycling stability is greatly improved (the capacity retention is >92 % after 200 cycles).

[Communication]
Na Wu, Wei Wang, Lu-Qing Kou, Xue Zhang, Ya-Ru Shi, Tao-Hai Li, Feng Li, Jing-Ming Zhou, Yu Wei
Chem. Eur. J., March 13, 2018, https://doi.org/10.1002/chem.201800215 Read article

POM & MOF-based Electrocatalysts for Energy-related Reactions

POM & MOF‐based Electrocatalysts for Energy‐related Reactions

Energy for humanity: A global-scale sustainable energy system, based in renewable energy storage and conversion technologies, is crucial for the future of humanity. POM- & MOF-based materials are promising electrocatalysts for the energy-related electrochemical reactions (oxygen reduction and evolution reactions and hydrogen evolution reaction).

[Review]
Cristina Freire, Diana M. Fernandes, Marta Nunes, Victor K. Abdelkader
ChemCatChem, March 13, 2018, https://doi.org/10.1002/cctc.201701926 Read article

Facile Synthesis of A 3D Flower-Like Mesoporous Ni@C Composite Material for High-Energy Aqueous Asymmetric Supercapacitors

Facile Synthesis of A 3D Flower‐Like Mesoporous Ni@C Composite Material for High‐Energy Aqueous Asymmetric Supercapacitors

Flower power: A new 3D flower-like mesoporous Ni@C composite material was synthesized by using a one-pot hydrothermal method. At a calcination temperature of 700 °C, the Ni@C composite delivered the best electrochemical performance, with high capacity (1306 F g−1 at a current density of 2 A g−1) and excellent cycling performance (96.7 % retention after 5000 cycles).

[Full Paper]
Song Liu, Cuihua An, Lei Zang, Xiaoya Chang, Huinan Guo, Lifang Jiao, Yijing Wang
Chem. Asian J., March 13, 2018, https://doi.org/10.1002/asia.201800056 Read article

Electrochemical Exfoliation of Pillared-Layer Metal–Organic Framework to Boost the Oxygen Evolution Reaction

Electrochemical Exfoliation of Pillared‐Layer Metal–Organic Framework to Boost the Oxygen Evolution Reaction

MOF slicing: A pillared-layer metal–organic framework (MOF), in which the catechol functionalized pillars can be oxidized and removed in an electrochemical process, gives ultrathin nanosheets (2 nm). These are efficient electrocatalysts for water oxidation at pH 13 with a low overpotential and high turnover frequency (TOF).

[Communication]
Jin Huang, Yun Li, Rui-Kang Huang, Chun-Ting He, Li Gong, Qiong Hu, Lishi Wang, Yan-Tong Xu, Xiao-Yun Tian, Si-Yang Liu, Zi-Ming Ye, Fuxin Wang, Dong-Dong Zhou, Wei-Xiong Zhang, Jie-Peng Zhang
Angew. Chem. Int. Ed., March 13, 2018, https://doi.org/10.1002/anie.201801029 Read article

Confinement Effects on the Benzene Orientational Structure

Confinement Effects on the Benzene Orientational Structure

Nanoscale confinement: Benzene molecules confined in pores have a different structure than in the bulk phase. The confined benzene molecules are studied experimentally by total neutron scattering. Discrepancies are marked in molecule–molecule distances and molecule–molecule orientation.

[Communication]
Marta Falkowska, Daniel T. Bowron, Haresh Manyar, Tristan G. A. Youngs, Christopher Hardacre
Angew. Chem. Int. Ed., March 13, 2018, https://doi.org/10.1002/anie.201713115 Read article

An Organic Mixed-Valence Ligand for Multistate Redox-Active Coordination Networks

An Organic Mixed‐Valence Ligand for Multistate Redox‐Active Coordination Networks

A redox-active coordination network was prepared in a solvent-free molten-metal process with the new multistate redox-active/multi-interactive ligand H2TPP. The ligand as well as the network can adopt multiple redox states, including mixed-valence (MV) states, owing to the two redox-active moieties in the H2TPP ligand.

[Communication]
Joo Yeon Ha, Jin Young Koo, Hiroyoshi Ohtsu, Yumi Yakiyama, Kimoon Kim, Daisuke Hashizume, Masaki Kawano
Angew. Chem. Int. Ed., March 13, 2018, https://doi.org/10.1002/anie.201713035 Read article

Electrophoretic Nuclei Assembly for Crystallization of High-Performance Membranes on Unmodified Supports

Electrophoretic Nuclei Assembly for Crystallization of High‐Performance Membranes on Unmodified Supports

A novel electrophoretic nuclei assembly for crystallization of thin-films approach is presented, which allows control over the heterogeneous nucleation of metal–organic frameworks (MOFs) on a wide range of unmodified supports, facilitating the growth of ultrathin MOF membranes. The resulting ZIF-8 membrane shows one of the best gas separation performances for MOF membranes.

[Full Paper]
Guangwei He, Mostapha Dakhchoune, Jing Zhao, Shiqi Huang, Kumar Varoon Agrawal
Adv. Funct. Mater., March 12, 2018, https://doi.org/10.1002/adfm.201707427 Read article

Web-Like Interconnected Carbon Networks from NaCl-Assisted Pyrolysis of ZIF-8 for Highly Efficient Oxygen Reduction Catalysis

Web‐Like Interconnected Carbon Networks from NaCl‐Assisted Pyrolysis of ZIF‐8 for Highly Efficient Oxygen Reduction Catalysis

A hierarchically porous carbon network with interconnectivity is prepared from salt/metal–organic framework composites. The carbon network demonstrates comparable activity and durability toward the oxygen reduction reaction compared with Pt/C. When it is equipped in the cathodes of primary Zn–air batteries, a 150 h battery life can be achieved, which triples that of the batteries catalyzed by noble metals.

[Full Paper]
Yuhong Qian, Tao An, Karl Erik Birgersson, Zhaolin Liu, Dan Zhao
Small, March 09, 2018, https://doi.org/10.1002/smll.201704169 Read article

Designed Meso-macroporous Silica Framework Impregnated with Copper Oxide Nanoparticles for Enhanced Catalytic Performance

Designed Meso‐macroporous Silica Framework Impregnated with Copper Oxide Nanoparticles for Enhanced Catalytic Performance

Twin peaks: The template efficacy of solid lipid nanoparticles for generating porous silica materials with the amalgamation of Cu-functionalized cetylpyridinium chloride has been explored. Impregnation of CuO nanoparticles (∼10–12 nm) onto the silica matrix proved to be a propitious route for the fabrication of twin sized porous, highly active catalytic materials.

[Full Paper]
Rohini Kanwar, Rekha Bhar, Surinder Kumar Mehta
ChemCatChem, March 09, 2018, https://doi.org/10.1002/cctc.201701630 Read article

Anisotropic Thermal and Guest-Induced Responses of an Ultramicroporous Framework with Rigid Linkers

Anisotropic Thermal and Guest‐Induced Responses of an Ultramicroporous Framework with Rigid Linkers

The metal–organic framework [Cu3(cdm)4] exhibits areal negative thermal expansion over a broad temperature range. In situ neutron scattering and DFT calculations provided considerable insight into the underlying atomistic causes of this phenomenon, the influence of adsorbed guest molecules, and the implications for potential temperature-mediated adsorption in ultramicroporous frameworks (see figure).

[Communication]
Josie E. Auckett, Samuel G. Duyker, Ekaterina I. Izgorodina, Chris S. Hawes, David R. Turner, Stuart R. Batten, Vanessa K. Peterson
Chem. Eur. J., March 08, 2018, https://doi.org/10.1002/chem.201800261 Read article

Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitors and Redox Electrolyte Energy Storage

Ultrathin Hierarchical Porous Carbon Nanosheets for High‐Performance Supercapacitors and Redox Electrolyte Energy Storage

Shape-controlled 2D hierarchical nanoporous carbon sheets derived from metal–organic framework achieving excellent surface-area-normalized capacitance are prepared. Further, the effect of the addition of KI redox-active species in the aqueous electrolyte to enhance the performance is explored.

[Communication]
Kolleboyina Jayaramulu, Deepak P. Dubal, Bhawna Nagar, Vaclav Ranc, Ondrej Tomanec, Martin Petr, Kasibhatta Kumara Ramanatha Datta, Radek Zboril, Pedro Gómez-Romero, Roland A. Fischer
Adv. Mater., March 08, 2018, https://doi.org/10.1002/adma.201705789 Read article

Lipase Encapsulation onto ZIF-8: A Comparison between Biocatalysts Obtained at Low and High Zinc/2-Methylimidazole Molar Ratio in Aqueous Medium

Lipase Encapsulation onto ZIF‐8: A Comparison between Biocatalysts Obtained at Low and High Zinc/2‐Methylimidazole Molar Ratio in Aqueous Medium

Low vs. high molar ratio: Rhizomucor miehei and Pseudomonas fluorescens lipases were encapsulated on ZIF-8 support by a “one-pot” aqueous synthesis. The effect of two different zinc/ligand molar ratios on enzyme loading and activity was investigated.

[Full Paper]
Federica Pitzalis, Cristina Carucci, Maryam Naseri, Lida Fotouhi, Edmond Magner, Andrea Salis
ChemCatChem, March 07, 2018, https://doi.org/10.1002/cctc.201701984 Read article

Nanoscaled Metal-Organic Frameworks for Biosensing, Imaging, and Cancer Therapy

Nanoscaled Metal‐Organic Frameworks for Biosensing, Imaging, and Cancer Therapy

The recent progress in the development of nanoscaled metal-organic frameworks for biomedical application is reviewed via a broad perspective. Typical examples in biosensing, molecular imaging, cancer treatment, and cancer theranostics are discussed. The remaining problems and promising breakthroughs in this field are also outlined.

[Review]
Jingrong Zhou, Gan Tian, Lijuan Zeng, Xueer Song, Xiu-wu Bian
Adv. Healthcare Mater., March 06, 2018, https://doi.org/10.1002/adhm.201800022 Read article

Controlled Polymerization of Isoprene with Chromium-Based Metal-Organic Framework Catalysts: Switching from Cyclic to cis-1,4-Selectivity Depending on Activator

Controlled Polymerization of Isoprene with Chromium‐Based Metal‐Organic Framework Catalysts: Switching from Cyclic to cis‐1,4‐Selectivity Depending on Activator

Chromium-MIL-100/101 in combination with activator and AlR3 serve as first heterogeous single-site quasi-living catalysts for the controlled polymerization of isoprene with high activities, high molecular weight cis-1,4-polyisoprenes (PIPs) or low molecular weight cyclic PIPs depending on the activator used. The confinement effect originated from the coordination of byproduct from activator with metal centers of MOFs might give an explanation for these changes.

[Communication]
Fei Gao, Li Zhang, Chao Yu, Xinwen Yan, Shaowen Zhang, Xiaofang Li
Macromol. Rapid Commun., March 05, 2018, https://doi.org/10.1002/marc.201800002 Read article

Metal–Organic-Framework-Assisted In Vivo Bacterial Metabolic Labeling and Precise Antibacterial Therapy

Metal–Organic‐Framework‐Assisted In Vivo Bacterial Metabolic Labeling and Precise Antibacterial Therapy

A novel strategy for in vivo bacterial metabolic labeling and precise antibacterial therapy is developed based on the combination of a metal–organic framework (MOF) as a carrier for amino acid delivery and photosensitizers with aggregation-induced emission characteristics for image and therapy. The formulated MOF-assisted strategy represents a promising alternative to antibiotics in image-guided antibacterial therapy.

[Communication]
Duo Mao, Fang Hu, Kenry, Shenglu Ji, Wenbo Wu, Dan Ding, Deling Kong, Bin Liu
Adv. Mater., March 05, 2018, https://doi.org/10.1002/adma.201706831 Read article

High Capacitive Storage Performance of Sulfur and Nitrogen Codoped Mesoporous Graphene

High Capacitive Storage Performance of Sulfur and Nitrogen Codoped Mesoporous Graphene

Power of two: Sulfur and nitrogen codoped mesoporous graphene derived from the calcination of a composite of mesoporous graphene and thiourea not only presents high porosity, but also exhibits outstanding capacitive behavior, with respect to that of symmetric supercapacitors and lithium-ion hybrid capacitors.

[Full Paper]
Xinlong Ma, Daowei Gao
ChemSusChem, March 02, 2018, https://doi.org/10.1002/cssc.201702457 Read article

Synthesis of N-Doped Mesoporous Carbon Nanorods through Nano-Confined Reaction: High-Performance Catalyst Support for Hydrogenation of Phenol Derivatives

Synthesis of N‐Doped Mesoporous Carbon Nanorods through Nano‐Confined Reaction: High‐Performance Catalyst Support for Hydrogenation of Phenol Derivatives

Totally tubular: N-Doped mesoporous carbon nanorods have been prepared through nano-confined decomposition in silica nanotubes with porous shells, in which limited and slow release of the gaseous water and finite precursor inside the silica nanotubes are responsible for the formation of mesoporous structures (see figure).

[Full Paper]
Xueteng Liu, Fei Pang, Jianping Ge
Chem. Asian J., March 02, 2018, https://doi.org/10.1002/asia.201800112 Read article

Defect-Free Mixed-Matrix Membranes with Hydrophilic Metal-Organic Polyhedra for Efficient Carbon Dioxide Separation

Defect‐Free Mixed‐Matrix Membranes with Hydrophilic Metal‐Organic Polyhedra for Efficient Carbon Dioxide Separation

Flawless M&Ms: Defect-free mixed-matrix membranes (MMMs) were prepared by incorporating hydrophilic metal-organic polyhedra (MOPs) into cross-linked polyethylene oxide (XLPEO) for efficient CO2 separation. In comparison with conventional neat XLPEO, the homogenous dispersion of 5-tri(ethylene glycol) (EG3)-MOPs in XLPEO enhanced CO2 permeability of MMMs. Upon increasing the amount of EG3-MOPs, the membrane performance such as CO2/N2 selectivity was steadily improved because of unsaturated CuII sites at paddle-wheel units.

[Communication]
Yang No Yun, Muhammad Sohail, Jong-Ho Moon, Tae Woo Kim, Kyeng Min Park, Dong Hyuk Chun, Young Cheol Park, Churl-Hee Cho, Hyunuk Kim
Chem. Asian J., February 27, 2018, https://doi.org/10.1002/asia.201701647 Read article

Fabrication of Mesoporous Titania Nanoparticles with Controlled Porosity and Connectivity for Studying the Photovoltaic Properties in Perovskite Solar Cells

Fabrication of Mesoporous Titania Nanoparticles with Controlled Porosity and Connectivity for Studying the Photovoltaic Properties in Perovskite Solar Cells

Mesoporous titania (m-TiO2) nanoparticles are synthesized by treating prehydrolyzed titanium precursors with amphiphilic polyethylene glycol (PEG). By varying the amount of PEG, the physical properties of m-TiO2 are tuned in terms of surface area, pore size/volume, and electrical conductivity. These were employed in electron transport layers for studying the photovoltaic properties of perovskite solar cells.

[Full Paper]
Yuki Tanaka, Siew Lay Lim, Wei Peng Goh, Changyun Jiang, Si Yin Tee, Tao Ye, Xianqiang Li, Khoa Ha Nguyen, Coryl Jing Jun Lee, Ning Ding, Zhaolin Liu, Jishan Wu, Jie Zhang, Ming-Yong Han
ChemNanoMat, February 26, 2018, https://doi.org/10.1002/cnma.201800009 Read article

Emergence of Surface- and Interface-Induced Structures and Properties in Metal–Organic Framework Thin Films

Emergence of Surface‐ and Interface‐Induced Structures and Properties in Metal–Organic Framework Thin Films

[Microreview]
Tomoyuki Haraguchi, Kazuya Otsubo, Hiroshi Kitagawa
Eur. J. Inorg. Chem., February 20, 2018, https://doi.org/10.1002/ejic.201701234 Read article

Self-Assembled Nickel Nanoparticles Supported on Mesoporous Aluminum Oxide for Selective Hydrogenation of Isophorone

Self‐Assembled Nickel Nanoparticles Supported on Mesoporous Aluminum Oxide for Selective Hydrogenation of Isophorone

The Ni for speed: Nickel nanoparticles doped on a mesoporous aluminum oxide catalyst (Ni/MA) were shown to be effective for the selective hydrogenation of the C=C bond in isophorone. The mesoporous structure is believed to play an important role in the high activity and high selectivity through facilitating the mass transfer of substrate and the products.

[Full Paper]
Leilei Hou, Wenqiang Du, Minjie Qu, Xinhong Wang, Shuwei Wang, Song Shi, Ying Sun, Jin Gao, Jie Xu
Asian J. Org. Chem., February 16, 2018, https://doi.org/10.1002/ajoc.201800043 Read article

Growth-Oriented Fe-Based MOFs Synergized with Graphene Aerogels for High-Performance Supercapacitors

Growth‐Oriented Fe‐Based MOFs Synergized with Graphene Aerogels for High‐Performance Supercapacitors

Growth-oriented, rod-like MIL-88-Fe is synthesized on the surface of graphene via one-step solvothermal method, which immensely enhances the electrochemical performances for supercapacitors. The results point to the possibility of using metal–organic framework and functionalized graphene to prepare high-performance electrode with high capacitive volume, fast charge/discharge rate, and reliable cycling stability.

[Full Paper]
Lin Liu, Yang Yan, Zihe Cai, Shengxuan Lin, Xiaobin Hu
Adv. Mater. Interfaces, February 08, 2018, https://doi.org/10.1002/admi.201701548 Read article

Precise Synthesis of Well-defined Inorganic-organic Hybrid Particles

Precise Synthesis of Well‐defined Inorganic‐organic Hybrid Particles

The application of flow reactors to prepare well-defined hybrid particles composed of inorganic oxide and organic compound is summarized. Thanks to the homogeneous reaction achieved by a flow reactor, compositional and structural homogeneity and, on the other hand, complex hierarchical structure are achieved. Flow reactor syntheses of some metal-organic frameworks and graphene-based hybrids are also introduced.

[Personal Account]
Kota Shiba, Makoto Ogawa
Chem. Rec., January 10, 2018, https://doi.org/10.1002/tcr.201700077 Read article

Six Coordination Polymers based on 4-(1H-Imidazol-1-yl)phthalic Acid: Structural Diversities, Magnetism and Luminescence Properties

Six Coordination Polymers based on 4‐(1H‐Imidazol‐1‐yl)phthalic Acid: Structural Diversities, Magnetism and Luminescence Properties

[Article]
Jiye Liang, Wenyan Zhang, Yangtian Yan, Yunlong Wu, Gaopeng Li, Wenquan Tong, Yaoyu Wang
Z. Anorg. Allg. Chem., January 08, 2018, https://doi.org/10.1002/zaac.201700338 Read article

Chemistry in Confinement: Copper and Palladium Catalyzed Ecofriendly Organic Transformations within Porous Frameworks

Chemistry in Confinement: Copper and Palladium Catalyzed Ecofriendly Organic Transformations within Porous Frameworks

Kasi Pitchumani (1954) received his M.Sc., Ph.D. and D.Sc. degrees in Chemistry from Madurai Kamaraj University (MKU), Madurai, India. At present, he is working as a CSIR-Emeritus Scientist in Chemistry and also in Centre for Green Chemistry Processes at School of Chemistry, MKU. He has 35 years of teaching experience in organic and natural products chemistry and published over 190 research articles in peer reviewed journals. Prof. Pitchumani is a recipient of the Tamil Nadu Scientist Award in 2003 under the category of Chemical Sciences and Basic Science Research award from the University Grants Commission, New Delhi. His research interests involve developing green chemical processes using clays, zeolites, cyclodextrins, metal organic frameworks, covalent organic polymers and nanostructured materials for heterogeneous catalytic applications, organic photochemistry and supramolecular chemistry.

[Personal Account]
Basuvaraj Suresh Kumar, Kasi Pitchumani
Chem. Rec., November 24, 2017, https://doi.org/10.1002/tcr.201700056 Read article

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