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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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Immobilization of Alcohol Dehydrogenase from E. coli onto Mesoporous Silica for Application as a Cofactor Recycling System

Immobilization of Alcohol Dehydrogenase from E. coli onto Mesoporous Silica for Application as a Cofactor Recycling System

Back and forth: Alcohol dehydrogenase (ADH) from Escherichia coli was electrostatically immobilized onto the surface of aminopropyl modified mesoporous cellular siliceous foams (MCF-NH2) to enable its use as a cofactor recycling system in the reversible conversion of 2-propanol into acetone. Several pH values for the immobilization were examined along with the MCF-NH2 amount. The ADH uptakes, long-term stabilities, and leaching behavior as well as the Michaelis-Menten kinetics were monitored.

[Full Paper]
Michael Dreifke, Felix J. Brieler, Michael Fröba
ChemCatChem, February 21, 2017, DOI: 10.1002/cctc.201601288. Read article

Synthesis of Dual-Stimuli-Responsive Microcontainers with Two Payloads in Different Storage Spaces for Preprogrammable Release

Synthesis of Dual‐Stimuli‐Responsive Microcontainers with Two Payloads in Different Storage Spaces for Preprogrammable Release

Out of the box: Dual-responsive hybrid microcontainers with two payloads in separate storage spaces—Nile red in the mesopores of silica nanoparticles and 5(6)-carboxyfluorescein diacetate (CFDA) in the hollow core of the microcapsules—were prepared by the straightforward UV-initiated polymerization of Pickering emulsions. The release of Nile red and CFDA could be selectively activated by changing the temperature or pH value (see picture).

[Communication]
Ying Cong, Qiuju Li, Min Chen, Limin Wu
Angew. Chem. Int. Ed., February 21, 2017, DOI: 10.1002/anie.201612291. Read article

Metal–Organic Framework Photosensitized TiO2 Co-catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System

Metal–Organic Framework Photosensitized TiO2 Co‐catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System

To dye for: A 3D metal–organic framework constructed from an anthracene derivative was employed as an efficient sensitizer for anatase TiO2. The co-catalyst was prepared by mechanical mixing, which should be regarded as the simplest synthetic strategy in materials science. The co-catalyst can efficiently photo-eliminate organic dyes under visible light irradiation. Photodegradation experiments were carried out to study the possible mechanism.

[Full Paper]
Ming-Hua Xie, Rong Shao, Xin-Guo Xi, Gui-Hua Hou, Rong-Feng Guan, Peng-Yu Dong, Qin-Fang Zhang, Xiu-Li Yang
Chem. Eur. J., February 20, 2017, DOI: 10.1002/chem.201605282. Read article

Boosting Oxidative Desulfurization of Model and Real Gasoline over Phosphotungstic Acid Encapsulated in Metal–Organic Frameworks: The Window Size Matters

Boosting Oxidative Desulfurization of Model and Real Gasoline over Phosphotungstic Acid Encapsulated in Metal–Organic Frameworks: The Window Size Matters

The window size to success: Phosphotungstic acid (PTA) encapsulated in mesoporous MIL-100(Fe), which has a larger window size than UiO-66 and ZIF-8, exhibits an efficient desulfurization performance for gasoline because of the confinement of the PTA in the pores of the metal–organic framework. This ensures the accessibility of all the organic sulfurs into the confined active sites in the pores.

[Full Paper]
Xu-Sheng Wang, Lan Li, Jun Liang, Yuan-Biao Huang, Rong Cao
ChemCatChem, February 14, 2017, DOI: 10.1002/cctc.201601450. Read article

Low-Temperature Preparation of a Mesoporous Silica Superbase by Employing the Multifunctionality of a La2O3 Interlayer

Low‐Temperature Preparation of a Mesoporous Silica Superbase by Employing the Multifunctionality of a La2O3 Interlayer

Resisting the structural collapse: Mesostructured superbasic sites were generated by employing the formation of La2O3–SBA-15-supported KF through thermal treatment at a low activation temperature of 350 °C under air atmosphere.

[Full Paper]
Ning Liu, Zhimin Wu, Meng Li, Shanshan Li, Zhantao Luo, Yongfei Li, Langsheng Pan, Yuejin Liu
ChemCatChem, February 08, 2017, DOI: 10.1002/cctc.201601246. Read article

Effect of Heat Treatment on the Nitrogen Content and Its Role on the Carbon Dioxide Adsorption Capacity of Highly Ordered Mesoporous Carbon Nitride

Effect of Heat Treatment on the Nitrogen Content and Its Role on the Carbon Dioxide Adsorption Capacity of Highly Ordered Mesoporous Carbon Nitride

Feel the heat! Mesoporous carbon nitrides (MCNs) with rod-shaped morphology and tunable nitrogen contents have been synthesized through a calcination-free method by using ethanol-washed mesoporous SBA-15 as a template at different carbonization temperatures (see figure). Temperature is an effective tool to tune the nitrogen content and CO2 adsorption capacity of mesoporous carbon nitride.

[Full Paper]
Kripal S. Lakhi, Dae-Hwan Park, Stalin Joseph, Siddulu N. Talapaneni, Ugo Ravon, Khalid Al-Bahily, Ajayan Vinu
Chem. Asian J., February 08, 2017, DOI: 10.1002/asia.201601707. Read article

Strategies for Enhancing the Catalytic Performance of Metal–Organic Frameworks in the Fixation of CO2 into Cyclic Carbonates

Strategies for Enhancing the Catalytic Performance of Metal–Organic Frameworks in the Fixation of CO2 into Cyclic Carbonates

A stable MOF: The metal–organic framework MIL-100(Cr) is presented as a promising new heterogeneous catalyst with high activity, selectivity and reusability in the solvent-free synthesis of styrene carbonate from CO2 at mild conditions. Two strategies to increase the reusability of the MOF catalysts are proposed.

[Full Paper]
Masoumeh Taherimehr, Ben Van de Voorde, Lik H. Wee, Johan A. Martens, Dirk E. De Vos, Paolo P. Pescarmona
ChemSusChem, February 06, 2017, DOI: 10.1002/cssc.201601768. Read article

MFI Acid Catalysts with Different Crystal Sizes and Porosity for the Conversion of Furanic Compounds in Alcohol Media

MFI Acid Catalysts with Different Crystal Sizes and Porosity for the Conversion of Furanic Compounds in Alcohol Media

Material changes: Zeolite ZSM-5 can be modified to improve the potential as a heterogeneous catalyst for the conversion of biomass-derived compounds. Solid acid catalysts possessing MFI topology and different crystal sizes and porosities were explored for the conversion of α-angelica lactone (AnL) and 5-(hydroxymethyl)furfural (HMF), in 1-butanol at T=120–170 °C, to give levulinate esters (LE) and furanic ethers.

[Full Paper]
Margarida M. Antunes, Sérgio Lima, Auguste Fernandes, Ana L. Magalhães, Patrícia Neves, Carlos M. Silva, Maria F. Ribeiro, David Chadwick, Klaus Hellgardt, Martyn Pillinger, Anabela A. Valente
ChemCatChem, February 06, 2017, DOI: 10.1002/cctc.201601236. Read article

PEG-Induced Synthesis of Coordination-Polymer Isomers with Tunable Architectures and Iodine Capture

PEG‐Induced Synthesis of Coordination‐Polymer Isomers with Tunable Architectures and Iodine Capture

Iodine can′t get away! Three supramolecular isomers of coordination polymers with the same framework formula and different architectures have been synthesized by using a PEG-induced approach. The dynamic processes of iodine capture and structure–property relationship in these crystal materials have been investigated.

[Full Paper]
Si-Si Zhao, Li Chen, Xiaohua Zheng, Lei Wang, Zhigang Xie
Chem. Asian J., February 03, 2017, DOI: 10.1002/asia.201700018. Read article

MOF Template-Directed Fabrication of Hierarchically Structured Electrocatalysts for Efficient Oxygen Evolution Reaction

MOF Template‐Directed Fabrication of Hierarchically Structured Electrocatalysts for Efficient Oxygen Evolution Reaction

A new strategy for the fabrication of hierarchically structured composites as highly effective and stable electrocatalysts is proposed. The oxidation, sulfurization, carbonization, and phosphorization of premade cobalt carbonate hydroxide@zeolitic-imidazolate-framework-67 (CCH@ZIF-67) produced Co3O4@X (X = Co3O4, CoS, C, and CoP) derivatives, respectively, which as electrocatalysts exhibit excellent performance in the oxygen evolution reaction with low overpotential and high stability.

[Full Paper]
Jian Zhou, Yibo Dou, Awu Zhou, Rui-Mei Guo, Min-Jian Zhao, Jian-Rong Li
Adv. Energy Mater., February 02, 2017, DOI: 10.1002/aenm.201602643. Read article

Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: From Nanospheres to Nanowires

Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: From Nanospheres to Nanowires

In good shape: Periodic mesoporous organosilica (PMO) nanoparticles have been synthesized with tunable morphologies ranging from nanospheres to nanowires via the addition of organic co-solvent(s) to the aqueous template (see figure). The morphology strongly influences the properties and in vitro toxicities of these nanoparticles.

[Communication]
Yevhen Fatieiev, Jonas G. Croissant, Kholod Alamoudi, Niveen M. Khashab
ChemPlusChem, January 31, 2017, DOI: 10.1002/cplu.201600560. Read article

Carbonyl-Grafted g-C3N4 Porous Nanosheets for Efficient Photocatalytic Hydrogen Evolution

Carbonyl‐Grafted g‐C3N4 Porous Nanosheets for Efficient Photocatalytic Hydrogen Evolution

Behind the sheets: Carbonyl-grafted g-C3N4 porous nanosheets (COCNPNS) were fabricated by a two-step thermal process using melamine and oxalic acid as starting reagents followed by thermal etching by O2 (see figure). Under visible-light illumination, the prepared COCNPNS exhibited a superior photocatalytic hydrogen evolution rate.

[Full Paper]
Feng-Yun Su, Wei-De Zhang
Chem. Asian J., January 31, 2017, DOI: 10.1002/asia.201601518. Read article

Rational Design of Metal-Organic Framework Derived Hollow NiCo2O4 Arrays for Flexible Supercapacitor and Electrocatalysis

Rational Design of Metal‐Organic Framework Derived Hollow NiCo2O4 Arrays for Flexible Supercapacitor and Electrocatalysis

A novel hollow and porous NiCo2O4 nanowall array on carbon cloth is fabricated and utilized as an efficient electrode for flexible supercapacitor and oxygen evolution reaction catalysis.

[Full Paper]
Cao Guan, Ximeng Liu, Weina Ren, Xin Li, Chuanwei Cheng, John Wang
Adv. Energy Mater., January 25, 2017, DOI: 10.1002/aenm.201602391. Read article

Metal–Organic Frameworks Derived Cobalt Phosphide Architecture Encapsulated into B/N Co-Doped Graphene Nanotubes for All pH Value Electrochemical Hydrogen Evolution

Metal–Organic Frameworks Derived Cobalt Phosphide Architecture Encapsulated into B/N Co‐Doped Graphene Nanotubes for All pH Value Electrochemical Hydrogen Evolution

Metal–organic framework derived cobalt phosphide nanoparticles encapsulated B/N co-doped graphene nanotubes are fabricated through pyrolysis and phosphidation, which exhibit excellent electrocatalytic activity for hydrogen evolution reaction.

[Communication]
Hassina Tabassum, Wenhan Guo, Wei Meng, Asif Mahmood, Ruo Zhao, Qingfei Wang, Ruqiang Zou
Adv. Energy Mater., January 25, 2017, DOI: 10.1002/aenm.201601671. Read article

Catalyst@Metal Hybrids in a One-Pot Multistep Opposing Oxidation and Reduction Reaction Sequence

Catalyst@Metal Hybrids in a One‐Pot Multistep Opposing Oxidation and Reduction Reaction Sequence

All in one: We report the feasibility of the catalysis of contrasting reactions, oxidation and reduction, in a multistep process that also involves a condensation reaction, all performed with hybrids of catalytic organometallic complexes entrapped within metals ([complex]@metal). Two routes are explored for the multistep process: the combination of an oxidizing Ir complex entrapped in Ag ([Ir]@Ag) and a reducing Rh complex entrapped in Ag ([Rh]@Ag), and [Ir]@Pd, in which [Ir] acts as the oxidizing catalyst, and the Pd was the reducing catalyst.

[Full Paper]
Leora Shapiro, David Avnir
ChemCatChem, January 18, 2017, DOI: 10.1002/cctc.201601386. Read article

Ordered Mesoporous Silica Monoliths as a Versatile Platform for the Study of Magnetic and Photomagnetic Prussian Blue Analogue Nanoparticles

Ordered Mesoporous Silica Monoliths as a Versatile Platform for the Study of Magnetic and Photomagnetic Prussian Blue Analogue Nanoparticles

The use of mesoporous silica as a matrix for the formation of nanoparticles of magnetic and photomagnetic coordination compounds enables the study of the properties of the compounds at the nanoscale owing to the versatility of the synthetic pathway.

[Full Paper]
Robinson Moulin, Emilie Delahaye, Amélie Bordage, Emiliano Fonda, Jean-Pierre Baltaze, Patricia Beaunier, Eric Rivière, Giulia Fornasieri, Anne Bleuzen
Eur. J. Inorg. Chem., January 17, 2017, DOI: 10.1002/ejic.201601196. Read article

A Continuous Carbon Nitride Polyhedron Assembly for High-Performance Flexible Supercapacitors

A Continuous Carbon Nitride Polyhedron Assembly for High‐Performance Flexible Supercapacitors

A continuous carbon nitride polyhedron assembly is developed using a facile pyrolysis method and is further constructed into a flexible supercapacitor with a highly ion-conductive interpenetrating polymer network electrolyte. The high energy capacity of the device along with excellent flexibility demonstrates advancement of the novel assembly strategy, providing new insight into rational design of electrode materials for long-lived flexible energy storage devices.

[Full Paper]
Chao Lu, Dongxing Wang, Jingjing Zhao, Song Han, Wei Chen
Adv. Funct. Mater., January 16, 2017, DOI: 10.1002/adfm.201606219. Read article

Superior Performance of Microporous Aluminophosphate with LTA Topology in Solar-Energy Storage and Heat Reallocation

Superior Performance of Microporous Aluminophosphate with LTA Topology in Solar‐Energy Storage and Heat Reallocation

High-density storage of solar energy or waste heat is offered by a microporous aluminophosphate. Storage is based on sorption of water within the material's pores and is not prone to thermal losses. The aluminophosphate withstands repeated adsorption and desorption without degradation. It is convenient for seasonal energy storage or for the enhancement of the heat-pump performance.

[Full Paper]
Andraž Krajnc, Jure Varlec, Matjaž Mazaj, Alenka Ristić, Nataša Zabukovec Logar, Gregor Mali
Adv. Energy Mater., January 09, 2017, DOI: 10.1002/aenm.201601815. Read article

Structural Diversity of Three Pyrazoyl–Carboxyl Bifunctional Ligand-Based Metal–Organic Frameworks: Luminescence and Magnetic Properties

Structural Diversity of Three Pyrazoyl–Carboxyl Bifunctional Ligand‐Based Metal–Organic Frameworks: Luminescence and Magnetic Properties

Two in one: Three MOFs have been synthesized from the same bifunctional pyrazoyl–carboxyl ligand. Complexes 1 (see figure) and 3 contain dinuclear clusters and reveal a gis zeolite 3D net and a 2D structure, respectively. Complex 3 shows red luminescence as a result of energy transfer from the organic ligand to the EuIII ion. Complex 2 reveals a rare (3,8)-connected tfz-d; UO3 net with an unusual Mn4(COO)6 cluster and shows antiferromagnetic properties.

[Full Paper]
Gao-Peng Li, Hong-Yun Yang, Yong-Zhi Li, Lei Hou, Bin Liu, Yao-Yu Wang
ChemPlusChem, November 29, 2016, DOI: 10.1002/cplu.201600521. Read article

Immobilization of Redox Enzymes on Nanoporous Gold Electrodes: Applications in Biofuel Cells

Immobilization of Redox Enzymes on Nanoporous Gold Electrodes: Applications in Biofuel Cells

Enzymatic fuel cells: Nanoporous gold (NPG) electrodes with tunable pore size from 5 to 60 nm were prepared and utilized for the immobilization of bilirubin oxidase (BOx) and glucose dehydrogenase (GDH) for use in biofuel cells. The devices with NPG-confined enzymes show high power outputs and enhanced long-term operation and storage stability, an improvement associated with the physical confinement of the enzyme within the porous network (see figure).

[Full Paper]
Till Siepenkoetter, Urszula Salaj-Kosla, Xinxin Xiao, Peter Ó Conghaile, Marcos Pita, Roland Ludwig, Edmond Magner
ChemPlusChem, November 25, 2016, DOI: 10.1002/cplu.201600455. Read article

Crystal Engineering of a Two-Dimensional Lead-Free Perovskite with Functional Organic Cations by Second-Sphere Coordination

Crystal Engineering of a Two‐Dimensional Lead‐Free Perovskite with Functional Organic Cations by Second‐Sphere Coordination

Functional cations: A new two-dimensional Cu perovskite containing an optoelectronically active organic cation (orange in the figure) has been synthesized using second-sphere coordination interactions. The material shows near-UV/blue photoluminescence and is stable for months under ambient conditions.

[Communication]
Daniele Cortecchia, Cesare Soci, Massimo Cametti, Annamaria Petrozza, Javier Martí-Rujas
ChemPlusChem, November 10, 2016, DOI: 10.1002/cplu.201600477. Read article

Crystalline, highly oriented MOF thin film: the fabrication and application

Crystalline, highly oriented MOF thin film: the fabrication and application

Crystalline, highly oriented Metal-organic framework (MOF) thin films suggest intriguing possibilities as gas separator, catalysis, proton conduction, photovoltaic device and so on. The current review illustrates some fabrication methods and brings some updated applications of oriented MOF thin films. It is understatement to predict that the highly ordered MOF films will have a promising future for the MOF-based devices.

[Personal Account]
Zhihua Fu, Gang Xu
Chem. Rec., October 24, 2016, DOI: 10.1002/tcr.201600109. Read article

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