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.
Double duty: MOF-derived carbons with high nitrogen contents are used as solid-base catalysts and as the support for Pd nanoparticles in tandem catalysis.
Xinle Li, Biying Zhang, Yuhui Fang, Weijun Sun, Zhiyuan Qi, Yuchen Pei, Shuyan Qi, Pengyu Yuan, Xuechen Luan, Tian Wei Goh, Wenyu Huang
Chem. Eur. J., March 24, 2017, https://doi.org/10.1002/chem.201605852 Read article
In full site: A combined biomimetic platform, consisting of a metalloporphyrinic framework, N-hydroxyphthalimide (NHPI), and a polyoxometalate, exhibits enzyme-like features in the aerobic oxidation of arylalkanes under mild conditions with very high efficiency, selectivity, and sustainability by imitating the structural features, active sites, and catalytic mechanism of enzymes; yields up to 99 % and a turnover number of 25 600 are realized.
Min Zhao, Chuan-De Wu
ChemCatChem, March 23, 2017, https://doi.org/10.1002/cctc.201601606 Read article
All in one: Phosphomolybdic acid encapsulated in MIL-101 (PMA–MIL-101) with high Brønsted acidity and moderate redox potential is evaluated as a promising catalyst for the synthesis of 2,5-diformylfuran (DFF) directly from fructose. 2 PMA–MIL-101 is shown to be an efficient and recyclable bifunctional catalyst in this one-pot, one-step reaction in DMSO and is able to achieve a DFF yield of 75.1 %.
Jun Zhao, Jayakumar Anjali, Yibo Yan, Jong-Min Lee
ChemCatChem, March 23, 2017, https://doi.org/10.1002/cctc.201601546 Read article
Promising MOF structures: Single-crystalline multi-shelled hollow metal–organic frameworks (MSHMs) were synthesized through step-by-step crystal growth and subsequent etching processes. The cavity size and shell thickness of each layer in the MSHMs was regulated through careful nucleation and crystallization of the metal–organic frameworks. The MSHM crystals show significantly increased catalytic activity.
Wenxian Liu, Jijiang Huang, Qiu Yang, Shiji Wang, Xiaoming Sun, Weina Zhang, Junfeng Liu, Fengwei Huo
Angew. Chem. Int. Ed., March 23, 2017, https://doi.org/10.1002/anie.201701604 Read article
Let there be light: Solid-confinement conversion provides a facile way to in situ encapsulate semiconductor fluorescent quantum dots (QDs) into a porous, thermally stable, and hydrophobic ZIF-8 thin film for high-performance white light-emitting diodes (LEDs). The resulting QDs@ZIF-8 thin film shows a photoluminescence quantum yield of 86 %, good thermal stability, and long-term durability in air.
Wen Ying, Yiyin Mao, Xiaobing Wang, Yi Guo, Haiping He, Zhizhen Ye, Shuit-Tong Lee, Xinsheng Peng
ChemSusChem, March 22, 2017, https://doi.org/10.1002/cssc.201700223 Read article
Selectivity to 2-methylfuran: Cu-based catalysts are synthesized through the complexation of Cu species with the amine groups used as a template for the synthesis of mesoporous silica materials, and subsequent calcination and reduction leads to the formation of small Cu nanoparticles, which are highly active and selective for the hydrogenation of furfural to 2-methylfuran.
Carmen Pilar Jiménez-Gómez, Juan A. Cecilia, Ramón Moreno-Tost, Pedro Maireles-Torres
ChemSusChem, March 22, 2017, https://doi.org/10.1002/cssc.201700086 Read article
MOF, meet CNT: A unique coupling of intertwined CNTs and strung porous carbon polyhedrons was developed as self-standing cathode host for lithium–sulfur batteries. The resultant sulfur electrode showed excellent cyclability and ultra-high energy density.
Yazhi Liu, Gaoran Li, Jing Fu, Zhongwei Chen, Xinsheng Peng
Angew. Chem. Int. Ed., March 22, 2017, https://doi.org/10.1002/anie.201700686 Read article
All about adsorption: A time-lapse view of the CO2 adsorption process in the CPO-27-M family is obtained with the help of powder synchrotron X-ray diffraction. The results provide insights into the host–guest structures of the CO2 molecules within the metal–organic frameworks on the molecular level and the temperature-dependent order of occupation of the different adsorption sites in the pores.
Breogán Pato-Doldán, Mali H. Rosnes, Pascal D. C. Dietzel
ChemSusChem, March 16, 2017, https://doi.org/10.1002/cssc.201601752 Read article
Dendrimer-like mesoporous silica nanospheres are used as hard templates to fabricate porous hollow carbon nanospheres containing many small Pd nanoparticles on their inner surfaces. The materials exhibit high catalytic activity and selectivity as well as good recyclability in the catalytic oxidation of benzyl alcohol.
Xin Du, Caixia Zhao, Xiaoyu Li, Hongwei Huang, Junhui He, Yongqiang Wen, Xueji Zhang
Eur. J. Inorg. Chem., March 15, 2017, https://doi.org/10.1002/ejic.201700203 Read article
MOF sensor: A luminescent metal-organic framework (MOF) was synthesized and applied to the activity assay of polyphenol oxidase (PPO). With selective response to the o-quinone product, this MOF sensor could reflect the kinetics of PPO-catalyzed phenol oxidation through a fluorescence intensity change in real time. This label-free heterogeneous method exhibits the advantages of high sensitivity, wide substrate adaptability, and minimal effects on the enzymatic reaction.
Yue Li, An Guo, Lan Chang, Wen-Juan Li, Wen-Juan Ruan
Chem. Eur. J., March 15, 2017, https://doi.org/10.1002/chem.201605992 Read article
Ultra-fine (≤2 nm) transition metal (oxide) nanoparticles (NPs), presenting unusual thermal stability, are obtained by a melt infiltration strategy that allows selective diffusion of precursors into the intra-wall pores of a mesoporous scaffold. Catalytic hydrogenation experiments highlight the outstanding activity of the ultra-fine, thermally stable metal (oxide) NPs.
Carmen Ciotonea, Irina Mazilu, Brindusa Dragoi, Cezar Catrinescu, Emil Dumitriu, Adrian Ungureanu, Houshang Alamdari, Sabine Petit, Sébastien Royer
ChemNanoMat, March 14, 2017, https://doi.org/10.1002/cnma.201700014 Read article
Just passing through: The use of a new porous urea-containing metal–organic framework (MOF) that acts as a hydrogen-bond-donating catalyst (HBD) for Friedel–Crafts reactions is explored. Structural arrangement of this MOF creates a porous environment with spatial isolation of the urea moiety, which can potentially solve the problem of self-recognition and aggregation of the urea derivative during the catalytic process.
Purna Chandra Rao, Sukhendu Mandal
ChemCatChem, March 14, 2017, https://doi.org/10.1002/cctc.201601583 Read article
The new zif on the block: Self-assembled supramolecular structures of poly(p-vinylbenzoic acid)-block-polystyrene (PVBA-b-PS) were prepared in selective solvents and used as templates in the synthesis of ZIF-8 nanocrystals. PVBA-b-PS/ZIF-8 composites showed high catalytic performance in the Knoevenagel condensation reaction at room temperature.
Yongfang Yang, Hua Li, Yue Zhang, Hefang Wang, Lidong Xu, Hanying Zhao
Chem. Asian J., March 14, 2017, https://doi.org/10.1002/asia.201700011 Read article
A series of metal-organic gels and aerogels based on the assembly of 1D-coordination polymer nanofibers of formula [M(DTA)]n (MII: Ni, Cu, Pd; DTA: dithiooxamidato) are reported, in which properties such as porosity, chemical inertness, mechanical robustness, and stimuli-responsive electrical conductivity are brought together into an unprecedented material. Gelation approach provides a valuable tool to achieve metal-organic mesoporous materials.
Daniel Vallejo-Sánchez, Pilar Amo-Ochoa, Garikoitz Beobide, Oscar Castillo, Michael Fröba, Frank Hoffmann, Antonio Luque, Pilar Ocón, Sonia Pérez-Yáñez
Adv. Funct. Mater., March 10, 2017, https://doi.org/10.1002/adfm.201605448 Read article
Cleaning up with MOFs: Recent progress in the design and synthesis of metal–organic frameworks (MOFs) and MOF-derived nanomaterials for applications in lithium-ion batteries, sodium-ion batteries, supercapacitors, dye-sensitized solar cells, and heavy-metal-ion detection and removal is reviewed. Remaining major challenges in these fields are discussed and some perspectives for future research efforts in the development of MOFs are also provided.
Zhiqiang Xie, Wangwang Xu, Xiaodan Cui, Ying Wang
ChemSusChem, March 09, 2017, https://doi.org/10.1002/cssc.201601855 Read article
Controlled water dosage: The interaction of controlled doses of water vapor with aminopropyl groups grafted on the surface of mesoporous silica nanoparticles is studied by solid-state NMR and IR spectroscopy and ab initio calculations (see figure). The presence of hydrogen-bonded species, weakly interacting aminopropyl chains with restricted mobility, and a small amount of NH3+ groups was found
Geo Paul, Giorgia Elena Musso, Emanuela Bottinelli, Maurizio Cossi, Leonardo Marchese, Gloria Berlier
ChemPhysChem, March 09, 2017, https://doi.org/10.1002/cphc.201601135 Read article
Enzyme immobilization: A nanoporous carbon derived from metal–organic framework is used as a support for the immobilization of Burkholderia cepacia lipase, and the resulting catalytic system shows good activity for biodiesel production.
Li-Hao Liu, Yung-Han Shih, Wan-Ling Liu, Chia-Her Lin, Hsi-Ya Huang
ChemSusChem, March 07, 2017, https://doi.org/10.1002/cssc.201700142 Read article
A new oriented and homogenous cobalt-metalloporphyrin network thin film by liquid phase epitaxial method is prepared. The thickness of the obtained thin films can be well controlled and their photocurrent property also can be tuned. The present -oriented PIZA-1 thin film has much higher selectivity of benzene over others than that of powder PIZA-1, which can be used as sensor of volatile organic compounds.
De-Jing Li, Zhi-Gang Gu, Ismail Vohra, Yao Kang, Yong-Sheng Zhu, Jian Zhang
Small, March 03, 2017, https://doi.org/10.1002/smll.201604035 Read article
A new generation of photosensitizers, which includes metal-organic framework nanoparticles built from the photosensitizer itself as organic building unit, is described. The precise spatial control over the photosensitizer assembly into well-defined metal-organic framework scaffolds resolve the current solubility and aggregation issues and should therefore potentiate the outcome of nanoparticles-based cancer photodynamic therapy and allow for opening new perspectives in the field.
Marjorie Lismont, Laurent Dreesen, Stefan Wuttke
Adv. Funct. Mater., March 03, 2017, https://doi.org/10.1002/adfm.201606314 Read article
Capturing MOFs: A simple screening strategy is proposed to follow the CO2 adsorption behaviour of 45 metal– organic frameworks (MOFs) that are pre-equilibrated with varying amounts of H2O. Different behaviours are observed and discussed, ranging from large decreases in CO2 uptake with degree of wetting to a negligible influence of water. Materials showing promising CO2 uptake are highlighted as of interest for further studies.
Nicolas Chanut, Sandrine Bourrelly, Bogdan Kuchta, Christian Serre, Jong-San Chang, Paul A. Wright, Philip L. Llewellyn
ChemSusChem, March 02, 2017, https://doi.org/10.1002/cssc.201601816 Read article
Offering support: Enzymes can be immobilized on metal–organic framework (MOF) supports in a rapid and facile manner under mild conditions, and the enzymes retain their catalytic activities.
Victoria Gascón, Cristina Carucci, Mayra B. Jiménez, Rosa M. Blanco, Manuel Sánchez-Sánchez, Edmond Magner
ChemCatChem, March 02, 2017, https://doi.org/10.1002/cctc.201601342 Read article
Some like it hot: The robust hydrophilic and microporous Al dicarboxylate MIL-160(Al) is synthesized on the laboratory pilot scale, following an optimized environmentally benign synthesis route, and shaped as pellets. It is then evaluated under the conditions of a long-term heat-storage application, revealing that MIL-160(Al) outperforms the best inorganic porous solids reported so far.
Anastasia Permyakova, Oleksandr Skrylnyk, Emilie Courbon, Maame Affram, Sujing Wang, U-Hwang Lee, Anil H. Valekar, Farid Nouar, Georges Mouchaham, Thomas Devic, Guy De Weireld, Jong-San Chang, Nathalie Steunou, Marc Frère, Christian Serre
ChemSusChem, March 01, 2017, https://doi.org/10.1002/cssc.201700164 Read article
Powerful ternary mix: A composite of CuO, Fe2O3, and mesocarbon microbeads is prepared by high-energy ball milling and applied as a conversion anode in lithium-ion batteries with a high-voltage Li1.35Ni0.48Fe0.1Mn1.72O4 spinel cathode. The cell has a working voltage of 3.6 V and delivers a capacity of 110 mAh gcathode−1 with a Coulombic efficiency above 99 % after 100 cycles at 148 mA gcathode−1.
Daniele Di Lecce, Roberta Verrelli, Daniele Campanella, Vittorio Marangon, Jusef Hassoun
ChemSusChem, March 01, 2017, https://doi.org/10.1002/cssc.201601638 Read article
Iron grafted over mesoporous silica (8 wt %Fe/SBA-15) is a sustainable, efficient heterogeneous iron catalyst for direct arylation of biphenyl methane C(sp3)−H and benzene C(sp2)−H bonds (see scheme; DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone, DCE=dichloroethane; DTBP=di-tert-butyl peroxide). Unlike homogeneous iron, the 8 wt %Fe/SBA-15 catalyst does not need support from an electron-withdrawing group and additives to arylate benzene and could be successfully recycled five times.
C. Rajendran, G. Satishkumar
ChemCatChem, March 01, 2017, https://doi.org/10.1002/cctc.201601562 Read article
In virtue of the heterogeneous contraction process induced by nonequilibrium heat treatment, Ni x Co3− x O4 multishelled hollow microspheres originating from bimetal–organic frameworks are successfully achieved for high-performance lithium-ion batteries as anode materials. This presented strategy paves the way for a broad range of practical applications of metal–organic framework-derived materials with multishelled hollow structures.
Lan-Lan Wu, Zhuo Wang, Yan Long, Jian Li, Yu Liu, Qi-Shun Wang, Xiao Wang, Shu-Yan Song, Xiaogang Liu, Hong-Jie Zhang
Small, February 28, 2017, https://doi.org/10.1002/smll.201604270 Read article
Biocompatible nanoporphyrin metal–organic framework (NPMOF) built from a porphyrin and Zr exhibits excellent drug adsorption, photodynamic therapy efficiency, and fluorescent imaging property. The integrity of these capabilities into a single platform makes NPMOF advantageous to offer fluorescent imaging-guided chemotherapy-and-photodynamic dual-therapy. This fresh model makes cancer treating more efficient and safe.
Wei Liu, Yong-Mei Wang, Yu-Hao Li, Shi-Jiao Cai, Xue-Bo Yin, Xi-Wen He, Yu-Kui Zhang
Small, February 28, 2017, https://doi.org/10.1002/smll.201603459 Read article
The coupling of TiO2 with the narrow-band-gap semiconductor CdS is utilized to improve the photoresponse of TiO2, and the introduction of graphene into the binary TiO2/CdS material as a charge-transfer promoter is highly expected to enhance the photovoltaic activity.
Yanan Zhang, Chengxiang Wang, Zhimin Yuan, Luyuan Zhang, Longwei Yin
Eur. J. Inorg. Chem., February 27, 2017, https://doi.org/10.1002/ejic.201601535 Read article
A hybrid material of SnO2-based N-doped carbon architectures with robust structures is prepared for lithium-ion battery anodes. The well-optimized hybrid nanostructure effectively prevents the structural degradation caused by the expansion and contraction during cycling, and therefore exhibits high specific capacity, good cycling stability and rate capability.
Dong-Hui Yang, Xianlong Zhou, Ming Zhong, Zhen Zhou, Xian-He Bu
ChemNanoMat, February 22, 2017, https://doi.org/10.1002/cnma.201600371 Read article
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.
Michael Dreifke, Felix J. Brieler, Michael Fröba
ChemCatChem, February 21, 2017, https://doi.org/10.1002/cctc.201601288 Read article
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.
Ning Liu, Zhimin Wu, Meng Li, Shanshan Li, Zhantao Luo, Yongfei Li, Langsheng Pan, Yuejin Liu
ChemCatChem, February 08, 2017, https://doi.org/10.1002/cctc.201601246 Read article
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.
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, https://doi.org/10.1002/cctc.201601236 Read article
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.
Jian Zhou, Yibo Dou, Awu Zhou, Rui-Mei Guo, Min-Jian Zhao, Jian-Rong Li
Adv. Energy Mater., February 02, 2017, https://doi.org/10.1002/aenm.201602643 Read article
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.
Yevhen Fatieiev, Jonas G. Croissant, Kholod Alamoudi, Niveen M. Khashab
ChemPlusChem, January 31, 2017, https://doi.org/10.1002/cplu.201600560 Read article
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).
Till Siepenkoetter, Urszula Salaj-Kosla, Xinxin Xiao, Peter Ó Conghaile, Marcos Pita, Roland Ludwig, Edmond Magner
ChemPlusChem, November 25, 2016, https://doi.org/10.1002/cplu.201600455 Read article
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.
Daniele Cortecchia, Cesare Soci, Massimo Cametti, Annamaria Petrozza, Javier Martí-Rujas
ChemPlusChem, November 10, 2016, https://doi.org/10.1002/cplu.201600477 Read article
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.
Zhihua Fu, Gang Xu
Chem. Rec., October 24, 2016, https://doi.org/10.1002/tcr.201600109 Read article