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.
Superior catalytic performance of MIL-100(V): The catalytic performance of the MIL-100(M) isostructural series (M=Al, Cr, Fe, In, Sc, V) has been investigated for the Prins condensation of β-pinene and paraformaldehyde to produce nopol (see figure). The catalytic activity of MIL-100(M) correlates linearly with the concentration of accessible Lewis acid sites. Its high activity, stability, and recyclability make MIL-100(V) a promising material for application in various heterogeneous catalytic processes.
Gema Gómez-Pozuelo, Carlos Palomino Cabello, Maksym Opanasenko, Michal Horáček, Jiří Čejka
ChemPlusChem, October 21, 2016, DOI: 10.1002/cplu.201600456. Read article
Porous microsphere electrodes: Olivine-structured composite LiMn0.6Fe0.4PO4/C, which consists of porous microspheres, is synthesized from a coprecipitated transition-metal phosphate as intermediate, followed by spray drying and annealing (see figure). It delivers enhanced electrochemical performance as a cathode material for lithium-ion batteries.
Jianlong Li, Yan Wang, Jinhua Wu, Hang Zhao, Hao Wu, Yun Zhang, Heng Liu
ChemElectroChem, October 21, 2016, DOI: 10.1002/celc.201600467. Read article
Fine tuning of porosity: Controlled in situ ester hydrolysis during metal complexation enables the formation of isostructural phosphonate monoester and phosphonate MOFs with very different gas sorption properties. By tuning of the synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate with increased affinity for CO2.
Benjamin S. Gelfand, Racheal P. S. Huynh, Roger K. Mah, George K. H. Shimizu
Angew. Chem. Int. Ed., October 21, 2016, DOI: 10.1002/anie.201607745. Read article
Four-step SCO: A porous 3D spin crossover (SCO) framework material that displays a four-step transition with long-range ordering of FeII sites is reported. From only one unique site in the high-spin state, three intermediate phases with individual high-spin/low-spin patterns are produced upon cooling to the fully low-spin state.
John E. Clements, Jason R. Price, Suzanne M. Neville, Cameron J. Kepert
Angew. Chem. Int. Ed., October 21, 2016, DOI: 10.1002/anie.201605418. Read article
CO2 triggers a series of environmental and energy problems as the primary greenhouse gas in our daily life. MOFs (metal-organic frameworks) are applied as outstanding heterogeneous catalysts for CO2 chemical transformations. A systematic overview of the development of MOF-based catalysts for CO2 chemical transformations are reviewed, from the first example to the most recent publication.
Hongming He, Jason A. Perman, Guangshan Zhu, Shengqian Ma
Small, October 20, 2016, DOI: 10.1002/smll.201602711. Read article
Going nuclear: Functionalized hierarchical porous frameworks were used for the efficient removal of perrhenate from aqueous solution (see figure).
Debasis Banerjee, Sameh K. Elsaidi, Briana Aguila, Baiyan Li, Dongsang Kim, Michael J. Schweiger, Albert A. Kruger, Christian J. Doonan, Shengqian Ma, Praveen K. Thallapally
Chem. Eur. J., October 20, 2016, DOI: 10.1002/chem.201603908. Read article
A new type of oxygen reduction reaction (ORR) catalyst of Co-N-doped mesoporous carbon hollow sphere (Co-N-mC) is prepared by pyrolysis from elaborately fabricated polystyrene@polydopamine-Co precursors. The obtained catalysts with active Co sites including coordinating Co moieties and Co nanoparticles distributed in highly graphitized mesoporous N-doped carbon hollow spheres exhibit outstanding ORR activity and stability.
Feng Hu, Hongchao Yang, Changhong Wang, Yejun Zhang, Huan Lu, Qiangbin Wang
Small, October 18, 2016, DOI: 10.1002/smll.201602507. Read article
Porous skeletons provide a unique molecular platform for designing photoluminescent materials. Here, the progress and recent achievements in developing new design principles and synthetic strategies for AIE-based porous luminescent materials are summarized. Cutting-edge functions are designed, fundamental issues that need to be addressed presented, and future directions from chemistry, physics, and materials perspectives are predicted.
Sasanka Dalapati, Cheng Gu, Donglin Jiang
Small, October 14, 2016, DOI: 10.1002/smll.201602427. Read article
Dual-emitting MOFs: The anionic luminescent MOF [(CH3)2NH2]2[(Zn2O)L]⋅5 DMF (NENU-519, NENU=Northeast Normal University) was synthesized and is a rare example of an interpenetrated framework with a zeolite BCT topology. The dual-emitting Rh6@NENU-519 composite (Rh6=Rhodamine 6G) can detect volatile organic molecules and distinguishes between the isomers of o-, m-, and p-xylene and ethylbenzene.
Wei Xie, Wen-Wen He, Shun-Li Li, Kui-Zhan Shao, Zhong-Min Su, Ya-Qian Lan
Chem. Eur. J., October 14, 2016, DOI: 10.1002/chem.201603487. Read article
Energy storage: Hierarchically porous carbon materials with a sandwich-like structure have been synthesized through a facile tri-template approach for high-performance symmetric and asymmetric supercapacitors (see figure).
Yiju Li, Chaoji Chen, Tingting Gao, Dongming Zhang, Xiaomei Huang, Yue Pan, Ke Ye, Kui Cheng, Dianxue Cao, Guiling Wang
Chem. Eur. J., October 13, 2016, DOI: 10.1002/chem.201603145. Read article
Mesoporous carbon with a nitrogen-enriched surface was fabricated through pyrolysis of polyelectrolyte brushes. The formed materials exhibited promising electrocatalytic activity towards the oxygen reduction reaction in basic medium and were suitable for carbon dioxide adsorption.
Xiaofeng Li, Fangfang Zhang, Jiao Yuan, Haining Zhang, Mu Pan, Chi Huang, Haolin Tang
ChemNanoMat, October 12, 2016, DOI: 10.1002/cnma.201600252. Read article
Wired up: Nanoporous platinum with small and uniform nanopores, L2-ePt, is electrochemically investigated in rat embryo brain with electrochemical impedance spectroscopy at the dc bias, which is selected to minimize faradaic reactions. Use of a lower electrode impedance leads to less drop of potential at the interface between the electrode and extracellular solution.
Beom Jin Kim, Yang-Rae Kim, Minjee Seo, Eun Joong Kim, Joohee Jeon, Taek Dong Chung
ChemElectroChem, October 12, 2016, DOI: 10.1002/celc.201600404. Read article
Two steps ahead: A novel formate metal–organic framework and activated carbon fiber composite (ACF) was fabricated through a facile two-step strategy involving homogeneous precipitation and template replication. The resultant core–shell composite, ACF@[Ni3(HCOO)6], exhibited superior adsorption performance both in selectivity and capacity for the separation of CH4/N2 to most of other state-of-the-art adsorbents.
Xiao-Wei Liu, Jiang-Liang Hu, Tian-Jun Sun, Ya Guo, Thomas D. Bennett, Xin-Yu Ren, Shu-Dong Wang
Chem. Asian J., October 12, 2016, DOI: 10.1002/asia.201601134. Read article
A metal-organic framework cathode based on vanadium hexacyanoferrate Prussian blue analogues (V/Fe PBAs) is proposed as a breakthrough for high-performance aqueous rechargeable batteries. The V/Fe PBAs provide significantly improved energy storage capacity compared to previously reported other kinds of PBAs, taking advantage of multiple electron involved redox reaction occurring in both of V and Fe ions.
Ji-Hoon Lee, Ghulam Ali, Dong Hyun Kim, Kyung Yoon Chung
Adv. Energy Mater., October 12, 2016, DOI: 10.1002/aenm.201601491. Read article
Diana Julião, Ana C. Gomes, Martyn Pillinger, Rita Valença, Jorge C. Ribeiro, Baltazar de Castro, Isabel S. Gonçalves, Luís Cunha Silva, Salete S. Balula
Eur. J. Inorg. Chem., October 11, 2016, DOI: 10.1002/ejic.201600442. Read article
Makin the most of MOFs: The epoxidation of ethylene into ethylene oxide with nitrous oxide on Fe–1,3,5-benzentricarboxylate metal–organic frameworks is studied by density functional calculations with the M06-L functional.
Thana Maihom, Saowapak Choomwattana, Sippakorn Wannakao, Michael Probst, Jumras Limtrakul
ChemPhysChem, October 11, 2016, DOI: 10.1002/cphc.201600836. Read article
One stroke: Imparting both magnetic properties and enhanced visible-light photocatalytic activity on the hierarchical Fe3O4/MIL-88B(Fe) composite in a one-pot preparation.
Zhaokui Jin, Wenjun Dong, Mu Yang, Jingjing Wang, Hongyi Gao, Ge Wang
ChemCatChem, October 11, 2016, DOI: 10.1002/cctc.201600952. Read article
Controlling the structure of biomaterials on a molecular level is crucial for their performance. The synthesis and post-synthetic modification of ideal network polymer thin films via orthogonal metal-free click chemistries is described and it is demonstrated that these surface-grafted gels (SURGELs) combined with post-synthetic surface biofunctionalization are suitable materials for implant coatings and nanomedicine.
Sophia Schmitt, Julia Hümmer, Saskia Kraus, Alexander Welle, Sylvain Grosjean, Maximilian Hanke-Roos, Axel Rosenhahn, Stefan Bräse, Christof Wöll, Cornelia Lee-Thedieck, Manuel Tsotsalas
Adv. Funct. Mater., October 10, 2016, DOI: 10.1002/adfm.201603054. Read article
A novel mesoporous nanocomposite of the copper-based metal–organic framework (Cu-benzene tricarboxylic acid) with oxidized graphitic carbon nitride nanospheres is synthesized. Its textural and surface chemical features suggest that the formed nanospheres of oxidized g-C3N4 act as “giant” linkers between the copper sites. A marked alteration in the optical properties suggests an increase in photoreactivity.
Dimitrios A. Giannakoudakis, Nikolina A. Travlou, Jeff Secor, Teresa J. Bandosz
Small, October 06, 2016, DOI: 10.1002/smll.201601758. Read article
Hand in hand: CoIII(porphyrin) pairs in an interpenetrating metal–organic frameworks work hand in hand to activate both substrates for highly efficient hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent CoIII(porphyrins) in the two networks parallel to each other, with a distance of about 8.8 Å, which is ideal for the simultaneous activation of both substrates of the reaction.
Zekai Lin, Zhi-Ming Zhang, Yu-Sheng Chen, Wenbin Lin
Angew. Chem. Int. Ed., October 06, 2016, DOI: 10.1002/anie.201605802. Read article
In situ confinement pyrolysis strategy without using any template is proposed to construct nitrogen-enriched meso-microporous carbon (NEMC) frameworks from a metal organic framework for use as metal-free oxygen reduction electrocatalysts. Uing a very simple but effective strategy, the NEMC catalysts with well-defined 1D–3D morphology can be easily realized and they demonstrate excellent electrocatalytic performance through optimizing the channel structures and nitrogen-doped sites.
Qingxue Lai, Yingxuan Zhao, Yanyu Liang, Jianping He, Junhong Chen
Adv. Funct. Mater., October 06, 2016, DOI: 10.1002/adfm.201603607. Read article
A new energetic MOF, [Cu2(to)(dns)(H2O)]n (1; H2to = 1,2,4-triazol-5-one, H2dns = 3,5-dinitrosalicylic acid), has been synthesized and characterized. The superior density, thermostability, insensitivity, and detonation properties of 1 might be due to the coordination of the nitro group as well as its compact 3D framework.
Qi Yang, Xiaxia Song, Guowei Zhao, Guoli Yang, Langlei Yang, Qing Wei, Gang Xie, Sanping Chen, Shengli Gao
Eur. J. Inorg. Chem., October 04, 2016, DOI: 10.1002/ejic.201600814. Read article
Cu-MOF stability: The stability of a series of isoreticular MOFs has been thoroughly evaluated with regard to the nature of their metal centers (Co2+, Cu2+, and Zn2+) and ligand donors (see figure). The copper-based MOFs are generally more stable than the cobalt- and zinc-based MOFs. The combined experimental/computational approach employed in this work has demonstrated that both N-oxide and amido groups play important roles in adsorbate–adsorbent interactions, the former remarkably enhancing the heat of adsorption and CO2/CH4, CO2/CO, and CO2/N2 selectivity at room temperature.
Ying Xiong, Yan-Zhong Fan, Daiane Damasceno Borges, Cheng-Xia Chen, Zhang-Wen Wei, Hai-Ping Wang, Mei Pan, Ji-Jun Jiang, Guillaume Maurin, Cheng-Yong Su
Chem. Eur. J., October 04, 2016, DOI: 10.1002/chem.201603299. Read article
Luminescent sensing MOFs: Two unusual isostructural nanocage-based three-dimensional Ln-MOFs, 1-Ln (Ln=Tb and Eu; see figure), are constructed using a new diisophthalate ligand with active Lewis basic triazole sites. 1-Eu exhibits highly efficient luminescent sensing for Fe3+ cations and Cr2O72− anions, and selective capture of CO2 over CH4.
Jian-Qiang Liu, Gao-Peng Li, Wei-Cong Liu, Qing-Lin Li, Bao-Hong Li, Robert W. Gable, Lei Hou, Stuart R. Batten
ChemPlusChem, September 30, 2016, DOI: 10.1002/cplu.201600289. Read article
A great pore-formance: A hydrothermal reaction followed by heat treatment is used to prepare mesoporous dysprosium oxide microspheres (Dy2O3-ms). These can be used to achieve dynamic hydrogen peroxide detection with prominent performance.
Yibo Yan, Jun Zhao, Jong-Min Lee
ChemElectroChem, September 30, 2016, DOI: 10.1002/celc.201600421. Read article
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.
Ioannis Vamvasakis, Bin Liu, Gerasimos S. Armatas
Adv. Funct. Mater., September 26, 2016, DOI: 10.1002/adfm.201603292. Read article
Breathe in! The breathing behavior of a porous CuI metal–organic framework provides the first example of guest-induced high conductivity under humid conditions and relatively high temperature for a series of proton-carrier guests of different size, shape, and functionality (see figure).
Sajal Khatua, Arun Kumar Bar, Sanjit Konar
Chem. Eur. J., September 23, 2016, DOI: 10.1002/chem.201601964. Read article
Hyun-Chul Kim, Ja-Min Gu, Youngmee Kim, Do Nam Lee, Seong Huh
Eur. J. Inorg. Chem., September 20, 2016, DOI: 10.1002/ejic.201600645. Read article
A superior MOF! Two new Ln–MOFs with an uncommon one-dimensional channel (25 Å) have been synthesized and show high stability towards water in the pH range 3–10 (see figure). MOF 1-Eu is a promising luminescent probe for sensing Fe3+ in aqueous solution and is also selective towards rhodamine B with a superior adsorption capacity.
Shanghua Xing, Qiming Bing, Lifei Song, Guanghua Li, Jingyao Liu, Zhan Shi, Shouhua Feng, Ruren Xu
Chem. Eur. J., September 20, 2016, DOI: 10.1002/chem.201603102. Read article
Core–shell metal–organic framework Fe3O4/Cu3(btc)2 microspheres have been successfully synthesized by a one-step solvothermal method and a subsequent layer-by-layer strategy. The superparamagnetic heterogeneous catalyst exhibits efficient activity and high selectivity in the aerobic oxidation of alcohols and the epoxidation of olefins. The catalyst shows excellent recyclability.
Jie Li, Hongyi Gao, Li Tan, Yi Luan, Mu Yang
Eur. J. Inorg. Chem., September 19, 2016, DOI: 10.1002/ejic.201600761. Read article
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.
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
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.
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
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.
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
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.
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
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.
Jonathan Albo, Daniel Vallejo, Garikoitz Beobide, Oscar Castillo, Pedro Castaño, Angel Irabien
ChemSusChem, August 25, 2016, DOI: 10.1002/cssc.201600693. Read article
The fabrication of Pt@TiO2@In2O3@MnOx mesoporous hollow spheres that can absorb both UV and visible light is described by J. Gong and co-workers in their Communication on page 13734 ff. TiO2@In2O3 double-layered shells were selectively decorated with Pt nanoparticles and MnOx on the inner and outer surfaces, respectively. Owing to the presence of thin heterojunctions and spatially separated cocatalysts, charge recombination is significantly reduced. These spheres are efficient photocatalysts for water and alcohol oxidation.
Ang Li, Xiaoxia Chang, Zhiqi Huang, Chengcheng Li, Yijia Wei, Lei Zhang, Tuo Wang, Jinlong Gong
Angew. Chem. Int. Ed., August 25, 2016, DOI: 10.1002/anie.201607765. Read article
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.
Hongguang Song, Dong Liu, Jia Yang, Lei Wang, Hangxun Xu, Yujie Xiong
ChemNanoMat, August 24, 2016, DOI: 10.1002/cnma.201600203. Read article
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).
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
Mesoporous hollow spheres with the composition Pt@TiO2@In2O3@MnOx can absorb both UV and visible light. Owing to the presence of thin heterojunctions and spatially separated cocatalysts, charge recombination is efficiently reduced in both the bulk phase and the surface/subsurface. These hollow spheres can be used as efficient photocatalysts for water and alcohol oxidation.
Ang Li, Xiaoxia Chang, Zhiqi Huang, Chengcheng Li, Yijia Wei, Lei Zhang, Tuo Wang, Jinlong Gong
Angew. Chem. Int. Ed., July 22, 2016, DOI: 10.1002/anie.201605666. Read article