The quest for advanced designer adsorbents for air filtration and monitoring hazardous trace gases has recently been more and more driven by the need to ensure clean air in indoor, outdoor, and industrial environments. How to increase safety with regard to personal protection in the event of hazardous gas exposure is a critical question for an ever-growing population spending most of their lifetime indoors, but is also crucial for the chemical industry in order to protect future generations of employees from potential hazards. Metal-organic frameworks (MOFs) are already quite advanced and promising in terms of capacity and specific affinity to overcome limitations of current adsorbent materials for trace and toxic gas adsorption. Due to their advantageous features (e.g., high specific surface area, catalytic activity, tailorable pore sizes, structural diversity, and range of chemical and physical properties), MOFs offer a high potential as adsorbents for air filtration and monitoring of hazardous trace gases. Three advanced topics are considered here, in applying MOFs for selective adsorption: (i) toxic gas adsorption toward filtration for respiratory protection as well as indoor and cabin air, (ii) enrichment of hazardous gases using MOFs, and (iii) MOFs as sensors for toxic trace gases and explosives.
The contributions of terephthalic acid and Zn(2+)-coordinated water in N,N-diethylformamide (DEF) to the overall proton activity in the synthesis of MOF-5 (Zn4O(BDC)3, BDC = 1,4-benzenedicarboxylate) were quantitatively determined by combined electrochemical and UV-vis spectroscopic measurements. Structural transformations of zinc carboxylate-based metal organic frameworks due to their exposure to environments with variable water concentrations and the chemical means necessary to revert these transitions have been investigated. It was found that the water-induced structural transition of MOF-5 to the hydroxide structure Zn3(OH)2(BDC)2 x 2 DEF (MOF-69c) can be reverted by a thermal treatment of the obtained compound and its subsequent exposure to anhydrous DEF. MOF-5 syntheses from simple carboxylates as well as a water-free synthesis based on nitrate decomposition are presented. The latter demonstrates that nitrate can serve as the sole source for the oxide ion in MOF-5.
Enhancing ionic conductivity of quasi‐solid‐state electrolytes (QSSEs) is one of the top priorities, while conventional metal–organic frameworks (MOFs) severely impede ion migration due to their abundant grain boundaries. Herein, ZIF‐4 glass, a subset of MOFs, is reported as QSSEs (LGZ) for lithium‐metal batteries. With lean Li content (0.12 wt%) and solvent amount (19.4 wt%), LGZ can achieve a remarkable ion conductivity of 1.61 × 10−4 S cm−1 at 30 °C, higher than those of crystalline ZIF‐4‐based QSSEs (LCZ, 8.21 × 10−5 S cm−1) and the reported QSSEs containing high Li contents (0.32–5.4 wt%) and huge plasticizer (30–70 wt%). Even at −56.6 °C, LGZ can still deliver a conductivity of 5.96 × 10−6 S cm−1 (vs 4.51 × 10−7 S cm−1 for LCZ). Owing to the grain boundary‐free and isotropic properties of glassy ZIF‐4, the facilitated ion conduction enables a homogeneous ion flux, suppressing Li dendrites. When paired with LiFePO4 cathode, LGZ cell demonstrates a prominent cycling capacity of 101 mAh g−1 for 500 cycles at 1 C with the near‐utility retention, outperforming LCZ (30.7 mAh g−1) and the explored MOF‐/covalent–organic frameworks (COF)‐based QSSEs. Hence, MOF glasses will be a potential platform for practical quasi‐solid‐state batteries in the future.
Noncollinear magnets provide essential ingredients for the next generation memory technology. It is a new prospect for the Heusler materials, already well known due to the diverse range of other fundamental characteristics. Here, we present a combined experimental and theoretical study of novel noncollinear tetragonal Mn(2)RhSn Heusler material exhibiting unusually strong canting of its magnetic sublattices. It undergoes a spin-reorientation transition, induced by a temperature change and suppressed by an external magnetic field. Because of the presence of Dzyaloshinskii-Moriya exchange and magnetic anisotropy, Mn(2)RhSn is suggested to be a promising candidate for realizing the Skyrmion state in the Heusler family.
A simple two-component procedure was developed to synthesize not only classical zinc-based IRMOFs represented by MOF-5 but also the cobalt and beryllium homologues of this most prominent MOF. The procedure is the first manifestation of mirroring the IRMOF series with other metal centers taken from main-group as well as transition-metal elements. Because of the existence of many suitable precursors, the procedure promises the generation of a large number of IRMOF homologues. Since the IRMOF series together with the MIL series is the MOF group with the largest number of representatives, the possibility of choosing the metal centers of the secondary building units from an extended set will tremendously expand the number of obtainable structures in a predictive, crystal-engineering-type way. Use of metal centers other than zinc will allow the addition of new features to the existing IRMOF structures, such as magnetic properties in the example of cobalt.
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