• Michelsen Lawrence posted an update 4 hours, 38 minutes ago

    A2M3O12-based materials have received considerable attention owing to their wide range of negative thermal expansion (NTE) and chemical flexibility toward novel materials design. However, the structure and NTE mechanism remain challenging. Here, Zr4+ and V5+ are used as a unit to compensatorily replace Sc3+ and Mo6+ in Sc2Mo3O12 to tune its thermal expansion. Its crystal structure, phase transition, NTE property, and corresponding mechanisms are studied by high-resolution synchrotron X-ray diffraction, powder X-ray diffraction, ultralow-frequency Raman spectroscopy, and density functional theory calculations. The results show that Zr0.3Sc1.7Mo2.7V0.3O12 adopts an orthorhombic (Pbcn) structure at room temperature, with V atoms occupying the position of Mo1 atoms and Zr atoms occupying the position of Sc atoms, and transforms to monoclinic (P21/a) structure at ∼133 K (45 K lower than that of Sc2Mo3O12). It exhibits excellent NTE in a broader range. Most of the phonon modes below 350 cm-1 have negative Grüneisen parameters, of which the lowest and next-lowest frequency (38.5 and 45.8 cm-1) optical phonon modes arising from the translational vibrations of the Sc/Zr and Mo/V atoms in the plane of the nonlinear linkage Sc/Zr-O-Mo/V have the largest and next-largest negative Grüneisen parameters and positive total anharmonicity, and contribute most to the NTE.The incorporation of a mechanically interlocked molecule such as pseudorotaxane into metal-organic coordination polymers has afforded plenty of new hybrid materials with special structures and unique properties. In this work, we employ a weakly bound cucurbit[6]uril (CB[6])-bipyridinium pseudorotaxane as a supramolecular precursor to assemble with uranyl, aiming to construct uranyl-rotaxane coordination polymers (URCPs) with intriguing structures. By adjusting the synthetic conditions, a new kinked-helix uranyl rotaxane compound (URCP3), together with three other compounds URCP1, URCP2, and URCP4 varying from 1D chains to 2D interwoven networks, was obtained. Detailed structural analyses indicate that the pseudorotaxane ligand (C8BPCA@CB[6]) shows great configuration diversity in the construction of URCPs, which is most probably due to the weak binding strength between the host and guest molecules. Specifically, based on the monodentate coordination of the end carboxyl groups of C8BPCA forced by the surrounding unilaterally-chelated oxalate, the entire flexible pseudorotaxane linker will be more likely to undergo conformational change, thereby binding to the uranyl center from both sides of the uranyl equatorial plane and promoting the formation of a kinked helix structure of URCP3 that is shaped like a Chinese knot along [001]. This work enriches the library of actinide-rotaxane compounds and provides a new approach to construct metal-organic compounds with complicated structures using weakly bonded pseudorotaxanes as well.Conductive polymers are potential selective ion-exchange membrane materials. In this study, a novel redox transistor electrodialyzer consisting of two chambers separated by a polypyrrole (PPy) membrane electrode was designed for potassium ion (K+) recovery from water. The PPy membrane electrode was fabricated by depositing PPy on a stainless-steel wire mesh through the electrochemical method. Based on ion-exchange results, the PPy membrane exhibited electrodialysis selectivity for K+ in the presence of Na+, with a K+/Na+ separation factor of 2.10. Adding modified active carbon to PPy provided a larger electroactive area and better conductivity, resulting in higher ion-exchange capacity (1.04 mmol/L) compared with the original PPy membrane. Even for seawater containing a very low concentration of K+ (16.18 mmol/L), the PPy membrane still demonstrated K+ selectivity (separation factor of 2.18). Energy consumption in the electrodialyzer was 3.80 kW h/kg K, which was 37% lower than that in traditional electrodialysis. Furthermore, the PPy membrane exhibited antiscaling/fouling ability with the help of a pulse voltage. selleck chemicals These findings highlight a novel redox transistor electrodialysis process with great potential application in K+ recovery from wastewater with relatively low energy consumption.By using the reduced Schiff base tricarboxylate ligand H3cip, one novel 3D Cd-based coordination polymer (Cd-CP) with the formula [Cd(Hcip)(bpea)0.5(H2O)]n (H3cip = 5-(3-carboxybenzylamino)isophthalic acid, bpea = 1,2-bis(4-pyridyl)ethane) has been solvothermally synthesized. The prepared Cd-CP possesses a 4-connected CdSO4 net based on dinuclear Cd2 units. Luminescence measurements revealed that the complex exhibited ratiometric turn-on luminescence responses toward Al3+ and Cr3+ with a significant color change, which could be easily distinguished by the naked eye under ultraviolet light. Cd-CP can also respond to Fe3+ through a turn-off mechanism. Interestingly, the luminescence quenched by Fe3+@Cd-CP can be recovered and increased significantly by adding some competitive Al3+, while Cr3+ can only marginally increase the luminescence intensity of Fe3+@Cd-CP. Moreover, the detection of the three aforementioned metal ions can be realized by using Cd-CP-coated test papers, extending the potential application regions of the reported material to point-of-care tests and environmental field studies.The occurrence of persistent organic pollutants (POPs) in the Arctic has been of constant concern, as these chemicals cause reproductive effects and mortality in organisms. The Arctic acts as a chemical sink, which makes this system an interesting case for bioaccumulation studies. However, as conducting empirical studies for all Arctic species and POPs individually is unfeasible, in silico methods have been developed. Existing bioaccumulation models are predominately validated for temperate food chains, and do not account for a large variation in trophic levels. This study applies Monte Carlo simulations to account for variability in trophic ecology on Svalbard when predicting bioaccumulation of POPs using the optimal modeling for ecotoxicological applications (OMEGA) bioaccumulation model. Trophic magnification factors (TMFs) were calculated accordingly. Comparing our model results with monitored POP residues in biota revealed that, on average, all predictions fell within a factor 6 of the monitored POP residues in biota.