Confined Water Cluster Formation in Water Harvesting by Metal-Organic Frameworks: CAU-10-H versus CAU-10-CH3.

Several metal-organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10-30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH3 are studied with H, CH3 corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of H by CH3 in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials' structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework µï£¿OH groups, while for CAU-10-CH3, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.

Control of zeolite framework flexibility for ultra-selective carbon dioxide separation.

Molecular sieving membranes with uniform pore size are highly desired for carbon dioxide separation. All-silica zeolite membranes feature well-defined micropores, but the size-exclusion effect is significantly compromised by the non-selective macro-pores generated during detemplation. Here we propose a template modulated crystal transition (TMCT) approach to tune the flexibility of Decadodecasil 3 R (DD3R) zeolite to prepare ultra-selective membranes for CO2/CH4 separation. An instantaneous overheating is applied to synchronize the template decomposition with the structure relaxation. The organic template molecules are transitionally converted to tight carbon species by the one-minute overheating at 700 °C, which are facilely burnt out by a following moderate thermal treatment. The resulting membranes exhibit CO2/CH4 selectivity of 157~1,172 and CO2 permeance of (890~1,540) × 10-10 mol m-2 s-1 Pa-1. The CO2 flux and CO2/CH4 mixture selectivity reach 3.6 Nm3 m-2 h-1 and 43 even at feed pressure up to 31 bar. Such strategy could pave the way of all-silica zeolite membranes to practical applications.

Polytypism in mcalpineite: a study of natural and synthetic Cu3TeO6.

Synthetic and naturally occurring forms of tricopper orthotellurate, CuII3TeVIO6 (the mineral mcalpineite) have been investigated by 3D electron diffraction (3D ED), X-ray powder diffraction (XRPD), Raman and infrared (IR) spectroscopic measurements. As a result of the diffraction analyses, CuII3TeVIO6 is shown to occur in two polytypes. The higher-symmetric CuII3TeVIO6-1C polytype is cubic, space group Ia3, with a = 9.537 (1) Šand V = 867.4 (3) Å3 as reported in previous studies. The 1C polytype is a well characterized structure consisting of alternating layers of CuIIO6 octahedra and both CuIIO6 and TeVIO6 octahedra in a patchwork arrangement. The structure of the lower-symmetric orthorhombic CuII3TeVIO6-2O polytype was determined for the first time in this study by 3D ED and verified by Rietveld refinement. The 2O polytype crystallizes in space group Pcca, with a = 9.745 (3) Å, b = 9.749 (2) Å, c = 9.771 (2) Šand V = 928.3 (4) Å3. High-precision XRPD data were also collected on CuII3TeVIO6-2O to verify the lower-symmetric structure by performing a Rietveld refinement. The resultant structure is identical to that determined by 3D ED, with unit-cell parameters a = 9.56157 (19) Å, b = 9.55853 (11) Å, c = 9.62891 (15) Šand V = 880.03 (2) Å3. The lower symmetry of the 2O polytype is a consequence of a different cation ordering arrangement, which involves the movement of every second CuIIO6 and TeVIO6 octahedral layer by (1/4, 1/4, 0), leading to an offset of TeVIO6 and CuIIO6 octahedra in every second layer giving an ABAB* stacking arrangement. Syntheses of CuII3TeVIO6 showed that low-temperature (473 K) hydrothermal conditions generally produce the 2O polytype. XRPD measurements in combination with Raman spectroscopic analysis showed that most natural mcalpineite is the orthorhombic 2O polytype. Both XRPD and Raman spectroscopy measurements may be used to differentiate between the two polytypes of CuII3TeVIO6. In Raman spectroscopy, CuII3TeVIO6-1C has a single strong band around 730 cm-1, whereas CuII3TeVIO6-2O shows a broad double maximum with bands centred around 692 and 742 cm-1.

Oxygen vacancy ordering in SrFe0.25Co0.75O2.63 perovskite material.

SrFe0.25Co0.75O2.63 was synthesized by a solid-state reaction. Its structural study at room temperature using conventional X-ray as well as neutron powder diffraction, electron diffraction and high-resolution transmission electron microscopy is presented. An oxygen-vacancy ordering related to the "314" model known for the Sr3Y1Co4O10.5 oxide is proposed despite neither an A-site ordering nor an A-site mismatch. By means of Mössbauer spectroscopy, Mohr salt titration and the difference in the neutron cross sections of Fe and Co, a cation distribution within the crystallographic sites as the following Sr4(Fe0.143+Co0.363+)48h(Fe0.114+Co0.144+Co0.253+)48fO10.52 is suggested, highlighting a natural layered structure with Fe and Co in higher oxidation states in the oxygen replete layers than in the oxygen deficient ones.

Coxsackievirus B3 protease 3C: expression, purification, crystallization and preliminary structural insights.

Viral proteases are proteolytic enzymes that orchestrate the assembly of viral components during the viral life cycle and proliferation. Here, the expression, purification, crystallization and preliminary X-ray diffraction analysis are presented of protease 3C, the main protease of an emerging enterovirus, coxsackievirus B3, that is responsible for many cases of viral myocarditis. Polycrystalline protein precipitates suitable for X-ray powder diffraction (XRPD) measurements were produced in the presence of 22-28%(w/v) PEG 4000, 0.1 M Tris-HCl, 0.2 M MgCl2 in a pH range from 7.0 to 8.5. A polymorph of monoclinic symmetry (space group C2, unit-cell parameters a = 77.9, b = 65.7, c = 40.6 Å, ß = 115.9°) was identified via XRPD. These results are the first step towards the complete structural determination of the molecule via XRPD and a parallel demonstration of the accuracy of the method.

Magnetic structures of the low temperature phase of Mn3(VO4)2 - towards understanding magnetic ordering between adjacent Kagomé layers.

In this article we report on a detailed analysis of the magnetic structures of the magnetic phases of the low temperature (lt-) phase of Mn3(VO4)2 (=Mn3V2O8) with a Kagomé staircase structure determined by means of powder neutron diffraction. Two magnetic transitions were found at ∼25 K (HT1 phase, Cmc'a') and ∼17 K (LT1 phase, Pmc'a'), in excellent agreement with previous reports. The LT1 phase is characterized by commensurate magnetic ordering of the magnetic moments on two magnetic sites of the Mn1a/b (2a + 2d) and Mn2 (8i) ions of the nuclear structure (where for the latter site two different overall orientations of magnetic moments within the ab-plane (Mn2a and Mn2b) can be distinguished. This results in mainly antiferromagnetic interactions between edge-sharing Mn-octahedra within the Kagomé planes. The HT1 phase is characterised by strong spin frustration resulting from the loss of ordering of the magnetic moments of Mn2a/b ions along the b-axis. Both magnetic structures are in agreement with the previously reported ferrimagnetic properties of lt-Mn3(VO4)2 and shed light on the magnetic phase diagram of the compound reported previously. The magnetic structures are discussed with respect to superexchange interaction pathways within the Kagomé layers, which appear to be predominantly antiferromagnetic. The magnetic structures of Mn3(VO4)2 are different compared to those reported for Ni3(VO4)2 and Co3(VO4)2 and represent an unique commensurate way out of spin frustration for compounds with strong antiferromagnetic superexchange interactions within the Kagomé layers. Additionally, we derive a superexchange model, which will be called redox-mediated M-M(')(d(0))-M superexchange and which can help to understand the exclusively ferromagnetic ordering of adjacent Kagomé layers found only for lt-Mn3(VO4)2.

Structural and magnetic properties of the low-dimensional fluoride ß-FeF3(H2O)2·H2O.

We have reinvestigated the crystal structure of the low-dimensional fluoride ß-FeF3(H2O)2·H2O using high resolution neutron and X-ray diffraction data. Moreover we have studied the magnetic behavior of this material combining medium resolution and high flux neutron powder diffraction together with magnetic susceptibility measurements. This fluoride compound exhibits vertex-shared 1D Fe(3+) octahedral chains, which are extended along the c-axis. The magnetic interactions between adjacent chains involve super-superexchange interactions via an extensive network of hydrogen bonds. This interchain hydrogen bonding scheme is sufficiently strong to induce a long range magnetic order appearing below T = 20(1) K. The magnetic order is characterized by the propagation vector k = (0, 0, 1/2), giving rise to a strictly antiferromagnetic structure where the Fe(3+) spins are lying within the ab-plane. Magnetic exchange couplings extracted from magnetization measurements are found to be J∥/kb = -18 K and J⊥/kb = -3 K. These values are in good agreement with the neutron diffraction data, which show that the system became antiferromagnetically ordered at ca. TN = 20(1) K.

Magnetic properties of the RbMnPO4 zeolite-ABW-type material: a frustrated zigzag spin chain.

The crystal structure and magnetic properties of the RbMnPO4 zeolite-ABW-type material have been studied by temperature-dependent neutron powder diffraction, low-temperature magnetometry, and heat capacity measurements. RbMnPO4 represents a rare example of a weak ferromagnetic polar material, containing Mn(2+) ions with TN = 4.7 K. The neutron powder diffraction pattern recorded at T = 10 K shows that the compound crystallizes in the chiral and polar monoclinic space group P2(1) (No. 4) with the unit cell parameters: a = 8.94635(9), b = 5.43415(5), and c = 9.10250(8) Å and ß = 90.4209(6)°. A close inspection of the crystal structure of RbMnPO4 shows that this material presents two different types of zigzag chains running along the b axis. This is a unique feature among the zeolite-ABW-type materials exhibiting the P2(1) symmetry. At low temperature, RbMnPO4 exhibits a canted antiferromagnetic structure characterized by the propagation vector k1 = 0, resulting in the magnetic symmetry P2(1)'. The magnetic moments lie mostly along the b axis with the ferromagnetic component being in the ac plane. Due to the geometrical frustration present in this system, an intermediate phase appears within the temperature range 4.7-5.1 K characterized by the propagation vector k2 = (kx, 0, kz) with kx/kz ≈ 2. This ratio is reminiscent of the multiferroic phase of the orthorhombic RMnO3 phases (R = rare earth), suggesting that RbMnPO4 could present some multiferroic properties at low temperature. Our density functional calculations confirm the presence of magnetic frustration, which explains this intermediate incommensurate phase. Taking into account the strongest magnetic interactions, we are able to reproduce the magnetic structure observed experimentally at low temperature.

Magnetic order through super-superexchanges in the polar magnetoelectric organic-inorganic hybrid Cr[(D3N-(CH2)2-PO3)(Cl)(D2O)].

The crystal and magnetic structures of the organic-inorganic hybrid compound Cr(II) ammoniumethylphosphonate chloride monohydrate, Cr[D(3)N-(CH(2))(2)-PO(3))(Cl)(D(2)O)] (1), have been studied by temperature-dependent neutron powder diffraction and superconducting quantum interference device (SQUID) magnetometry. The compound represents a rare example of a magnetoelectric polar organic-inorganic hybrid solid, containing high spin Cr(2+) ions (S = 2) and is a canted antiferromagnet (weak ferromagnet) below T(N) = 5.5 K. The neutron powder diffraction pattern recorded at T = 10 K, shows that the partially deuterated compound crystallizes in the same non centrosymmetric monoclinic space group P2(1) (No. 4) with the following unit-cell parameters: a = 5.24041(4) Å, b =13.93113(8) Å, c = 5.26081(4) Å, and ß = 105.4347(5)°. Powder neutron diffraction of a partially deuterated sample has enabled us, for the first time, to locate the water molecule. At low temperature, the compound presents a canted antiferromagnetic state characterized by k = 0 resulting in the magnetic symmetry P2(1)'. This symmetry is in agreement with the previously reported large magnetodielectric effect. The crystal structure of (1) can be described as being built up of triangular lattice planes made up of [Cr(II)O(4)Cl] square pyramids which are separated by ammonium ethyl groups along the b axis. The transition from paramagnetic to weakly ferromagnetic state results from super-superexchanges only. Surprisingly, while the overall magnetic behavior is antiferromagnetic, the Cr(II)O(4)Cl planes are ferromagnetic, and the strongest antiferromagnetic coupling is via the ammonium ethyl groups. Our density functional calculations confirm these aspects of the spin exchange interactions of (1) and that the spin exchange interactions between Cr(II) ions are considerably weak compared with the single-ion anisotropy of Cr(II).

Observation of multiferroic properties in pyroxene NaFeGe2O6.

We report the observation of multiferroicity in a clinopyroxene NaFeGe(2)O(6) polycrystal from the investigation of its electrical and magnetic properties. Following the previously known first magnetic transition at T(N1) = 13 K, a second magnetic transition appears at T(N2) = 11.8 K in the temperature dependence of the magnetization. A ferroelectric polarization starts to develop clearly at T(N2) rather than T(N1) and its magnitude increases up to ~13 µC m(-2) at 5 K, supporting the idea that the ferroelectric state in NaFeGe(2)O(6) stems from a helical spin order stabilized below T(N2). When a magnetic field of 90 kOe is applied, the electric polarization decreases to 9 µC m(-2) and T(N2) slightly increases by 0.5 K. At intermediate magnetic fields, around 28 and 78 kOe, anomalies in the magnetoelectric current, magnetoelectric susceptibility, and field derivative of magnetization curves are found, indicating field-induced spin-state transitions. Based on these electrical and magnetic properties, we provide a detailed low temperature phase diagram up to 90 kOe, and discuss the nature of each phase of NaFeGe(2)O(6).

The incommensurately modulated structures of the perovskites NaCeMnWO6 and NaPrMnWO6.

The structures of the doubly ordered perovskites NaCeMnWO(6) and NaPrMnWO(6), with rock salt ordering of the Mn(2+) and W(6+)B-site cations and layered ordering of the Na(+) and (Ce(3+)/Pr(3+)) A-site cations, have been studied by transmission electron microscopy, electron diffraction, neutron and synchrotron X-ray powder diffraction. Both compounds possess incommensurately modulated crystal structures. In NaCeMnWO(6) the modulation vector (with reference to the ideal ABX(3) perovskite subcell) is q ≈ 0.067a* (∼58.7 Å) and in NaPrMnWO(6)q ≈ 0.046a* (∼85.3 Å). In both compounds the superstructures are primarily the two-dimensional chessboard type, although some crystals of NaCeMnWO(6) were found with one-dimensional stripes. In some crystals of NaPrMnWO(6) there is a coexistence of chessboards and stripes. Modeling of neutron diffraction data shows that octahedral tilting plays an important role in the structural modulation.