Approach for quality deep-ultraviolet nonlinear optical crystals a substitution strategy of channel species in zeolite.

Exploring the connections between the ion substitution of a material, its crystal structure, and its performance in applications is a regular task in synthetic chemistry. However, there still remain major challenges in the substitution of polyanionic groups for single ions. Herein, a strategy of channel species substitution of single anions by polyanionic groups in a zeotype rigid framework to design a new deep-ultraviolet nonlinear zincophosphate, {[LiNa(SiF)]Cs}[(ZnPO)], and tune physicochemical properties was proposed.

Strategy for a Rational Design of Deep-Ultraviolet Nonlinear Optical Materials from Zeolites.

Deep-ultraviolet (DUV) nonlinear optical (NLO) materials play a crucial role in cutting-edge laser technology. In order to solve the serious layered growth tendency of the sole commercial DUV NLO crystal KBeBOF (KBBF), developing alternative systems of compounds with bulk crystal habits has become an urgent task for practical applications. Herein, a novel strategy was developed by applying non-centrosymmetric (NCS) cancrinite (CAN)-type zincophosphates {Na(OH)(HO)}Cs[ZnPO] with bulk-crystal habits as the prototype to design new DUV NLO crystals.

Two Noncentrosymmetric Bismuth Phosphates: Rational Design Synthesis and Optical Properties.

Developing strategies to rational design noncentrosymmetric structure still attract much interest for their applications in nonlinear optical and piezoelectric materials. Two noncentrosymmetric (NCS) alkaline earth metal bismuth phosphates have been successfully achieved via partial replacement of Bi with Ca or Sr ions. BiCa(HPO) (designated as CaBiPO) and BiSr(HPO) (designated as SrBiPO), together with their solid solution Bi(SrCa)(HPO) (0 < ≤ 0.

Industrial-scale extraction of high value-added kaolin from excavation waste: Demonstration from Xiamen, China.

Excavation waste from the construction of subways and other underground infrastructures is mainly composed of gravel, sand and clay of minimal economic value, which commonly ends up in landfills. Although the coarse sand and gravel of the excavation waste are typically recycled on site, a large amount of the fine-grained residue must be disposed of due to the prohibition of marine land reclamation in Xiamen, China, leading to an increasingly severe shortage of landfills. In this contribution, a new strategy was successfully developed for industrial-scale extraction of high value-added kaolin from the excavation waste of Xiamen.

Facile synthesis of rose-like composites of zeolites and layered double hydroxides: Growth mechanism and enhanced properties.

Excellent performances of various materials often depend on high specific surface areas. Therefore, increase of specific surface areas is one of the most important means to improve the properties and performances of materials. Herein, we report a facile strategy to prepare novel composite materials of zeolites and hydrotalcite-like layered double hydroxides, with high specific surface areas.

Crystal structure and magnetic properties of the magnetically isolated zigzag chain in KGaCu(PO).

Magnetism of any material depends on its crystal structure. However, two isostructural compounds such as MCuMoO4(OH) (M = Na, K) can have markedly different magnetic properties. Herein, we introduce a new method to describe the linkages between the O-atoms and their bridged Cu2+ ions in order to clearly illustrate the structure-magnetic property relationships.

Rational Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Fluorinated Orthophosphate: BaZn(PO)F.

Rational design and tailored synthesis of noncentrosymmetric compounds with nonlinear optical (NLO) properties, especially in the deep-ultraviolet (deep-UV) region, remains a great challenge. Herein, we report on the development of a modified fluoro-solvo-hydrothermal method with two additive reagents (trimethylamine and NaF solution) as the solvents, using BaFe(PO)(OH) ( P222) as the prototype, for the rational design and tailored synthesis of the first deep-UV fluorinated orthophosphate, BaZn(PO)F. It crystallizes in the polar space group Pna2 and exhibits transparency down to deep-UV region (<190 nm) with SHG effect at 0.

Identifying the Structural Evolution of the Sodium Ion Battery Na FePO F Cathode.

Na FePO F is a promising cathode material for Na-ion batteries owing to its relatively high discharge voltage and excellent cycling performance. Now, the long- and short-range structural evolution of Na FePO F during cycling is studied by in situ high-energy X-ray diffraction (XRD), ex situ solid-state nuclear magnetic resonance (NMR), and first-principles DFT calculations. DFT calculations suggest that the intermediate phase, Na FePO F, adopts the space group of P2 /c, which is a subgroup (P2 /b11, No.

Structural diversities induced by cation sizes in a series of fluorogermanophosphates: A[GeF(HPO)] (A = Na, K, Rb, NH, and Cs).

Germanophosphates, in comparison with other metal phosphates, have been less studied but potentially exhibit more diverse structural chemistry with wide applications. Herein we applied a hydro-/solvo-fluorothermal route to make use of both the "tailor effect" of fluoride for the formation of low dimensional anionic clusters and the presence of alkali cations of different sizes to align the anionic clusters to control the overall crystal symmetries of germanophosphates. The synergetic effects of fluoride and alkali cations led to structural changes from chain-like structures to layered structures in a series of five novel fluorogermanophosphates: A[GeF(HPO)] (A = Na, K, Rb, NH, and Cs, denoted as Na, K, Rb, NH4, and Cs).

Strong spin frustration and negative magnetization in LnCu(OH)Cl (Ln = Nd and Sm) with triangular lattices: the effects of lanthanides.

Herbertsmithite- and kapellasite-type compounds with triangular lattices (i.e. Kagomé) as the most promising candidates for realizing the exotic quantum spin liquid (QSL) state have recently attracted significant attention in condensed matter physics and materials science but are often adversely affected by dimensional imperfections arising from significant cation mixing.

A High Capacity, Good Safety and Low Cost NaFeSiO-Based Cathode for Rechargeable Sodium-Ion Battery.

Rechargeable sodium-ion batteries (SIBs) are receiving intense interest because the resource abundance of sodium and its lithium-like chemistry make them low cost alternatives to the prevailing lithium-ion batteries in large-scale energy storage devices. Two typical classes of materials including transition metal oxides and polyanion compounds have been under intensive investigation as cathodes for SIBs; however, they are still limited to poor stability or low capacity of the state-of-art. Herein, we report a low cost carbon-coated NaFeSiO with simultaneous high capacity and good stability, owing to the highly pure Na-rich triclinic phase and the carbon-incorporated three-dimensional network morphology.

KB(PO)F: a novel acentric deep-ultraviolet material.

Two challenges to grow KBeBOF (KBBF), the best known deep-ultraviolet nonlinear optical (NLO) material to date, are the limited crystal sizes and the use of a highly toxic element (Be). Herein we report on the discovery of a novel anhydrous non-centrosymmetric alkali fluorinated borophosphate KB(PO)F (KBPF) featuring a cut-off wavelength of less than 200 nm and a large second-harmonic generation (SHG) effect similar to KHPO (KDP), hence representing a new promising deep-ultraviolet NLO material. The KBPF crystals consisting of common elements can be grown using green and cost effective processes and do not show any detectable hygroscopicity.

Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities.

Anhydrous compounds are crucially important for many technological applications, such as achieving high performance in lithium/sodium cells, but are often challenging to synthesize under hydrothermal conditions. Herein we report that a modified solvo-/hydro-fluorothermal method with fluoride-rich and water-deficient condition is highly effective for synthesizing anhydrous compounds by the replacement of hydroxyl groups and water molecules with fluorine. Two anhydrous phosphate germanium fluorides, namely, Na[GeF(PO)] and K[GeF(PO)], with chainlike structures involving multiple fluorine substitutions, were synthesized using the modified solvo-/hydro-fluorothermal method.

Zero-Strain Na2FeSiO4 as Novel Cathode Material for Sodium-Ion Batteries.

A new cubic polymorph of sodium iron silicate, Na2FeSiO4, is reported for the first time as a cathode material for Na-ion batteries. It adopts an unprecedented cubic rigid tetrahedral open framework structure, i.e.

(11)B MAS NMR and First-Principles Study of the [OBO3] Pyramids in Borates.

Borates are built from the [Bϕ3] planar triangles and the [Bϕ4] tetrahedral groups, where ϕ denotes O or OH. However, the [Bϕ4] groups in some borates are highly distorted to include three normal B-O bonds and one anomalously long B-O bond and, therefore, are best described as the [OBO3] pyramids. Four synthetic borates of the boracite-type structures (Mg3B7O13Br, Cu3B7O13Br, Zn3B7O13Cl, and Mg3B7O13Cl) containing a range of [OBO3] pyramids were investigated by multifield (7.

Dimensional Reduction From 2D Layer to 1D Band for Germanophosphates Induced by the "Tailor Effect" of Fluoride.

The "tailor effect" of fluoride, exclusively as a terminal rather than a bridge, was applied successfully to design low-dimensional structures in the system of transition metal germanophosphates for the first time. Two series of new compounds with low-dimensional structures are reported herein. K[M(II)Ge(OH)2(H0.

Polymorphism of NaVO2F2: a P2₁/c superstructure with pseudosymmetry of P2₁/m in the subcell.

The ADDSYM routine in the program PLATON [Spek (2015). Acta Cryst. C71, 9-18] has helped researchers to avoid structures of (metal-)organic compounds being reported in an unnecessarily low symmetry space group.

Synthesis and characterization of mixed-valence manganese fluorophosphate and analogues with clathrate-like structures: Mn(III)6F12(PO3(OH))8[Na8(Kx(H3O)4-x(H2O)2)M(IV)(OH)6] (M(IV) = Mn, Ti, Ge).

A novel, mixed- and high-valence manganese (Mn(3+)/Mn(4+)) fluorophosphate, Mn(III)6F12(PO3(OH))8[Na8(Kx(H3O)4-x(H2O)2)Mn(IV)(OH)6] (denoted as MN), has been prepared via a water-deficient hydrothermal route with phosphoric acid as the sole solvent. This compound features a cubic three-dimensional open-framework structure built from corner-sharing [Mn(III)O4F2] octahedra and [HPO4] groups, which encapsulates a clathrate-like "guest cluster" of Na8(Kx(H3O)4-x(H2O)2)Mn(IV)(OH)6. The guest cluster is architecturally composed of a [Mn(IV)(OH)6] octahedron in a cubic cage of Na(+) cations, which in turn is surrounded by an octahedral arrangement of K(+)/H2O ions, resulting in an unprecedented octahedral @ cubic @ octahedral @ cubic arrangement (OCOC).

Hematite concave nanocubes and their superior catalytic activity for low temperature CO oxidation.

Hematite (α-Fe2O3) concave nanocubes bound by high-index {1344̄} and {123̄8} facets were synthesized and their catalytic activity for CO oxidation were also investigated.

Structural assembly from phosphate to germanophosphate by applying germanate as a binder.

Structural assembly from phosphate to germanophosphate by applying germanate as a binder has been achieved. Two isotypic porous compounds, K3[M(II)4(HPO4)2][Ge2O(OH)(PO4)4]·xH2O (M(II) = Fe, Cd; x = 2 for Fe and 3 for Cd, denoted as KFeGePO-1 and KCdGePO-1, respectively), contain a known transition-metal phosphate (TMPO) layer, (∞)(2){[M2(HPO4)3]2–}, which is built from chains of trans-edge-sharing MO6 octahedra bridged by MO5 trigonal bipyramids that were further linked and decorated by phosphate tetrahedra. The layers are bound by infinite chains of GeO5(OH) octahedra, resulting in a 3D open-framework structure with 1D 12-ring channels that are occupied by K+ ions and water molecules.

MnBa(2)(HPO(4))(2)(H(2)PO(4))(2).

Crystals of manganese(II) dibarium bis-(hydrogenphosphate) bis-(dihydrogenphosphate), MnBa(2)(HPO(4))(2)(H(2)PO(4))(2), were obtained by hydro-thermal synthesis. The title compound is isotypic with its Cd(II) and Ca(II) analogues. The structure is built up of an infinite {[Mn(HPO(4))(2)(H(2)PO(4))(2)](4-)}(n) chain running along [100], which consists of alternate MnO(6) octa-hedra and [PO(4)] tetra-hedra, in which the centrosymmetric MnO(6) octa-hedra share their four equatorial O-atom corners with tetra-hedral [PO(3)(OH)] groups and their two axial apices with tetra-hedral [PO(2)(OH)(2)] groups.

Tetra-aqua-tetra-manganese(II) catena-[germanodihydroxidodi(hydrogen-phosphate)diphosphate].

The title compound, Mn(4)(H(2)O)(4)[Ge(OH)(2)(HPO(4))(2)(PO(4))(2)], was synthesized by the solvothermal method. Its crystal structure is isotypic with the iron and cobalt analogues [Huang et al. (2012 ▶).

Redetermination of Ce[B(5)O(8)(OH)(H(2)O)]NO(3)·2H(2)O.

The crystal structure of Ce[B(5)O(8)(OH)(H(2)O)]NO(3)·2H(2)O, cerium(III) aqua-hydroxidoocta-oxidopenta-borate nitrate dihydrate, has been redetermined from single-crystal X-ray diffraction data. In contrast to the previous determination [Li et al. (2003 ▶).

Cerium(III) dihydroxidohexa-oxidotetra-borate chloride.

The crystal structure of the title compound, Ce[B(4)O(6)(OH)(2)]Cl, is built from polyborate sheets parallel to the (001) plane. These sheets stack along the [001] direction and are linked by Ce atoms exhibiting an CeO(8)Cl(2) coordination sphere. O-H⋯O and O-H⋯Cl hydrogen bonds additionally stabilize the structural set-up.

Two isotypic transition metal germanophosphates M(II)4(H2O)4[Ge(OH)2(HPO4)2(PO4)2] (M(II) = Fe, Co): synthesis, structure, Mössbauer spectroscopy, and magnetic properties.

Synthetic, structural, thermogravimetric, Mössbauer spectroscopic, and magnetic studies were performed on two new isotypic germanophosphates, M(II)(4)(H(2)O)(4)[Ge(OH)(2)(HPO(4))(2)(PO(4))(2)] (M(II) = Fe, Co), which have been prepared under hydro-/solvo-thermal conditions. Their crystal structures, determined from single crystal data, are built from zigzag chains of M(II)O(6)-octahedra sharing either trans or skew edges interconnected by [GeP(4)O(14)(OH)(4)](8-) germanophosphate pentamers to form three-dimensional neutral framework structure. The edge-sharing M(II)O(6)-octahedral chains lead to interesting magnetic properties.