Experimental and Theoretical Solid-State 29Si NMR Studies on Defect Structures in La9.33+x(SiO4)6O2+1.5x Apatite Oxide Ion Conductors.

Oxide ion conductors can be used as electrolytes in solid oxide fuel cells, a promising energy-conversion technology. Local structures around the defects in oxide ion conductors are key for understanding the defect stabilization and migration mechanisms. As the defect contents are generally low, it is rather difficult to characterize the defect structure and therefore elucidate how oxide ions migrate. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for probing the local structures. However, the interpretation of NMR signals mainly based on the empirical knowledge could lead to unprecise local structures. There is still controversy regarding the defect structures in the apatite-type interstitial oxide ion conductors containing isolated tetrahedral units. Here, we combine the experimental solid-state 29Si NMR spectroscopy with theoretical density functional theory calculations to investigate the defect structures in La9.33+x(SiO4)6O2+1.5x apatites. The results indicate that the 29Si resonance signals on the high field side of the main peak corresponding to the Si atoms in the bulk structure are related to La vacancies and there is no steady-state SiO5 in the defect structures. This finding provides new atomic-level understanding to the stabilization and migration of interstitial oxide ions in silicate apatites, which could guide the design and discovery of new solid oxide fuel cell electrolyte materials.

An Interrupted Zeolite PKU-26 and Its Transformation to a Fully Four-Connected Zeolite PKU-27 upon Calcination.

The thermal stability and structural transformation mechanism are critical for the industrial applications of zeolites and the design of new framework types. Herein, a new zeolite PKU-26 has been hydrothermally synthesized under fluoride conditions using a tetraethylammonium (TEA+ ) cation as the structure-directing agent (SDA) and its framework contains partial Q3 T atoms [Q3 for T(-O-T)3 OH]. Upon calcination, PKU-26 processed a single-crystal to single-crystal transformation to another novel zeolite PKU-27 with the elimination of terminal -OH groups and enhanced thermal stability up to 650 °C, exhibiting the first Q3 →Q4 transformation [Q4 for T(-O-T)4 ] in 3D zeolite frameworks. The mechanism of the structural transformation, involving proton transfer, framework dehydration, and TO4 reconstruction, is proposed and supported by theoretical calculations.

Discovery of Layered Indium Hydroxide via a Hydroperoxyl Anion Coordinated Precursor at Room Temperature.

All reported layered metal hydroxides have brucite-like metal-hydroxyl host layers, and the discovery of other types of layered metal hydroxides could significantly extend the layered metal hydroxide families, which is meaningful in both theory and applications. Here, through hydroperoxyl anion coordinated In3+ cations as a precursor, a new layered indium hydroxide was synthesized, where only a three-dimensional cubic phase had existed before. The layer of the product exhibits an unusual structure where In(OH)6 octahedra share edges and vertexes with each other to form layers, which is completely different from the common edge-sharing brucite-like metal-hydroxyl layers. By investigating the formation mechanism, the new layered structure is found to be formed by changing the traditional crystallization path through the hydroperoxyl anion coordinated intermediates. Many other new phases could also be discovered by following the same intrinsic principle.

Superconductivity in Perovskite Ba1-xLnx(Bi0.20Pb0.80)O3-δ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu).

Solid solutions Ba1-xLnx(Bi0.20Pb0.80)O3-δ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 0.00 ≤ x ≲ 0.15) have been prepared under 850 °C. They all crystallize in space group P1 at room temperature. XPS data indicate that the valences are 5+ and 3+ for bismuth, 4+ and 2+ for lead, and 3+ or 4+ for lanthanide. Some of them are superconductors. The superconductive transition temperature Tczero decreases or remains constant with an increase of Ln in the sample when Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. However, Tczero first decreases, then increases, and finally decreases when Ln = Ce, Pr, which is due to the corresponding sample changes from hole-doped to electron-doped superconductors with an increase of Ce or Pr in the sample.

Enhancement of Ferroelectricity for Orthorhombic (Tb0.861Mn0.121)MnO3-δ by Copper Doping.

Copper-doped (Tb0.861Mn0.121)MnO3-δ has been synthesized by the conventional solid state reaction method. X-ray, neutron, and electron diffraction data indicate that they crystallize in Pnma space group at room temperature. Two magnetic orderings are found for this series by neutron diffraction. One is the ICAM (incommensurate canted antiferromagnetic) ordering of Mn with a wave vector qMn = (∼0.283, 0, 0) with a ≈ 5.73 Å, b ≈ 5.31 Å, and c ≈ 7.41 Å, and the other is the CAM (canted antiferromagnetic) ordering of both Tb and Mn in the magnetic space group Pn'a21' with a ≈ 5.73 Å, b ≈ 5.31 Å, and c ≈ 7.41 Å. A dielectric peak around 40 K is found for the samples doped with Cu, which is higher than that for orthorhombic TbMnO3.

Multiferroicity Broken by Commensurate Magnetic Ordering in Terbium Orthomanganite.

TbMnO3 is an important multiferroic material with strong coupling between magnetic and ferroelectric orderings. Incommensurate magnetic ordering is suggested to be vital for this coupling in TbMnO3 , which can be modified by doping at the site of Tb and/or Mn. Our study shows that a self-doped solid solution Tb1-x Mny MnO3 (y≤x) can be formed with Mn doped into the site of Tb of TbMnO3 . When y is small Tb1-x Mny MnO3 shows both ferroelectric and incommensurate magnetic orders at low temperature, which is similar to TbMnO3 . However, if y is large enough, a commensurate antiferromagnetic ordering appears along with the incommensurate magnetic ordering to prevent the appearance of multiferroicity in Tb1-x Mny MnO3 . That is to say, the magnetoeletric coupling can be broken by the co-existence of a commensurate antiferromagnetic ordering. This finding may be useful to the study of TbMnO3 .

A 3D 12-ring zeolite with ordered 4-ring vacancies occupied by (H2O)2 dimers.

A germanate zeolite, PKU-14, with a three- dimensional large-pore channel system was structurally characterized by a combination of high-resolution powder X-ray diffraction, rotation electron diffraction, NMR, and IR spectroscopy. Ordered Ge4 O4 vacancies inside the [4(6) .6(12) ] cages has been found in PKU-14, in which a unique (H2 O)2 dimer was located at the vacancies and played a structure-directing role. It is the first time that water clusters are found to be templates for ordered framework vacancies.

Quaternary sulfide Ba6Zn6ZrS14: synthesis, crystal structure, band structure, and multiband physical properties.

Ba6Zn6ZrS14 was synthesized by a traditional salt-melt method with KI as flux. The pale yellow crystals of Ba6Zn6ZrS14 crystallize in the tetragonal space group I4/mcm with a=16.3481 (4) Šand c=9.7221(6) Å. The structure features unique one-dimensional parallel [Zn6S9](6-) and [ZrS5](6-) straight chains. The D2h-symmetric [Zn6S9](6-) cluster serves as the building block of the [Zn6S9](6-) chains. A powder sample was investigated by X-ray diffraction, optical absorption, and photoluminescence measurements. The compound shows multiple-absorption character with three optical absorption edges around 1.78, 2.50, and 2.65 eV, respectively, which are perfectly consistent with the results of first-principles calculations. Analysis of the density of states further revealed that the three optical absorption bands are attributable to the three S(3p(6))→Zr(4d(0)) transitions due to the splitting of the Zr 4d orbitals in the D4h crystal field. The multiband nature of Ba6Zn6ZrS14 also results in photocatalytic activity under visible-light irradiation and three band-edge emissions.

Synthesis, structure, and magnetic properties of (Tb(1-x)Mn(y))MnO(3-δ).

Two compounds (Tb(1-x)Mn(y))MnO(3-δ) (W1, x = 0.089, y = 0.063; W2, x = 0.122, y = 0.102) have been synthesized by solid-state method and characterized using neutron diffraction and magnetic measurements. They crystallize in space group Pnma at room temperature and Pna21 at low temperature. W1 shows a sinusoidal antiferromagnetic order, and W2 shows both sinusoidal and canted commensurate antiferromagnetic orders. The magnetic moments of the commensurate antiferromagnetic order for W2 are antiferromagnetically coupled along the a- and c-axes, and ferromagnetically coupled along the b-axis in the Pna21 setting. Strong ferromagnetic response is induced by doping more Mn into the Tb site of (Tb(1-x)Mn(y))MnO(3-δ).

Solid-State (29)Si NMR and neutron-diffraction studies of Sr(0.7)K(0.3)SiO(2.85) oxide ion conductors.

K/Na-doped SrSiO3-based oxide ion conductors were recently reported as promising candidates for low-temperature solid-oxide fuel cells. Sr0.7K0.3SiO2.85, close to the solid-solution limit of Sr1-xKxSiO3-0.5x, was characterized by solid-state (29)Si NMR spectroscopy and neutron powder diffraction (NPD). Differing with the average structure containing the vacancies stabilized within the isolated Si3O9 tetrahedral rings derived from the NPD study, the (29)Si NMR data provides new insight into the local defect structure in Sr0.7K0.3SiO2.85. The Q(1)-linked tetrahedral Si signal in the (29)Si NMR data suggests that the Si3O9 tetrahedral rings in the K-doped SrSiO3 materials were broken, forming Si3O8 chains. The Si3O8 chains can be stabilized by either bonding with the oxygen atoms of the absorbed lattice water molecules, leading to the Q(1)-linked tetrahedral Si, or sharing oxygen atoms with neighboring Si3O9 units, which is consistent with the Q(3)-linked tetrahedral Si signal detected in the (29)Si NMR spectra.

On the structure of α-BiFeO3.

Polycrystalline and monocrystalline α-BiFeO3 crystals have been synthesized by solid state reaction and flux growth method, respectively. X-ray, neutron, and electron diffraction techniques are used to study the crystallographic and magnetic structure of α-BiFeO3. The present data show that α-BiFeO3 crystallizes in space group P1 with a = 0.563 17(1) nm, b = 0.563 84(1) nm, c = 0.563 70(1) nm, α = 59.33(1)°, ß = 59.35(1)°, γ = 59.38(1)°, and the magnetic structure of α-BiFeO3 can be described by space group P1 with magnetic modulation vector in reciprocal space q = 0.0045a* - 0.0045b*, which is the magnetic structure model proposed by I. Sosnowska (1) applied to the new P1 crystal symmetry of α-BiFeO3.

Achieving ultrahigh electrochemical performance by surface design and nanoconfined water manipulation.

The effects of nanoconfined water and the charge storage mechanism are crucial to achieving the ultrahigh electrochemical performance of two-dimensional transition metal carbides (MXenes). We propose a facile method to manipulate nanoconfined water through surface chemistry modification. By introducing oxygen and nitrogen surface groups, more active sites were created for Ti3C2 MXene, and the interlayer spacing was significantly increased by accommodating three-layer nanoconfined water. Exceptionally high capacitance of 550 F g-1 (2000 F cm-3) was obtained with outstanding high-rate performance. The atomic scale elucidation of the layer-dependent properties of nanoconfined water and pseudocapacitive charge storage was deeply probed through a combination of 'computational and experimental microscopy'. We believe that an understanding of, and a manipulation strategy for, nanoconfined water will shed light on ways to improve the electrochemical performance of MXene and other two-dimensional materials.

Syntheses, structure, and luminescent properties of novel hydrated rare earth borates Ln2B6O10OH4•H2O (Ln = Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Y).

Ln(2)B(6)O(10)(OH)(4)•H(2)O (Ln = Pr, Nd, Sm-Gd, Dy, Ho, and Y), a new series of hydrated rare earth borates, have been synthesized under hydrothermal conditions. A single crystal of Nd analogue was used for the structure determination by X-ray diffraction. It crystallizes in the monoclinic space group C2/c with lattice constants a = 21.756(4), b = 4.3671(9), c = 12.192(2) Å, and ß = 108.29(3)°. The other compounds are isostructural to Nd(2)B(6)O(10)(OH)(4)•H(2)O. The fundamental building block (FBB) of the polyborate anion in this structure is a three-membered ring [B(3)O(6)(OH)(2)](5-). The FBBs are connected by sharing oxygen atoms forming an infinite [B(3)O(5)(OH)(2)](3-) chain, and the chains are linked by hydrogen bonds, establishing a two-dimensional (2-D) [B(6)O(10)(OH)(4)•H(2)O](6-) layer. The 2-D borate layers are thus interconnected by Ln(3+) ions to form the complex three-dimensional structure. Ln(2)B(6)O(10)(OH)(4)•H(2)O dehydrates stepwise, giving rise to two new intermediate compounds Ln(2)B(6)O(10)(OH)(4) and Ln(2)B(6)O(11)(OH)(2). The investigation on the luminescent properties of Gd(2-2x)Eu(2x)B(6)O(10)(OH)(4)•H(2)O (x = 0.01-1.00) shows a high efficiency of Eu(3+) f-f transitions and the existence of the energy transfer process from Gd(3+) to Eu(3+). Eu(2)B(6)O(10)(OH)(4)•H(2)O and its two dehydrated products, Eu(2)B(6)O(10)(OH)(4) and Eu(2)B(6)O(11)(OH)(2), present the strongest emission peak at 620 nm ((5)D(0) → (7)F(2) transition), which may be potential red phosphors.

Syntheses and crystal structures of two new bismuth hydroxyl borates containing [Bi2O2]2+ layers: Bi2O2[B3O5(OH)] and Bi2O2[BO2(OH)].

Two new bismuth hydroxyl borates, Bi(2)O(2)[B(3)O(5)(OH)] (I) and Bi(2)O(2)[BO(2)(OH)] (II), have been synthesized under hydrothermal conditions. Their structures were determined by single-crystal and powder X-ray diffraction data, respectively. Compound I crystallizes in the orthorhombic space group Pbca with the lattice constants of a = 6.0268(3) Å, b = 11.3635(6) Å, and c = 19.348(1) Å. Compound II crystallizes in the monoclinic space group Cm with the lattice constants of a = 5.4676(6) Å, b = 14.6643(5) Å, c = 3.9058(1) Å, and ß = 135.587(6)°. The borate fundamental building block (FBB) in I is a three-ring unit [B(3)O(6)(OH)](4-), which connects one by one via sharing corners, forming an infinite zigzag chain along the a direction. The borate chains are further linked by hydrogen bonds, showing as a borate layer within the ab plane. The FBB in II is an isolated [BO(2)(OH)](2-) triangle, which links to two neighboring FBBs by strong hydrogen bonds, resulting in a borate chain along the a direction. Both compounds contain [Bi(2)O(2)](2+) layers, and the [Bi(2)O(2)](2+) layers combine with the corresponding borate layers alternatively, forming the whole structures. These two new bismuth borates are the first ones containing [Bi(2)O(2)](2+) layers in borates. The appearance of Bi(2)O(2)[BO(2)(OH)] (II) completes the series of compounds Bi(2)O(2)[BO(2)(OH)], Bi(2)O(2)CO(3), and Bi(2)O(2)[NO(3)(OH)] and the formation of Bi(2)O(2)[B(3)O(5)(OH)] provides another example in demonstrating the polymerization tendency of borate groups.

Microporous aluminoborates with large channels: structural and catalytic properties.

Channel zapping: PKU-1 and newly synthesized PKU-2 (Al(2)B(5)O(9)(OH)(3)⋅n H(2)O; see picture) possess microporous structures with 18-ring and 24-ring channels, respectively. They show high reactivity and size selectivity in the cyanosilylation of aldehydes as heterogeneous Lewis acid catalysts. The different channel sizes determine the substrate selectivity. These examples demonstrate the potential of octahedron-based aluminoborate channels in catalysis.

Seroconversion of hepatitis B surface antigen among those with previously successful immune response in Southern China.

Recommendations promoted worldwide have suggested a period of protection lasting more than 20 years against hepatitis B (HB) following primary immunization. Starting in 1987, universal HB vaccinations were carried out in Long An County, Guangxi Province, one of the earliest counties in which plasma-derived HB vaccine was delivered to newborns across China. Data collection targeted toward understanding the long term (26-33 years since primary immunization) immune effects of the plasma-derived HB vaccine was conducted in 2015; a second data collection was carried out in 2019 to assess seroconversion in the same cohort. This study qualitatively compared positive vs negative results and quantitatively assessed HB biomarkers - HB surface antigen (HBsAg), antibody to HBsAg (anti-HBs), HB e-antigen (HBeAg), antibody to HBeAg (anti-HBe), and antibody to HB core antigen (anti-HBc) - in serum 26-33 years after the full initial course of HB vaccination, then analyzed anti-HBs seroconversion using the two-phase sampling method in the same cohort and calculated the anti-HBs seroconversion rate from 2015 to 2019. The protective sero-conversion rate (anti-HBs ≥10mIU/mL) was 37.6% (192/511); the HBsAg-positive rate was 5.3% (27/511); the anti-HBs mean geometric titer (GMT) was 11.1 mIU/mL. Among the 143 participants involved in both 2015 and 2019 data collections, the seroconversion rate was 3.5% (5/143); two individuals had protective anti-HBs levels in 2015. These findings indicate that anti-HBs status can be seroconverted to a protective concentration level 4 years earlier in a high HBV epidemic region. The role of genomic mutations and the disappearance of immune memory and seroconversion should be investigated.

PKU-10: a new 3D open-framework germanate with 13-ring channels.

PKU-10, a germanate with the formula [(CH(3))(4)N](3)Ge(11)O(19)(OH)(9), is synthesized under hydrothermal conditions, and its structure is determined by single-crystal X-ray diffraction data. PKU-10 possesses 3D intersected 13-ring channels and presents a new 6-connectedness linkage mode of the Ge(7) cluster, T(3)P(2)O, forming a pcu topological network. Each Ge(7) cluster is, in fact, surrounded by eight Ge(7) clusters in a nearly perfect cube because the hydrogen bonds between Ge(7) clusters are also taken into account. The structure-directing agent tetramethylammonium (TMA(+)) ions, locating in the channels, can be partially exchanged by Li(+) with retention of the germanate framework. The germanate framework collapses with decomposition of the TMA(+) ions at temperatures higher than 240 °C.

Synthesis, structure, and characterization of the series BaBi(1-x)Ta(x)O(3) (0

The series BaBi(1-x)Ta(x)O(3) (0

Mullite-type Ga4B2O9: structure and order-disorder phenomenon.

Ga(4)B(2)O(9), an aluminium-free mullite-type compound, was prepared by a boric-acid flux method and its structure was determined using powder X-ray diffraction techniques, in combination with transmission electron microscopy, solid-state (11)B MAS-NMR and IR spectroscopies. GaO(6) octahedra share edges in a trans-manner forming one-dimensional chains along the b direction, and the chains are further cross-linked by GaO(5), BO(3) and BO(4) groups into a three-dimensional mullite-type structure. The disorder of the inter-chain groups results in a small unit cell for Ga(4)B(2)O(9) compared with that for Al(4)B(2)O(9), an ordered compound with a superstructure. By deconstructing the structure of Ga(4)B(2)O(9), we were able to identify the fundamental building units and their linking rules which can be used to reconstruct the ordered and disordered structures. For Ga(4)B(2)O(9), we found that the structure is intrinsically disordered within the ac plane, but ordered along the b axis. The three-dimensional structure can then be constructed by stacking the disordered ac sheets along the b axis ((1/2)b) with a (1/2)a shift. The fundamental building units and exclusivity rules identified in this gallium borate mullite may also be useful for understanding other related mullite phases. The structure analysis applying the proposed method is used to recognize the structural features of Al(4)B(2)O(9) and Al(18)B(4)O(33).

Synthesis and characterization of a fluorotitanophosphate (NH4)0.16K1.84[Ti2F2(PO4)2(PO3OH)] with a unique lamella framework.

(NH4)(0.16)K(1.84)[Ti(2)F(2)(PO(4))(2)(PO(3)OH)] (1) has been synthesized under hydrothermal conditions. The structure, the composition, and the thermal stability of 1 were determined by single-crystal X-ray diffraction; inductively coupled plasma-optical emission spectroscopy; IR spectroscopy; elemental analysis; thermogravimetric analysis-differential scanning calorimetry-mass spectrometry; and solid-state (1)H, (31)P, and (19)F NMR, and the phase purity of the bulk sample was checked by powder X-ray diffraction. Complex 1 is a fluorotitanophosphate having a unique lamella framework with both TiO(5)F octahedra and PO(3)OH tetrahedra on the surface of the layer, which leads to two different hydrogen bondings involving both P-OH and Ti-F groups.