Penternary Wurtzitic Nitrides Li1-xZnxGe2-xGaxN3: Powder Synthesis, Crystal Structure, and Potentiality as a Solar-Active Photocatalyst.

We developed a new penternary wurtzitic nitride system Li1-xZnxGe2-xGaxN3 (0 ≤ x ≤ 1) by hybridizing LiGe2N3 and ZnGeGaN3. Fairly stoichiometric fine powder samples were synthesized by the reduction-nitridation process at 900 °C. While the end member LiGe2N3 possessed a relatively large band gap of 4.16 eV, the band gap of the developed penternary system varied in a broad range of 3.81 to 3.10 eV, showing promising responsivity to the solar spectrum. The crystal structure of LiGe2N3 was precisely determined by time-of-flight neutron powder diffraction for the first time, revealing the complete ordering of Li and Ge in the Cmc21 structure. The structural evolution from completely ordered LiGe2N3 to fully disordered ZnGeGaN3 was quantitatively analyzed by Rietveld refinement based on a partially disordered Cmc21 model, and the obtained results were also supported by 71Ga solid-state NMR spectroscopy. The synthesized Li1-xZnxGe2-xGaxN3 powder samples exhibited photocatalytic activities for the water reduction and oxidation reactions under solar light irradiation, with the H2 evolution rate of 0.3-59.0 µmol/h and the O2 evolution rate of 3.1-296.2 µmol/h, depending on the composition. Stable solar hydrogen generation of up to 48 h was demonstrated by the x = 0.80 sample, with the total amount of H2 evolved over 1.6 mmol and an external quantum efficiency of 2.1%.

Quaternary Wurtzitic Nitrides (1 - x)ZnGeN2-2xGaN (x = 0.02, 0.05): Disorder-Induced Band-Gap Narrowing and Potentiality as a Solar-Active Photocatalyst.

We examined the ZnGeN2-GaN solid-solution system (Zn1-xGe1-xGa2xN2) in the unexplored compositional region of x < 0.10 to reveal the transitional structural and optical properties caused by the introduction of Ga. Fairly stoichiometric fine powder specimens with compositions of x = 0.02 and 0.05 were prepared by the gas-reduction-nitridation method, and their partially ordered Pna21 structure was identified by solid-state 71Ga NMR spectroscopy and time-of-flight neutron powder diffraction. The Rietveld refinement results of the neutron diffraction data showed that the introduction of 2 atom % Ga readily retards the cation ordering in ZnGeN2, and this composition-induced transition to the wurtzite disordered phase proceeds mostly in the range of x < 0.10. The synthesized samples showed gradual red shifts of the absorbance and photoluminescence excitation spectra with their x value, consistent with their degree of disorder, indicating that the narrowing of the band gap achieved in the current system results primarily from the disorder of the cation sublattice accompanied by octet-rule violation, as has been predicted theoretically. The test reactions for photocatalytic water splitting resulted in improved H2 evolution rates of 6.1-72.6 µmol/h under UV-visible-light irradiation, and stable solar H2 evolution of up to 5 days was demonstrated.

Disposable Nitric Oxide Generator Based on a Structurally Deformed Nitrite-Type Layered Double Hydroxide.

The inhalation of nitric oxide (NO), which acts as a selective vasodilator of pulmonary blood vessels, is an established medical treatment. However, its wide adoption has been limited by the lack of a convenient delivery technique of this unstable gas. Here we report that a solid mixture of FeIISO4·7H2O and a layered double hydroxide (LDH) containing nitrite (NO2-) in the interlayer spaces (NLDH) stably generates NO at a therapeutic level (∼40 ppm over 12 h from freshly mixed solids; ∼80 ppm for 5-10 h from premixed solids) under air flow (0.25 L min-1) if the NLDH has been prepared by using a reconstruction method. Mg/Al-type LDH was calcined at 550 °C to remove interlayer CO32- and then treated with NaNO2 in water to reconstruct the NLDH. This one-pot, organic solvent-free process can be performed at large scales and is suitable for mass production. Humid air promotes anion exchange between NO2- and SO42- in the solid mixture, resulting in persistent interactions of NO2- and Fe2+, generating NO. In contrast to the previously reported NLDH prepared using an anion-exchange method, the reconstructed NLDH exhibits stable and persistent generation of NO because of partial deformation of the layered structures (e.g., particle aggregation, reduced crystallinity, and enhanced basicity). Degradation of the solid mixture is suppressed under dry conditions, so that a portable cartridge column that is readily available as an NO source for emergency situations can be prepared. This work demonstrates that the interlayer nanospace of LDH serves as a reaction mediator for excellent controllability of solid-state reactions. This inexpensive and disposable NO generator will facilitate NO inhalation therapy in developing countries and nonhospital locations.

Separated quadrupole and shift interactions of 2H NMR spectra in paramagnetic solids by asymmetric pulse sequences.

Separated pure-quadrupole (PQ) and -shift (PS) spectra of 2H nuclear magnetic resonance (NMR) of paramagnetic solids are obtained and correlated by simple pulse sequences that can acquire the full magnetization under ideal conditions. Two-dimensional NMR signals obtained using an asymmetric π-pulse-inserted quadrupole-echo (APIQE) sequence yielded separated spectra through the skew operation of an affine transform (AT) before a Fourier transform. Modified APIQE sequences that acquire whole echo signals were fabricated, and separated PQ and PS spectra were obtained by applying a combination of AT, such as rotation and skew operations, to the signal data. These methods were demonstrated for diamagnetic Zn(CD3CO2)2⋅2H2O and paramagnetic Nd(CD3CO2)3⋅1.5H2O. Further, the dynamics of the D2O molecule and [Co(D2O)6]2+ ion in paramagnetic CoSiF6⋅6D2O was analyzed based on the temperature dependence of the separated spectra.

Why Do Carbonate Anions Have Extremely High Stability in the Interlayer Space of Layered Double Hydroxides? Case Study of Layered Double Hydroxide Consisting of Mg and Al (Mg/Al = 2).

Layered double hydroxides (LDHs) are promising compounds in a wide range of fields. However, exchange of CO32- anions with other anions is necessary, because the CO32- anions are strongly affixed in the LDH interlayer space. To elucidate the reason for the extremely high stability of CO32- anions intercalated in LDHs, we investigated in detail the chemical states of CO32- anions and hydrated water molecules in the LDH interlayer space by synchrotron radiation X-ray diffraction, solid-state NMR spectroscopy, and Raman spectroscopy. We found the rigidity of the network structure formed between the CO32- anions, hydrated water molecules, and the hydroxyl groups on the metal hydroxide layer surface to be a crucial factor underlying the stability of CO32- anions in the LDH interlayer space.

Constancy of the quadrupolar interaction product in nanocrystalline gallium nitride revealed by 71Ga MAS NMR shift distribution.

The question of whether the broad 71,69Ga nuclear magnetic resonance (NMR) signal of hexagonal gallium nitride (h-GaN) at 530-330 ppm is related to the Knight shift (caused by the presence of carriers in semiconductors) is the subject of intense debate. The intensity increase observed for the narrower 71Ga magic angle spinning (MAS) NMR signals above 1050 °C suggests that the broader signals do not reflect the decomposition of h-GaN. Herein, we utilized 71Ga multi-quantum (MQ) MAS NMR spectroscopy to reveal that the quadrupolar interaction products for the broad signal of nanocrystalline h-GaN are almost constant in the entire shift range that we investigated, equaling 1.7 ±â€¯0.1 MHz or similar values. Since the above parameter is sensitive to the local chemical symmetry around the Ga atom, the NMR shift distribution is considered not to be related to that of the chemical environment. Consistent with the most recent reports, including those on double-resonance 15N{71Ga} measurements, the Knight shift may be ascribed to defects serving as shallow donors and populating the conduction band. Thus, MQMAS measurements performed using a low-field NMR instrument or by choosing half-integer quadrupole nuclei with a large quadrupole constant such as 69Ga are expected to provide important information for each Knight shift value and for analyzing the nature of semiconductors other than GaN.

Investigation of the effects of sintering and indium-doping of zinc oxide using 67Zn magic angle spinning NMR analysis.

Indium-doped zinc oxide, a potential alternative material to indium tin oxide, was analyzed in powder form via 67Zn magic angle spinning nuclear magnetic resonance (MAS NMR). The 67Zn MAS NMR results show that the line shapes of zinc oxide were broadened by sintering, which was also observed for indium-doped zinc oxide, in which the broadening also depended on the sintering time. Furthermore, the line shapes of indium-doped zinc oxide were significantly broader than those of the corresponding zinc oxide, and were independent of the degree of indium doping. This indicates that indium atoms are associated into cluster-like structures in this compound.

Na-α'-GeGaON Solid Solution Analogous to α'-SiAlON: Synthesis, Crystal Structure, and Potentiality as a Photocatalyst.

We demonstrated, for the first time, formation of the Na-α'-GeGaON (NamGe12-(m+n)Gam+nOnN16-n) solid solution, an analogue of the well-established α'-SiAlON system. We successfully synthesized single-phase powder samples by reduction-nitridation of Na2CO3-GeO2-Ga2O3, in the solubility range of m ≈ 0.8-1.7 with n ≈ 0.2-0.3. The Rietveld refinement of powder X-ray diffraction data for Na-α'-GeGaON was conducted on the basis of the space group P31c of α'-SiAlON, and the refinement converged with RB = 1.78% and RF = 1.02% for the composition of Na1.26(1)Ge10.50Ga1.50O0.24(1)N15.76(1), indicating reliably the isomorphism between the SiAlON and GeGaON systems. The results of (23)Na solid-state nuclear magnetic resonance (NMR) spectroscopy clearly showed a single peak at the chemical shift of ∼ 16 ppm, further proving the accommodation of Na in the α'-GeGaON matrix with the expected coordination environment. The synthesized Na-α'-GeGaON exhibited stable photocatalytic activity for the evolution of H2 from water under ultraviolet irradiation, which was comparable to that attained by ß-Ge3N4.

Electron localization of polyoxomolybdates with ε-Keggin structure studied by solid-state 95Mo NMR and DFT calculation.

We report electron localization of polyoxomolybdates with ε-Keggin structure investigated by solid-state (95)Mo NMR and DFT calculation. The polyoxomolybdates studied are the basic ε-Keggin crystals of [Me3NH]6[H2Mo12O28(OH)12{MoO3}4] · 2H2O (1), the crystals suggested to have a disordered {ε-Mo12} core of [PMo12O36(OH)4{La(H2O)2.75Cl1.25}4]·27H2O (2), and the paramagnetic Keggin crystals of [H2Mo12O30(OH)10{Ni(H2O)3}4] · 14H2O (3). The spectra of (95)Mo static NMR of these samples were measured under moderate (9.4 and 11.7 T) and ultrahigh magnetic fields (21.8 T). From spectral simulation and quantum chemical calculation, the NMR parameters of the chemical shift and quadrupole interactions for (95)Mo were estimated. By the analysis based on the result for 1, it was found for 2 that although the {ε-Mo12} core is disordered, the eight d(1) electrons in it are not completely localized on four Mo-Mo bonds. Furthermore, it was shown for 3 that the d(1) electrons are localized to make the Mo-Mo bonds, while the unpaired electrons are also almost localized on the paramagnetic Ni(II) ions.

Dynamic breathing of CO2 by hydrotalcite.

The carbon cycle of carbonate solids (e.g., limestone) involves weathering and metamorphic events, which usually occur over millions of years. Here we show that carbonate anion intercalated layered double hydroxide (LDH), a class of hydrotalcite, undergoes an ultrarapid carbon cycle with uptake of atmospheric CO2 under ambient conditions. The use of (13)C-labeling enabled monitoring by IR spectroscopy of the dynamic exchange between initially intercalated (13)C-labeled carbonate anions and carbonate anions derived from atmospheric CO2. Exchange is promoted by conditions of low humidity with a half-life of exchange of ~24 h. Since hydrotalcite-like clay minerals exist in Nature, our finding implies that the global carbon cycle involving exchange between lithosphere and atmosphere is much more dynamic than previously thought.

Hidden chemical order in disordered Ba7Nb4MoO20 revealed by resonant X-ray diffraction and solid-state NMR.

The chemical order and disorder of solids have a decisive influence on the material properties. There are numerous materials exhibiting chemical order/disorder of atoms with similar X-ray atomic scattering factors and similar neutron scattering lengths. It is difficult to investigate such order/disorder hidden in the data obtained from conventional diffraction methods. Herein, we quantitatively determined the Mo/Nb order in the high ion conductor Ba7Nb4MoO20 by a technique combining resonant X-ray diffraction, solid-state nuclear magnetic resonance (NMR) and first-principle calculations. NMR provided direct evidence that Mo atoms occupy only the M2 site near the intrinsically oxygen-deficient ion-conducting layer. Resonant X-ray diffraction determined the occupancy factors of Mo atoms at the M2 and other sites to be 0.50 and 0.00, respectively. These findings provide a basis for the development of ion conductors. This combined technique would open a new avenue for in-depth investigation of the hidden chemical order/disorder in materials.

Intra- and intermolecular effects on 1H chemical shifts in a silk model Peptide determined by high-field solid state 1H NMR and empirical calculations.

A combination of solid state 1H NMR chemical shift measurements and empirical chemical shift calculations has been used to interpret 1H solid state chemical shifts of a model peptide (Ala-Gly)15 for the crystalline domain of Bombyx mori silk fibroin in silk I and silk II structures, including a treatment of both intra- and intermolecular arrangements. Silk I and silk II are the structures of silk fibroin before and after spinning, respectively. Two peaks with equal intensity were observed for the amide protons of (AG)15 in silk I, whereas only one broad peak was observed for silk II, reflecting a difference of 1.1 ppm in Ala HN shift between silk I and silk II, but a difference of only 0.2 ppm in Gly HN shift. Chemical shift calculations predicted chemical shifts that are in good agreement with the experimental observations and showed that the origin of these chemical shift differences was predominantly the magnetic anisotropy effect from the C=O bond that hydrogen bonds with HN, which has a more favorable geometry for Ala HN in silk II than for the other HN. This result shows that we could distinguish between proton chemical shift effects arising from intermolecular interactions and those from intramolecular interactions by combining observation of the solid state 1H NMR chemical shift and empirical chemical shift calculation.

Improvement of 1H-2H cross polarization under magic-angle spinning by using amplitude/frequency modulation.

In 1H-2H cross polarization (CP) under magic-angle spinning (MAS), it has been pointed out that modulation of a H2 resonance frequency caused by MAS acts as adiabatic frequency sweep and efficient CP over the broad H2 powder pattern can be achieved. The adiabaticity, however, does not hold when the MAS frequency becomes faster, leading to insufficient CP enhancement. In this work, it is demonstrated that by applying amplitude/frequency modulation for H2 irradiation during CP, CP efficiency at faster MAS can be improved appreciably. By examining 1H-2H CP spectra taken at off-amplitude or off-resonance conditions, it is suggested that the improvement is ascribed to accumulation of CP signals from various parts of the broad H2 resonance, whose orientational dependence is time-dependent and is partially averaged under MAS.

High field 17O solid-state NMR study of alanine tripeptides.

(17)O chemical shifts of Ala-Ala-Ala, with parallel and anti-parallel beta-sheet structures, are observed using a 930-MHz high-resolution solid-state NMR spectrometer. Ala-Ala-Ala serves as a model sheet-forming peptide because it can be easily prepared as either a parallel or an anti-parallel beta-sheet structure. Spectral differences between the two samples are observed which arise from molecular packing differences between the two sheet structures. DFT chemical shift calculations are performed for the two samples, and the calculated spectra are in good agreement with the experimental spectra. The DFT calculations provide insight into the nature of the chemical shift differences observed between the two sheet structures.

Conformational and microstructural characteristics of poly(L-lactide) during glass transition and physical aging.

The glass transition and physical aging processes of poly(L-lactide) (PLLA) were studied by variable-temperature Fourier transform infrared (FTIR) spectroscopy and (13)C solid-state NMR spectroscopy. The glass transition temperature (T(g)) of PLLA can be well determined from the temperature-dependent FTIR intensity. Nearby T(g), a distinct change in the slope of spectral intensity versus temperature plot is detected. FTIR results suggest that the energy-favorable gauche-trans (gt) conformers rearrange into the less energy-favorable gauche-gauche (gg) counterparts with heating over the glass transition region, which becomes more distinct at temperature above T(g). Besides, the 1267 cm(-1) band, which shows different trends of variation from the other bands upon heating, was assigned to be more sensitive to the nu(as)(C-O-C)+delta(CH) vibration mode of the less energy-favorable gg conformers in PLLA. By comparing the FTIR spectra of the aged and deaged PLLA, it was demonstrated that the rearrangement from the high- to low-energy conformers, i.e., gg to gt, occurs with physical aging. (13)C spin-lattice relaxation measurements indicate that the relaxation rate distribution broadens with aging, which agrees with the previous suggestion that the locally ordered domains are formed during physical aging. Because of the larger variation in the conformational state and microstructure, the FTIR intensities vary much more abruptly for the aged sample with heating to nearby T(g).

11B nuclear magnetic resonance in boron-doped diamond.

This review summarizes recent results obtained by 11B solid-state nuclear magnetic resonance (NMR) on boron-doped diamond, grown by the high-pressure high-temperature (HPHT) or chemical vapor deposition techniques. Simple single-pulse experiments as well as advanced two-dimensional NMR experiments were applied to the boron sites in diamond. It is shown that magic-angle spinning at magnetic fields above 10 T is suitable for observation of high-resolution 11B spectra of boron-doped diamond. For boron-doped HPHT diamonds, the existence of the excess boron that does not contribute to electrical conductivity was confirmed and its 11B NMR signal was characterized. The point-defect structures (B+H complexes and -B-B-/-B-C-B- clusters), postulated previously for the excess boron, were discarded and graphite-like structures were assigned instead.

High-field 1H MAS and 15N CP-MAS NMR studies of alanine tripeptides and oligomers: distinction of antiparallel and parallel beta-sheet structures and two crystallographically independent molecules.

beta-Strand peptides are known to assemble into either antiparallel (AP) or parallel (P) beta-sheet forms which are very important motifs for protein folding and fibril formations occurring in silk fibroin or amyloid proteins. Well-resolved 1H NMR signals including NH protons were observed for alanine tripeptides (Ala)3 with the AP and P structures as well as (Ala)n (n = 4-6) by high-field/fast magic-angle spinning NMR. Amide NH and amino NH3+ 1H signals of (Ala)3 with the P structure were well resonated at 7.5 and 8.9 ppm, respectively, whereas they were not resolved for the AP structure. Notably, NH 1H signals of (Ala)3 and (Ala)4 taking the P structure are resonated at higher field than those of the AP structure by 1.0 and 1.1 ppm, respectively. Further, NH 15N signals of (Ala)3 with the AP structure were resonated at lower field by 2 to 5 ppm than those of (Ala)3 with the P structure. These relative 1H and 15N hydrogen bond shifts of the P structure with respect to those of the AP structure are consistent with the relative hydrogen bond lengths of the interstrand N-H...O=C bonds. Distinction between the two crystallographically independent chains present in the AP and P structures was feasible by 15N chemical shifts but not by 1H chemical shifts because of insufficient spectral resolution in the latter. Calculated 1H and 15N shielding constants by density functional theory are generally consistent with the experimental data, although some discrepancies remain depending upon the models used.

Ce-Doped La3Si6.5Al1.5N9.5O5.5, a Rare Highly Efficient Blue-Emitting Phosphor at Short Wavelength toward High Color Rendering White LED Application.

Phase pure nondoped and Ce doped La3Si6.5Al1.5N9.5O5.5 (Al containing La N-phase) samples have been obtained by solid-state reaction synthesis for the first time. 1% Ce-doped La3Si6.5Al1.5N9.5O5.5 phosphor displays a broad excitation band ranging from UV to 410 nm, with a maximum at 355 nm. UV light excitation results in a narrow Ce3+ 5d-4f emission band (fwhm = 68 nm) centered at 418 nm. The emission can be tuned from 417 nm at 0.5% Ce to 450 nm at 50% Ce. A high internal quantum efficiency up to 84% is achieved for a 1% Ce doped sample, which has CIE chromaticity coordinates of x = 0.157 and y = 0.069, close to the NTSC blue standard (x = 0.155; y = 0.070). Compared to La3Si8O4N11:Ce phosphor, the quantum efficiency and thermal stability have been enhanced for La3Si6.5Al1.5N9.5O5.5:Ce phosphor without shifting the emission peak wavelength. La3Si6.5Al1.5N9.5O5.5:Ce shows less thermal quenching than La3Si8O4N11:Ce and no shift or change in the shape of emission spectra with increasing the temperature from 4 to 573 K. These results show that La3Si6.5Al1.5N9.5O5.5:Ce is more efficient than any other (oxy-)nitride phosphor with an emission in the short wavelength blue region (400-450 nm). A white LED was fabricated using the La3Si6.5Al1.5N9.5O5.5:5%Ce as a blue phosphor. The high color rendering index (Ra = 93.2, R9 = 91.4, and R12 = 89.5) obtained shows that the phosphor is a very promising conversion phosphor for white LEDs.

Manipulation of shell morphology of silicate spheres from structural evolution in a purely inorganic system.

We have investigated the structural transformation of solid silica spheres into various more complex spherical structures including flower-like, thick or thin nanosheet-shelled and porous shelled spheres. In the absence of organic additives, sodium salts contained in this inorganic reaction system apparently direct the silica dissolution and regrowth of dissolved silicate at the nanometer-scale, leading to the formation of a nanosheet network rather than solid aggregates. Subsequent removal of the salts by simple water washing results in voids in the siloxane network and a significant availability of surface silanol groups so that the resulting nanosheets and spheres composed of them possess large surface areas, pore volumes, and morphological flexibility, which can be varied by an applied stimulus. The results represent a rare example of the transformation of a simple silicate structure into a much more complex spherical structure involving a purely inorganic reaction system.