Development of the Sb4O5Cl2@NbSe2 Composite: The Impact of 2H-NbSe2 Nanoparticles on Sb4O5Cl2 and Their Application for the Removal of Cr(VI)/Fe(III) and Methyl Orange from Wastewater.

A potential adsorbent, Sb4O5Cl2@NbSe2 composite, was generated from the Sb4O5Cl2 photocatalyst and 5 wt % layered 2H-NbSe2 nanoparticles for the highly effective removal of Cr(VI) and Fe(III) ions and methyl orange (MO) from aqueous solution, and a comparison was drawn against the precursors. Sb4O5Cl2 crystallites and NbSe2 nanoparticles were synthesized hydrothermally, and the composite was prepared by the incipient wetness impregnation technique. The crystal structure of Sb4O5Cl2 was determined by single-crystal X-ray diffraction (SCXRD) data. Powder X-ray diffraction (PXRD) study revealed the 2H phase of NbSe2 nanoparticles. Field emission scanning electron microscopy (FESEM) analysis confirmed the formation of the spherical-shaped NbSe2 nanoparticles from rod-shaped bulk 2H-NbSe2. Morphological changes from the hexagonal to irregular prismatic shape were found upon the formation of the Sb4O5Cl2@NbSe2 composite compared to pure Sb4O5Cl2. Negative ζ-potential values indicated that electrostatic interactions were the predominant factor for the adsorption process. Sb4O5Cl2@NbSe2 provided removal efficiencies of 99% for MO in 6 h, 96.52% for Cr(VI) within 2.5 h, and 92.43% for Fe(III) within 4 h of 10 mg/L initial concentration. The maximum adsorption capacities of the composite for MO, Fe(III), and Cr(VI) were found to be 66.56, 131.48, and 122.30 mg/g, respectively, as calculated using the Langmuir isotherm equation.

Multi-Functional Applications of H-Glass Embedded with Stable Plasmonic Gold Nanoislands.

Metal nanoparticles (MNPs) are synthesized using various techniques on diverse substrates that significantly impact their properties. However, among the substrate materials investigated, the major challenge is the stability of MNPs due to their poor adhesion to the substrate. Herein, it is demonstrated how a newly developed H-glass can concurrently stabilize plasmonic gold nanoislands (GNIs) and offer multifunctional applications. The GNIs on the H-glass are synthesized using a simple yet, robust thermal dewetting process. The H-glass embedded with GNIs demonstrates versatility in its applications, such as i) acting as a room temperature chemiresistive gas sensor (70% response for NO2 gas); ii) serving as substrates for surface-enhanced Raman spectroscopy for the identifications of Nile blue (dye) and picric acid (explosive) analytes down to nanomolar concentrations with enhancement factors of 4.8 × 106 and 6.1 × 105 , respectively; and iii) functioning as a nonlinear optical saturable absorber with a saturation intensity of 18.36 × 1015 W m-2 at 600 nm, and the performance characteristics are on par with those of materials reported in the existing literature. This work establishes a facile strategy to develop advanced materials by depositing metal nanoislands on glass for various functional applications.

Zn3Sb4O6F6 and KI-Doped Zn3Sb4O6F6: A Metal Oxyfluoride System for Photocatalytic Activity, Knoevenagel Condensation, and Bacterial Disinfection.

Zn3Sb4O6F6 crystallites were synthesized by a pH-regulated hydrothermal synthetic approach, while doping on Zn3Sb4O6F6 by KI was performed by the "incipient wetness impregnation technique." The effect of KI in Zn3Sb4O6F6 is found with the changes in morphology in the doped compound, i.e., needle-shaped particles with respect to the irregular cuboid and granular shaped in the pure compound. Closer inspection of the powder diffraction pattern of doped compounds also reveals the shifting of Braggs' peaks toward a lower angle and the difference in cell parameters compared to the pure compound. Both metal oxyfluoride comprising lone pair elements and their doped compounds have been successfully applied as photocatalysts for methylene blue dye degradation. Knoevenagel condensation reactions were performed using Zn3Sb4O6F6 as the catalyst and confirmed 99% yield even at 60 °C temperature under solvent-free conditions. Both pure and KI-doped compounds were tested against several standard bacterial strains, i.e., Enterobacter sp., Escherichia coli, Staphylococcus sp., Salmonella sp., Bacillus sp., Proteous sp., Pseudomonas sp., and Klebsiella sp. by the "disk diffusion method" and their antimicrobial activities were confirmed.

Ferromagnetic Ni1-xVxO1-y Nano-Clusters for NO Detection at Room Temperature: A Case of Magnetic Field-Induced Chemiresistive Sensing.

Surface modulation of functional nanostructures is an efficient way of improving gas sensing properties in chemiresistive materials. However, synthesis methods employed so far in achieving desired performances are cumbersome and energy intensive. Moreover, nano-engineering-induced magnetic properties of these materials which are expected to enhance sensing responses have not been utilized until now in improving their interaction with target gases. In particular for gasses with paramagnetic nature such as NO or NO2, the inherent magnetic property of the chemiresistor might assist in enabling superior sensing performance. In this work, vanadium-doped NiO nano-clusters with ferromagnetic behavior at room temperature have been synthesized by a simple and effective combination of soft chemical routes and employed in efficient and selective detection of paramagnetic NO gas. While NiO is typically anti-ferromagnetic, the nanoscale engineering of NiO- and V-doped NiO samples have been found to tune the inherent anti-ferromagnetic behavior into room-temperature ferromagnetism. Surface modification in terms of formation of nano-clusters led to an increased Brunauer-Emmett-Teller surface area of ∼120 m2/g. The sample Ni0.636V0.364O has been observed to exhibit a selective and high response of ∼98% to 1 ppm NO at room temperature with fast response (14 s) and recovery (95 s). The improved sensing response of this sample compared to other doped NiO variants could be explained in terms of lower remnant magnetic moment of the sample accompanied with higher excess negative charge at the surface. The sensing response of this sample was increased by 30% in the presence of an external magnetic field of 280 gauss, highlighting the importance of magnetic ordering in chemiresistive gas sensing between the magnetic sensor material and target analyte. This material stands as a potential gas sensor with excellent NO detection properties.

Chemiresistive NH3 detection at sub-zero temperatures by polypyrrole- loaded Sn1-xSbxO2 nanocubes.

Chemiresistive gas sensors operate mainly at high temperatures, primarily due to the need of energy for surface adsorption-desorption of analytes. As a result, the operating temperature of the chemiresistive sensors could be reduced only to room temperature. Hence, a plethora of sensing requirements at temperatures below ambient have remained outside the scope of chemiresistive materials. In this work, we have developed an antimony-doped SnO2 nanocube-supported expanded polypyrrole network that could detect low ppm ammonia gas (≤20 ppm) at sub-zero temperatures with high response (∼4), selectivity, and short response and recovery times. The low temperature chemiresistive sensing has been explained in terms of the interplay of an extended conducting network of an in situ deposited polymer, effective transport properties of majority charge carriers and a loosely bound exciton-like electron-hole pair formation and breakage mechanism.

pH-regulated hydrothermal synthesis and characterization of Sb4O5X2 (X = Br/Cl) and its use for the dye degradation of methyl orange both with and without light illumination.

A pH-regulated hydrothermal synthesis method was employed to synthesize Sb4O5Br2 and Sb4O5Cl2 crystallites. Characterization is done by single crystal X-ray diffraction, powder X-ray diffraction, infra-red spectroscopy, scanning electron microscopy and DFT studies. The compounds crystallize in monoclinic symmetry with a P21/c space group. Complete structural analysis of the Sb4O5Br2 compound by using single crystal X-ray diffraction data is performed for the first time and a comparative study with Sb4O5Cl2 is also discussed. The SEM study reveals that the surface morphology changes with the variation of pH for bromide compounds, whereas pH change does not affect the morphology of the chloride analogues. Electronic band structures of the synthesized oxyhalides were investigated in order to understand their catalytic effects in the dye degradation reactions in dark as well as sunlight conditions.

Boranes: The Boron Subhydride B104.67H3 with a Distorted ß-Boron Crystal Structure.

A single crystal of the boron subhydride B104.67(4)H3 was serendipitously obtained while attempting to synthesize ß-boron. An accurate crystal structure analysis revealed a distorted ß-boron framework with the noncentrosymmetric space group R3m. We have found one interstitial site occupied by boron. The site related by inversion remains empty. The distortions of the framework result in ideal environments for the interstitial boron atom, and for the three hydrogen atoms at bridging positions between icosahedral B12 groups, they result in ideal B-H distances of 1.33 Å. B104.67(4)H3 is a borane with the lowest amount of hydrogen recorded to date, and it is the first compound with a noncentrosymmetrically distorted ß-boron framework.

Influence of pressure on the transport, magnetic, and structural properties of superconducting Cr0.0009NbSe2 single crystal.

We investigate the superconducting critical current density (J c), transition temperature (T c), and flux pinning properties under hydrostatic pressure (P) for Cr0.0009NbSe2 single crystal. The application of P enhances T c in both electrical resistivity (∼0.38 K GPa-1: 0 ≤ P ≤ 2.5 GPa) and magnetization (∼0.98 K GPa-1: 0 ≤ P ≤ 1 GPa) measurements, which leads to a monotonic increase in J c and flux pinning properties. The field-dependent J c at various temperatures under P is analyzed within the collecting pinning theory and it shows that δT c pinning is the crossover to δl pinning above the critical pressure (P c ∼0.3 GPa). Our systematic analysis of the flux pinning mechanism indicates that both the density of pinning centers and pinning forces greatly increase with the application of P, which leads to an enhancement in the vortex state. Structural studies using synchrotron X-ray diffraction under pressure illustrate a stable hexagonal phase without any significant impurity phase and lattice parameter reduction with P shows highly anisotropic nature.

The Z' = 12 superstructure of Λ-cobalt(III) sepulchrate trinitrate governed by C-H...O hydrogen bonds.

Λ-Cobalt(III) sepulchrate trinitrate crystallizes in P6322 with Z = 2 (Z' = 1/6) at room temperature. Slabs perpendicular to the hexagonal axis comprise molecules Co(sepulchrate) alternating with nitrate groups A and B. Coordinated by six sepulchrate molecules, highly disordered nitrate groups C are accommodated between the slabs. Here we report the fully ordered, low-temperature crystal structure of Co(sep)(NO3)3. It is found to be a high-Z' structure with Z' = 12 of the 12-fold 6a_{h}\times\sqrt{3}b_{h}\times c_{h} superstructure with monoclinic symmetry P21 (c unique). Correlations between structural parameters are effectively removed by refinements within the superspace approach. Superstructure formation is governed by a densification of the packing in conjunction with ordering of nitrate group C, the latter assuming different orientations for each of the Z' = 12 independent copies in the superstructure. The Co(sep) moiety exhibits small structural variations over its 12 independent copies, while orientations of nitrate groups A and B vary less than the orientations of the nitrate group C do. Molecular packing in the superstructure is found to be determined by short C-H...H-C contacts, with H...H distances of 2.2-2.3 Å, and by short C-H...O contacts, with H...O distances down to 2.2 Å. These contacts presumably represent weak C-H...O hydrogen bonds, but in any case they prevent further densification of the structure and strengthening of weak N-H...O hydrogen bonds with observed H...O distances of 2.4-2.6 Å.

Disorder and defects are not intrinsic to boron carbide.

A unique combination of useful properties in boron-carbide, such as extreme hardness, excellent fracture toughness, a low density, a high melting point, thermoelectricity, semi-conducting behavior, catalytic activity and a remarkably good chemical stability, makes it an ideal material for a wide range of technological applications. Explaining these properties in terms of chemical bonding has remained a major challenge in boron chemistry. Here we report the synthesis of fully ordered, stoichiometric boron-carbide B13C2 by high-pressure-high-temperature techniques. Our experimental electron-density study using high-resolution single-crystal synchrotron X-ray diffraction data conclusively demonstrates that disorder and defects are not intrinsic to boron carbide, contrary to what was hitherto supposed. A detailed analysis of the electron density distribution reveals charge transfer between structural units in B13C2 and a new type of electron-deficient bond with formally unpaired electrons on the C-B-C group in B13C2. Unprecedented bonding features contribute to the fundamental chemistry and materials science of boron compounds that is of great interest for understanding structure-property relationships and development of novel functional materials.

Resonance-stabilized partial proton transfer in hydrogen bonds of incommensurate phenazine-chloranilic acid.

The co-crystal of phenazine (Phz) and chloranilic acid (H2ca) becomes ferroelectric upon cooling through the loss of inversion symmetry. Further cooling results in the development of an incommensurate ferroelectric phase, followed by a lock-in transition towards a twofold superstructure. Here we present the incommensurately modulated crystal structure of Phz-H2ca at T = 139 K with a symmetry given by the superspace group P2(1)(½ σ(2) ½)0 and σ(2) = 0.5139. The modulation mainly affects the positions of the protons within half of the intermolecular hydrogen bonds that are responsible for the spontaneous polarization in all three low-temperature phases. Evidence for proton transfer in part of the hydrogen bonds is obtained from the correlated dependence on the phase of the modulation of the lengths of bonds involved in resonance stabilization of the acidic anion, and much smaller variations of bond lengths of atoms not involved in the resonance mechanism. Incommensurability is explained as competition between proton transfer favored for single hydrogen bonds on the basis of pKa values and avoiding unfavorable Coulomb repulsion within the lattice of the resulting ionic molecules.

Charge density distribution of 3-(1-aminoethylidene)-2-methoxy-2-oxo-2,3-dihydro-2λ(5)-benzo[e][1,2]oxaphosphinin-4-one.

A combined experimental and theoretical study of one oxaphosphinane derivative was made on the basis of a topological analysis of its electron density distributions. The electron density was determined from a high-resolution X-ray diffraction data set measured with synchrotron radiation at 100 K, whereas theoretical calculations were performed using density functional theory (DFT) methods at the B3LYP\6-311++G(3df,3pd) level of approximation. The charge-density distribution and analysis of topological properties revealed that the P-O bond is of the transit closed-shell type. The crystal structure possesses one intra- and several intermolecular hydrogen bonds. They were characterized quantitatively by topological properties using Bader's Atoms in Molecules theory. All hydrogen bonds were classified as weak. Further analysis of the experimental electron density by the source function allowed the intramolecular hydrogen bond to be characterized as an isolated hydrogen bond, in contrast to the resonance-assisted hydrogen bond in related molecules, such as chromone derivatives.

Electron densities by the maximum entropy method (MEM) for various types of prior densities: a case study on three amino acids and a tripeptide.

Dynamic model densities according to Mondal et al. [(2012), Acta Cryst. A68, 568-581] are presented for independent atom models (IAM), IAMs after high-order refinements (IAM-HO), invariom (INV) models and multipole (MP) models of α-glycine, DL-serine, L-alanine and Ala-Tyr-Ala at T ≃ 20 K. Each dynamic model density is used as prior in the calculation of electron density according to the maximum entropy method (MEM). We show that at the bond-critical points (BCPs) of covalent C-C and C-N bonds the IAM-HO and INV priors produce reliable MEM density maps, including reliable values for the density and its Laplacian. The agreement between these MEM density maps and dynamic MP density maps is less good for polar C-O bonds, which is explained by the large spread of values of topological descriptors of C-O bonds in static MP densities. The density and Laplacian at BCPs of hydrogen bonds have similar values in MEM density maps obtained with all four kinds of prior densities. This feature is related to the smaller spatial variation of the densities in these regions, as expressed by small magnitudes of the Laplacians and the densities. It is concluded that the use of the IAM-HO prior instead of the IAM prior leads to improved MEM density maps. This observation shows interesting parallels to MP refinements, where the use of the IAM-HO as an initial model is the accepted procedure for solving MP parameters. A deconvolution of thermal motion and static density that is better than the deconvolution of the IAM appears to be necessary in order to arrive at the best MP models as well as at the best MEM densities.

Experimental dynamic electron densities of multipole models at different temperatures.

It is shown that the dynamic electron density corresponding to a structure model can be computed by inverse Fourier transform of accurately calculated structure factors, employing the method of fast Fourier transform. Maps free of series-termination effects are obtained for resolutions better than 0.04 Šin direct space, corresponding to resolutions larger than 6 Å(-1) in reciprocal space. Multipole (MP) models of α-glycine and D,L-serine at different temperatures have been determined by refinement against X-ray diffraction data obtained from the scientific literature. The successful construction of dynamic electron densities is demonstrated by their topological properties, which indicate local maxima and bond-critical points (BCPs) at positions expected on the basis of the corresponding static electron densities, while non-atomic maxima have not been found. Density values near atomic maxima are much smaller in dynamic than in static electron densities. Static and low-temperature (∼20 K) dynamic electron-density maps are found to be surprisingly similar in the low-density regions. Especially at BCPs, values of the ∼20 K dynamic density maps are only slightly smaller than values of the corresponding static density maps. The major effect of these zero-point vibrations is a modification of the second derivatives of the density, which is most pronounced for values at the BCPs of polar C-O bonds. Nevertheless, dynamic MP electron densities provide an estimate of reasonable accuracy for the topological properties at BCPs of the corresponding static electron densities. The difference between static and dynamic electron densities increases with increasing temperature. These differences might provide information on temperature-dependent molecular or solid-state properties like chemical stability and reactivity. In regions of still lower densities, like in hydrogen bonds, static and dynamic electron densities have similar appearances within the complete range of temperatures that have been considered (20-298 K), providing similar values of both the density and its Laplacian at BCPs in static and dynamic electron densities at all temperatures.

A new half-condensed Schiff base compound: highly selective and sensitive pH-responsive fluorescent sensor.

A new probe, 3-[(3-benzyloxypyridin-2-ylimino)methyl]-2-hydroxy-5-methylbenzaldehyde (1-H) behaves as a highly selective fluorescent pH sensor in a Britton-Robinson buffer at 25 °C. The pH titrations show a 250-fold increase in fluorescence intensity within the pH range of 4.2 to 8.3 with a pK(a) value of 6.63 which is valuable for studying many of the biological organelles.

Electron-deficient and polycenter bonds in the high-pressure γ-B28 phase of boron.

The peculiar bonding situation in γ boron is characterized on the basis of an experimental electron-density distribution which is obtained by multipole refinement against low-temperature single-crystal x-ray diffraction data. A topological analysis of the electron-density distribution reveals one-electron-two-center bonds connecting neighboring icosahedral B(12) clusters. A unique polar-covalent two-electron-three-center bond between a pair of atoms of an icosahedral cluster and one atom of the interstitial B(12) dumbbell explains the observed charge separation in this high-pressure high-temperature polymorph of boron.

Modulated anharmonic ADPs are intrinsic to aperiodic crystals: a case study on incommensurate Rb2ZnCl4.

A combination of structure refinements, analysis of the superspace MEM density and interpretation of difference-Fourier maps has been used to characterize the incommensurate modulation of rubidium tetrachlorozincate, Rb(2)ZnCl(4), at a temperature of T = 196 K, close to the lock-in transition at T(lock-in) = 192 K. The modulation is found to consist of a combination of displacement modulation functions, modulated atomic displacement parameters (ADPs) and modulated third-order anharmonic ADPs. Up to fifth-order Fourier coefficients could be refined against diffraction data containing up to fifth-order satellite reflections. The center-of-charge of the atomic basins of the MEM density and the displacive modulation functions of the structure model provide equivalent descriptions of the displacive modulation. Modulations of the ADPs and anharmonic ADPs are visible in the MEM density, but extracting quantitative information about these modulations appears to be difficult. In the structure refinements the modulation parameters of the ADPs form a dependent set, and ad hoc restrictions had to be introduced in the refinements. It is suggested that modulated harmonic ADPs and modulated third-order anharmonic ADPs form an intrinsic part, however small, of incommensurately modulated structures in general. Refinements of alternate models with and without parameters for modulated ADPs lead to significant differences between the parameters of the displacement modulation in these two types of models, thus showing the modulation of ADPs to be important for a correct description of the displacive modulation. The resulting functions do not provide evidence for an interpretation of the modulation by a soliton model.

Dimethyl 6-methoxy-4abeta-methyl-9-oxo-1,2,3,4,4a,9,10,10abeta-octahydrophenanthrene-1,1-dicarboxylate.

In the title tricyclic keto-diester, C(20)H(24)O(6), a potential intermediate in the synthesis of bioactive podocarpic acid, the outer cyclohexane ring (in a chair conformation) is cis fused to the central cyclohexanone ring (in a half-chair conformation). The conformational analysis of the compound, investigated by semi-empirical quantum mechanical AM1 calculations, shows a good agreement with the X-ray structure, except for the orientation of the methyl, methoxyphenyl and methoxycarbonyl substituents.

(1SR,2RS,5RS,6SR,8RS)-7,7-Dimethyltricyclo[6.2.1.0(1,6)]undecane-2,5,6-triol: a supramolecular framework built from O-H...O hydrogen bonds.

In the title compound, C(13)H(22)O(3), the asymmetric unit has two independent molecules linked by a strong O-H...O hydrogen bond. The cyclohexane ring is trans fused to the cyclopentane ring bridged through an ethyl moiety. The hydroxyl groups act as donors as well as acceptors, resulting in an extensive two-dimensional hydrogen-bonded network in the (011) plane. Intermolecular O-H...O bonds between centrosymmetrically related molecules form a four-membered supramolecular assembly, leading to infinite chains parallel to the [011] direction, crosslinked in the [100] direction.