Comprehensive and High-throughput Electrolysis of Water and Urea by 3–5 nm Nickel and Copper Coordination Polymers

Metal-organic coordination polymers (CP) have attracted the scientific attention for electrochemical water oxidation as it has the similar coordination structure like natural photosynthetic coordinated complex. However, the harsh synthesis conditions and bulky nature pose a major challenge in the field of catalysis. Herein, 3–5 nm CP particles synthesized at room temperature using aqueous solutions of Ni²⁺/Cu²⁺ and 2,5-dihydroxyterepthalic acid as precursor were applied for alkaline water and urea electrolysis. The overpotential required is only 300 mV at 10 mA cm⁻² by Nano-Ni CP for water oxidation, with turnover frequency (TOF) of 21.4 s⁻¹ which is around 8 times higher than its bulk-counterpart. Overall water and urea splitting were achieved with Nano-Cu (−) ∥ Nano-Ni (+) couple on Ni foam at 1.69 and 1.52 V to achieve 10 mA cm⁻², respectively. High electrochemical surface area (ECSA), high TOF, and enhanced mass diffusion are found to be the key parameters responsible for the state-of-the-art water and urea splitting performances of nano-CPs as compared to their bulk counterparts.     

Bending of Light and Gravitational Signals in Certain On-Brane and Bulk Geometries

In this article, we first investigate the bending of light rays in 4D line elements representing spherically symmetric, static on–brane geometries. The amount of bending in these four dimensional, strong and weak field solutions is derived. Signatures, which appear in the bending formulae, due to the presence of extra dimensions are discussed. Subsequently, as a separate exercise, we calculate the bending of null geodesic trajectories in a bulk five dimensional spacetime with a Schwarzschild line element on the 3-brane section. We interpret the deviation of null trajectories as that of gravitational signals or five dimensional photons, which are, unlike light rays confined to four dimensions, allowed to propagate along the fifth (extra) dimension. Features of the presence of extra dimensions in the effective potentials and the bending formula are analysed in this context.     

Floating and sinking: the imprint of massive scalars around rotating black holes

We study the coupling of massive scalar fields to matter in orbit around rotating black holes. It is generally expected that orbiting bodies will lose energy in gravitational waves, slowly inspiraling into the black hole. Instead, we show that the coupling of the field to matter leads to a surprising effect: because of superradiance, matter can hover into "floating orbits" for which the net gravitational energy loss at infinity is entirely provided by the black hole's rotational energy. Orbiting bodies remain floating until they extract sufficient angular momentum from the black hole, or until perturbations or nonlinear effects disrupt the orbit. For slowly rotating and nonrotating black holes floating orbits are unlikely to exist, but resonances at orbital frequencies corresponding to quasibound states of the scalar field can speed up the inspiral, so that the orbiting body sinks. These effects could be a smoking gun of deviations from general relativity.     

Mössbauer Studies of Nanosize CuFe2O4 Particles

⁵⁷Fe Mössbauer spectra of pulsed-laser deposited (PLD) films of CoFe₂O₄ of 0.3 µm thickness is investigated using transmission geometry is reported. Mössbauer parameters were determined for the tetrahedral (A) and octahedral (B) sites. The PLD processed films gave measurable spectra with no visible evidence of clustering or multiple phases present. Results on the films agreed with those of the bulk material. The films exhibited magnetic hyperfine and quadruple splittings similar to that of bulk CoFe₂O₄. This work demonstrates that measurable transmission Mössbauer spectra may be obtained for PLD deposited CoFe₂O₄ thick films.     

Mössbauer studies of ɛ-Fe3−x Ni x N and γ′-Fe4−y Ni y N nanoparticles

Nanocrystalline ?-Fe_3?x Ni _x N (0.0?≤?×?≤?0.8) particles are synthesized by precursor technique and nitridation of decomposed products in NH₃ (g) in the temperature range 673 K-823 K. For x?=?0.1–0.4 compositions, single phase ?-Fe_3?x Ni _x N hexagonal structure with space group P6₃/mmc is formed, while for x?=?0.5–0.8, fcc γ′-Fe_4?y Ni _y N phase is also precipitated. The room temperature Mössbauer spectrum for all the compositions shows the presence of superparamagnetic doublet, which is attributed to ?-Fe_3?x Ni _x N phase. For x?=?0.5–0.8 compositions, two additional sextets are observed corresponding to two different iron sites, the corner position (Fe^c) and the fcc position (Fe^f), in γ′-Fe_4?y Ni _y N. The added Ni atoms preferentially substitute the corner Fe^c positions. The isomer shift, quadrupole splitting and hyperfine field values are found to change with the Ni content.     

An optimization study using response surface methods on the decolorization of Reactive Blue 19 from aqueous solution by ultrasound

The decolorization of reactive dye C.I. Reactive Blue 19 from aqueous solution was studied by using ultrasound, activated carbon and combined ultrasound/activated carbon. The combined effects of independent variables, such as ultrasound power, temperature, time, activated carbon concentration, dye concentration and initial pH were investigated on the decolorization by using the central composite design. The decolorization of RB 19 was modelled statistically and optimized by means of the Matlab computer software. The decolorization were accomplished at optimum conditions by using ultrasound, activated carbon and combined ultrasound/activated carbon as 36%, 91% and 99.9%, respectively. The application of ultrasonic irradiation was found to be beneficial for decolorization of RB 19 from aqueous solution by adsorption.     

Silanylidene and Germanylidene Anions: Valence‐Isoelectronic Species to the Well‐Studied Phosphinidene

The reduction of TipMCl₃ (Tip=2,4,6‐triisopropylphenyl) (M=Si, Ge) with KC₈ in the presence of cyclic alkyl(amino) carbene (cAAC) afforded the acyclic silanylidene and germanylidene anions in the form of potassium salt [K(cAAC)MTip]₂ (M=Si ( 1 ); Ge ( 2 )). The silanylidene and germanylidene anions are valence‐isoelectronic to the well‐studied phosphinidene and are a new class of acyclic anions of Group 14. Compounds 1 and 2 were isolated and well characterized by NMR and single‐crystal X‐ray structure analysis. Furthermore, the structure and bonding of compounds 1 and 2 was investigated by computational methods.     

Two-dimensional infrared investigation of N-acetyl tryptophan methyl amide in solution

The linear infrared and two-dimensional infrared (2D IR) spectra in the amide-I region of N-acetyl tryptophan methyl amide (NATMA) in solvents of varying polarity are reported. The two amide-I transitions have been assigned unambiguously by using 13C isotopic substitution of the carbonyl group. The amide unit at the amino end shows a lower transition frequency in CH2Cl2 and methanol, while the acetyl end has a lower transition frequency in D2O. Multiple conformers exist in CH2Cl2 and methanol, but only one conformer is evident in D2O. The 2D IR cross peaks from the intermode coupling yield off-diagonal anharmonicities 2.5 +/- 0.5, 3.25 +/- 0.5, and 3.0 +/- 0.5 cm(-1) in CH2Cl2, methanol, and D2O, respectively, which by simple matrix diagonalization yield the coupling constants 8.0 +/- 0.5, 8.0 +/- 1.0, and 5.5 +/- 1.0 cm(-1). The major conformer in CH2Cl2 corresponds to a C7 structure, in agreement with that found in the gas phase [Dian, B. C.; Longarte, A.; Mercier, S.; Evans, D. A.; Wales, D. J.; Zwier, T. S. J. Chem. Phys. 2002, 117, 10688-10702] with intramolecular hydrogen bonding between the acetyl end C=O and the amino end N-H. The backbone dihedral angles (phi, psi) are determined to be in the ranges of (-55 +/- 5 degrees , 30 +/- 5 degrees ), (120 +/- 10 degrees , -20 +/- 10 degrees ), and (+/-160 +/- 10 degrees , +/-75 +/- 10 degrees ) in CH2Cl2, methanol, and D2O, respectively.