A fully automatic system for underway N2O measurements based on cavity ring-down spectroscopy

N₂O is one of the most important greenhouse and ozone-depleting gases and has been the source of considerable concern in recent years. The oceans account for ~ 1/4 of the global N₂O emission budget; however, the oceanic N₂O source/sink characteristics are not well understood. To enhance the study of oceanic N₂O source/sink characteristics, our laboratory developed a fully automatic underway system for surface water N₂O concentration and atmospheric N₂O mole fraction measurements consisting of a cavity ring-down spectroscopy (CRDS) instrument and an upstream device. The developed device can be programmed to switch the CRDS measurements from the equilibrator headspace to the atmospheric sample and the reference gas sample. The surface water N₂O concentration is calculated from the equilibrium headspace N₂O mole fraction in the equilibrator. The response time of this equilibrator is ~ 3.4 min, and the estimated precision of this method for surface water N₂O measurements is better than 0.5% (relative standard deviation, RSD), which is one order of magnitude better than that of traditional gas chromatographic methods and can be further optimised. Data are acquired every 20 s, and the calibration frequency requirement of this system is approximately 7–10 days. This labor-saving underway system is a powerful tool for high-precision and high-resolution measurements of atmospheric and oceanic N₂O and can significantly improve the study of the characteristics of oceanic N₂O sources/sinks and their response to climate change.     

Facile fabrication of cerium niobate nano-crystalline fibers by electrospinning technology

In this study, one-dimensional (1D) cerium niobate nano-crystalline fibers were first prepared by a facile sol–gel and electrospinning process, followed by heat treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TG), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM) were used to characterize the samples. It can be seen from SEM images that the as-prepared xerogel samples and those annealed at 900 °C presented uniform fibrous morphology, with the diameter of 100–300 nm and length of several centimeters. The XRD and FT-IR results showed that cerium niobate samples had well-crystallized phase of CeNbO_4.25 with the crystallite size of about 28.6 nm at a heat treatment temperature of 900 °C, which can also be validated with the TEM image. The AC impedance of annealed disks made from the CeNbO_4.25 nano-crystalline fibers has been probed.     

Coinage metal complexes of N‐heterocyclic carbene bearing nitrile functionalization: Synthesis and photophysical properties

A new series of N‐heterocyclic carbene (NHC) ligand precursors ( 1 and 2 ) with their [Ag(I)(NHC)₂]PF₆ complexes ( 3 and 4 ) and [ClAu(I)(NHC)] complexes ( 5 and 6 ) are reported. Complexes 5 and 6 were synthesized via transmetalation reaction using either 3 or 4 and AuCl(SMe₂) as reactants, respectively. All the synthesized compounds were fully characterized using elemental analyses and Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies. In the crystal structures of 3 , 5 and 6 , the Ag(I) and Au(I) ions are in a linear geometry. The entire structure of 3 is stabilized by significant π–π interactions, while the structures of 5 and 6 are stabilized with the presence of aurophilic interactions between the adjacent Au(I) ions as well as CH–π or π–π interactions. From photoluminescence studies, complexes 5 and 6 show dual‐emission characteristics. The higher‐energy fluorescence originates from ¹XLCT mixed with ¹MLCT, while the lower‐energy phosphorescence is ascribed to ³XLCT and ³MLCT with small contribution of ³ILCT, as evidenced by density functional theory (DFT) and time‐dependent DFT calculations of the modelled molecules.     

The Uncommon Channel‐Based Ln‐MOFs for Highly Selective Fe3+ Detection and Superior Rhodamine B Adsorption

Two new isostructural 3D lanthanide–organic frameworks [H₂N(Me)₂] [Ln₃(OH)(bpt)₃(H₂O)₃] (DMF)₂?(H₂O)₄ ( 1‐Ln ; Ln=Sm and Eu) with a 1D channel (25 Å) have been successfully assembled from the rare trinuclear [Ln₃(OH)(COO)₉] clusters and biphenyl‐3,4′,5‐tricarboxylic acid (H₃bpt) and exhibit high stability towards water in the pH range 3–10. MOF 1‐Eu is a promising luminescent probe for sensing Fe³⁺ in aqueous solution and is also selective towards rhodamine B (RhB) with a superior adsorption capacity of 735 mg g^?1, which is the highest among the reported Ln‐MOFs for RhB removal so far. Periodic DFT calculations further confirmed the selective adsorption of rhodamine B over other dyes.     

Advances in value-added aromatics by oxidation of lignin with transition metal complexes

Transition Metal Chemistry - Lignin is the second most abundant component in biomass, considered as the most abundant and available renewable source of aromatics in Nature. The depolymerization of...     

Pressure-dependent structure,mechanical and thermodynamic properties of tetragonal AsTiZr arsenide: A density functional theory study

Recent discoveries of the novel properties of arsenides prompt us to theoretically predict the tetragonal AsTiZr ternary compound under pressure, in order to exploit new functional materials. The structure, elastic and thermodynamic properties of AsTiZr have been investigated under various pressures, based on density functional theory (DFT). For the sake of consistency, the approach of the generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof (PBE) was used. The calculated structural data at zero pressure are in good agreement with previous report. The dependence of relative changes of lattice parameters (a₀ and c₀) and volume V₀, elastic constants, bulk, shear and Young's modulus, and Debye temperature on pressure has been investigated. The thermodynamic properties like heat capacity C, enthalpy E, free energy F and entropy S with pressure are successfully obtained and discussed.     

Solution-based processing of carbon nitride composite for boosted photocatalytic activities

Thanks to the dissolution of bulk carbon nitride (CN), a heterojunction of CN and sulfur-doped CN was constructed via a solution-based processing way, which led to a more homogeneous composite and an improved photocatalytic H₂ production activity up to 230% with respect to that by conventional impregnating.