Inorganica Chimica Acta最新文献

Herein, low cost stainless steel foils are employed as current collectors in aqueous Na-ion supercapacitors, while the foils are coated with following conducting polymers, namely, polyimide (PI), Schiff base polymer (SBP), polyanthraquinone sulfide (PAQS) and polyaniline (PANI). The foremost purpose of these polymeric coatings is the prevention of corrosion, and the resultant improvements in device performances. Notwithstanding, these polymeric coatings provide few additional benefits in device characteristics, and these are following: (i) enhancement of electrolyte stability window, (ii) contributing charge storage capacitance, (iii) conversion of 2D pristine substrate to 3D porous current collector. The four coating polymers are electrochemically characterized, and PI is selected for fabricating Na-ion supercapacitor cells. The PI-coating reduces the stainless steel’s corrosion rate ∼ 68 times, expands the electrolyte stability window ∼ 1.2 times, and delivers ∼ 2 times higher capacitance with respect to pristine current collector, whereas no appreciable interfacial resistances are observed. The supercapacitor cell with PI-functionality demonstrates ∼ 6.6 times improved capacitance than that of pristine cell at 25 mA/g current density, while > 95 and ∼ 90 % Faradaic efficiencies are noted for former and latter, respectively. The distinct enhancement of cell performances clearly demonstrates the effectiveness of multifunctional polymeric coating on corrosion-prone metallic current collectors.

Recently, significant advancements have been made in low-entropy Cu₃Sn catalysts, showcasing their efficient catalytic CO oxidation capabilities. Hence, the atomic models of the Cu₃Sn are worth established to further investigate their catalytic mechanisms. Here, the structural features and stability of (Cu₃Sn)_n clusters (n = 1–6) are investigated using the genetic algorithm combined with the density functional theory (DFT). The results reveal the structural evolution of these clusters from hollow cages to compact icosahedrons, where Cu atoms predominantly tend to grow together, while Sn atoms are dispersed at the edge positions. The E_b, E_f and Δ₂E analyses show that the icosahedral (Cu₃Sn)₃ has a higher stability than that of its neighbors. The molecular dynamics simulations demonstrates its stability even at 1000 K. The molecular orbitals and density of states reveal that the (Cu₃Sn)₃ has an 1S²1P⁶1D¹⁰2S²1F¹ superatomic electronic configuration. Electrostatic potential surfaces show that (Cu₃Sn)_n clusters have significant σ-hole regions at the Cu atomic sites, which can make the CO stretching frequency and bond length have a large red-shift. Moreover, the adsorption energy between the (Cu₃Sn)₃ and CO is the largest, reaching 1.17 eV. Our work provides inferences to the structural characteristics and adsorptions of the CuSn alloys at the atomic level.

A new luminescent MOF were synthesized by solvothermal method based on 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (TPPE), with the molecular structure of [Zn₂(TPPE)_0.5(ndc)₂]_n (ndc = 1,4-Naphthalenedicarboxylic acid) (LMOF-1). The single crystal structure indicates that LMOF-1 stacks in a three-dimensional structure. The fluorescence test results indicate that LMOF-1 emits blue light with quantum yield at 37.93 %, due to ligand–ligand charge transfer. PXRD and TG analysis confirmed that LMOF-1 has good stability, and PXRD analysis after different solvent exchanges confirmed that LMOF-1 has good stability in water. The results of ion titration experiments show that Fe³⁺, CrO₄²⁻, and Cr₂O₇²⁻ have significant quenching effects on LMOF-1, and the detection limits are 3.83 × 10⁻⁶ M, 2.57 × 10⁻⁵ M, and 4.33 × 10⁻⁶ M, respectively. Indicating that LMOF-1 can serve as a multifunctional ion detector.

Zinc oxide has been increasingly gaining popularity due to its various multifunctional features and applications in nanotechnology. Zinc oxide nanoparticles (ZnO NPs) are versatile, as these are utilized in multiple areas like gas sensing, biomedical applications, rubber composites, cosmetics formulations, food, and agriculture industry, etc. ZnO NPs have excellent features like biocompatibility, electrochemical activities, chemical stability, non-toxic nature, high surface area, high-electron communicating properties, ease of synthesis, and many more. This review paper comprehensively explores the advancements and trends of synthesis, characterization, and industrial applications of ZnO NPs. Synthesis methods including physical, chemical, and green manner are discussed herewith. General exploration of fields and applications, with special emphasis on rubber, biomedical, and sensors has been elucidated. Investigators have emphasized the photocatalytic applications, of the ZnO NPs especially in the removal of pollutants from wastewater. Further emphasizing the need for eminent research to unlock the full potential of ZnO NPs in commercializing from the laboratory to the industry.

Silver nanoparticles were synthesized by ionic exchange with zeolites and further reduction with hydrogen flux. Core electron binding energies were determined by X-ray photoelectron spectroscopy at different times of the reduction process. Electron propagator calculations of core electron binding energies were performed including scalar relativistic effects using effective core potentials and zero order regular approximation. Theoretical results were compared to the experiment to get insight into the origin of the experimental signals for carbon, oxygen, silicon, aluminum and silver. Small model molecules and zeolite fragments were used for the calculation of core electron binding energies. It is evidenced that although binding energies tend to converge, fluctuations of more than 1 eV are found for non-symmetric structures in neutral and cationic silver clusters. Detailed analysis shows that these fluctuations originate on the different coordination numbers of ionized silver atoms and charge fluctuations.

CO₂ adsorption on Pt₄ and on Pt₂M₂ (M = Co, Ni, and Cu) clusters supported on N-doped graphene (PNG) was analyzed using density functional theory. The Pt₂M₂ (M = Co, Ni) clusters supported on PNG had the maximum binding energy and charge transfer. Furthermore, the adsorption energy and charge transfer of CO₂ were high for Pt₂M₂ (M = Co, Ni, and Cu) supported on PNG. In addition, bond elongation and bending angle were observed in the CO₂ molecule after it was adsorbed on metal clusters supported on PNG. Non-covalent interaction contours revealed a repulsive interaction due to the steric effect between Pt₂M₂ (M = Co, Ni, and Cu) and PNG, whereas the Pt₄/PNG composite showed a combination of repulsive and van der Waals interactions. This investigation proved that Pt₂M₂ (M = Co, Ni, and Cu) clusters supported on PNG are promising candidates for CO₂ adsorption and activation.

Developing simple and effective receptors for instantaneous detection of l-amino acids is vital for the recognition of life-threatening diseases in their early stage. Here, we report the synthesis and characterization of 2,6-di(pyrazin-2-yl)pyridine (dppy) based ligand L (L = 2,2′-(4-(3,4-diethoxyphenyl)pyridine-2,6-diyl)dipyrazine) and its copper (II) complex, [Cu(NO₃)₂L]. The in-situ prepared [Cu(H₂O)₂L](NO₃)₂ receptor in aqueous acetonitrile (4:1 v/v, 10 mM HEPES buffer, pH 7.4) medium displayed instantaneous responses towards biologically important bio-thiol l-Cysteine (Cys) and essential amino acid l-Histidine (His) over other l-amino acids through UV–Visible absorption spectral studies. Additionally, the competitive experiments confirmed that in-situ prepared [Cu(H₂O)₂L](NO₃)₂ receptor selectively detects Cys (1 equivalent) in the presence of other l-amino acids. The detection limits of Cys and His were calculated to be 8.23 × 10⁻⁷ M and 2.55 × 10⁻⁶ M, respectively. The density functional theory (DFT) calculation shows that selectivity of [Cu(H₂O)₂L](NO₃)₂ towards Cys is due to the reduction of Cu(II) to Cu(I) in the presence of Cys, while Cys is oxidized to cystine (Cys-Cys). For His, selectivity observed due to the formation of [Cu(His)₂] moiety between Cu(II) ion with one His via N,O coordination mode and another His via N,N,O-coordination mode.

Two new nickel (II) substituted thiosemicarbazone Schiff base complexes [Ni(meph)₂] (1) [where H₂meph = (2E)-N-methyl-2-[1-(pyridin-2-yl)ethylidene]hydrazine-1-carbothioamide] and [Ni(hmm)₂](NO₃)₂·2H₂O (2) [where H₂hmm = (2E)-2-[(2-hydroxyphenyl)methylidene]-N-methylhydrazine-1-carbothioamide] have been designed and synthesized by the condensation of 4-methyl-3-thiosemicarbazide with 2-acetylpyridine and salicylaldehyde respectively. Both the metal complexes 1 and 2 are characterized using different available spectroscopic techniques like FT-IR, UV–Vis spectroscopy, elemental analysis, and single crystal X-ray structure analysis. X-ray crystal structure analysis reveal that complex 1 and 2 are octahedral Ni(II) complexes. The calf-thymus CT-DNA-binding property of 1 and 2 has been evaluated by employing UV–Vis and fluorescence spectral titration. All the results show that CT-DNA binds with both nickel(II) complexes 1 and 2. In vitro cytotoxicity activity of complexes 1 and 2 toward A375 and MDA-MB-231 was evaluated using MTT assay and other methods which confirm that both complexes 1 and 2 behave as promising anti-cancer agents.

The reaction of [X][Hfe(CO)₄] (X = mainly PPh₄, but also NEt₄, K and Ph₃PNPPh₃) with chlorophosphines for the synthesis of low coordinated phosphorus complexes is reviewed. Diphosphene (PP), phospha-alkene (PC<), phospha-allene (PCC<), and phosphide (>P) iron complexes have been in particular obtained, and characterized by ³¹P NMR, and by X-ray diffraction in several cases.

This study presents a new uncharged platinum(II) complex with a pyrazolyliodonium ligand, which features an exceptionally large σ-hole on the iodine atom. Single-crystal X-ray diffraction analysis reveals the structure of the [LPtCl₃]·2DMF complex, highlighting two types of intermolecular halogen bonds: a C−I⋯O bond with DMF and C−I⋯Cl bonds with the platinum complex. Quantum chemical calculations confirm the high positive electrostatic potential on the iodine σ-hole, demonstrating its significant halogen bond donor ability.