Investigation on the catalytic activity of doped low-percentage oxide catalysts Mn/ZnO obtained from oxalate precursor

The precursors with a low manganese content ≤ 0.07% Mn were synthesized by spontaneous crystallization from Zn²⁺, Mn²⁺ and C₂O₄ ²⁻-containing solutions. The initial ratio Zn²⁺:C₂O₄ ²⁻ = 1:1 and 1:2 influences the morphology and prevailing orientations of the crystallites in the oxalate samples. The presence of such small Mn content in the samples does not change the morphology or size of the crystals. The ZnO and Mn/ZnO oxides with manganese content from 0.51×10⁻² to 15.1×10⁻² Wt % are obtained after thermal decomposition of the oxalates. The oxides preserved the morphology of the precursors. The catalytic tests show that the pure ZnO has a poor activity for CO oxidation reaction. Its doping with Mn promotes the catalytic activity (up from twice to five times) in spite of the very low contents of the dopants. The observed increase of the activity depends on both dopant concentration and Zn²⁺:C₂O₄ ²⁻ ratio, probably due to the different mechanism of the manganese inclusion and different morphology of the oxides. The catalysts of the 1:2 series are more active in CO oxidation reaction.      

Crystal structures and thermal decomposition kinetics of lanthanide complexes with 3,4,5-trimethoxybenzoic acid and 1,10-phenanthroline

A series of lanthanide complexes with the 3,4,5-trimethoxybenzoic acid(3,4,5-tmoba) and 1,10-phenanthroline(phen),[Ln(3,4,5-tmoba) 3 phen] 2(Ln = Pr(1),Nd(2) and Ho(3)),have been synthesized and characterized by a series of techniques including elemental analysis,IR spectra,X-ray crystallography and TG/DSC-FTIR technology.The three complexes have two kinds of coordination modes,in which the Pr 3+ and Nd 3+ cations are nine-coordinated and the Ho 3+ cation is eight-coordinated.The three-dimensional IR accumulation spectra of gaseous products for complexes 1-3 were analyzed and the gaseous products were identified by the typical IR spectra obtained from the 3D surface graphs.Meanwhile,we obtained the activation energy E of the first steps of complexes 1-3 by the integral isoconversional non-linear(NL-INT) method and discussed the non-isothermal kinetics of complexes 1-3 using the Malek method.Finally,SB(m,n) was defined as the kinetic method of the first-step thermal decomposition.The thermodynamic parameters △G≠,△H≠ and △S≠ of activation at the peak temperature were also calculated.     

Spectroscopic study on the interaction between[Hg（SCN）4]2- and hemoglobin

The interaction between[Hg（SCN）₄]^2- and hemoglobin（Hb） under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering（RRS） spectroscopy and circular dichroism（CD） spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg（SCN）₄]^2- and Hb.The possible mechanism suggested for the interaction was that ten Hg（SCN）₄]^2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg（SCN）₄]^2- with Trp was the major cause of the fluorescence quenching of Hb.     

Synthesis, Structure and Luminescent Property of a Zinc(Ⅱ) Coordination Polymer Incorporating Flexible Cyclohexane-1,2,3,4,5,6-hexacarboxylate Ligand

The hydrothermal reaction of Zn(NO3)2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate (H6LI·H2O, cis-conformation LI: a,e,a,e,a,e) and 2,2'-bpy yielded a new coordination polymer [Zn2(H2LII)(2,2'-bpy)]·2H2O(trans-conformation LII: e,e,e,e,e,e), which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD(X-ray powder diffraction). This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922(5) nm, b=0.97291(8) nm, c=1.22184(9) nm, ...     

Controlled formation of novel supramolecular microbelts or microprisms from aniline and H2PdCl4 driven by coordination and π–π interactions

In this communication, I report the formation of novel supramolecular one-dimensional (1D) structures including microbelts and microprisms by a direct mix of aniline and H₂PdCl₄ aqueous solutions at room temperature. As-formed supramolecular structures were characterised by scanning electron microscopy, X-ray photoelectron spectra and X-ray diffraction techniques. Both coordination and π–π interactions are expected to be responsible for these 1D microstructures. It suggests that the molar ratio of the reactants is crucial to the formation of such 1D structures.     

Selective Synthesis of 2,5‐Diformylfuran by Sustainable 4‐acetamido‐TEMPO/Halogen‐Mediated Electrooxidation of 5‐Hydroxymethylfurfural

A new method was developed for the selective gram‐scale synthesis of 2,5‐diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass‐derived 5‐hydroxylmethylfurfural (HMF) catalyzed by 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐AcNH‐TEMPO) in a two‐phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I₂ (co‐)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62–65 % yield of DFF. This novel method provides a sustainable pathway for waste‐free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical.     

2-巯基乙磺酸铜配位聚合物的合成与晶体结构

以2-巯基乙磺酸钠为配体,2,2'-联吡啶,4,4'-联吡啶为辅助配体,与硝酸铜反应,得到一种一维链状配位聚合物 [CuL(4,4'-bipy)(2,2'-bipy)H2O]n (L=-O3S-CH2-CH2-S-S-CH2-CH2-SO-3),通过元素分析、红外光谱对其进行了表征,并用X射线衍射测定了其结构.结果表明:该配合物属于单斜晶系,P2(1)/c空间群,晶胞参数为:a=0.8385(2) nm,b=1.3764(3) nm,c=2.1719(5) nm,β = 93.391(3) °,V = 2.5023(10) nm3,Z = 4.     

微弧氧化陶瓷膜封孔后处理及抗高温氧化性能的研究

在铝酸盐体系中,利用微等离体氧化脉冲电源在Ti-6Al-4V合金表面制备了以Al2TiO5为主晶相的陶瓷膜层,然后采用钛酸四丁酯/乙醇和硅酸钠溶液的封孔方法对微弧氧化陶瓷膜进行封孔后处理。通过SEM及高温氧化测试,分析比较了陶瓷膜层在封孔前后的表面形貌以及抗高温氧化性能的变化情况。结果表明:封孔后膜层孔洞明显变小。经700℃高温氧化测试,采用钛酸四丁酯/乙醇溶液封孔方法不仅没有带来抗高温氧化性能的提高反而下降,而硅酸钠溶液的封孔方法提高了抗高温氧化性能。     

Synthesis and Characterization of an α-Fe2O3-Decorated g-C3N4 Heterostructure for the Photocatalytic Removal of MO

This study describes the preparation of graphitic carbon nitride (g-C₃N₄), hematite (α-Fe₂O₃), and their g-C₃N₄/α-Fe₂O₃ heterostructure for the photocatalytic removal of methyl orange (MO) under visible light illumination. The facile hydrothermal approach was utilized for the preparation of the nanomaterials. Powder X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray (EDX), and Brunauer–Emmett–Teller (BET) were carried out to study the physiochemical and optoelectronic properties of all the synthesized photocatalysts. Based on the X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance (DRS) results, an energy level diagram vs. SHE was established. The acquired results indicated that the nanocomposite exhibited a type-II heterojunction and degraded the MO dye by 97%. The degradation ability of the nanocomposite was higher than that of pristine g-C₃N₄ (41%) and α-Fe₂O₃ (30%) photocatalysts under 300 min of light irradiation. The formation of a type-II heterostructure with desirable band alignment and band edge positions for efficient interfacial charge carrier separation along with a larger specific surface area was collectively responsible for the higher photocatalytic efficiency of the g-C₃N₄/α-Fe₂O₃ nanocomposite. The mechanism of the nanocomposite was also studied through results obtained from UV-vis and XPS analyses. A reactive species trapping experiment confirmed the involvement of the superoxide radical anion (O₂^•−) as the key reactive oxygen species for MO removal. The degradation kinetics were also monitored, and the reaction was observed to be pseudo-first order. Moreover, the sustainability of the photocatalyst was also investigated.     

The Phosphorus Bond,or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.