Theoretical Study of the AlCl Disproportionation Reaction Mechanism on the Al(100) Surface

The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.

Study on experiment and mechanism of thermal dissolved sulfuration of low grade lead-zinc oxide ore in lanpin

The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S＋3H2O=2S^2-＋S2O3^2--＋6H^＋. The dynamics process is studied and the first-order reaction rate equation -1n（1-a）=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.

Synthesis, Structure and Catalytic Activity of a Manganese(Ⅲ) Complex Based on 2-(2-Hydroxyphenyl)-5,6-dichlorobenzimidazole Ligands

A new ligand, 2-（2-hydroxyphenyl）-5,6-dichlorobenzimidazole, H2pbmCl2（1）, and a novel MnIII complex, [MnIII（HpbmCl2）（pbmCl2）（DMF）2]（2）,（DMF = N,N-dimethylformamide）, have been synthesized and characterized. The crystal of compound 1（C13H8Cl2N2O, Mr = 279.12） belongs to the monoclinic system, space group P21 with a = 3.770（5）, b = 25.20（3）, c = 5.865（7） A, = 92.727（17）o, V = 556.6（12） A3, Z = 2, Dc = 1.665 g/cm^3, S = 1.137, μ= 0.568 mm^-1, F（000） = 284, the final R = 0.0876 and wR = 0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O–H group of phenol and N atom of imidazole. H2pbmCl2（1） molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds（N–H…O and C–H…Cl）. The crystal of complex 2（C32H27Cl4MnN6O4, Mr = 756.34） belongs to the monoclinic system, space group P21/c with a = 19.043（10）, b = 10.808（5）, c = 18.704（11）A, β= 115.540（6）°, V = 3473（3） A3, Z = 4, Dc = 1.446 g/cm^3, S = 1.3, μ = 0.733 mm-1, F（000） = 1544, the final R = 0.1219 and wR = 0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The [MnIII（HpbmCl2）（pbmCl2）（DMF）2] molecules are arranged into a three-dimensional structure through hydrogen bonds（N–H…N, C–H…N and C–H…Cl） and weak π···πinteractions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.

Stable large-area monodomain in as-grown bulk ferroelectric single crystal Sn_(2)P_(2)S_(6)

Driven by the minimization of total energy,the multi-domain morphology is preferred in as-grown ferroelectrics to reduce the depolarization and strain energy during the paraelectric to ferroelectric phase transition.However,the complicated multi-domain is not desirable for certain high-performance ferroelectric electro-optic devices.In this work,we achieve a reproducible and stable large-area monodomain in as-grown bulk ferroelectric single crystal Sn_(2)P_(2)S_(6).The monodomain dominates the entire single crystal,which is attributed to the internal charge carriers from the photoexcited disproportionation reaction of Sn ions.The charge carriers effectively screen the depolarization field and therefore decrease the depolarization energy and facilitate the formation of monodomain.This work offers a potential approach for engineering bulk ferroelectrics with a stable monodomain,which is desirable for the high-performance ferroelectric electro-optic devices.

Manipulation and observation of atomic-scale superlattices in perovskite manganate

Superlattices in crystals,particularly in perovskite oxides with strong correlation effects,can create new states of matter and produce peculiar physicochemical phenomena.However,the newfangled perovskite superlattices depend on physical deposition with unit-cell precision.It has been challenging to explore a new suitable chemical method to tailor perovskite superlattices.Herein,we present a new bottomup strategy to precisely prepare atomic-scale oxide superlattices of(LaMnO_(3))_(1)-(La_(1-x-y)Ca_(x)K_(y)MnO_(3))_(2)in a monodispersed perovskite La_(0.66)Ca_(0.29)K_(0.05)MnO_(3)(LCKMO).The special atomic-scale perovskite superlattices are demonstrated using SAED,HAADF-STEM,XRD,and atomic-resolution elemental mapping.Our experiments reveal that the perovskite superlattices can be fabricated under extreme hydrothermal conditions utilizing ultra-high concentrations of KOH.An approximate molten salt system in the hydrothermal process can induce the disproportionation reaction of MnO_(2)solids,which is vital to the growth of ordered perovskite superlattices.This work not only clarifies the hydrothermal growth process of perovskite oxides in extreme conditions,but also proposes a novel engineering route toward perovskite superlattices.

Performance of TiC coating prepared by in situ conversion of organic carbon film on 316L bipolar plate

TiC coating on 316L stainless steel surface is prepared by molten salt disproportionation reaction by using carbon layer converted from organic carbon solution as carbon source.The Raman and morphology characterizations show that the carbon layer and TiC coating are successfully prepared on the surface of 316L stainless steel,the prepared carbon layer and 316L matrix have good adhesion,and the prepared TiC coating is smooth and dense.In the simulated cathodic environment of the proton exchange membrane fuel cell,the potentiostatic and potentiodynamic polarization measurements show that the TiC coating has smaller and more stable current density fluctuation than the 316L stainless steel substrate,and the electrochemical impedance test lasting for 275 h still shows better stable corrosion resistance than that of the 316L stainless steel substrate.Finally,in the water contact angle and interface contact resistance tests,the TiC coating consistently maintained better hydrophobicity and lower interface contact resistance values than 316L stainless steel.