Structural,electronic and elastic properties of the Laves phases WFe2, MoFe2, WCr2 and MoCr2 from first-principles

A theoretical analysis of the phase stability, electronic and mechanical properties, and Debye temperatures of the C14-type Laves phases (WFe₂, MoFe₂, WCr₂ and MoCr₂) has been presented from density functional theory. The phase stability follows the order: WFe₂>MoFe₂>WCr₂>MoCr₂. An exchange of electrons takes place between Fe and W/Mo atoms, and there is also electron transfer between Cr and W/Mo. The W–W and Mo–Mo bonds are of the valence character, while the Fe–W/Mo and Cr–W/Mo bonds are of ionic character. The bonding force of A–A is greater than that of A–B in C-14 AB₂ type Laves phases (WFe₂, MoFe₂, WCr₂ and MoCr₂). The ductility of MoCr₂ is higher than others. The hardness of WFe₂ (14.1 GPa) is the highest, and the hardness of MoCr₂ is the lowest. The incompressibility for these laves phases along c-axis is larger than that along a-axis. The Debye temperature (θ_D) of MoFe₂ is 619 K, which is the highest in those phases. These laves phases also have high melting points, which follows the order: WFe₂>MoFe₂>WCr₂>MoCr₂.     

Bildung siliciumorganischer Verbindungen. 89. Selektive Photobromierung von Si-methylierten Carbosilanen

Formation of Organosilicon Compounds. 89. Selective Photobromination of Si-methylated Carbosilanes A selective photobromination of the C atoms in the skeleton of Si-methylated carbosilanes is reported. (me₃Si? CH₂)₂Sime₂ reacts to me₃Si? CBr₂? Sime₂? CH₂? Sime₃ in good yields (me = CH₃); the second CH₂ group is considerably slower brominated. Photobromination of (me₂Si? CH₂)₃ consecutively yields a and b . Also from (me₂Si? CH₂)₄ the derivative with one CBr₂ group is accessible. Bromination of tertiary CH groups is highly preferred; this is shown by the selective formation of c . The C-bromination of SiBr-substituted carbosilanes is significantly more difficult; nevertheless (Brme₂Si)₂CH₂ selectively forms (Brme₂Si)₂CBr₂. Brme₂Si? CH₂? Sime₂? CH₂? Sime₃ forms Brme₂Si? CH₂? Sime₂? CBr₂? Sime₃, i. e., only the CH₂ group non-adjacent to SiBr is attacked. The formation of CHBr groups could not be detected. Higher temperatures and longer reaction times increase the formation of polymers.     

三维有序大孔Ag/ZrO2-TiO2：制备及紫外光催化降解染料和水杨酸性能

采用聚苯乙烯(PS)微球作为模板剂,经溶胶-凝胶及煅烧后处理的方法制备了三维有序大孔(3DOM)复合材料Ag/ZrO2-TiO2。通过FTIR、XRD、XPS、N2吸附-脱附和SEM-EDS等对其进行了表征。结果显示,经PS微球作用后的复合材料Ag/ZrO2-TiO2具有锐钛矿晶型结构,其Ag以单质形式存在。该复合材料的孔结构高度有序,属三维有序大孔,平均孔直径为120 nm,孔壁由紧密堆积的Ag/ZrO2-TiO2纳米晶粒组成,孔收缩率约为40%。该复合材料表现出较好的紫外光催化降解水杨酸和甲基橙等染料性能,其活性明显高于商用光催化剂(Degussa P-25)、Ag/ZrO2-TiO2和3DOM ZrO2-TiO2,在90 min内对甲基橙的降解率达80.1%。     

Mechanism,kinetics, and environmental assessment of OH-initiated transformation of CTDE in the atmosphere

The transformation mechanism and kinetics of 2-chloro-1,1,2-trifluoroethyl-difluoromethyl-ether (CTDE, CHF₂OCF₂CHFCl) triggered by OH radicals are studied by density-functional theory methods and canonical variational transition state theory. The computational rate constant including small-curvature tunneling correction is found to be in commendable agreement with the experimental data. Two hydrogen abstraction channels to form the alkyl radicals of C·F₂OCF₂CHFCl and CHF₂OCF₂C·FCl are observed, and the formation of CHF₂OCF₂C·FCl is found to be more favorable than C·F₂OCF₂CHFCl kinetically and thermodynamically. Subsequent evolution of CHF₂OCF₂C·FCl in the presence of NO and O₂ indicates that the organic nitrate (CHF₂OCF₂CONO₂FCl) is the stable product. The dechlorinate of alkoxy radical (CHF₂OCF₂C(O·)FCl) is the most favorable degradation channel, and the estimated ozone depletion potential for CTDE relative to chlorofluorocarbon-11 is 0.0204, which could lead to ozone depletion as a consequence. The computed atmospheric lifetime for CTDE is found to be 3.69 years by considering the combined contributions from OH radicals and Cl atoms. The total radiative forcing and global warming potential of CTDE are, respectively, 0.547 W m⁻² ppbv and 628.58 (100 years) at 298 K, suggesting that the contribution of CTDE to the greenhouse effect is moderate.     

Metal–Organic Framework (MOF)-Derived Carbon-Mediated Interfacial Reaction for the Synthesis of CeO2−MnO2 Catalysts

CeO₂-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO₂ and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO₄ to synthesize CeO₂−MnO₂, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO₂ crystallites under a high calcination temperature and, more importantly, intimate contact within CeO₂/C is conveyed to CeO₂/MnO₂ after the interfacial reaction; this is responsible for the high catalytic activity of CeO₂−MnO₂ towards CO oxidation.     

The reaction of MgCl2·4H2O with CCl2F2

A new reaction of MgCl₂·4H₂O with CCl₂F₂ is investigated by DTA and TG from room temperature to 350 °C. It is observed that MgF₂ was obtained between 252 and 350 °C, Below the temperature, MgCl₂·4H₂O dehydrates and hydrolyzes to MgCl₂ and Mg(OH)Cl, which are the real reactants of the reaction with CCl₂F₂. The formation of MgF₂ is ascribed to the reaction of MgCl₂ and Mg(OH)Cl with HF, which forms by decomposition of CCl₂F₂ with the taking part in of H₂O released from dehydration of hydrated magnesium chloride on the surface of MgCl₂ and Mg(OH)Cl, which catalyzes the decomposition of CCl₂F₂ in this case. Consequently, the reactions are tested in the fluid-bed condition. It is found that MgF₂ formed at temperatures down to 200 °C in a fluid-bed reactor. This reaction may be used as a method of disposing of the environmentally sensitive CCl₂F₂ (rather than release into the atmosphere). It is also a method for the preparation of MgF₂.     

Theoretical study of the structure and fundamental properties of AZn2N2 (A = Ca,Sr, Ba)

The structure, stability, elastic, electronic, and optical properties of trigonal AZn₂N₂ (A = Ca, Sr, Ba) are simulated and compared in this work. The stability and physical properties of BaZn₂N₂ are mainly highlighted. According to the calculated results, three compounds are thermodynamically and mechanically stable, and they are brittle materials. The stability of trigonal BaZn₂N₂ is confirmed by using the different theoretical approaches. The direct band gap transition is allowed at the Γ point for each compound. The predicted direct band gaps are 1.733, 1.507, and 1.510 eV for CaZn₂N₂, SrZn₂N₂, and BaZn₂N₂, respectively. The valence band is mostly composed of the N-2p orbitals, while the conduction band is mainly contributed from the Ca-3d/Sr-4d/Ba-5d orbitals. The results show that the electron shows high mobility for carrier transport, and the value of exciton binding energy is less than 80 meV. Furthermore, compared to CaZn₂N₂ and SrZn₂N₂, BaZn₂N₂ shows excellent light absorption capacity in the visible region. This study indicates that BaZn₂N₂ is a desirable material for solar cell applications.     

Simultaneous hydrogen and peroxide production by photocatalytic water splitting

Photocatalytic oxidation of water is a promising method to realize large-scale H₂O₂ production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO₂(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H₂ and H₂O₂ production. Both H₂ and H₂O₂ are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^–1 h^–1 (first 1 h) for H₂ and H₂O₂, respectively, which is much higher than that of a commercial Pt/TiO₂(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H₂O₂, compared with the four-electron oxidation of water to O₂.     

Photolytically Induced Reaction of Monomeric AlCl with Dihydrogen in a Solid Ar Matrix at 12 K: Generation and Characterization of the Previously Unknown Monomeric Aluminium Hydride ClAlH2

Monomeric AlCl is shown to react with H₂ under photoactivation to yield the new monomeric aluminium hydride ClAlH₂. The planar, C_2v symmetric molecule is characterized by its IR spectra, taking in the effects of isotopic substitution (H₂, D₂ and HD), allied with detailed quantum chemical calculations. A normal coordinate analysis is performed to calculate accurate force constants. The properties of this species are compared to the ones of other related compounds featuring either an Al‐H or an Al‐Cl bond. Finally, the dimerization to give the D_2h symmetric H₂Al(μ‐Cl)₂AlH₂ is investigated theoretically. This dimer is of interest as a possible reagent to prepare dialane, Al₂H₆. The enthalpy for the reaction of H₂Al(μ‐Cl)₂AlH₂ in the gas‐phase with solid LiAlH₄ to give gaseous Al₂H₆ and solid LiCl is calculated.     

Synthesis, characterization and thermogravimetric study of zinc group halides adducts with imidazole

The synthesis, characterization and thermogravimetric study of the adducts ZnCl₂·2Imi, ZnBr₂·2Imi, CdCl₂·Imi, CdCl₂·2Imi, CdBr₂·2Imi, CdBr₂·3Imi, CdI₂·2.5Imi, HgCl₂·2Imi, HgBr₂·1.5Imi and HgI₂·1.5Imi (Imi = imidazole) is reported. The following sequence of thermal stability is observed for the synthesized adducts: Zn>Hg>Cd. It is also verified that larger cations, as well as larger anions, result in a smaller number of imidazole molecules in the coordination sphere of the considered cation and that hard acids exhibit stronger bonds to imidazole than soft acids, and this fact is reflected in the thermal stability sequence. ZnCl₂·2Imi behaves as a non-electrolyte in acetonitrile and ethanol, whereas ZnBr₂·2Imi is a non-electrolyte in acetonitrile and a 1:1 electrolyte in ethanol. CdI₂·2.5Imi is a non-electrolyte in acetonitrile and a 1:2 electrolyte in ethanol.     

Methanol conversion over CuO supported on CeO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript>: An in situ IR spectroscopic study

The main reactions yielding hydrogen are the recombination of hydrogen atoms on copper clusters and methyl formate decomposition. Methyl formate results from the interaction between the linear methoxy group and the formate complex located on CuO. The source of CO₂ appearing in the gas phase is the formate complex, and the source of CO is methyl formate. The rates of methoxy group conversion and product formation over supports (ZrO₂, CeO₂, Ce_0.8Zr_0.2O₂) and copper-containing catalysts (5%Cu/CeO₂, 5%Cu/ZrO₂, 2%Cu/Ce_0.8Zr_0.2O₂, 2%Cu/Ce_0.1Y_0.1Zr_0.8) are compared. The dominant process in methoxy group conversion over the supports and copper-containing catalysts is methanol decomposition to H₂ and CO and to H₂ and CO₂, respectively. The methoxy group conversion rate is proportional to the H₂ and CO₂ formation rate and is determined by the concentration of supported copper.     

Re-examination of the crystal structure of Na2Al2B2O7: stacking faults and twinning

The crystal structure of the layered compound Na₂Al₂B₂O₇ is re-examined. It is found that stacking faults can be introduced easily in the sequence of [Al₂B₂O₇]_∞²⁻ lamellae. Both rotation and reflection twinning can form in the crystal by introducing appropriate stacking faults. A domain of the Sr₂Be₂B₂O₇-type structure might occur at the twin boundary. Single crystal refinement is performed successfully with the twinning model. A similar analysis and discussion is extended to the structures of Sr₂Be₂B₂O₇ and AEAl₂B₂O₇ (AE=Alkaline earth elements Ca, Sr and Ba).     

Rapid Thermolysis Studies of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O）

T-jump/FT-IR spectroscopy was used to study the rapid thermal decomposition activity of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O） under 0.1 MPa Ar atmosphere. The results show that the main gaseous products of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O are NH3, H2O and HONO, while CO and NO are the major gaseous products of flash pyrolysis of Cd（CHZ）2（TNR）（H2O）. Thus Cd（CHZ）2（TNR）（H2O） is not an eco-friendly and chemically compatible primary explosive. Both compounds liberate volatile metal carbonate, oxide and isocyanate compounds. The combustion temperature and products of the two compounds were calculated by Real code. The results of theoretical calculation show that the combustion temperature of [Pb2（TNR）2（CHZ）2（H2O）2].4H2O is higher than that of Cd（CHZ）2（TNR）（H2O）, there is no HNCO in the combus- tion products and the amount of NO is less than the experiment result from T-jump/FTIR.     

Mesityloxomolybdän- und -wolfram-Verbindungen. I. Die Struktur von LiMoO2Me2Mes(OEt2)2

Mesityl Oxo Molybdenum and Tungsten Compounds. I. Structure of LiMoO₂Me₂Mes(OEt₂)₂ LiMoO₂Me₂Mes(OEt₂)₂ 2 is prepared by literature method [2] from MoO₂Mes₂ 1 and LiMe. Its x-ray structure and NMR-spectral data are presented. 2 adopts a dimer structure in which two [MoO₂Me₂Mes]^? anions are linked via two bridging [Li(OEt₂)₂]⁺ cations bonded to the oxo ligands. The resulting [‥OMoOLi‥]₂ ring is planar.     

Siloxymethylamines as Aminomethylation Reagents for Amines Leading to Labile Diaminomethanes That can be Trapped as Their [Mo(CO)4] Complexes

Compound Et₃SiOCH₂NMe₂ transfers Me₂NCH₂ to R₂NH (R₂=Et₂, PhMe, [Cr(η⁶‐C₆H₅)(CO)₃]Me, PhH) to form previously unknown diaminomethanes, Me₂NCH₂NR₂ and, in the case of R₂=PhH, the triamine Me₂NCH₂N(Ph)CH₂NMe₂. The diaminomethanes exhibit an unreported disproportionation to a mixture of (R₂N)₂CH₂, (Me₂N)₂CH₂, and Me₂NCH₂NR₂, which can be trapped as their [Mo(CO)₄(diamine)] complexes. Whereas PhMeNCH₂NMe₂ is a labile material, the metal‐substituted ([(η⁶‐C₆H₅)Cr(CO)₃]MeNCH₂NMe₂ is a stable material. The triamine Me₂NCH₂N(Ph)CH₂NMe₂ is unstable with respect to transformation to 1,3,5‐triphenyltriazine, but is readily trapped as the bidentate‐triamineMo(CO)₄. All metal complexes were characterized by single‐crystal X‐ray diffraction.     

Sulfinylimine: Wichtige neue Bausteine zur Entwicklung der Chemie der Polysulfanmono- und -disulfonsäuren

Sulfinylimines: Important Building Blocks for Developing the Polysulfanemonoand -disulfonic Acid Chemistry Besides hydrolysis of perfluoroorganosulfanesulfinylimines in closed systems, reactions of R_fS_xCl with K₂S₂O₅ or M₂S₂O₃ are also productive methods for the preparation of perfluoroorganosulfanemonosulfonates. The free acid CF₃SSSO₃H is made by treating the potassium salt with a strong acidic cation resin. It is unstable and shows a pK_s-value of approx. –0,5 providing an acidity comparable with polyphosphoric acids. Metathetical reactions of the potassium salts with [(C₆H₅)₄M]Cl (M = P, As) or [R₄N][ClO₄] (R = n-C₃H₇, n-C₄H₉) respectively lead to well crystallized salts. Single crystals are used for x-ray structure analysis. These prove the polysulfanesulfon-moiety to be present in these molecules. Sulfur-sulfur-bonds can also be evidenced by chlorolysis reactions. Not only with Cl₂ but also with SCl₂ R_fS_xCl or R_fS_x+1Cl and ClSO₂OM are formed respectively. In this way CF₃SSSCl is prepared for the first time. The reaction of CF₃SeBr and K₂S₂O₅ provides K[CF₃SeSO₃] which is unstable and decomposes to CF₃SeSeCF₃, K₂S₂O₆, SO₂ and KBr. When S₂Cl₂ is reacted with (CH₃)₃SiNSO besides the main product S₂(NSO)₂ also minor amounts of S_x(NSO)₂ (x = 3, 4, 5) are formed. While hydrolysis of S₂(NSO)₂ leads quantitively to (NH₄)₂S₄O₆, a mixture of ammoniumpolysulfanedisulfonates are obtained from S_x(NSO)₂ which could not be separated. It is demonstrated that chemical reactivity is dominated by disproportionation of S₂(NSO)₂ into S(NSO)₂ and sulfur. Additonal sulfinylimines are obtained by metathesis of XNSO (X = Cl, Br) and AgSCN or AgSeCN respectively. The structures of S₂(NSO)₂ and OSNSCN are established by x-ray methods. By spectroscopical evidence it is shown that OSNSeCN is isostructured with OSNSCN.     

O2 和 CO 在 Co2B2/TiO2 和 Co2B2Pt/TiO2 表面吸附的密度泛函研究

 采用密度泛函理论探讨了 TiO2 表面负载 Co2B2 和 Co2B2Pt 合金簇可能的负载构型. 结果表明, Co2B2 和 Co2B2Pt 合金簇倾向于以两个 Co 的形式负载在两个氧上. 态密度分析发现, 负载后, Co2B2 合金簇中部分 Co 原子和 B 原子成键加强, Co2B2Pt 合金簇中 Pt 原子和 B 原子成键也加强, 形成新的轨道. CO 和 O2 在 Co2B2/TiO2 和 Co2B2Pt/TiO2 表面吸附的结果表明, Co2B2Pt/TiO2 催化氧化 CO 性能的提高是由于 Pt 原子提高了 Co2B2 合金簇吸附 CO 和 O2 的能力.     

Au Modified F-TiO2 for Efficient Photocatalytic Synthesis of Hydrogen Peroxide

In this work, Au-modified F-TiO₂ is developed as a simple and efficient photocatalyst for H₂O₂ production under ultraviolet light. The Au/F-TiO₂ photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H₂O₂ synthesis, as in a pure TiO₂ reaction system. The F⁻ modification inhibits the H₂O₂ decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H₂O₂ production. We compared the activity of TiO₂ with F⁻ modification and without F⁻ modification in the presence of Au, and found that the H₂O₂ production rate over Au/F-TiO₂ reaches four times that of Au/TiO₂. In situ electron spin resonance studies have shown that H₂O₂ is produced by stepwise single-electron oxygen reduction on the Au/F-TiO₂ photocatalyst.     

Synergistic and Diminutive Effects between Regium and Aerogen Bonds

The aerogen bond is formed in complexes of HCN−XeF₂O and C₂H₄−XeF₂O. The lone pair on the N atom of HCN is a better electron donor in the aerogen bond than the π electron on the C=C bond of C₂H₄. The coinage substitution strengthens the aerogen bond in MCN−XeF₂O (M=Cu, Ag, and Au) and its enhancing effect becomes larger in the Au<Cu<Ag pattern. The aerogen bond is further enhanced by the regium bond in C₂H₂−MCN−XeF₂O and C₂H₄−MCN−XeF₂O, but is weakened by the regium bond in MCN−C₂H₄−XeF₂O and C₂(CN)₄−MCN−XeF₂O. Simultaneously, the regium bond is also strengthened or weakened in these triads. The synergistic and diminutive effects between regium and aerogen bonds have been explained by means of charge transfer and electrostatic potentials.     

Ternary Complexes Stabilized by Chalcogen and Alkaline-Earth Bonds: Crucial Role of Cooperativity and Secondary Noncovalent Interactions

High-level G4 calculations show that the strength of chalcogen interactions is enhanced dramatically if chalcogen compounds simultaneously form alkaline-earth bonds. This phenomenon is studied by exploring binary YX₂⋅⋅⋅N-Base complexes and two types of ternary MCl₂⋅⋅⋅YX₂⋅⋅⋅N-Base, YX₂⋅⋅⋅N-Base⋅⋅⋅MCl₂ complexes, in which YX₂ is a chalcogen compound (Y=S, Se; X=F, Cl), the N-Bases are sp, sp², and sp³ bases (NCH, HN=CH₂, NH₃), and MCl₂ are alkaline-earth BeCl₂ or MgCl₂ derivatives. Starting from the chalcogen-bonded complexes YX₂⋅⋅⋅NH₃ and YX₂⋅⋅⋅HN=CH₂, the binding site of a new incoming alkaline-earth bond is found, surprisingly, to depend on the nature of the halogen atom attached to the chalcogen. For the YF₂ binary complexes the association site is the F atom of the YF₂ subunit, whereas for YCl₂ it is the N atom of the nitrogen base. Regarding YX₂⋅⋅⋅NCH complexes, N is the most favorable site for an alkaline-earth interaction in ternary complexes, regardless of which YX₂ derivative is used. The explanation relies on the interplay of all the noncovalent interactions involved: the strong cooperativity between chalcogen and alkaline-earth bonds, and the appearance of secondary noncovalent interactions in the form of hydrogen bonds.