Raspberry-like Hierarchical Au/Pt Nanoparticle Assembling Hollow Spheres with Nanochannels: An Advanced Nanoelectrocatalyst for the Oxygen Reduction Reaction

In this contribution, we for the first time report the synthesis of raspberry-like hierarchical Au/Pt nanoparticle (NP) assembling hollow spheres (RHAHS) with pore structure and complex morphology through one in situ sacrificial template approach without any post-treatment procedure. This method has some clear advantages including simplicity, quickness, high quality, good reproducibility, and no need of a complex post-treatment process (removing templating). Furthermore, the present method could be extended to other metal-based NP assembling hollow spheres. Most importantly, the as-prepared RHAHS exhibited excellent electrocatalytic activity for oxygen reduction reaction (ORR). For instance, the present RHAHS-modified electrode exhibited more positive potential (the half-wave potential at about 0.6 V), higher specific activity, and higher mass activity for ORR than that of commercial platinum black (CPB). Rotating ring-disk electrode (RRDE) voltarnmetry demonstrated that the RHAHS-modified electrode could almost catalyze a four-electron reduction of O-2 to H2O in a 0.5 M air-saturated H2SO4 solution.

Electronic structures and chemical bonding in 4d transition metal monohalides

Bond distances, vibrational frequencies, dipole moments, dissociation energies, electron affinities, and ionization potentials of NIX (XM = Y-Cd, X = F, Cl, Br, I) molecules in neutral, positively, and negatively charged ions were studied by density functional method, B3LYP. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the 4d transition metal s, d orbitals, and the p orbital of halogen. For both neutral and charged molecules, the fluorides have the shortest bond distance, iodides the longest. Although the opposite situation is observed for vibrational frequency, that is, fluorides have the largest value, iodides the smallest. For neutral and anionic species, the dissociation energy tends to decrease with the increasing atomic number from Y to Cd, suggesting the decreasing or weakening of the bond strength. For cationic species, the trend is observed from Y to Ag.

Density functional studies of diatomic LaO to LuO

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies and dipole moments of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the metal s, d and f orbitals and oxygen p orbitals. Contrary to the well known lanthanide contraction, the bond distance is not regular from LaO to LuO for both neutral and charged molecules. An obvious population at 5d orbital was observed through the lanthanide series. 4f electrons also participate the chemical bonding for CeO to NdO and TbO to TmO. For EuO, GdO, YbO and LuO, 4f electrons tend to be localized. The spin multiplicity is regular for neutral and charged molecules. The spin multiplicity of the charged molecules can be obtained by -1 (or +1 for TbO+, DyO+, YbO- and YbO+) compared with the corresponding neutral molecules.

Rare earth metal complexes bearing thiophene-amido ligand: Synthesis and structural characterization

2,6-Diisopropyl-N-(2-thienylmethyl) aniline ( H2L) has been prepared, which reacted with equimolar rare earth metal tris( alkyl)s, Ln( CH2SiMe3)(3)( THF)(2), afforded rare earth metal mono( alkyl) complexes, LLn(CH2SiMe3)(THF)(3) ( 1: Ln = Lu; 2: Ln = Y). In this process, H2L was deprotonated by one metal alkyl species followed by intramolecular C-H activation of the thiophene ring to generate dianionic species L2- with the release of two tetramethylsilane. The resulting L2- combined with three THF molecules and an alkyl unit coordinates to Y3+ and Lu3+ ions, respectively, in a rare N,C-bidentate mode, to generate distorted octahedron geometry ligand core. Whereas, with treatment of H2L with equimolar Sc(CH2SiMe3)(3)( THF)(2), a heteroleptic complex ( HL)( L) Sc( THF) ( 3) was isolated as the main product, where the dianionic L2- species bonds to Sc3+ via chelating N, C atoms whilst the monoanionic HL connects to Sc3+ in an S,N-bidentate mode. All complexes 1-3 have been characterized by NMR spectroscopy and X-ray diffraction analysis.

The real role of carbon in Pt/C catalysts for oxygen reduction reaction

A new electrocatalysis of carbon materials for oxygen reduction reaction (ORR) on Pt/C catalysts was discovered. It was found that there exist two kinds of electroactive sites on these supports of carbon materials, which can effectively electrocatalyze the reduction of peroxide intermediated from oxygen reduction on Pt, as this provides continuous driving force to move the equilibrium toward the production of peroxide from ORR.

Syntheses and crystal structures of [Mn(H2O)(4)(bpy)]L center dot 4H(2)O, [Mn(H2O)(4)(bpy)]L ' center dot 4H(2)O (H2L = SUCCINIC ACID, H2L ' = FUMARIC ACID)

Reactions of freshly prepared M(OH)(2-2x)(CO3)(x) (.) yH(2)O (M = Mn, Zn) and 4,4'-bipyridine (bpy) with succinic acid (H2L) or famaric acid (H2L') in CH3OH-H2O afforded [Mn(H2O)(4)(bpy)]L (.) 4H(2)O, 1, [Mn(H2O)(4)(bpy)]L' (.) 4H(2)O, 2 and [Zn(H2O)(4)(bpy)]L (.) 4H(2)O, 3. The three coordination polymers are isostructural and consist of (1)(infinity)[M(H2O)(4)(bpy)(2/2)](2+) cationic chains, crystal H2O molecules and dicarboxylate anions (succinate or fumarate anions). Within the chains, the metal atoms are each octahedrally coordinated by four aqua oxygen atoms and two pyridyl nitrogen atoms from two 4,4'-bipyridine ligands. The crystal H2O molecules are hydrogen bonded to dicarboxylate anions to form ribbon-like anionic chains. The cationic and anionic chains are interconnected via hyqrogen bonds to generate a 3D network. Crystal data: 1 triclinic, P (1) over bar, a = 7.235(1), b = 7.749(2), c = 10.020(2) Angstrom, alpha = 79.95(3), beta = 88.79(3), gamma = 71.39(3)degrees, V = 523.9(2) Angstrom(3) and D-cal = 1.494 g cm(-3) for Z = 1; 2 triclinic, P (1) over bar, a = 7.127(1), b = 7.800(2), c = 9.945(2) Angstrom, alpha = 80.26(3), beta = 87.86(3), gamma = 72.69(3)degrees, V = 520.2(2) Angstrom(3) and D-cal = 1.498 g cm(-3) for Z = 1; 3 triclinic, P (1) over bar, a = 7.189(1), b = 7.764(2), c = 9.843(2) Angstrom, alpha = 79.16(3), beta = 87.80(3), gamma = 71.29(3)degrees, V = 510.9(2) Angstrom(3) and D-cal = 1.559 g cm(-3) for Z = 1.

Electronic structures and chemical bonding in transition metal monosilicides MSi (M=3d, 4d, 5d elements)

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies, and dipole moments of the title molecules in neutral, positively, and negatively charged ions were studied using the density functional method. Ground state was assigned for each species. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides an ionic component, covalent bonds are formed between the metal s, d orbitals and the silicon 3p orbital. The covalent character increases from ScSi (YSi) to NiSi (PdSi) for 3d (4d) metal monosilicides, then decreases. For 5d metal monosilicides, the covalent character increases from LaSi to OsSi, then decreases. For the dissociation of cations, the dissociation channel depends on the magnitude of the ionization potential between metal and silicon. If the ionization potential of the metal is smaller than that of silicon, channel MSi+-> M++Si is favored. Otherwise, MSi+-> M+Si+ will be favored. A similar behavior was observed for anions, in which the dissociation channel depends on the magnitude of electron affinity.

Effect of metal ions on Ru(bpy)(3)(2+) electrochemiluminescence

Ethylenediaminetetraacetate (EDTA) was chosen for the investigation of the effect of metal ions on Ru(bpy)(3)(2+) electrochemiluminescence (ECL). Metal ions that are preferentially bound to the oxygen atoms (MIO) have no effect on the intensity of ECL except for Al3+ and Y3+, whereas metal ions that are preferentially bound to the nitrogen atoms (MIN) preclude the oxidation of EDTA and decrease the ECL intensity.

STUDIES ON ORGANOLANTHANIDE COMPLEXES .40. SYNTHESIS AND X-RAY STRUCTURE OF BIS (2-METHOXYETHYLCYCLOPENTADIENYL) YTTRIUM AND YTTERBIUM TETRAHYDROBORATES

New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

A NOVEL METAL THIAMINE COMPLEX WITH A CYCLIC DIMER FORMED BY METAL-BRIDGED 2 THIAMINE LIGANDS - CRYSTAL-STRUCTURE OF [MN(THIAMINE)CL2(H2O)]2[THIAMINE]2CL4.2H2O

The crystal structure of [Mn(thiamine)Cl2(H2O)]2[thiamine]2Cl4.2H2O has been determined by X-ray diffraction methods. The compound contains a cyclic dimer of a complex cation with two thiamine ligands bridged by two Mn(II) ions across a crystallographic center of symmetry. Each Mn(II) is coordinated by two chloride atoms, a water molecule, a N(1') atom of the pyrimidine from a thiamine and an O(53) atom of the hydroxyethyl side chain from another thiamine. There are two free-base thiamine molecules related by a center of symmetry in the unit cell, which form a base-pair through the hydrogen bonds. Both the independent thiamine molecules in the asymmetric unit assume the common F conformation with phi-T = 10.0(9) and 3.6(10) and phi-P = 85.6(7) and 79.6(7), respectively. The compound provides a possible model for a metal-bridged enzyme-coenzyme complex in thiamine catalysis. Crystallographic data: triclinic, space group P1BAR, a = 12.441(4), b = 13.572(4), c = 11.267(3) angstrom, alpha = 103.15(2), beta 89.03(3), gamma = 115.64(2)-degrees, Z = 1, D(calc) = 1.524 g cm-3, and R = 0.050 for 3019 observed reflections with I > 3-sigma(I).

STUDIES ON THE REACTION AND STRUCTURE OF THE COMPLEXES OF ALKALINE-EARTH METAL WITH CHLOROPHOSPHONAZO-DBC

In this paper, the reaction and structure of the complexes of alkaline earth metal (Ca, Sr, Ba) with 2-(4'-chloro-2'-phosphonazo)-7-(2', 6'-dibromo-4'-chlorophenylazo 1, 8-dihydroxy-3, 6-naphthalene disulfonic acid (Chlorophosphonazo-DBC) have been studied. This ligand has eight forms under different acidity. The protonation reactions take place at [H+] > 0.36 mol.dm-3. The ligand begins dissociations at pH > 0.5. Two protons are released in the complexes formation reactions(Me2+ + 2HI half-arrow-pointing-left and half-arrow-pointing-right MeL2 + 2H+). The stability constants of the complexes of Calcium, Strontium and Barium have been determined by Yoe-Jone method, Majumder-Chakrabartty method and calculation method. The order of the stability of complexes is as follows: Sr > Ba > Ca. The structure of the complexes have also been studied by infrared spectroscopy, Laser Raman spectroscopy, NMR, and EPR. The results show that these groups of N = N, PO3H2 and OH are active groups in the complex reactions. The structure of the complexes of Strontium, Barium and Calcium with chlorophosphonazo-DBC are represented and the reaction and the complex bonds are discussed in this paper.

XPS STUDY ON RARE-EARTH PHTHALOCYANINE COMPLEXES

The rare earth monophthalocyanine complexes, LnPcCl and LnPc(OAc)2 (Ln = Tb, Ho, Tm, Lu, Pc=Phthalocyanine, OAc = Acetate), were synthesized. The electronic structures of the complexes have been studied by means of XPS. The experimental results of binding energies for the complexes indicate that the bonds of the complexes have a certain covalent character depending on L-->Ln charge transfer. This L-->Ln charge transfer process of phythalocyanine complexes differs from that of crown ether complexes. Both coordination and substitution are included in the former case, but only coordination in the latter. Phthalocyanine ring is an electrophilic group and its electronegativity is large. So, the O1s binding energies of coordinating oxygen atoms of acetate in LnPc(OAc)2 are larger than those of Ln(OAc)3. The magnitude of valent charge delocalized from ligand onto metal atom is dependent on electronegativity, coordination number, valence state and so on. Because coordination number of Ln in LnPc(OAc)2 is larger than that in LnPcCl and electronegativity of Clin LnPcCl is larger than that of O in LnPc(OAc)2, the Ln4d5/2 binding energies of LnPc (OAc)2 are less than those of LnPcCl.

Investigations on the promoting effect of metal oxides on La-V-O catalyst in propane oxidative dehydrogenation

The addition of reducible metal oxides as promoters shows a positive effect on the catalytic behavior of lanthanum vanadate (LaVO4). A C3H6 yield increase of 6.5% is observed at 500 degreesC on molybdenum-promoted LaVO4, which can be attributed to the change of the redox properties, the blocking of the strong oxidation sites of the catalysts and to an increase of the accessibility of the labile oxygen toward the reactant. The influence of the catalyst preparation method and of the Mo loading as well as the additional promoting effect of CO2 in the gas feed was also examined.

Liquid phase oxidation of toluene to benzaldehyde with molecular oxygen over copper-based heterogeneous catalysts

We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper-based binary metal oxides. Among the copper-based binary metal oxides, iron-copper binary oxide (Fe/Cu = 0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5-2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 It, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia-Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.