Cobalt titanate–cobalt oxide composite thin films deposited from heterobimetallic precursor

A single molecular heterobimetallic complex, [Co₂Ti(μ₃‐O)(TFA)₆(THF)₃] (1) [TFA = trifluoroacetate, THF = tetrahydrofuran], was synthesized, structurally and spectroscopically characterized and implemented as a single‐source precursor for the preparation of CoTiO₃–CoO composite thin films by aerosol‐assisted chemical vapour deposition (AACVD). The precursor complex was prepared by interaction of Co(OAc)₂.4H₂O [OAc = (CH₃COO^?)] with Ti(iso‐propoxide)₄ in the presence of trifluoroacetic acid in THF, and was analysed by melting point, CHN, FT‐IR, single‐crystal X‐ray diffraction and thermogravimetric analysis. The precursor complex thermally decomposed at 480 °C to give a residual mass corresponding to a CoTiO₃–CoO composite material. Good‐quality crystalline CoTiO₃–CoO composite thin films deposited at 500 °C by AACVD and characterized through powder X‐ray diffraction and scanning electron microscopy/energy‐dispersive X‐ray spectroscopy show that the crystallites have a rose‐flower‐like morphology with an average petal size in the range of 2–6 µm. Copyright © 2012 John Wiley & Sons, Ltd.     

Aqueous Gold Overgrowth of Silver Nanoparticles: Merging the Plasmonic Properties of Silver with the Functionality of Gold

To date, it has not been possible to combine the high optical quality of silver particles with the good chemical stability and synthetic convenience in a fully aqueous system, while simultaneously allowing chemical surface functionalization. We present a synthetic pathway for future developments in information, energy and medical technology where strong optical/electronic properties are crucial. Therefore, the advantages inherent to gold are fused with the plasmonic properties of silver in a fully aqueous Au/Ag/Au core–shell shell system. These nanoparticles inherit low dispersity from their masked gold cores, yet simultaneously exhibit the strong plasmonic properties of silver. Protecting the silver surface with a thin gold layer enables oxidant stability and functionality without altering the Ag‐controlled optical properties. This combines both worlds—optical quality and chemical stability—and is not limited to a specific particle shape.     

第一性原理计算N掺杂对InNbO4电子结构的影响

宽带隙（3.83 eV）半导体光催化材料InNbO4在紫外光作用下具有分解水和降解有机物的性能。最近实验发现了N掺杂InNbO4具有可见光下分解水制氢的活性。为了从理论上解释这一实验现象，本文采用基于密度泛函理论的第一性原理计算了N掺杂对InNbO4的能带结构、态密度和光学性质的影响。分析能带结构可得，N掺杂后在InNbO4的价带（O 2p）上方形成N 2p局域能级，导致电子跃迁所需的能量减小。吸收光谱表明，N掺杂后InNbO4的光吸收边出现了红移，实现了可见光吸收。     

Improved efficiency of organic solar cells with modified hole‐extraction layers

The aim of this work has been to study the influence of modified hole‐extraction layers on the performance of organic solar cells (OSCs) based on blends of poly (3‐hexylthiophene) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester. The hole‐extraction layers consist of poly (3,4‐ethylene dioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) doped with different concentrations of bromine. Compared with pristine OSC without adding bromine to the hole‐extraction layer, the bromine‐doped OSCs show a 49% increase in the power conversion efficiency (from 2.12 to 3.16%), which could be attributed to the increase of electrical and optical properties of PEDOT:PSS films after the addition of bromine. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 125–128, 2012     

Photocatalytic activity of divalent ion (copper,zinc and magnesium) doped NiAl2O4

Nickel aluminate (NiAl₂O₄) and doped nickel aluminate (Ni_1-xM_xAl₂O₄; M = Mg, Zn, Cu; x = 0.1) were prepared by sol-gel method using citric acid. The synthesized compounds were analyzed by various techniques such as powder XRD, FTIR, SEM-EDAX and UV-DRS. The lattice parameter was found to increase with the copper, zinc and magnesium doping in nickel aluminate. The band gap was decreased from 3.0 eV (NiAl₂O₄) to 2.9 (zinc doped), 2.7 eV (magnesium doped) and increased to 3.1 eV in the case of copper doping. The catalytic study was carried out for a cationic (methylene blue) and an anionic dye (methyl orange). The percentage degradation of methyl orange using Zn_0.1Ni_0.9Al₂O₄ and Mg_0.1Ni_0.9Al₂O₄ was found to be 92% (180 min) and 96% (90 min). 93% (120 min) and 97% (120 min) degradation of methylene blue was observed using zinc doped and magnesium doped nickel aluminate respectively. These results are comparatively higher than its parent analogue (94% (180 min) degradation against methyl orange and 91% (120 min) against methylene blue). Whereas the percentage degradation was found to be less in the case of Cu_0.1Ni_0.9Al₂O₄ (83% (180 min) against methyl orange and 90% (120 min) against methylene blue).     

Degradation of p-nitrophenol (PNP) in aqueous solution by mFe/Cu-air-PS system

In this study, batch experiments were conducted to investigate the performance of microscale Fe/Cu bimetallic particles-air-persulfate system (mFe/Cu-air-PS) for p-nitrophenol (PNP) treatment in aqueous solution. The results indicate that toxic and refractory PNP in aqueous solution could be decomposed effectively and transformed into lower toxicity intermediates.     

In Situ Generation of ArCu from CuF2 Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient

A bimetallic system of Pd/CuF₂, catalytic in Pd and stoichiometric in Cu, is very efficient and selective for the coupling of fairly hindered aryl silanes with aryl, anisyl, phenylaldehyde, p‐cyanophenyl, p‐nitrophenyl, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by Cu^II, followed by disproportionation and transmetalation from the Cu^I(aryl) to Pd^II, upon which coupling takes place. Cu^III formed during disproportionation is reduced to Cu^I(aryl) by excess aryl silane, so that the CuF₂ system is fully converted into Cu^I(aryl) and used in the coupling. Moreover, no extra source of fluoride is needed. Interesting size selectivity towards coupling is found in competitive reactions of hindered aryl silanes. Easily accessible [PdCl₂(IDM)(AsPh₃)] (IDM = 1,3‐dimethylimidazol‐2‐ylidene) is by far the best catalyst, and the isolated products are essentially free from As or Pd (<1 ppm). The mechanistic aspects of the process have been experimentally examined and discussed.     

非金属掺杂改性g-C3N4光催化降解水中有机污染物的研究进展

近年来，石墨相氮化碳(g-C₃N₄)以其合适的带隙宽度、丰富的活性位点和成本低廉等优点，成为新兴的可见光响应非金属光催化剂，被广泛应用于光催化降解有机污染物领域。然而，纯g-C₃N₄对可见光的吸收效率较低且光生电子和空穴复合速率快，导致其光催化活性处于较低水平。基于g-C₃N₄的非金属特性，通过非金属掺杂可以有效提高g-C₃N₄的光催化性能，引起了学者们的广泛关注。本文介绍了目前非金属掺杂g-C₃N₄复合材料常见的制备方法，着重归纳了不同类型的非金属掺杂g-C₃N₄光催化降解水中有机污染物的相关研究进展，探讨其作为光催化剂在可见光条件下降解有机污染物的相关机理。最后，提出目前g-C₃N₄基复合材料在光催化降解水中有机污染物中所面临的挑战，旨在为非金属掺杂g-C₃...     

Ultraviolet Photoelectron Spectra of Potassium Dosed Higher Fullerenes

Abstract

Ultraviolet photoelectron spectra of potassium dosed higher fullerenes are measured with a synchrotron radiation light source. Potassium dosing to higher fullerenes brings a new structure between the spectral onset of pristine fullerenes and the Fermi level. As the spectral edge of the new structure does not cross the Fermi level, potassium dosed higher fullerenes are not metallic but semiconductive. When the potassium is excessively dosed to the fullerenes, the lower binding energy structures above 5 eV become faint. In contrast to this phenomenon, four distinct structures appear between 5 and 14 eV.     

Engineering Lithium Ions Embedded in NiFe Layered Double Hydroxide Lattices To Activate Laminated Ni2+ Sites as High-Efficiency Oxygen Evolution Reaction Catalysts

NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni²⁺ to the surroundings of Li⁺, resulting in electron-deficient properties of the Ni sites, which would function as “electron-hungry” sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li−NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm⁻², which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO₂. Reasonable intercalation adjustment effectively activates laminated Ni²⁺ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials.