Molecule‐Doped Nickel Oxide: Verified Charge Transfer and Planar Inverted Mixed Cation Perovskite Solar Cell

Both conductivity and mobility are essential to charge transfer by carrier transport layers (CTLs) in perovskite solar cells (PSCs). The defects derived from generally used ionic doping method lead to the degradation of carrier mobility and parasite recombinations. In this work, a novel molecular doping of NiO_x hole transport layer (HTL) is realized successfully by 2,2′‐(perfluoronaphthalene‐2,6‐diylidene)dimalononitrile (F6TCNNQ). Determined by X‐ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy, the Fermi level (E_F) of NiO_x HTLs is increased from ?4.63 to ?5.07 eV and valence band maximum (VBM)‐E_F declines from 0.58 to 0.29 eV after F6TCNNQ doping. The energy level offset between the VBMs of NiO_x and perovskites declines from 0.18 to 0.04 eV. Combining with first‐principle calculations, electrostatic force microscopy is applied for the first time to verify direct electron transfer from NiO_x to F6TCNNQ. The average power conversion efficiency of CsFAMA mixed cation PSCs is boosted by ≈8% depending on F6TCNNQ‐doped NiOx HTLs. Strikingly, the champion cell conversion efficiency of CsFAMA mixed cations and MAPbI₃‐based devices gets to 20.86% and 19.75%, respectively. Different from passivation effect, the results offer an extremely promising molecular doping method for inorganic CTLs in PSCs. This methodology definitely paves a novel way to modulate the doping in hybrid electronics more than perovskite and organic solar cells.     

Eucalyptus Camaldulensis Invasion in Riparian Zones Reveals Few Significant Effects on Soil Physico‐Chemical Properties

Many invasive alien plants alter soil‐nutrient regimes of invaded ecosystems, affecting management outcomes. We assessed the effects of Eucalyptus camaldulensis invasions on physical and chemical properties of riparian soils in the Western Cape Province, South Africa. Samples were collected from topsoil beneath the canopy of uninvaded and a gradient of invaded sites, namely, light, moderate and heavy over four seasons. We quantified soil moisture, temperature, litter depth and thickness, primary textural components, concentrations of soil macro (C, N, P and K) and micro (Mn, Zn, Cu and Fe) nutrients, and pH. Available N (NO₃^?‐N and NH₄⁺‐N) and P, as well as exchangeable Ca and Mg were also assessed. Soil pH levels were significantly lower in invaded than in uninvaded sites in all seasons. Soil moisture decreased consistently with invasion intensity. Concentrations of macro, micro and available nutrients did not vary significantly along the invasion gradient (p > 0.05), but exchangeable cation content was significantly higher in uninvaded than in invaded sites, especially in winter and spring. Sites invaded by E. camaldulensis had higher litter build‐up than non‐invaded sites, but this appears to have little effect on soil‐nutrient regimes. It appears that restoration following removal of invasive stands of E. camaldulensis will not require major interventions to return soil to pre‐invasion conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Cation effects in the oxidative dehydrogenation of methane on sulphates

The oxidative coupling of methane has been studied on Mg, Ca, Sr and Ba sulphate. The conversions and selectivities are found to be dependent on the nature of the cation and to be approximately correlated with their electronegativities, thus implying that the C-H bond scission in CH₄, at least with these catalysts, is heterolytic, is rate determining, and further, that the formation of C₂₊ hydrocarbons is dependent, among other factors, on the concentration of methyl radicals.     

Electroluminescence from polyvinylcarbazole films: 1. Carbazole cations

The cation-forming reactions between antimony pentachloride and various carbazole compounds were studied with a view to developing a positive charge-injecting electrode for an electroluminescent device based on films of polyvinylcarbazole. Use of polyvinylcarbazole in the reaction produced a very different cation yield from that obtained by use of a carbazole dimer and reasons for this, associated with dimerization of the monocarbazole groups, are suggested. The ionization potential and cation extinction coefficient of dimeric carbazole were measured and changes in the visible absorption spectrum of the cations were observed that are related to their microscopic environment.     

通过络合方法强化电渗析对二价同电荷重金属离子分离效果的初步研究

对二价过渡金属离子选择适当的配位体以形成不同的络合物,通过改变电荷,离子在膜内的淌度此及分配系数,或络合物的稳定常数的差异来达到同电荷离子彼此分离的目的。研究结果表明,对形成铜氨络离子—镁离子溶液体系和铜乙二胺络离子—镁离子溶液体系,采用常规电渗析方法进行分离,其T_(Mg)~(Cu)值较常规溶液体系分别提高近一倍和25%;对铜—镁混合溶液和钴—镍混合溶液采用EDTA 络合剂和特殊电渗析工艺,可使T_(Mg)~(Cu)→0或T_(Nl)~(Co)→∞,达到完全分离。本研究开发的分离同电荷离子的电渗析新工艺,对于开拓电渗析技术的新应用领域具有一定的指导意义。     

Role of Selected Cations and Gas Speciation on the Reduction of Fayalite at 1300°C

Pure fayalite liquid was reduced at 1300°C in variable C/H ratio gas mixtures, all with constant f _O2 both with and without various cation additives that included Cr₂O₃, MnO, CaO, TiO₂, Al₂O₃, Na₂O, and K₂O. Similar studies were also performed on Carol Lake iron ore pellets without these cation additives. The role of cation additives in reduction with CO-rich gases is minimally important. In hydrogen-rich reduction studies, the reduction per hour was increased 50% by a 2.5 wt% addition of CaO, increased by about 75% by a 2.5 wt% addition of Cr₂O₃, and increased by about 50% for a 2.5 wt% addition of MnO as compared to the reduction rate of pure fayalite liquid. Much more dramatic than any cation additive effect is the role of the hydrogen content of the gas mixture. At 1300°C and a fixed –log f _O2= 13, the reduction per hour of pure fayalite liquid triples with the replacement of the CO by hydrogen even with just the first 10 vol% of hydrogen. Theoretical discussions of the role of cation additives and gas speciation on fayalite melt structure are presented.     

Effects of modification of highly dispersed cobalt catalysts with alkali cations on the hydrogenation of carbon monoxide

In the hydrogenation of carbon monoxide, alkali cations were found to be effective as modifiers for highly dispersed cobalt catalyst to improve the selectivities of C₂-oxygenated compounds, especially acetic acid and acetaldehyde, and to increase the olefin/paraffin ratio of hydrocarbons. These effects are ascribed to depression of the hydrogenating ability of the catalyst by modification with alkali cations.     

NO2 formation and its effect on the selective catalytic reduction of NO over Co/ZSM-5

Catalytic performance of Co/ZSM-5 with different metal loadings and of HZSM-5 was compared in the NO + O₂, C₃H₈ + O₂, and NO + C₃H₈ + O₂ reactions. It was found that Co/ZSM-5 catalysts containing only isolated cobalt ions in cationic positions are inactive in NO₂ formation. To achieve appreciable NO conversion in the SCR process over these catalysts higher reaction temperatures are required. These results make it possible to suggest that NO₂ formation is not a prerequisite for the SCR of NO with hydrocarbons over Co/ZSM-5. With increasing Co loading, however, Co/ZSM-5 begins to exhibit activity in NO₂ formation. This is explained by the formation of cobalt oxide particles on the zeolite carrier, which are active in the NO₂ formation. Increase in NO₂ formation strongly enhances catalytic activity in SCR of NO at lower reaction temperatures. Comparison of the C₃H₈ conversion in the C₃H₈ + O₂ and C₃H₈ + O₂ + NO reactions provides evidence that NO₂ activates hydrocarbon molecules resulting in the formation of the reaction intermediates of the SCR process.On leave from N.D. Zelinskii Institute of Organic Chemistry, Leninskii Pr. 47, Moscow, Russia.     

Some environmentally friendly formulations as inhibitors for mild steel corrosion in sulfuric acid solution

The corrosion resistance of mild steel in 1 M H₂SO₄ solution was evaluated after addition of Sn²⁺ and Zn²⁺, N-acetylcystein (ACC) and S-benzylcystein (BzC) as a function of concentration (5–1000 μM) and solution temperature (35–50°C). Eight blends were also investigated. Both polarization resistance (R _p) and electrochemical impedance spectroscopy (EIS) were employed. For single additives, Zn²⁺ ions acted as accelerator for mild steel corrosion while the other additives showed good performance. The most effective additive was Sn²⁺. Adsorption of Sn²⁺, ACC and BzC obeyed the Temkin adsorption isotherm and had a very high negative value of free energy of adsorption (−ΔG°_ads). All blends provided good inhibition which increased with rise in temperature. Corrosion kinetic parameters such as activation energy (E _a) and the pre-exponential factor (λ) were calculated and discussed. EIS revealed that the interface of the uninhibited and inhibited systems can be represented by the simple equivalent circuit R _e(R _ct Q _dl).