Atomistic chemical computation of Olefin polymerization reaction catalyzed by (pyridylamido)hafnium(IV) complex: Application of Red Moon simulation

We have realized the microscopic simulation of olefin polymerization, that is, the simulation of the catalytic polymerization (CP) reaction system composed of (pyridylamido)hafnium(IV) complex as the catalyst. For this purpose, we adopted Red Moon (RM) method, a novel molecular simulation method to simulate the complex reaction system. First, according to the previous research, with the help of the QM calculation, we proposed a model system and elementary processes and explained the theoretical treatment of the simulation by the RM method (the RM simulation). In addition, we also proposed a macroscopic simulation based on chemical kinetics simulation. Then, we performed two simulations and compared them in terms of the effective time evolution of the three macroscopic physical quantities, the number-average molecular weight M_n , the mass-average molecular weight M_w , and the molar-mass dispersity Đ_M . The comparison showed that the two simulations are in quantitative or partially qualitative agreement with each other. Therefore, it is concluded that the RM simulation could not only simulate the CP reaction process microscopically, but also it is connected essentially to reproduce the time evolution of the macroscopic physical quantities on the basis of its microscopic simulation data. © 2018 Wiley Periodicals, Inc.     

磷灰石结构荧光粉Ba10(PO4)6F2:Ce3+,Tb3+的合成、发光和能量传递

采用高温固相法合成了系列Ce~(3+)和Ce~(3+)/Tb~(3+)激活的具有磷灰石结构荧光粉Ba_(10)(PO_4)_6F_2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO4)6F2∶x Ce~(3+)的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的激发光谱为240～330 nm的宽带,发射光谱呈现出Ce~(3+)的5d→4f跃迁紫外光(335和358 nm)发射和Tb~(3+)的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce~(3+)→Tb~(3+)能量传递,能量传递效率可以达到60%。计算Ce~(3+)和Tb~(3+)的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce~(3+)和Tb~(3+)之间的能量传递和发光的过程。通过调节Tb~(3+)的掺杂浓度,对荧光粉发光色坐标与Tb~(3+)的掺杂浓度之间的关系也进行了研究,随着Tb~(3+)的掺杂量从0增加0.52,荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。     

Microscopic Elucidation of Solid‐Electrolyte Interphase (SEI) Film Formation via Atomistic Reaction Simulations: Importance of Functional Groups of Electrolyte and Intact Additive Molecules

Secondary batteries such as Li‐ion battery are expected to be utilized as not only ubiquitous electric power sources such as mobile phones but also large‐scale electricity storage devices. Therefore, it is urgent to develop the higher performance secondary batteries. Their lifetime and stability are found to be strongly dependent on the nature of passivation film called solid electrolyte interphase (SEI) film formed on the anode surface in the initial charge‐discharge cycle. However, since it is difficult to directly observe the film formation processes in experiment, its microscopic mechanism is still not found. On the other hand, although the theoretical methods are useful complement to the experiment, some new methodologies are necessary to understand the long‐term processes of SEI film, which is produced as a result of that a lot of chemical reactions proceed simultaneously. Under the circumstances, we have developed Red Moon method that can simulate such complex chemical reaction systems, and were able to analyze for the first time the SEI film formation processes on the anode surface at the atomistic level. Then, we clarified theoretically the microscopic mechanism of the additive effect which is essential to improve the Na‐ion battery performance so as to enhance the SEI film formation. This new microscopic insight must provide an important guiding principle for use in designing the most suitable electrolytes for developing high‐performance secondary batteries.     

Luminescence of samarium-activated cubic boron nitride

Under high pressure conditions, we have obtained samples of samarium-activated cubic boron nitride in the form of micropowders, ceramic samples, and polycrystals having high-intensity discrete photoluminescence in the red region of the spectrum that is stable in the temperature range 6 K to 300 K and is assigned to internal f-f electronic transitions in the Sm³⁺ ions. The materials obtained on the basis of cBN are intended for use as phosphors and light emitters (sources of red light) having thermal and chemical stability. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 88–93, January–February, 2008.     

Highly enhanced luminescence of ZnO green phosphors by calcining ZnS with NH4Br as additive

Zinc oxide (ZnO) phosphors with highly efficient green emission have been prepared by calcining ZnS with NH₄Br as additive in air atmosphere. The luminescent properties of as-prepared ZnO phosphors were characterized by X-ray photoelectron spectroscopy and photoluminescence. Our results reveal that the green emission is ascribed to a transition of a photo-generated electron from the localized defect centers (V_o⁺) to a deeply trapped hole (V_Zn⁻) within the band gap. The addition of NH₄Br enhances the luminescent emission of ZnO by promoting the formation of vacancies of both oxygen and zinc.     

Exciplex emission in the blend of two blue luminescent materials

Organic light-emitting diodes (OLEDs) based on the blend of two blue luminescent materials N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-diphenyl-4,4′-diamine (NPB) and 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD) were fabricated. The electroluminescence (EL) spectra of this device showed a new emission that is different from their intrinsic exciton emission. Compared with the photoluminescence (PL) spectra of single layer NPB and PBD, respectively, there was an apparent red shift in that of their blend. Thus the exciplex formation in the blend can be concluded due to the similar emission in both PL and EL spectra. The exciplex formation process and the effect of applied voltage were analyzed by Gaussian fitting.     

New red Y0.85Bi0.1Eu0.05V1−yMyO4 (M=Nb, P) phosphors for light-emitting diodes

The Y_0.85Bi_0.1Eu_0.05V_1−yM_yO₄ (M=Nb, P) as new near-ultraviolet excited phosphors were synthesized and their luminescence properties under 365 nm excitation were investigated in detail. It indicated that by doping small amount of P⁵⁺ into V⁵⁺ sites, the excitation intensity of charge transfer (CT) band of Bi–O (330–400 nm) was greatly improved. By substituting Nb⁵⁺ for V⁵⁺, both the CT bands of Bi–O and Eu–O (240–320 nm) were significantly enhanced. As a result, the emission intensity of Y_0.85Bi_0.1Eu_0.05V_1−yM_yO₄ (M=Nb, P) could be improved about 90% by doping 5 mol% P⁵⁺ and 110% by doping 5 mol% Nb⁵⁺. Comparing with the commercial Y₂O₂S:Eu³⁺ phosphors, the Y_0.85Bi_0.1Eu_0.05V_0.95M_0.05O₄ (M=Nb, P) phosphors exhibited excellent color purity and much higher brightness. The results showed that these Y_0.85Bi_0.1Eu_0.05V_1−yM_yO₄ (M=Nb, P) phosphors could be considered as promising red phosphors for application in LED.     

Fabrication and luminous properties of phosphor ceramic for application in automotive laser headlight

We report on the optimization of fabrication of a ceramic phosphor plate (CPP) using α-Al₂O₃ as functional materials for an automotive laser headlamp. The prepared CPP shows the high luminous characteristics with increasing α-Al₂O₃ contents because of the light scattering of the hexagonal structure of α-Al₂O₃ materials. We investigated the correlation between α-Al₂O₃ and thickness of CPP. The luminous properties of the CPP are improved and optimized according to the variables of one. We found that the prepared sample is a potential material for future solid-state laser lighting in application as an automotive headlamp.     

Complexation of Sc(III), Ga(III), In(III) and Ln(III) with Eriochrome Red B

Cyclic linear-sweep voltammetry was used to study the complexation of Sc(III), Ga(III), In(III) and Ln(III) with eriochrome red B (ERB). It was established that all metal ions investigated form complex compounds with azodye having a mole ratio, M(III):ERB = 1:2. The hydroxo forms of M(III) ions, which take part in interaction with ERB, were determined by the Nazarenko method. The stability constants for the formation of these chelates are nearly the same. It was shown that the reduction of the ligand in the complex does not only depend on the peculiarities of complexation, but the processes occurring in pre-electrode layer also influence it.     

Environmental remediation by hydroxyapatite: Solid state synthesis utilizing waste chicken eggshell and adsorption experiment with Congo red dye

This study reports the adsorption efficacy of hydroxyapatite (HAp) for removing Congo Red (CR) dye from aqueous solution. HAp was synthesized utilizing chicken eggshell as a precursor of Ca source. Solid state synthesis method was implemented which comprised calcination at 950 °C (E-HAp950). XRD analysis confirmed the formation of bi-phasic HAp with 15.5% of β-TCP. Elemental composition was evaluated by XPS and EDX analysis. FESEM analysis revealed the particles are of plate and spherical shaped also confirmed by the TEM images. DLS particle size, zeta potential, BET surface area and point of zero charge were also evaluated. Adsorption efficacy of E-HAp950 for removing CR was evaluated by batch adsorption experiment. Maximum adsorption capacity (q_max) was found to be 9.64 mgg⁻¹ which was best explained by the non-linear fitting (R² = 0.98) of Langmuir isotherm. Adsorption kinetics profusely followed pseudo second order kinetic model (R² = 0.999) with q_{e (experimental)} being very much closer to q_{e (calculative)} for this model. Thus, hydroxyapatite prepared by utilizing eggshell waste through solid state method has the potential to remove toxic dyes.