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991.
The potential energy surface for the reaction of OH with CH2═CHCH2I has been studied at the CCSD(T)//M06-2X/6-311++G(d,p) level of theory. Three different reaction entrances were revealed, namely, terminal-C addition, central-C addition, and H-abstraction, leading to CH2OHCHCH2I (IM1), CH2CHOHCH2I (IM2), and H2O?+?C3H4I, respectively. Several conceivable decomposition and isomerization channels were also examined for IM1 and IM2. The total and individual rate constants were calculated by using multichannel RRKM and TST theories over a wide range of temperatures (200–3000 K) and pressures(10?14–1014 Torr). 相似文献
992.
In the present study, it is attempted to scrutinize the hydrogen bonding interaction between Carmustine drug and DNA pyrimidine bases by means of density functional theory calculations regarding their geometries, binding energies, vibrational frequencies, and topological features of the electron density in the gas phase and the water solution. Based on the density functional theory results, it is found that the process of intermolecular interaction between Carmustine drug and nucleobases is exothermic and all of the optimized configurations are stable. Furthermore, the negative stability energy represented by a polarizable continuum model shows the significant increase in the solubility of the nucleobase after hydrogen bonding intermolecular interaction in the presence of water solvent. It is also found that the intermolecular hydrogen bonds between drug and the nucleobases play the significant role in the stability of the physisorption configurations. Hydrogen bond energies for hydrogen-bonded complexes are obtained from Espinosa method and the atoms-in-molecules theory are also applied to get a more precise insight into the nature of the intermolecular hydrogen bond interactions. 相似文献
993.
İlyas Gönül Ender Fakı Burak Ay Muhammet Köse Selahattin Serin 《Transition Metal Chemistry》2018,43(1):73-81
A Schiff base ligand (HL), 2,4-dimethoxy-N-(5-chloro-2-hydroxybenzylidene)-benzenamine, derived from 5-chloro-2-hydroxybenzaldehyde and 2,4-dimethoxyaniline, and its metal complexes [Co(L)2]·CH3OH (1), [Ni(L)2] (2), [Cu(L)2] (3) have been synthesized. The compounds were characterized by analytical and spectroscopic methods. In addition, the structures of the Schiff base HL and its Co(II) complex were determined by single-crystal X-ray analysis. The Co(II) center is six-coordinate, being coordinated to two imine nitrogen, two phenolate oxygen and two methoxy oxygen atoms of two crystallographically independent Schiff base ligands. Luminescence properties of HL and its complexes were investigated both in solution and in the solid state. 相似文献
994.
Chenlu Zhang Xing Li Zhongshan Chen Tao Wen Shuyi Huang Tasawar Hayat Ahmed Alsaedi Xiangke Wang 《中国科学:化学(英文版)》2018,61(3):281-293
An extremely effortless method was applied for successful synthesis of mesoporous carbonaceous materials(MCMs) using well-ordered mesoporous silica as template. Various characterizations(scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), Raman, X-ray photoelectron spectroscopy(XPS), Brunner-Emmet-Teller(BET) and Zeta potential) confirmed that MCMs had large surface area, uniform pore size distribution, and abundant oxygen-containing functional groups. The batch techniques were employed to study U(VI) adsorption on MCMs under a wide range of experiment conditions. The adsorption kinetics of U(VI) onto MCMs were well-fitted by pseudo-second-order kinetic model, indicating a chemisorption process. The excellent adsorption capacity of MCMs calculated from the Langmuir model was 293.95 mg g~(-1) at pH 4.0. The FT-IR and XPS analyses further evidenced that the binding of U(VI) onto MCMs was ascribed to the plentiful adsorption sites(–OH and –COOH groups) in the internal mesoporous structure, which could efficiently trap guest U(VI) ions. The results presented herein revealed that MCMs were ideal adsorbents in the efficient elimination of uranium or other lanthanides/actinides from aqueous solutions, which would play an important role in environmental pollution management application. 相似文献
995.
Kongzhao Su Mingyan Wu Wenjing Wang Mi Zhou Daqiang Yuan Maochun Hong 《中国科学:化学(英文版)》2018,61(6):664-669
Two novel 3D metal-organic frameworks(MOFs)with cds network,{[Me NH_3]_7[Ln_8(Pg C_2)_2(H_2O)_y(HCOO)_7]}_n·x(Solvent)(FJI-Y4,FJI=Fujian Institute,Ln=Gd,y=12;FJI-Y5,Ln=Dy,y=11;Pg C_2=C-ethylpyrogallol[4]arene),based on unprecedented dimeric pyrogallol[4]arene-based Ln_8metal-organic nanocapsule(MONC)supramolecular building blocks and formate linkers,have been prepared under solvothermal conditions.To our best of knowledge,they present not only the first two examples of 3D hierarchical structures constructed from MONCs in metal-pyrogallol[4]arene system,but also the first two examples of MOFs based on lanthanide MONCs.Remarkably,the inner cavity volume of the Ln_8capsule in FJI-Y4 and FJI-Y5 is approximately151?~3,which is larger than those found in previous transition metal-seamed dimeric Pg C_n-based MONCs.Magnetic investigation on FJI-Y4 suggests a significant magnetocaloric effect(23.97 J kg~(-1)K~(-1),ΔH=7 T,2.5 K),while FJI-Y5 exhibits slow relaxation of the magnetization. 相似文献
996.
Qiang Ma Qi Deng Hang Sheng Wei Ling Hong-Rui Wang Hai-Wen Jiao Xiong-Wei Wu Wen-Xin Zhou Xian-Xiang Zeng Ya-Xia Yin Yu-Guo Guo 《中国科学:化学(英文版)》2018,61(6):732-738
A mild and simple synthesis process for large-scale vanadium redox flow batteries (VRFBs) energy storage systems is desirable. A graphite felt/MnO2 (GF-MNO) composite electrode with excellent electrocatalytic activity towards VO2+/VO2+ redox couples in a VRFB was synthesized by a one-step hydrothermal process. The resulting GF-MNO electrodes possess improved electrochemical kinetic reversibility of the vanadium redox reactions compared to pristine GF electrodes, and the corresponding energy efficiency and discharge capacity at 150 mA cm?2 are increased by 12.5% and 40%, respectively. The discharge capacity is maintained at 4.8 A h L?1 at the ultrahigh current density of 250 mA cm?2. Above all, 80% of the energy efficiency of the GFMNO composite electrodes is retained after 120 charge-discharge cycles at 150 mA cm?2. Furthermore, these electrodes demonstrated that more evenly distributed catalytic active sites were obtained from the MnO2 particles under acidic conditions. The proposed synthetic route is facile, and the raw materials are low cost and environmentally friendly. Therefore, these novel GFMNO electrodes hold great promise in large-scale vanadium redox flow battery energy storage systems. 相似文献
997.
Controlling the nucleation and growth of organic-inorganic hybrids perovskite is of key importance to improve the morphology and crystallinity of perovskite films. However, the growth mechanism of perovskite films based on classical crystallization theory is not fully understood. Here, we develop a supersaturation controlled strategy (SCS) to balance the nucleation and crystal growth speeds. By this strategy, we are able to find an ideal supersaturation region to realize a balance of nucleation and crystal growth, which yields highly crystallized perovskite films with micrometer-scale grains. Besides, we provide a thoughtful analysis of nucleation and growth based on the fabrication of the perovskite films. As a result, the highest photovoltaic power conversion efficiencies (PCE) of 19.70% and 20.31% are obtained for the planar and the meso-superstructured devices, respectively. This strategy sheds some light for understanding the film growth mechanism of high quality perovskite film, and it provides a facile strategy to fabricate high efficiency perovskite solar cells. 相似文献
998.
Exploration of novel organic luminophores that exhibit thermally activated delayed fluorescence (TADF) in the aggregated state is very crucial for advance of delayed luminescence-based applications such as time-gated bio-sensing and temperature sensing. We report herein that synthesis, photophysical properties, molecular and crystal structures, and theoretical calculations of 2,6-bis (diarylamino)benzophenones. Absorption spectra in solution and calculations using density functional theory (DFT) method revealed that the optical excitation took place through intramolecular charge-transfer from one diarylamino moiety to an aroyl group. While the benzophenones did not luminesce in solution, the solids of the benzophenones emitted green light with moderate-to-good quantum yields. Thus, the benzophenones exhibit aggregation-induced emission. Based on the lifetime measurement, the green emission of the solids was found to include TADF. The emergence of the TADF is supported by the small energy gap between the excited singlet and triplet states, which was estimated by time-dependent DFT calculations. Thin films of poly(methyl methacrylate) doped by the benzophenones also showed green prompt and delayed fluorescence whose lifetimes were in the order of microseconds. Linear correlation between logarithm value of TADF lifetime and temperature was observed with the benzophenone in powder, suggesting that the benzophenones can serve as molecular thermometers workable under aqueous conditions. 相似文献
999.
The tandem hydrolysis and hydrogenation of saccharides into sorbitol is an especially attractive reaction in the conversion of biomass. Here, an economical and efficient bimetallic catalyst for the transformation of glucose and cellobiose into sorbitol is reported. Non-precious metal based catalysts such as NiCo, Ni, and Co, were prepared via modified impregnation method, and NiCo/HZSM-5 showed superior performance for the synthesis of sorbitol (86.9% from cellobiose, 98.6% from D-glucose). Various characterizations, such as Brunner-Emmet-Teler (BET), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), confirmed that NiCo alloy formed and highly dispersed in NiCo/HZSM-5 catalyst. The high performance of fabricated catalyst would be attributed to the formation of nickel-cobalt alloy over HZSM-5 zeolite surface. High temperature and H2 pressure were favorable for the tandem hydrolysis and hydrogenation reaction. Besides, the reaction pathway was also proposed based on the kinetics study. Cellobitol was detected as the intermediate in the reaction mixture. Furthermore, in the catalytic stability study, it was found that active metal species of NiCo/HZSM-5 were stable. The deactivation of catalyst would be due to the covering of acidic sites over NiCo/HZSM-5. 相似文献
1000.
Metal halide perovskite nanomaterials emerged as attractive emitting materials for light-emitting diodes (LEDs) devices due to their high photoluminescence quantum yield (PLQY), narrow bandwidth, high charge-carrier mobility, bandgap tunability, and facile synthesis. In the past few years, it has been witnessed an unprecedented advance in the field of metal halide perovskite nanomaterials based LEDs (PeLEDs) with a rapid external quantum efficiency (EQE) increase from 0.1% to 14.36%. From the viewpoint of material chemistry, the chemical regulation of metal halide perovskite nanomaterials made a great contribution to the efficiency improvement of PeLEDs. In this review, we categorize the strategies of chemical regulation as A-site cation engineering, B-site ion doping, X-site ion exchange, dimensional confinement, ligand exchange, surface passivation and interface optimization of transport layers for improving the EQEs of PeLEDs. We also show the potentials of chemical regulation strategies to enhance the stability of PeLEDs. Finally, we present insight toward future research directions and an outlook to further improve EQEs and stabilities of PeLEDs aiming to practical applications. 相似文献