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11.
Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)
Jian Wang Cun-Qin Lv Jian-Hong Liu Rong-Rong Ren Gui-Chang Wang 《International Journal of Hydrogen Energy》2021,46(2):1592-1604
It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural. 相似文献
12.
针对平面并联机构无奇异位置工作空间求解困难、过程繁琐、计算量大等问题,提出了基于CAD求解平面并联机构工作空间的三维螺旋扫描方法。将[n]自由度平面并联机构分解成[n]条支链进行独立分析,得到每条支链下末端执行器的可达区域,再将所有支链可达区域取交集即为平面并联机构工作空间。应用SolidWorks软件建立平面并联机构模型,进行几何特征处理,通过自动求解器求解,将求解过程图形化,快速得到同轴布局5R机构和平面3-RPR并联机构的无奇异位置工作空间。通过同轴布局5R机构的运动学实验,验证了该求解方法的可行性。 相似文献
13.
14.
The morphology of the photoactive layer critically affects the performance of the bulk heterojunction polymer solar cells (PSCs). To control the morphology, we introduced a hydrophobic fluoropolymer polyvinylidene fluoride (PVDF) as nonvolatile additive into the P3HT:PCBM active layer. The effect of PVDF on the surface and the bulk morphology were investigated by atomic force microscope and transmission electron microscopy, respectively. Through the repulsive interactions between the hydrophilic PCBM and the hydrophobic PVDF, much more uniform phase separation with good P3HT crystallinity is formed within the active layer, resulting enhanced light harvesting and improved photovoltaic performance in conventional devices. The PCE of the conventional device can improve from 2.40% to 3.07% with PVDF additive. The PVDF distribution within the active layer was investigated by secondary ion mass spectroscopy, confirming a bottom distribution of PVDF. Therefore, inverted device structure was designed, and the PCE can improve from 2.81% to 3.45% with PVDF additive. Our findings suggest that PVDF is a promising nonvolatile processing additive for high performance polymer solar cells. 相似文献
15.
Novel core-shell-like Ni-supported hierarchical beta zeolite catalysts on bioethanol steam reforming
《International Journal of Hydrogen Energy》2020,45(33):16409-16420
Hierarchical-Beta zeolites have been hydrothermally synthesized by adding a new gemini organic surfactant. The used gemini surfactant play the role of a “pore-forming agents” on the mesoscale, on the same time, providing alkaline environment for the system. With this hierarchical Beta zeolite as the core support, we successfully prepared a shell layer of Ni-containing (22 wt%) petal-like core-shell-like catalyst and applied it to bioethanol steam reforming. At the reaction temperature of 350 °C–550 °C, the conversion rate of ethanol and the selectivity of hydrogen were always above 85% and 70%. After reaction of 100 h on stream at 400 °C, there were not obvious inactivation could be observed on NiNPs/OH-MBeta catalyst. 相似文献
16.
Industrialized white organic light-emitting diodes (OLEDs) currently require host-guest doping, a complicated process necessitating precise control of the guest concentration to get high efficiency and stability. Two doping-free, hybrid white OLEDs with fluorescent blue, and phosphorescent green and red emissive layers (EMLs) are reported in this work. An ultra-thin red phosphorescent EML was situated in a blue-emitting electron transport layer (ETL), while the ultra-thin green phosphorescent EML was placed either in the ETL (Device 1), or the hole transport layer (HTL) (Device 2). Device 2 exhibits higher efficiency and more stable spectrum due to the enhanced utilization of excitons by ultra-thin green EML at the exciton generation zone within the HTL. Values of current efficiency (CE), power efficiency (PE), and CRI obtained for the optimized hybrid white OLEDs fabricated through a doping-free process were of 23.2 cd/A, 20.5 lm/W and 82 at 1000 cd/m2, respectively. 相似文献
17.
《Carbon》2015
The development is presented of a model of the thermodynamic functions of enthalpy, entropy and Gibbs energy for the elements carbon and hydrogen in coke crystallites. It is applicable to varying degrees of graphitization, described by the crystallite length La and the crystallite height Lc. The model parameters are derived from known properties such as bond enthalpies and entropies of formation. Good agreement has been obtained between the predicted thermal dehydrogenation of petroleum cokes and experimental data. The removal of hydrogen from idealized coke crystallites is predicted to occur mostly between 1100 and 1300 K. Agreement has also been found in the comparison of the predicted thermodynamic stability of coke relative to graphite, in a previous experimental study. This stability has been determined as at ≈900 J g−1 at temperatures between 950 and 1250 K and for La = 10 nm. The current predictive capacity of the present model is valid for temperatures up to 2500 K. 相似文献
18.
Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th4(1,4) with high hole mobility (μh) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μh of 1.06 cm2 (V s)−1 were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications. 相似文献
19.
In this paper we provide a convergence analysis of the alternating RGLS (Recursive Generalized Least Square) algorithm used for the identification of the reduced complexity Volterra model describing stochastic non-linear systems. The reduced Volterra model used is the 3rd order SVD-PARAFC-Volterra model provided using the Singular Value Decomposition (SVD) and the Parallel Factor (PARAFAC) tensor decomposition of the quadratic and the cubic kernels respectively of the classical Volterra model. The Alternating RGLS (ARGLS) algorithm consists on the execution of the classical RGLS algorithm in alternating way. The ARGLS convergence was proved using the Ordinary Differential Equation (ODE) method. It is noted that the algorithm convergence canno׳t be ensured when the disturbance acting on the system to be identified has specific features. The ARGLS algorithm is tested in simulations on a numerical example by satisfying the determined convergence conditions. To raise the elegies of the proposed algorithm, we proceed to its comparison with the classical Alternating Recursive Least Squares (ARLS) presented in the literature. The comparison has been built on a non-linear satellite channel and a benchmark system CSTR (Continuous Stirred Tank Reactor). Moreover the efficiency of the proposed identification approach is proved on an experimental Communicating Two Tank system (CTTS). 相似文献
20.
《Intermetallics》2015
Drop-tube processing was used to rapidly solidify droplets of Ni64.7Fe10Si25.3 and Ni59.7Fe15Si25.3 alloys. In the larger droplets, and therefore at low cooling rates, only two phases, γ-Ni31Si12 and β1-Ni3Si were observed. Conversely, in the smaller droplets, and therefore at higher cooling rates, the metastable phase Ni25Si9 was also observed. The critical cooling rate for the formation of Ni25Si9 was estimated as 5 × 103 K s−1. SEM and TEM analysis reveals three typical microstructures: (I) a regular structure, comprising single-phase γ-Ni31Si12 and a eutectic structure between γ-Ni31Si12 and β1-Ni3Si; (II) a refined lamellar structure with a lamellar spacing <50 nm comprising γ-Ni31Si12 and β1-Ni3Si; (III) an anomalous structure with a matrix of Ni25Si9 and only a very small proportion of a second, and as yet unidentified, phase. These results indicate that there is an extended stability field for Ni25Si9 in the Ni-rich part of the Ni–Fe–Si ternary system in comparison to the Ni–Si binary system. With an increase of cooling rate, an increasing fraction of small droplets experience high undercoolings and, therefore, can be undercooled into the Ni25Si9 stability field forming droplets consisting of only the anomalous structure (III). The Fe atoms are found to occupy different substitutional sites in different phase, i.e. Fe substitutes for Ni in the γ phase and Si in the L12 (β1) phase respectively. 相似文献