Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

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.     

Identification of active sites in CO2 activation on MgO supported Ni cluster

In this work, initial activation mechanism of CO₂ over MgO supported Ni catalysts has been systematically studied through the periodic DFT calculations. In addition, the role of metal cluster, interface and support for CO₂ activation is investigated and the active site is identified. CO₂ is most favored to be activated on the interface instead of neither Ni cluster nor MgO support. The effective energy for this process is around 0.67 eV, and the dissociation of CO₂ (0.62 eV) is the rate-determining step, since it requires much higher energy than that of the CO₂ adsorption process (0.05 eV). Thus, the interface between metal cluster and support plays a key role for C=O bond activation. Moreover, CO1 is preferred to be adsorbed on the Ni cluster, while the O1 is likely to bind on Mg atom of support. To illustrate the adsorption behavior of CO₂ at different sites, the Mulliken atomic charge and electron density difference have been calculated. It was found that the total amount of electron gain for CO₂ binding at different sites follows the order of Interface (−0.03 e) < MgO support (−0.05 e) < Ni cluster (−0.07 e), and effective energy barrier rises linearly with the increase of electron gain of CO₂ binding at different sites. In addition, electron gain of oxygen atom O1 and oxygen atom O2 of CO₂ is the same for Ni cluster and MgO support, however, the electron gain of O1 and O2 is different for Interface. The difference of electron gain for two oxygen atoms shows the electron unbalance of CO₂ molecule, which is in favor of C=O activation. This study could shed some light on understanding the active sites of CO₂ thermal-catalytic activation over MgO supported Ni catalysts, and is helpful to elucidate the reaction on an atomic level.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

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 (μ_h) 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 μ_h 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.     

Origin of CO promoted methanol oxidation in alkaline media catalyzed by gold: A first-principle investigation

We performed density functional theory calculations to investigate the kinetics of methanol oxidation into formic acid catalyzed by Au(111) with and without CO in alkaline media. The calculation results show that the surface with pre-adsorbed molecular CO reduces the adsorption energy of possible species. The pre-adsorbed CO species promotes almost every step of methanol oxidation both thermochemically and kinetically, which agrees well with the experimental observation. This finding may be associated with the relatively strong basicity of OH species in the presence of adsorbed CO species, thereby enhancing their ability to strip the H atoms.     

Performance improvement of conventional and inverted polymer solar cells with hydrophobic fluoropolymer as nonvolatile processing additive

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.     

物联网信息的智能采集方法研究

随着近几年来互联网技术的不断发展,大数据技术开始应用到了各行各业的生产中,大数据技术已经与当前的互联网、物联网建设有了直接关联。大数据技术也因此成为了物联网信息智能采集系统设计的重要技术内容之一。在与大数据环境下,物联网信息智能采集方法的研究工作成为重点,本文对大数据环境下物联网信息智能采集方法进行了详细研究。     

Electrically conductive aluminosilicate/graphene nanocomposite

Highly electrically conductive ceramic material based on aluminosilicate/graphene nanocomposite has been prepared by high pressure (400 MPa) compaction of montmorillonite intercalated with polyaniline followed with the high temperature (1400 °C) treatment in argon atmosphere. Tablets pressed from polyaniline/montmorillonite intercalate exhibits strong texture due to the disk-shaped montmorillonite particles and, consequently, the high anisotropy in conductivity. The high temperature induced phase transformation of montmorillonite into cristobalite and mullite preserved the aluminosilicate layered structure and created good conditions for formation of graphene sheets from polyaniline layers intercalated in montmorillonite. Therefore, the texture and anisotropy in conductivity remain preserved in resulting aluminosilicate/graphene tablets, while the in-plane conductivity in aluminosilicate/graphene tablets is 23,000× higher than the conductivity of uncalcined polyaniline/montmorillonite tablets. Simple fabrication method of aluminosilicate/graphene tablets is very promising for the manufacturing of the electrically conductive and tough ceramic material, which can be exposed to corrosive environment as well as to high temperatures.     

冲击加载下Al2O3/SiC复合陶瓷的动态力学行为

陶瓷材料动态力学性能与微观断裂机制研究,对冲击加载下材料的损伤机理认识至关重要。针对Al₂O₃/SiC复合陶瓷,采用分离式霍普金森压杆装置完成对试样的一维应力波加载,回收破碎试样颗粒并进行扫描电子显微镜分析。结果表明：一维应力波加载试验实现了对试样的均匀加载,且随着应变率的增加,Al₂O₃/SiC复合陶瓷的强度逐渐增大,具有正相关的应变率敏感性;受材料微观结构控制,Al₂O₃/SiC复合陶瓷的强度与致密化较高的Al₂O₃陶瓷（AD995、AD999等）强度较接近,强度随应变率变化趋势介于AD95陶瓷和致密化较高陶瓷之间;试样边侧受稀疏波的影响,存在大量沿晶断裂和少量穿晶断裂模式,且在穿晶断裂区域出现了剪应力引起的滑移线;试样内部碎片断裂表面较为光滑,更多的是穿晶断裂区域,只含有少量剪切滑移线,且在断裂核心区域的周围晶粒上并不存在微观解理断裂特征。     

X射线背光成像诊断的球面晶体分析器研究

在激光约束聚变和箍缩聚爆实验中,为了分析内爆 靶丸推进层的运动过程和评估激光辐射驱动的对称性和均匀性, 需要得到靶丸内爆单色X射线二维空间分辨信息。为了诊断内爆高温等离子体X射线二维空间 信息,利用晶体布喇格衍射 原理研制了新型的成像系统。系统的核心元件为球面晶体分析器,球面晶体为云母球面晶体 ,弯曲半径为143.3mm。在中 国工程物理研究院进行了单色X射线背光成像实验,磷屏成像板获得了清晰的Cr靶单色X射线 二维网格图像。通过对实验 所得背光图像分析,云母球面晶体成像系统得到的空间分辨率为86 μm。实验结果表明,云母球面晶体可以应用于等离子体X射线的背光成像诊断研究。     

Synthesis of a porphyrinic polymer for highly efficient oxidation of arylalkanes in water

A highly stable covalent-porphyrinic framework Mn-CPF-1 was synthesized by reaction of cyanuric chloride and tetraphenylamine porphyrin (TAPP) and subsequent metallation. Mn-CPF-1 exhibits remarkable catalytic activity and stability on catalytic oxidation of arylalkanes in water under mild conditions, which is much superior to the homogeneous analog Mn-tetraphenylporphyrin (Mn-TPP) under identical conditions.