Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Alcohol/water-soluble porphyrins as cathode interlayers in high-performance polymer solar cells

Three alcohol/water-soluble porphyrins,Zn-TPy PMe I:zinc(II)meso-tetra(N-methyl-4-pyridyl)porphyrin tetra-iodide,ZnTPy PAd Br:zinc(II)meso-tetra[1-(1-adamantylmethyl ketone)-4-pyridyl]porphyrin tetra-bromide and Mn Cl-TPy PAd Br:manganese(III)meso-tetra[1-(1-adamantylmethyl ketone)-4-pyridyl]porphyrin tetra-bromide were employed as cathode interlayers to fabricate polymer solar cells(PSCs).The PC71BM([6,6]-phenyl C71 butyric acid methyl ester)and PCDTBT(poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)])-blend films were used as active layers in polymer solar cells(PSCs).The PSCs with alcohol/water-soluble porphyrins interlayer showed obviously higher power conversion efficiency(PCE)than those without interlayers.The highest PCE,6.86%,was achieved for the device with Mn ClTPy PAd Br as an interlayer.Ultraviolet photoemission spectroscopic(UPS),carrier mobility,atomic force microscopy(AFM)and contact angle( )characterizations demonstrated that the porphyrin molecules can result in the formation of interfacial dipole layer between active layer and cathode.The interfacial dipole layer can obviously improve the open-circuit voltage(Voc)and charge extraction,and sequentially lead to the increase of PCE.     

Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers(DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.     

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is important for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 C for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.     

Scale-up of bubbling fluidized beds with continuous particle flow based on particle-residence-time distribution

Few studies have investigated scale-up of the residence-time distribution（RTD） of particles in bubbling fluidized beds（BFBs） with continuous particle flow.Two approaches were investigated in this study:first,using well-known scaling laws that require changes in particle properties and gas velocity;second,using a simple approach keeping the same particles and gas velocity for different beds.Our theoretical analysis indicates it is possible to obtain similar RTDs in different BFBs with scaling laws if the plug-flow residence time(t_plug) is changed as m^0.5,where m is the scaling ratio of the bed;however,neither approach can ensure similar RTDs if t_plugis kept invariant.To investigate RTD variations using two approaches without changing t_plug,we performed experiments in three BFBs.The derivatives d?（θ）/dθ（where E（θ） is the dimensionless RTD density function and θ is the dimensionless time） in the early stage of the RTDs always varied with m-1,which was attributed to the fact that the particle movement in the early stage were mainly subject to dispersion.Using the simple approach,we obtained similar RTDs by separately treating the RTDs in the early and post-stages.This approach guarantees RTD similarity and provides basic rules for designing BFBs.     

VIBRATION AND SOUND RADIATION OF AN ASYMMETRIC LAMINATED PLATE IN THERMAL ENVIRONMENTS

Analytical studies on the vibration and sound radiation characteristics of an asymmetric laminated rectangular plate are carried out in this paper. Theoretical formulations, in which the effects of thermal environments are taken into account, are derived for the vibration and sound radiation based on both first-order shear deformation plate theory and Rayleigh integral. It is found that the natural frequencies, the resonant amplitudes of vibration response and the sound pressure level decrease with the temperature rising. The natural frequencies of asymmetric plates are smaller than those of symmetric plates and the velocity responses of asymmetric plates are larger than those of symmetric plates.     

Effects of ultrasound on the desulfurization performance of hot coal gas over Zn-Mn-Cu supported on semi-coke sorbent prepared by high-pressure impregnation method

Zn-Mn-Cu/SC(U) sorbent was hydrothermally synthesized by ultrasound-assisted high-pressure impregnation method with semi-coke(SC)as support and the mixed solution of zinc nitrate,manganese nitrate and copper nitrate as active component precursors.The desulfurization performances of hot coal gas on the prepared sorbent at a mid-temperature of 500°C were tested in fixed-bed reactor.Morphology and pore structure of the prepared sorbent were also characterized by TEM,N2adsorption/desorption isotherms and XRD.For comparison,the sorbent of Zn-Mn-Cu/SC prepared by conventional high-pressure impregnation was also evaluated and characterized in order to study the effects of ultrasound treatment.Zn-Mn-Cu/SC(U) sorbent prepared by high-pressure impregnation under ultrasound-assisted condition showed a better desulfurization performance than Zn-Mn-Cu/SC.It could remove H2 S from 1000×10-6m3/m3 to 0.1×10-6m3/m3 at 500°C and maintained for 12.5 h with the sulfur capacity of 7.74%,in which both the breakthrough time and sulfur capacity were about 32% and 51% higher than those of Zn-Mn-Cu/SC sorbent.The introduction of ultrasound during high-pressure impregnation process greatly improved the morphology and pore structure of the sorbent.The ultrasonic treatment made particle size of active components smaller and made them more evenly disperse on semi-coke support,which provided more opportunities to contact with H2S in coal-based gases.However,there were no any difference in compositions and existing forms of active components on the Zn-Mn-Cu/SC and Zn-Mn-Cu/SC(U) sorbents.     

Catalytic carbon dioxide hydrogenation to methane: A review of recent studies

Recently,various efforts have been put forward on the development of technologies for the synthesis of methane from CO₂ and H₂,since it can offer a solution for renewable H₂ storage and transportation.In parallel,this reaction is considered to be a critical step in reclaiming oxygen within a closed cycle.Over the years,extensive fundamental research works on CO₂ methanation have been investigated and reported in the literatures.In this updated review,we present a comprehensive overview of recent publications during the last 3 years.Various aspects on this reaction system are described in detail,such as thermodynamic considerations,catalyst innovations,the influence of reaction conditions,overall catalytic performance,and reaction mechanism.Finally,the future development of CO₂ methanation is discussed.