Hydrodechlorination of chlorophenols over Pd catalysts supported on zeolite Y,MCM-41 and graphene

Hydrodechlorination (HDC) reaction of chlorophenols was carried out using Pd catalysts supported over zeolite Y, MCM-41 or graphene. Pd-MCM-41 and Pd-Y zeolite were prepared by impregnation and ion-exchange method, respectively. Pd-graphene (Pd-G) was prepared by hydrazine hydrate reduction of palladium ion dispersed on graphene oxide. The catalysts were characterized by several analytical tools such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). These catalysts were subjected to HDC reaction of chlorophenols, such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 3,4-dichlorophenol (3,4-DCP). The reaction rate of HDC of chlorophenols catalyzed by Pd catalysts with various solid bases, such as KF/Al₂O₃ (alumina), sodium acetate (NaOAc) and K₂CO₃ was compared. First, Pd-MCM-41 and Pd-Y catalysts were compared. 2,4- and 3,4-DCPs were completely decomposed within 6 h, in the case of Pd-MCM-41 with NaOAc. Using Pd-Y instead of Pd-MCM-41 with NaOAc, much faster decomposition was observed. Faster decomposition of 4-CP and DCPs was observed with NaOAc base than K₂CO₃ or KF/Al₂O₃ under the same condition. In the case of Pd-Y with KF/Al₂O₃, slower decomposition of 4-CP and DCPs was observed. These base effects were interpreted using the solubility of NaCl and KCl in alcohol and the basic sites of KF/Al₂O₃. Because the solubility of NaCl is known to be larger than KCl solubility in alcohol, byproduct NaCl could be easily dissolved and ionized in solvents. For Pd-Y with KF/Al₂O₃, the small pore size of Y zeolite can interfere with the diffusion of HCl to KF/Al₂O₃ basic site. Second, three catalysts, including Pd-graphene, were compared. 2,4-DCP was decomposed within 2 h using Pd-G with either K₂CO₃, NaOAc or KF/Al₂O₃. Pd-G catalyst showed the highest catalytic activity among Pd-G, Pd-MCM-41 and Pd-Y catalysts. The high activity and stability of the Pd-G could be attributed to the strong metal–support interaction with an electron-deficient site and a critical Pd particle size (ca. 3.5 nm) of Pd-G nanocatalyst with a stronger resistance to the deactivation and good affinity toward aromatic organic molecules, especially phenols. The progress of HDC reaction was monitored by gas chromatography with flame ionization detection (GC/FID), and a feasible degradation process could be explained by analyzing the degradation products such as phenol, cyclohexanone and cyclohexanol from resulting GC chromatograms. The effect of reaction temperature on HDC in Pd-G catalyst was also discussed. In conclusion, Pd-G is an efficient catalyst for decomposition of chlorophenols and can be applied to remediation of chlorophenol-contaminated water under mild conditions.     

Composition dependent phase transformation of Pt0.5−x Mn0.5+x from A1 to L10 phase

Pt_0.5−x Mn_0.5+x films were prepared by sputtering deposition of Pt foil and Mn target to study the order-disorder transition from a thermodynamic metastable fcc (A1) phase to L1₀ phase. Both Differential Scanning Calorimetry and High Temperature X-Ray Diffraction studies showed the phase transformation from fcc to the L1₀ structure for the Pt_0.50Mn_0.50 and Pt_0.40Mn_0.60 samples but along completely different kinetic paths. A composition dependent phase transformation was observed by comprehensive Differential Scanning Calorimetry studies on a series of Pt_0.5−x Mn_0.5+x samples. The changes of the lattice parameter and the cell volume of L1₀ Pt_0.5−x Mn_0.5+x as a function of composition suggest that the anti-site is not the dominant point defect for L1₀ Pt_0.5−x Mn_0.5+x .     

Superiority of zoom lens coupling in designing a novel X-ray image detector

We design a novel X-ray image detector by lens coupling a Gd2O2S:Tb intensifying screen with a high performance low-light-level (L3,which often means luminescence less than 10-3 Lux) image intensifier.Different coupling effects on imaging performance between zoom lens and fix-focus lens are analyzed theoretically.In experiment,for designing a detector of 15-inch visual field,the system coupled by zoom lens is of 12.25-1p/cm resolution,while the one with fix-focus lens is 10 lp/cm.The superiority of zoom lens is validated.It is concluded that zoom lens preserves the image information better than fix-focus lens and improves the imaging system's performance in this design,which is referential to the design of other optical imaging systems.     

A Robust Algorithm for Blind Total Variation Restoration

Image restoration is a fundamental problem in image processing. Blind image restoration has a great value in its practical application. However, it is not an easy problem to solve due to its complexity and difficulty. In this paper, we combine our robust algorithm for known blur operator with an alternating minimization implicit iterative scheme to deal with blind deconvolution problem, recover the image and identify the point spread function（PSF）. The only assumption needed is satisfy the practical physical sense. Numerical experiments demonstrate that this minimization algorithm is efficient and robust over a wide range of PSF and have almost the same results compared with known PSF algorithm.     

What is Q-Curvature?

Branson’s Q-curvature is now recognized as a fundamental quantity in conformal geometry. We outline its construction and present its basic properties.     

Effect of oxygen addition on the hydrogen production from ethanol steam reforming in a Pd–Ag membrane reactor

In this communication, a porous stainless steel (PSS) tube was electrolessly plated into Pd–Ag membrane reactor which was used for separating hydrogen produced in an ethanol steam reforming reaction with the addition of oxygen, which has not been reported before. Palladium and silver were deposited on porous stainless steel tube via the sequential electroless plating procedure with an overall film thickness of 20 μm and Pd/Ag weight ratio of 78/22. Ethanol–water mixture (n_water/n_ethanol = 1 or 3) and oxygen (n_oxygen/n_ethanol = 0.2 or 0.7) were fed concurrently into the membrane reactor packed with MDC-3. The reaction temperatures were set at 593–723 K and the pressures 3–10 atm. The effect of oxygen addition plays a vital role on the ethanol steam reforming reaction, especially for the Pd–Ag membrane reactor in which a higher flux of hydrogen is required. If oxygen in the feed is not sufficient, it would be possible that steam reforming reaction prevails. Inversely, high O₂ addition will shift the reaction scenario to be partial oxidation dominating, and selectivity of CO₂ increases with increasing oxygen feed. At high pressure, autothermal reaction of ethanol would be easily reached.     

Laser absorption spectroscopy for combustion diagnosis in reactive flows: A review

Laser absorption spectroscopy (LAS) has been rapidly developed and widely applied to combustion diagnosis in recent decades. As a cost-effective tool for measuring multiple combustion parameters, LAS provides unique properties in terms of accuracy and sensitivity for understanding the reactions and kinetics in reactive flows. Line-of-sight and tomographic LAS techniques have stimulated numerous applications and been proved to be robust for in situ combustion diagnosis in uniform and non-uniform combustion fields, respectively. This review highlights the breakthroughs in the evolution of LAS techniques from the viewpoints of key principles, sensors and instrumentations developed for combustion diagnosis, with particular emphasis on a series of spatially-resolved LAS techniques with their recent applications on obtaining high-fidelity measurement results with minimal intrusion to the practical combustors. Along the way, we note some challenges and requirements for further development of the LAS-based combustion diagnosis.     

基团电负性

在电负性均衡原理基础上,提出了一个新的计算基团电负性公式用上式计算了528个开链基团和环状基团的电负性,计算结果与国内外流行几套基团电负性颇为一致,且呈明显的变化规律.