Relationship between 1H chemical shifts of deuterated pyridinium ions and Brønsted acid strength of solid acids

Deuterated pyridine (pyridine-d5) is one of the NMR probe molecules widely used for determination of acid strength of solid catalysts. However, the correlation between the 1H chemical shift of adsorbed pyridine-d5 and the Br?nsted acid strength of solid acids has rarely been investigated. Here, an 8T zeolite model with different Si-H bond lengths is used to represent the Br?nsted acid sites with different strengths (from weak, strong, to superacid) and to predict the pyridine adsorption structure as well as the 1H chemical shift. The theoretical calculation suggests that a smaller 1H chemical shift of the pyridinium ions on the solid acids indicates a stronger acid strength. On the basis of the results of theoretical calculations, a linear correlation between the pyridine-d5 1H chemical shift and the proton affinity (PA) of the Br?nsted acid site has been derived. In combination with the available 1H MAS NMR experimental data, we conclude that pyridine-d5 can be used as a scale to characterize the solid acid strength.     

Sign-changing solutions of a class of nonlocal quasilinear elliptic boundary value problems

This paper is concerned with nonlocal Kirchhoff?s equation

     

代铬镀层的研究进展

六价铬会严重破坏环境并危害人类的健康,所以开发无六价铬的代铬镀层电镀工艺具有重要的现实意义。本文主要介绍了几种代铬镀层的研究进展,包括合金代装饰铬镀层、电镀及化学镀合金代硬铬镀层以及复合镀代铬镀层等,重点论述了其特点、典型电镀工艺及其应用,并结合其研究现状对代铬镀层的发展进行了展望。     

New Insight into the Hydrocarbon‐Pool Chemistry of the Methanol‐to‐Olefins Conversion over Zeolite H‐ZSM‐5 from GC‐MS,Solid‐State NMR Spectroscopy,and DFT Calculations

Over zeolite H‐ZSM‐5, the aromatics‐based hydrocarbon‐pool mechanism of methanol‐to‐olefins (MTO) reaction was studied by GC‐MS, solid‐state NMR spectroscopy, and theoretical calculations. Isotopic‐labeling experimental results demonstrated that polymethylbenzenes (MBs) are intimately correlated with the formation of olefin products in the initial stage. More importantly, three types of cyclopentenyl cations (1,3‐dimethylcyclopentenyl, 1,2,3‐trimethylcyclopentenyl, and 1,3,4‐trimethylcyclopentenyl cations) and a pentamethylbenzenium ion were for the first time identified by solid‐state NMR spectroscopy and DFT calculations under both co‐feeding ([¹³C₆]benzene and methanol) conditions and typical MTO working (feeding [¹³C]methanol alone) conditions. The comparable reactivity of the MBs (from xylene to tetramethylbenzene) and the carbocations (trimethylcyclopentenyl and pentamethylbenzium ions) in the MTO reaction was revealed by ¹³C‐labeling experiments, evidencing that they work together through a paring mechanism to produce propene. The paring route in a full aromatics‐based catalytic cycle was also supported by theoretical DFT calculations.     

Theoretical predictive study on N7H7 hydronitrogen compounds

Geometric structures and energy properties of 25 isomers of N₇H₇ hydronitrogen compounds have been studied at the B3LYP/6-311++G(d,p) level. Atoms in molecules (AIM) and nature bond orbital (NBO) theories are applied to analyze the bond nature and the origin of structure and energy variations. The result indicates that the hyperconjugation from the lone pair of nitrogen to the neighboring NN bond plays an important role in the NN bond length variation and the relative stability of the 25 isomers can be attributed to the steric and hyperconjugative effects. G3MP2 calculations show that the heats of formation (HOFs) of all the isomers, especially those of the cyclic isomers, are positive and large, suggesting their potential to be energy molecules. Furthermore, the HOFs of the cyclic isomers decrease with increase of the number of substituents.     

The excited state dynamics study of di‐2‐pyridylketone in the A‐band and B‐band absorptions by using resonance Raman spectroscopy,IR and UV–visible spectroscopy

Excitation wavelengths of 282.4, 273.9 (A band), 252.7, 239.5 and 228.7 nm (B band) resonance Raman spectra were acquired for di‐2‐pyridylketone, and density functional calculations were carried out to help in the elucidation of the photo relaxation dynamics of A‐band and B‐band electronic transitions. The resonance Raman spectra show that the intensity pattern of the A band presents great difference from that of the B band, which indicate that the short‐time A‐band (S₀→S₄) photo relaxation dynamics have substantial difference from that of B band (S₀→S₁₀) . The overall picture of short‐time dynamics and the vibronic coupling mechanisms are interpreted using Albrecht's theory. Copyright © 2012 John Wiley & Sons, Ltd.