In-situ UV-Raman study on soot combustion over TiO2 or ZrO2-supported vanadium oxide catalysts

UV-Raman spectroscopy was used to study the molecular structures of TiO₂ or ZrO₂-supported vanadium oxide catalysts. The real time reaction status of soot combustion over these catalysts was detected by in-situ UV-Raman spectroscopy. The results indicate that TiO₂ undergoes a crystalline phase transformation from anatase to rutile phase with the increasing of reaction temperature. However, no obvious phase transformation process is observed for ZrO₂ support. The structures of supported vanadium oxides also depend on the V loading. The vanadium oxide species supported on TiO₂ or ZrO₂ attain monolayer saturation when V loading is equal to 4 (4 is the number of V atoms per 100 support metal ions). Interestingly, this loading ratio (V₄/TiO₂ and V₄/ZrO₂) gave the best catalytic activities for soot combustion reaction on both supports (TiO₂ and ZrO₂). The formation of surface oxygen complexes (SOC) is verified by in-situ UV Raman spectroscopy and the SOC mainly exist as carboxyl groups during soot combustion. The presence of NO in the reaction gas stream can promote the production of SOC. Supported by the National Natural Science Foundation of China (Grant Nos. 20473053, 20773163 and 20525621), the Beijing Natural Science Foundation (Grant No. 2062020), and the 863 Program of China (Grant No. 2006AA06Z346)     

Stopped-flow injection analysis. The influence of diffusion on dispersion of normal and reverse flow injection

A relationship is derived to enable the comparison of the dispersion heights of normal and reverse flow injection analysis (FIA). A single channel flow system is employed in the absence of a chemical reaction. The stopped-flow injection method is used to probe the influence of molecular diffusion on the overall dispersion of normal and reverse FIA, which appeared to demonstrate fundamentally different diffusion behaviors. Small discrepancies are observed between the dispersion heights, which are enhanced by the stopped-flow period, especially when unmatched matrix ionic compositions of the indicator and counter solutions were involved. For these conditions, the diffusion flux rate is enhanced considerably, displaying a peak, in addition to the transient, for both methods. The influence of diffusion on the dispersion characteristics of normal and reverse FIA is discussed theoretically. Diffusion in the proposed model is postulated to oppose dispersion by convection. The latter initiates concentration gradients in the injection zone and propagates it with flow time over the dispersion zone profile. The diffusion flux then reacts in order to confine the indicator dispersion for normal FIA and to enhance it for reverse FIA. This model is consistent with the experimental results and accounts for most of the phenomena encountered. Probably owing to the influence of secondary flow phenomena, the use of coiled tubes has suppressed the effects of diffusion on the overall dispersion behavior.Part of the experimental work was performed at IMI Institute for Research and Development, Haifa, Israel.     

Addition of palladium and platinum tri-tert-butylphosphine groups to Re-Sn and Re-Ge bonds

The reaction of Re2(CO)8[mu-eta2-C(H)=C(H)Bu(n)](mu-H) with Ph3SnH at 68 degrees C yielded the new compound Re2(CO)8(mu-SnPh2)2 (10) which contains two SnPh2 ligands bridging two Re(CO)(4) groups, joined by an unusually long Re-Re bond. Fenske-Hall molecular orbital calculations indicate that the bonding in the Re2Sn2 cluster is dominated by strong Re-Sn interactions and that the Re-Re interactions are weak. The 119Sn M?ssbauer spectrum of 10 exhibits a doublet with an isomer shift (IS) of 1.674(12) mm s(-1) and a quadrupole splitting (QS) of 2.080(12) mm s(-1) at 90 K,characteristic of Sn(IV) in a SnA2B2 environment. The IS is temperature dependent, -1.99(14) x 10(-4) mm s(-1) K(-1); the QS is temperature independent. The temperature-dependent properties are consistent with the known Gol'danskii-Kariagin effect. The germanium compound Re2(CO)8(mu-GePh2)2 (11) was obtained from the reaction of Re2(CO)8[mu-eta2-C(H)=C(H)Bu(n)](mu-H) with Ph3GeH. Compound 11 has a structure similar to that of 10. The reaction of 10 with Pd(PBu(t)3)2 at 25 degrees C yielded the bis-Pd(PBu(t)3) adduct, Re2(CO)8(mu-SnPh2)2[Pd(PBu(t)3)]2 (12); it has two Pd(PBu(t)3) groups bridging two of the four Re-Sn bonds in 10. Fenske-Hall molecular orbital calculations show that the Pd(PBu(t)3) groups form three-center two-electron bonds with the neighboring rhenium and tin atoms. The mono- and bis-Pt(PBu(t)3) adducts, Re2(CO)8(mu-SnPh2(2)[Pt(PBu(t)3)] (13) and Re2(CO)8(mu-SnPh2)2[Pt(PBu(t)3)]2 (14), were formed when 10 was treated with Pt(PBu(t)3)2. A mono adduct of 11, Re2(CO)8(mu-GePh2)2[Pt(PBu(t)3)] (15), was obtained similarly from the reaction of 11 with Pt(PBu(t)3)2.     

Markov Chains with finite convergence time

We study the properties of finite ergodic Markov Chains whose transition probability matrix P is singular. The results establish bounds on the convergence time of P^m to a matrix where all the rows are equal to the stationary distribution of P. The results suggest a simple rule for identifying the singular matrices which do not have a finite convergence time. We next study finite convergence to the stationary distribution independent of the initial distribution. The results establish the connection between the convergence time and the order of the minimal polynomial of the transition probability matrix. A queuing problem and a maintenance Markovian decision problem which possess the property of rapid convergence are presented.     

Application of synchronous fluorescence to parchment characterization

A nondestructive method for quantitative parchment characterization and sensitive indication of its deterioration stage was developed. Synchronous fluorescence (SF) measurements were applied for the first time to parchment samples. The method provides detailed spectral features, which are useful for parchment characterization. The discrimination of parchment samples into groups (modern, historical, and artificially aged) was successfully performed. The SF spectra could be resolved into specific fluorophores, which were related to the parchment condition. The spectral data indicate a continuous change in the collagen-to-gelatin ratio during the aging process. Depth-resolved synchronous fluorescence spectra were also measured. The data indicate that parchments possess a layered structure, and the dominant fluorophore in the upper layer is different from those in the lower layers. Layer-resolved profiling allows for quantifying the contribution of each fluorophore in each given layer. This way, significant differences between modern, artificially aged, and historical samples can be observed.     

Mössbauer studies and magnetic properties of Ln2SrCu2O6 compounds

Mössbauer and magnetic susceptibility measurements were used to study the magnetic properties of Ln_1.9Sr_1.1Cu₂O₆ (Ln=Pr,Nd) and La₂SrCu₂O₆ materials. These compounds were prepared by solid-state reaction and crystallize in a tetragonal structure, space group I4/mmm with two formula units per unit cell. There is only one crystallographic site for Cu atoms, which form a double layer of CuO₅ pyramids. These compounds are not superconducting, but we show, using Mössbauer spectroscopy (MS) on iron doped samples and susceptibility measurements, that the Cu planes order antiferromagnetically. The hyperfine fields on iron nuclei at 4.2 K extend from 472 kOe for La₂SrCu₂O₆ to 501 kOe for Nd_1.9Sr_1.1Cu₂O₆. The ordering temperaturesT _N are: R20, 190, and 250 K for Ln=La, Pr and Nd, respectively.