The Use of Derivative Thermogravimetry to Estimate Degree of Thermal Degradation

It is difficult to estimate the degree of thermal degradation which has taken place in complex parts composed of cellulosics and polymeric insulation unless complete failure has occurred. There is a definite need for a parameter which can quickly and easily measure the relative degree of thermal attack on organic insulation subjected to various known environmental and processing conditions. This paper reports preliminary work using derivative thermogravimetry to perform this function. Derivative thermogravimetric analysis (TGA) was used to produce a value, TGA Index, related to the peak height of the major TGA derivative signal. This TGA Index was found to correlate with the copper number of insulating paper measured after thermal degradation. The application of TGA Index to evaluation of polymer degradation after thermal shock, water absorption, and accelerated UV attack is also discussed. Finally, preliminary studies on the use of derivative TGA to evaluate coatings exposed to various outdoor environments around the country are reported.     

Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L3-edge Puzzle

The Ce L₃ edge XAS spectra of CeO₂ and cerocene [Ce(C₈H₈)₂] were calculated with relativistic ab-initio multireference wavefunction approaches capable of reproducing the observed spectra accurately. The study aims to resolve the decades-long puzzle regarding the relationship between the number and relative intensities of the XAS peaks and the 4f electron occupation in the ground state (GS) versus the core-excited states (ESs). CeO₂ and cerocene exemplify the different roles of covalent bonding and wavefunction configurational composition in the observed intensity patterns. Good agreement is found between the calculated GS 4f-shell occupations and the value derived from XAS measurements using peak areas (n_f). The identity of the two-peaked Ce L₃ edge is fully rationalized from the perspective of the relaxed wavefunctions for the GS and core ESs. The states underlying the different peaks differ from each other in a surprisingly simple way that can be associated with 4f¹ vs. 4f⁰ sub-configurations. Furthermore, part of one of the cerocene spectral peaks is associated with 4f² sub-configurations. The pattern therefore reveals excited states that can be interpreted in terms of Ce IV and III oxidation numbers, as long assumed, with Ce II states additionally appearing in the cerocene spectrum. While this work demonstrates the rough accuracy of the conventional approach to determining n_f from Ce L₃-edge XAS, limitations are highlighted in terms of the ultimate accuracy of this approach and the potential of observing new types of excited states. The need to determine the sources of n_f by calculations, is stressed.     

Electronic and adsorption properties of Ce‐Ag layers

Silver has rarely been considered as the catalyst for CO oxidation, although it has been recognized to be very active in several partial oxidation reactions such as ethylene epoxidation and formaldehyde synthesis. It is generally believed that a metal support interaction plays an important role in catalytic processes. Therefore in our study, we examined electronic and adsorption properties of cerium deposited onto a polycrystalline silver substrate. Layers of approximately one monolayer of cerium deposited on a clean silver substrate were examined in situ using surface‐sensitive techniques—by XPS, ultraviolet photoelectron spectroscopy (UPS) and low energy ion scattering (LEIS). CO molecular adsorption was observed by UPS and LEIS; experimental results exhibited CO adsorption on Ce atoms sites. Oxygen adsorption on deposited layers led to a strong oxidation; stoichiometry of oxidized layers was given by amount of adsorbed oxygen and by temperature. Copyright © 2011 John Wiley & Sons, Ltd.     

改性ZrO2-MnO2基整体式催化剂上NH3选择性催化还原NO

采用共沉淀法制备了ZrO2-MnO2催化剂,考察了CeO2,MoO3和WO3的添加对ZrO2-MnO2整体式催化剂上NH3选择性催化还原(NH3-SCR)NOx的影响,并利用低温N2吸附-脱附、X射线衍射、X射线光电子能谱、NH3和NO程序升温脱附等方法对催化剂进行了表征,结果表明催化剂物相为Mn0.2Zr0.8O1....     

Manipulation of Single‐Stranded DNA by Using an Artificial Site‐Selective DNA Cutter Composed of Cerium(IV)/EDTA and Phosphonate–Oligonucleotide Conjugates

An artificial site‐selective DNA cutter to hydrolyze single‐stranded DNA at a desired site was prepared from Ce^IV/ethylenediamintetraacetic acid (EDTA) and two ethylenediamine‐N,N,N′,N′‐tetrakis(methylenephosphonic acid)–oligonucleotide conjugates. By using this cutter, the sense strand of a blue fluorescent protein (BFP) gene was selectively cut at a predetermined site in the chromophore‐coding region. The upstream fragment obtained by the site‐selective scission was ligated with the downstream fragment of the closely related green fluorescent protein (GFP) gene so that the 5′‐ and 3′‐end portions of the chromophore came from the BFP fragment and the GFP fragment, respectively. The recombinant gene was successfully expressed in E. coli and the chimeric chromophore emitted green fluorescence as expected.     

CeO_2修饰炭载体负载PdPt二元合金催化剂及其在甲酸氧化电催化中的应用

用CeO2修饰炭粉做载体,使用有机溶胶法还原PdPt二元合金的方法制备了一系列PdPt/CeO2-C催化剂.借助电化学测试,探讨催化剂中不同Pd与Pt原子比例的PdPt二元合金和不同含量的CeO2对于甲酸电氧化催化活性的影响.不断减少PdPt合金中Pt的比例可以促使甲酸氧化的起始电位前移,当Pd：Pt=15：1时氧化电流出现极值;同时,随着催化剂中CeO2含量的增加,催化剂对于HCOOH氧化的电流密度增加,当含量为15%时达到最大值.相对于Pd/C催化剂,在Pd15Pt1/15CeO2-C催化剂表面的甲酸氧化反应起始电位负移至少0.1V,氧化的电流密度提高60%以上.结合X射线衍射（XRD）,X射线光电子能谱（XPS）,透射电镜（TEM）和热重（TG）等测试数据可以发现,当极少量的Pt与Pd形成合金,Pt与Pd之间产生电子效应,使得合金表面HCOOH氧化的过电位降低;而CeO2的添加不仅有助于PdPt二元合金的分散,更有可能改变甲酸在PdPt表面的氧化反应路径,发挥双功能机理.     

Synergistic effects of cerium phosphate and intumescent flame retardant on EPDM/PP composites

An intumescent flame retardant system composed of ammonium polyphosphate (APP) and pentaerythritol (PER) was used for flame retarding ethylene–propylene–diene‐modified elastomer (EPDM)/polypropylene (PP) blends. Cerium phosphate (CeP) was synthesized and the effect on flame retardancy and thermal stability of EPDM/PP composites based on intumescent flame retardant (IFR) were studied by limiting oxygen index (LOI), UL‐94, and thermogravimetic analysis (TGA), respectively. Scanning electron microscopy (SEM) and Fourier transform infrared spectrometry (FTIR) were used to analyze the morphological structure and the component of the residue chars formed from the EPDM/PP composites, and the mechanical properties of the materials were also studied. The addition of CeP to the EPDM/PP/APP/PER composites gives better flame retardancy than that of EPDM/PP/APP/PER composites. TGA and RT‐FTIR studies indicated that an interaction occurs among APP, PER, and EPDM/PP. The incorporation of CeP improved the mechanical properties of the materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Time‐Resolved,In Situ DRIFTS/EDE/MS Studies on Alumina‐Supported Rhodium Catalysts: Effects of Ceriation and Zirconiation on Rhodium–CO Interactions

The effects of ceria and zirconia on the structure–function properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ‐Al₂O₃) during CO exposure are described. Ceria and zirconia are introduced through two preparation methods: 1) ceria is deposited on γ‐Al₂O₃ from [Ce(acac)₃] and rhodium metal is subsequently added, and 2) through the controlled surface modification (CSM) technique, which involves the decomposition of [M(acac)_x] (M=Ce, x=3; M=Zr, x=4) on Rh/γ‐Al₂O₃. The structure–function correlations of ceria and/or zirconia‐doped rhodium catalysts are investigated by diffuse reflectance infrared Fourier‐transform spectroscopy/energy‐dispersive extended X‐ray absorption spectroscopy/mass spectrometry (DRIFTS/EDE/MS) under time‐resolved, in situ conditions. CeO_x and ZrO₂ facilitate the protection of Rh particles against extensive oxidation in air and CO. Larger Rh core particles of ceriated and zirconiated Rh catalysts prepared by CSM are observed and compared with Rh/γ‐Al₂O₃ samples, whereas supported Rh particles are easily disrupted by CO forming mononuclear Rh geminal dicarbonyl species. DRIFTS results indicate that, through the interaction of CO with ceriated Rh particles, a significantly larger amount of linear CO species form; this suggests the predominance of a metallic Rh phase.