The Elamite Cylinder Seal Corpus, c.3500 - 1000 BC

The ancient region of Elam (southwestern Iran) has produced a significant assemblage of cylinder seals across a considerable chronological span. Unlike the glyptic material from the related and neighbouring region Mesopotamia, the Elamite cylinder seals have not previously been studied in detailed reference to one another, nor has there been an established paradigm of stylistic development articulated. This study addresses this lacuna by compiling all the published cylinder seals from Elam (as defined here, thus incorporating the historical provinces of Khuzistan, Luristan and Fars), from their earliest appearance (c.3500 BC), throughout the era of their typological dominance (over stamp seals, thus this study departs c.1000 BC). This compilation is presented in the Elamite Cylinder Seal Catalogue (Volume II), and is annotated and described through the annunciation of eighteen chronologically defined developmental styles (with another two non-chronological type classifications and four miscellaneous groups). Through the further analysis of this data, including the newly formulated and articulated styles, several facets and problems of Elamite glyptic material have been addressed (and thus the reliance upon assumed similarity in type and function with the Mesopotamian glyptic material is abandoned). These problems particularly pertain to the function of cylinder seals in Elam and the type and form of the Elamite-Mesopotamian glyptic interaction. In regards to function, a standard administrative function can be discerned, though of varying types and forms across the region and the period of study. Other, non-standard, symbolic glyptic functions can also be demonstrated in the Corpus, including the apparent proliferation of a form known as the ‘votive’ seal, perhaps a specifically Elamite form. The analysis of the style type (whether ‘Elamite’, ‘Mesopotamian Related’ or ‘Shared Elamite-Mesopotamian’), in association with their relative geographical and chronological distribution, has also enabled the discussion of the nature of Elamite-Mesopotamian glyptic interaction, and thereby the constitution of Elamite civilisation (especially in regards to Mesopotamian cultural impact and influence, and thus the testing of several previously presented paradigms [Amiet 1979a; 1979b; Miroschedji 2003])

Synthesis and characterisation of carbon-supported PtGe electrocatalysts for CO oxidation

Platinum-germanium catalysts supported on carbon were synthesised from organometallic precursors using surface organometallic chemistry (SOMC). The catalysts were characterised using chemisorption, X-ray absorption spectroscopy, transmission electron microscopy, energy dispersive X-ray analysis, X-ray diffraction and cyclic voltammetry. Physical characterisation provided evidence for the selective deposition of the germanium with the platinum using SOMC, existing mainly as platinum metal in association with GeO2. From anodic stripping cyclic voltammetry it can be inferred that the presence of GeO2, at the platinum sites changes the CO oxidation profile of strongly adsorbed CO, increasing its oxidation at 0.68 V versus RHE relative to the main oxidation at 0.85 V versus RHE. The peak potentials appear to be independent of the germanium loading; however, significant changes were observed in the peak current densities, with an increased promotional effect at higher germanium content. We believe the change in the relative distribution between these sites is mainly due to changes in the surface structure of the platinum on addition of GeO2. Further promotional activity is seen, with a limited oxidation activity evident at an onset of 0.35 V versus RHE. (C) 2001 Elsevier Science Ltd. All rights reserved

Effect of Ru surface composition on the CO tolerance of Ru modified carbon supported Pt catalysts

A series of ruthenium modified carbon supported catalysts have been prepared by surface organometallic chemistry (SOMC) with the following nominal Ru:Pt surface ratios, (1:4)RuPt/C, (1:2)RuPt/C, (3:4)RuPt/C and (1:1)RuPt/C. The catalysts were characterised using X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), cyclic voltammetry (CV), and half-cell polarisation studies. The XRD measurements showed that a bulk PtRu alloy was not formed following SONIC modification. However, the EXAFS measurements indicated that a surface alloy is formed upon electrochemical reduction of the Ru modified catalysts. The CV studies show that the electrooxidation of CO on the Ru modified Pt/C catalysts occurs at lower potentials than on the unmodified Pt/C catalysts, but at higher potentials than on an alloyed PtRu/C with a bulk composition of 1:1 Pt:Ru. Half cell polarisation measurements in 100 ppm CO in H-2 show that the CO tolerance of the SONIC RuPt/C catalysts approached that of the conventional PtRu/C alloy catalyst. The results therefore indicate that a bulk alloy phase is not an essential factor in the improvement in CO tolerance of PtRu/C catalysts over that of Pt/C

Controlled modification of carbon supported platinum electrocatalysts by Mo

A carbon-supported platinum electrocatalyst was modified with molybdenum using surface organometallic chemistry. The catalyst was characterized using transmission electron microscopy, cyclic voltammetry (CV), polarization studies, and in situ fluorescence extended X-ray absorption fine structure (EXAFS) studies. The CV and polarization studies show that CO oxidation starts at low overpotentials. similar to those of a conventionally prepared PtCoMo/C electrocatalyst. EXAFS at the Mo K edge recorded at 0.65 V show that the Mo exists as an oxide species associated with the Pt surface with a Mo-O distance of 1.75 Angstrom. At 0.05 V this oxide is reduced with the formation of a metal-metal bond between the Mo and Ft, with a bond distance of 2.63 Angstrom

Potential dependence of segregation and surface alloy formation of a Ru modified carbon supported Pt catalyst

Ruthenium modified carbon supported platinum catalysts have been shown to have a similar activity towards carbon monoxide oxidation as conventionally prepared bimetallic PtRu alloy catalysts. In this study the effect of the applied electrode potential and potential cycles on the location and oxidation state of the Ru species in such Ru modified Pt/C catalysts was investigated using in situ EXAFS collected at both the Ru K and Pt L3 absorption edges. The as prepared catalyst was found to consist of a Pt core with a Ru oxy/hydroxide shell. The potential dependent data indicated alloying to form a PtRu phase at 0.05 V versus RHE and subsequent dealloying to return to the Ru oxy/hydroxide decorated Pt surface at potentials greater than 0.7 V. The Ru–O distances obtained indicate that both Ru3+ and Ru4+ species are present on the surface of the Pt particles at oxidising potentials; the former is characteristic of the as prepared Ru modified Pt/C catalyst and following extensive periods at potentials above 0.7 V and the latter of the Ru oxide species on the PtRu alloy.<br/