Permeation of electroactive organic probes through an electroinactive and passivating poly-ophenylenediamine (PPD) film electropolymerized on Pt and glassy carbon (GC) electrodes has been investigated by cyclic and rotating disk electrode (RDE) voltammetry. The access of solutes to the metal-polymer interface appears mainly governed by specific chemical interactions, influencing partition, and diffusion phenomena, rather than by exclusion effects based on molecular size or charge. Potential cycling of the film induces fine modifications in the chemical/physical structure of the polymer, as evidenced by electron spectroscopy for chemical analysis (ESCA) measurements and by an enhanced permeation of certain solutes. The membrane is, however, stable in the pH and potential range usually employed in its application, that is, as an enzyme-entrapping membrane in amperometric biosensors; because of membrane permselectivity, the electrochemical response of the most common electroactive interferents is deeply depressed.
Articles you may be interested inLow contact resistivity of metals on nitrogen-doped cuprous oxide (Cu2O) thin-films J. Appl. Phys. 112, 084508 (2012); 10.1063/1.4758305Structure and corrosion behavior of platinum/ruthenium/nitrogen doped diamondlike carbon thin films An x-ray photoelectron spectroscopy ͑XPS͒ analysis was performed of polypyrroles ͑PPy͒ electrosynthesized on Pt in aqueous solution. Spectra were recorded both for the as-synthesized ͑pristine͒ polymer ͑specimen 1͒ and for the so-called ''overoxidized'' PPy ͑specimen 2͒. Electrosynthesis was accomplished potentiostatically at ϩ0.7 V vs SCE in KCl 10 mM containing pyrrole 0.4 M. Overoxidized PPy was obtained by keeping the pristine polymer at the electrosynthesis potential for 5 h, in phosphate buffer solution ͑pH 7͒. C, N, O ͑1s͒, and Cl 2p ͑pristine͒ spectra are included. Some minor elements, P ͑in the overoxidized polymer͒, Na ͑in some overoxidized samples͒, and Si ͑in other samples of both types of PPy, but not in those here reported͒, were also detected.
X-ray photoelectron spectroscopy (XPS) is used in the present study to investigate the oxidation state and the structural role of titanium in two melanites with different Ti0 2 content (-3 % and-6 % wt) from M.Vulture (Italy). The Ti2p-XPS spectra can be satisfactorily fitted when Ti 3+ is lodged on octahedral and Ti 4+ distributed over octahedral and tetrahedral sites. The XPS direct estimates of Ti site populations match very weil with those indirectly obtained from Mössbauer spectroscopy (MS) through the Fe distribution. In addition, good agreement between the Fe 2+ JFe 3+ ratios estimated by both XPS and MS has been found using Fe 3 0 4 as a standard for interpreting Fe2p photoelectron spectra.
In the present interlaboratory comparison, the consistency and validity of the Shirley, straight-line and Tougaard methods for determination of peak intensities from measured XPS spectra have been studied by analysis of data on Au and Ni taken at eight laboratories. The reproducibility of the individual measuring systems was determined to be 26%. The RMS scatter around their mean values of the ratio of the peak intensity to the Au 4d peak intensity was 6% for the Tougaard method, 9-10% for the Shirley method and 8-9% for the straight-line method. The increase in root mean square (RMS) scatter of data due to data being recorded in different laboratories amounts to 3-4%, independent of the method applied for background correction. The RMS deviation from theory of intensity ratios of peaks from Ni and Au to the Au 4d peak intensity is 14% for the Tougaard method, 33% for the Shirley method and 31% for the straight-line method. The absolute accuracy of the methods cannot be established to better than the accuracy on the theoretical peak intensity ratios and the uncertainty in the energy dependence of the analyser response function. It is, however, reasonable to expect the combined uncertainty of these factors to be at least 10-15%. The peak intensity ratios obtained with the Tougaard method then falls within the expected accuracy of the theoretical ratios.
INTRODUCTIONThe present intercomparison work follows a previous extensive study' of the validity and consistency of methods for determination of XPS peak intensities. The notation and procedures for data analysis used in the present work are the same as in Ref. 1 and will only be summarized briefly here.Quantitative surface composition analysis by XPS relies on peak intensities. Peak areas are used as a measure of the peak intensity. Procedures to determine the peak area from a measured spectrum is complicated by the inelastic scattering events that the photoelectrons undergo as they leave the solid. This gives rise to an inelastic background intensity, which is subtracted to define the peak areas. Several methods have been used to define this background. Among these, the Shirley and the straight-line methods are most widely used. these methods, uncertainty arises from the problem of defining suitable start and end points for the evaluation of the background signal. More recently, a method that relies on a detailed description of the physical processes involved was proposed by T~ugaard.~.' This method has been applied by several groups, who have named the procedure the Tougaard method. To be consistent with this convention, we shall use here the same name for this background correction method. The complexity of the method is similar to that of the Shirley method. Because of shake-up processes, the XPS peak intensity extends over an energy range of 50-200 eV.5 To account for these shake-up processes, which vary with the sample composition, it is necessary to measure spectra over at least this energy range. For inhomogeneous samples, analysis of wide-scan spectra als...
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