The chemistry of Cr(VI) adsorption on to poly(p-phenylenediamine) adsorbent.

Water pollution due to industrial processes has necessitated and spurred robust research into the development of adsorbent materials for remediation. Polyphenylenediamines (PPD) have attracted significant attention because of their dual cationic and redox properties. They are able to reduce Cr(VI) to Cr(III) in solution. Interrogation of the chemical processes involved in the Cr(VI) adsorption on para-PPD was primarily by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectroscopy. It was confirmed that the underlying oxidation of the amino groups to imines during the reduction of Cr(VI) to Cr(III) was irreversible. This process occurred at both acidic and alkaline conditions. Reduction was accompanied by Cr(III) chelation on the adsorbent surface. Further, regeneration with dilute aqueous NaOH and HCl extended the polymer's adsorptive capacity beyond exhaustion of its redox potentials.

In Situ Electrochemical-AFM and Cluster-Ion-Profiled XPS Characterization of an Insulating Polymeric Membrane as a Substrate for Immobilizing Biomolecules.

The electrochemical oxidation of ortho-aminophenol (oAP) by cyclic voltammetry (CV), on platinum substrates in neutral solution, produces a polymeric film (PoAP) that grows to a limiting thickness of about 10 nm. The insulating film has potential use as a bioimmobilizing substrate, with its specificity depending on the orientation of its molecular chains. Prior investigations suggest that the film consists of alternating quinoneimine and oAP units, progressively filling all the platinum sites during the electrosynthesis. This work concerns the evaluation of the growth orientation of PoAP chains, which until now was deduced only from indirect evidence. Atomic force microscopy (AFM) has been used in situ with an electrochemical cell so that PoAP deposition on a specific area can be observed, thus avoiding any surface reorganization during ex situ transport. In parallel with microscopy, XPS experiments have been performed using cluster ion beams to profile this film, which is exceptionally thin, without damage while retaining molecular information.

Surface properties of nanocrystalline PbS films deposited at the water-oil interface: a study of atmospheric aging.

Nanocrystalline thin films of PbS are obtained in a straightforward reaction by precipitation at the interface between toluene (containing a Pb precursor) and water (containing Na2S). Lead thiobiuret [Pb(SON(CN(i)Pr2)2)2] and lead diethyldithiocarbamate [Pb(S2CNEt2)2] precursors are used. The films are characterized by X-ray diffraction and electron microscopy, revealing typical particle sizes of 10-40 nm and preferred (200) orientation. Synchrotron-excited depth-profiling X-ray photoelectron spectroscopy (XPS) is used to determine the depth-dependent chemical composition as a function of surface aging in air for periods of up to 9 months. The as-synthesized films show a 1:1 Pb/S composition. Initial degradation occurs to form lead hydroxide and small quantities of surface-adsorbed -SH species. A lead-deficient Pb1-xS phase is produced as the aging proceeds. Oxidation of the sulfur occurs later to form sulfite and sulfate products that are highly localized at the surface layers of the nanocrystals. These species show logarithmic growth kinetics, demonstrating that the sulfite/sulfate layer acts to passivate the nanocrystals. Our results demonstrate that the initial reaction of the PbS nanocrystals (forming lead hydroxide) is incongruent. The results are discussed in the context of the use of PbS nanocrystals as light-harvesting elements in next-generation solar technology.

Water Dissociates at the Aqueous Interface with Reduced Anatase TiO2 (101).

Elucidating the structure of the interface between natural (reduced) anatase TiO2 (101) and water is an essential step toward understanding the associated photoassisted water splitting mechanism. Here we present surface X-ray diffraction results for the room temperature interface with ultrathin and bulk water, which we explain by reference to density functional theory calculations. We find that both interfaces contain a 25:75 mixture of molecular H2O and terminal OH bound to titanium atoms along with bridging OH species in the contact layer. This is in complete contrast to the inert character of room temperature anatase TiO2 (101) in ultrahigh vacuum. A key difference between the ultrathin and bulk water interfaces is that in the latter water in the second layer is also ordered. These molecules are hydrogen bonded to the contact layer, modifying the bond angles.

Versailles Project on Advanced Materials and Standards Interlaboratory Study on Measuring the Thickness and Chemistry of Nanoparticle Coatings Using XPS and LEIS.

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) inter-laboratory study on the measurement of the shell thickness and chemistry of nanoparticle coatings. Peptide-coated gold particles were supplied to laboratories in two forms: a colloidal suspension in pure water and; particles dried onto a silicon wafer. Participants prepared and analyzed these samples using either X-ray photoelectron spectroscopy (XPS) or low energy ion scattering (LEIS). Careful data analysis revealed some significant sources of discrepancy, particularly for XPS. Degradation during transportation, storage or sample preparation resulted in a variability in thickness of 53 %. The calculation method chosen by XPS participants contributed a variability of 67 %. However, variability of 12 % was achieved for the samples deposited using a single method and by choosing photoelectron peaks that were not adversely affected by instrumental transmission effects. The study identified a need for more consistency in instrumental transmission functions and relative sensitivity factors, since this contributed a variability of 33 %. The results from the LEIS participants were more consistent, with variability of less than 10 % in thickness and this is mostly due to a common method of data analysis. The calculation was performed using a model developed for uniform, flat films and some participants employed a correction factor to account for the sample geometry, which appears warranted based upon a simulation of LEIS data from one of the participants and comparison to the XPS results.