Attaching photochemically active ruthenium polypyridyl complex units to amorphous hydrogenated carbon (a-C:H) layers

Amorphous hydrogenated carbon (a-C:H) films are applied 500 nm thick on Si(100) via plasma-enhanced chemical vapor deposition (PECVD) using ethyne. Present plasma conditions enrich the sp(2)-content especially toward the outermost a-C:H layers, which in turn are used to attach a photoactive Ru-polypyridyl complex to the surface. An azo-bridged dinuclear Ru-polypyridyl complex is optimized in synthesis and the final mononuclear fragment attached on a-C:H photochemically under UV-irradiation with concomitant N-2 release. The Ru-polypyridyl complex is characterized by MS, NMR, IR, UV/vis, fluorescence spectroscopy, and time-dependent density functional theory (DFT) calculations. Crystallographic data for the intermediate 4-nitro-2-(pyridin-2-yl)pyridine 1-oxide as essential precursor are established. Morphological characteristics of the a-C:H @ Si and final Ru(complex) @ a-C:H @ Si combinations are determined by atomic force microscopy (AFM) revealing individual grain-like structures. The presence of Ru on the a-C:H @ Si surface is initially verified qualitatively by laser-induced breakdown spectroscopy (LIBS) and by inductively coupled plasma-sector field mass spectrometry (ICP-SF-MS) after chemical digestion. With laser ablation-ICP-MS mapping, full Ru coverage is proven, also revealing inhomogeneities in terms of "Ru hot spots". The current investigation proves the successful attachment of a Ru-complex on a-C:H and indicates a starting point for the development of further material combinations for feasible sunlight to energy conversions

Atomic spectrometry update: review of advances in atomic spectrometry and related techniques

This review of 151 references covers developments in ‘Atomic Spectrometry’ published in the twelve months from November 2014 to November 2015 inclusive. It covers atomic emission, absorption, fluorescence and mass spectrometry, but excludes material on speciation and coupled techniques which are included in a separate review. It should be read in conjunction with the previous review1 and the other related reviews in the series.2–6 A critical approach to the selection of material has been adopted, with only novel developments in instrumentation, techniques and methodology being included. Most of the techniques discussed have reached a stage of maturity where major advances are less common, with many of the novel developments falling under the category of ‘applications’ and advances in instrumentation being confined to component parts, such as sample introduction and sample preparation systems. There have been some developments in mass spectrometry, with reports of distance of flight (DOF)-MS and zoom-TOF-MS to improve speed of data collection and resolution respectively; and further insights into space charge effects in the ICP channel and ion beam of ICP-MS. The development of components for portable systems continues to be of interest, covering areas such as plasma sources for OES, fibre-optic laser systems for LIBS, and compact components for planetary exploration. The quest for high sensitivity and precision and low noise has driven developments in MC-ICP-MS in order to improve precision of IR measurements for geochronology and other applications