Developments in near infrared spectroscopy

Vibrational spectroscopy at high excitation is an important research frontier for two reasons. Firstly, the near infrared is proving to be an important area for the analytical applications of spectroscopy, and we would therefore like to understand how the spectra we observe relate to the molecular structure of the absorbing species. Secondly, there is a fundamental interest in understanding molecular dynamics and energy flow within a polyatomic molecule at high excitation, because this is the boundary between spectroscopy and chemistry through which we try to understand the details of a chemical reaction. In this presentation I shall survey recent progress in this field.

In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti-6Al-4V in simulated body fluid at 25 degrees C and 37 degrees C

The corrosion resistance of Ti and Ti-6Al-4V was investigated through electrochemical impedance spectroscopy, EIS, potentiodynamic polarisation curves and UV-Vis spectrophotometry. The tests were done in Hank solution at 25 degrees C and 37 degrees C. The EIS measurements were done at the open circuit potential at specific immersion times. An increase of the resistance as a function of the immersion time was observed, for Ti (at 25 degrees C and 37 degrees C), and for Ti-6Al-4V (at 25 degrees C), which was interpreted as the formation and growth of a passive film on the metallic surfaces. (C) 2009 Elsevier Ltd. All rights reserved.

Real-time, in-situ, extinction spectroscopy studies on silver-nanoseed formation

In this paper, real-time extinction spectroscopy was employed to analyze in situ the fast formation process of silver seeds. The influencing factors for silver-seed formation, including the concentration of the reducer (NaBH 4), the amount of stabilizer (citrate), and the addition procedure of NaBH4, were evaluated. The configuration of the surface plasmon resonance (SPR) spectra of silver nanoparticles, which reflected the morphology of the produced silver seeds, was found to be distinctly affected by the NaBH4 concentration. Homogeneous silver nanoparticles were obtained when the added NaBH4 was lower in concentration than 2.00 mM. In contrast, higher concentrations of reducing agent (>3.00 mM NaBH4) resulted in uneven silver nanoparticles. Mie theory was applied to clarify the correlation of the SPR and the size of the silver seeds. Repeated additions of a small amount of the reducing agent could increase the monodispersity and isotropy of silver seeds. Real-time extinction spectroscopy is a convenient technique that achieves the in-situ and nondestructive measurement of intermediates in the formation process of silver nanoseeds.

High-resolution summer temperature reconstruction from Lake Silvaplana based on in-situ reflectance spectroscopy

Annually laminated (varved) sediments of proglacial Lake Silvaplana (46 ̊27’N, 9 ̊48’E, 1791 m a.s.l., Engadine, eastern Swiss Alps) provide an excellent archive for quantitative high-resolution (seasonal – annual) reconstruction of high- and lowfrequency climate signals back to AD 1580. The chronology of the core is based on varve counting, Cs-137, Pb-210 and event stratigraphy. In this study we present a reconstruction based on in-situ reflectance spectroscopy. In situ reflectance spectroscopy is known as a cost- and time-effective non destructtive method for semi-quantitative analysis of pigments (e.g., chlorines and carotenoids) and of lithoclastic sediment fractions. Reflectance-dependent absorption (RDA) was measured with a Gretac Macbeth spectrolino at 2 mm resolution. The spectral coverage ranges from 380 nm to 730 nm at 10 nm band resolution. In proglacial Lake Silvaplana, 99% of the sediment is lithoclastic prior to AD 1950. Therefore, we concentrate on absorption features that are characteristic for lithoclastic sediment fractions. In Lake Silvaplana, two significant correlations that are stable in time were found between RDA typical for lithoclastics and meteorological data: (1) the time series R 570 /R 630 (ratio between RDA at 570 nm and 630 nm) of varves in Lake Silvaplana and May to October temperatures at nearby station of Sils correlate highly significantly (calibration period AD 1864 – 1951, r = 0.74, p < 0.01 for 5ptsmoothed series; RMSE is 0.28 ̊C, RE = 0.41 and CE = 0.38), and (2) the minimum reflectance within the 690nm band (min690) data correlate with May to October (calibration period AD 1864 – 1951, r = 0.68, p < 0.01 for 5pt-smoothed series; RMSE = 0.22 ̊C, RE = 0.5, CE = 0.31). Both proxy series (min690nm and R 570 /R 630 values) are internally highly consistent (r = 0.8, p < 0.001). In proglacial Lake Silvaplana the largest amount of sediment is transported by glacial meltwater. The melting season spans approximately from May to October, which gives us a good understanding of the geophysical processes explaining the correlations between lithoclastic proxies and the meteorological data. The reconstructions were extended back to AD 1580 and show a broad corresponddence with fully independent reconstructions from tree rings and documentary data.

Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

A New Approach for Automatic Removal of Movement Artifacts in Near-Infrared Spectroscopy Time Series by Means of Acceleration Data

Abstract: Near-infrared spectroscopy (NIRS) enables the non-invasive measurement of changes in hemodynamics and oxygenation in tissue. Changes in light-coupling due to movement of the subject can cause movement artifacts (MAs) in the recorded signals. Several methods have been developed so far that facilitate the detection and reduction of MAs in the data. However, due to fixed parameter values (e.g., global threshold) none of these methods are perfectly suitable for long-term (i.e., hours) recordings or were not time-effective when applied to large datasets. We aimed to overcome these limitations by automation, i.e., data adaptive thresholding specifically designed for long-term measurements, and by introducing a stable long-term signal reconstruction. Our new technique (“acceleration-based movement artifact reduction algorithm”, AMARA) is based on combining two methods: the “movement artifact reduction algorithm” (MARA, Scholkmann et al. Phys. Meas. 2010, 31, 649–662), and the “accelerometer-based motion artifact removal” (ABAMAR, Virtanen et al. J. Biomed. Opt. 2011, 16, 087005). We describe AMARA in detail and report about successful validation of the algorithm using empirical NIRS data, measured over the prefrontal cortex in adolescents during sleep. In addition, we compared the performance of AMARA to that of MARA and ABAMAR based on validation data.

New insights on electrochemical hydrogen storage in nanoporous carbons by in situ Raman spectroscopy

In situ Raman spectroscopy was exploited to analyze the interaction between carbon and hydrogen during electrochemical hydrogen storage at cathodic conditions. Two different activated carbons were used and characterized by different electrochemical techniques in two electrolytes (6 M KOH and 0.5 M Na2SO4). The in situ Raman spectra collected showed that, in addition to the D and G bands associated to the graphitic carbons, two bands appear simultaneously at about 1110 and 1500 cm−1 under cathodic conditions, and then they disappear when the potential increases to more positive values. This indicates that carbon–hydrogen bonds are formed reversibly in both electrolytes during cathodic conditions. Comparing the two activated carbons, it was confirmed that, in both electrolytes, the hydrogenation of carbon atoms is produced more easily for the sample with lower amount of surface oxygen groups. In KOH medium, for the two samples, the formation of carbon–hydrogen bonds proceeds at more positive potential with respect to the thermodynamic potential value for hydrogen evolution. Furthermore, changes in the shape of the D band (due to an intensity increase of the D1 band) during the formation of carbon–hydrogen bonds suggest that hydrogenation of the carbon atoms increases the number of edge planes.

Characterization of a zeolite-templated carbon by electrochemical quartz crystal microbalance and in situ Raman spectroscopy

Electrochemical quartz crystal microbalance was used to monitor the mass changes during the electrochemical characterization of a zeolite-templated carbon (ZTC) in 1 M H2SO4 medium. Under electrochemical oxidation conditions, a high anodic current and a net mass increase were recorded, resulting in the increase of the specific capacitance owing to the contribution of the pseudocapacitance, mainly derived from the hydroquinone–quinone redox couple. Under more severe electrochemical conditions, a net mass loss was observed, revealing that electrochemical gasification took place. Surface chemistry, before and after the electrochemical treatments, was analyzed through temperature programmed desorption experiments. Furthermore, in situ Raman spectroscopy was used to further characterize the structural changes produced in ZTC under the electrochemical conditions applied, supporting that high potential values produce the electrochemical oxidation and degradation of the carbon material.

In situ microscopic FTIR spectroelectrochemistry study of oxidation of L-ascorbic acid in polymer electrolyte (PEG/LiClO4)

In situ microscopic FTIR spectroelectrochemistry behavior of L-ascorbic acid (H(2)A) in polymer electrolyte is reported for the first time. H(2)A undergoes a two-step oxidation, The oxidation waves shift towards more anodic potential values when the scan rate increases. The peak currents of the oxidation waves are proportional to the square roots of scan rate up to 100 mV/s, The in situ infrared spectra suggest that the product of the oxidation be dehydroascorbic acid, which may exist as a dimer.

The effects of the specific adsorption of anion on the reactivity of the Ru(0001) surface towards CO adsorption and oxidation: in situ FTIRS studies

The dynamics of adsorption and oxidation of CO on Ru(0001) electrode in sulfuric acid solution have been studied using in situ FTIR spectroscopy under potential control and at open circuit, the latter at 20 and 55 degrees C. The in situ IR data show clearly that the bisulfate anion adsorbs on the Ru(0001) surface over the potential range from -200 mV to 350 mV (vs. Ag/AgCl) at 20 degrees C in the absence and presence of adsorbed CO; however, increasing the temperature to 55 degrees C and/ or increasing the concentration of dissolved O-2 reduces the bisulfate adsorption. The formation of surface (hydro-) oxide at higher potentials replaces the bisulfate adsorbates. Both linear (COL) and three-fold hollow bonded CO (COH) adsorbates were produced following CO adsorption at Ru(0001) in H2SO4, as was observed in our previous studies in HClO4. However, the amount of adsorbed CO observed in H2SO4 was ca. 10% less than that in HClO4; in addition, the COL and COH frequencies were higher in H2SO4, and the onset potential for COads oxidation 25 mV lower. These new results are interpreted in terms of a model in which the adsorbed bisulfate weakens the CO adlayer, allowing the active Ru oxide layer to form at lower potentials. Significantly different results were observed at open circuit in H2SO4 compared both to the data under potential control and to our earlier data in HClO4, and these observations were rationalized in terms of the adsorbed HSO4- anions (pre-adsorbed at -200 mV) inhibiting the oxidation of the surface at open circuit (after stepping from the initial potential of -200 mV), as the latter was no longer driven by the imposed electrochemical potential but via chemical oxidation by trace dissolved O-2. Results from experiments at open circuit at 55 degrees C and using oxygen-saturated H2SO4 supported this model. The difference in Ru surface chemistry between imposed electrochemical control and chemical control has potential implications with respect to fuel cell electrocatalysis.

Catalysis of CO electrooxidation at Pt, Ru, and PtRu alloy. An in situ FTIR study

A comparative study of CO electrooxidation on different catalysts using in situ FTIR spectroscopy is presented. As electrode materials, polycrystalline Pt and Ru and a PtRu (50:50) alloy are used. The latter is one of the well-known active alloys for CO oxidation. The potential dependence of the band frequencies for the CO stretch indicates the formation of relatively compact islands at pure Pt and Ru, and a loose adlayer structure at the alloy. This loose structure has a positive effect on the rate of oxidative desorption. CO submonolayer coverages are obtained by integrating the absorption bands for CO produced upon oxidation of adsorbed CO. The band intensities measured at Pt, Ru, and PtRu indicate an influence of the substrate on the absorption coefficient of the CO stretch. It is shown that for a correct description of the catalyst properties toward CO electrooxidation, it must be distinguished between bulk and adsorbed CO. In contrast to the statement of most of the recent papers that a PtRu alloy (50:50) is the material with the highest activity for CO oxidation, it is demonstrated and rationalized in the present paper that for bulk CO oxidation pure Ru is the best catalyst. © 1999 American Chemical Society.

In situ FTIR studies of the effect of temperature on the adsorption and electrooxidation of CO at the Ru(0001) electrode surface

The adsorption and electrooxidation of CO at a Ru(0001) electrode in perchloric acid solution have been investigated as a function of temperature, potential and time using in situ FTIR spectroscopy. This builds upon and extends previous work on the same system carried out at room temperature. As was observed at room temperature, both linear (CO) and 3-fold-hollow (CO) binding CO adsorbates (bands at 2000-2045 cm and 1768-1805 cm, respectively) were detected on the Ru(0001) electrode at 10°C and 50°C. However, the temperature of the Ru(0001) electrode had a significant effect upon the structure and behavior of the CO adlayer. At 10°C, the in-situ FTIR data showed that the adsorbed CO species still remain in rather compact islands up to ca. 1100 mV vs Ag/AgCl as the CO oxidation reaction proceeds, with oxidation occurring only at the boundaries between the CO and active surface oxide/hydroxide domains. However, the IR data collected at 50°C strongly suggest that the adsorbed CO species are present as relatively looser and weaker structures, which are more easily electro-oxidized. The temperature-, potential-, and coverage-dependent relaxation and compression of the CO adlayer at low coverages are also discussed.

In situ FTIR spectroscopic studies of the oxidation of CO adsorbates on Ru(0 0 0 1) electrodes under open circuit conditions

This paper reports the first observation, using in situ FTIR spectroscopy, of the oxidation of CO adsorbates on the Ru(0001) electrode to CO under open circuit (oc) conditions in both perchloric acid and sulphuric acid solution at 20 and 55 °C. While the significant oc oxidation of the adsorbed CO on the Ru(0001) electrode was observed in perchloric acid solution, much less oc oxidation took place in sulfuric acid solution due to the specific adsorption of bisulfate at the Ru surface which inhibits the surface oxidation and reduces the reactivity of the surface towards the oxidation of CO . The oc oxidation of the CO depends strongly on the oxygen concentration in the solution and the temperature. The data so obtained are compared to those observed at the gas|solid interface, as well as to those obtained from the electro-oxidation of CO , and possible new catalytic oxidation reaction mechanisms are discussed. In addition, it is shown that the C-O frequency of the adsorbed CO may be used as an effective probe of the open circuit potential. © 2003 Elsevier B.V. All rights reserved.