Excitonic Effects in Energy-Loss Spectra of Freestanding Graphene.

In this work, we perform electron energy-loss spectroscopy (EELS) of freestanding graphene with high energy and momentum resolution to disentangle the quasielastic scattering from the excitation gap of Dirac electrons close to the optical limit. We show the importance of many-body effects on electronic excitations at finite transferred momentum by comparing measured EELS to ab initio calculations at increasing levels of theory. Quasi-particle corrections and excitonic effects are addressed within the GW approximation and the Bethe-Salpeter equation, respectively. Both effects are essential in the description of the EEL spectra to obtain a quantitative agreement with experiments, with the position, dispersion, and shape of both the excitation gap and the π plasmon being significantly affected by excitonic effects.

Molybdenum Mobility During Managed Aquifer Recharge in Carbonate Aquifers.

The mobility of molybdenum (Mo) in groundwater systems has received little attention, although a high intake of Mo is known to be detrimental to human and animal health. Here, we used a comprehensive hydrochemical data set collected during a multi-cycle aquifer storage and recovery test to study the mechanisms that control the mobility of Mo under spatially and temporally varying hydrochemical conditions. The model-based interpretation of the data indicated that the initial mobilization of Mo occurs as a sequence of reactions, in which (i) the aerobic injectant induces pyrite oxidation, (ii) the released acidity is partially buffered by the dissolution of dolomite that (iii) leads to the release of Mo with highly soluble sulfurized organic matter prevailing between the intercrystalline spaces of the dolomite matrix or incorporated in dolomite crystals. Once released, Mo mobility was primarily controlled by pH-dependent surface complexation reactions to the sediments and, to a lesser extent, the capture by iron sulfides (FeS). In the studied system, Mo mobilization could be effectively mitigated by reducing or eliminating pyrite oxidation, which decreases the likelihood of dolomite dissolution and associated Mo release.

Highly Sensitive and Selective Formaldehyde Gas Sensors Based on Polyvinylpyrrolidone/Nitrogen-Doped Double-Walled Carbon Nanotubes.

A highly sensitive and selective formaldehyde sensor was successfully fabricated using hybrid materials of nitrogen-doped double-walled carbon nanotubes (N-DWCNTs) and polyvinylpyrrolidone (PVP). Double-walled carbon nanotubes (DWCNTs) and N-DWCNTs were produced by high-vacuum chemical vapor deposition using ethanol and benzylamine, respectively. Purified DWCNTs and N-DWCNTs were dropped separately onto the sensing substrate. PVP was then dropped onto pre-dropped DWCNT and N-DWCNTs (hereafter referred to as PVP/DWCNTs and PVP/N-DWCNTs, respectively). As-fabricated sensors were used to find 1,2-dichloroethane, dichloromethane, formaldehyde and toluene vapors in parts per million (ppm) at room temperature for detection measurement. The sensor response of N-DWCNTs, PVP/DWCNTs and PVP/N-DWCNTs sensors show a high response to formaldehyde but a low response to 1,2-dichloroethane, dichloromethane and toluene. Remarkably, PVP/N-DWCNTs sensors respond sensitively and selectively towards formaldehyde vapor, which is 15 times higher than when using DWCNTs sensors. This improvement could be attributed to the synergistic effect of the polymer swelling and nitrogen-sites in the N-DWCNTs. The limit of detection (LOD) of PVP/N-DWCNTs was 15 ppm, which is 34-fold higher than when using DWCNTs with a LOD of 506 ppm. This study demonstrated the high sensitivity and selectivity for formaldehyde-sensing applications of high-performance PVP/N-DWCNTs hybrid materials.

Momentum-Dependent Oscillator Strength Crossover of Excitons and Plasmons in Two-Dimensional PtSe2.

The 1T-phase layered PtX2 chalcogenide has attracted widespread interest due to its thickness dependent metal-semiconductor transition driven by strong interlayer coupling. While the ground state properties of this paradigmatic material system have been widely explored, its fundamental excitation spectrum remains poorly understood. Here we combine first-principles calculations with momentum (q) resolved electron energy loss spectroscopy (q-EELS) to study the collective excitations in 1T-PtSe2 from the monolayer limit to the bulk. At finite momentum transfer, all the spectra are dominated by two distinct interband plasmons that disperse to higher energy with increasing q. Interestingly, the absence of long-range screening in the two-dimensional (2D) limit inhibits the formation of long wavelength plasmons. Consequently, in the small-q limit, excitations in monolayer PtSe2 are exclusively of excitonic nature, and the loss spectrum coincides with the optical spectrum. The qualitatively different momentum dependence of excitons and plasmons enables us to unambiguously disentangle their spectral fingerprints in the excited state spectrum of layered 1T-PtSe2. This will help to discern the charge carrier plasmon and locally map the optical conductivity and trace the layer-dependent semiconductor to metal transition in 1T-PtSe2 and other 2D materials.

Molybdenum Release Triggered by Dolomite Dissolution: Experimental Evidence and Conceptual Model.

The injection of oxygenated water into anoxic aquifers during managed aquifer recharge (MAR) can cause the mobilization of metal(loid)s. Here, we study the processes controlling MAR-induced molybdenum (Mo) release in dolomitic aquifers. Sequential chemical extractions and energy dispersive X-ray spectroscopy combined with scanning electron microscopy point to an association of Mo with easily soluble sulfurized organic matter present in intercrystalline spaces of dolomites or directly incorporated within dolomite crystals. The easily soluble character was confirmed by a batch experiment that demonstrated the rapid mobilization of Mo, dissolved organic carbon, and sulfur. The type and time of batch solution contact with the sulfurized organic matter impacted the release of Mo, as demonstrated by a 36% increase in Mo concentrations when shaking was intensified. Based on the experimental results, a conceptual model for the release of Mo was formulated, where (i) the injection of oxygenated water causes the oxidation of pyrite in the aquifer matrix, and (ii) the associated release of protons (H+) induces the dissolution of dolomite as a buffering reaction, which (iii) enhances the accessibility of the injectant to intercrystalline and incorporated sulfurized organic matter within dolomite, causing the release of Mo.

Unravelling the Complete Raman Response of Graphene Nanoribbons Discerning the Signature of Edge Passivation.

Controlling the edge morphology and terminations of graphene nanoribbons (GNR) allows tailoring their electronic properties and boosts their application potential. One way of making such structures is encapsulating them inside single-walled carbon nanotubes. Despite the versatility of Raman spectroscopy to resolve strong spectral signals of these systems, discerning the response of long nanoribbons from that of any residual precursor remaining outside after synthesis has been so far elusive. Here, the terrylene dye is used as precursor to make long and ultra-narrow armchair-edged GNR inside nanotubes. The alignment and characteristic length of terrylene encapsulated parallel to the tube's axis facilitates the ribbon formation via polymerization, with high stability up to 750 °C when the hybrid system is kept in high vacuum. A high temperature annealing is used to remove the terrylene external molecules and a subtraction model based on the determination of a scaling factor related to the G-band response of the system is developed. This not only represents a critical step forward toward the analysis of the nanoribbon-nanotube system, but it is a study that enables unraveling the Raman signatures of the individual CH-modes (the signature of edge passivation) for GNR for the first time with unprecedented detail.

Tip-Enhanced Stokes-Anti-Stokes Scattering from Carbyne.

Carbyne, a linear chain of carbon atoms, is the truly one-dimensional allotrope of carbon and the strongest known Raman scatterer. Here, we use tip-enhanced Raman scattering (TERS) to further enhance the Raman response of a single carbyne chain confined inside a double-walled carbon nanotube. We observe an increase of the anti-Stokes scattering by a factor of 3290 and a 22-fold enhancement of the anti-Stokes/Stokes ratio relative to far-field measurements. The power dependence of the anti-Stokes/Stokes ratio under TERS conditions is indicative of coherent Stokes-anti-Stokes scattering mediated by an excited phonon. The role of resonance effects and laser-induced heating are discussed and potential opportunities are outlined.

Tree-rings reveal two strong solar proton events in 7176 and 5259 BCE.

The Sun sporadically produces eruptive events leading to intense fluxes of solar energetic particles (SEPs) that dramatically disrupt the near-Earth radiation environment. Such events have been directly studied for the last decades but little is known about the occurrence and magnitude of rare, extreme SEP events. Presently, a few events that produced measurable signals in cosmogenic radionuclides such as 14C, 10Be and 36Cl have been found. Analyzing annual 14C concentrations in tree-rings from Switzerland, Germany, Ireland, Russia, and the USA we discovered two spikes in atmospheric 14C occurring in 7176 and 5259 BCE. The ~2% increases of atmospheric 14C recorded for both events exceed all previously known 14C peaks but after correction for the geomagnetic field, they are comparable to the largest event of this type discovered so far at 775 CE. These strong events serve as accurate time markers for the synchronization with floating tree-ring and ice core records and provide critical information on the previous occurrence of extreme solar events which may threaten modern infrastructure.

Optimization and assessment of a sequential extraction procedure for calcium carbonate rocks.

Sequential extraction analyses are widely used for the determination of element speciation in sediments and soils. Typical sequential extraction protocols were developed to extract from low-carbonate samples and therefore are not necessarily suitable for high-carbonate samples. In this study, we tested increased reagent to sample ratios to adjust an existing sequential extraction procedure to analyze high-CaCO3 samples with concentrations ranging from 70 to above 90 %. Complete dissolution of the CaCO3 phase, and a higher extraction efficiency of manganese associated with the carbonate phase, was achieved when using four times the original reagent to sample ratio in the 2nd extraction step. This increase of reagent did not compromise the extraction of subsequent phases as shown by unaffected Fe concentrations in a low-carbonate sample. Hence, an essential outcome was that increasing the solution to sample ratio did not lead to the dissolution of other sedimentary phases, such as hydrous and crystalline iron oxides or sulfides. Thus, compared to other extraction protocols that use a lower reagent to sample ratio in the carbonate dissolution step, the new protocol allowed the complete extraction of oxide and sulfide phases in the following extraction steps. Furthermore, the study demonstrated the benefit of replacing Na-acetate with NH4-acetate to extract exchangeable ions and carbonates. We observed increased intensities for several analytes, i.e., trace metals such as Mo and As, due to less suppression of the analyte signal by NH4-acetate than by Na-acetate during analysis by inductively coupled plasma optical emission spectrometry (ICP-OES).

Anti-Stokes Raman Scattering of Single Carbyne Chains.

We investigate the anti-Stokes Raman scattering of single carbyne chains confined inside double-walled carbon nanotubes. Individual chains are identified using tip-enhanced Raman scattering (TERS) and heated by resonant excitation with varying laser powers. We study the temperature dependence of carbyne's Raman spectrum and quantify the laser-induced heating based on the anti-Stokes/Stokes ratio. Due to its molecular size and its large Raman cross section, carbyne holds great promise for local temperature monitoring, with potential applications ranging from nanoelectronics to biology.

Deciphering the Intense Postgap Absorptions of Monolayer Transition Metal Dichalcogenides.

Rich valleytronics and diverse defect-induced or interlayer pre-bandgap excitonics have been extensively studied in transition metal dichalcogenides (TMDCs), a system with fascinating optical physics. However, more intense high-energy absorption peaks (∼3 eV) above the bandgaps used to be long ignored and their underlying physical origin remains to be unveiled. Here, we employ momentum resolved electron energy loss spectroscopy to measure the dispersive behaviors of the valley excitons and intense higher-energy peaks at finite momenta. Combined with accurate Bethe-Salpeter equation calculations, non-band-nesting transitions at the Q valley and at the midpoint of KM are found to be responsible for the high-energy broad absorption peaks in tungsten dichalcogenides and present spin polarizations similar to A excitons, in contrast with the band-nesting mechanism in molybdenum dichalcogenides. Our experiment-theory joint research will offer insights into the physical origins and manipulation of the intense high-energy excitons in TMDC-based optoelectronic devices.

Isotopic Labelling of Confined Carbyne.

Carbyne is a one-dimensional allotrope of carbon consisting of a linear chain of carbon atoms bonded to each other with exceptional strength. Its outstanding mechanical, optical, and electronic properties have been theoretically predicted, but its stability has only been achieved when grown encapsulated in the hollow core of carbon nanotubes. One of the advantages of this confinement is that its properties can be controlled by the chain's length and surrounding environment. We investigated an alternative way of gaining control of its properties is using isotope labelling as tuning mechanism. The optimized liquid precursor was first chosen among several options, which can greatly enhance the yield of the confined carbyne. Then isotopic labelled liquid precursor was encapsulated for further synthesis of isotopic labelled confined carbyne. This allowed us to obtain pioneering results on isotope engineered carbyne with around 11.9 % of 13 C-labelling using 13 C-methanol as precursor.

Toward Confined Carbyne with Tailored Properties.

Confining carbyne to a space that allows for stability and controlled reactivity is a very appealing approach to have access to materials with tunable optical and electronic properties without rival. Here, we show how controlling the diameter of single-walled carbon nanotubes opens the possibility to grow a confined carbyne with a defined and tunable band gap. The metallicity of the tubes has a minimal influence on the formation of the carbyne, whereas the diameter plays a major role in the growth. It has been found that the properties of confined carbyne can be tailored independently from its length and how these are mostly determined by its interaction with the carbon nanotube. Molecular dynamics simulations have been performed to interpret these findings. Furthermore, the choice of a single-walled carbon nanotube host has been proven crucial even to synthesize an enriched carbyne with the smallest energy gap currently reported and with remarkable homogeneity.

In situ laser annealing as pathway for the metal free synthesis of tailored nanographenes.

Tailored synthesis of nanographenes, and especially graphene nanoribbons (GNR), has been achieved on metal substrates via a bottom-up approach from organic precursors, which paves the way to their application in nanoelectronics and optoelectronics. Since quantum confinement in nanographenes leads to the creation of peculiar band structures, strongly influenced by their topological characteristics, it is important to be able to exactly engineer them in order to precisely tune their electronic, optical and magnetic properties. However practical application of these materials requires post-synthesis transfer to insulating substrates. Recently, cyclodehydrofluorination of fluorinated organic precursors has been shown to be a promising pathway to achieve metal-free bottom-up synthesis of nanographenes. Here we present how to apply in situ laser annealing to induce cyclodehydrofluorination leading to nanographene formation directly on non-metallic surfaces. In this work, we analyze the changes in the Raman fingerprint of the fluorinated precursor tetrafluoro-diphenyl-quinquephenyl (TDQ) during the laser annealing process in high vacuum (HV), demonstrating that both heating and photo-induced processes influence the cyclization process. Hence, in situ laser annealing allows not only to influence chemical reactions, but also to have a fast and contact-free monitoring of the reaction products. Optimization of the laser annealing process adds a new level of control in the tailored synthesis of nanographenes on non-metallic substrates. This is a very promising pathway to unravel the full application potential of nanographenes in general and GNR in particular, enabling a fast optimization of precursor molecules and substrate geometry engineered for specific applications.

Exclusive Substitutional Nitrogen Doping on Graphene Decoupled from an Insulating Substrate.

The on-surface synthesis of atomically flat N-doped graphene on oxidized copper is presented. Besides circumventing the almost standard use of metallic substrates for growth, this method allows producing graphene with ∼2.0 at % N in a substitutional configuration directly decoupled from the substrate. Angle-resolved photoemission shows a linear energy-momentum dispersion where the Dirac point lies at the Fermi level. Additionally, the N functional centers can be selectively tailored in sp2 substitutional configuration by making use of a purpose-made molecular precursor: dicyanopyrazophenanthroline (C16H6N6).

Raman Scattering Cross Section of Confined Carbyne.

We experimentally quantify the Raman scattering from individual carbyne chains confined in double-walled carbon nanotubes. We find that the resonant differential Raman cross section of confined carbyne is on the order of 10-22 cm2 sr-1 per atom, making it the strongest Raman scatterer ever reported.

Probing Exciton Dispersions of Freestanding Monolayer WSe_{2} by Momentum-Resolved Electron Energy-Loss Spectroscopy.

Excitons, as bound electron-hole paired quasiparticle, play an essential role in the energy transport in the optical-electric properties of semiconductors. Their momentum-energy dispersion relation is a fundamental physical property of great significance to understand exciton dynamics. However, this dispersion is seldom explored especially in two-dimensional transition metal dichalcogenides with rich valleytronic properties. In this work, momentum resolved electron energy-loss spectroscopy was used to measure the dispersions of excitons in freestanding monolayer WSe_{2}. Besides the parabolically dispersed valley excitons, a subgap dispersive exciton was observed at nonzero momenta for the first time, which can be introduced by the prolific Se vacancies. Our work provides a paradigm to directly probe exciton dispersions in 2D semiconductors and could be generalized to many low-dimensional systems.

Cadmium Background Levels in Groundwater in an Area Dominated by Agriculture.

Cadmium is a highly toxic trace metal, which can be of geogenic or anthropogenic origin, for example, minerals, phosphate fertilizers, and combustion emissions. Due to its low sorption affinity compared to other heavy metals, Cd is easily mobilized, potentially resulting in elevated Cd concentrations in groundwater. This study assessed background levels of Cd in groundwater related to hydrogeology and hydrogeochemical processes through evaluation of a large hydrogeochemical data set composed of groundwater analyses from 6300 wells in Northwestern Germany. Calculated Cd background levels in groundwater were between 0.01 µg/L in hydrogeological units with mainly reducing conditions and 0.98 µg/L in less reducing groundwater recharge areas. The results showed that groundwater Cd concentrations above 0.5 µg/L (the German threshold value) are not necessarily elevated but could be the regional or ambient background level, depending on the hydrogeological unit. What would be considered as ambient background levels, however, indicated the influence by continuous intensive land use as well as the local geology, which is dominated by glacial deposits. Cadmium concentrations in groundwater were mainly controlled by hydrogeochemical and hydrogeological parameters and not by the amount of anthropogenic Cd input, in particular through the use of phosphate fertilizers. Instead, analyses of the solid phase revealed that Cd release from the aquifer matrix due to changes in hydrogeochemical parameters was more likely. Aquifer sediments in Northwestern Germany can be enriched in Cd originating from multiple sources, which in turn can cause elevated Cd concentrations in groundwater. Integr Environ Assess Manag 2019;00:1-11. © 2019 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Characterizing the maximum number of layers in chemically exfoliated graphene.

An efficient route to synthesize macroscopic amounts of graphene is highly desired and bulk characterization of such samples, in terms of the number of layers, is equally important. We present a Raman spectroscopy-based method to determine the typical upper limit of the number of graphene layers in chemically exfoliated graphene. We utilize a controlled vapour-phase potassium intercalation technique and identify a lightly doped stage, where the Raman modes of undoped and doped few-layer graphene flakes coexist. The spectra can be unambiguously distinguished from alkali doped graphite, and modeling with the typical upper limit of the layers yields an upper limit of flake thickness of five layers with a significant single-layer graphene content. Complementary statistical AFM measurements on individual few-layer graphene flakes find a consistent distribution of the layer numbers.