Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma–atomic emission spectrometry

In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma–atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w− 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

Effect of Cyclic Topology on Charge-Transfer Properties of Organic Molecular Semiconductors: The Case of Cycloparaphenylene Molecules

We have studied the role played by cyclic topology on charge-transfer properties of recently synthesized π -conjugated molecules, namely the set of [n]cycloparaphenylene compounds, with n the number of phenylene rings forming the curved nanoring. We estimate the charge-transfer rates for holes and electrons migration within the array of molecules in their crystalline state. The theoretical calculations suggest that increasing the size of the system would help to obtain higher hole and electron charge-transfer rates and that these materials might show an ambipolar behavior in real samples, independently of the different mode of packing followed by the [6]cycloparaphenylene and [12]cycloparaphenylene cases studied.

Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Improving the photoactivity of bismuth vanadate thin film photoanodes through doping and surface modification strategies

Currently, one of the most attractive and desirable ways to solve the energy challenge is harvesting energy directly from the sunlight through the so-called artificial photosynthesis. Among the ternary oxides based on earth–abundant metals, bismuth vanadate has recently emerged as a promising photoanode. Herein, BiVO4 thin film photoanodes have been successfully synthesized by a modified metal-organic precursor decomposition method, followed by an annealing treatment. In an attempt to improve the photocatalytic properties of this semiconductor material for photoelectrochemical water oxidation, the electrodes have been modified (i) by doping with La and Ce (by modifying the composition of the BiVO4 precursor solution with the desired concentration of the doping element), and (ii) by surface modification with Au nanoparticles potentiostatically electrodeposited. La and Ce doping at concentrations of 1 and 2 at% in the BiVO4 precursor solution, respectively, enhances significantly the photoelectrocatalytic performance of BiVO4 without introducing important changes in either the material structure or the electrode morphology, according to XRD and SEM characterization. In addition, surface modification of the electrodes with Au nanoparticles further enhances the photocurrent as such metallic nanoparticles act as co-catalysts, promoting charge transfer at the semiconductor/solution interface. The combination of these two complementary ways of modifying the electrodes has resulted in a significant increase in the photoresponse, facilitating their potential application in artificial photosynthesis devices.

A systematic study on the influence of carbon on the behavior of hard-to-ionize elements in inductively coupled plasma–mass spectrometry

A systematic study on the influence of carbon on the signal of a large number of hard-to-ionize elements (i.e. B, Be, P, S, Zn, As, Se, Pd, Cd, Sb, I, Te, Os, Ir, Pt, Au, and Hg) in inductively coupled plasma–mass spectrometry has been carried out. To this end, carbon matrix effects have been evaluated considering different plasma parameters (i.e. nebulizer gas flow rate, r.f. power and sample uptake rate), sample introduction systems, concentration and type of carbon matrix (i.e. glycerol, citric acid, potassium citrate and ammonium carbonate) and type of mass spectrometer (i.e. quadrupole filter vs. double-focusing sector field mass spectrometer). Experimental results show that P, As, Se, Sb, Te, I, Au and Hg sensitivities are always higher for carbon-containing solutions than those obtained without carbon. The other hard-to-ionize elements (Be, B, S, Zn, Pd, Cd, Os, Ir and Pt) show no matrix effect, signal enhancement or signal suppression depending on the experimental conditions selected. The matrix effects caused by the presence of carbon are explained by changes in the plasma characteristics and the corresponding changes in ion distribution in the plasma (as reflected in the signal behavior plot, i.e. the signal intensity as a function of the nebulizer gas flow rate). However, the matrix effects for P, As, Se, Sb, Te, I, Au and Hg are also related to an increase in analyte ion population caused as a result of charge transfer reactions involving carbon-containing charged species in the plasma. The predominant specie is C+, but other species such as CO+, CO2+, C2+ and ArC+ could also play a role. Theoretical data suggest that B, Be, S, Pd, Cd, Os, Ir and Pt could also be involved in carbon based charge transfer reactions, but no experimental evidence substantiating this view has been found.

Structural and photoelectrochemical properties of porous TiO2 nanofibers decorated with Fe2O3 by sol-flame

The hybrid structure of Fe2O3 nanoparticles/TiO2 nanofibers (NFs), combines the merits of large surface areas of TiO2 NFs and absorption in ultraviolet light–visible light range. This structure can be used for many applications such as photoelectrochemical water splitting and photo-catalysis. Here, a sol-flame method is used for depositing Fe2O3 on TiO2 NFs that were prepared by hydrothermal on Ti sheets. The obtained materials were characterized by XRD, SEM, UV/Vis diffuse reflectance, Raman, and XPS. The results revealed the formation of rutile and anatase crystalline phases together with Fe2O3. This process moves the absorption threshold of TiO2 NFs support into visible spectrum range and enhances the photocurrent in comparison to bare TiO2 NFs, although no hole scavenger was used. The impedance measurement at low and high frequencies revealed an increase in series resistance and a decrease in resistance of charge transfer with sol-flame treatment time. A mechanism for explaining the charge transfer in these TiO2 NFs decorated with Fe2O3 nanoparticles was proposed.

Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma–mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w− 1) have been compared with the corresponding signals for a 1% w w− 1− nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10–20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

Successful functionalization of superporous zeolite templated carbon using aminobenzene acids and electrochemical methods

A novel and selective electrochemical functionalization of a highly reactive superporous zeolite templated carbon (ZTC) with two different aminobenzene acids (2-aminobenzoic and 4-aminobenzoic acid) was achieved. The functionalization was done through potentiodynamic treatment in acid media under oxidative conditions, which were optimized to preserve the unique ZTC structure. Interestingly, it was possible to avoid the electrochemical oxidation of the highly reactive ZTC structure by controlling the potential limit of the potentiodynamic experiment in presence of aminobenzene acids. The electrochemical characterization demonstrated the formation of polymer chains along with covalently bonded functionalities to the ZTC surface. The functionalized ZTCs showed several redox processes, producing a capacitance increase in both basic and acid media. The rate performance showed that the capacitance increase is retained at scan rates as high as 100 mV s−1, indicating that there is a fast charge transfer between the polymer chains formed inside the ZTC porosity or the new surface functionalities and the ZTC itself. The success of the proposed approach was also confirmed by using other characterization techniques, which confirmed the presence of different nitrogen groups in the ZTC surface. This promising method could be used to achieve highly selective functionalization of highly porous carbon materials.

Stabilizing and Modulating Color by Copigmentation: Insights from Theory and Experiment

Natural anthocyanin pigments/dyes and phenolic copigments/co-dyes form noncovalent complexes, which stabilize and modulate (in particular blue, violet, and red) colors in flowers, berries, and food products derived from them (including wines, jams, purees, and syrups). This noncovalent association and their electronic and optical implications constitute the copigmentation phenomenon. Over the past decade, experimental and theoretical studies have enabled a molecular understanding of copigmentation. This review revisits this phenomenon to provide a comprehensive description of the nature of binding (the dispersion and electrostatic components of π–π stacking, the hydrophobic effect, and possible hydrogen-bonding between pigment and copigment) and of spectral modifications occurring in copigmentation complexes, in which charge transfer plays an important role. Particular attention is paid to applications of copigmentation in food chemistry.

On the behavior of the Pt(1 0 0) and vicinal surfaces in alkaline media

We address in this paper a voltammetric study of the charge transfer processes characteristic of Pt(1 0 0) and vicinal surfaces in alkaline media. The electrochemical behavior of a series of stepped surfaces of the type Pt(S)[n(1 0 0) × (1 1 1)] has been characterized using cyclic voltammetry at different pHs, charge displacement measurements and FTIR experiments for adsorbed CO. The results from these techniques allow assigning the different peaks appearing in the voltammogram to hydrogen and/or OH adsorption on the different sites of these surfaces, namely, terrace and step sites. Additionally, the potential of zero total charge (pztc) of the electrodes was determined. The resulting pztc values shift to more negative values when the step density increases on the surface up to n = 5. FTIR spectroscopy experiments have been used to monitor the adsorption of CO on the different surfaces as well as the consequent CO oxidation, accompanying a positive potential sweep. The oxidation of adsorbed CO on (1 0 0) terraces is catalyzed by the presence of the (1 1 1) steps. The FTIR spectra revealed that CO is mostly bonded in bridge configuration at low potentials interconverting to on-top when the electrode potential is increased.