Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

The electro-oxidation of carbon materials enormously degrades their performance and limits their wider utilization in multiple electrochemical applications. In this work, the positive influence of phosphorus functionalities on the overall electrochemical stability of carbon materials has been demonstrated under different conditions. We show that the extent and selectivity of electroxidation in P-containing carbons are completely different to those observed in conventional carbons without P. The electro-oxidation of P-containing carbons involves the active participation of phosphorus surface groups, which are gradually transformed at high potentials from less-to more-oxidized species to slow down the introduction of oxygen groups on the carbon surface (oxidation) and the subsequent generation of (C*OOH)-like unstable promoters of electro-gasification. The highest-oxidized P groups (–C–O–P-like species) seem to distribute the gained oxygen to neighboring carbon sites, which finally suffer oxidation and/or gasification. So it is thought that P-groups could act as mediators of carbon oxidation although including various steps and intermediates compared to electroxidation in P-free materials.

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.

Gold Nanoparticles Supported on Polyacrylamide Containing a Phosphorus Ligand as an Efficient Heterogeneous Catalyst for Three-Component Synthesis of Propargylamines in Water

Gold nanoparticles supported on a polyacrylamide containing a phosphinite ligand have been synthesized and characterized using different techniques such as TEM, SEM, EDX, XPS, and solid UV analyses. The new material was successfully applied as a heterogeneous catalyst for the three-component A3 coupling of amines, aldehydes, and alkynes to give propargylamines. Reactions are performed in neat water at 80 °C with only 0.05 mol% catalyst loading. The heterogeneous catalyst is recyclable during seven consecutive runs with small decrease in activity.

Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.

Global assessment of soil phosphorus retention potential

Limited availability of P in soils to crops may be due to deficiency and/or severe P retention. Earlier studies that drew on large soil profile databases have indicated that it is not (yet) feasible to present meaningful values for "plant-available" soil P, obtained according to comparable analytical methods, that may be linked to soil geographical databases derived from 1:5 million scale FAO Digital Soil Map of the World, such as the 5 x 5 arc-minute version of the ISRIC-WISE database. Therefore, an alternative solution for studying possible crop responses to fertilizer-P applied to soils, at a broad scale, was sought. The approach described in this report considers the inherent capacity of soils to retain phosphorus (P retention), in various forms. Main controlling factors of P retention processes, at the broad scale under consideration, are considered to be pH, soil mineralogy, and clay content. First, derived values for these properties were used to rate the inferred capacity for P retention of the component soil units of each map unit (or grid cell) using four classes (i.e., Low, Moderate, High, and Very High). Subsequently, the overall soil phosphorus retention potential was assessed for each mapping unit, taking into account the P-ratings and relative proportion of each component soil unit. Each P retention class has been assigned to a likely fertilizer P recovery fraction, derived from the literature, thereby permitting spatially more detailed, integrated model-based studies of environmental sustainability and agricultural production at the global and continental level (< 1:5 million). Nonetheless, uncertainties remain high; the present analysis provides an approximation of world soil phosphorus retention potential.

Geochemistry of sediments of stage 5 of the Nordic seas

Stable isotope, foraminifera and ice rafted detritus (IRD) records covering the last interglacial (the Eemian) from 7 sediment cores in a transect from the Norwegian to the Greenland Sea are presented. The percentages of Neogloboquadrina pachyderma (s.) and Globigerina quinqueloba, foraminiferal content, and to some extent planktonic stable isotope records, demonstrate marked, regional changes in surface water conditions. Importantly, the variability in the abundances of subpolar foraminifera and foraminiferal content are not coherent, implying that these two types of proxies fluctuated independently of each other and most likely reflect changes in sea surface temperature and surface water carbonate productivity, respectively. Paleoceanographic reconstructions demonstrate significant movements of the oceanographic fronts. At the warmest periods, the Arctic front was located far west of the present-day location, at least within the Iceland Sea region. At 126-125 ka, this was most probably due to a stronger or more westerly located Norwegian current. Within the later warm intervals, higher heat flux to the western part of the basin reflects a combination of a stronger Irminger current and/or a weaker east Greenland current. During the main cold spell at ~124 ka, a diffuse Arctic front had a more southeasterly location than today, and intrusion of Atlantic surface waters was probably limited to a narrow corridor in the Eastern Norwegian Sea. A general correspondence between minima in sea surface temperatures and light benthic delta18O may indicate enhanced influx of freshwater to the basin within the cold events. At least in the Norwegian Sea, we find some evidence that the changes in surface water conditions are associated with changes in deep water ventilation. The majority of the fluctuations may be related to occasional breakdown or reduction of the thermohaline circulation within the Nordic seas. In the earliest Eemian, this could result from meltwater forcing. During the remaining part of the last interglacial the fine balance between temperature and salinity, which the deep water formation is depending on, may have been disturbed by periodic increases in fresh water supply or variable influx of warm Atlantic surface waters.