Crystal Structure Prediction and Lattice Dynamical Calculations for the Rare Platinum-Group Mineral Zaccariniite (RhNiAs)

The crystal structures of newly found minerals are routinely determined using single-crystal techniques. However, many rare minerals usually form micrometer-sized aggregates that are difficult to study with conventional structural methods. This is the case for numerous platinum-group minerals (PGMs) such as, for instance, zaccariniite (RhNiAs), the crystal structure of which was first obtained by studying synthetic samples. The aim of the present work is to explore the usefulness of USPEX, a powerful crystal structure prediction method, as an alternative means of determining the crystal structure of minerals such as zaccariniite, with a relatively simple crystal structure and chemical formula. We show that fixed composition USPEX searches with a variable number of formula units, using the ideal formula of the mineral as the only starting point, successfully predict the tetragonal structure of a mineral. Density functional theory (DFT) calculations can then be performed in order to more tightly relax the structure of the mineral and calculate different fundamental properties, such as the frequency of zone-center Raman-active phonons, or even their pressure behavior. These theoretical data can be subsequently compared to experimental results, which, in the case of newly found minerals, would allow one to confirm the correctness of the crystal structure predicted by the USPEX code.

Compositions and Ni-Cu-Platinum Group Element Tenors of Nova-Bollinger Ores with Implications for the Origin of Pt Anomalies in Platinum Group Element-Poor Massive Sulfides

The Nova-Bollinger Ni-Cu-platinum group element (PGE) deposit in the Fraser zone of the Albany-Fraser orogen consists of two main orebodies, Nova and Bollinger, hosted by the same tube-shaped intrusion but having distinctly different Ni tenors of around 6.5 and 4.8 wt %, respectively. Nova is also higher in Pd, but Cu and Pt tenors are similar. Both deposits have very low PGE tenors, with average Pd concentrations of 110 ppb in massive sulfide at Bollinger and 136 ppb at Nova. The Nova and Bollinger orebodies show relatively little internal differentiation overall on deposit scale but show strong differentiation into chalcopyrite-rich and chalcopyrite-poor regions at a meter scale. This differentiation is more prevalent at Nova, where massive sulfide-filled vein arrays are more extensively developed, and in massive ores, particularly veins, than in net-textured ores. Net-textured and disseminated ores have on average Ni and Cu grades and tenors similar to those of massive, semimassive, and breccia ores in the same orebody but a smaller range of variation, largely due to a more limited extent of sulfide liquid fractionation and higher average concentrations of Pt and Pd than adjacent massive ores. Unusually for differentiated magmatic sulfides, there is no systematic positive correlation between Pt, Pd, and Cu. A partial explanation for the lack of a Pd-Cu correlation is that Pd was partitioned into peritectic pentlandite in the middle stages of sulfide liquid solidification. This explanation is not applicable to Pt, as Pt characteristically forms its own phases rather than residing in base metal sulfides. PGE tenors are very low in both orebodies, very similar to those observed in other Ni-Cu-Co sulfide ores in orogenic settings, notably the Savannah and Savannah North orebodies. This depletion is attributed to sulfide retention in the mantle source of the parent magmas rather than to previous fractional extraction of sulfide liquid in staging chambers or feeder networks. The higher Ni and Pd tenors at Nova are attributed to reworking and upgrading of precursor sulfide liquid originally deposited upstream at the Bollinger site. Replicate analyses of multiple jaw-crusher splits returned highly variable Pt and Au assays but much smaller relative errors in the other PGEs. The poor Pt and Au reproducibilities are attributed to nugget effects, explicable by much of the Pt and Au in the samples being present in sparse Pt- and Au-rich grains. This is principally true for Pt in massive rather than disseminated ores, accounting for a strong contrast in the distribution of Pt/Pd ratios between the two ore types. Numerical simulation suggests that Pt is predominantly resident in Pt-rich platinum group minerals with grain diameters of 100 μm or more and that at the low (<100 ppb) concentrations in these ores, this results in most assays significantly underreporting Pt. This is likely to be true in other low-PGE ores, such that apparent negative Pt anomalies in massive ores may in such cases be attributable to sampling artifacts.

The Uptake Characteristics of Prussian-Blue Nanoparticles for Platinum-Group Metal and Molybdenum Ions in a Nitric Acid Solution Toward Application for the Recovery of Precious Metals from Nuclear and Electronic Wastes

We have examined the uptake mechanisms of platinum-group-metals (PGMs) and molybdenum (Mo) ions into PBNPs in a nitric acid solution for 24-h sorption test, using inductively coupled plasma atomic emission spectroscopy, powder XRD, and UV-Vis-NIR spectroscopy in combination with first-principles calculations, and revealed that the Ru4+ and Pd2+ ions are incorporated into PBNPs by substitution with Fe3+ and Fe2+ ions of the PB framework, respectively, whereas the Rh3+ ion is incorporated into PBNPs by substitution mainly with Fe3+ and minorly with Fe2+ ion, and Mo6+ ion is incorporated into PBNPs by substitution with both Fe2+ and Fe3+ ions, with maintaining the crystal structure before and after the sorption test. Assuming that the amount of Fe elusion is equal to that of PGMs/Mo substitution, the substitution efficiency is estimated to be 39.0% for Ru, 47.8% for Rh, 87% for Pd, and 17.1% for Mo6+. This implies that 0.13 g of Ru, 0.16 g of Rh, 0.30 g of Pd, and 0.107 g of Mo can be recovered by using 1g PBNPs with a chemical form of KFe(III)[Fe(II)(CN)6].

Wafer-scale two-dimensional platinum monosulfide ultrathin film via metal sulfurization for high performance photoelectronics

2D nonlayered materials have attracted enormous research interests due to their novel physical and chemical properties with the confined dimensions. Platinum sulfide as one of the most common platinum-group minerals...

One-pot synthesis of Au-based nanocrystals via a platinum group metal anions controlled growth strategy in citrate medium

The platinum group metals (PGM, Pd, Pt, Ir, etc.) possess unique chemical and physical properties, the properties often vary dramatically with their size, morphology, crystal structure, phase and composition. However,...

Variation in Platinum group metals determination using ICP OES induced by the effect of complex matrices and the correction method based on multivariate calibration

The presence of interelements due to sample complexity can produce significant effects on the quantitative determination of Platinum group metals (PGMs) by using inductively coupled plasma optical emission spectrometry (ICP...