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30 pages, 4217 KB  
Review
Overview of Platinum Group Minerals (PGM): A Statistical Perspective and Their Genetic Significance
by Federica Zaccarini, Giorgio Garuti, Maria Economou-Eliopoulos, John F. W. Bowles, Hannah S. R. Hughes, Jens C. Andersen and Saioa Suárez
Minerals 2026, 16(1), 108; https://doi.org/10.3390/min16010108 - 21 Jan 2026
Viewed by 857
Abstract
The six platinum group elements (PGE) are among the rarest elements in the upper continental crust of the earth. Higher values of PGE have been detected in the upper mantle and in chondrite meteorites. The PGE are siderophile and chalcophile elements and are [...] Read more.
The six platinum group elements (PGE) are among the rarest elements in the upper continental crust of the earth. Higher values of PGE have been detected in the upper mantle and in chondrite meteorites. The PGE are siderophile and chalcophile elements and are divided into the following: (1) the Ir subgroup (IPGE) = Os, Ir, and Ru and (2) the Pd subgroup (PPGE) = Rh, Pt, and Pd. The IPGE are more refractory and less chalcophile than the PPGE. High concentrations of PGE led, in rare cases, to the formation of mineral deposits. The PGE are carried in discrete phases, the platinum group minerals (PGM), and are included as trace elements into the structure of base metal sulphides (BM), such as pentlandite, chalcopyrite, pyrite, and pyrrhotite. Similarly to PGE, the PGM are also divided into two main groups, i.e., IPGM composed of Os, Ir, and Ru and PPGM containing Rh, Pt, and Pd. The PGM occur both in mafic and ultramafic rocks and are mainly hosted in stratiform reefs, sulphide-rich lenses, and placer deposits. Presently, there are only 169 valid PGM that represent about 2.7% of all 6176 minerals discovered so far. However, 496 PGM are listed among the valid species that have not yet been officially accepted, while a further 641 are considered as invalid or discredited species. The main reason for the incomplete characterization of PGM resides in their mode of occurrence, i.e., as grains in composite aggregates of a few microns in size, which makes it difficult to determine their crystallography. Among the PGM officially accepted by the IMA, only 13 (8%) were discovered before 1958, the year when the IMA was established. The highest number of PGM was discovered between 1970 and 1979, and 99 PGM have been accepted from 1980 until now. Of the 169 PGM accepted by the IMA, 44% are named in honour of a person, typically a scientist or geologist, and 31% are named after their discovery localities. The nomenclature of 25% of the PGM is based on their chemical composition and/or their physical properties. PGM have been discovered in 25 countries throughout the world, with 64 from Russia, 17 from Canada and South Africa (each), 15 from China, 12 from the USA, 8 from Brazil, 6 from Japan, 5 from Congo, 3 from Finland and Germany (each), 2 from the Dominican Republic, Greenland, Malaysia, and Papua New Guinea each, and only 1 from Argentine, Australia, Bulgaria, Colombia, Czech Republic, England, Ethiopia, Guyana, Mexico, Serbia, and Tanzania each. Most PGM phases contain Pd (82 phases, 48% of all accepted PGM), followed, in decreasing order of abundances, by those of Pt 35 phases (21%), Rh 23 phases (14%), Ir 18 phases (11%), Ru 7 phases (4%), and Os 4 phases (2%). The six PGE forming the PGM are bonded to other elements such as Fe, Ni, Cu, S, As, Te, Bi, Sb, Se, Sn, Hg, Ag, Zn, Si, Pb, Ge, In, Mo, and O. Thirty-two percent of the 169 valid PGM crystallize in the cubic system, 17% are orthorhombic, 16% hexagonal, 14% tetragonal, 11% trigonal, 3% monoclinic, and only 1% triclinic. Some PGM are members of a solid-solution series, which may be complete or contain a miscibility gap, providing information concerning the chemical and physical environment in which the mineral was formed. The refractory IPGM precipitate principally in primitive, high-temperature, mantle-hosted rocks such as podiform and layered chromitites. Being more chalcophile, PPGE are preferentially collected and concentrated in an immiscible sulphide liquid, and, under appropriate conditions, the PPGM can precipitate in a thermal range of about 900–300 °C in the presence of fluids and a progressive increase of oxygen fugacity (fO2). Thus, a great number of Pt and Pd minerals have been described in Ni-Cu sulphide deposits. Two main genetic models have been proposed for the formation of PGM nuggets: (1) Detrital PGM represent magmatic grains that were mechanically liberated from their primary source by weathering and erosion with or without minor alteration processes, and (2) PGM reprecipitated in the supergene environment through a complex process that comprises solubility, the leaching of PGE from the primary PGM, and variation in Eh-pH and microbial activity. These two models do not exclude each other, and alluvial deposits may contain contributions from both processes. Full article
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18 pages, 6397 KB  
Article
Pyrite Trace-Element Signatures of Porphyry-Epithermal Systems in Xizang: Implications for Metallogenic Discrimination and Hydrothermal Evolution
by Hongzhong Guan, Jiancuo Luosang, Lutong Gao and Fuwei Xie
Minerals 2025, 15(11), 1113; https://doi.org/10.3390/min15111113 - 26 Oct 2025
Viewed by 1056
Abstract
The Zhunuo porphyry Cu deposit (2.9 Mt Cu @ 0.48%) in the Gangdese belt, southern Xizang, represents a key Miocene post-collisional system. This study integrates textural, major-, and trace-element analyses of pyrite from distinct alteration zones to unravel its hydrothermal evolution and metal [...] Read more.
The Zhunuo porphyry Cu deposit (2.9 Mt Cu @ 0.48%) in the Gangdese belt, southern Xizang, represents a key Miocene post-collisional system. This study integrates textural, major-, and trace-element analyses of pyrite from distinct alteration zones to unravel its hydrothermal evolution and metal precipitation mechanisms. Our study identifies four distinct pyrite types (Py1-Py4) that record sequential hydrothermal stages: main-stage Py2-Py3 formed at 354 ± 48 to 372 ± 43 °C (based on Se thermometry), corresponding to A and B vein formation, respectively, and late-stage Py4 crystallized at 231 ± 30 °C, coinciding with D-vein development. LA-ICP-MS data revealed pyrite contains diverse trace elements with concentrations mostly below 1000 ppm, showing distinct distribution patterns among different pyrite types (Py1-Py4). Elemental correlations revealed coupled behaviors (e.g., Au-As, Zn-Cd positive correlations; Mo-Sc negative correlation). Tellurium variability (7–82 ppm) records dynamic fO2 fluctuations during system cooling. A comparative analysis of pyrite from the regional deposits (Xiongcun, Tiegelongnan, Bada, and Xiquheqiao) highlighted discriminative geochemical signatures: Zhunuo pyrite was enriched in Co-Bi-Ag-Pb (galena inclusions); Tiegelongnan exhibited the highest Cu but low Au-As; Xiquheqiao had the highest Au-As coupling; and Bada showed epithermal-type As enrichment. Partial Least Squares Discriminant Analysis (PLS-DA) identified Cu, As, and Bi as key discriminators for deposit types (VIP > 0.8), with post-collisional systems (Zhunuo and Xiquheqiao) showing intermediate Cu-Bi and elevated As versus arc-related deposits. This study establishes pyrite trace-element proxies (e.g., Se/Te, Co/Ni, and As-Bi-Pb) for reconstructing hydrothermal fluid evolution and proposes mineral-chemical indicators (Cu-As-Bi) to distinguish porphyry-epithermal systems in the Qinghai-Tibet Plateau. The results underscore pyrite’s utility in decoding metallogenic processes and exploration targeting in collisional settings. Full article
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19 pages, 6385 KB  
Review
An Updated Review of BiCuSeO-Based Thermoelectric Materials
by Haitao Zhang, Bo Feng, Suoluosu Yang, Ruolin Ruan, Rong Zhang, Tongqiang Xiong, Biyu Xu, Zhipeng Zheng, Guopeng Zhou, Yang Zhang, Kewei Wang, Yin Zhong, Yanhua Fan and Xiaoqiong Zuo
Micromachines 2025, 16(6), 703; https://doi.org/10.3390/mi16060703 - 12 Jun 2025
Cited by 1 | Viewed by 1834
Abstract
Since 2010, BiCuSeO has emerged as a captivating subject of investigation within the realm of thermoelectric materials. Its allure lies in a remarkable confluence of characteristics: a distinctive natural super-lattice structure, an elevated Seebeck coefficient, and a low thermal conductivity, all of which [...] Read more.
Since 2010, BiCuSeO has emerged as a captivating subject of investigation within the realm of thermoelectric materials. Its allure lies in a remarkable confluence of characteristics: a distinctive natural super-lattice structure, an elevated Seebeck coefficient, and a low thermal conductivity, all of which have collectively piqued the intense interest of scientists worldwide. Over the subsequent eight-year period, an extensive array of research endeavors has been meticulously carried out, delving deep into the multifaceted properties of BiCuSeO and exploring avenues for performance enhancement. In this comprehensive review, we embark on a detailed exploration of the fundamental properties of BiCuSeO, encompassing its preparation methodologies, as well as its thermoelectric and mechanical attributes. A thorough synthesis of diverse strategies for optimizing the composition and structure of BiCuSeO is presented, elucidating how these modifications contribute to the enhancement of its thermoelectric and mechanical performance. Finally, the current state of research on N-type BiCuSeO is systematically summarized, offering a panoramic view of the advancements and challenges in this particular area. Full article
(This article belongs to the Special Issue Functional Materials and Microdevices, 2nd Edition)
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8 pages, 3501 KB  
Communication
Angle-Engineered Bi0.94La0.06CuSeO Thin Films for High-Performance Transverse Thermoelectric Devices
by Mingjing Chen, Chenming Yue, Tianchang Qin, Haixu Liu, Guoying Yan and Shufang Wang
Sensors 2025, 25(9), 2791; https://doi.org/10.3390/s25092791 - 29 Apr 2025
Cited by 1 | Viewed by 760
Abstract
BiCuSeO has emerged as a highly promising material for transverse thermoelectric (TTE) applications, with its performance significantly enhanced through La doping. In this study, we investigate the effect of inclination angle on the TTE performance of inclined Bi0.94La0.06CuSeO thin [...] Read more.
BiCuSeO has emerged as a highly promising material for transverse thermoelectric (TTE) applications, with its performance significantly enhanced through La doping. In this study, we investigate the effect of inclination angle on the TTE performance of inclined Bi0.94La0.06CuSeO thin films fabricated using the pulsed laser deposition technique. A huge output voltage of 31.4 V was achieved in the 10° inclined Bi0.94La0.06CuSeO film under 308 nm ultraviolet pulsed laser irradiation. Furthermore, the films also exhibited significant response with excellent linearity when exposed to continuous-wave lasers across a broad spectral range (360 nm to 10,600 nm) and a point-like heat source. Notably, the voltage is directly proportional to sin2θ, where θ is the inclination angle. These findings not only provide a clear optimization strategy for TTE performance through inclination angle engineering but also highlight the material’s great potential for developing high-performance optical and thermal sensing TTE devices. Full article
(This article belongs to the Section Nanosensors)
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28 pages, 6012 KB  
Review
Semiconductor-Based Photoelectrocatalysts in Water Splitting: From the Basics to Mechanistic Insights—A Brief Review
by W. J. Pech-Rodríguez, Nihat Ege Şahin, G. G. Suarez-Velázquez and P. C. Meléndez-González
Materials 2025, 18(9), 1952; https://doi.org/10.3390/ma18091952 - 25 Apr 2025
Cited by 3 | Viewed by 3914
Abstract
Hydrogen and oxygen serve as energy carriers that can ease the transition of energy due to their high energy densities. Nonetheless, their production processes entail the development of efficient and low-cost storage and conversion technologies. In this regard, photoelectrocatalysts are materials based on [...] Read more.
Hydrogen and oxygen serve as energy carriers that can ease the transition of energy due to their high energy densities. Nonetheless, their production processes entail the development of efficient and low-cost storage and conversion technologies. In this regard, photoelectrocatalysts are materials based on the photoelectronic effect where electrons and holes interact with H2O, producing H2 and O2, and in some cases, this is achieved with acceptable efficiency. Although there are several reviews on this topic, most of them focus on traditional semiconductors, such as TiO2 and ZnO, neglecting others, such as those based on non-noble metals and organic ones. Herein, semiconductors like CdSe, NiWO4, Fe2O3, and others have been investigated and compared in terms of photocurrent density, band gap, and charge transfer resistance. In addition, this brief review aims to discuss the mechanisms of overall water-splitting reactions from a photonic point of view and subsequently discusses the engineering of material synthesis. Advanced composites are also addressed, such as WO3/BiVO4/Cu2O and CN-FeNiOOH-CoOOH, which demonstrate high efficiency by delivering photocurrent densities of 5 mAcm−2 and 3.5 mA cm−2 at 1.23 vs. RHE, respectively. Finally, the authors offer their perspectives and list the main challenges based on their experience in developing semiconductor-based materials applied in several fields. In this manner, this brief review provides the main advances in these topics, used as references for new directions in designing active materials for photoelectrocatalytic water splitting. Full article
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12 pages, 1742 KB  
Article
Simulation of Lead-Free Perovskite Solar Cells with Improved Performance
by Saood Ali, Praveen Kumar, Khursheed Ahmad and Rais Ahmad Khan
Crystals 2025, 15(2), 171; https://doi.org/10.3390/cryst15020171 - 10 Feb 2025
Cited by 10 | Viewed by 2192
Abstract
At present, lead halide PVSKSCs are promising photovoltaic cells but have some limitations, including their low stability in ambient conditions and the toxicity of lead. Thus, it will be of great significance to explore lead-free perovskite materials as an alternative absorber layer. In [...] Read more.
At present, lead halide PVSKSCs are promising photovoltaic cells but have some limitations, including their low stability in ambient conditions and the toxicity of lead. Thus, it will be of great significance to explore lead-free perovskite materials as an alternative absorber layer. In recent years, the numerical simulation of perovskite solar cells (PVSKSCs) via the solar cell capacitance simulation (SCAPS) method has attracted the attention of the scientific community. In this work, we adopted SCAPS for the theoretical study of lead (Pb)-free PVSKSCs. A cesium bismuth iodide (CsBi3I10; CBI) perovskite-like material was used as an absorber layer. The thickness of the CBI layer was optimized. In addition, different electron transport layers (ETLs), such as titanium dioxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), and zinc selenide (ZnSe), and different hole transport layers, such as spiro-OMeTAD (2,2,7,7-tetrakis(N,N-di(4-methoxyphenylamine)-9,9′-spirobifluorene), poly(3-hexylthiophene-2,5-diyl) (P3HT), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA), and copper oxide (Cu2O), were explored for the simulation of CBI-based PVSKSCs. A device structure of FTO/ETL/CBI/HTL/Au was adopted for simulation studies. The simulation studies showed the improved photovoltaic performance of CBI-based PVSKSCs using spiro-OMeTAD and TiO2 as the HTL and ETL, respectively. An acceptable PCE of 11.98% with a photocurrent density (Jsc) of 17.360258 mA/cm2, a fill factor (FF) of 67.10%, and an open-circuit voltage (Voc) of 1.0282 V were achieved under the optimized conditions. It is expected that the present study will be beneficial for researchers working towards the development of CBI-based PVSKSCs. Full article
(This article belongs to the Section Materials for Energy Applications)
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13 pages, 3566 KB  
Article
Enhancing the Thermoelectric Performance of Bi2O2Se Ceramics via Multi-Element Doping
by Hongquan Zhao, Linan Ding, Yulang Xu, Zhihao Zeng and Songtao Dong
Coatings 2025, 15(2), 180; https://doi.org/10.3390/coatings15020180 - 5 Feb 2025
Cited by 2 | Viewed by 1373
Abstract
Bi2O2Se, as the n-type counterpart of p-type BiCuSeO, has garnered considerable attention. The lower carrier concentration leads to reduced electrical conductivity, prompting extensive research efforts aimed at enhancing its electrical performance. This study prepared Bi2−3x(CeTiSn)xO [...] Read more.
Bi2O2Se, as the n-type counterpart of p-type BiCuSeO, has garnered considerable attention. The lower carrier concentration leads to reduced electrical conductivity, prompting extensive research efforts aimed at enhancing its electrical performance. This study prepared Bi2−3x(CeTiSn)xO2Se (x = 0, 0.02, 0.03, and 0.04) ceramics using a combination of high-energy ball milling and cold isostatic pressing techniques. Results demonstrated that the incorporation of multiple elements led to an increase in the carrier concentration within the Bi2O2Se system, thereby improving electrical conductivity. The electrical conductivity increased from 5.1 S/cm for Bi2O2Se to 154.1 S/cm for Bi1.88(CeTiSn)0.04O2Se at 323 K. Furthermore, the maximum power factor value of Bi1.88(CeTiSn)0.04O2Se was 112 μW m−1 K−2 at 763 K. Doping led to a slight increase in thermal conductivity. The figure of merit ZTmax value of Bi1.88(CeTiSn)0.04O2Se was ~0.16, marking a significant enhancement of about 1.45 times compared to that of the pure sample (~0.11). Full article
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15 pages, 4915 KB  
Article
Impurity Behavior in Cast Copper Anodes: Implications for Electrorefining in a Circular Economy
by Agustin Morales-Aragon, Daniel Sánchez-Rodas, Guillermo Ríos and Michael S. Moats
Metals 2025, 15(2), 113; https://doi.org/10.3390/met15020113 - 24 Jan 2025
Cited by 2 | Viewed by 2865
Abstract
The behavior of impurities in cast copper was investigated to simulate production with increased utilization of secondary sources within the framework of a circular economy. The incorporation of impurities, particularly Ni, Sn, and Sb, from recycled Cu may significantly impact the electrorefining process. [...] Read more.
The behavior of impurities in cast copper was investigated to simulate production with increased utilization of secondary sources within the framework of a circular economy. The incorporation of impurities, particularly Ni, Sn, and Sb, from recycled Cu may significantly impact the electrorefining process. In this study, commercial anodes were doped with Ni, Sn, and Sb concentrations of 2500–6500 g/t, 300–900 g/t, and 450–950 g/t, respectively. Anode concentrations of Pb and Bi were maintained at 1000 g/t and 350 g/t, respectively. As concentrations were examined at two levels, 860 or 1700 g/t, depending on the commercial anode used to create the doped samples. Electron microscopy with microprobe analysis revealed that the commercial anodes contained three predominant phases: Cu2O, (Cu,Ag)2(Se,Te), and a complex oxide phase of Cu, Pb, As, Sb, and/or Bi. Ni, the main impurity, primarily accumulated within the Cu grains, while Sn and Sb tended to form oxidized inclusions. The distribution of Ni in Cu grains was ca. 20% lower in the anodes doped at higher Ni concentrations due to the formation of nickel-bearing inclusions, such as Kupferglimmer and NiO. The doped anodes showed lower quantities of Cu2O inclusions than the commercial anodes due to the preferential formation of oxides with other impurities, including SnO2. These findings highlight potential challenges for Cu electrorefining in a circular economy, as Ni, Sb, and Sn may impact the deportment of these impurities to slimes or electrolyte and may cause copper depletion in the refining electrolyte. Full article
(This article belongs to the Section Metal Casting, Forming and Heat Treatment)
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22 pages, 4121 KB  
Article
Geochemistry and Fluid Inclusion of Epithermal Gold-Silver Deposits in Kamchatka, Russia
by Maria Shapovalova, Elena Shaparenko and Nadezhda Tolstykh
Minerals 2025, 15(1), 2; https://doi.org/10.3390/min15010002 - 24 Dec 2024
Cited by 6 | Viewed by 3609
Abstract
The work focuses on five epithermal Au-Ag deposits of the Kamchatka volcanogenic belts: Rodnikovoe, Baranyevskoe, Kumroch, Lazurnoe (adularia-sericite type–Ad-Ser) and Maletoyvayam (acid-sulfate type–Ac-Sul). The geochemical characteristics of the deposits were presented based on the results of ICP-OES and fire-assay analysis. The compositions and [...] Read more.
The work focuses on five epithermal Au-Ag deposits of the Kamchatka volcanogenic belts: Rodnikovoe, Baranyevskoe, Kumroch, Lazurnoe (adularia-sericite type–Ad-Ser) and Maletoyvayam (acid-sulfate type–Ac-Sul). The geochemical characteristics of the deposits were presented based on the results of ICP-OES and fire-assay analysis. The compositions and physicochemical parameters of ore-forming fluids were based on microthermometry, Raman spectroscopy and gas chromatography-mass spectrometry. It was shown that all deposits were comparable in terms of temperatures, salinity and the predominance of H2O and CO2 in ore-forming fluids. The deposits were formed at temperatures of 160–308 °C by aqueous fluids with salinities of 0.5–6.8 wt. % (NaCl-eq.). The Maletoyvayam deposit differed from the other ones in significant enrichment in Se, Te, Sb, Bi and As, as well as much higher concentrations of hydrocarbons, nitrogenated and sulfonated compounds (31.4 rel.% in total) in the composition of fluid inclusions. This gave us a reason to assume that organic compounds favourably affected the concentrations of these elements in the mineralising fluid. Kumroch and Lazurnoe were distinguished from Rodnikovoe and Baranyevskoe by high Zn, Pb and Cu contents, where each of them represented a single system combining both Ad-Ser type epithermal gold-silver and copper porphyry mineralisations. The presence of alkanes, esters, ketones, carboxylic acids and aldehydes in different quantities at all deposits were indicators of the combination of biogenic and thermogenic origins of organic compounds. The contents of ore-forming elements in ores were consistent with the specificity of mineral assemblages in the Kamchatka deposits. Full article
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28 pages, 2282 KB  
Article
Variation in the Composition of Municipal Solid Waste Incineration Ash
by Bruno Valentim, Alexandra Guedes, Iwona Kuźniarska-Biernacka, Joana Dias and Georgeta Predeanu
Minerals 2024, 14(11), 1146; https://doi.org/10.3390/min14111146 - 12 Nov 2024
Cited by 4 | Viewed by 3104
Abstract
Unlike municipal solid waste bottom ash (MSWBA), fly ash (MSWFA) is landfilled due to its toxicity. However, MSWFA may also be a source of elements. Ash samples collected from a Portuguese MSW incinerator from different locations and over six months were analyzed. Their [...] Read more.
Unlike municipal solid waste bottom ash (MSWBA), fly ash (MSWFA) is landfilled due to its toxicity. However, MSWFA may also be a source of elements. Ash samples collected from a Portuguese MSW incinerator from different locations and over six months were analyzed. Their geochemical composition was normalized to the upper continental crust (UCC) and compared since metal enrichment may be used as an indicator for potential recovery. The potential recovery economic viability was also assessed for metals K, Sb, Cu, Pb, and Zn, considering the ore cut-off grade and minimum industrial grade (MIG) from Chinese geological and mineral industry standards. Compared to the global samples, only the Baghouse 1 FA size fraction’s coarse fraction showed a slight enrichment (1- to 5-fold) in Bi, Nb, and Zr. After wet sieving, most trace elements were enriched in all fractions, but Sb, Bi, Pb, Zn, Ag, As, Cd, Sn, Se, and Hg were depleted in the coarse fractions and enriched in the fine ones. For Baghouse 1 samples collected over 6 months, the normalization to the UCC showed enrichment of Zn and Pb between 10× and 50×, Zr, Cu, In, and Se between 50× and 100×, and Ag, Mn, Cd, Sb, and Bi at more than 100×. Over six months, the Baghouse 1 FA soluble fraction ranged between 21 wt.% and 30 wt.%, and its precipitates comprised 27% CaO, 6% Na2O, and 9% K2O. The K concentration in the MSWFA was above the cut-off and the MIG, and K could be concentrated in precipitates via simple washing. Full article
(This article belongs to the Special Issue Circular Economy of Remining Secondary Raw Materials)
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15 pages, 3847 KB  
Article
2,1,3-Benzoselenadiazole as Mono- and Bidentate N-Donor for Heteroleptic Cu(I) Complexes: Synthesis, Characterization and Photophysical Properties
by Valentina Ferraro, Fabian Hoffmann, Olaf Fuhr, Burkhard Luy and Stefan Bräse
Inorganics 2024, 12(8), 201; https://doi.org/10.3390/inorganics12080201 - 25 Jul 2024
Cited by 2 | Viewed by 2158
Abstract
Mono- and binuclear Cu(I) complexes were isolated employing 2,1,3-benzoselenadiazole (BSeD) as the N-donor ligand, and triphenylphosphine or bis[(2-diphenylphosphino)phenyl] ether (DPEphos) as P-donors. Then, 77Se NMR was measured for the free ligand and the corresponding Cu(I) derivatives, and the related signal was downshifted [...] Read more.
Mono- and binuclear Cu(I) complexes were isolated employing 2,1,3-benzoselenadiazole (BSeD) as the N-donor ligand, and triphenylphosphine or bis[(2-diphenylphosphino)phenyl] ether (DPEphos) as P-donors. Then, 77Se NMR was measured for the free ligand and the corresponding Cu(I) derivatives, and the related signal was downshifted by 12.86 ppm in the case of [Cu(BSeD)(PPh3)2(ClO4)], and around 15 ppm for the binuclear species. The structure of [Cu(BSeD)(PPh3)2(ClO4)] and [Cu22-BSeD)(DPEphos)2(ClO4)2] was confirmed by single-crystal X-ray diffraction. The geometry of the Cu(I) complexes was optimized through DFT calculations, and the nature of the Cu···O interaction was investigated through AIM analysis. The three Cu(I) complexes were characterized by intense absorption under 400 nm and, after being excited with blue irradiation, [Cu(BSeD)(PPh3)2(ClO4)] and [Cu22-BSeD)(PPh3)4(ClO4)2] exhibited weak red emissions centered at 700 nm. The lifetimes comprised between 121 and 159 μs support the involvement of triplet excited states in the emission process. The photoluminescent properties of [Cu(BSeD)(PPh3)2(ClO4)] were supported by TDDFT computations, and the emission was predicted at 710 nm and ascribed to a metal-to-ligand charge transfer (3MLCT) process, in agreement with the experimental data. Full article
(This article belongs to the Special Issue State-of-the-Art Inorganic Chemistry in Germany)
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17 pages, 3662 KB  
Article
Enhancing Bi2Te2.70Se0.30 Thermoelectric Module Performance through COMSOL Simulations
by Md. Kamrul Hasan, Mehmet Ali Üstüner, Hayati Mamur and Mohammad Ruhul Amin Bhuiyan
Thermo 2024, 4(2), 185-201; https://doi.org/10.3390/thermo4020011 - 6 May 2024
Cited by 3 | Viewed by 3214
Abstract
This research employs the COMSOL Multiphysics software (COMSOL 6.2) to conduct rigorous simulations and assess the performance of a thermoelectric module (TEM) meticulously crafted with alumina (Al2O3), copper (Cu), and Bi2Te2.70Se0.30 thermoelectric (TE) materials. [...] Read more.
This research employs the COMSOL Multiphysics software (COMSOL 6.2) to conduct rigorous simulations and assess the performance of a thermoelectric module (TEM) meticulously crafted with alumina (Al2O3), copper (Cu), and Bi2Te2.70Se0.30 thermoelectric (TE) materials. The specific focus is on evaluating diverse aspects of the Bi2Te2.70Se0.30 thermoelectric generator (TEG). The TEM design incorporates Bi2Te2.70Se0.30 for TE legs of the p- and n-type positioned among the Cu layers, Cu as the electrical conductor, and Al2O3 serving as an electrical insulator between the top and bottom layers. A thorough investigation is conducted into critical parameters within the TEM, which include arc length, electric potential, normalized current density, temperature gradient, total heat source, and total net energy rate. The geometric configuration of the square-shaped Bi2Te2.70Se0.30 TEM, measuring 1 mm × 1 mm × 2.5 mm with a 0.25 mm Al2O3 thickness and a 0.125 mm Cu thickness, is scrutinized. This study delves into the transport phenomena of TE devices, exploring the impacts of the Seebeck coefficient (S), thermal conductivity (k), and electrical conductivity (σ) on the temperature differential across the leg geometry. Modeling studies underscore the substantial influence of S = ±2.41 × 10−3 V/K, revealing improved thermal conductivity and decreased electrical conductivity at lower temperatures. The findings highlight the Bi2Te2.70Se0.30 TEM’s high potential for TEG applications, offering valuable insights into design and performance considerations crucial for advancing TE technology. Full article
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17 pages, 7383 KB  
Article
Genesis of Cu-Sn Mineralization in the Shuangjianzishan Super-Large Silver Deposit, Inner Mongolia: Trace Element Constraints from Chalcopyrite and Cassiterite
by Yu Liu, Biao Jiang, Yuchuan Chen, Liwen Wu, Yushan Zuo and Zhao Liu
Appl. Sci. 2024, 14(9), 3822; https://doi.org/10.3390/app14093822 - 30 Apr 2024
Cited by 3 | Viewed by 2354
Abstract
The Shuangjianzishan silver polymetallic deposit is located in the copper–tin–lead–zinc–silver polymetallic metallogenic belt in the Southern Great Xing’an Range, with silver resources of more than 18,000 t, which is the largest silver polymetallic deposit in Asia. Early studies concluded that the Shuangjianzishan deposit [...] Read more.
The Shuangjianzishan silver polymetallic deposit is located in the copper–tin–lead–zinc–silver polymetallic metallogenic belt in the Southern Great Xing’an Range, with silver resources of more than 18,000 t, which is the largest silver polymetallic deposit in Asia. Early studies concluded that the Shuangjianzishan deposit is typically an epithermal Ag-Pb-Zn deposit that lacks a high-temperature mineralization stage. In recent years, with the deepening of research, a large amount of Cu-Sn mineralization has been found in the deep part of the Shuangjianzishan deposit, but it is less studied. The laser-ablation inductively coupled mass spectroscopy (LA-ICP-MS) technique is used to investigate the distribution and substitution of trace elements in chalcopyrite and cassiterite. In this paper, the trace element study of chalcopyrite and cassiterite from the Shuangjianzishan deposit reveals that Sn, In, As, Se, Sb, and Tl mainly exist in chalcopyrite in isomorphic form, while Pb, Bi, and Ni mainly exist in chalcopyrite in the form of mineral inclusions. The enrichment of the high-temperature elements Sn and Se in chalcopyrite, and the deficit of the middle- and low-temperature elements Ga, Sb, etc., reflect that the chalcopyrite in the Shuangjianzishan deposit was formed in a middle- and high-temperature environment, and it also indicates that the early ore-forming hydrothermal solution may be rich in Sn. Fe, In, Co, and Ni mainly exist in cassiterite in isomorphic form, and the content of W in cassiterite is high. There are two main forms, one is isomorphic and the other is wolframite inclusion. Cassiterite has Fe-rich and W-U-poor characteristics, indicating that cassiterite from the Shuangjianzishan deposit was formed under relatively oxidized conditions, and the relative enrichment of elements such as Fe, W, Zr, and Hf indicates that the temperature of cassiterite formation was high. The elemental content and inter-ionic coupling relationships suggest that the cassiterite from the Shuangjianzishan deposit may have an elemental replacement mechanism of W6+ + Fe2+ ↔ 2Sn4+ or Fe3+ + OH ↔ Sn4+ + O2−. The trace elements in cassiterite of the Shuangjianzishan deposit are rich in Fe and Mn and depleted in Nb and Ta, according to the Fe-W diagram, and the tin mineralization of the Shuangjianzishan deposit belongs to cassiterite–sulfide-type tin mineralization. Chalcopyrite Co/Ni ratios >1 are consistent with the characteristics of chalcopyrite genesis in hydrothermal deposits. Full article
(This article belongs to the Special Issue New Advances, Challenges, and Illustrations in Applied Geochemistry)
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11 pages, 2303 KB  
Article
Effect of NaF Doping on the Microstructure and Thermoelectric Performance of BiCuSeO Ceramics
by Zhenbing Pei, Guangqi Xiang, Xin Sun, Zhuang Fu, Yanxin Qiao, Lei Wang, Songtao Dong and Jian Chen
Coatings 2023, 13(12), 2069; https://doi.org/10.3390/coatings13122069 - 12 Dec 2023
Cited by 4 | Viewed by 1900
Abstract
The layered oxyselenide BiCuSeO has attracted significant attention due to its ability to demonstrate low thermal conductivity and a high Seebeck coefficient. This research project involved the synthesis of Bi1−xNaxCuSeO1−xFx (x = 0, 0.05, [...] Read more.
The layered oxyselenide BiCuSeO has attracted significant attention due to its ability to demonstrate low thermal conductivity and a high Seebeck coefficient. This research project involved the synthesis of Bi1−xNaxCuSeO1−xFx (x = 0, 0.05, 0.10, 0.15, and 0.20) ceramics using high-energy ball milling and cold isostatic pressing techniques. A comprehensive investigation was conducted to examine the influence of co−doping NaF on the thermoelectric properties of BiCuSeO ceramics. The substitution of Bi3+ with Na+ introduces a substantial number of holes, resulting in a remarkable improvement in the electrical conductivity and power factor. The conductivity was significantly increased from 9.10 S cm−1 (BiCuSeO) to 94.5 S cm−1 (Bi0.85Na0.15CuSeO0.85F0.15) at 323 K. Additionally, at 823 K, the power factor of the Bi0.85Na0.15CuSeO0.85F0.15 sample reached 44.8 × 10−5 W/m K2. Furthermore, the Bi1−xNaxCuSeO1−xFx ceramics demonstrated a minimum thermal conductivity of 0.43 W m−1 K−1. Consequently, the Bi0.85Na0.15CuSeO0.85F0.15 sample achieved a maximum ZT value of 0.78, which is 7.09 times higher than that of the pure BiCuSeO sample (0.11). Full article
(This article belongs to the Topic Properties of the Corroding Interface)
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17 pages, 4915 KB  
Article
Precious-Metal Mineralization and Formation Conditions of the Biche-Kadyr-Oos Epithermal Au-Ag Ore Occurrence (Eastern Sayan, Russia)
by Renat V. Kuzhuget, Natalia N. Ankusheva, Ailai K. Hertek, Yuri A. Kalinin, Bulat B. Damdinov, Franco Pirajno, Yuri V. Butanaev, Nadezhda V. Suge-Maadyr and Sholban N. Soldup
Minerals 2023, 13(12), 1529; https://doi.org/10.3390/min13121529 - 8 Dec 2023
Cited by 1 | Viewed by 2098
Abstract
The Biche-Kadyr-Oos epithermal Au-Ag ore occurrence is a prospective object in the Ak-Sug porphyry copper ore cluster (Eastern Sayan) in the northern part of the Central Asian orogenic belt (CAOB). The mineralization consists of gold-sulfide-quartz and gold-polysulfide-carbonate-quartz veins with argillic zones in the [...] Read more.
The Biche-Kadyr-Oos epithermal Au-Ag ore occurrence is a prospective object in the Ak-Sug porphyry copper ore cluster (Eastern Sayan) in the northern part of the Central Asian orogenic belt (CAOB). The mineralization consists of gold-sulfide-quartz and gold-polysulfide-carbonate-quartz veins with argillic zones in the Lower Cambrian volcanic-sedimentary rocks. The origin of the Au-Ag ore occurrence is still debatable. To determine the origin, we examined the mineralogical and geochemical features, conditions of formation, and fluid sources of the Biche-Kadyr-Oos ore. A mineralogical and geochemical investigation outlines three stages of mineral formation: early argillic stage; gold-sulfide-quartz stage with pyrite, marcasite, pyrrhotite, arsenopyrite, chalcopyrite, less frequently sphalerite, hessite, gold, and electrum; and late gold-polysulfide-carbonate-quartz stage with gold, electrum, Hg-electrum, Se-acanthite, Se-galena, bornite, tennantite, tetrahedrite, hessite, tellurobismuthite, bismuthinite, matildite, jamesonite, ourayite, native Bi, and barite. Fluid inclusion study (thermometry, Raman spectroscopy) in quartz and mineral thermometry (electrum and sphalerite paragenesis) determined that ore veins were formed at P~0.5 kbar from CO2-water Na-K-chloride fluid (4.9–9.6 wt % NaCl eqv) and temperatures from 300 to 200 °C (early gold-sulfide-quartz veins at 300–230 °C, and late gold-polysulfide-carbonate-quartz veins at 290–200 °C) and variations in fO2, fS2, fSe2 and fTe2. The S isotopic composition in sulfides and δ34SH2S values of the fluid are +1.3‰ and +4.7‰, respectively, (T = 300–275 °C) indicating magmatic S in ore formation. The oxygen isotope data indicate that during the formation of veins, the magmatic fluid mixed with meteoric water (δ18Ofluid is from +3.4 to +6.4‰). The isotopic data that were obtained combined with mineralogical and geochemical features and conditions of ore formation indicate the similarity of Biche-Kadyr-Oos ore occurrence with epithermal Au-Ag deposits of intermediate sulfidation (IS) type. The presence of epithermal Au-Ag mineralization of the Biche-Kadyr-Oos IS type in ore cluster of the Ak-Sug Cu-Au-Mo porphyry deposit indicates the existence of a single porphyry-epithermal ore-magmatic system. Full article
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