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The high-throughput scalable production of cheap, efficient and durable electrocatalysts that work well at high current densities demanded by industry is a great challenge for the large-scale implementation of electrochemical technologies. Here we report the production of a two-dimensional molybdenum disulfide-based ink-type electrocatalyst by a scalable exfoliation technique followed by a thermal treatment. The catalyst delivers a high current density of 1000 mA cm −2 at an overpotential of 412 mV for the hydrogen evolution. Using the same method, we produce a cheap mineral-based catalyst possessing excellent performance for high-current-density hydrogen evolution. Noteworthy, production rate of this catalyst is one to two orders of magnitude higher than those previously reported, and price of the mineral is five orders of magnitude lower than commercial Pt electrocatalysts. These advantages indicate the huge potentials of this method and of mineral-based cheap and abundant natural resources as catalysts in the electrochemical industry. The large-scale implementation of electrochemical technologies will require the high-throughput production of high-performance, inexpensive catalysts. Here, authors demonstrate earth abundant molybdenite as raw materials to produce efficient MoS 2 catalysts for high current density H 2 evolution.

The Yandong porphyry Cu deposit is located at the south margin of the Dananhu–Tousuquan arc belt in eastern Tianshan, northwest China. The Cu ores comprise mainly disseminations and vein zones in the potassic and phyllic alteration zones, and are predominantly hosted in diorite porphyry, tonalite, and quartz porphyry, which intruded into Carboniferous Qi’eshan Group volcanic rocks. The U–Pb ages indicate that four intrusions were emplaced between 338.6 ± 2.9 and 326.1 ± 2.6 Ma. Five molybdenite samples yield Re–Os model ages of 333.8–329.5 Ma with a weighted average age of 331.8 ± 2.1 Ma. Fourteen pyrite samples have 206Pb/204Pb of 17.776–18.959, 207Pb/204Pb of 15.410–15.534, and 208Pb/204Pb of 37.323–38.127, similar to the age-corrected data of the Yandong tonalite. The tonalite shows adakite-like characteristics (e.g., high Sr/Y ratios and low Y contents), and has positive εNd(t) and εHf(t) values, and low zircon O isotopes (3.7–4.6 ‰), suggesting that the melt was derived from partial melting of a subducted oceanic slab followed by mantle peridotite interaction. The diorite porphyry exhibits high Mg# and low Sr/Y values, slightly negative Eu anomalies, and positive εHf(t) values, indicating a lithospheric mantle source. The quartz porphyry, with stronger negative Eu anomalies, less evolved εHf(t) values, and low δ18O values (4.7–5.5 ‰), was probably derived from mantle melts that experienced mixing with lower crustal materials (melts or assimilation). The new data suggest that the Yandong intrusions formed in an arc setting. As the tonalite is genetically linked to the Cu mineralization, subduction-related slab melts must have played a key role in the formation of the Yandong deposit.

The Huashandong W deposit (7.7 Mt @ 0.26% WO3) is a newly discovered Neoproterozoic scheelite-dominated deposit in the world-class Jiangnan tungsten belt, South China. It occurs largely in metasedimentary rocks near the western margin of the Neoproterozoic Jiuling batholith and mainly consists of W-bearing exogreisen, hydrothermal breccias, and quartz veins. Two episodes of Neoproterozoic granite magmatism are identified with zircon U-Pb ages of ca. 830–823 and 807–804 Ma, respectively. According to cross-cutting relationships and mineral assemblages, two periods of hydrothermal alteration and W mineralization, corresponding to the two episodes of granite magmatism, are recognized in the Huashandong deposit. The early period is dominated by greisenization and associated scheelite mineralization whereas the late period is characterized by sericitization, hydrothermal brecciation, quartz veining, and associated scheelite and minor wolframite mineralization. Molybdenite Re-Os dating indicates that the early- and late-period W mineralization took place at ca. 828 and 800 Ma, respectively. Zircon trace element characteristics suggest that the Jiuling granite crystallized from reduced granitic magmas and has the potential for W mineralization. The petrologic and geochemical features of the Jiuling granite, coupled with the zircon U-Pb ages and Hf isotopic signatures and molybdenite Re-Os ages, imply that the Huashandong W deposit is genetically related to two phases of evolved granodiorites in the Jiuling batholith. The magmatic-hydrothermal nature of both metallogenic events is confirmed by H-O isotopes on hydrothermal quartz.

The Yinyan porphyry tin deposit in western Guangdong is spatially associated with quartz porphyry and granite porphyry. LA–ICP–MS zircon U–Pb dating defined an emplacement age of 78.5 ± 0.4 Ma for the quartz porphyry and 79.2 ± 0.9 Ma for the granite porphyry. LA–ICP–MS cassiterite U–Pb dating yielded Tera–Wasserburg lower intercept ages of 78.5 ± 0.6, 78.6 ± 1.2, and 78.2 ± 0.7 Ma, for cassiterite from a cassiterite–sulfide vein, cassiterite–sulfide ore, and a cassiterite–topaz–quartz stringer, respectively. Re–Os dating of molybdenite from seven different veins yielded an isochron age of 77.0 ± 0.5 Ma. All these new age data are indistinguishable within analytical uncertainty and, therefore, indicate a genetic relationship between the Sn mineralization and the porphyry magmatism in the Yinyan deposit. The REE tetrad effect and very low Nb/Ta and Zr/Hf ratios indicate that the quartz porphyry and the granite porphyry are highly evolved. The U–Pb dated cassiterite is enriched in Fe, W, and U and in high field strength elements (HFSEs) such as Zr, Hf, Nb, and Ta. The high Fe, Nb, and Ta contents may be responsible for the dark luminescence of cassiterite in CL images. The Zr/Hf ratio of cassiterite may potentially be used to distinguish the mineralization type. Cassiterite from pegmatites has lower Zr/Hf ratios (~ 5–6) in comparison with granite/greisen-related (~ 9–30) cassiterite. Cassiterite from the early hydrothermal stage typically contains higher amounts of Ti, Nb, Ta, Zr, and Hf than that from the late hydrothermal stage. In combination with published geochronological data of other Sn–W deposits in the western Guangdong Province, two Sn–W metallogenic events at ca. 85 and 77–80 Ma have been identified. These two metallogenic events are part of a larger-scale 75–100 Ma Sn–W mineralization event in South China, which we suggest was probably related to the subduction of the Neo-Tethyan oceanic plate.

Porphyry-epithermal veins hosting Re-rich molybdenite and rheniite (ReS2) from the Maronia Cu-Mo ± Re ± Au porphyry in Thrace, NE Greece, provide new insights into the hydrothermal processes causing extreme Re enrichment. Quartz trace element chemistry (Al/Ti, Ge/Ti), Ti-in-quartz thermometry, and cathodoluminescence imaging reveal multiple quartz generations in consecutive hydrothermal quartz-sulfide veins associated with potassic, sericitic, and argillic alteration. Fluid inclusions in different quartz generations indicate that phase separation and fluid cooling are the main ore-forming processes in the porphyry stage (~ 500 – 350 °C), whereas mixing of a vapor-rich fluid with metalliferous (e.g., Pb, Zn, Au) meteoric water forms the epithermal veins (~ 280 °C). These processes are recorded by trace element ratios in pyrite that are sensitive to changes in fluid temperature (Se/Te), fluid salinity (As/Sb, Co/As), and mixing between fluids of magmatic and meteoric origin (Se/Ge). Highly variable intra-grain δ34S values in pyrite record S isotope fractionation during SO2 disproportionation and phase separation, emphasizing the importance of in situ δ34S analysis to unravel ore-forming processes. High δ34S (~ 4.5‰) values of sulfides are indicative of low SO42−/H2S fluid ratios buffered by the local host rocks and mixing of the magma-derived fluid with meteoric water. The formation of Re-rich molybdenite (~ 6600 ppm) is favored by cooling and reduction of a magma-derived, high-temperature (~400 °C), oxidized, and Re-rich fluid triggering efficient Re precipitation in early veins in the potassic alteration zone. The systematic temporal fluid evolution therefore reveals that coeval cooling and reduction of oxidized Re-rich fluids cause extreme Re enrichment at the Maronia porphyry system.

The inhibiting mechanism of high pH on the molybdenite flotation was studied using an experimental and DFT method. The experimental results found that adverse effects of pH on molybdenite flotation should be attributed to the adsorption of OH− on molybdenite [100] surface (MS100). The DFT results show the adsorption energy of H2O/OH− to molybdenite [001] surface (MS001) and MS100 is −8.61/288.30 kJ·mol−1 and −226.81/−302.44 kJ·mol−1. These indicate that H2O is weakly adsorbed on MS001, while OH− is not. Both H2O and OH− can be adsorbed onto MS100. The adsorption energy of OH− to MS100 is much stronger than that of H2O. The results of state density and charge transfer of the adsorption of OH− on MS100 further show that OH− can be chemically adsorbed on MS100 through the bonding of the O atom of OH− and the Mo atom of MS100. This causes a significant reduction in the MS100 hydrophobicity and deteriorates the fine molybdenite flotation.

Northeastern China is an important Mo resource region in China, with more than 80 Mo deposits and occurrences. The Huojihe deposit located in the Lesser Xing’an Range represents one of the many Mesozoic porphyry Mo deposits in NE China and has been selected for investigation attempting to clarify the possible mechanisms controlling Mo mineralization. In this study, accessory minerals, including zircon and apatite from the causative intrusions (biotite monzogranite and granodiorite), have been analyzed to reveal their chemical and isotopic compositions, which provide insights into the nature of the source magmas and a better understanding of the factors affecting their mineralization potential. Zircon U-Pb dating shows that the biotite monzogranite from the Huojihe deposit formed at 181.6 ± 0.6 Ma, which is identical to the previously reported molybdenite Re-Os age (~181 Ma), indicating that the Mo mineralization is probably genetically related to the intrusion. The intrusion samples share homogeneous geochemical and Sr-Nd isotopic compositions, with initial Sr/ Sr ratios of 0.7072–0.7075 and slightly negative ε (t) values from –2.3 to –1.4, reflecting a uniform magma source. The least-altered apatites show similar (or slightly enriched) initial Sr/ Sr ratios (0.7080–0.7108) and ε (t) values (–4.0 to –1.8), whereas the hydrothermally altered apatites are characterized by significantly higher initial Sr/ Sr ratios (0.7091–0.7119) and more negative ε (t) values (–4.9 to –4.4), probably due to the interaction between the hydrothermal fluids and wall rocks. The zircon ε (t) values vary from –0.9 to 1.7, corresponding to a restricted range of T ages from 1279 to 1120 Ma. The Sr-Nd-Hf isotope results suggest that the primary magmas associated with the Mo mineralization could be generated from a dominantly Mesoproterozoic lower crust source, with rare contributions from the depleted mantle. The low Ga and Ce and high Eu contents in the magmatic apatite demonstrate that the original magmas have a relatively high oxygen fugacity, which is also supported by the high zircon Ce /Ce * (22–568) and Eu /Eu * (0.38–0.71) values. Estimates of absolute sulfur concentrations in the mineralization-related melt using available partitioning models for apatite return relatively low magmatic sulfur concentrations in Huojihe (20–100 ppm), indistinguishable from those of larger or smaller deposits or even barren magmatic bodies. Using the sulfur concentration data, a minimum volume of 10–50 km magma has been suggested to be necessary to produce the Huojihe Mo deposit based on mass balance modeling. Besides, the Mo concentration in the original magma has also been roughly estimated based on the magma size (10–50 km ) and the contained Mo in Huojihe (0.275 Mt). The magmatic Mo concentrations (2–10 ppm) are similar to many other porphyry Mo systems (e.g., the Climax-type porphyry Mo deposits), and are also comparable to subeconomic to barren magma systems. This study suggests that pre-degassing enrichments of Mo and S in the original magma is not necessarily important in the formation of the Huojihe Mo deposit; rather, factors other than melt composition may be more critical in forming a porphyry Mo deposit. This understanding might also apply to other porphyry Mo mineralized systems worldwide.

Altar is a large porphyry Cu (Au) deposit located in the Main Cordillera of Argentina, 20 km to the north of the giant Los Pelambres–El Pachón porphyry copper cluster, at the southern portion of the Pampean flat-slab segment of the Andes. Although this region hosts telescoped porphyry-epithermal deposits, the precise temporal relationship between porphyry emplacement, mineralization, cooling, and regional orogenic uplift are still poorly understood. New Re–Os molybdenite ages indicate that Altar orebodies are associated with two magmatic hydrothermal centers: Altar East (11.16 ± 0.06 Ma) and Altar Central (10.38 ± 0.05 Ma) formed at temporally distinct periods. New (U–Th)/He ages from the Early Permian and Late Eocene plutons, and the Middle Miocene subvolcanic stocks associated with Cu–Au mineralization of the Altar region reflect a rapid cooling pulse during the Middle Miocene (15.02 to 10.66 Ma) coeval with a major phase of tectonic shortening and regional uplift. The main pulse of rapid cooling and related tectonic uplift in the Altar region was synchronous with the formation of the hydrothermal systems and resulted in an increased focused metal endowment (Au–Cu grades) due to the telescoping of epithermal mineralization over the rapidly uplifted porphyry system. This 11–10 Ma tectonically triggered exhumation event coincides with the collision of the E-trending segment of the Juan Fernández Ridge with the Peru–Chile trench, at this latitude. Collision and ensuing ridge subduction may have driven a localized pulse of rapid cooling and exhumation of the Main Cordillera that has not been well documented to the north or south of the Altar–Los Pelambres region.

Molybdenum concentrate, as Molybdenite (MoS2), is nowadays obtained as a byproduct of the processing of porphyry copper ores, being molybdenite considered a minor component. The procedure for the commercial extraction of molybdenum from such a sulfide ore, involves the operations of roasting the concentrate, purifying the resulting calcination, either by distillation of molybdenum trioxide (MoO3) or by a hydrometallurgical pathway, and finally reducing the trioxide of molybdenum with hydrogen to obtain the metal. The objective of the present work is to study the production of molybdenum from molybdenite concentrates using aqueous solution of hydrochloric acid (HCl) as a lixiviant, sodium chloride (NaCl) as a catalyst, sodium hydroxide (NaOH) as a pH regulator, and lastly ferric chloride (FeCl3) as an oxidant. The results show that working pH greater than 8, temperature of 50 °C, hydrochloric acid concentration of 5%, solid/liquid ratio of 10:1, stirring rate of 200-300 rpm and the addition of 2% ferric chloride. Mo leaching was 70% under experimental conditions at a time of 180 minutes, with a complete removal of iron. El concentrado de molibdenita (MoS2) es obtenido actualmente como un subproducto en el procesamiento de minerales provenientes de un pórfido de cobre, siendo la molibdenita considerada un componente menor. El procedimiento para la extracción comercial de molibdeno desde un sulfuro, la molibdenita, implica tostar el concentrado, purificar el calcinado resultante, ya sea por destilación de tiroxido de molibdeno (MoO3 )o por una ruta hidrometalúrgica, y finalmente reducir el trióxido con hidrógeno para obtener el metal El objetivo del presente trabajo es estudiar la producción de molibdeno desde concentrados de molibdenita usando una solución acuosa de ácido clorhídrico (HCl) como lixiviante, cloruro de sodio (NaCl) como catalizador, hidróxido de sodio (OHNa) como regulador de pH, y por último cloruro férrico (FeCl3) como un oxidante. Los resultados muestran que trabajando en un pH más grande que 8 temperatura de 50ºC, con una concentración de ácido clorhídrico de 5% y una relación solida / liquido de 10:1, velocidad de agitación de 200- 300 rpm y la adición de un 2% de cloruro férrico, La lixiviación de Mo fue del 70% en condiciones experimentales en un tiempo de 180 minutos, con una remoción completa del hierro.

The selective separation of molybdenite from copper sulfide concentrate in flotation process is realized using sodium hydrosulfide (NaHS) to depress the chalcopyrite and permit only the flotation of the molybdenite. However, this reagent is a highly toxic and flammable gas. The objective of this research was to study the feasible application of commercial lignosulfonates (LSs) in the separation by froth flotation process of molybdenite and chalcopyrite in seawater to present a novel application for LSs, as well as an alternative reagent to sodium hydrosulfide (NaHS). To achieve this, microflotation, absorbance tests and zeta potential measures were performed at pH 8 in seawater and 0.01 M NaCl. The results obtained in this study showed that it is possible to achieve selective separation of copper and molybdenum in both aqueous media due to high depressant effect of molybdenite and low depression of chalcopyrite in microflotation tests at 10 ppm of LSs, when the collector, PAX, is added prior to the addition of LSs. Absorbance study and zeta potential measurements showed that LSs adhere more to the molybdenite surface in seawater than in freshwater. This is related to the high ionic charge of the media that influences a greater interaction of LSs with the mineral surface.