Search

The Zhijin phosphorite (P)-bearing rare earth element (REE) deposit in Guizhou Province (China) hosts vast ore resources (P: 1.348 billion tonnes; REE: 1.44 Mt). Up to date, the Zhijin phosphorite resource has not been exploited because of the uncertain occurrence of the associated REEs, which hampers mineral processing and extraction. In this study, the structure, the valence state, and the coordination position of Y in the REE-yttrium-rich bioclastic samples from Zhijin were revealed by means of synchrotron radiation X-ray absorption fine structure analysis. The results show that the Y occurs as Y(iii) in the samples, and that the form of Y is different from the Y2O3 form in standard xenotime samples. Yttrium in the samples was in a complex coordination position without Y–O–Y bonding, and the Y–O bond lengths range widely without clear patterns. We suggest that Y in the samples is surrounded by organic or macro-molecular compounds, rather than in inorganic ones. Thus, Y in collophanite is unlikely to be in the form of isomorphism.

The utilization of green hydrogen sources in H2O for alkynols electrocatalytic semihydrogenation reaction (ESHR) at ambient temperature provides a promising pathway toward the sustainable conversion of alkynols. However, it is still a great challenge to construct specific interfacial structure to adjust the electronic structure of Pd for the purpose of altering the strong adsorption of Pd with active hydrogen to enhance the production of alkenols. Here, the atomically dispersed GaOx‐PdMo bimetallene nanoribbons (GaOx‐PdMo BNRs) via oxygen bridging Ga atoms is designed to the surface of PdMo BNRs for 2‐methyl‐3‐butyn‐2‐ol (MBY) ESHR to the synthesis of 2‐methyl‐3‐buten‐2‐ol (MBE). The GaOx‐PdMo BNRs achieve the excellent MBE selectivity (≈97.4%), Faraday efficiency (≈96.1%), and maintain long‐term stability. Density functional theory demonstrates that the top electron‐enriched Ga atoms and the bottom electron‐deficient Pd atoms construct a "pyramidal" interface via the oxygen bridge. The unique surface can effectively activate H2O and weaken interaction between catalyst and MBE, thus promoting MBE generation. Moreover, the electron bridge effect between Ga‐O‐PdMo can induce p‐d orbital hybridization to achieve lower the d‐band center of surface Pd thus modulating the reactants adsorption. This work provides a strategy to improve ESHR performance by electron bridge effect to modulate interfacial electron distribution. [ABSTRACT FROM AUTHOR]

In-situ stress plays a pivotal role in influencing the desorption, adsorption, and transportation of coalbed methane. The reservoir gas content represents a pivotal physical parameter, encapsulating both the coalbed methane enrichment capacity and the underlying enrichment law of the reservoir. This investigation collates, computes, and consolidates data concerning pore pressure, breakdown pressure, closure pressure, triaxial principal stress, gas content, lateral pressure coefficient, and other pertinent variables from coal reservoirs within several coal-bearing synclines in the Liupanshui coalfield, China. This study elucidates the characteristics of longitudinal stress development in the study area, the gas content of the longitudinal reservoirs and their interrelationships. The study area is situated within the middle-high stress zone, exhibiting discernible evolution patterns from reverse fault mechanism to strike-slip fault mechanism to normal fault mechanism, progressing from shallow to deep. In the deeper stratigraphy, a strike-slip-normal fault mechanism emerges. The relationship between burial depth and triaxial principal stress is subjected to linear regression, resulting in the proposal of a simplified model for vertical in-situ stress. The hyperbolic regression algorithm was employed in order to derive both the envelope and median formulas for lateral pressure coefficient (k values). The k value displays discrete behavior along the vertical axis in shallow depths, gradually converging in deeper strata and ultimately stabilising at approximately 0.65 with increasing depth. A comprehensive examination of the k value substantiates the efficacy of the simplified in-situ stress model along the vertical axis, offering profound insights into the vertical interrelationships and evolving patterns of the triaxial principal stresses. The mean gas content in the study area was found to be 11.89 m³/t, exhibiting a general increase in depth, followed by a subsequent decrease. The pore pressure (Pp) displays a discernible positive correlation with gas content. This study comprehensively elucidates the developmental patterns of the stress field, the simplified model of vertical in-situ stress, the attributes of the stress ratio (KH, kh, lateral pressure coefficient k), the characteristics of reservoir gas content, and the corresponding and transformative relationships between coupled geostress field parameters and gas content. The lateral pressure coefficient conversion depth, in-situ stress conversion depth, and gas inversion depth are delineated, accompanied by a detailed exposition of their definition process, physical significance, and interrelations. Within the study area, the lateral pressure coefficient conversion depth is estimated to range between 450 and 500 m, while the critical depth for in-situ stress conversion is approximately 670 m. Moreover, the critical depth for gas content conversion falls within the range of 700–800 m. It is noteworthy that the critical depth for deep coalbed methane within the Liupanshui coalfield has been identified as approximately 800 m. Subsequently, a vertical "in-situ stress-gas content mode" relationship model for coalbed methane development was formulated, thereby providing a structured framework for understanding the dynamic interactions between vertical in-situ stress and gas content. [ABSTRACT FROM AUTHOR]

The early Cambrian is a critical interval of dramatic oceanic and biochemical changes in geological history. The black shale deposits, which are rich in Mo, Ni, V, and platinum group elements (PGE), are a reflection of that interval. Among all known Cambrian black shale deposits in South China, the vanadium deposits are poorly constrained by geochronology. The newly discovered tuff layer in the Sansui Bagong vanadium deposit in Guizhou Province can provide excellent constraints on the age of vanadium deposits. In this study, we obtain a new zircon U–Pb isotopic age, which can constrain the age of the vanadium deposit. This tuff occurs in the middle part of the ore bed, and the age of the tuff layer can reflect the mineralization age of the V deposit. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used in this study to obtain the zircon U–Pb age of the tuff and indicates that the event of volcanic activity took place at 520.9 ± 1 Ma. This age is close to the boundary between the Cambrian Terreneuvian and Series 2. This result provides a good constraint on the age of the vanadium deposits in South China and makes the vanadium deposits to be comparable with other Mo–Ni–PGE deposits. The alteration of organic carbon isotope (δ 13Corg) values can reflect changes in the marine environment and is widely used in stratigraphic correlation. The analysis of the δ 13Corg values of the ore bed in the present study reveals a positive excursion at the bottom of the deposit and a negative excursion in the V-enriched layer. The δ 13Corg values in the Bagong section are comparable to those in the Xiaotan and Longbizui sections. The ages of the Sansui vanadium deposit constrained by the U–Pb isotopic age of the tuff and the δ 13Corg values are consistent. All of the data lead us to infer that the vanadium deposit formed at approximately 521 Ma.

Electrocatalytic alkynol semi‐hydrogenation for the high‐value chemicals alkenol with mild conditions and carbon‐free emission is a potentially green and sustainable alternative to conventional thermocatalytic routes, which generally involves the design of electrocatalysts with high activity and high selectivity. Here, the rare‐earth single‐atom (Ln = La, Nd, Pr) coordinated Pd metallene (Ln1Pdene) is reported for electrocatalytic 2‐methyl‐3‐butyn‐2‐ol (MBY) semi‐hydrogenation reaction (MBY ESHR) to synthesis of 2‐methyl‐3‐buten‐2‐ol (MBE). Typically, in alkaline medium containing 0.1 m MBY, MBY conversion and MBE selectivity of La1Pdene are as high as ≈97% and ≈95%, respectively, with excellent electrocatalytic stability. Meanwhile, in situ infrared spectra reveal the conversion of MBY to MBE during the dynamic electrocatalytic process. Theoretical calculations reveal that the interaction between La single‐atom and Pd host triggers an unconventional transformation of the intermediate MBE* adsorption configuration during electrocatalytic hydrogenation, achieving the optimal desorption energy between La1Pd and target product and optimizing the reaction energy barriers to inhibit the over‐hydrogenation of MBE. Moreover, La single‐atom as the adsorption active site of the hydrogen supplier H2O effectively reduces the competition adsorption between the reactants MBY and H2O, rendering La single‐atom and Pd host as the synergistic co‐catalytic active sites to promote the electrocatalytic MBY semi‐hydrogenation reaction. [ABSTRACT FROM AUTHOR]

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C6H11NO) from cyclohexanone (C6H10O) and nitrogen oxide (NOx) is a promising alternative to traditional environment‐unfriendly industrial technologies for green synthesis of C6H11NO. Precisely controlling the reaction pathway of the C6H10O/NOx‐involved electrochemical reductive coupling reaction is crucial for selectively producing C6H11NO, which is yet still challenging. Herein, we report a porous high‐entropy alloy PdCuAgBiIn metallene (HEA‐PdCuAgBiInene) to boost the electrosynthesis of C6H11NO from C6H10O and nitrite, achieving a high Faradaic efficiency (47.6 %) and almost 100 % yield under ambient conditions. In situ Fourier transform infrared spectroscopy and theoretical calculations demonstrate that unconventional orbital hybridization between d‐block metals and p‐block metals could regulate the local electronic structure of active sites and induce electron localization of electron‐rich Pd sites, which tunes the active hydrogen supply, facilitates the generation and enrichment of key intermediates NH2OH* and C6H10O*, and efficiently promotes their C−N coupling to selectively produce C6H11NO. [ABSTRACT FROM AUTHOR]

During the Ediacaran–Cambrian transition, a series of stratal continuous and well-preserved siliceous rock and phosphorite assemblages developed in Qingzhen, Guizhou Province, China, facilitating research on the biological evolution, marine chemistry, and palaeoecological environment of this period. Therefore, we investigated the paleontology, trace and rare earth elements, total organic carbon, total sulfur content, and Zn isotopes of the phosphorus-bearing rock series in the Taozichong Formation of the Cambrian period in Qingzhen. Geochemical analysis reveals that the sedimentary rocks in this area were formed in the oxygen-rich seawater environment and were not affected by high-temperature hydrothermal activity. The upwelling ocean current provided abundant rare earth elements and other nutrient elements, as well as conditions for the prosperity of biota in Qingzhen. In addition, the δ66Zn value (−0.21‰–0.41‰ range and 0.17‰ mean) in the Qingzhen phosphorous rock series was much lower than that in seawater, indicating a strong level of biological productivity. The variation trend of δ13C, δ18O, and δ66Zn exhibited four stages and three obvious drift events. The results suggest that climate change during this period led to the intermittent flourishing and extinction of organisms, which triggered the negative drift of δ13C and δ18O in the ocean, resulting in a coordinated response of δ66Zn. The unique ecological environment of the Taozichong Formation in Qingzhen also provides favorable conditions for the population continuation of Ediacaran-type benthic soft-bodied metazoon dominated by discoid fossils, Shaanxilithes, worm fossils, and sponge fossils in the Cambrian strata, as well as participation in the global biological explosion events. The study area provides new insights for rebuilding the global Ediacaran–Cambrian ecosystem during the transition period. [ABSTRACT FROM AUTHOR]