The oblique transfer zone in the Fushan Sag, a syndepositional dome sandwiched between the Bailian and Huangtong sub-sags, has been the most important exploration target. The major oil observation ...occurs in the E
2
l
1
L+M
and the E
2
l
3
U
. 46 oil and rock samples reveal that the oil in the transfer zone is mostly contributed by the Bailian sub-sag, though the source rock conditions, hydrocarbon generation and expulsion histories of the Bailian and Huangtong sub-sags are similar. The E
2
l
3
U
oil, characterized by high maturity, Pr/Ph ratio and oleanane/C
30
-hopane ratio, shows a close genetic affinity with the E
2
l
3
b
source rocks, while the E
2
l
1
L+M
oil, characterized by lower maturity, Pr/Ph ratio and oleanane/C
30
-hopane ratio, is suggested to be derived from the E
2
l
1+2
b
source rocks. The homogenization temperatures of aqueous fluid inclusions, taking the burial history of the reservoirs into account, reflect that the oil charge mainly occurred from mid-Miocene to Pliocene in the oblique transfer zone. The oil transporting passages include connected sand bodies, unconformities and faults in the Fushan Sag. Of these, the faults are the most complicated and significant. The faults differ sharply in the west area, the east area and the oblique transfer zone, resulting in different influence on the oil migration and accumulation. During the main hydrocarbon charge stage, the faults in the west area are characterized by bad vertical sealing and spatially dense distribution. As a result, the oil generated by the Huangtong source rocks is mostly lost along the faults during the vertical migration in the west area. This can be the mechanism proposed to explain the little contribution of the Huangtong source rocks to the oil in the oblique transfer zone. Eventually, an oil migration and accumulation model is built in the oblique transfer zone, which may provide theoretical and practical guides for the oil exploration.
Hollow nanoporous carbon architectures (HNCs) present significant utilitarian value for a wide variety of applications. Facile and efficient preparation of HNCs has long been pursued but still ...remains challenging. Herein, we for the first time demonstrate that single‐component metal–organic frameworks (MOFs) crystals, rather than the widely reported hybrid ones which necessitate tedious operations for preparation, could enable the facile and versatile syntheses of functional HNCs. By controlling the growth kinetics, the MOFs crystals (STU‐1) are readily engineered into different shapes with designated styles of crystalline inhomogeneity. A subsequent one‐step pyrolysis of these MOFs with intraparticle difference can induce a simultaneous self‐hollowing and carbonization process, thereby producing various functional HNCs including yolk‐shell polyhedrons, hollow microspheres, mesoporous architectures, and superstructures. Superior to the existing methods, this synthetic strategy relies only on the complex nature of single‐component MOFs crystals without involving tedious operations like coating, etching, or ligand exchange, making it convenient, efficient, and easy to scale up. An ultra‐stable Na‐ion battery anode is demonstrated by the HNCs with extraordinary cyclability (93 % capacity retention over 8000 cycles), highlighting a high level of functionality of the HNCs.
It is for the first time found that single‐component MOFs (STU‐1) crystals with inner crystalline inhomogeneity could enable the facile and versatile syntheses of hollow nanoporous carbon architectures (HNCs) through an unexplored spontaneous hollowing mechanism. The obtain HNCs can act as a high‐capacity and ultra‐stable anode for Na‐ion batteries.
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•Meshed Co coating Ni catalyst is designed and fabricated via atomic layer deposition.•The meshed structure partitions Ni‘s surface to prevent coking network formation.•The Co-Ni ...interfaces reduce coking intermediates and enhance catalytic activity.
Nickel nanoparticles are effective catalysts for the dry reforming of methane (DRM) in terms of catalytic activity and cost. Yet when applied to DRM reaction under realistic conditions, it is of great challenge overcoming the related durability problems due to sintering and coke deposition. Atomically thin meshed-like Co coating catalytic structure is designed and fabricated to decorate Ni nanoparticles via atomic layer deposition. The coating structure improves the catalytic activity and effectively eliminates carbon deposition for the DRM reaction. Optimized catalytic performance is achieved by fine tuning the density of Co coating on nickel particles. The meshed coating structure partitions the Ni surface to prevent continuous carbon nanotubes network formation. The Co component helps stabilizing the metallic phase of Ni in the DRM reaction. The Co-Ni interfaces created are beneficial for reducing carbon intermediates CHx formation and accelerate carbon removal. The amount of carbon formation can be reduced to 2.9%, which is a significant improvement (reduction over 2 to 6 times) compared with a series of state-of-the-art research reports (8–23%) on Ni-based catalysts in the severe coking temperature range (around 650 °C). The Co coating layer provides physical confinement and also improves the thermal stability of Ni nanoparticles from sintering and agglomeration up to 850 °C.
Employing “solid-state” mechanism can avoid polysulfides dissolution in lithium-sulfur batteries but lead to limited reactivity. It is desirable to eliminate polysulfides dissolution under ...“dissolution-deposition” mechanism but merely impossible with S8 due to its intrisic parasitic reaction pathway. However, sulfurized polyacrylonitrile (S@pPAN) is suggested to involve S3-4 and soluble intermediates Li2S3-4, thus a fast and reversible conversion to insoluble Li2S2 and Li2S can avoid dissolution. Herein, Te is used as eutectic accelerator in S@pPAN to accelerate the redox conversion and prevent polysulfides dissolution under “dissolution-deposition” mechanism. In TexS1-x@pPAN (Te-doped S@pPAN) cathodes, Te can be uniformly distributed through Te-S bond and accelerate the reactivity while contribute capacity, resulting in compatiblity with both ether and carbonate electrolytes, high capacities of 1507 and 861 mA h g−1 at 0.1 and 10 A g−1, and stable cyling over 600 cycles in ether electrolyte (0.05% decay per cycle). Good performance is also demonstrated with 3.11 mg cm−2 sulfur loading and 6 μL mg−1 electrolyte/sulfur ratio. Further studies confirm that Te promotes the diffusion of Li ion and reduces reaction resistance during charge/discharge process, which affords significantly enhanced reaction kinetics and mitigates polysulfides dissolution. This work shows a high performance lithium-sulfur batteries operated under “dissolution-deposition” without polysulfides dissolution.
Sulfurized polyacrylonitrile with Tellurium as eutectic accelerator delivers high performance in both carbonate and ether electrolytes for lithium-sulfur batteries. The electrochemical methods and theoretical calculation suggest that Te-doping lowers reaction overpotential and promotes the diffusion of lithium ions and charge transfer. The fast redox kinetics and unique reaction pathway of Te-doped sulfurized polycrylonitrile prevent polysulfides dissolution under the “dissolution-deposition” mechanism. Display omitted
•Te0.04S0.96@pPAN with Te as eutectic accelerator affords high performance in carbonate and ether electrolytes.•Te0.04S0.96@pPAN cathode (3.11 mg cm−2 sulfur loading and 6 μl mg−1 electrolyte sulfur ratio) delivers decent performance.•Te-doping lowers reaction overpotential and boosts reaction kinetics.•Fast redox conversion and unique reaction pathway prevent polysulfide dissolution under dissolution-deposition mechanism.
Hematite (α-Fe2O3) is a promising photoanode candidate for photoelectrochemical water splitting under visible light irradiation. In-situ Co and ex-situ Sn are co-doped into α-Fe2O3 nanorods to ...improve the photoelectrochemical response of the photoanode. It is found that Sn mono-doping enhances the photocurrent density to 0.93 mA/cm2 under AM 1.5 G illumination. However, the onset potential of the photocurrent shifts positively by ∼100 mV. By introducing additional Co dopant, the photocurrent density can be further improved to 1.25 mA/cm2 at 1.23 V (vs. RHE), about four folds that of pristine Fe2O3 photoanode. Moreover, the onset potential of the (Co, Sn) co-doped Fe2O3 photoanode exhibits ∼ 140 mV cathodic shift comparing with that of Sn mono-doped one. Electrochemical analysis suggests that the Sn doping mainly contributes to the increased carriers density, while Co doping mostly improves the surface kinetics of oxygen evolution reaction on Fe2O3 nanorods. The cooperation of Co and Sn into Fe2O3 nanorods yields a high incident photon-to-current conversion efficiencies of 23% at 350 nm. Our work provides a facile co-doping method to improve both the photocurrent and onset potential of the Fe2O3 photoanode.
•Co and Sn are co-doped into α-Fe2O3 nanorods to improve its PEC performance.•Sn doping enhances the photocurrent with onset potential positively shifting 100 mV.•Additional introduction of Co suppresses the shift of onset potential by 140 mV.•Sn contributes to the improved Nd and Co improves the surface kinetics of OER.
To compare the clinical effect on intestinal dysfunction of spinal cord injury (SCI) between the comprehensive therapy of
moxibustion (moxibustion for opening the governor vessel and regulating the ...spirit) and rehabilitation training and the simple treatment with rehabilitation training.
A total of 60 patients with intestinal dysfunction of SCI were randomized into a comprehensive therapy group and a rehabilitation group, 30 cases in each one (3 cases were dropped out in each group). On the base of the routine western medicine treatment and rehabilitation training, the bowel training and rectal function training were provided, once a day in the rehabilitation group. In the comprehensive therapy group, on the base of the treatment as the rehabilitation group, the
moxibustion was exerted at Yaoyangguan (GV 3), Mingmen (GV 4), Zhiyang (GV 9), Dazhui (GV 14) and Baihui (GV 20), etc, once a day, 30 min each time. In both groups, the treatment for 4 weeks was as one course and 3 courses of treatment were required.
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•NO oxidation of SmMn2O5 is studied via first-principles based microkineitc models.•MvK and ER mechanisms separately contribute to high activity of pristine SmMn2O5.•Ba doping ...destabilizes NO∗ species for high reaction activity along MvK route.•Sr and La doping enhance the O2∗ dissociation for high reactivity via ER pathway.
Using first-principles based microkinetic analysis, we conduct a comprehensive investigation on the NO oxidation process on SmMn2O5 mullite’s active surface under experimentally relevant conditions. The influencing factor for NO oxidation activity is identified and Mars-van Krevelen (MvK) and Eley-Rideal (ER) mechanisms are found to contribute to the high activity of pristine SmMn2O5 mullites in high and low temperature regions, respectively. We further study the activity of surface (Ba/Sr/La) doped SmMn2O5. It is found that surface doping of Ba primarily destabilizes the nitrite (NO∗) species to promote NO oxidation performance via MvK mechanism. Due to the stronger ability of O2 (O2∗) dissociation along the ER route, Sr and La doped mullites are predicted to have greatly enhanced reaction activity in a wide temperature region. Our study gives insight into the NO oxidation ability of pristine and surface doped SmMn2O5 that are beneficial for further optimization of mullite based catalyst performance.
Cu-based materials are promising catalysts for the electrochemical CO2 reduction reaction (CO2RR). However, they frequently have a low Faradaic efficiency (FE) and selectivity for a specific single ...product. Particularly, the precise construction of a Cu microenvironment is a great challenge in the design and fabrication of excellent Cu-based CO2RR catalysts. In order to systematically regulate the Cu metal site environment, the classic HKUST-1 containing paddle-wheel Cu coordination nodes was used as a template and modified with the atomic layer infiltration (ALI) technique in this work. A detailed structural analysis shows that a uniform distribution of Zn–O–Zn sites is introduced into HKUST-1 and linked to neighboring Cu nodes without changing the original morphology and structure. In comparison with pristine HKUST-1, the FE for CO increases from 20–30% to 70–80% for the ALI-modified HKUST-1 within the tested overpotential range. Density functional theory (DFT) simulations prove that the modification with Zn–O–Zn by ALI enhances the adsorption enthalpy of CO2 and strengthens the bonding interaction between the COOH* intermediate and the adsorption center, thereby reducing the whole reaction barrier and accelerating CO formation. The proposed ALI technique elucidates the reliance of CO2RR selectivity on the Cu microenvironment and provides a platform for regulating the coordination environments of Cu or other metal-based electrocatalysts to facilitate the high selectivity of CO2RR in the future.
Uniform p-type CuBi2O4 thin film was prepared through a spin coating method on fluorine-doped tin oxide (FTO) coated glass substrate, with a subsequent hypoxic post-annealing process under ...semi-sealed condition to enhance its photoelectrochemical efficiency for hydrogen evolution reaction. Compared to CuBi2O4 specimen annealed in open-air environment, the semi-sealed annealed CuBi2O4 photocathode presents a remarkable improvement in cathodic photocurrent, from 0.42 mA/cm2 to 0.7 mA/cm2 at 0.25 VRHE. X-ray photoelectron spectroscopy study revealed that the electronic structure of CuBi2O4 film was significantly modified during the post-annealing process and higher carrier concentration was obtained through Mott-Schottky measurement on semi-annealed CuBi2O4. We also demonstrate that the synthesized CuBi2O4 film with a thin overlayer of sputtered TiO2 can retain good stability and efficiency as a photocathode. This work provides insights into the mechanism of the high efficiency CuBi2O4 photocathode achieved from the unique post-annealing treatment.
•A facile post-annealing method enhances the photoelectrochemical performance.•Hypoxic calcination increased the carrier concentration.•TiO2 protection layer improved the stability and photoelectrochemical efficiency.
Recent experiments about the selective coating of transition-metal oxide on Pt nanoparticles have aroused great interest in molecular catalysis for the promotion of both activity and stability. In ...this work, first-principles calculations combined with microkinetic methods are employed to shed light on the edge-selective growth mechanism of 3d-transition metal oxide on Pt nanoparticles in atomic layer deposition (ALD) from the metal cyclopentadienyl precursors (MCp2, M = Fe, Co, and Ni). The MCp2 decomposition on the surface of Pt nanoparticles exhibits robust preferential growth, following the order of edge > (100) > (111), which indicates that edges are naturally selected to be covered and the (111) facets could survive toward the MCp2 precursors. The preferred deposition on the edge site is attributed to a more favorable splitting path for the precursors. On the other hand, competing reactions make the overall reaction rates of MCp2 precursors on edge sites follow the order of NiCp2 > FeCp2 > CoCp2. Moreover, the reaction rate analysis indicates that the edge selectivity of MCp2 on Pt nanoparticles is temperature-dependent, and a high temperature will suppress the selectivity between different sites. FeCp2 could maintain high selectivity in a wide temperature range among the three precursors. The theoretical predictions about the edge-selective growth of MCp2 are confirmed by the Fourier transform infrared measurements of CO signals on successive ALD-coated Pt nanoparticles. The combination of theoretical and experimental study demonstrates the robust edge-selective growth of MCp2 on Pt nanoparticles, which may open up a new avenue for the design of metal-oxide composite catalyst with specific site passivation.
