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1.
Active crystal facets can generate special properties for various applications. Herein, we report a (001) faceted nanosheet-constructed hierarchically porous TiO2/rGO hybrid architecture with unprecedented and highly stable lithium storage performance. Density functional theory calculations show that the (001) faceted TiO2 nanosheets enable enhanced reaction kinetics by reinforcing their contact with the electrolyte and shortening the path length of Li+ diffusion and insertion-extraction. The reduced graphene oxide (rGO) nanosheets in this TiO2/rGO hybrid largely improve charge transport, while the porous hierarchy at different length scales favors continuous electrolyte permeation and accommodates volume change. This hierarchically porous TiO2/rGO hybrid anode material demonstrates an excellent reversible capacity of 250 mAh g–1 at 1 C (1 C = 335 mA g–1) at a voltage window of 1.0–3.0 V. Even after 1000 cycles at 5 C and 500 cycles at 10 C, the anode retains exceptional and stable capacities of 176 and 160 mAh g–1, respectively. Moreover, the formed Li2Ti2O4 nanodots facilitate reversed Li+ insertion-extraction during the cycling process. The above results indicate the best performance of TiO2-based materials as anodes for lithium-ion batteries reported in the literature.  相似文献   

2.
Most metal–organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to alkaline aqueous solutions, thus precluding their use as potential electrode materials for electrochemical energy storage devices. Here, we present the design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co3O4 nanocube@Co-MOF (Co3O4@Co-MOF), via a controllable and facile one-pot hydrothermal method under highly alkaline conditions. The obtained composite possesses exceptional alkaline stability, retaining its original structure in 3.0 M KOH for at least 15 days. Benefitting from the exceptional alkaline stability, unique structure, and larger surface area, the Co3O4@Co-MOF composite shows a specific capacitance as high as 1020 F g−1 at 0.5 A  g−1 and a high cycling stability with only 3.3% decay after 5000 cycles at 5 A g−1. The as-constructed solid-state flexible device exhibits a maximum energy density of 21.6 mWh cm−3.  相似文献   

3.
Designing new cathodes with high capacity and moderate potential is the key to breaking the energy density ceiling imposed by current intercalation chemistry on rechargeable batteries. The carbonaceous materials provide high capacities but their low potentials limit their application to anodes. Here, we show that Fermi level tuning by p-type doping can be an effective way of dramatically raising electrode potential. We demonstrate that Li(Na)BCF2/Li(Na)B2C2F2 exhibit such change in Fermi level, enabling them to accommodate Li+(Na+) with capacities of 290–400 (250–320) mAh g−1 at potentials of 3.4–3.7 (2.7–2.9) V, delivering ultrahigh energy densities of 1000–1500 Wh kg−1. This work presents a new strategy in tuning electrode potential through electronic band structure engineering.  相似文献   

4.
Applying metal organic frameworks (MOFs) in electrochemical systems is a currently emerging field owing to the rich metal nodes and highly specific surface area of MOFs. However, the problems for MOFs that need to be solved urgently are poor electrical conductivity and low ion transport. Here we present a facile in situ growth method for the rational synthesis of MOFs@hollow mesoporous carbon spheres (HMCS) yolk–shell-structured hybrid material for the first time. The size of the encapsulated Zeolitic Imidazolate Framework-67 (ZIF-67) is well controlled to 100 nm due to the spatial confinement effect of HMCS, and the electrical conductivity of ZIF-67 is also increased significantly. The ZIF@HMCS-25% hybrid material obtained exhibits a highly efficient oxygen reduction reaction activity with 0.823 V (vs. reversible hydrogen electrode) half-wave potential and an even higher kinetic current density (JK = 13.8 mA cm−2) than commercial Pt/C. ZIF@HMCS-25% also displays excellent oxygen evolution reaction performance and the overpotential of ZIF@HMCS-25% at 10 mA cm−2 is 407 mV. In addition, ZIF@HMCS-25% is further employed as an air electrode for a rechargeable Zn–air battery, exhibiting a high power density (120.2 mW cm−2 at 171.4 mA cm−2) and long-term charge/discharge stability (80 h at 5 mA cm−2). This MOFs@HMCS yolk–shell design provides a versatile method for the application of MOFs as electrocatalysts directly.  相似文献   

5.
Large-scale low-cost synthesis methods for potassium ion battery (PIB) anodes with long cycle life and high capacity have remained challenging. Here, inspired by the structure of a biological cell, biomimetic carbon cells (BCCs) were synthesized and used as PIB anodes. The protruding carbon nanotubes across the BCC wall mimicked the ion-transporting channels present in the cell membrane, and enhanced the rate performance of PIBs. In addition, the robust carbon shell of the BCC could protect its overall structure, and the open space inside the BCC could accommodate the volume changes caused by K+ insertion, which greatly improved the stability of PIBs. For the first time, a stable solid electrolyte interphase layer is formed on the surface of amorphous carbon. Collectively, the unique structural characteristics of the BCCs resulted in PIBs that showed a high reversible capacity (302 mAh g−1 at 100 mA g−1 and 248 mAh g−1 at 500 mA g−1), excellent cycle stability (reversible capacity of 226 mAh g−1 after 2100 cycles and a continuous running time of more than 15 months at a current density of 100 mA g−1), and an excellent rate performance (160 mAh g−1 at 1 A g−1). This study represents a new strategy for boosting battery performance, and could pave the way for the next generation of battery-powered applications.  相似文献   

6.
Sodium-based dual-ion batteries (Na-DIBs) show a promising potential for large-scale energy storage applications due to the merits of environmental friendliness and low cost. However, Na-DIBs are generally subject to poor rate capability and cycling stability for the lack of suitable anodes to accommodate large Na+ ions. Herein, we propose a molecular grafting strategy to in situ synthesize tin pyrophosphate nanodots implanted in N-doped carbon matrix (SnP2O7@N-C), which exhibits a high fraction of active SnP2O7 up to 95.6 wt% and a low content of N-doped carbon (4.4 wt%) as the conductive framework. As a result, this anode delivers a high specific capacity ∼400 mAh g−1 at 0.1 A g−1, excellent rate capability up to 5.0 A g−1 and excellent cycling stability with a capacity retention of 92% after 1200 cycles under a current density of 1.5 A g−1. Further, pairing this anode with an environmentally friendly KS6 graphite cathode yields a SnP2O7@N-C||KS6 Na-DIB, exhibiting an excellent rate capability up to 30 C, good fast-charge/slow-discharge performance and long-term cycling life with a capacity retention of ∼96% after 1000 cycles at 20 C. This study provides a feasible strategy to develop high-performance anodes with high-fraction active materials for Na-based energy storage applications.  相似文献   

7.
Lithium metal is one of the most promising anode materials for high-energy-density Li batteries. However, low stability caused by dendrite growth and volume change during cycling hinders its practical application. Herein, we report an ingenious design of bio-inspired low-tortuosity carbon with tunable vertical micro-channels to be used as a host to incorporate nanosized Sn/Ni alloy nucleation sites, which can guide Li metal''s plating/stripping and meanwhile accommodate the volume change. The pore sizes of the vertical channels of the carbon host can be regulated to investigate the structure–performance correlation. After compositing Li, the bio-inspired carbon host with the smallest pore size (∼14 μm) of vertical channels exhibits the lowest overpotential (∼18 mV at 1 mA cm−2), most stable tripping/plating voltage profiles, and best cycling stability (up to 500 cycles) in symmetrical cells. Notably, the carbon/Li composite anode is more rewarding than Li foil when coupled with LiFePO4 in full cells, exhibiting a much lower polarization effect, better rate capability and higher capacity retention (90.6% after 120 cycles). This novel bio-inspired design of a low-tortuosity carbon host with nanoalloy coatings may open a new avenue for fabricating advanced Li-metal batteries with high performance.  相似文献   

8.
Resolving regional carbon budgets is critical for informing land-based mitigation policy. For nine regions covering nearly the whole globe, we collected inventory estimates of carbon-stock changes complemented by satellite estimates of biomass changes where inventory data are missing. The net land–atmospheric carbon exchange (NEE) was calculated by taking the sum of the carbon-stock change and lateral carbon fluxes from crop and wood trade, and riverine-carbon export to the ocean. Summing up NEE from all regions, we obtained a global ‘bottom-up’ NEE for net land anthropogenic CO2 uptake of –2.2 ± 0.6 PgC yr−1 consistent with the independent top-down NEE from the global atmospheric carbon budget during 2000–2009. This estimate is so far the most comprehensive global bottom-up carbon budget accounting, which set up an important milestone for global carbon-cycle studies. By decomposing NEE into component fluxes, we found that global soil heterotrophic respiration amounts to a source of CO2 of 39 PgC yr−1 with an interquartile of 33–46 PgC yr−1—a much smaller portion of net primary productivity than previously reported.  相似文献   

9.
Development of novel catalysts for nitrogen reduction at ambient pressures and temperatures with ultrahigh ammonia (NH3) yield and selectivity is challenging. In this work, an atomic catalyst with separated Pd atoms on graphdiyne (Pd-GDY) was synthesized, which shows fascinating electrocatalytic properties for nitrogen reduction. The catalyst has the highest average NH3 yield of 4.45 ± 0.30 mgNH3 mgPd−1 h−1, almost tens of orders larger than for previously reported catalysts, and 100% reaction selectivity in neutral media. Pd-GDY exhibits almost no decreases in NH3 yield and Faradaic efficiency. Density functional theory calculations show that the reaction pathway prefers to perform at the (Pd, C1, C2) active area because of the strongly coupled (Pd, C1, C2), which elevates the selectivity via enhanced electron transfer. By adjusting the p–d coupling accurately, reduction of self-activated nitrogen is promoted by anchoring atom selection, and side effects are minimized.  相似文献   

10.
Hollow nanoparticles with large specific surface area and high atom utilization are promising catalysts for the hydrogen evolution reaction (HER). We describe herein the design and synthesis of a series of ultra-small hollow ternary alloy nanostructures using a simple one-pot strategy. The same technique was demonstrated for hollow PtNiCu nanoparticles, hollow PtCoCu nanoparticles and hollow CuNiCo nanoparticles. During synthesis, the displacement reaction and oxidative etching played important roles in the formation of hollow structures. Moreover, our hollow PtNiCu and PtCoCu nanoparticles were single crystalline, with an average diameter of 5 nm. Impressively, ultra-small hollow PtNiCu nanoparticles, containing only 10% Pt, exhibited greater electrocatalytic HER activity and stability than a commercial Pt/C catalyst. The overpotential of hollow PtNiCu nanoparticles at 10 mA cm−2 was 28 mV versus reversible hydrogen electrode (RHE). The mass activity was 4.54 A mgPt−1 at −70 mV versus RHE, which is 5.62-fold greater than that of a commercial Pt/C system (0.81 A mgPt−1). Through analyses of bonding and antibonding orbital filling, density functional theory calculations demonstrated that the bonding strength of different metals to the hydrogen intermediate (H*) was in the order of Pt > Co > Ni > Cu. The excellent HER performance of our hollow PtNiCu nanoparticles derives from moderately synergistic interactions between the three metals and H*. This work demonstrates a new strategy for the design of low-cost and high-activity HER catalysts.  相似文献   

11.
We report on low-cost fabrication and high-energy density of full-cell lithium-ion battery (LIB) models. Super-hierarchical electrode architectures of Li2SiO3/TiO2@nano-carbon anode (LSO.TO@nano-C) and high-voltage olivine LiMnPO4@nano-carbon cathode (LMPO@nano-C) are designed for half- and full-system LIB-CR2032 coin cell models. On the basis of primary architecture-power-driven LIB geometrics, the structure keys including three-dimensional (3D) modeling superhierarchy, multiscale micro/nano architectures and anisotropic surface heterogeneity affect the buildup design of anode/cathode LIB electrodes. Such hierarchical electrode surface topologies enable continuous in-/out-flow rates and fast transport pathways of Li+-ions during charge/discharge cycles. The stacked layer configurations of pouch LIB-types lead to excellent charge/discharge rate, and energy density of 237.6 Wh kg−1. As the most promising LIB-configurations, the high specific energy density of hierarchical pouch battery systems may improve energy storage for long-driving range of electric vehicles. Indeed, the anisotropic alignments of hierarchical electrode architectures in the large-scale LIBs provide proof of excellent capacity storage and outstanding durability and cyclability. The full-system LIB-CR2032 coin cell models maintain high specific capacity of ∼89.8% within a long-term life period of 2000 cycles, and average Coulombic efficiency of 99.8% at 1C rate for future configuration of LIB manufacturing and commercialization challenges.  相似文献   

12.
As a non-invasive therapeutic method without penetration-depth limitation, magnetic hyperthermia therapy (MHT) under alternating magnetic field (AMF) is a clinically promising thermal therapy. However, the poor heating conversion efficiency and lack of stimulus–response obstruct the clinical application of magnetofluid-mediated MHT. Here, we develop a ferrimagnetic polyethylene glycol-poly(2-hexoxy-2-oxo-1,3,2-dioxaphospholane) (mPEG-b-PHEP) copolymer micelle loaded with hydrophobic iron oxide nanocubes and emodin (denoted as EMM). Besides an enhanced magnetic resonance (MR) contrast ability (r2 = 271 mM−1 s−1) due to the high magnetization, the specific absorption rate (2518 W/g at 35 kA/m) and intrinsic loss power (6.5 nHm2/kg) of EMM are dozens of times higher than the clinically available iron oxide nanoagents (Feridex and Resovist), indicating the high heating conversion efficiency. Furthermore, this composite micelle with a flowable core exhibits a rapid response to magnetic hyperthermia, leading to an AMF-activated supersensitive drug release. With the high magnetic response, thermal sensitivity and magnetic targeting, this supersensitive ferrimagnetic nanocomposite realizes an above 70% tumor cell killing effect at an extremely low dosage (10 μg Fe/mL), and the tumors on mice are completely eliminated after the combined MHT–chemotherapy.  相似文献   

13.
Hydrothermal fluid is essential for transporting metals in the crust and mantle. To explore the potential of Cu isotopes as a tracer of hydrothermal-fluid activity, Cu-isotope fractionation factors between Cl-bearing aqueous fluids and silicate magmas (andesite, dacite, rhyolite dacite, rhyolite and haplogranite) were experimentally calibrated. Fluids containing 1.75–14 wt.% Cl were mixed together with rock powders in Au95Cu5 alloy capsules, which were equilibrated in cold-seal pressure vessels for 5–13 days at 800–850°C and 2 kbar. The elemental and Cu-isotopic compositions of the recovered aqueous fluid and solid phases were analyzed by (LA-) ICP–MS and multi-collector inductively coupled plasma mass spectrometry, respectively. Our experimental results show that the fluid phases are consistently enriched in heavy Cu isotope (65Cu) relative to the coexisting silicates. The Cu-isotope fractionation factor (Δ65CuFLUID-MELT) ranges from 0.08 ± 0.01‰ to 0.69 ± 0.02‰. The experimental results show that the Cu-isotopic fractionation factors between aqueous fluids and silicates strongly depend on the Cu speciation in the fluids (e.g. CuCl(H2O), CuCl2– and CuCl32−) and silicate melts (CuO1/2), suggesting that the exsolved fluids may have higher δ65Cu than the residual magmas. Our results suggest the elevated δ65Cu values in Cu-enriched rocks could be produced by addition of aqueous fluids exsolved from magmas. Together with previous studies on Cu isotopes in the brine and vapor phases of porphyry deposits, our results are helpful for better understanding Cu-mineralization processes.  相似文献   

14.
Complex oxides with tunable structures have many fascinating properties, though high-quality complex oxide epitaxy with precisely controlled composition is still out of reach. Here we have successfully developed solution-based single-crystalline epitaxy for multiferroic (1-x)BiTi(1-y)/2FeyMg(1-y)/2O3–(x)CaTiO3 (BTFM–CTO) solid solution in large area, confirming its ferroelectricity at the atomic scale with strong spontaneous polarization. Careful compositional tuning leads to a bulk magnetization of 0.07 ± 0.035 μB/Fe at room temperature, enabling magnetically induced polarization switching exhibiting a large magnetoelectric coefficient of 2.7–3.0 × 10−7 s/m. This work demonstrates the great potential of solution processing in large-scale complex oxide epitaxy and establishes novel room-temperature magnetoelectric coupling in epitaxial BTFM–CTO film, making it possible to explore a much wider space of composition, phase, and structure that can be easily scaled up for industrial applications.  相似文献   

15.
In the past three decades, China has built more than 87 000 dams with a storage capacity of ≈6560 km3 and the total surface area of inland water has increased by 6672 km2. Leaching of N from fertilized soils to rivers is the main source of N pollution in China, but the exposure of a growing inland water area to direct atmospheric N deposition and N leaching caused by N deposition on the terrestrial ecosystem, together with increased N deposition and decreased N flow, also tends to raise N concentrations in most inland waters. The contribution of this previously ignored source of  N deposition to freshwaters is estimated in this study, as well as mitigation strategies. The results show that the annual amounts of N depositions ranged from 4.9 to 16.6 kg · ha−1 · yr−1 in the 1990s to exceeding 20 kg · ha−1 · yr−1 in the 2010s over most of regions in China, so the total mass of ΔN (the net contribution of N deposition to the increase in N concentration) for lakes, rivers and reservoirs change from 122.26 Gg N · yr−1 in the 1990s to 237.75 Gg N · yr−1 in the 2010s. It is suggested that reducing the N deposition from various sources, shortening the water-retention time in dams and decreasing the degree of regulation for rivers are three main measures for preventing a continuous increase in the N-deposition pollution to inland water in China.  相似文献   

16.
Rechargeable magnesium batteries have received extensive attention as the Mg anodes possess twice the volumetric capacity of their lithium counterparts and are dendrite-free. However, Mg anodes suffer from surface passivation film in most glyme-based conventional electrolytes, leading to irreversible plating/stripping behavior of Mg. Here we report a facile and safe method to obtain a modified Mg metal anode with a Sn-based artificial layer via ion-exchange and alloying reactions. In the artificial coating layer, Mg2Sn alloy composites offer a channel for fast ion transport and insulating MgCl2/SnCl2 bestows the necessary potential gradient to prevent deposition on the surface. Significant improved ion conductivity of the solid electrolyte interfaces and decreased overpotential of Mg symmetric cells in Mg(TFSI)2/DME electrolyte are obtained. The coated Mg anodes can sustain a stable plating/stripping process over 4000 cycles at a high current density of 6 mA cm−2. This finding provides an avenue to facilitate fast ion diffusion kinetics of Mg metal anodes in conventional electrolytes.  相似文献   

17.
Understanding the correlation between exposed surfaces and performances of controlled nanocatalysts can aid effective strategies to enhance electrocatalysis, but this is as yet unexplored for the nitrogen reduction reaction (NRR). Here, we first report controlled synthesis of well-defined Pt3Fe nanocrystals with tunable morphologies (nanocube, nanorod and nanowire) as ideal model electrocatalysts for investigating the NRR on different exposed facets. The detailed electrocatalytic studies reveal that the Pt3Fe nanocrystals exhibit shape-dependent NRR electrocatalysis. The optimized Pt3Fe nanowires bounded with high-index facets exhibit excellent selectivity (no N2H4 is detected), high activity with NH3 yield of 18.3 μg h−1 mg−1cat (0.52 μg h−1 cm−2ECSA; ECSA: electrochemical active surface area) and Faraday efficiency of 7.3% at −0.05 V versus reversible hydrogen electrode, outperforming the {200} facet-enclosed Pt3Fe nanocubes and {111} facet-enclosed Pt3Fe nanorods. They also show good stability with negligible activity change after five cycles. Density functional theory calculations reveal that, with high-indexed facet engineering, the Fe-3d band is an efficient d-d coupling correlation center for boosting the Pt 5d-electronic exchange and transfer activities towards the NRR.  相似文献   

18.
Determining the thermal conductivity of iron alloys at high pressures and temperatures are essential for understanding the thermal history and dynamics of the Earth''s metallic cores. The authors summarize relevant high-pressure experiments using a diamond-anvil cell and discuss implications of high core conductivity for its thermal and compositional evolution.

The thermal conductivity of iron alloys is a key to understanding the mechanism of convection in the Earth''s liquid core and its thermal history. The Earth''s magnetic field is formed by a dynamo action that requires convection in the liquid core. Present-day outer core convection can be driven by the buoyancy of light-element-enriched liquid that is released upon inner core solidification in addition to thermal buoyancy associated with secular cooling. In contrast, before the birth of the inner core, the core heat loss must be more than the heat conducted down the isentropic gradient in order to drive convection by thermal buoyancy alone, which can be a tight constraint upon the core thermal evolution.Recent mineral physics studies throw the traditional value of the Earth''s core thermal conductivity into doubt (Fig. ​(Fig.1).1). Conventionally the thermal conductivity of the outer core had been considered to be ∼30 W m−1 K−1, an estimate based on shock experiments and simple physical models including the Wiedemann-Franz law: κel = LTρ−1, where κel, L, T and ρ are electronic thermal conductivity, Lorenz number, temperature and electrical resistivity, respectively [1]. Such relatively low core conductivity indicates that liquid core convection could have been driven thermally even with relatively slow cooling rate. However, in 2012–2013, our conventional view was challenged by both computational and experimental studies showing much higher core conductivity [2–4].Open in a separate windowFigure 1.(a) Electrical resistivity and (b) thermal conductivity values at the top of the Earth''s core in the literature [1,2,4–7,9,16]. Filled symbols were calculated on the basis of the Wiedemann-Franz law with ideal Lorenz number (L0 = 2.44 × 10−8 W Ω K−2). Gray bands indicate (a) the range of saturation resistivity [9] and (b) thermal conductivity computed from the saturation resistivity and the Wiedemann-Franz law.Since then, experimental determinations of the thermal conductivity of iron and alloys have been controversial (Fig. ​(Fig.1).1). Ohta et al. [5] measured the electrical resistivity of iron under core conditions in a laser-heated diamond-anvil cell (DAC). The results demonstrate relatively high thermal conductivity of ∼90 W m−1 K−1 for liquid Fe-Ni-Si alloy based on their measured resistivity for pure iron, Matthissen''s rule and Wiedemann-Franz law, which is compatible with ab initio simulations [2,4]. On the other hand, flash laser-heating and fast thermal radiation detection experiments demonstrated the low core conductivity of 20–35 W m−1 K−1 based on finite element method simulations [6,7], in accordance with the traditional estimate [1]. Since transport properties that describe non-equilibrium phenomena are difficult to measure, the fact that determinations of the iron conductivity under core conditions have become viable these days is a remarkable success in mineral physics. Nevertheless, the discrepancy in core conductivity makes a big difference in the expected age of the inner core, mechanism of liquid core convection and thermal history [3].Despite a number of subsequent studies based on a variety of different techniques, we still see a dichotomy of proposed core conductivity values (Fig. ​(Fig.1).1). The ‘saturation’ resistivity, which is derived from the fact that the mean free path of electron–phonon interaction cannot be longer than the interatomic distance, gives the lower bound for conductivity. Such saturation resistivity lies between two clusters of reported high and low resistivity values. While the resistivity saturation is important in highly resistive transition metals and their alloys [3,8] (Fig. ​(Fig.2),2), the conventional estimate [1] did not include the effect of saturation in their models, which resulted in much higher resistivity than the saturation value and hence low core conductivity. The core electrical resistivity measured by recent DAC experiments [3,5,9] shows resistivity saturation (Fig. ​(Fig.2),2), demonstrating the high core conductivity as far as the Wiedemann-Franz law holds with ideal Lorenz number (Fig. ​(Fig.1).1). Additionally, since temperature has a large effect on resistivity, temperature gradient in a laser-heated sample is an issue. An internally-resistance-heated DAC provides homogenous and stable sample heating and is thus a promising technique for conductivity measurements at high pressure and temperature (P–T) [9]. The validity of the Wiedemann-Franz law under extreme conditions has also been an issue. Simultaneous measurements of the electrical resistivity and the thermal conductivity of iron alloy under core high P–T conditions will provide decisive evidence for it.Open in a separate windowFigure 2.Temperature response of the electrical resistivity of (a) fcc iron estimated at 1 bar [8] (blue curve) and (b) hcp iron at 115 GPa [5]. Red curve and black line with gray uncertainty band indicate the predicted resistivity based on the Bloch-Grüneisen model with and without the resistivity saturation, respectively.As introduced above, the most recent high P–T measurements for Fe containing 2, 4, 6.5 wt.% Si using an internally-resistance-heated DAC have demonstrated that the thermal conductivity of Fe-12.7 wt.% (22.5 at.%) Si is ∼88 W m−1 K−1 at core-mantle boundary (CMB) conditions when the effects of resistivity saturation, melting and crystallographic anisotropy at measurements are taken into account [9] (Fig. ​(Fig.1).1). Thermal conductivity of Fe-10 at.% Ni-22.5 at.% Si alloy, a possible outer core composition, could be ∼79 W m−1 K−1 considering the impurity effect of Ni [10]. Si exhibits the largest ‘impurity resistivity’, indicating that the 79 W m−1 K−1 is the lower bound for the thermal conductivity of the Earth''s liquid core. The core thermal evolution models by Labrosse [11] demonstrated that if liquid core convection has been driven by thermal buoyancy with the core thermal conductivity of 79 W m−1 K−1 at the CMB and no radiogenic heating in the core, the CMB temperature is calculated to be ∼5500 K at 3.2 Ga and ∼4800 K at 2.0 Ga. Such high CMB temperature suggests that the whole mantle was fully molten until 2.0–3.2 Ga. It is not consistent with geological records, calling for a different mechanism of core convection.Chemical buoyancy may be an alternate means of driving convection in the core from the early history of the Earth. It has been proposed that the compositional buoyancy in the core could arise from the exsolution of MgO, SiO2 or both [12–14]. Recent core formation models based on the core-mantle distributions of siderophile elements suggest that core metals segregated from silicate at high temperatures, typically at 3000–4000 K and possibly higher [13,15], which enhances the incorporation of lithophile elements including Si and O, and possibly Mg into metals. It is suggested that the (Si, O)-rich liquid core may have become saturated with SiO2 upon secular cooling [14]. Indeed, the original core compositions proposed in recent core formation models include Si and O beyond the saturation limit at CMB conditions [15], i.e. 136 GPa and 4000 K, leading to SiO2 crystallization [13]. The rate of SiO2 crystallization required to sustain geodynamo is as low as 1 wt.% per 109 years, which corresponds to a cooling rate of 100–200 K Gyr−1 [14]. The most recent model of the core compositional evolution by Helffrich et al. [13] showed that MgO saturation follows SiO2 saturation only when >1.7 wt.% Mg in the core. If this is the case, in addition to solid SiO2, (Mg, Fe)-silicate melts exsolve from the core and transfer core-hosted elements such as Mo, W and Pt to the mantle. The core-derived silicate melts may have evolved toward FeO-rich compositions and now represent the ultra-low velocity zones above the CMB.  相似文献   

19.
It is highly desirable to design hollow structures with multi-scale functions by mimicking cells for the construction of micro/nanoreactors. Herein, we report the construction of hollow-structured submicrometer-photoreactors with bimetallic catalysts loaded within mesoporous silicas. The synthesis parameters are optimized to study the evolution of hollow structure through hydrothermal treatment and an ‘adhesive-contraction’ formation mechanism is proposed. AuPt@HMZS catalysts exhibited a broader absorbance region under visible light and the adsorption edge displayed a red-shift, indicating the strong metal–metal interactions at the alloy interface. The reaction performance of the coupled Au-Pt catalysts can be tuned to achieve excellent catalytic activity in cinnamyl alcohol oxidation to cinnamic acid for 3.1 mmol g−1 with 99% selectivity. The proposed strategy to build hollow structures as multifunctional micro/nanoreactors is promising for the design of high-performance and sustainable catalysts for chemical synthesis.  相似文献   

20.
The present study was designed to understand the cigarette smoking-induced alterations in hormones and the resulting changes in platelet serotonin (5-hydroxytryptamine, 5-HT) and monoamine oxidase (MAO-B) activity in chronic smokers. Human male volunteers aged 35 ± 8 years, were divided into two groups, namely controls and smokers (12 ± 2 cigarettes per day for 7–10 years). Results showed that cigarette smoking significantly (p < 0.05) elevated plasma triiodothyronine (T3), cortisol and testosterone levels with significant (p < 0.05) reduction in plasma tryptophan and thyroxin (T4). Moreover, smokers showed reduced platelet 5-HT levels and MAO-B activity. In smokers, plasma cortisol was negatively correlated with tryptophan (r = −0.386), platelet MAO-B (r = −0.264), and 5-HT (r = −0.671), and positively correlated with testosterone (r = 0.428). However, testosterone was negatively correlated with platelet MAO-B (r = −0.315), and 5-HT (r = −.419) in smokers. Further, smokers plasma T3 levels were negatively correlated with platelet MAO-B (r = −0.398), and 5-HT (r = −0.541), whereas T4 levels were positively correlated with platelet MAO-B (r = 0.369), and 5-HT (r = 0.454). In conclusion, our study showed that altered testosterone and cortisol levels may aggravate behavior, mood disturbances and symptoms of depression by decreasing platelet 5-HT and MAO-B activity in smokers.  相似文献   

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