PtCo-based nanocatalyst for oxygen reduction reaction:Recent highlights on synthesis strategy and catalytic mechanism

Oxygen reduction reaction over Pt-based catalyst is one of the most significant cathode reactions in fuel cells.However,low reserves and high price of Pt have motivated researchers worldwide seeking enhanced utilization efficiency and durability by doping non-noble metals to form Pt-based alloy catalysts.Alloying Pt with Co has been recognized as one of the most effective approaches to achieve this goal.PtCo bimetal combination is one of the most promising candidates to synthesize highly efficient catalysts for oxygen reduction reaction(ORR)applications,owing to its relatively more suitable oxygen binding energy for four-electron transfer reactions.Recently,impressive strategies have been developed to fabricate more active and stable PtCo-based multimetallic alloys with tailorable size and morphology.This paper aims to summarize the most recent highlights on the study of the relationship between preparation strategies,morphologies,electroactivities of the PtCo-based catalyst at atomic level and further the relevant reaction mechanism.The challenges and opportunities on the further development of electrocatalysts for fuel cells are included to provide reference for the practical application.

Pitfalls of acid leaching method for determining organic and inorganic carbon contents in marine sediments

Organic and inorganic carbon contents of marine sediments are important to reconstruct marine productivity,global carbon cycle, and climate change. A proper method to separate and determine organic and inorganic carbons is thus of great necessity. Although the best method is still disputable, the acid leaching method is widely used in many laboratories because of its ease-of-use and high accuracy. The results of the elemental analysis of sediment trap samples reveal that organic and inorganic carbon contents cannot be obtained using the acid leaching method, causing an infinitely amplified error when the carbon content of the decarbonated sample is 12%±1% according to a mathematical derivation. Acid fumigation and gasometric methods are used for comparison, which indicates that other methods can avoid this problem in organic carbon analysis. For the first time, this study uncovers the pitfalls of the acid leaching method, which limits the implication in practical laboratory measurement, and recommends alternative solutions of organic/inorganic carbon determination in marine sediments.

Observations of marine snow and fecal pellets in a sediment trap mooring in the northern South China Sea

Sediment traps are an important tool for studying the source, composition and sedimentation processes of sinking particulate matter in the ocean. An in situ observational mooring(TJ-A-1) is located in the northern South China Sea(20.05°N, 117.42°E) at a water depth of 2 100 m and equipped with two sediment traps deployed at 500 m and 1 950 m. Samples were collected at 18-day intervals, and 20 samples were obtained at both depths from May 2014 to May 2015. Large amounts of fecal matter and marine snow were collected in the lower trap. The fluxes of marine snow and fecal pellets exhibited a fluctuating decrease between May 2014 and early August 2014 and then stabilized at a relatively low level. Scanning electron microscopy observations revealed that the main components of the marine snow and fecal pellets were diatoms, coccolithophores, radiolarians, and other debris, all of which are planktons mostly produced in photic zone. Used in conjunction with the particle collection range estimates from the lower trap and data on ocean surface chlorophyll, these marine snow and fecal pellets were related to the lateral transport of deep water and not vertical migrations from overlying water column. Moreover, the source area might be southwest of Taiwan.

East Asian paleoclimate change in the Weihe Basin (central China) since the middle Eocene revealed by clay mineral analysis

Obtaining a continuous sedimentary record of Cenozoic East Asian paleoclimate change is key to understand the origin,evolution and driving mechanism of the East Asian monsoon and climate change.Based on the continuous Cenozoic fluvial and lacustrine sedimentary sequence in the Weihe Basin,central China,we carried out research on the content and crystal parameters of clay minerals.The paleoclimate change since the middle Eocene was reconstructed accordingly.The results show that smectite and illite are the dominant clay minerals in fluvial-lacustrine sediments of Weihe Basin.The crystallinity of illite,the chemical index of illite,the ratio of smectite to illite and chlorite decrease gradually,which indicates that chemical weathering in the Weihe River watershed stepwise weakened since the middle Eocene,under the background of a semi-arid and semi-humid climate.The formation of palygorskite may be affected by a weak diagenesis.In this case,the content of smectite and the illite crystallinity caused by the weathering in the corresponding period may be actually higher than that of the current,which indicates that the climate in the Weihe Basin region was relatively warm and humid from the middle Eocene to Pliocene.With the decrease of Cenozoic global temperature and the continuous accumulation of sediments,the intensity of chemical weathering in the Weihe Basin gradually weakened,and the East Asian monsoon climate gradually evolved until becoming dry in the Quaternary.Evidence from clay minerals also indicates that the aridification in the Weihe Basin from the late Eocene to the Oligocene may be a response to the global cooling event at the Eocene-Oligocene transition.

Temporal and spatial evolution of a deep-reaching anticyclonic eddy in the South China Sea

The temporal and spatial evolution of a deep-reaching anticyclonic eddy(AE) is studied using a combination of satellite measurements, moored observations and ocean model reanalysis data in the South China Sea(SCS). Three evolutionary stages in eddy's lifecycle are identified from changes in eddy dynamical characteristics estimated from satellite altimetry: birth(22 days), growth(64 days), and decay(47 days). Similar patterns are also distinguished from dynamic signals in HYCOM.Further, flows reversal and upwelling of cold water below 1500 m were captured by the in-situ records when this energetic,highly nonlinear and long-lived(over 19 weeks) AE passed by our mooring position. Its detailed vertical structure is examined through temperature anomalies, vertical shear of horizontal velocities, and horizontal streamlines estimated from ocean model reanalysis data. Results from the model reveal a mesoscale AE with first-mode baroclinic structure: a bowl-shaped anticyclonic flow in the upper ocean connected to a slant-cylinder cyclonic flow at depth, with a transition layer at depths between 400 and 700 m. It is in good agreement with moored observations but showing a shallower transition depth, suggesting a slight deficiency in the model due to limited deep-sea observations. Last, we estimate eddy heat transport at different depths and stages along the AE's path based on the model data. The result reveals that pronounced heat fluxes occur during growth stage(depths <400 m),counting for 73.03% of the total value. In the decay stage, major heat transport occurs at deeper depth(depths >700–1500 m).Dynamical characteristics suggest that the vertical structure and temporal evolution of the eddy play significant roles in basinscale movement and heat transferring. Considering that mesoscale eddies are ubiquitous in the SCS, our results support a recently-proposed mechanism, whereby upper ocean flows produce changes in the deep-sea circulation, potentially influencing boundary layer dynamics. For the first time to track and link an individual AE observed by satellite altimetry and ocean model,comparisons indicate that assimilative HYCOM outputs may be useful for examining the deep ocean properties within the SCS,especially under the impact of such an intensified surface-detected eddy.

Seasonal variability of tides in the deep northern South China Sea

Tides are the major energy source for ocean mixing, regulating the variation of oceanic circulation and sediment transport in the deep sea. Here twenty months of high-resolution current profiles, which were observed via a mooring system at a water depth of 2100 m in the northern South China Sea(SCS), are used to investigate seasonal variability in deep-sea tides.Spectral analysis shows that tides in this region are dominated by diurnal tide, and both diurnal and semidiurnal tide are vertical mode-1 dominant. Baroclinic diurnal tidal current exhibits pronounced seasonal variability, showing its kinetic energy was the strongest in summer, and the maximum depth-averaged value was up to 86.7 cm^2 s^(-2), which was about 1.5 times of that in winter and twice that in spring and autumn. In contrast, baroclinic semidiurnal tide displays no evident seasonal variability. Such seasonal variability in baroclinic tide was mainly modulated by the barotropic forcing from the Luzon Strait. On the other hand,two anticyclonic eddies and one cyclonic eddy, which originated off southwestern Taiwan in winter, crossed the mooring system.The cyclonic eddy had weak impact on current velocity in the deep sea, but the two deep-reaching anticyclonic eddies enhanced the current velocity through the full-water column by inducing strong subinertial flows. Consequently, the kinetic energy of tides was strengthened and the incoherent variance of baroclinic diurnal tide increased in winter, which contributed ～85% of the variability in diurnal tide. Meanwhile, the velocity of baroclinic diurnal tide was reduced in winter, which was attributed to the weakened stratification induced by the passage of anticyclonic eddies in the deep sea. The seasonal variability of tides in the deep northern SCS can provide a dynamic mechanism for interpreting sediment transport processes in the deep sea on different time scales.

High-resolution clay mineral assemblages in the inner shelf mud wedge of the East China Sea during the Holocene: Implications for the East Asian Monsoon evolution

The inner shelf mud wedge of the East China Sea(ECS) is a high-sedimentation-rate fine-grained sediment unit that has preserved a continuous environmental evolution history since the last deglaciation. We present a high-resolution clay mineralogical study from Core MD06-3040 to semi-quantitatively evaluate terrigenous sediment contributions from various potential provenances throughout the Holocene. The results showed that the clay mineral assemblage is composed of dominant illite(34–49%), moderate smectite(16–41%) and chlorite(15–28%), and minor kaolinite(5–12%). Provenance analysis suggested that most fine-grained terrigenous sediments originated from the Yangtze River, with minor sediments derived from Taiwan island and negligible sediments from nearby Zhejiang and Fujian provinces. Time series variation in the contribution of the Yangtze source fluctuated in the range of 38–80%, whereas that of Taiwan island had a converse variation pattern from ~10%to ~55%, and the contribution of Fujian was relatively stable in the range of 7–11% throughout the Holocene. The fluctuations of clay mineral assemblages and variations of clay mineral contributions from different provenances of Core MD06-3040 were controlled by the variability of precipitation in the Yangtze drainage associated with periodic fluctuations in the East Asian monsoonal circulation.

Clay mineral assemblages of the oceanic red beds in the northern South China Sea and their responses to the Middle Miocene Climate Transition

The Middle Miocene Climate Transition(MMCT,~14 Ma)is the largest cooling event in the Cenozoic“Coolhouse”,which significantly impacts the global chemical weathering pattern.In this paper,the responses of the MMCT global cooling event in the deep South China Sea were studied by clay mineral assemblages analysis of the oceanic red beds(ORB)at International Ocean Discovery Program(IODP)Expedition 368 Site U1502.The results show that the clay mineral assemblages of the ORB at Site U1502 are mainly composed of smectite(56–88%),illite(7–29%),and kaolinite(6–20%),without chlorite.The contents of these clay minerals and illite crystallinity show a four-stage variation pattern during early-middle Miocene(22.8–10.8 Ma).Smectite decreased from average 81%during 22.8–16.2 Ma and 16.2–14.4 Ma to average 67%during 13.8–10.8 Ma,with a rapid decrease of~14%during 14.4–13.8 Ma.On the contrary,illite and kaolinite increased rapidly by~8%and~6%,respectively,during 14.4–13.8 Ma.Illite crystallinity increased from average 0.18°Δ2θduring 22.8–16.2 Ma to average 0.19°Δ2θduring 16.2–14.4 Ma,and then decreased rapidly by~0.02°Δ2θduring 14.4–13.8 Ma.The provenance analysis of clay minerals shows that illite and kaolinite mainly originated from South China landmass due to physical erosion,while smectite mainly came from the Luzon arc as the product of chemical weathering.Therefore,smectite/illite ratio and illite crystallinity are used as proxies of chemical weathering intensity in the early-middle Miocene.High values of the ratio and the crystallinity represent the enhanced chemical weathering,whereas low values indicate the weakened chemical weathering or the strengthened physical erosion process.The smectite/illite ratio and illite crystallinity both decreased rapidly during 14.4–13.8 Ma,indicating the chemical weathering in the surrounding area of the South China Sea weakened rapidly,which we believe is the result of the MMCT event forcing.In addition,their values increased slightly during 16.2–14.4 Ma,which is in response to the relatively enhanced chemical weathering during the Middle Miocene Climate Optimum(MMCO).The variation pattern of clay mineral assemblages of the early-middle Miocene ORB in the South China Sea and its rapid transformation during the MMCT reveal that the Cenozoic cooling played a specific role in controlling the chemical weathering of the Earth’s surface.