According to the hydrochemical characteristics, hydrogen and oxygen isotope characteristics and the ratio of noble gas isotopes of the sandstone aquifer and basalt aquifer, this study calculated the recharge temperatu...According to the hydrochemical characteristics, hydrogen and oxygen isotope characteristics and the ratio of noble gas isotopes of the sandstone aquifer and basalt aquifer, this study calculated the recharge temperature and residence time of groundwater in the Weishan area of Wudalianchi, also calculating the contribution of noble gas components from different sources to the samples. Based on the characteristics of hydrogen and oxygen isotopes and noble gases Xe and Ne, the recharge altitude and recharge temperature of the two aquifers were estimated, and the recharge temperature fitting with the NGT model as verified, the results showing that the main recharge altitude of groundwater in the region was 500–600 m, the recharge temperature being 2–7°C. He_(eq) and He_(ea) of the samples have been simulated using the OD model, the content of radioactive ~4He in the crust being obtained, the groundwater ages under the two conditions(closed condition and open condition) both being simulated. The results show that groundwater from the sandstone layer water is older than groundwater from the basalt layer. Hydrochemical characteristics and noble gas isotope ratios indicate that in the basalt aquifer and sandstone aquifer in the Weishan area, in addition to atmospheric and crustal helium, there is also an input of mantle-derived helium. The fault constitutes the uplift channel for groundwater containings mantle components, which results in the mantle source composition in water samples near the fault being much higher than those form non-fault areas.展开更多
Isotopic and chemical compositions of pore water(PW) are highly relevant to environmental and forensic study. Five lake water(LW)samples and five sediment samples were collected to investigate the effects of pore size...Isotopic and chemical compositions of pore water(PW) are highly relevant to environmental and forensic study. Five lake water(LW)samples and five sediment samples were collected to investigate the effects of pore sizes of sediments on PW chemistry and stable isotopes and determine mechanisms controlling their variations. Six pore water fractions were extracted from different-sized pores in each sediment sample at six sequential centrifugal speeds for chemical and isotopic analysis. The sediments consisted mainly of quartz, feldspar, and clay minerals. The hydrogen and oxygen isotopic compositions of PW are mainly controlled by the overlying LW, although the lag effect of exchange between overlying LW and PW results in isotopic differences when recharge of LW is quicker than isotopic exchange in PW. Identical isotopic compositions of PW from sediments with different pore sizes indicate that isotopic exchange of water molecules with different pore sizes is a quick process. The ratio of average total dissolved solid(TDS) concentration of PW to TDS concentration of LW shows a strong relationship with adsorption capacity of sediments, demonstrating that remobilization of ions bound to sediments mainly causes a chemical shift from LW to PW.Concentrations of Ca^(2+), Mg^(2+),and Cl^-in PW remain unchanged,while concentrations of Na^+,K^+,and SO_4^(2-) slightly increase with decreasing pore size. Chemical differences of PW from sediments with different pore sizes are governed by ion adsorption properties and surface characteristics of different-si zed particles.展开更多
The Ordovician was an important transitional period for global climate and organic evolution,the global was in the flood and glacial,Onganism was extinction(Zhan,2007;Trotter et al.,2008;Axel et al.,2010).Under the
The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically,it belongs to the Sanjiang Block. Vapor–liquid two-phase fluid inclusions, CO_2-bearing fluid inclusions, and da...The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically,it belongs to the Sanjiang Block. Vapor–liquid two-phase fluid inclusions, CO_2-bearing fluid inclusions, and daughter-bearing inclusions were identified in sulfide-rich quartz veins. Microthermometric and Raman spectroscopy studies revealed their types of ore-forming fluids:(1) low-temperature, low-salinity fluid;(2) medium-temperature, low salinity CO_2-bearing; and(3) high-temperature, Fe-rich,high sulfur fugacity. The δ^(18)O values of chalcopyritebearing quartz ranged from 4.96‰ to 5.86‰, with an average of 5.40‰. The δD values of ore-forming fluid in equilibrium with the sulfide-bearing quartz were from-87‰ to-107‰, with an average of-97.86‰. These isotopic features indicate that the ore-forming fluid is a mixing fluid between magmatic fluid and meteoric water.The δ^(34)S values of chalcopyrite ranged from 13.3‰ to15.5‰, with an average of 14.3‰. Sulfur isotope values suggest that the sulfur in the deposit most likely derived from seawater. Various fluid inclusions coexisted in the samples; similar homogenization temperature to different phases suggests that the Badi fluid inclusions might have been captured under a boiling system. Fluid boiling caused by fault activity could be the main reason for the mineral precipitation in the Badi deposit.展开更多
The Yueguang gold deposit is located in Fengjia,Xinhua County,Hunan Province,South China.It represents a recently discovered small-scale gold deposit situated in the southwestern region of the Jiangnan Orogenic Belt,w...The Yueguang gold deposit is located in Fengjia,Xinhua County,Hunan Province,South China.It represents a recently discovered small-scale gold deposit situated in the southwestern region of the Jiangnan Orogenic Belt,west of the Baimashan granitic batholith.In order to discern the characteristics of the ore-formingfluids,the underlying mineralization processes,and establish a foundation for the origin of the Yueguang gold depositfluid inclusion micro-thermometry,as well as quartz hydrogen and oxygen isotope analysis,have been carried out on samples obtained from various stages of mineralization.The hydrothermal miner-alization stages within the Yueguang gold deposit can be categorized into three stages:(i)the barren,pre-ore quartz-pyrite stage(Stage Ⅰ),the quartz-pyrite-gold stage(Stage Ⅱ),and the post-ore quartz-carbonate stage(Stage Ⅲ),with the second stage being the main mineralization stage.Thefluid inclusions identified in samples from the main min-eralization stage can predominantly be described with the NaCl–H_(2)O and CO_(2)–NaCl–H_(2)O systems.These inclusions display homogenization temperatures ranging from 158.8 to 334.9℃,and thefluid salinity ranges from 0.3%to 4.0%(wt.%NaCl equiv.).Laser Raman spectroscopy analysis of individual inclusions further reveals the presence of gas-phases such as CO_(2),CH_(4),and N_(2).Isotopic analysis indicatesδ^(18)Ofluid values ranging from 3.95 to 6.7‰ and δDH_(2)O values ranging from-71.9 to-55.7‰.These results indi-cate that the ore-formingfluid of the Yueguang gold deposit belongs to metamorphic hydrothermalfluids of middle-low temperature and low salinity.In the process of ore formation,gold is transported in the form of Au(HS)2-complexes,with gold deposition being driven byfluid immiscibility.Therefore,the Yueguang gold deposit is categorized as an orogenic gold deposit dominated by metamorphic hydrother-malfluid.It may become a new target for gold exploration in the Baimashan region,central Hunan Province.展开更多
By studying the light isotopic compositions of carbon,oxygen,and hydrogen,combined with previous research results on the ore-forming source of the deposit,the authors try to uncover its metallogenic origin.The δ^(18)...By studying the light isotopic compositions of carbon,oxygen,and hydrogen,combined with previous research results on the ore-forming source of the deposit,the authors try to uncover its metallogenic origin.The δ^(18)O and δ^(13)C isotope signatures of dolomite samples vary between 10.2 and 13.0‰,and between−7.2 and−5.2‰,respectively,implying that the carbon derives from the upper mantle.δD and δ^(18) O of quartz,biotite,and muscovite from diff erent ore veins of the deposit vary between−82 and−59‰,and between 11.6 and 12.4‰,respectively,implying that the metallogenic solutions are mainly magmatic.According to the relevant research results of many isotope geologists,the fractionation degree of hydrogen isotopes increases as the depth to the Earth’s core increases,and the more diff erentiated the hydrogen isotopes are,the lower their values will be.In other words,mantle-derived solutions can have extremely low hydrogen isotope values.This means that the δD‰ value−134 of the pyrrhotite sample numbered SD-34 in this article may indicate mantle-derived oreforming fl uid of the deposit.The formation of the Dashuigou tellurium deposit occurred between 91.71 and 80.19 Ma.展开更多
Photosynthesis is the most important biochemical reaction on Earth. It has co-evolved and developed with the Earth, driving the biogeochemical cycle of all elements on the planet and serving as the only chemical proce...Photosynthesis is the most important biochemical reaction on Earth. It has co-evolved and developed with the Earth, driving the biogeochemical cycle of all elements on the planet and serving as the only chemical process in nature that can convert light energy into chemical energy. Some heavy oxygen isotopic(^(18)O) labeling experiments have"conclusively" demonstrated that the oxygen released by photosynthesis comes only from water and are written into textbooks. However, it is not difficult to find that bicarbonate has never been excluded from the direct substrate of photosynthesis from beginning to end during the history of photosynthesis research. No convincing mechanism can be used to explain photosynthetic oxygen evolution solely from water photolysis. The bicarbonate effect, the Dole effect, the thermodynamic convenience of bicarbonate photolysis, the crystal structure characteristics of photosystem Ⅱ, and the reinterpretation of heavy oxygen isotopic labeling(^(18)O)experiments all indicate that the photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis. The recently proposed view that bicarbonate photolysis is the premise of water photolysis, bicarbonate photolysis and water photolysis work together with a 1:1(mol/mol) stoichiometric relationship, and the stoichiometric relationship between oxygen and carbon dioxide released during photosynthetic oxygen evolution is also 1:1, has excellent applicability and objectivity, which can logically and reasonably explain the precise coordination between light and dark reactions during photosynthesis, the bicarbonate effect, the Dole effect, the Kok cycle and the neutrality of water and carbon in nature.This is of great significance for constructing the bionic artificial photosynthetic reactors and scientifically answering the question of the source of elemental stoichiometric relationships in nature.展开更多
Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactiv...Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.展开更多
The Lomagundi-Jatuli Event(LJE)refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoi...The Lomagundi-Jatuli Event(LJE)refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic(2.22-2.06 Ga).Theδ^(13)C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05‰-4.95‰(V-PDB;maximum:4.95‰)in this study,which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group.They are much higher than theδ^(13)C values of marine carbonates(-1.16‰on average).Theδ^(13)C values of other formations in the Paleoproterozoic Yimen Group are negative.The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block,which is reported for the first time.Furthermore,they are comparable to theδ^(13)C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton,the Wuzhiling Formation of the Songshan Group in the Xiong'er area,Henan Province,and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area,Liaoning Province.Therefore,it can be further concluded that the LJE is a global event.This study reveals that LJE occurred in Central Yunnan at 2.15-2.10 Ga,lasting for about 50 Ma.The macro-columnar,bean-shaped,and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group.They are the direct cause for the LJE and are also the oldest paleontological fossils ever found.The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event(first occurrence),the global Superiortype banded iron formations(BIFs),the Huronian glaciation,the Great Oxygenation Event(second occurrence),the explosion of multicellular eukaryotes,the positive carbon isotope excursion,and the global anoxic and selenium-rich sedimentary event.The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.展开更多
In this study,the nitrogen and oxygen isotope compositions of nitrite in the upper 150 m water column of the Amundsen Sea in the summer of 2019 and 2020 were measured to reveal the distribution and transformation of n...In this study,the nitrogen and oxygen isotope compositions of nitrite in the upper 150 m water column of the Amundsen Sea in the summer of 2019 and 2020 were measured to reveal the distribution and transformation of nitrite in the euphotic zone of the Southern Ocean.We found that primary nitrite maxima(PNMs)are widely present in the Amundsen Sea,where the depth of occurrence deepens from east to west and nitrite concentrations increases.Evidence from dual isotopes suggests that the formation of PNMs in all regions of the Amundsen Sea is dominated by ammonia oxidation.More importantly,the nitrogen and oxygen isotope compositions of nitrite in the Amundsen Sea mixed layer are abnormal,and their depth profiles are mirror symmetrical.Isotopic anomalies exhibit spatial variations,with central surface water having the lowest nitrogen isotope composition(−89.9‰±0.2‰)and western surface water having the highest oxygen isotope composition(63.3‰±0.3‰).Isotopic exchange reaction between nitrate and nitrite is responsible for these isotope anomalies,as both nitrogen and oxygen isotopes have large isotopic fractionation and opposite enrichment effects.This proves that isotopic exchange reaction operates extensively in different regions of the Amundsen Sea.Our study highlights the unique role of dual isotopes of nitrite in deepening the understanding of nitrogen cycle.Further studies on ammonia oxidation and isotopic exchange between nitrate and nitrite are warranted in the future to understand their roles in the nitrogen cycle in the Southern Ocean.展开更多
Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of re...Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.展开更多
Crop root system plays an important role in the water cycle of the soil-plant-atmosphere continuum.In this study,combined isotope techniques,root length density and root cell activity analysis were used to investigate...Crop root system plays an important role in the water cycle of the soil-plant-atmosphere continuum.In this study,combined isotope techniques,root length density and root cell activity analysis were used to investigate the root water uptake mechanisms of winter wheat(Triticum aestivum L.)under different irrigation depths in the North China Plain.Both direct inference approach and multisource linear mixing model were applied to estimate the distribution of water uptake with depth in six growing stages.Results showed that winter wheat under land surface irrigation treatment(T_s)mainly absorbed water from 10-20 cm soil layers in the wintering and green stages(66.9 and 72.0%,respectively);0-20 cm(57.0%)in the jointing stage;0-40(15.3%)and 80-180 cm(58.1%)in the heading stage;60-80(13.2%)and 180-220 cm(35.5%)in the filling stage;and 0-40(46.8%)and 80-100 cm(31.0%)in the ripening stage.Winter wheat under whole soil layers irrigation treatment(T_w)absorbed more water from deep soil layer than T_s in heading,filling and ripening stages.Moreover,root cell activity and root length density of winter wheat under T_w were significantly greater than that of T_s in the three stages.We concluded that distribution of water uptake with depth was affected by the availability of water sources,the root length density and root cell activity.Implementation of the whole soil layers irrigation method can affect root system distribution and thereby increase water use from deeper soil and enhance water use efficiency.展开更多
Antarctica’s marginal seas are of great importance to atmosphere-ocean-ice interactions and are sensitive to global climate change.Multiple factors account for the freshwater budget in these regions,including glacier...Antarctica’s marginal seas are of great importance to atmosphere-ocean-ice interactions and are sensitive to global climate change.Multiple factors account for the freshwater budget in these regions,including glacier melting,seasonal formation/decay of sea ice,and precipitation.Hydrogen(H)and oxygen(O)isotopes represent useful proxies for determining the distribution and migration of water masses.We analyzed the H and O isotopic compositions of 190 seawater samples collected from the Amundsen Sea during the 34th Chinese Antarctic Research Expedition in 2017/2018.The upper-oceanic structure(<400 m)and freshwater(meteoric water and sea ice melt)distribution in the Amundsen Sea were identified based on conductivity-temperature-depth data and the H and O isotopic composition.Antarctic Surface Water,characterized as cold and fresh with low H and O isotopic ratios,was found distributed mainly in the upper~150 m between the Antarctic Slope Front and Polar Front,where it had been affected considerably by upwelled Upper Circumpolar Deep Water(UCDW)between 68°S and 71°S.A three-endmember(meteoric water,sea ice melt,and Circumpolar Deep Water)mixing model indicated that waters with relatively high proportions(>3%)of freshwater generally lie in the upper~50 m and extend from Antarctica to~65°S in the meridional direction(anomalously low freshwater proportion occurred between 68°S and 71°S).Winter Water mainly occupied the layer between 50 and 150 m south of 71°S in the western Amundsen Sea.The water structure and spatial distribution of freshwater in the upper Amundsen Sea were found influenced mainly by the rates of basal and surficial melting of ice shelves,seasonal alternation of sea ice melt/formation,wind forcing,and regional bathymetry.Owing to the distance between heavy sea ice boundary(HSIB)and ice shelves is much shorter in the western HSIB than the east HSIB,the western part of the heavy sea ice boundary includes a higher proportion of freshwater than the eastern region.This study,which highlighted the distribution and extent of freshwater derived from ice(ice shelves and sea ice)melt,provides important evidence that the offshore drift pathway of cold and fresh Antarctic continental shelf water is likely interrupted by upwelled UCDW in the Amundsen Sea.展开更多
The electrocatalytic water splitting technology can generate highpurity hydrogen without emitting carbon dioxide,which is in favor of relieving environmental pollution and energy crisis and achieving carbon neutrality...The electrocatalytic water splitting technology can generate highpurity hydrogen without emitting carbon dioxide,which is in favor of relieving environmental pollution and energy crisis and achieving carbon neutrality.Electrocatalysts can effectively reduce the reaction energy barrier and increase the reaction efficiency.Facet engineering is considered as a promising strategy in controlling the ratio of desired crystal planes on the surface.Owing to the anisotropy,crystal planes with different orientations usually feature facet-dependent physical and chemical properties,leading to differences in the adsorption energies of oxygen or hydrogen intermediates,and thus exhibit varied electrocatalytic activity toward hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this review,a brief introduction of the basic concepts,fundamental understanding of the reaction mechanisms as well as key evaluating parameters for both HER and OER are provided.The formation mechanisms of the crystal facets are comprehensively overviewed aiming to give scientific theory guides to realize dominant crystal planes.Subsequently,three strategies of selective capping agent,selective etching agent,and coordination modulation to tune crystal planes are comprehensively summarized.Then,we present an overview of significant contributions of facet-engineered catalysts toward HER,OER,and overall water splitting.In particular,we highlight that density functional theory calculations play an indispensable role in unveiling the structure–activity correlation between the crystal plane and catalytic activity.Finally,the remaining challenges in facet-engineered catalysts for HER and OER are provided and future prospects for designing advanced facet-engineered electrocatalysts are discussed.展开更多
This study evaluated the Cretaceous(Campanian–Maastrichtian) kaolinitic sediments of the Ajali/Mamu and Enugu/Nkporo Formations from the Lower Benue Trough of Nigeria. A combined method of inductively coupled plasma...This study evaluated the Cretaceous(Campanian–Maastrichtian) kaolinitic sediments of the Ajali/Mamu and Enugu/Nkporo Formations from the Lower Benue Trough of Nigeria. A combined method of inductively coupled plasma–mass spectrometry and isotope ratio mass spectrometry was used to investigate trace and rareearth element geochemistry and hydrogen and oxygen isotopic compositions. These data were then used to infer the sediments' provenance and paleoclimatic conditions during their deposition. The sediments contained low concentrations of most trace elements, with the exceptions of Zr(651–1352 ppm), Ba(56–157 ppm), V(38–90 ppm),and Sr(15.1–59.6 ppm). Average values of Co and Ni were1.5 and 0.7 ppm, respectively. Trace and rare earth element values were lower than corresponding values for upper continental crust and Post-Archean Australian Shale, with the exception of Zr. The samples showed only slight light rare-earth enrichment and nearly flat heavy rare-earth depletion patterns, with negative Eu and Tm anomalies,typical of felsic sources. Geochemical parameters such as La/Sc, Th/Sc, and Th/Co ratios support that the kaolinitic sediments were derived from a felsic rock source, likely deposited in an oxic environment.^(18 )O values ranged from+ 15.4 to + 21.2% for the investigated samples, consistent with a residual material derived from chemicalweathering of felsic rock and redeposited in a sedimentary basin(typical values of + 19 to + 21.2%). While in the basin, the sediments experienced extended interactions with meteoric water enriched in d D and d16 O. However,the variation in d D and d16 O values for the investigated samples is attributed to the high temperature of formation(54–91 °C). The d D and d^(18 )O values suggest that the sediments, although obtained from different localities within the Lower Benue Trough, formed under similar hot,tropical climatic conditions.展开更多
Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising...Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.展开更多
Developing highly-active,earth-abundant non-precious-metal catalysts for hydrogen evolution reaction(HER)in alkaline solution would be beneficial to sustainable energy storage.Perovskite oxides are generally regarded ...Developing highly-active,earth-abundant non-precious-metal catalysts for hydrogen evolution reaction(HER)in alkaline solution would be beneficial to sustainable energy storage.Perovskite oxides are generally regarded as low-active HER catalysts,due to their inapposite hydrogen adsorption and water dissociation.Here,we report a detailed study on perovskite LaCoO_(3)epitaxial thin films as a model catalyst to significantly enhance the HER performance via an electrochemical activation process.As a result,the overpotential for the activation films to achieve a current density of 0.36 m A/cm^(2)is 238 m V,reduced by more than 200 m V in comparison with that of original samples.Structural characterization revealed the activation process dramatically increases the concentration of oxygen vacancies(Vo)on the surface of LaCoO_(3).We established the relationship between the electronic structure induced by Vo and the enhanced HER activity.Further theoretical calculations revealed that the Vo optimizes the hydrogen adsorption and dissociation of water on the surface of LaCoO_(3)thin films,thus improving the HER catalytic activity.This work may promote a deepened understanding of perovskite oxides for HER mechanism by Vo adjusting and a new avenue for designing highly active electrochemical catalysts in alkaline solution.展开更多
MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial applicati...MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial application.Herein,2D TiO_(2) nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH_(2)/TiO_(2) heterostructure with enhanced hydrogen storage performances.Particularly,the onset hydrogen desorption temperature of the MgH_(2)/TiO_(2) heterostructure is lowered down to 180℃(295℃ for blank MgH_(2)).The initial desorption rate of MgH_(2)/TiO_(2) reaches 2.116 wt% min^(-1) at 300℃,35 times of the blank MgH_(2) under the same conditions.Moreover,the capacity retention is as high as 98.5% after 100 cycles at 300℃,remarkably higher than those of the previously reported MgH_(2)-TiO_(2) composites.Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species,accelerated electron transportation caused by oxygen vacancies,formation of catalytic Mg-Ti oxides,and stabilized MgH_(2) NPs confined by TiO_(2) nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite.The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.展开更多
A gold tube simulation device was used to study the cleavage of representative compounds into gas.The goal of this study is to investigate hydrogen isotope composition change of gaseous hydrocarbons during maturity.Ga...A gold tube simulation device was used to study the cleavage of representative compounds into gas.The goal of this study is to investigate hydrogen isotope composition change of gaseous hydrocarbons during maturity.Gas chromatography and isotopic analyses were conducted to determine how the yield of natural gas components and their hydrogen isotopic composition were related to experimental temperature and heating rate.A chemical kinetic model for the generation of each component of the natural gas and for the hydrogen isotopic fractionation was established and calibrated based on the results.Results indicate that the hydrogen isotopic fractionation during the evolution of various gas-forming organic materials can be satisfactorily described by chemical kinetic models.During regular methane generation,the reactions at low-activation-energy region had a greater contribution than the high-activation-energy region.While the reactions with high-activation-energy region had greater contribution of deuterium-rich methane.Compared with carbon isotope fractionation,this results in a greater hydrogen isotopic fractionation,which is more sensitive to changes in maturity.This study lays a foundation for further investigations of genesis and maturity of natural gas provided by hydrogen isotopic fractionation.It also provides fundamental knowledge for investigating the filling history of natural gas reservoir and for identifying.展开更多
基金financially supported by the China Geological Survey (No. 1212011220014)。
文摘According to the hydrochemical characteristics, hydrogen and oxygen isotope characteristics and the ratio of noble gas isotopes of the sandstone aquifer and basalt aquifer, this study calculated the recharge temperature and residence time of groundwater in the Weishan area of Wudalianchi, also calculating the contribution of noble gas components from different sources to the samples. Based on the characteristics of hydrogen and oxygen isotopes and noble gases Xe and Ne, the recharge altitude and recharge temperature of the two aquifers were estimated, and the recharge temperature fitting with the NGT model as verified, the results showing that the main recharge altitude of groundwater in the region was 500–600 m, the recharge temperature being 2–7°C. He_(eq) and He_(ea) of the samples have been simulated using the OD model, the content of radioactive ~4He in the crust being obtained, the groundwater ages under the two conditions(closed condition and open condition) both being simulated. The results show that groundwater from the sandstone layer water is older than groundwater from the basalt layer. Hydrochemical characteristics and noble gas isotope ratios indicate that in the basalt aquifer and sandstone aquifer in the Weishan area, in addition to atmospheric and crustal helium, there is also an input of mantle-derived helium. The fault constitutes the uplift channel for groundwater containings mantle components, which results in the mantle source composition in water samples near the fault being much higher than those form non-fault areas.
基金supported by the National Natural Science Foundation of China(Grants No.41672225 and 41222020)the Program of the China Geology Survey(Grant No.12120113103700)the Fundamental Research Funds for the Central Universities(Grant No.2652013028)
文摘Isotopic and chemical compositions of pore water(PW) are highly relevant to environmental and forensic study. Five lake water(LW)samples and five sediment samples were collected to investigate the effects of pore sizes of sediments on PW chemistry and stable isotopes and determine mechanisms controlling their variations. Six pore water fractions were extracted from different-sized pores in each sediment sample at six sequential centrifugal speeds for chemical and isotopic analysis. The sediments consisted mainly of quartz, feldspar, and clay minerals. The hydrogen and oxygen isotopic compositions of PW are mainly controlled by the overlying LW, although the lag effect of exchange between overlying LW and PW results in isotopic differences when recharge of LW is quicker than isotopic exchange in PW. Identical isotopic compositions of PW from sediments with different pore sizes indicate that isotopic exchange of water molecules with different pore sizes is a quick process. The ratio of average total dissolved solid(TDS) concentration of PW to TDS concentration of LW shows a strong relationship with adsorption capacity of sediments, demonstrating that remobilization of ions bound to sediments mainly causes a chemical shift from LW to PW.Concentrations of Ca^(2+), Mg^(2+),and Cl^-in PW remain unchanged,while concentrations of Na^+,K^+,and SO_4^(2-) slightly increase with decreasing pore size. Chemical differences of PW from sediments with different pore sizes are governed by ion adsorption properties and surface characteristics of different-si zed particles.
文摘The Ordovician was an important transitional period for global climate and organic evolution,the global was in the flood and glacial,Onganism was extinction(Zhan,2007;Trotter et al.,2008;Axel et al.,2010).Under the
基金jointly supported by the Geological Survey of China (Grant No. 1212011140050)the National Natural Science Foundation of China (Grant No. 41663006)
文摘The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically,it belongs to the Sanjiang Block. Vapor–liquid two-phase fluid inclusions, CO_2-bearing fluid inclusions, and daughter-bearing inclusions were identified in sulfide-rich quartz veins. Microthermometric and Raman spectroscopy studies revealed their types of ore-forming fluids:(1) low-temperature, low-salinity fluid;(2) medium-temperature, low salinity CO_2-bearing; and(3) high-temperature, Fe-rich,high sulfur fugacity. The δ^(18)O values of chalcopyritebearing quartz ranged from 4.96‰ to 5.86‰, with an average of 5.40‰. The δD values of ore-forming fluid in equilibrium with the sulfide-bearing quartz were from-87‰ to-107‰, with an average of-97.86‰. These isotopic features indicate that the ore-forming fluid is a mixing fluid between magmatic fluid and meteoric water.The δ^(34)S values of chalcopyrite ranged from 13.3‰ to15.5‰, with an average of 14.3‰. Sulfur isotope values suggest that the sulfur in the deposit most likely derived from seawater. Various fluid inclusions coexisted in the samples; similar homogenization temperature to different phases suggests that the Badi fluid inclusions might have been captured under a boiling system. Fluid boiling caused by fault activity could be the main reason for the mineral precipitation in the Badi deposit.
基金support from several sources,including the Backbone Teacher Training Program(10912-SJGG2021-04233)the Teaching Reform Project of Chengdu University of Technology(JG2130131)+1 种基金the University-Industry Collaborative Education Project,Ministry of Education,China(22097130210756)National Natural Science Foundation of China(42272129).
文摘The Yueguang gold deposit is located in Fengjia,Xinhua County,Hunan Province,South China.It represents a recently discovered small-scale gold deposit situated in the southwestern region of the Jiangnan Orogenic Belt,west of the Baimashan granitic batholith.In order to discern the characteristics of the ore-formingfluids,the underlying mineralization processes,and establish a foundation for the origin of the Yueguang gold depositfluid inclusion micro-thermometry,as well as quartz hydrogen and oxygen isotope analysis,have been carried out on samples obtained from various stages of mineralization.The hydrothermal miner-alization stages within the Yueguang gold deposit can be categorized into three stages:(i)the barren,pre-ore quartz-pyrite stage(Stage Ⅰ),the quartz-pyrite-gold stage(Stage Ⅱ),and the post-ore quartz-carbonate stage(Stage Ⅲ),with the second stage being the main mineralization stage.Thefluid inclusions identified in samples from the main min-eralization stage can predominantly be described with the NaCl–H_(2)O and CO_(2)–NaCl–H_(2)O systems.These inclusions display homogenization temperatures ranging from 158.8 to 334.9℃,and thefluid salinity ranges from 0.3%to 4.0%(wt.%NaCl equiv.).Laser Raman spectroscopy analysis of individual inclusions further reveals the presence of gas-phases such as CO_(2),CH_(4),and N_(2).Isotopic analysis indicatesδ^(18)Ofluid values ranging from 3.95 to 6.7‰ and δDH_(2)O values ranging from-71.9 to-55.7‰.These results indi-cate that the ore-formingfluid of the Yueguang gold deposit belongs to metamorphic hydrothermalfluids of middle-low temperature and low salinity.In the process of ore formation,gold is transported in the form of Au(HS)2-complexes,with gold deposition being driven byfluid immiscibility.Therefore,the Yueguang gold deposit is categorized as an orogenic gold deposit dominated by metamorphic hydrother-malfluid.It may become a new target for gold exploration in the Baimashan region,central Hunan Province.
基金Support for this study was received from Orient Resources Ltd.in Canada,Wuhan Institute of Technology,China,and College of Earth Sciences,Jilin University,China.
文摘By studying the light isotopic compositions of carbon,oxygen,and hydrogen,combined with previous research results on the ore-forming source of the deposit,the authors try to uncover its metallogenic origin.The δ^(18)O and δ^(13)C isotope signatures of dolomite samples vary between 10.2 and 13.0‰,and between−7.2 and−5.2‰,respectively,implying that the carbon derives from the upper mantle.δD and δ^(18) O of quartz,biotite,and muscovite from diff erent ore veins of the deposit vary between−82 and−59‰,and between 11.6 and 12.4‰,respectively,implying that the metallogenic solutions are mainly magmatic.According to the relevant research results of many isotope geologists,the fractionation degree of hydrogen isotopes increases as the depth to the Earth’s core increases,and the more diff erentiated the hydrogen isotopes are,the lower their values will be.In other words,mantle-derived solutions can have extremely low hydrogen isotope values.This means that the δD‰ value−134 of the pyrrhotite sample numbered SD-34 in this article may indicate mantle-derived oreforming fl uid of the deposit.The formation of the Dashuigou tellurium deposit occurred between 91.71 and 80.19 Ma.
基金the Support Plan Projects of Science and Technology Department of Guizhou Province [No.(2021)YB453]。
文摘Photosynthesis is the most important biochemical reaction on Earth. It has co-evolved and developed with the Earth, driving the biogeochemical cycle of all elements on the planet and serving as the only chemical process in nature that can convert light energy into chemical energy. Some heavy oxygen isotopic(^(18)O) labeling experiments have"conclusively" demonstrated that the oxygen released by photosynthesis comes only from water and are written into textbooks. However, it is not difficult to find that bicarbonate has never been excluded from the direct substrate of photosynthesis from beginning to end during the history of photosynthesis research. No convincing mechanism can be used to explain photosynthetic oxygen evolution solely from water photolysis. The bicarbonate effect, the Dole effect, the thermodynamic convenience of bicarbonate photolysis, the crystal structure characteristics of photosystem Ⅱ, and the reinterpretation of heavy oxygen isotopic labeling(^(18)O)experiments all indicate that the photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis. The recently proposed view that bicarbonate photolysis is the premise of water photolysis, bicarbonate photolysis and water photolysis work together with a 1:1(mol/mol) stoichiometric relationship, and the stoichiometric relationship between oxygen and carbon dioxide released during photosynthetic oxygen evolution is also 1:1, has excellent applicability and objectivity, which can logically and reasonably explain the precise coordination between light and dark reactions during photosynthesis, the bicarbonate effect, the Dole effect, the Kok cycle and the neutrality of water and carbon in nature.This is of great significance for constructing the bionic artificial photosynthetic reactors and scientifically answering the question of the source of elemental stoichiometric relationships in nature.
基金supported by the National Key Research and Development Program of China(2022YFE03170002)the National Natural Science Foundation of China(52071286 and U2030208)the Scientific Research Fund of Zhejiang Provincial Education Department(Y202353551).
文摘Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.
基金financially supported by the project entitled 1∶50000 Regional Geological Survey of Samaki,Yinmin,Guicheng,and Shugu Sheets in Yunnan Province(D201905)organized by the Land and Resources Department of Yunnan ProvinceTraining Object Project of technological innovation talents in Yunnan Province(202205AD160073)+2 种基金the project entitled“1∶50000 Regional Geological Survey of Dazhuang,Fabiao,Ditu,and Dianzhong Sheets in Yunnan Province”(S53A00722001048-007)“Joint Foundation Project between Yunnan Science and Technology Department and Yunnan University”(CY21624103)the project entitled“Area Summary and Service Product Development of Regional Geological Surveys in Yunnan Province”initiated by the China Geological Survey(121201102000150012-02)。
文摘The Lomagundi-Jatuli Event(LJE)refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic(2.22-2.06 Ga).Theδ^(13)C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05‰-4.95‰(V-PDB;maximum:4.95‰)in this study,which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group.They are much higher than theδ^(13)C values of marine carbonates(-1.16‰on average).Theδ^(13)C values of other formations in the Paleoproterozoic Yimen Group are negative.The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block,which is reported for the first time.Furthermore,they are comparable to theδ^(13)C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton,the Wuzhiling Formation of the Songshan Group in the Xiong'er area,Henan Province,and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area,Liaoning Province.Therefore,it can be further concluded that the LJE is a global event.This study reveals that LJE occurred in Central Yunnan at 2.15-2.10 Ga,lasting for about 50 Ma.The macro-columnar,bean-shaped,and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group.They are the direct cause for the LJE and are also the oldest paleontological fossils ever found.The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event(first occurrence),the global Superiortype banded iron formations(BIFs),the Huronian glaciation,the Great Oxygenation Event(second occurrence),the explosion of multicellular eukaryotes,the positive carbon isotope excursion,and the global anoxic and selenium-rich sedimentary event.The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.
基金The Impact and Response of Antarctic Seas to Climate Change under contract Nos IRASCC 02-01-01 and IRASCC 01-01-02Cthe National Natural Science Foundation of China under contract No.41721005.
文摘In this study,the nitrogen and oxygen isotope compositions of nitrite in the upper 150 m water column of the Amundsen Sea in the summer of 2019 and 2020 were measured to reveal the distribution and transformation of nitrite in the euphotic zone of the Southern Ocean.We found that primary nitrite maxima(PNMs)are widely present in the Amundsen Sea,where the depth of occurrence deepens from east to west and nitrite concentrations increases.Evidence from dual isotopes suggests that the formation of PNMs in all regions of the Amundsen Sea is dominated by ammonia oxidation.More importantly,the nitrogen and oxygen isotope compositions of nitrite in the Amundsen Sea mixed layer are abnormal,and their depth profiles are mirror symmetrical.Isotopic anomalies exhibit spatial variations,with central surface water having the lowest nitrogen isotope composition(−89.9‰±0.2‰)and western surface water having the highest oxygen isotope composition(63.3‰±0.3‰).Isotopic exchange reaction between nitrate and nitrite is responsible for these isotope anomalies,as both nitrogen and oxygen isotopes have large isotopic fractionation and opposite enrichment effects.This proves that isotopic exchange reaction operates extensively in different regions of the Amundsen Sea.Our study highlights the unique role of dual isotopes of nitrite in deepening the understanding of nitrogen cycle.Further studies on ammonia oxidation and isotopic exchange between nitrate and nitrite are warranted in the future to understand their roles in the nitrogen cycle in the Southern Ocean.
基金funding support from the National Natural Science Foundation of China(2200206852272222,and 52072197)+12 种基金the Taishan Scholar Young Talent Program(tsqn201909114)the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(2019KJC004)the Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)the Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09Youth Innovation Team Development Program of Shandong Higher Education Institutions(2022KJ155)the Major Scientific and Technological Innovation Project(2019JZZY020405)the Shandong Province“Double-Hundred Talent Plan”(WST2020003)Project funded by the China Postdoctoral Science Foundation(2021M691700)the Natural Science Foundation of Shandong Province of China(ZR2019BB002ZR2018BB031)the Postdoctoral Innovation Project of Shandong Province(SDCXZG-202203021)the Scientific and Technological Innovation Promotion Project for Small-medium Enterprises of Shandong Province(2022TSGC1257)the Major Research Program of Jining City(2020ZDZP024)。
文摘Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.
基金supported by the National Natural Science Foundation of China(50979065,51109154 and 51249002)the Natural Science Foundation of Shanxi Province,China(2012021026-2)+2 种基金the Program for Science and Technology Development of Shanxi Province,China(20110311018-1)the Specialized Research Fund for the Doctoral Program of Higher Education,China(20111402120006,20121402110009)the Program for Graduate Student Education and Innovation of Shanxi Province,China(2015BY27)
文摘Crop root system plays an important role in the water cycle of the soil-plant-atmosphere continuum.In this study,combined isotope techniques,root length density and root cell activity analysis were used to investigate the root water uptake mechanisms of winter wheat(Triticum aestivum L.)under different irrigation depths in the North China Plain.Both direct inference approach and multisource linear mixing model were applied to estimate the distribution of water uptake with depth in six growing stages.Results showed that winter wheat under land surface irrigation treatment(T_s)mainly absorbed water from 10-20 cm soil layers in the wintering and green stages(66.9 and 72.0%,respectively);0-20 cm(57.0%)in the jointing stage;0-40(15.3%)and 80-180 cm(58.1%)in the heading stage;60-80(13.2%)and 180-220 cm(35.5%)in the filling stage;and 0-40(46.8%)and 80-100 cm(31.0%)in the ripening stage.Winter wheat under whole soil layers irrigation treatment(T_w)absorbed more water from deep soil layer than T_s in heading,filling and ripening stages.Moreover,root cell activity and root length density of winter wheat under T_w were significantly greater than that of T_s in the three stages.We concluded that distribution of water uptake with depth was affected by the availability of water sources,the root length density and root cell activity.Implementation of the whole soil layers irrigation method can affect root system distribution and thereby increase water use from deeper soil and enhance water use efficiency.
基金supported by the Natural Science Foundation of China(Grant no.41806229)the Ministry of Natural Resources of the People’s Republic of China(Impact and Response of Antarctic Seas to Climate Change,Grant no.IRASCC 02-04-01).
文摘Antarctica’s marginal seas are of great importance to atmosphere-ocean-ice interactions and are sensitive to global climate change.Multiple factors account for the freshwater budget in these regions,including glacier melting,seasonal formation/decay of sea ice,and precipitation.Hydrogen(H)and oxygen(O)isotopes represent useful proxies for determining the distribution and migration of water masses.We analyzed the H and O isotopic compositions of 190 seawater samples collected from the Amundsen Sea during the 34th Chinese Antarctic Research Expedition in 2017/2018.The upper-oceanic structure(<400 m)and freshwater(meteoric water and sea ice melt)distribution in the Amundsen Sea were identified based on conductivity-temperature-depth data and the H and O isotopic composition.Antarctic Surface Water,characterized as cold and fresh with low H and O isotopic ratios,was found distributed mainly in the upper~150 m between the Antarctic Slope Front and Polar Front,where it had been affected considerably by upwelled Upper Circumpolar Deep Water(UCDW)between 68°S and 71°S.A three-endmember(meteoric water,sea ice melt,and Circumpolar Deep Water)mixing model indicated that waters with relatively high proportions(>3%)of freshwater generally lie in the upper~50 m and extend from Antarctica to~65°S in the meridional direction(anomalously low freshwater proportion occurred between 68°S and 71°S).Winter Water mainly occupied the layer between 50 and 150 m south of 71°S in the western Amundsen Sea.The water structure and spatial distribution of freshwater in the upper Amundsen Sea were found influenced mainly by the rates of basal and surficial melting of ice shelves,seasonal alternation of sea ice melt/formation,wind forcing,and regional bathymetry.Owing to the distance between heavy sea ice boundary(HSIB)and ice shelves is much shorter in the western HSIB than the east HSIB,the western part of the heavy sea ice boundary includes a higher proportion of freshwater than the eastern region.This study,which highlighted the distribution and extent of freshwater derived from ice(ice shelves and sea ice)melt,provides important evidence that the offshore drift pathway of cold and fresh Antarctic continental shelf water is likely interrupted by upwelled UCDW in the Amundsen Sea.
基金support from the National Natural Science Foundation of China(No.22005147)Dr.You acknowledges the financial support from the National Key Research and Development Program of China(2021YFA1600800)+1 种基金the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)the Open Research Fund of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST),Ministry of Education(2021JYBKF03).
文摘The electrocatalytic water splitting technology can generate highpurity hydrogen without emitting carbon dioxide,which is in favor of relieving environmental pollution and energy crisis and achieving carbon neutrality.Electrocatalysts can effectively reduce the reaction energy barrier and increase the reaction efficiency.Facet engineering is considered as a promising strategy in controlling the ratio of desired crystal planes on the surface.Owing to the anisotropy,crystal planes with different orientations usually feature facet-dependent physical and chemical properties,leading to differences in the adsorption energies of oxygen or hydrogen intermediates,and thus exhibit varied electrocatalytic activity toward hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this review,a brief introduction of the basic concepts,fundamental understanding of the reaction mechanisms as well as key evaluating parameters for both HER and OER are provided.The formation mechanisms of the crystal facets are comprehensively overviewed aiming to give scientific theory guides to realize dominant crystal planes.Subsequently,three strategies of selective capping agent,selective etching agent,and coordination modulation to tune crystal planes are comprehensively summarized.Then,we present an overview of significant contributions of facet-engineered catalysts toward HER,OER,and overall water splitting.In particular,we highlight that density functional theory calculations play an indispensable role in unveiling the structure–activity correlation between the crystal plane and catalytic activity.Finally,the remaining challenges in facet-engineered catalysts for HER and OER are provided and future prospects for designing advanced facet-engineered electrocatalysts are discussed.
文摘This study evaluated the Cretaceous(Campanian–Maastrichtian) kaolinitic sediments of the Ajali/Mamu and Enugu/Nkporo Formations from the Lower Benue Trough of Nigeria. A combined method of inductively coupled plasma–mass spectrometry and isotope ratio mass spectrometry was used to investigate trace and rareearth element geochemistry and hydrogen and oxygen isotopic compositions. These data were then used to infer the sediments' provenance and paleoclimatic conditions during their deposition. The sediments contained low concentrations of most trace elements, with the exceptions of Zr(651–1352 ppm), Ba(56–157 ppm), V(38–90 ppm),and Sr(15.1–59.6 ppm). Average values of Co and Ni were1.5 and 0.7 ppm, respectively. Trace and rare earth element values were lower than corresponding values for upper continental crust and Post-Archean Australian Shale, with the exception of Zr. The samples showed only slight light rare-earth enrichment and nearly flat heavy rare-earth depletion patterns, with negative Eu and Tm anomalies,typical of felsic sources. Geochemical parameters such as La/Sc, Th/Sc, and Th/Co ratios support that the kaolinitic sediments were derived from a felsic rock source, likely deposited in an oxic environment.^(18 )O values ranged from+ 15.4 to + 21.2% for the investigated samples, consistent with a residual material derived from chemicalweathering of felsic rock and redeposited in a sedimentary basin(typical values of + 19 to + 21.2%). While in the basin, the sediments experienced extended interactions with meteoric water enriched in d D and d16 O. However,the variation in d D and d16 O values for the investigated samples is attributed to the high temperature of formation(54–91 °C). The d D and d^(18 )O values suggest that the sediments, although obtained from different localities within the Lower Benue Trough, formed under similar hot,tropical climatic conditions.
基金supported by the National Natural Science Foundation of China(21421001 , 21573115)the 111 project (B12015)+1 种基金the Fundamental Research Funds for the Central Universities(63185015)the Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering (2017-K13)
文摘Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.
基金funding support by the National Natural Science Foundation of China(Grant No.21872116 and 22075232)the Mobility Program of the Sino-German Center for Research Promotion(Grant No.M-0377)the financial support by National Natural Science Foundation of China(Grant No.21991151,21991150,22021001)。
文摘Developing highly-active,earth-abundant non-precious-metal catalysts for hydrogen evolution reaction(HER)in alkaline solution would be beneficial to sustainable energy storage.Perovskite oxides are generally regarded as low-active HER catalysts,due to their inapposite hydrogen adsorption and water dissociation.Here,we report a detailed study on perovskite LaCoO_(3)epitaxial thin films as a model catalyst to significantly enhance the HER performance via an electrochemical activation process.As a result,the overpotential for the activation films to achieve a current density of 0.36 m A/cm^(2)is 238 m V,reduced by more than 200 m V in comparison with that of original samples.Structural characterization revealed the activation process dramatically increases the concentration of oxygen vacancies(Vo)on the surface of LaCoO_(3).We established the relationship between the electronic structure induced by Vo and the enhanced HER activity.Further theoretical calculations revealed that the Vo optimizes the hydrogen adsorption and dissociation of water on the surface of LaCoO_(3)thin films,thus improving the HER catalytic activity.This work may promote a deepened understanding of perovskite oxides for HER mechanism by Vo adjusting and a new avenue for designing highly active electrochemical catalysts in alkaline solution.
基金the support from the National Natural Science Foundation (No. 52171186)the Science and Technology Commission of Shanghai Municipality under No. 19511108100+1 种基金Shanghai Education Commission “Shuguang” scholar Project (16SG08)the financial support from the Center of Hydrogen Science, Shanghai Jiao Tong University
文摘MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial application.Herein,2D TiO_(2) nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH_(2)/TiO_(2) heterostructure with enhanced hydrogen storage performances.Particularly,the onset hydrogen desorption temperature of the MgH_(2)/TiO_(2) heterostructure is lowered down to 180℃(295℃ for blank MgH_(2)).The initial desorption rate of MgH_(2)/TiO_(2) reaches 2.116 wt% min^(-1) at 300℃,35 times of the blank MgH_(2) under the same conditions.Moreover,the capacity retention is as high as 98.5% after 100 cycles at 300℃,remarkably higher than those of the previously reported MgH_(2)-TiO_(2) composites.Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species,accelerated electron transportation caused by oxygen vacancies,formation of catalytic Mg-Ti oxides,and stabilized MgH_(2) NPs confined by TiO_(2) nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite.The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.
基金the National Natural Science Foundation of China(41672130,41772131)the National Oil and Gas Major Project(2016ZX05061-003-001,2016ZX05029002-002)+1 种基金the Sinopec Scientific and Technological Research Project(P17027-3)the Ministry of Education’s Independent Innovation Fund Project(14CX02224A)for financial support of this study。
文摘A gold tube simulation device was used to study the cleavage of representative compounds into gas.The goal of this study is to investigate hydrogen isotope composition change of gaseous hydrocarbons during maturity.Gas chromatography and isotopic analyses were conducted to determine how the yield of natural gas components and their hydrogen isotopic composition were related to experimental temperature and heating rate.A chemical kinetic model for the generation of each component of the natural gas and for the hydrogen isotopic fractionation was established and calibrated based on the results.Results indicate that the hydrogen isotopic fractionation during the evolution of various gas-forming organic materials can be satisfactorily described by chemical kinetic models.During regular methane generation,the reactions at low-activation-energy region had a greater contribution than the high-activation-energy region.While the reactions with high-activation-energy region had greater contribution of deuterium-rich methane.Compared with carbon isotope fractionation,this results in a greater hydrogen isotopic fractionation,which is more sensitive to changes in maturity.This study lays a foundation for further investigations of genesis and maturity of natural gas provided by hydrogen isotopic fractionation.It also provides fundamental knowledge for investigating the filling history of natural gas reservoir and for identifying.
