Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributi...Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributions of salinity,nutrients [nitrate(NO_(3)^(-)),nitrite,ammonium,and phosphate],and the stable isotopic composition of NO_(3)^(-)(δ^(15)N and δ^(18)O) were used to investigate sources of dissolved inorganic nitrogen(DIN) to Hangzhou B ay.Spatial distributions of nitrate,salinity,and nitrate δ^(18)O indicate that the Qiantang River,the Changjiang River,and nearshore coastal waters may all contribute nitrate to the bay.Based on the isotopic compositions of nitrate in these potential source waters and conservative mixing of nitrate in our study area,we suggest that the NO_(3)^(- )in Hangzhou B ay was likely derived mainly from soils,synthetic N fertilizer,and manure and sewage.End-member modeling indicates that in the upper half of the bay,the Qiantang River was a very important DIN source,possibly contributing more than 50% of DIN in the bay head area.In the lower half of the bay,DIN was sourced mainly from strongly intruding coastal water.DIN coming directly from the Changjiang River made a relatively small contribution to Hangzhou Bay DIN in August 2019.展开更多
Understanding the relationship between forest management and water use efficiency(WUE)is important for evaluating forest adaptability to climate change.However,the effects of thinning and understory removal on WUE and...Understanding the relationship between forest management and water use efficiency(WUE)is important for evaluating forest adaptability to climate change.However,the effects of thinning and understory removal on WUE and its key controlling processes are not well understood,which limits our comprehension of the physiological mechanisms of various management practices.In this study,four forest management measures(no thinning:NT;understory removal:UR;light thinning:LT;and heavy thinning:HT)were carried out in Pinus massoniana plantations in a subtropical region of China.Photosynthetic capacity and needle stable carbon isotope composition(δ^(13)C)were measured to assess instantaneous water use efficiency(WUE_(inst))and long-term water use efficiency(WUE_(i)).Multiple regression models and structural equation modelling(SEM)identified the effects of soil properties and physiological performances on WUE_(inst)and WUE_(i).The results show that WUE_(inst)values among the four treatments were insignificant.However,compared with the NT stand(35.8μmol·mol^(-1)),WUE_(i)values significantly increased to 41.7μmol·mol^(-1)in the UR,50.1μmol·mol^(-1)in the LT and 46.6μmol·mol^(-1)in HT treatments,largely explained by photosynthetic capacity and soil water content.Understory removal did not change physiological performance(needle water potential and photosynthetic capacity).Thinning increased the net photosynthetic rate(A_n)but not stomatal conductance(g_s)or predawn needle water potential(ψ_(pd)),implying that the improvement in water use efficiency for thinned stands was largely driven by radiation interception than by soil water availability.In general,thinning may be an appropriate management measure to promote P.massoniana WUE to cope with seasonal droughts under future extreme climates.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
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
Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well...Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.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
The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)f...The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)fluxes and^(13)C/^(12)C ratio of vegetation,organic matter,and soil gases from no disturbed soils of Chaco Pampean Plain(Argentina)with different soil properties and environmental conditions(PL and PA units).Soil organic decomposition from individual layers was accompanied byδ^(13)C of total organic carbon(δ^(13)C-TOC)values more enriched to depth.δ^(13)C-TOC values in the upper soil profile~ca.0–15 cm were like the plant community of this area(~−33 to−29‰)whileδ^(13)CTOC varied stronger bellow horizon A,till~−24‰.Bothδ^(13)C-TOC and soilδ^(13)C-CO_(2)were similar(~−24 to 26‰)at deeper horizons(~50–60 cm).Toward the superficial layers,δ^(13)C-TOC andδ^(13)C-CO_(2)showed more differences(till~4‰),due influence of the diffusion process.Horizon A layer(~0–20 cm)from both PL and PA units contained the most enrichedδ^(13)C-CO_(2)values(~−15–17‰)because atmospheric CO_(2)permeated the soil air.A simple two-component mixing model between sources(atmosphericδ^(13)C-CO_(2)and soil CO_(2))confirmed that process.Isotopically,CO_(2)fluxes reflected the biodegradation of C3 plants(source),diffusive transport,and CO_(2)exchange(atmosphere/soil).Soil moisture content appeared as a determining factor in the diffusion process and the magnitude of CO_(2)surface emissions(12–60 g·m^(−2)·d^(−1)).That condition was confirmed by CO_(2)diffusion coefficients estimated by air-filled porosity parameters and soil radon gradient model.展开更多
Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and u...Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.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
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
The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetal...The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetallics composed of platinum and transition metals are considered to be promising candidates for this purpose.However,they typically face challenges such as unfavorable intrinsic activity and a propensity for particle aggregation,diminishing their ORR performance.Against this backdrop,we present our findings on a N-doped carbon confined Pt_(3)Co intermetallic doped with p-block metal tin(Pt_(3)Co_(x)Sn_(1-x)/NC).The introduction of Sn induces lattice strain due to its larger atomic size,which leads to the distortion of the Pt_(3)Co lattice structure,while the coupling of carbon polyhedra inhibits the particle aggregation.The optimized Pt_(3)Co_(0.8)Sn_(0.2)/NC catalyst demonstrates an impressive half-wave potential of 0.86 V versus RHE,surpassing both Pt_(3)Co/NC and Pt_(3)Sn/NC catalysts.Moreover,the Pt_(3)Co_(0.8)Sn_(0.2)/NC exhibits a mass-specific activity as high as 1.4 A mg_(Pt)^(-1),ranking it in the top level among the intermetallicsbased ORR electrocatalysts.When further employed as a cathode material in a self-assembled zinc-air battery,it shows stable operation for over 80 h.These results underscore the significant impact of lattice strain engineering through the strategic doping of p-block metal in the carbon-confined Pt_(3)Co intermetallic,thereby enhancing the catalytic efficiency for the ORR.展开更多
Both sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)are considered as promising candidates in grid-level energy storage devices.Unfortunately,the larger ionic radii of K+and Na+induce poor diffusion kineti...Both sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)are considered as promising candidates in grid-level energy storage devices.Unfortunately,the larger ionic radii of K+and Na+induce poor diffusion kinetics and cycling stability of carbon anode materials.Pore structure regulation is an ideal strategy to promote the diffusion kinetics and cyclic stability of carbon materials by facilitating electrolyte infiltration,increasing the transport channels,and alleviating the volume change.However,traditional pore-forming agent-assisted methods considerably increase the difficulty of synthesis and limit practical applications of porous carbon materials.Herein,porous carbon materials(Ca-PC/Na-PC/K-PC)with different pore structures have been prepared with gluconates as the precursors,and the amorphous structure,abundant micropores,and oxygen-doping active sites endow the Ca-PC anode with excellent potassium and sodium storage performance.For PIBs,the capacitive contribution ratio of Ca-PC is 82%at 5.0 mV s^(-1) due to the introduction of micropores and high oxygen-doping content,while a high reversible capacity of 121.4 mAh g^(-1) can be reached at 5 A g^(-1) after 2000 cycles.For SIBs,stable sodium storage capacity of 101.4 mAh g^(-1) can be achieved at 2 A g^(-1) after 8000 cycles with a very low decay rate of 0.65%for per cycle.This work may provide an avenue for the application of porous carbon materials in the energy storage field.展开更多
The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a...The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER catalysts.Here,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER conditions.These selftransformed CO_(3)^(2-)can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeO_(x)^(2-)for enhanced SeO_(x)^(2-)retention,which can accelerate the rate-limiting step for^(*)OOH formation during OER.Relative to CoOOH-SeO_(x)^(2-)with limited SeO_(x)^(2-)residues,CoOOH-CO_(3)^(2-)/SeO_(x)^(2-)with elevated SeO_(x)^(2-)retention by CO_(3)^(2-)regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards OER.This strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.展开更多
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membr...Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.展开更多
Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output t...Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output to 1925×108m3in 2020,making it the fourth largest gas-producing country in the world.Based on 1696 molecular components and carbon isotopic composition data of alkane gas in 70 large gas fields in China,the characteristics of carbon isotopic composition of alkane gas in large gas fields in China were obtained.The lightest and average values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become heavier with increasing carbon number,while the heaviest values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become lighter with increasing carbon number.Theδ^(13)C_(1)values of large gas fields in China range from-71.2‰to-11.4‰(specifically,from-71.2‰to-56.4‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-18.9‰for coal-derived gas,and from-35.6‰to-11.4‰for abiogenic gas).Based on these data,theδ^(13)C_(1)chart of large gas fields in China was plotted.Moreover,theδ^(13)C_(1)values of natural gas in China range from-107.1‰to-8.9‰,specifically,from-1071%o to-55.1‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-13.3‰for coal-derived gas,and from-36.2‰to-8.9‰for abiogenic gas.Based on these data,theδ^(13)C_(1)chart of natural gas in China was plotted.展开更多
Deep mixed oils with secondary alterations have been widely discovered in the Tarim Basin,but current methods based on biomarkers and isotopes to de-convolute mixed oil cannot calculate the exact mixing proportion of ...Deep mixed oils with secondary alterations have been widely discovered in the Tarim Basin,but current methods based on biomarkers and isotopes to de-convolute mixed oil cannot calculate the exact mixing proportion of different end-member oils,which has seriously hindered further exploration of deep hydrocarbons in the study area.To solve this problem,we constructed a novel method based on the carbon isotope(δ13C)of the group components to de-convolute mixed liquid hydrocarbons under the material balance principle.The results showed that the mixed oil in the Tazhong Uplift was dominantly contributed at an average proportion of 68% by an oil end-member with heavier d13C that was believed to be generated from the Cambrian-Lower Ordovician source rocks,whereas the mixed oil in the Tabei Uplift was predominantly contributed at an average proportion of 61% by an oil end-member with lighter d13C that was believed to be generated from the Middle-Upper Ordovician source rocks.This indicates that,on the basis of the detailed description of the distribution of effective source rocks,the proposed method will be helpful in realizing differential exploration and further improving the efficiency of deep liquid hydrocarbon exploration in the Tarim Basin.In addition,compared to traditional δ13C methods for whole oil and individual n-alkanes in de-convoluted mixed oil,the proposed method has a wider range of applications,including for mixed oils with variations in color and density,indicating potential for promoting the exploration of deep complex mixed oils in the Tarim Basin and even around the world.展开更多
Primary productivity in the Antarctic aquatic environment with simple ecosystems is sensitive to climate and environmental fluctuations.We investigatedδ13C values for n-alkanoic acids derived from phototrophic organi...Primary productivity in the Antarctic aquatic environment with simple ecosystems is sensitive to climate and environmental fluctuations.We investigatedδ13C values for n-alkanoic acids derived from phototrophic organisms in a lacustrine sediment core(IIL3)to indicate primary productivity in ponds on Inexpressible Island in the western Ross Sea,Antarctica.Short-chain n-alkanoic acids(C14–C18)were abundant in the IIL3 sediment profile.The carbon isotope ratios of short-chain n-alkanoic acids in the sediment samples and floating microbial mats were similar,indicating that the short-chain n-alkanoic acids in the IIL3 sediment profile predominantly originated from phototrophic organisms.Theδ13C values for the short-chain n-alkanoic acids varied widely through the sediment profile,and 13C-enrichment of n-alkanoic acids was most likely related to high productivity due to carbon-limited conditions caused by enhanced photosynthetic efficiency.Theδ13C values for the n-alkanoic acids changed over the past 3200 years in similar ways to organic proxies for aquatic productivity(n-alkanoic acid and sterol sedimentary fluxes).C16 n-alkanoic acid was enriched in 13C in periods of high aquatic productivity~750–1650 and 3000–3200 a BP but depleted in 13C in periods of relatively low productivity~150–600 and 2500–3000 a BP.The results indicated that carbon isotope ratios of lipids from phototrophic organisms could be used as new proxies to reconstruct paleo-productivity in Antarctic lakes and ponds and therefore improve our understanding of past climate changes.展开更多
Pedogenic carbonates, found extensively in arid and semiarid regions, are important in revealing regional climatic and environmental changes as well as the carbon cycle. In addition, stable carbon and oxygen isotopic ...Pedogenic carbonates, found extensively in arid and semiarid regions, are important in revealing regional climatic and environmental changes as well as the carbon cycle. In addition, stable carbon and oxygen isotopic compositions of pedogenic carbonates have been used to rebuild paleoecology (biomass and vegetation) and to estimate paleotemperature and paleoprecipitation during past geological time. By utilizing the stable carbon and oxygen isotopic compositions (δ13C and (δ18O) of secondary nodules in Ustic Vertisols, this study looked into the climatic and environmental changes in the dry valleys of the Yuanmou Basin, Yunnan Province, in southwestern China. The results showed that during the early Holocene, a warm-humid or hot-humid climate existed in the Yuanmou Basin, but since then fluctuations in climate have occurred, with a dry climate prevailing. A highly significant correlation (r = 0.92, n = 9) between δ13C and δ18O values of carbonates illustrated that there had been a continual shifting between cold-humid and warm-dry climates in southwestern China including the Yuanmou Basin since the early Holocene.展开更多
Zhenjia1 well located in the 2nd salt depression of the Northern Shaanxi Salt Basin(Zhang et al,2013),is the basis potash exploration wells,and its main purpose is marine potash prospection,combining with gas explorat...Zhenjia1 well located in the 2nd salt depression of the Northern Shaanxi Salt Basin(Zhang et al,2013),is the basis potash exploration wells,and its main purpose is marine potash prospection,combining with gas exploration.Drilling completion depth is 3443.6m,展开更多
基金The Zhejiang Provincial Natural Science Foundation of China under contract No.LZ22D060002the Key R&D Program of Zhejiang under contract No.2022C03044the National Key Research and Development Program of China under contract No.2021YFC3101702。
文摘Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributions of salinity,nutrients [nitrate(NO_(3)^(-)),nitrite,ammonium,and phosphate],and the stable isotopic composition of NO_(3)^(-)(δ^(15)N and δ^(18)O) were used to investigate sources of dissolved inorganic nitrogen(DIN) to Hangzhou B ay.Spatial distributions of nitrate,salinity,and nitrate δ^(18)O indicate that the Qiantang River,the Changjiang River,and nearshore coastal waters may all contribute nitrate to the bay.Based on the isotopic compositions of nitrate in these potential source waters and conservative mixing of nitrate in our study area,we suggest that the NO_(3)^(- )in Hangzhou B ay was likely derived mainly from soils,synthetic N fertilizer,and manure and sewage.End-member modeling indicates that in the upper half of the bay,the Qiantang River was a very important DIN source,possibly contributing more than 50% of DIN in the bay head area.In the lower half of the bay,DIN was sourced mainly from strongly intruding coastal water.DIN coming directly from the Changjiang River made a relatively small contribution to Hangzhou Bay DIN in August 2019.
基金supported by the National Key Research and Development Program of China(2016YFD0600201)the National Nonprofit Institute Research Grant of CAF(CAFYBB2017ZB003)+1 种基金the National Natural Science Foundation of China(3187071631670720)。
文摘Understanding the relationship between forest management and water use efficiency(WUE)is important for evaluating forest adaptability to climate change.However,the effects of thinning and understory removal on WUE and its key controlling processes are not well understood,which limits our comprehension of the physiological mechanisms of various management practices.In this study,four forest management measures(no thinning:NT;understory removal:UR;light thinning:LT;and heavy thinning:HT)were carried out in Pinus massoniana plantations in a subtropical region of China.Photosynthetic capacity and needle stable carbon isotope composition(δ^(13)C)were measured to assess instantaneous water use efficiency(WUE_(inst))and long-term water use efficiency(WUE_(i)).Multiple regression models and structural equation modelling(SEM)identified the effects of soil properties and physiological performances on WUE_(inst)and WUE_(i).The results show that WUE_(inst)values among the four treatments were insignificant.However,compared with the NT stand(35.8μmol·mol^(-1)),WUE_(i)values significantly increased to 41.7μmol·mol^(-1)in the UR,50.1μmol·mol^(-1)in the LT and 46.6μmol·mol^(-1)in HT treatments,largely explained by photosynthetic capacity and soil water content.Understory removal did not change physiological performance(needle water potential and photosynthetic capacity).Thinning increased the net photosynthetic rate(A_n)but not stomatal conductance(g_s)or predawn needle water potential(ψ_(pd)),implying that the improvement in water use efficiency for thinned stands was largely driven by radiation interception than by soil water availability.In general,thinning may be an appropriate management measure to promote P.massoniana WUE to cope with seasonal droughts under future extreme climates.
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 support from the Zhejiang Provincial Natural Science Foundation (No.LR22E070001),the National Natural Science Foundation of China (Nos.12275239 and 11975205)the Guangdong Basic and Applied Basic Research Foundation (No.2020B1515120048).
文摘Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.
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Financial support was provided through the Instituto de Geociencias Básicas,Aplicadas y Ambientales de Buenos Aires(IGEBA)and the Instituto de Geocronología y Geología Isotópica(INGEIS),both dependent of the Consejo Nacional de Investigaciones Científi cas y Técnicas(National Council for Scientific and Technological Research),and the Universidad de Buenos Aires(Buenos Aires University)of Argentinasupported by the Agencia Nacional de Promoción Científi ca y Tecnológica(National Agency for Scientific and Technological Promotion)projects PICT2010-0035 and PICT2010-2749。
文摘The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)fluxes and^(13)C/^(12)C ratio of vegetation,organic matter,and soil gases from no disturbed soils of Chaco Pampean Plain(Argentina)with different soil properties and environmental conditions(PL and PA units).Soil organic decomposition from individual layers was accompanied byδ^(13)C of total organic carbon(δ^(13)C-TOC)values more enriched to depth.δ^(13)C-TOC values in the upper soil profile~ca.0–15 cm were like the plant community of this area(~−33 to−29‰)whileδ^(13)CTOC varied stronger bellow horizon A,till~−24‰.Bothδ^(13)C-TOC and soilδ^(13)C-CO_(2)were similar(~−24 to 26‰)at deeper horizons(~50–60 cm).Toward the superficial layers,δ^(13)C-TOC andδ^(13)C-CO_(2)showed more differences(till~4‰),due influence of the diffusion process.Horizon A layer(~0–20 cm)from both PL and PA units contained the most enrichedδ^(13)C-CO_(2)values(~−15–17‰)because atmospheric CO_(2)permeated the soil air.A simple two-component mixing model between sources(atmosphericδ^(13)C-CO_(2)and soil CO_(2))confirmed that process.Isotopically,CO_(2)fluxes reflected the biodegradation of C3 plants(source),diffusive transport,and CO_(2)exchange(atmosphere/soil).Soil moisture content appeared as a determining factor in the diffusion process and the magnitude of CO_(2)surface emissions(12–60 g·m^(−2)·d^(−1)).That condition was confirmed by CO_(2)diffusion coefficients estimated by air-filled porosity parameters and soil radon gradient model.
基金supported by the National Natural Science Foundation of China(No.52171022,No.22105214)Zhejiang Provincial Natural Science Foundation of China(Grant No.LXR22B030001)+3 种基金Fujian Institute of Innovation and Chinese Academy of Sciences.K.C.Wong Education Foundation(GJTD-2019-13)the National Key Research and Development Program of China(2019YFB2203400)Ningbo Yongjiang Talent Introduction Programme(2021A-036-B)NingBo S&T Innovation 2025 Major Special Programme(No:2020z059)and the“111 Project”(B20030).
文摘Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.
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Natural Science Foundation of Jiangsu Province (BK20210735)National Natural Science Foundation of China (52201269, 52302296)+4 种基金Collaborative Innovation Center of Suzhou Nano Science and Technologythe 111 Projectthe Suzhou Key Laboratory of Functional Nano and Soft MaterialsJiangsu Key Laboratory for Carbon-Based Functional Materials & Devicesthe funding from the Gusu leading talent plan for scientific and technological innovation and entrepreneurship (ZXL2022487)。
文摘The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetallics composed of platinum and transition metals are considered to be promising candidates for this purpose.However,they typically face challenges such as unfavorable intrinsic activity and a propensity for particle aggregation,diminishing their ORR performance.Against this backdrop,we present our findings on a N-doped carbon confined Pt_(3)Co intermetallic doped with p-block metal tin(Pt_(3)Co_(x)Sn_(1-x)/NC).The introduction of Sn induces lattice strain due to its larger atomic size,which leads to the distortion of the Pt_(3)Co lattice structure,while the coupling of carbon polyhedra inhibits the particle aggregation.The optimized Pt_(3)Co_(0.8)Sn_(0.2)/NC catalyst demonstrates an impressive half-wave potential of 0.86 V versus RHE,surpassing both Pt_(3)Co/NC and Pt_(3)Sn/NC catalysts.Moreover,the Pt_(3)Co_(0.8)Sn_(0.2)/NC exhibits a mass-specific activity as high as 1.4 A mg_(Pt)^(-1),ranking it in the top level among the intermetallicsbased ORR electrocatalysts.When further employed as a cathode material in a self-assembled zinc-air battery,it shows stable operation for over 80 h.These results underscore the significant impact of lattice strain engineering through the strategic doping of p-block metal in the carbon-confined Pt_(3)Co intermetallic,thereby enhancing the catalytic efficiency for the ORR.
基金The authors are grateful for the financial support provided by the National Natural Science Foundation of China(52362010,52304326,22305055,and 52274297)the Start-up Research Foundation of Hainan University(KYQD(ZR)-23069,20008,23067,and 23073)the specific research fund of the Innovation Platform for Academicians of Hainan Province(YSPTZX202315).
文摘Both sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)are considered as promising candidates in grid-level energy storage devices.Unfortunately,the larger ionic radii of K+and Na+induce poor diffusion kinetics and cycling stability of carbon anode materials.Pore structure regulation is an ideal strategy to promote the diffusion kinetics and cyclic stability of carbon materials by facilitating electrolyte infiltration,increasing the transport channels,and alleviating the volume change.However,traditional pore-forming agent-assisted methods considerably increase the difficulty of synthesis and limit practical applications of porous carbon materials.Herein,porous carbon materials(Ca-PC/Na-PC/K-PC)with different pore structures have been prepared with gluconates as the precursors,and the amorphous structure,abundant micropores,and oxygen-doping active sites endow the Ca-PC anode with excellent potassium and sodium storage performance.For PIBs,the capacitive contribution ratio of Ca-PC is 82%at 5.0 mV s^(-1) due to the introduction of micropores and high oxygen-doping content,while a high reversible capacity of 121.4 mAh g^(-1) can be reached at 5 A g^(-1) after 2000 cycles.For SIBs,stable sodium storage capacity of 101.4 mAh g^(-1) can be achieved at 2 A g^(-1) after 8000 cycles with a very low decay rate of 0.65%for per cycle.This work may provide an avenue for the application of porous carbon materials in the energy storage field.
基金supported by the National Natural Science Foundation of China (22002046 and 22379119)the Qin Chuangyuan High-level Innovative and Entrepreneurial Talent Program of Shaanxi Province (QCYRCXM-2023-045)+1 种基金the Youth Talent Support Program of Xi’an Association for Science and Technology (959202313070)the Young Top-notch Talent Program of Xi’an Jiaotong University (HG6J028)。
文摘The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER catalysts.Here,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER conditions.These selftransformed CO_(3)^(2-)can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeO_(x)^(2-)for enhanced SeO_(x)^(2-)retention,which can accelerate the rate-limiting step for^(*)OOH formation during OER.Relative to CoOOH-SeO_(x)^(2-)with limited SeO_(x)^(2-)residues,CoOOH-CO_(3)^(2-)/SeO_(x)^(2-)with elevated SeO_(x)^(2-)retention by CO_(3)^(2-)regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards OER.This strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)。
文摘Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.
基金Supported by the National Natural Science Foundation of China(41472120)General Project of National Natural Science Foundation of China(42272188)+1 种基金Special Fund of PetroChina and New Energy Branch(2023YQX10101)Petrochemical Joint Fund of Fund Committee(U20B6001)。
文摘Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output to 1925×108m3in 2020,making it the fourth largest gas-producing country in the world.Based on 1696 molecular components and carbon isotopic composition data of alkane gas in 70 large gas fields in China,the characteristics of carbon isotopic composition of alkane gas in large gas fields in China were obtained.The lightest and average values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become heavier with increasing carbon number,while the heaviest values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become lighter with increasing carbon number.Theδ^(13)C_(1)values of large gas fields in China range from-71.2‰to-11.4‰(specifically,from-71.2‰to-56.4‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-18.9‰for coal-derived gas,and from-35.6‰to-11.4‰for abiogenic gas).Based on these data,theδ^(13)C_(1)chart of large gas fields in China was plotted.Moreover,theδ^(13)C_(1)values of natural gas in China range from-107.1‰to-8.9‰,specifically,from-1071%o to-55.1‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-13.3‰for coal-derived gas,and from-36.2‰to-8.9‰for abiogenic gas.Based on these data,theδ^(13)C_(1)chart of natural gas in China was plotted.
基金The authors are grateful for the financial supports provided by the National Science and Technology Major Project of the Ministry of Science and Technology of China(2016ZX04004-004)National Natural Science Foundation of China(41672125)。
文摘Deep mixed oils with secondary alterations have been widely discovered in the Tarim Basin,but current methods based on biomarkers and isotopes to de-convolute mixed oil cannot calculate the exact mixing proportion of different end-member oils,which has seriously hindered further exploration of deep hydrocarbons in the study area.To solve this problem,we constructed a novel method based on the carbon isotope(δ13C)of the group components to de-convolute mixed liquid hydrocarbons under the material balance principle.The results showed that the mixed oil in the Tazhong Uplift was dominantly contributed at an average proportion of 68% by an oil end-member with heavier d13C that was believed to be generated from the Cambrian-Lower Ordovician source rocks,whereas the mixed oil in the Tabei Uplift was predominantly contributed at an average proportion of 61% by an oil end-member with lighter d13C that was believed to be generated from the Middle-Upper Ordovician source rocks.This indicates that,on the basis of the detailed description of the distribution of effective source rocks,the proposed method will be helpful in realizing differential exploration and further improving the efficiency of deep liquid hydrocarbon exploration in the Tarim Basin.In addition,compared to traditional δ13C methods for whole oil and individual n-alkanes in de-convoluted mixed oil,the proposed method has a wider range of applications,including for mixed oils with variations in color and density,indicating potential for promoting the exploration of deep complex mixed oils in the Tarim Basin and even around the world.
基金supported by the National Natural Science Foundation of China (Grant nos. 42276240, 42206243, 41776188)the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant no. XDB40000000)+3 种基金the Shanghai Sailing Program (Grant no. 22YF1418800)the China Postdoctoral Science Foundation (Grant no. 2022M712038)the Shanghai Frontiers Science Center of Polar Science (SCOPS)the Chinese Arctic and Antarctic Administration (CAA) for supporting the project
文摘Primary productivity in the Antarctic aquatic environment with simple ecosystems is sensitive to climate and environmental fluctuations.We investigatedδ13C values for n-alkanoic acids derived from phototrophic organisms in a lacustrine sediment core(IIL3)to indicate primary productivity in ponds on Inexpressible Island in the western Ross Sea,Antarctica.Short-chain n-alkanoic acids(C14–C18)were abundant in the IIL3 sediment profile.The carbon isotope ratios of short-chain n-alkanoic acids in the sediment samples and floating microbial mats were similar,indicating that the short-chain n-alkanoic acids in the IIL3 sediment profile predominantly originated from phototrophic organisms.Theδ13C values for the short-chain n-alkanoic acids varied widely through the sediment profile,and 13C-enrichment of n-alkanoic acids was most likely related to high productivity due to carbon-limited conditions caused by enhanced photosynthetic efficiency.Theδ13C values for the n-alkanoic acids changed over the past 3200 years in similar ways to organic proxies for aquatic productivity(n-alkanoic acid and sterol sedimentary fluxes).C16 n-alkanoic acid was enriched in 13C in periods of high aquatic productivity~750–1650 and 3000–3200 a BP but depleted in 13C in periods of relatively low productivity~150–600 and 2500–3000 a BP.The results indicated that carbon isotope ratios of lipids from phototrophic organisms could be used as new proxies to reconstruct paleo-productivity in Antarctic lakes and ponds and therefore improve our understanding of past climate changes.
基金Project supported by the National Key Basic Research Support Foundation of China (No. G1998040800).
文摘Pedogenic carbonates, found extensively in arid and semiarid regions, are important in revealing regional climatic and environmental changes as well as the carbon cycle. In addition, stable carbon and oxygen isotopic compositions of pedogenic carbonates have been used to rebuild paleoecology (biomass and vegetation) and to estimate paleotemperature and paleoprecipitation during past geological time. By utilizing the stable carbon and oxygen isotopic compositions (δ13C and (δ18O) of secondary nodules in Ustic Vertisols, this study looked into the climatic and environmental changes in the dry valleys of the Yuanmou Basin, Yunnan Province, in southwestern China. The results showed that during the early Holocene, a warm-humid or hot-humid climate existed in the Yuanmou Basin, but since then fluctuations in climate have occurred, with a dry climate prevailing. A highly significant correlation (r = 0.92, n = 9) between δ13C and δ18O values of carbonates illustrated that there had been a continual shifting between cold-humid and warm-dry climates in southwestern China including the Yuanmou Basin since the early Holocene.
基金fuded by National Program on Key Basic Research Project of China-973 Program"Potash formation mechanism,conditions and late evolution in Ordovician ancient epicontinental sea basin,Erdos"(No.2011CB403001)China Geological survey work Program–"Potash resources investigation and evaluation in Northern Shaanxi Ordovician Salt Basin"(No.1212011085516)
文摘Zhenjia1 well located in the 2nd salt depression of the Northern Shaanxi Salt Basin(Zhang et al,2013),is the basis potash exploration wells,and its main purpose is marine potash prospection,combining with gas exploration.Drilling completion depth is 3443.6m,
