Response to the Lomagundi-Jatuli Event in the southwestern margin of the Yangtze Plate:Evidence from the carbon and oxygen isotopes of the Paleoproterozoic Yongjingshao Formation

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.

Stable Carbon and Oxygen Isotopes of Pedogenic Carbonates in Ustic Vertisols: Implications for Paleoenvironmental Change

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.

Characteristics and Implications Significance for Carbon and Oxygen Isotope Continuous Change of Zhenjia1 Well in The Northern Shaanxi Salt Basin

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,

Carbon and oxygen isotope characteristics of foraminiferan from northern South China Sea sediments and their significance to late Quaternary hydrate decomposition

Carbon and oxygen isotope and dating analyses of foraminiferan in sediment cores collected from three different areas of the northern slope of the South China Sea were conducted, in order to examine the records of the gas hydrate decomposition events since the late Quaternary under the conditions of methane seepage. The results show that： 1） the δ13C values of the benthic foraminiferan Uvigerina spp. （size range of 0.25-0.35 ram） are from -0.212% to -0.021% and the δ180 values of the planktonic foraminiferan Globigerinoides ruber （size range of 0.25-0.35 ram） are from -0.311% to -0.060%; 2） three cores （ZD2, ZD3 and ZS5） from the bottom of a hole are aged for 11 814, 26 616 and 64 090 a corresponding to the early oxygen isotope stage （MIS） Ⅰ, Ⅲ and Ⅳ final period, respectively; 3） a negative-skewed layer of carbon isotope corresponds to that of MIS II （cold period）, whose degree of negative bias is -0.2%0; and 4） the δ13C compositions of foraminiferans are similar to those of the Blake Ridge and the Gulf of Mexico sediments of the late Quaternary. According to the analysis, the reasons for these results are that the studied area is a typical area of methane seep environment in the area during MIS II due to the global sea-level fall and sea pressure decrease. Gas hydrate is decomposed and released, and a large number of light carbon isotopes of methane are released into the ocean, dissolved to inorganic carbon （DIC） pool and recorded in the foraminiferan shells. A pyrite layer developed in the negative bias layers of the foraminiferans confirms that the δ13C of foraminiferans is more affected by methane and less by the reduction of marine productivity and early diagenesis. The use of foraminiferan δ13C could accurately determine late Quaternary hydrate release events and provide evidence for both reconstructing the geological history of methane release events and exploring natural gas hydrate.

Fluid Inclusion and Carbon-Oxygen Isotope Studies of the Hujiayu Cu Deposit,Zhongtiao Mountains,China:Implications for Synmetamorphic Copper Remobilization

The Hujiayu Cu deposit,representative of the ＂HuBi-type＂ Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[（Co,Ni）_3S_4],and clausthalite[Pb（S,Se）].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions（type Ⅰ）,low-salinity,liquid-dominated,biphase aqueous inclusions（type Ⅱ）,solid-bearing aqueous inclusions（type Ⅲ）,and solid-bearing aqueous-carbonic inclusions（type Ⅳ）.Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions（type Ⅰa） and biphase CO_2-rich inclusions（with a visible aqueous phase）,and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral（type Ⅲa） and a subtype with multiple solids（type Ⅲb）.Various fluid inclusion assemblages（FIAs） were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions（type Ⅰa）,homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ^（13）C_（V-pdb） values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ^（18）O_（v-smow） values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.

Distribution of Carbon and Oxygen Isotopes in theSequence Stratigraphic Framework of the Middle andUpper Proterozoic in the Ming Tombs Area, Beijing

Abstract: This paper discusses the distribution pattern and geological significance of the carbon and oxygen isotopes (δ13C and δ18O) in the depositional sequences of Gaoyuzhuangian, Yangzhuangian and Wumishanian ages of the established Middle and Upper Proterozoic sequence stratigraphic framework in the Ming Tombs area lying in western Yanshan Mountain of Beijing. Besides, sketchy determination of δ13C and δ18O was also performed for other formations and members. The analytical results show the following: under the condition of clear-water carbonate sediments, δ13C and δ18O, featuring smaller variation of δ13C but larger variation of δ18O, can well delineate the relative change of sea level, which reflects the difference of primary sedimentary settings; in the presence of terrigenous substances, δ13C values vary greatly while δ18O slightly; the carbon and oxygen isotopes show marked changes at sequence boundaries. Besides, particular patterns can be found in regard to the distribution of carbon and oxygen isotopes within the sequences.

Estimation of Residence Times and Recharge Area of Groundwater in the Moulares Mining Basin by Using Carbon and Oxygen Isotopes (South Western Tunisia)

Radiogenic carbon (14C) of the DIC (Dissolved Inorganic Carbon) and oxygen-18 were used to understand the hydro- dynamic functioning of the multilayer aquifer system in the Moulares mining basin, southern Tunisia. The results of this study permits identify two groundwater types. A- an old paleoclimatic groundwater, marked by low carbon-14 (14C) activities. B - a recent groundwater, was distinguished by relatively high carbon-14 activities. In addition to these two water types, other groundwater, indicating a mixing effect, is resulting presumably from upward movement from the deeper groundwater. Based on 14C activity and the piston flow type theory the groundwater residence time varies from 5 Kyear to 35 Kyear. Carbon-14 activity and oxygen-18 in Groundwater are active since Mio-Plio-Quaternary and Upper Cretaceous aquifers lead to the identification of paleorecharged water probably during Late Pleistocene and Early to Middle Holocene. The water feedings of these aquifers are mainly provided by infiltration of precipitations, infiltration of irrigation water, lateral feeding from cretaceous relieves from the South and the North and along recent and fossil drainage networks that constitute major fresh water sources in groundwater tables.

The photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis

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.

Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

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.

Carbon and oxygen isotopes suggesting deep-water basin deposition associated with hydrothermal events(Shangsi Section, Northwest Sichuan Basin-South China)

Carbon and oxygen isotope records for Shangsi Section in Northwest Sichuan Basin, South China can help investigating depositional environments and processes, including the burial rate and possible contribution of hydrothermal events. Samples from the lower Chihsian Formation show δ13CPDB and δ18OPDB values close to those of typical marine limestone. However, the overlying Permian middle-upper Chihsian, Wujiaping, and Maokou Formation samples reveal negative δ18OSMOW values and strong positive δ13CPDB values. These indicate high biological productivity and rapid burial of organic carbon. Samples from the Dalong Formation present both negative δ13CPDB and negative δ18OPDB values, which are quite different from the underlying Permian strata. These abnormal carbon and oxygen isotope characteristics in the Dalong Formation may suggest that hydrothermal processes contributed to deposition.

Research on carbon and oxygen isotopes in phosphorus-bearing rock series of the Late Neoproteroic-Early Cambrian Taozichong Formation in Qingzhen City, Guizhou Province, Southwest China

In the study of the phosphate-bearing stratum at the bottom of the Cambrian system, the authors found that there occurred carbon isotope negative anomalies in the Taozichong section phosphate-bearing stratum in Qingzhen, Guizhou Province; they can be correspondingly compared with other synsedimentary carbon isotope negative anomalies both at home and abroad. The results showed that there occurred three negative anomalies of carbon isotopes in the Neoproterozoic-Early Cambrian Taozichong Formation, indicating that the temporal palaeo-oceanographical environment changed significantly, in which there happened two times of intensive carbon isotope variation, corresponding to creature extinction. Meanwhile, it is believed that the carbon isotope negative anomalies in phosphorites were caused by the ascending water mass of ocean current with the negative carbon isotopic composition of deep-ocean hydrothermal deposits.

Co/CoO heterojunction rich in oxygen vacancies introduced by O_(2) plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

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.

Tracing nitrate sources in one of the world's largest eutrophicated bays(Hangzhou Bay):insights from nitrogen and oxygen isotopes

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.

The Geochemical Characteristics of Stable Carbon and Oxygen Isotope and Analysis of Diagenetic Environment --A Case Study of Upper Permian Changxing Formation Dolostone in Northeast of Sichuan

四川盆地东北部上二叠统长兴组白云岩为重要的优质储层,近年来,长兴组白云岩成岩环境或成因问题成为研究者讨论的热点话题。在岩石学研究的基础上,运用稳定碳、氧同位素,对研究区长兴组白云岩进行综合研究表明,白云石化具有多期次的特点,按照成岩环境划分为蒸发环境下的准同生白云岩和埋藏条件下的早、中、晚期成岩白云岩。并划分为早、中、晚成岩阶段,结合碳、氧同位素分析结果进一步表明晚成岩阶段白云岩是构造热液白云石化的结果。

Unveiling the chemistry behind the electrolytic production of hydrogen peroxide by oxygenated carbon

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.

Tin-mediated carbon-confined Pt_(3)Co ordered intermetallic nanoparticles as highly efficient and durable oxygen reduction electrocatalysts for rechargeable zinc-air batteries

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.

Pore structure and oxygen content design of amorphous carbon toward a durable anode for potassium/sodium-ion batteries

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.

Calcium titanate corrosion inhibitor enabling carbon as inert anode for oxygen evolution in molten chlorides

The corrosion inhibition efficacy of titanate(CaTiO_(3))for carbon anodes in molten salts was investigated through various analytical techniques,including linear sweep voltammetry,X-ray diffraction,scanning electron microscopy,and energy dispersion spectroscopy.The results demonstrate that the addition of CaTiO_(3)corrosion inhibitor efficiently passivates the carbon anode and leads to the formation of a dense CaTiO_(3)layer during the electrolysis process in molten CaCl_(2)-CaO.Subsequently,the passivated carbon anode effectively undergoes the oxygen evolution reaction,with an optimal current density for passivation identified at 400 m A/cm~2.Comprehensive investigations,including CaTiO_(3)solubility tests in molten CaCl_(2)-CaO and numerical modeling of the stability of complex ionic structures,provide compelling evidence supporting“complexation-precipitation”passivation mechanism.This mechanism involves the initial formation of a complex containing TiO_(2)·nCaO by CaTiO_(3)and CaO,which subsequently decomposes to yield CaTiO_(3),firmly coating the surface of the carbon anode.In practical applications,the integration of CaTiO_(3)corrosion inhibitor with the carbon anode leads to the successful preparation of the FeCoNiCrMn high-entropy alloy without carbon contamination in the molten CaCl_(2)-Ca O.

Retaining the self-released chalcogenate at reconstructed cobalt sites by self-transformed carbonate regulation for boosted oxygen evolution

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.