Catalytically altering the redox pathway of sulfur in propylene carbonate electrolyte using dual-nitrogen/oxygen-containing carbon

Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries(LSBs)because of their successful implementation in commercial Li-ion batteries.The low-polysulfide-solubility feature of some carbonate solvents also makes them very promising for overcoming the shuttle effects of LSBs.However,regular sulfur electrodes experience undesired electrochemical mechanisms in carbonate electrolytes due to side reactions.In this study,we report a catalytic redox mechanism of sulfur in propylene carbonate(PC)electrolyte based on a compari-son study.The catalytic mechanism is characterized by the interactions between polysulfides and dual N/O functional groups on the host carbon,which largely prevents side reactions between polysulfides and the carbonate electrolyte.Such a mechanism coupled with the low-polysulfide-solubility feature leads to stable cycling of LSBs in PC electrolyte.Favorable dual N/O functional groups are identified via a density functional theory study.This work provides an alternative route for enabling LSBs in carbonate electrolytes.

Effect of drying-wetting cycles on pore characteristics and mechanical properties of enzyme-induced carbonate precipitation-reinforced sea sand

Enzyme-induced carbonate precipitation(EICP)is an emanating,eco-friendly and potentially sound technique that has presented promise in various geotechnical applications.However,the durability and microscopic characteristics of EICP-treated specimens against the impact of drying-wetting(D-W)cycles is under-explored yet.This study investigates the evolution of mechanical behavior and pore charac-teristics of EICP-treated sea sand subjected to D-W cycles.The uniaxial compressive strength(UCS)tests,synchrotron radiation micro-computed tomography(micro-CT),and three-dimensional(3D)recon-struction of CT images were performed to study the multiscale evolution characteristics of EICP-reinforced sea sand under the effect of D-W cycles.The potential correlations between microstructure characteristics and macro-mechanical property deterioration were investigated using gray relational analysis(GRA).Results showed that the UCS of EICP-treated specimens decreases by 63.7% after 15 D-W cycles.The proportion of mesopores gradually decreases whereas the proportion of macropores in-creases due to the exfoliated calcium carbonate with increasing number of D-W cycles.The micro-structure in EICP-reinforced sea sand was gradually disintegrated,resulting in increasing pore size and development of pore shape from ellipsoidal to columnar and branched.The gray relational degree suggested that the weight loss rate and UCS deterioration were attributed to the development of branched pores with a size of 100-1000 m m under the action of D-W cycles.Overall,the results in this study provide a useful guidancee for the long-term stability and evolution characteristics of EICP-reinforced sea sand under D-W weathering conditions.

Impact of effective stress on permeability for carbonate fractured-vuggy rocks

To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of effective stress on permeability for carbonate fractured-vuggy rocks(CFVR).It shows that the permeability performance curves under different pore and confining pressures(i.e.altered stress conditions)for the fractured core models and the vuggy core models have similar change patterns.The ranges of permeability variation are significantly wider at high pore pressures,indicating that permeability reduction is the most significant during the early stage of development for fractured-vuggy reservoirs.Since each obtained effective stress coefficient for permeability(ESCP)varies with the changes in confining pressure and pore pressure,the effective stresses for permeability of four representative CFVR show obvious nonlinear characteristics,and the variation ranges of ESCP are all between 0 and 1.Meanwhile,a comprehensive ESCP mathematical model considering triple media,including matrix pores,fractures,and dissolved vugs,was proposed.It is proved theoretically that the ESCP of CFVR generally varies between 0 and 1.Additionally,the regression results showed that the power model ranked highest among the four empirical models mainly applied in stress sensitivity characterization,followed by the logarithmic model,exponential model,and binomial model.The concept of“permeability decline rate”was introduced to better evaluate the stress sensitivity performance for CFVR,in which the one-fracture rock is the strongest,followed by the fracture-vug rock and two-horizontalfracture rock;the through-hole rock is the weakest.In general,this study provides a theoretical basis to guide the design of development and adjustment programs for carbonate fractured-vuggy reservoirs.

An experimental study on horizontal well waterflooding in the Cretaceous porous carbonate reservoir of Oman

Porous carbonate reservoirs,prevalent in the Middle East,are lithologically dominated by bioclastic limestones,exhibiting high porosity,low permeability,intricate pore structure,and strong heterogeneity.Waterflooding through horizontal wells is commonly used for exploiting these reservoirs.However,challenges persist,such as significant uncertainty and complex operational procedures regarding adjustment effects during the exploitation.The USH reservoir of the Cretaceous D oilfield,Oman exemplifies typical porous carbonate reservoirs.It initially underwent depletion drive using vertical wells,followed by horizontal well waterflooding in the late stage.Currently,the oilfield is confronted with substantial developmental challenges,involving the understanding of residual oil distribution,effective water cut control,and sustaining oil production since it has entered the late development stage.Employing a microscopic visualization displacement system equipped with electrodes,this study elucidated the waterflooding mechanisms and residual oil distribution in the late-stage development of the USH reservoir.The results reveal that the reservoir's vertical stacking patterns act as the main factor affecting the horizontal well waterflooding efficacy.Distinct water flow channels emerge under varying reservoir stacking patterns,with post-waterflooding residual oil predominantly distributed at the reservoir's top and bottom.The oil recovery can be enhanced by adjusting the waterflooding's flow line and intensity.The findings of this study will provide theoretical insights of waterflooding mechanisms and injection-production adjustments for exploiting other porous carbonate reservoirs in the Middle East through horizontal wells.

Method for evaluation of geological strength index of carbonate cliff rocks:Coupled hyperspectral-digital borehole image technique

The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and characteristics of discontinuities.It ignores the influence of mineral composition and shows a deficiency in assessing the integrity coefficient.In this context,hyperspectral imaging and digital panoramic borehole camera technologies are applied to analyze the mineral content and integrity of rock mass.Based on the carbonate mineral content and fissure area ratio,the strength reduction factor and integrity coefficient are calculated to improve the GSI evaluation method.According to the results of mineral classification and fissure identification,the strength reduction factor and integrity coefficient increase with the depth of rock mass.The rock mass GSI calculated by the improved method is mainly concentrated between 40 and 60,which is close to the calculation results of the traditional method.The GSI error rates obtained by the two methods are mostly less than 10%,indicating the rationality of the hyperspectral-digital borehole image coupled evaluation method.Moreover,the sensitivity of the fissure area ratio(Sr)to GSI is greater than that of the strength reduction factor(a),which means the proposed GSI is suitable for rocks with significant fissure development.The improved method reduces the influence of subjective factors and provides a reliable index for the deterioration evaluation of rock mass.

Hydrocarbon accumulation and orderly distribution of whole petroleum system in marine carbonate rocks of Sichuan Basin,SW China

Based on the situation and progress of marine oil/gas exploration in the Sichuan Basin,SW China,the whole petroleum system is divided for marine carbonate rocks of the basin according to the combinations of hydrocarbon accumulation elements,especially the source rock.The hydrocarbon accumulation characteristics of each whole petroleum system are analyzed,the patterns of integrated conventional and unconventional hydrocarbon accumulation are summarized,and the favorable exploration targets are proposed.Under the control of multiple extensional-convergent tectonic cycles,the marine carbonate rocks of the Sichuan Basin contain three sets of regional source rocks and three sets of regional cap rocks,and can be divided into the Cambrian,Silurian and Permian whole petroleum systems.These whole petroleum systems present mainly independent hydrocarbon accumulation,containing natural gas of affinity individually.Locally,large fault zones run through multiple whole petroleum systems,forming a fault-controlled complex whole petroleum system.The hydrocarbon accumulation sequence of continental shelf facies shale gas accumulation,marginal platform facies-controlled gas reservoirs,and intra-platform fault-and facies-controlled gas reservoirs is common in the whole petroleum system,with a stereoscopic accumulation and orderly distribution pattern.High-quality source rock is fundamental to the formation of large gas fields,and natural gas in a whole petroleum system is generally enriched near and within the source rocks.The development and maintenance of large-scale reservoirs are essential for natural gas enrichment,multiple sources,oil and gas transformation,and dynamic adjustment are the characteristics of marine petroleum accumulation,and good preservation conditions are critical to natural gas accumulation.Large-scale marginal-platform reef-bank facies zones,deep shale gas,and large-scale lithological complexes related to source-connected faults are future marine hydrocarbon exploration targets in the Sichuan Basin.

The Response of Carbonate System to Watershed Urbanization Process in a Semi-Arid River

Different from rivers in humid areas,the variability of riverine CO_(2) system in arid areas is heavily impacted by anthropogenic disturbance with the increasing urbanization and water withdrawals.In this study,the water chemistry and the controls of carbonate system in an urbanized river(the Fenhe River)on the semi-arid Loess Plateau were analyzed.The water chemistry of the river water showed that the high dissolved inorganic carbon(DIC)concentration(about 37 mg L^(-1))in the upstream with a karst land type was mainly sourced from carbonate weathering involved by H_(2)CO_(3) and H_(2)SO_(4),resulting in an oversaturated partial pressure of CO_(2)(pCO_(2))(about 800μatm).In comparison,damming resulted in the widespread appearance of non-free flowing river segments,and aquatic photosynthesis dominated the DIC and pCO_(2) spatiality demonstrated by the enriched stable isotope of DIC(δ^(13)CDIC).Especially in the mid-downstream flowing through major cities in warm and low-runoff August,some river segments even acted as an atmospheric CO_(2) sink.The noteworthy is wastewater input leading to a sudden increase in DIC(>55 mg L^(-1))and pCO_(2)(>4500μatm)in the downstream of Taiyuan City,and in cold November the increased DIC even extended to the outlet of the river.Our results highlight the effects of aquatic production induced by damming and urban sewage input on riverine CO_(2) system in semi-arid areas,and reducing sewage discharge may mitigate CO_(2) emission from the rivers.

Tailoring the microenvironment of Ti sites in Ti-containing materials for synergizing with Au sites to boost propylene epoxidation

Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

Mechanical Property and Microstructure of Cement Mortar with Carbonated Recycled Powder

Carbonated recycled powder as cementitious auxiliary material can reduce carbon emissions and realize high-quality recycling of recycled concrete.In this paper,microscopic property of recycled powder with three carbonation methods was tested through XRD and SEM,the mechanical property and microstructure of recycled powder mortar with three replacement rates were studied by ISO method and SEM,and the strengthening mechanism was analyzed.The results showed that the mechanical property of recycled powder mortar decreased with the increasing of replacement rate.It is suggested that the replacement rate of recycled powder should not exceed 20%.The strength index and activity index of carbonated recycled powder mortar were improved,in which the flexural strength was increased by 27.85%and compressive strength was increased by 20%at the maximum.Recycled powder can be quickly and completely carbonated,and the improvement effect of CH pre-soaking carbonation was the best.The activity index of carbonated recycled powder can meet the requirements of Grade II technical standard for recycled powder.Microscopic results revealed the activation mechanism of carbonated recycled powder such as surplus calcium source effect,alkaline polycondensation effect and carbonation enhancement effect.

Carbonation of Dicalcium Silicate Enhanced by Ammonia Bicarbonate and Its Mechanism

The strength development law of γ-type dicalcium silicate (γ-C_(2)S) under different carbonation processes was investigated,and the carbonation mechanism of γ-C_(2)S under the action of NH_(4)HCO_(3) was clarified by using a wide range of test methods,including XRD and SEM.A method of saturated NH_(4)HCO_(3) solution as a curing agent was identified to improve the carbonation efficiency and enhance the carbonation degree of γ-C_(2)S,and then a high-strength carbonated specimen was obtained.Microhardness analysis and SEM morphology analysis were conducted on the carbonised specimens obtained under atmospheric pressure carbonisation conditions using the curing agent.It was found that γ-C_(2)S could perform carbonisation well under atmospheric pressure,which promoted the carbonisation efficiency and decreased the carbonisation cost simultaneously.Therefore,a new carbonisation process solution was proposed for the rapid carbonisation of γ-C_(2)S.

Catalytic Reaction Kinetics of Propylene Dimerization to 4-Methyl-1-Pentene Using Cu-K/K_(2)CO_(3) Solid Base Catalyst

The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.

Highly dispersed MgInCe-mixed metal oxides catalyzed direct carbonylation of glycerol and CO_(2)into glycerol carbonate

Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.

A general descriptor for guiding the electrolysis of CO_(2)in molten carbonate

Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.

Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.

Sedimentary build-ups of pre-salt isolated carbonate platforms and formation of deep-water giant oil fields in Santos Basin,Brazil

In response to the problems of unclear distribution of deep-water pre-salt carbonate reservoirs and formation conditions of large oil fields in the Santos passive continental margin basin,based on comprehensive utilization of geological,seismic,and core data,and reconstruction of Early Cretaceous prototype basin and lithofacies paleogeography,it is proposed for the first time that the construction of pre-salt carbonate build-ups was controlled by two types of isolated platforms:inter-depression fault-uplift and intra-depression fault-high.The inter-depression fault-uplift isolated platforms are distributed on the present-day pre-salt uplifted zones between depressions,and are built on half-and fault-horst blocks that were inherited and developed in the early intra-continental and inter-continental rift stages.The late intra-continental rift coquinas of the ITP Formation and the early inter-continental rift microbial limestones of the BVE Formation are continuously constructed;intra-depression fault-high isolated platforms are distributed in the current pre-salt depression zones,built on the uplifted zones formed by volcanic rock build-ups in the early prototype stage of intra-continental rifts,and only the BVE microbial limestones are developed.Both types of limestones formed into mound-shoal bodies,that have the characteristics of large reservoir thickness and good physical properties.Based on the dissection of large pre-salt oil fields discovered in the Santos Basin,it has been found that both types of platforms could form large-scale combined structural-stratigraphic traps,surrounded by high-quality lacustrine and lagoon source rocks at the periphery,and efficiently sealed by thick high-quality evaporite rocks above,forming the optimal combination of source,reservoir and cap in the form of“lower generation,middle storage,and upper cap”,with a high degree of oil and gas enrichment.It has been found that the large oil fields are all bottom water massive oil fields with a unified pressure system,and they are all filled to the spill-point.The future exploration is recommended to focus on the inter-depression fault-uplift isolated platforms in the western uplift zone and the southern section of eastern uplift zones,as well as intra-depression fault-high isolated platforms in the central depression zone.The result not only provides an important basis for the advanced selection of potential play fairways,bidding of new blocks,and deployment of awarded exploration blocks in the Santos Basin,but also provides a reference for the global selection of deep-water exploration blocks in passive continental margin basins.

Effects of Different Concentrations of Sulfate Ions on Carbonate Crude Oil Desorption:Experimental Analysis and Molecular Simulation

Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.

Efficient C-N coupling in electrocatalytic urea generation on copper carbonate hydroxide electrocatalysts

Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.

Experimental investigation into the salinity effect on the physicomechanical properties of carbonate saline soil

For engineering structures with saline soil as a filling material,such as channel slope,road subgrade,etc.,the rich soluble salt in the soil is an important potential factor affecting their safety performance.This study examines the Atterberg limits,shear strength,and compressibility of carbonate saline soil samples with different NaHCO3 contents in Northeast China.The mechanism underlying the influence of salt content on soil macroscopic properties was investigated based on a volumetric flask test,a mercury intrusion porosimetry(MIP)test,and a scanning electron microscopic(SEM)test.The results demonstrated that when NaHCO3 contents were lower than the threshold value of 1.5%,the bound water film adsorbed on the surface of clay particles thickened continuously,and correspondingly,the Atterberg limits and plasticity index increased rapidly as the increase of sodium ion content.Meanwhile,the bonding force between particles was weakened,the dispersion of large aggregates was enhanced,and the soil structure became looser.Macroscopically,the compressibility increased and the shear strength(mainly cohesion)decreased by 28.64%.However,when the NaHCO3 content exceeded the threshold value of 1.5%,the salt gradually approached solubility and filled the pores between particles in the form of crystals,resulting in a decrease in soil porosity.The cementation effect generated by salt crystals increased the bonding force between soil particles,leading to a decrease in plasticity index and an improvement in soil mechanical properties.Moreover,this work provides valuable suggestions and theoretical guidance for the scientific utilization of carbonate saline soil in backfill engineering projects.

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.