Common anode materials in aqueous alkaline electrolytes,such as cadmium,metal hydrides and zinc,usually suffer from remarkable biotoxicity,high cost,and serious side reactions.To overcome these problems,we develop a c...Common anode materials in aqueous alkaline electrolytes,such as cadmium,metal hydrides and zinc,usually suffer from remarkable biotoxicity,high cost,and serious side reactions.To overcome these problems,we develop a conjugated porous polymer(CPP)in-situ grown on reduced graphene oxide(rGO)and Ketjen black(KB),noted as C_(4)N/rGO and C_(4)N/KB respectively,as the alternative anodes.The results show that C_(4)N/rGO electrode delivers a low redox potential(−0.905 V vs.Ag/AgCl),high specific capacity(268.8 mAh g^(-1) at 0.2 A g^(-1)),ultra-stable and fast sodium ion storage behavior(216 mAh g^(-1) at 20 A g^(-1))in 2 M NaOH electrolyte.The assembled C_(4)N/rGO//Ni(OH)_(2) full battery can cycle stably more than 38,000 cycles.Furthermore,by adding a small amount of antifreeze additive dimethyl sulfoxide(DMSO)to adjust the hydrogen bonding network,the low-temperature performance of the electrolyte(0.1 DMSO/2 M NaOH)is significantly improved while hydrogen evolution is inhibited.Consequently,the C_(4)N/rGO//Ni(OH)_(2) full cell exhibits an energy density of 147.3 Wh Kg^(-1) and ultra-high cycling stability over a wide temperature range from−70 to 45℃.This work provides an ultra-stable high-capacity CPPbased anode and antifreeze electrolyte for aqueous alkaline batteries and will facilitate their practical applications under extreme conditions.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to thei...Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.展开更多
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically slug...Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.展开更多
BACKGROUND Chronic hepatitis B often progresses silently toward hepatocellular carcinoma(HCC),a leading cause of mortality worldwide.Early detection of HCC is crucial,yet challenging.AIM To investigate the role of dyn...BACKGROUND Chronic hepatitis B often progresses silently toward hepatocellular carcinoma(HCC),a leading cause of mortality worldwide.Early detection of HCC is crucial,yet challenging.AIM To investigate the role of dynamic changes in alkaline phosphatase to prealbumin ratio(APR)in hepatitis B progression to HCC.METHODS Data from 4843 patients with hepatitis B(January 2015 to January 2024)were analyzed.HCC incidence rates in males and females were compared using the log-rank test.Data were evaluated using Kaplan–Meier analysis.The Linear Mixed-Effects Model was applied to track the fluctuation of APR levels over time.Furthermore,Joint Modeling of Longitudinal and Survival data was employed to investigate the temporal relationship between APR and HCC risk.RESULTS The incidence of HCC was higher in males.To ensure the model’s normality assumption,this study applied a logarithmic transformation to APR,yielding ratio.Ratio levels were higher in females(t=5.26,P<0.01).A 1-unit increase in ratio correlated with a 2.005-fold higher risk of HCC in males(95%CI:1.653-2.431)and a 2.273-fold higher risk in females(95%CI:1.620-3.190).CONCLUSION Males are more prone to HCC,while females have higher APR levels.Despite no baseline APR link,rising APR indicates a higher HCC risk.展开更多
Ti(C,N)-Mo_(2)C-Ni cermet as alternative materials was explored for use in alkaline conditions,replacing the WC-Co cemented carbides,since Co is classified as a potentially carcinogenic substance and there is potentia...Ti(C,N)-Mo_(2)C-Ni cermet as alternative materials was explored for use in alkaline conditions,replacing the WC-Co cemented carbides,since Co is classified as a potentially carcinogenic substance and there is potential hazard of“hard metal disease”under the exposure to cobalt dust.The changes in microstructure,corrosion rate and volumetric loss rate of the two materials were compared under electrochemical corrosion and erosion-corrosion in alkaline environment.The results demonstrates that Ti(C,N)-Mo_(2)C-Ni cermet undergoes passivation when exposed to electrochemical corrosion of NaOH solution,resulting in a significant increase in oxygen content on the corroded surface.The corrosion rate of cermet is approximately one order of magnitude lower than that of the cemented carbide.Under the erosion-corrosion of an alkaline sand-water mixture,both the cermet and cemented carbide experience a gradual increase in volumetric loss rate with prolonging the erosion time.During erosion,the rim phase in cermet is fragile,so cracks easily penetrate it while the core phase remains intact.The medium-grained cemented carbide commonly demonstrates transgranular fracture mode,while in the fine-grained cemented carbide,cracks tend to propagate along phase boundaries.The erosive wear and damage caused by sand particles play a predominant role in the erosion-corrosion process of alkaline sand-water mixtures.This process represents an accelerated destructive phenomenon influenced and intensified by the combined effects of corrosion and erosion.It is confirmed that using cermet as an alternative anti-wear material to cemented carbides is feasible under alkaline conditions,and even better.展开更多
Alkaline igneous rocks represent one of the most economically important resources of radioactive minerals and rare metals.New field observations and petrographic studies are integrated with whole-rock geochemical anal...Alkaline igneous rocks represent one of the most economically important resources of radioactive minerals and rare metals.New field observations and petrographic studies are integrated with whole-rock geochemical analyses and Gamma ray spectroscopy data of alkaline rocks associated with the Amreit complex.The fieldwork was achieved by the collection of more than forty samples from alkaline granites and alkaline syenites.The youngest rocks cropping out in the study area are the cogenetic alkaline rocks,ranging from alkaline granite to alkaline syenite.These alkaline rocks are composed essentially of K-feldspar,alkali amphiboles(arfvedsonite),and sodic pyroxene,with accessories such as zircon,apatite,and ilmenite.Mineral characterization of the highly radioactive zones in both alkaline granite and alkaline syenite displays enrichment in monazite,thorite,zircon,ferro-columbite,xenotime,and allanite minerals.Geochemical analyses indicate that the Amreit rocks are alkaline with peralkaline affinity and have high concentrations of total alkalis(K_(2)O+Na_(2)O),large ion lithophile elements(LILEs;Ba and Rb),high field strength elements(HFSEs;Y,Zr and Nb),rare earth elements(REEs)and significantly depleted in K,Sr,P,Ti,and Eu,typically of post-collision A-type granites.Typically,the Amreit alkaline igneous rocks are classified as within plate granites and display A2 subtype characteristics.The fractionation of K-feldspars played a distinctive role during the magmatic evolution of these alkaline rocks.The geochemical characteristics indicate that the studied alkaline igneous rocks which were originated by fractional crystallization of alkaline magmas were responsible for the enrichment of the REE and rare metals in the residual melt.The high radioactivity is essentially related to accessory minerals,such as zircon,allanite,and monazite.The alkaline granite is the most U-and Thrich rock,where radioactivity level reaches up to 14.7 ppm(181.55 Bq/kg)e U,40.6 ppm(164.84 Bq/kg)e Th,whereas in alkaline syenite radioactivity level is 8.5 ppm(104.96 Bq/kg)e U,30.2 ppm(122.61 Bq/kg)e Th.These observations suppose that these alkaline rocks may be important targets for REEs and radioactive mineral exploration.展开更多
This study presents an achievement of laser cooling of alkaline-earth atoms in the Chinese Space Station’s strontium(Sr)atomic space optical clock.The system’s core components,physical unit,optical unit,and electric...This study presents an achievement of laser cooling of alkaline-earth atoms in the Chinese Space Station’s strontium(Sr)atomic space optical clock.The system’s core components,physical unit,optical unit,and electrical unit,have a total volume of 306 L and a total mass of 163.8 kg.These compact and robust units can overcome mechanical vibrations and temperature fluctuations during space launch.The laser sources of the optical unit are composed of diode lasers,and the injection locking of slave lasers is automatically performed by a program.In the experiment,a blue magneto-optical trap of cold atoms was achieved,with the atom numbers estimated to be approximately(1.50±0.13)×10^(6) for 87Sr and(8.00±0.56)×10^(6) for 88Sr.This work establishes a foundation for atomic confinement and high-precision interrogation in space-based optical clocks and expands the frontiers of cold atom physics in microgravity.展开更多
Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen ev...Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen evolution reaction(HER)kinetics of commercial catalysts.To overcome this limitation,this study focuses on the development of a highly efficient electrocatalyst for alkaline HER.Ni-based intermetallic compounds exhibit remarkable catalytic activity for HER,with the NiMo alloy being among the most active catalysts in alkaline environments.Here,we designed and fabricated self-supported multiscale porous NiZn/NiMo intermetallic compounds on a metal foam substrate using a versatile dealloying method.The resulting electrode exhibits excellent HER activity,achieving an overpotential of just 204 mV at 1000 mA/cm^(2),and dem-onstrates robust long-term catalytic stability,maintaining performance at 100 mA/cm^(2) for 400 h in an alkaline electrolyte.Thesefindings underscore the potential of nanosized intermetallic compounds fabricated via a dealloying approach to deliver exceptional catalytic performance for alkaline water electrolysis.展开更多
Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active ...Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates.Metal-organic frameworks(MOFs)show excellent prospects in many fields because of their structural regularity and designability,but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity.Here,a MOF material(Cu-TCNQ)with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method.Subsequently,Cu-TCNQ and graphene oxide(GO)were directly self-assembled to form a Cu-TCNQ/GO composite,which improved the conductivity of the catalyst while maintained the atomically precise controllability.The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude(1663.6-2.7 W/cm)compared with pure Cu-TCNQ.The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH,even better than that of commercial 20%Pt/C.In alkaline polymer electrolyte fuel cells(APEFCs),the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 m W/cm^(2),respectively,which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.展开更多
A thorough understanding of the oxygen evolution reaction(OER)in Mo-based materials is crucial for the advancement of water-splitting technologies.However,the identification of the active phase in Mo-based systems rem...A thorough understanding of the oxygen evolution reaction(OER)in Mo-based materials is crucial for the advancement of water-splitting technologies.However,the identification of the active phase in Mo-based systems remains a subject of debate,largely due to the dissolution of molybdenum oxides in alkaline electrolytes.In this review,we provide a comprehensive overview of recent advances in the application of Mo-based materials for OER in alkaline media,with an emphasis on their diverse roles in catalysis.Various design strategies employed to optimize Mo-based materials are discussed,focusing on how these approaches influence their physicochemical properties and the specific effects of different design perspectives on their OER performance.Additionally,the structure-performance relationship underlying these materials is explored,offering insights into how structural modifications impact catalytic efficiency.Lastly,key challenges for Mo-based materials in OER applications are provided,and future research directions for further improving the efficacy of sustainable water-splitting technologies in alkaline environments are proposed.展开更多
Alkaline lacustrine shale is highly heterogeneous,and the complex relationship between the organicinorganic porosity network and hydrocarbon occurrence restricts the effectiveness of shale oil exploration and developm...Alkaline lacustrine shale is highly heterogeneous,and the complex relationship between the organicinorganic porosity network and hydrocarbon occurrence restricts the effectiveness of shale oil exploration and development.Herein,we investigated the Fengcheng Formation(P_(1)f)in Mahu Sag.This study integrated geochemistry,Soxhlet extraction,scanning electron microscopy,gas adsorption,and nuclear magnetic resonance T_(1)-T_(2)spectroscopy to elucidate the microscopic oil occurrence mechanisms in shales.Results indicate the presence of felsic shale,dolomitic shale,lime shale,and mixed shale within the P_(1)f.Matrix pores and microfractures associated with inorganic minerals are the predominant pore types in P_(1)f.Adsorbed oil primarily resides on the surfaces of organic matter and clay minerals,while free oil predominantly occupies inorganic pores and microfractures with larger pore sizes.Variations exist in the quantity and distribution of shale oil accumulation across different scales,where free oil and adsorbed oil are governed by dominant pores with diameters exceeding 10 nm and ineffective pores with diameters below 10 nm,respectively.Shale oil occurrence characteristics are influenced by organic matter,pore structure,and mineral composition.Felsic shale exhibits a high abundance of dominant pores,possesses the highest oil content,predominantly harbors free oil within these dominant pores,and demonstrates good mobility.Fluid occurrence in dolomitic shale and lime shale is intricate,with low oil content and a free oil to adsorbed oil ratio of 1:1.Mixed shale exhibits elevated clay mineral content and a scarcity of dominant pores.Moreover,ineffective pores contain increased bound water,resulting in medium oil content and limited mobility predominantly due to adsorption.Presently,shale oil mainly occurs in the dominant pores with a diameter larger than 10 nm in a free state.During the exploration and development of alkaline lacustrine shale oil resources,emphasis should be placed on identifying sweet spots within the felsic shale characterized by dominant pores.展开更多
Alkaline soil is characterized by high soluble salt content,elevated pH levels,and ionic imbalance,all of which collectively intensify the harmful effects of alkaline stress on plants.To gain molecular insights into a...Alkaline soil is characterized by high soluble salt content,elevated pH levels,and ionic imbalance,all of which collectively intensify the harmful effects of alkaline stress on plants.To gain molecular insights into alkaline tolerance(AT),we evaluated 13 AT-related traits in 508 diverse rice accessions from the 3K Rice Germplasm Project at the seedling stage.A total of 2929764,2059114,and 1365868 single nucleotide polymorphisms were used to identify alkaline-tolerance QTLs via genome-wide association studies(GWAS)in the entire population as well as in the xian and geng subpopulations,respectively.Candidate genes and their superior haplotypes were further identified through gene-based association,haplotype analysis,and gene function annotation.In total,99 QTLs were identified for AT by GWAS,and three genes(LOC_Os03g49050 for qSSD3.1,LOC_Os05g48760 for qSKC5,and LOC_Os12g01922 for qSNC12)were selected as the most promising candidate genes.Furthermore,we successfully mined superior alleles of key candidate genes from natural variants associated with AT-related traits.This study identified crucial candidate genes and their favorable alleles for AT traits,laying a foundation for further gene cloning and the development of AT rice varieties via marker-assisted selection.展开更多
Transition metal cobalt exhibits strong activation capabilities for alkanes,however,the instability of Co sites leads to sintering and coke deposition,resulting in rapid deactivation.Hierarchical zeolites,with their d...Transition metal cobalt exhibits strong activation capabilities for alkanes,however,the instability of Co sites leads to sintering and coke deposition,resulting in rapid deactivation.Hierarchical zeolites,with their diverse pore structures and high surface areas,are used to effectively anchor metals and enhance coke tolerance.Herein,a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports,which were subsequently loaded with Co species for propane dehydrogenation catalyst.The results indicate that the application of NaOH,an inorganic base,produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH,an organic base.UV-vis,Raman,and XPS analyses reveal that Co in the 0.5Co/SN-1-0.05 catalyst is mainly in the form of tetrahedral Co^(2+),which effectively activates C-H bonds.In contrast,the 0.5Co/S-1 catalyst contains mainly Co_(3)O_(4)species.Co^(2+)supported on hierarchical zeolites shows better propane conversion(58.6%)and propylene selectivity(>96%)compared to pure silica zeolites.Coke characterization indicates that hierarchical zeolites accumulate more coke,but it is mostly in the form of easily removable disordered carbon.The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation,effectively preventing deactivation from sintering and coke coverage.展开更多
Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte.However,Zn metal anode in alkaline electr...Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte.However,Zn metal anode in alkaline electrolyte usually suffers more severe corrosion,passivation,and hydrogen evolution reaction.Herein,an interface chemical regulation strategy employs to in-situ construct a Zn-Sn alloy layer during cycling.The K_(2)[Sn(OH)_(6)]has been introduced into the electrolyte as the deposition overpotential of Zn and Sn in alkaline electrolyte is approximate leading to their simultaneously plating.The Zn-Sn alloy layer not only prevents Zn anode corrosion and suppresses the dendrite growth but also promotes the reaction kinetics.Therefore,the Zn||Zn cell exhibits a long life of 400 h in alkaline electrolyte about 20 times of that in without K_(2)[Sn(OH)_(6)]electrolyte.Moreover,the N-NCP@PQ_(x)||Zn full cell displays a superior cycle performance of 4000 cycles with 93%capacity retention at 2 A/g.展开更多
In view of the difference in coordination capacity of the glycine ion(Gly−),a selective leaching process for treating with spent lithium-ion batteries(LIBs)in the alkaline glycinate system was proposed.The effects of ...In view of the difference in coordination capacity of the glycine ion(Gly−),a selective leaching process for treating with spent lithium-ion batteries(LIBs)in the alkaline glycinate system was proposed.The effects of retention time,leaching temperature,concentration of glycine ligand,liquid-solid ratio(L/S),pH,stirring speed,and H_(2)O_(2) dosage on the leaching efficiency of valuable metals and the dissolution of impurities were investigated.When the spent LIBs were leached in 3 mol/L glycine aqueous solution with pH of 8,L/S of 5 mL:1 g and H_(2)O_(2) dosage of 5 vol.%at 90℃and stirring speed of 400 r/min for 3 h,lithium,cobalt,nickel,and manganese recoveries were 96.31%,83.18%,91.56%,and 31.16%,respectively,but Ca,Al,Fe,and Cu were almost insoluble.Meanwhile,the kinetic study showed that the activation energies for the leaching of Li,Co,Ni,and Mn were all in the range of 45−61 kJ/mol.The results indicate that the leaching process is all controlled by chemical reactions.展开更多
Seawater electrolysis for hydrogen production faces inherent challenges, including side reactions, corrosion, and scaling, stemming from the intricate composition of seawater. In response, researchers have turned to c...Seawater electrolysis for hydrogen production faces inherent challenges, including side reactions, corrosion, and scaling, stemming from the intricate composition of seawater. In response, researchers have turned to continuous water splitting using forward osmosis(FO)-driven seawater desalination. However, the necessity of a neutral electrolyte hampers this strategy due to the limited current density and scarcity of precious metals. Herein, this study applies alkali-durable FO membranes to enable self-sustaining seawater splitting, which can selectively withdraw water molecules, from seawater, via concentration gradient. The membranes demonstrates outstanding perm-selectivity of water/ions(~5830 mol mol^(-1)) during month-long alkaline resistance tests, preventing electrolyte leaching(>97% OHàretention) while maintaining ~95%water balance(V_(FO)= V_(electrolysis)) via preserved concentration gradient for consistent forward-osmosis influx of water molecules. With the consistent electrolyte environment protected by the polyamide FO membranes, the Ni Fe-Ar-P catalyst exhibits promising performance: a sustain current density of 360 m A cmà2maintained at the cell voltage of 2.10 V and 2.15 V for 360 h in the offshore seawater, preventing Cl/Br corrosion(98% rejection) and Mg/Ca passivation(99.6% rejection). This research marks a significant advancement towards efficient and durable seawater-based hydrogen production.展开更多
The presence of residual alkaline compounds in the ultrahigh-nickel layered oxide cathodes(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x≥_(0.9))aggravates structural degradation,increases surface reactivity,and promotes slurry gel...The presence of residual alkaline compounds in the ultrahigh-nickel layered oxide cathodes(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x≥_(0.9))aggravates structural degradation,increases surface reactivity,and promotes slurry gelation,leading to the capacity decay of batteries with these cathodes and complicating their manufacturing.Traditional approaches for addressing this issue,including direct removal,coverage,and utilization,are complex and require surface regeneration.Herein,we propose neutralizing residual alkaline compounds with 3-thiopheneboronic acid(3-TBA)to improve the performance of LiNi_(0.9)5Co_(0.04)Mn_(0.01)O_(2)(NCM)cathode material,a facile strategy that does not require any post-treatment.The suggested reaction yields a uniform and thin organic-modified layer on the surface of the NCM cathode,improving its chemical stability toward the electrolyte,as demonstrated by multiple characterization methods.The modified NCM cathode exhibited impressive cyclic and rate performances,achieving a capacity retention of 83.34%after 200 cycles at 1.0 C and a specific capacity of 162.00 mAh·g^(−1) at 10.0 C.Most importantly,the proposed approach can efficiently suppress unfavorable phase transitions,severe electrolyte degradation,and CO_(2) gas evolution,improving the application potential of ultrahigh-nickel layered oxide cathode materials.展开更多
The phase composition and microstructure of alkaline vanadium slag were characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy(SEM-EDS)and X-ray diffraction(XRD).A crystallization mo...The phase composition and microstructure of alkaline vanadium slag were characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy(SEM-EDS)and X-ray diffraction(XRD).A crystallization model of spinel was established to calculate the effects of basicity(the mass ratio of CaO to SiO_(2))and P_(2)O_(5) on crystal growth rates and precipitation patterns.Based on the crystal size distribution(CSD)theory,the size distribution and growth mechanisms of spinel crystals in alkaline vanadium slag at different temperatures were investigated.The results revealed that,at a cooling rate of 5 K/min,the mean grain size of spinel increased from 12.77 to 21.52μm as the temperature decreased from 1748 to 1598 K,with spinel growth being controlled by the interface.At 1548 K,the spinel particle size reached 31.04μm,indicating a supply-controlled growth mechanism as the temperature decreased from 1598 to 1548 K.Increased P_(2)O_(5) content hindered the crystal growth,while an increase in basicity promoted nucleation and growth.Furthermore,MnCr_(2)O_(4) preferentially crystallized and grew in alkaline vanadium slag.展开更多
Since the beginning of the 20th century,alkaline electrolysis has been used as a proven method for producing hydrogen on a megawatt scale.The existence of parasitic shunt currents in alkaline water electrolysis,which ...Since the beginning of the 20th century,alkaline electrolysis has been used as a proven method for producing hydrogen on a megawatt scale.The existence of parasitic shunt currents in alkaline water electrolysis,which is utilized to produce clean hydrogen,is investigated in this work.Analysis has been done on a 20-cell stack.Steel end plates,bipolar plates,and an electrolyte concentration of 6 M potassium hydroxide are all included in the model.The Butler-Volmer kinetics equations are used to simulate the electrode surfaces.Ohmic losses are taken into consideration in both the electrode and electrolyte phases,although mass transport constraints in the gas phase are not.Using an auxiliary sweep to solve equations,the model maintains an isothermal condition at 85℃ while adjusting the average cell voltage between 1.3 and 1.8 V.The results show that lower shunt currents in the outlet channels as opposed to the intake channels are the result of the electrolyte’s lower effective conductivity in the upper channels,which is brought on by a lower volume fraction of the electrolyte.Additionally,it has been seen that the shunt currents intensify as the stack gets closer to the conclusion.Efficiency is calculated by dividing the maximum energy output(per unit of time)that a fuel cell operating under comparable conditions might produce by the electrical energy needed to generate that output inside the stack.At first,energy efficiency increases due to the rise in coulombic efficiency,peaking around 1400 mA.The subsequent decline after reaching 1400 mA is linked to an increase in stack voltage at elevated current levels.展开更多
基金financial support by the National Natural Science Foundation of China(22371010,21771017 and 51702009)the“Hundred Talents Program”of the Chinese Academy of Science,Fundamental Research Funds for the Central Universities,Shenzhen Science and Technology Program(JCYJ20210324115412035 JCYJ2021-0324123202008,JCYJ20210324122803009 and ZDSYS20210813095534001)Guangdong Basic and Applied Basic Research Foundation(2021A1515110880).
文摘Common anode materials in aqueous alkaline electrolytes,such as cadmium,metal hydrides and zinc,usually suffer from remarkable biotoxicity,high cost,and serious side reactions.To overcome these problems,we develop a conjugated porous polymer(CPP)in-situ grown on reduced graphene oxide(rGO)and Ketjen black(KB),noted as C_(4)N/rGO and C_(4)N/KB respectively,as the alternative anodes.The results show that C_(4)N/rGO electrode delivers a low redox potential(−0.905 V vs.Ag/AgCl),high specific capacity(268.8 mAh g^(-1) at 0.2 A g^(-1)),ultra-stable and fast sodium ion storage behavior(216 mAh g^(-1) at 20 A g^(-1))in 2 M NaOH electrolyte.The assembled C_(4)N/rGO//Ni(OH)_(2) full battery can cycle stably more than 38,000 cycles.Furthermore,by adding a small amount of antifreeze additive dimethyl sulfoxide(DMSO)to adjust the hydrogen bonding network,the low-temperature performance of the electrolyte(0.1 DMSO/2 M NaOH)is significantly improved while hydrogen evolution is inhibited.Consequently,the C_(4)N/rGO//Ni(OH)_(2) full cell exhibits an energy density of 147.3 Wh Kg^(-1) and ultra-high cycling stability over a wide temperature range from−70 to 45℃.This work provides an ultra-stable high-capacity CPPbased anode and antifreeze electrolyte for aqueous alkaline batteries and will facilitate their practical applications under extreme conditions.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金financial support by the National Natural Science Foundation of China(No.52102241)Doctor of Suzhou University Scientific Research Foundation(Nos.2022BSK019,2020BS015)+2 种基金the Primary Research and Development Program of Anhui Province(No.201904a05020087)the Natural Science Research Project in Universities of Anhui Province in China(Nos.2022AH051386,KJ2021A1114)the Foundation(No.GZKF202211)of State Key Laboratory of Biobased Material and Green Papermaking Qilu University of Technology。
文摘Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
基金financially supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)the Natural Science Foundation of Jilin Province of China(No.20240101098JC)the National Natural Science Foundation of China(No.22469002)。
文摘Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
文摘BACKGROUND Chronic hepatitis B often progresses silently toward hepatocellular carcinoma(HCC),a leading cause of mortality worldwide.Early detection of HCC is crucial,yet challenging.AIM To investigate the role of dynamic changes in alkaline phosphatase to prealbumin ratio(APR)in hepatitis B progression to HCC.METHODS Data from 4843 patients with hepatitis B(January 2015 to January 2024)were analyzed.HCC incidence rates in males and females were compared using the log-rank test.Data were evaluated using Kaplan–Meier analysis.The Linear Mixed-Effects Model was applied to track the fluctuation of APR levels over time.Furthermore,Joint Modeling of Longitudinal and Survival data was employed to investigate the temporal relationship between APR and HCC risk.RESULTS The incidence of HCC was higher in males.To ensure the model’s normality assumption,this study applied a logarithmic transformation to APR,yielding ratio.Ratio levels were higher in females(t=5.26,P<0.01).A 1-unit increase in ratio correlated with a 2.005-fold higher risk of HCC in males(95%CI:1.653-2.431)and a 2.273-fold higher risk in females(95%CI:1.620-3.190).CONCLUSION Males are more prone to HCC,while females have higher APR levels.Despite no baseline APR link,rising APR indicates a higher HCC risk.
基金Chongqing Light Alloy Materials and Processing Engineering Technology Research Center Open Fund Project(GCZX201903)Yunnan Province Major Science and Technology Special Project Plan(202302AA310038)Sichuan University-Suining Municipal-University Cooperation Project(2023CDSN-12)。
文摘Ti(C,N)-Mo_(2)C-Ni cermet as alternative materials was explored for use in alkaline conditions,replacing the WC-Co cemented carbides,since Co is classified as a potentially carcinogenic substance and there is potential hazard of“hard metal disease”under the exposure to cobalt dust.The changes in microstructure,corrosion rate and volumetric loss rate of the two materials were compared under electrochemical corrosion and erosion-corrosion in alkaline environment.The results demonstrates that Ti(C,N)-Mo_(2)C-Ni cermet undergoes passivation when exposed to electrochemical corrosion of NaOH solution,resulting in a significant increase in oxygen content on the corroded surface.The corrosion rate of cermet is approximately one order of magnitude lower than that of the cemented carbide.Under the erosion-corrosion of an alkaline sand-water mixture,both the cermet and cemented carbide experience a gradual increase in volumetric loss rate with prolonging the erosion time.During erosion,the rim phase in cermet is fragile,so cracks easily penetrate it while the core phase remains intact.The medium-grained cemented carbide commonly demonstrates transgranular fracture mode,while in the fine-grained cemented carbide,cracks tend to propagate along phase boundaries.The erosive wear and damage caused by sand particles play a predominant role in the erosion-corrosion process of alkaline sand-water mixtures.This process represents an accelerated destructive phenomenon influenced and intensified by the combined effects of corrosion and erosion.It is confirmed that using cermet as an alternative anti-wear material to cemented carbides is feasible under alkaline conditions,and even better.
文摘Alkaline igneous rocks represent one of the most economically important resources of radioactive minerals and rare metals.New field observations and petrographic studies are integrated with whole-rock geochemical analyses and Gamma ray spectroscopy data of alkaline rocks associated with the Amreit complex.The fieldwork was achieved by the collection of more than forty samples from alkaline granites and alkaline syenites.The youngest rocks cropping out in the study area are the cogenetic alkaline rocks,ranging from alkaline granite to alkaline syenite.These alkaline rocks are composed essentially of K-feldspar,alkali amphiboles(arfvedsonite),and sodic pyroxene,with accessories such as zircon,apatite,and ilmenite.Mineral characterization of the highly radioactive zones in both alkaline granite and alkaline syenite displays enrichment in monazite,thorite,zircon,ferro-columbite,xenotime,and allanite minerals.Geochemical analyses indicate that the Amreit rocks are alkaline with peralkaline affinity and have high concentrations of total alkalis(K_(2)O+Na_(2)O),large ion lithophile elements(LILEs;Ba and Rb),high field strength elements(HFSEs;Y,Zr and Nb),rare earth elements(REEs)and significantly depleted in K,Sr,P,Ti,and Eu,typically of post-collision A-type granites.Typically,the Amreit alkaline igneous rocks are classified as within plate granites and display A2 subtype characteristics.The fractionation of K-feldspars played a distinctive role during the magmatic evolution of these alkaline rocks.The geochemical characteristics indicate that the studied alkaline igneous rocks which were originated by fractional crystallization of alkaline magmas were responsible for the enrichment of the REE and rare metals in the residual melt.The high radioactivity is essentially related to accessory minerals,such as zircon,allanite,and monazite.The alkaline granite is the most U-and Thrich rock,where radioactivity level reaches up to 14.7 ppm(181.55 Bq/kg)e U,40.6 ppm(164.84 Bq/kg)e Th,whereas in alkaline syenite radioactivity level is 8.5 ppm(104.96 Bq/kg)e U,30.2 ppm(122.61 Bq/kg)e Th.These observations suppose that these alkaline rocks may be important targets for REEs and radioactive mineral exploration.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB35010202)the National Natural Science Foundation of China(Grants No.62275268)。
文摘This study presents an achievement of laser cooling of alkaline-earth atoms in the Chinese Space Station’s strontium(Sr)atomic space optical clock.The system’s core components,physical unit,optical unit,and electrical unit,have a total volume of 306 L and a total mass of 163.8 kg.These compact and robust units can overcome mechanical vibrations and temperature fluctuations during space launch.The laser sources of the optical unit are composed of diode lasers,and the injection locking of slave lasers is automatically performed by a program.In the experiment,a blue magneto-optical trap of cold atoms was achieved,with the atom numbers estimated to be approximately(1.50±0.13)×10^(6) for 87Sr and(8.00±0.56)×10^(6) for 88Sr.This work establishes a foundation for atomic confinement and high-precision interrogation in space-based optical clocks and expands the frontiers of cold atom physics in microgravity.
基金Taishan Scholar Project of Shandong Province(No.tsqn202306226)Natural Science Foundation of Shandong Prov-ince(No.ZR2023ME155)+1 种基金The project of“20 Items of University”of Jinan(No.202228046)Luzhou Municipal Science and Technol-ogy Plan Project(Nos.2024JYJ016 and 2024JYJ018).
文摘Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen evolution reaction(HER)kinetics of commercial catalysts.To overcome this limitation,this study focuses on the development of a highly efficient electrocatalyst for alkaline HER.Ni-based intermetallic compounds exhibit remarkable catalytic activity for HER,with the NiMo alloy being among the most active catalysts in alkaline environments.Here,we designed and fabricated self-supported multiscale porous NiZn/NiMo intermetallic compounds on a metal foam substrate using a versatile dealloying method.The resulting electrode exhibits excellent HER activity,achieving an overpotential of just 204 mV at 1000 mA/cm^(2),and dem-onstrates robust long-term catalytic stability,maintaining performance at 100 mA/cm^(2) for 400 h in an alkaline electrolyte.Thesefindings underscore the potential of nanosized intermetallic compounds fabricated via a dealloying approach to deliver exceptional catalytic performance for alkaline water electrolysis.
基金supported by the National Key Research and Development Program of China(No.2022YFB3807500)the National Natural Science Foundation of China(No.22220102003)+1 种基金the Beijing Natural Science Foundation(No.JL23003)“Double-First-Class”construction projects(Nos.XK180301 and XK1804-02)。
文摘Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates.Metal-organic frameworks(MOFs)show excellent prospects in many fields because of their structural regularity and designability,but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity.Here,a MOF material(Cu-TCNQ)with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method.Subsequently,Cu-TCNQ and graphene oxide(GO)were directly self-assembled to form a Cu-TCNQ/GO composite,which improved the conductivity of the catalyst while maintained the atomically precise controllability.The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude(1663.6-2.7 W/cm)compared with pure Cu-TCNQ.The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH,even better than that of commercial 20%Pt/C.In alkaline polymer electrolyte fuel cells(APEFCs),the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 m W/cm^(2),respectively,which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.
基金financially supported by the National Natural Science Foundation of China(52162036 and 22378342)the Key Project of Nature Science Foundation of Xinjiang(2021D01D08)+1 种基金the Major Projects of Xinjiang(2022A01005-4 and 2021A01001-1)the Key Research and Development Project of Xinjiang(2023B01025-1)。
文摘A thorough understanding of the oxygen evolution reaction(OER)in Mo-based materials is crucial for the advancement of water-splitting technologies.However,the identification of the active phase in Mo-based systems remains a subject of debate,largely due to the dissolution of molybdenum oxides in alkaline electrolytes.In this review,we provide a comprehensive overview of recent advances in the application of Mo-based materials for OER in alkaline media,with an emphasis on their diverse roles in catalysis.Various design strategies employed to optimize Mo-based materials are discussed,focusing on how these approaches influence their physicochemical properties and the specific effects of different design perspectives on their OER performance.Additionally,the structure-performance relationship underlying these materials is explored,offering insights into how structural modifications impact catalytic efficiency.Lastly,key challenges for Mo-based materials in OER applications are provided,and future research directions for further improving the efficacy of sustainable water-splitting technologies in alkaline environments are proposed.
基金financially supported by the State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Efficient Development(33550000-22-ZC0613-0006)National Natural Science Foundation of China(42202133)+2 种基金CNPC Innovation Fund(2022DQ02-0106)Strategic Cooperation Technology Projects of the CNPC and CUPB(ZLZX2020-01-05)Key Laboratory of Tectonics and Petroleum Resources(China University of Geosciences),Ministry of Education,China(TPR-2023-05)。
文摘Alkaline lacustrine shale is highly heterogeneous,and the complex relationship between the organicinorganic porosity network and hydrocarbon occurrence restricts the effectiveness of shale oil exploration and development.Herein,we investigated the Fengcheng Formation(P_(1)f)in Mahu Sag.This study integrated geochemistry,Soxhlet extraction,scanning electron microscopy,gas adsorption,and nuclear magnetic resonance T_(1)-T_(2)spectroscopy to elucidate the microscopic oil occurrence mechanisms in shales.Results indicate the presence of felsic shale,dolomitic shale,lime shale,and mixed shale within the P_(1)f.Matrix pores and microfractures associated with inorganic minerals are the predominant pore types in P_(1)f.Adsorbed oil primarily resides on the surfaces of organic matter and clay minerals,while free oil predominantly occupies inorganic pores and microfractures with larger pore sizes.Variations exist in the quantity and distribution of shale oil accumulation across different scales,where free oil and adsorbed oil are governed by dominant pores with diameters exceeding 10 nm and ineffective pores with diameters below 10 nm,respectively.Shale oil occurrence characteristics are influenced by organic matter,pore structure,and mineral composition.Felsic shale exhibits a high abundance of dominant pores,possesses the highest oil content,predominantly harbors free oil within these dominant pores,and demonstrates good mobility.Fluid occurrence in dolomitic shale and lime shale is intricate,with low oil content and a free oil to adsorbed oil ratio of 1:1.Mixed shale exhibits elevated clay mineral content and a scarcity of dominant pores.Moreover,ineffective pores contain increased bound water,resulting in medium oil content and limited mobility predominantly due to adsorption.Presently,shale oil mainly occurs in the dominant pores with a diameter larger than 10 nm in a free state.During the exploration and development of alkaline lacustrine shale oil resources,emphasis should be placed on identifying sweet spots within the felsic shale characterized by dominant pores.
基金supported by the Shenzhen Science and Technology Program,China(Grant No.KCXFZ20211020163808012)the Nanfan Special Project,Chinese Academy of Agricultural Sciences,China(Grant No.YBXM2426).
文摘Alkaline soil is characterized by high soluble salt content,elevated pH levels,and ionic imbalance,all of which collectively intensify the harmful effects of alkaline stress on plants.To gain molecular insights into alkaline tolerance(AT),we evaluated 13 AT-related traits in 508 diverse rice accessions from the 3K Rice Germplasm Project at the seedling stage.A total of 2929764,2059114,and 1365868 single nucleotide polymorphisms were used to identify alkaline-tolerance QTLs via genome-wide association studies(GWAS)in the entire population as well as in the xian and geng subpopulations,respectively.Candidate genes and their superior haplotypes were further identified through gene-based association,haplotype analysis,and gene function annotation.In total,99 QTLs were identified for AT by GWAS,and three genes(LOC_Os03g49050 for qSSD3.1,LOC_Os05g48760 for qSKC5,and LOC_Os12g01922 for qSNC12)were selected as the most promising candidate genes.Furthermore,we successfully mined superior alleles of key candidate genes from natural variants associated with AT-related traits.This study identified crucial candidate genes and their favorable alleles for AT traits,laying a foundation for further gene cloning and the development of AT rice varieties via marker-assisted selection.
基金supported by the National Natural Science Foundation of China(Nos.22035009,22178381)the National Key R&D Program of China(Nos.2021YFA1501301,2021YFC2901100)the State Key Laboratory of Heavy Oil Processing(No.2021-03).
文摘Transition metal cobalt exhibits strong activation capabilities for alkanes,however,the instability of Co sites leads to sintering and coke deposition,resulting in rapid deactivation.Hierarchical zeolites,with their diverse pore structures and high surface areas,are used to effectively anchor metals and enhance coke tolerance.Herein,a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports,which were subsequently loaded with Co species for propane dehydrogenation catalyst.The results indicate that the application of NaOH,an inorganic base,produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH,an organic base.UV-vis,Raman,and XPS analyses reveal that Co in the 0.5Co/SN-1-0.05 catalyst is mainly in the form of tetrahedral Co^(2+),which effectively activates C-H bonds.In contrast,the 0.5Co/S-1 catalyst contains mainly Co_(3)O_(4)species.Co^(2+)supported on hierarchical zeolites shows better propane conversion(58.6%)and propylene selectivity(>96%)compared to pure silica zeolites.Coke characterization indicates that hierarchical zeolites accumulate more coke,but it is mostly in the form of easily removable disordered carbon.The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation,effectively preventing deactivation from sintering and coke coverage.
基金supported by Joint Funds of the National Natural Science Foundation of China(No.U22A20140)University of Jinan Disciplinary Cross-Convergence Construction Project 2023(No.XKJC-202309)+3 种基金Jinan City-School Integration Development Strategy Project(No.JNSX2023015)Independent Cultivation Program of Innovation Team of Ji’nan City(No.202333042)the Youth Innovation Group Plan of Shandong Province(No.2022KJ095)Special thanks to the Optical microscopy(Yuescope,YM710R).
文摘Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte.However,Zn metal anode in alkaline electrolyte usually suffers more severe corrosion,passivation,and hydrogen evolution reaction.Herein,an interface chemical regulation strategy employs to in-situ construct a Zn-Sn alloy layer during cycling.The K_(2)[Sn(OH)_(6)]has been introduced into the electrolyte as the deposition overpotential of Zn and Sn in alkaline electrolyte is approximate leading to their simultaneously plating.The Zn-Sn alloy layer not only prevents Zn anode corrosion and suppresses the dendrite growth but also promotes the reaction kinetics.Therefore,the Zn||Zn cell exhibits a long life of 400 h in alkaline electrolyte about 20 times of that in without K_(2)[Sn(OH)_(6)]electrolyte.Moreover,the N-NCP@PQ_(x)||Zn full cell displays a superior cycle performance of 4000 cycles with 93%capacity retention at 2 A/g.
基金Projects(51974137,52274299)supported by the National Natural Science Foundation of ChinaProject(2023M733190)supported by the China Postdoctoral Science Foundation。
文摘In view of the difference in coordination capacity of the glycine ion(Gly−),a selective leaching process for treating with spent lithium-ion batteries(LIBs)in the alkaline glycinate system was proposed.The effects of retention time,leaching temperature,concentration of glycine ligand,liquid-solid ratio(L/S),pH,stirring speed,and H_(2)O_(2) dosage on the leaching efficiency of valuable metals and the dissolution of impurities were investigated.When the spent LIBs were leached in 3 mol/L glycine aqueous solution with pH of 8,L/S of 5 mL:1 g and H_(2)O_(2) dosage of 5 vol.%at 90℃and stirring speed of 400 r/min for 3 h,lithium,cobalt,nickel,and manganese recoveries were 96.31%,83.18%,91.56%,and 31.16%,respectively,but Ca,Al,Fe,and Cu were almost insoluble.Meanwhile,the kinetic study showed that the activation energies for the leaching of Li,Co,Ni,and Mn were all in the range of 45−61 kJ/mol.The results indicate that the leaching process is all controlled by chemical reactions.
基金funding provided by the National Key R&D Program of China (Grant No. 2021YFB3801301)National Natural Science Foundation of China (Grant Nos. 22075076, 22208097 and 22378119)Shanghai Pilot Program for Basic Research (22TQ1400100-4)。
文摘Seawater electrolysis for hydrogen production faces inherent challenges, including side reactions, corrosion, and scaling, stemming from the intricate composition of seawater. In response, researchers have turned to continuous water splitting using forward osmosis(FO)-driven seawater desalination. However, the necessity of a neutral electrolyte hampers this strategy due to the limited current density and scarcity of precious metals. Herein, this study applies alkali-durable FO membranes to enable self-sustaining seawater splitting, which can selectively withdraw water molecules, from seawater, via concentration gradient. The membranes demonstrates outstanding perm-selectivity of water/ions(~5830 mol mol^(-1)) during month-long alkaline resistance tests, preventing electrolyte leaching(>97% OHàretention) while maintaining ~95%water balance(V_(FO)= V_(electrolysis)) via preserved concentration gradient for consistent forward-osmosis influx of water molecules. With the consistent electrolyte environment protected by the polyamide FO membranes, the Ni Fe-Ar-P catalyst exhibits promising performance: a sustain current density of 360 m A cmà2maintained at the cell voltage of 2.10 V and 2.15 V for 360 h in the offshore seawater, preventing Cl/Br corrosion(98% rejection) and Mg/Ca passivation(99.6% rejection). This research marks a significant advancement towards efficient and durable seawater-based hydrogen production.
基金the Yunnan Fundamental Research Projects(Grant Nos.202501AT070298,202401AU070163,and 202401AT070368)the National Natural Science Foundation of China(Grant No.52162030)+5 种基金the Yunnan Major Scientific and Technological Projects(Grant No.202202AG050003)the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(Grant No.2023-XMDJ-00617107)the University Service Key Industry Project of Yunnan Province(Grant No.FWCY-ZD2024005)the Yunnan Thousand Talents Program for Young Talents(Grant No.KKS2202052001)the Scientific Research Foundation of Kunming University of Science and Technology(Grant No.20220122)the Analysis and Testing Foundation of Kunming University of Science and Technology(Grant No.2023T20220122).
文摘The presence of residual alkaline compounds in the ultrahigh-nickel layered oxide cathodes(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x≥_(0.9))aggravates structural degradation,increases surface reactivity,and promotes slurry gelation,leading to the capacity decay of batteries with these cathodes and complicating their manufacturing.Traditional approaches for addressing this issue,including direct removal,coverage,and utilization,are complex and require surface regeneration.Herein,we propose neutralizing residual alkaline compounds with 3-thiopheneboronic acid(3-TBA)to improve the performance of LiNi_(0.9)5Co_(0.04)Mn_(0.01)O_(2)(NCM)cathode material,a facile strategy that does not require any post-treatment.The suggested reaction yields a uniform and thin organic-modified layer on the surface of the NCM cathode,improving its chemical stability toward the electrolyte,as demonstrated by multiple characterization methods.The modified NCM cathode exhibited impressive cyclic and rate performances,achieving a capacity retention of 83.34%after 200 cycles at 1.0 C and a specific capacity of 162.00 mAh·g^(−1) at 10.0 C.Most importantly,the proposed approach can efficiently suppress unfavorable phase transitions,severe electrolyte degradation,and CO_(2) gas evolution,improving the application potential of ultrahigh-nickel layered oxide cathode materials.
基金supported by the National Natural Science Foundation of China(No.51974047)the Natural Science Foundation of Chongqing,China(No.cstc2022ycjh-bgzxm0003)the Large Instrument Foundation of Chongqing University,China(No.202303150239)。
文摘The phase composition and microstructure of alkaline vanadium slag were characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy(SEM-EDS)and X-ray diffraction(XRD).A crystallization model of spinel was established to calculate the effects of basicity(the mass ratio of CaO to SiO_(2))and P_(2)O_(5) on crystal growth rates and precipitation patterns.Based on the crystal size distribution(CSD)theory,the size distribution and growth mechanisms of spinel crystals in alkaline vanadium slag at different temperatures were investigated.The results revealed that,at a cooling rate of 5 K/min,the mean grain size of spinel increased from 12.77 to 21.52μm as the temperature decreased from 1748 to 1598 K,with spinel growth being controlled by the interface.At 1548 K,the spinel particle size reached 31.04μm,indicating a supply-controlled growth mechanism as the temperature decreased from 1598 to 1548 K.Increased P_(2)O_(5) content hindered the crystal growth,while an increase in basicity promoted nucleation and growth.Furthermore,MnCr_(2)O_(4) preferentially crystallized and grew in alkaline vanadium slag.
文摘Since the beginning of the 20th century,alkaline electrolysis has been used as a proven method for producing hydrogen on a megawatt scale.The existence of parasitic shunt currents in alkaline water electrolysis,which is utilized to produce clean hydrogen,is investigated in this work.Analysis has been done on a 20-cell stack.Steel end plates,bipolar plates,and an electrolyte concentration of 6 M potassium hydroxide are all included in the model.The Butler-Volmer kinetics equations are used to simulate the electrode surfaces.Ohmic losses are taken into consideration in both the electrode and electrolyte phases,although mass transport constraints in the gas phase are not.Using an auxiliary sweep to solve equations,the model maintains an isothermal condition at 85℃ while adjusting the average cell voltage between 1.3 and 1.8 V.The results show that lower shunt currents in the outlet channels as opposed to the intake channels are the result of the electrolyte’s lower effective conductivity in the upper channels,which is brought on by a lower volume fraction of the electrolyte.Additionally,it has been seen that the shunt currents intensify as the stack gets closer to the conclusion.Efficiency is calculated by dividing the maximum energy output(per unit of time)that a fuel cell operating under comparable conditions might produce by the electrical energy needed to generate that output inside the stack.At first,energy efficiency increases due to the rise in coulombic efficiency,peaking around 1400 mA.The subsequent decline after reaching 1400 mA is linked to an increase in stack voltage at elevated current levels.
