NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.展开更多
Alkaline water electrolysis(AWE)represents a promising approach for green hydrogen production,yet the development of high-performance separators with gas impermeability,high ion conductivity,and stability under alkali...Alkaline water electrolysis(AWE)represents a promising approach for green hydrogen production,yet the development of high-performance separators with gas impermeability,high ion conductivity,and stability under alkaline operating conditions has proven challenging.To address this challenge,we develop a pre-concentration regulated phase separation strategy for scalable fabrication of asymmetric hierarchical porous membranes(AHPMs)for AWE.The resulting AHPMs demonstrate a hierarchical structure composed of an ultrathin dense skin layer and highly interconnected porous support.Benefitting from the structural advantages,the AHPMs exhibit outstanding characteristics,including a high bubble point pressure up to 12.4 bar,extremely low area resistance of 0.03Ωcm^(2) in 30 wt%KOH at 80℃,and excellent hydrophilicity and long-term alkaline stability.When applied in AWE with commercial catalysts,the AHPMs achieved an impressive current density of 1.9 A cm^(-2) at 2.0 V in 30 wt%KOH and the anodic hydrogen contents(AHCs)below 0.5 vol.%at a low current density of 0.1 A cm^(-2),differential pressure of 2 bar,and temperature of 80℃.Moreover,AHPMs demonstrate exceptional stability over 2,400 h of continuous operation and maintain superior performance in a 1 Nm^(3) h^(-1) industrialscale electrolyzer stack.This work advances the development of efficient separators for highperformance AWE systems,contributing to the advancement of hydrogen technologies in sustainable energy applications.展开更多
Examining carbonate dissolution kinetics at mineral-water interface is crucial to understand numerous environmental and geochemical processes,including global carbon cycling,CO_(2)sequestration in deep geological rese...Examining carbonate dissolution kinetics at mineral-water interface is crucial to understand numerous environmental and geochemical processes,including global carbon cycling,CO_(2)sequestration in deep geological reservoirs,and trace elements release in terrestrial and aquatic environments.Here we explored the effect of circumneutral to alkaline pH solutions(pH 6-11)on dissolution kinetics of pure dolomite and Ca and Mg release stoichiometry in flow-through reactor experiments at 25±1℃.Results revealed that the dolomite dissolution rates obtained from effluent Ca and Mg concentrations(R_(Ca)and R_(Mg)in mol/cm^(2)/s)were dependent on input solution pH and HCO_(3)^(-)log activity.The pH dependence of dissolution rates showed two distinct trends,i.e.,at circumneutral pH ranging between 6 and 8,the dissolution rate decreased with increasing pH,with minimum rate at pH 8.While in the highly alkaline pH range(pH 9-11),the dolomite dissolution rate increased with an increasing pH.Irrespective of the input pH,the dolomite dissolution rates indicated a reverse relationship with HCO_(3)^(-)log activity,with the lowest dissolution rate(R Ca=3.80×10^(-12)mol/cm^(2)/s)at pH 8 where HCO_(3)^(-)log activity attained the highest value(-3.957).The lower R Ca and R Mg obtained at pH 8 compared to all the other pH could possibly be attributed to an inhibition caused by high HCO_(3)^(-)log activity in solution at this pH.Dolomite dissolution rates were non-stoichiometric at all the experimental pH values,showing higher preferential Ca over Mg release(R_(Ca)>R_(Mg))whereas an opposite trend was observed at pH 8,with R_(Ca)<R_(Mg)at the steady state.Saturation index values calculated using geochemical speciation modelling were positive for Mg-bearing minerals(brucite,dolomite,artinite)at alkaline pH of 10-11,indicating favourable conditions for their precipitation under studied conditions.This study provides insights on the significance of log ion activities of HCO_(3)^(-)and Me-OH^(+)under varying pH for elucidating the dissolution mechanism of dolomite in circumneutral to alkaline aqueous environments.展开更多
Driven by the global energy transition and carbon neutrality targets,alkaline water electrolysis has emerged as a key technology for coupling variable renewable generation with clean hydrogen production,offering consi...Driven by the global energy transition and carbon neutrality targets,alkaline water electrolysis has emerged as a key technology for coupling variable renewable generation with clean hydrogen production,offering considerable potential for absorbing surplus power and enhancing grid flexibility.However,conventional control architectures typically treat the power converter and electrolyzer as independent units,neglecting their dynamic interactions and thereby limiting overall system performance under practical operating conditions.This review critically examines existing control approaches,ranging from classical proportional-integral schemes to model predictive control,fuzzy-logic algorithms,and data-driven methods,evaluating their effectiveness in managing dynamic response,multivariable coupling,and operational constraints as well as their inherent limitations.Attention is then focused on the performance requirements of the hydrogen-production converter,including current ripple suppression,rapid transient response,adaptive thermal regulation,and stable power delivery.An integrated co‑control framework is proposed,aligning converter output with electrolyzer demand across steady-state operation,variable renewable input,and emergency shutdown scenarios to achieve higher efficiency,extended equipment lifetime,and enhanced operational safety.Finally,prospects for advancing unified control methodologies are outlined,with emphasis on constraint-aware predictive control,machine-learning-enhanced modeling,and real‑time co‑optimization for future alkaline electrolyzer systems.展开更多
The pore structure of shale oil reservoir significantly affects the occurrence and mobility of hydrocarbons.The potential of a new type of alkaline lake shale oil has been demonstrated,but there are few reports on the...The pore structure of shale oil reservoir significantly affects the occurrence and mobility of hydrocarbons.The potential of a new type of alkaline lake shale oil has been demonstrated,but there are few reports on the pore system of alkaline lake shale,which restricts the efficient exploration and development of shale oil.This study investigates the Fengcheng Formation shale in the Mahu sag of the Junggar Basin,employing methods such as low-temperature nitrogecn adsorption(LTNA),mercury intrusion capillary pressure(MICP),and nuclear magnetic resonance(NMR)to quantitatively characterize the multi-scale pore structure and fractal characteristics of shale,while evaluating the applicability of these methods.Based on a comprehensive analysis of material composition,different pore types,and fractal dimensions,the controlling factors for the development of different pore types and their seepage capacity are discussed.The results indicate that inorganic mineral pores are the main development in alkaline lake shale,with the pore morphology being characterized by slit-like and ink-bottle shapes.The multi-scale pore size distribution(PSD)shows that Ⅱ-micropores(10-100 nm)and mesopores(100–1000 nm)are the main contributors to the pore system.The development of Ⅱ-micropores is associated with feldspar and calcareous minerals,the development of Ⅰ-micropores(<10 nm)and mesopores is related to quartz content,while large pores are mainly found in interlayer fissures of clay minerals.The development of Ⅰ-micropores increases the roughness of pore surface and enhances the adsorption capacity of the pores,while the development of Ⅱ-micropores associated with calcareous minerals hinders pore seepage capacity.Mesopores and macropores(>1000 nm)exhibit good flowability.The high content of siliceous minerals plays a positive role in the pore system of alkaline lake shale.The shale with higher fractal dimension Dmin exhibits greater adsorption capacity,which hinders the accumulation of free-state shale oil.Different types of pore space play different roles in the occurrence of shale oil,with free-state shale oil primarily occurring in micro-fractures and inorganic mineral pores,and the pore size is exceeding 10 nm.展开更多
Phosphorus(P)leaching in alkaline soils,exacerbated by excessive fertilizer application,represents a significant pathway for P loss.While soil pore structure and texture critically regulate P transport,mechanisms gove...Phosphorus(P)leaching in alkaline soils,exacerbated by excessive fertilizer application,represents a significant pathway for P loss.While soil pore structure and texture critically regulate P transport,mechanisms governing P loss in texturally diverse alkaline soils remain unclear.This study investigated P leaching dynamics and transport parameters across four alkaline soil textures(silty clay,clay loam,loam,sandy loam)using a one-dimensional convective-diffusion equation(CDE)based on column experiments.Results indicated that phosphorus leaching kinetics were predominantly governed by diffusion transport,evidenced by low Peclet numbers(P_(e))(ranged from 0.02 to 0.31)across varying textures and initial P concentrations(C_(0)).Comparative analysis of transport parameters revealed significant textural effects on dispersion coefficient(D),retardation factor(R),pore water velocity(V),P_(e),and diffusion coefficient(λ)(F>523.42,p<0.001).Among these,only D,P_(e) andλexhibited substantial differences in response to variations in C_(0)(F>89.47,p<0.001).Saturated hydraulic conductivity(K_(s))(R^(2)=62.9%,p<0.01)and total pore area(A)(R^(2)=12.4%,p<0.01)emerged as primary regulators of P leaching.Enhanced clay content increased total pore area while reducing average pore diameter,concurrently decreasing pore water velocity and saturated infiltration rates.These textural modifications amplified diffusive P transport within soil matrices.The findings provide mechanistic insights into texturedependent P mobility in alkaline environments,informing targeted strategies for agricultural phosphorus management.展开更多
Hexavalent chromium(Cr(Ⅵ)) is an extremely toxic pollutant in aqueous environment.Chemical reduction is the most employed method in decontamination of Cr(Ⅵ).However,the chemical reduction was usually conducted in ac...Hexavalent chromium(Cr(Ⅵ)) is an extremely toxic pollutant in aqueous environment.Chemical reduction is the most employed method in decontamination of Cr(Ⅵ).However,the chemical reduction was usually conducted in acidic media,resulting in considerable waste of acid reagents and the following neutralizing agents.In this study,kinetics and mechanisms of Cr(Ⅵ) reduction by sulfite in alkaline conditions(pH:7-10) were investigated.It reveals that Cr(Ⅵ) reduction follows pseudo-zero-order kinetics,where the rate constants increased markedly with an in situ irradiation of Far-UVC(UV_(222)).Decreasing pH levels slightly favored the reduction.Iodide ion displayed a notable accelerating effect,which not only save the energy input but also minimize the reductant usage.Chloride,sulfate,and carbonate ions exhibit little effect on the reduction,whereas nitrate and nitrite ions,dissolved oxygen as well as Cu(Ⅱ) suppressed the reduction significantly,implying that hydrated electrons produced by UV222 played the most important role in the reaction.Compared to the UV254/sulfite/iodide process,UV222/sulfite/iodide demonstrates clear advantages in the reduction kinetics and the sulfite utilization efficiency,underscoring its potential for effective Cr(Ⅵ) remediation in various environmental settings.展开更多
Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve t...Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve the migration of a highly efficient hydrogen species to Pt sites over Pt/Co@NC,which is obtained through a facile calcination and electrodeposition method.It exhibits an outstanding geometric activity(η_(10)=31 m V),which surpasses the commercial 20 wt%Pt/C(η_(10)=37 mV).Moreover,the mass activity of Pt/Co@NC is 5.6 A mg_(Pt)^(-1) at-50 mV vs.RHE,which is 2.23 times higher than that of 20 wt%Pt/C.Experimental and theoretical results indicate that the work function of the outer carbon layer,which is changed by the introduction of the inner cobalt core,plays a crucial role in reversing the direction of electron migration between the carbon layer and Pt.The negatively charged Pt^(δ-)can spontaneously attract positively charged protons via the electrostatic interaction effect,thereby achieving the directional migration of hydrogen species.This work presents a strategy for designing advanced alkaline HER electrocatalysts by the electrostatic effect.展开更多
With the in-depth implementation of sustainable development strategies,hydrogen energy as a clean energy source is receiving increasing attention[1,2].Among the various methods of hydrogen production,the electrocataly...With the in-depth implementation of sustainable development strategies,hydrogen energy as a clean energy source is receiving increasing attention[1,2].Among the various methods of hydrogen production,the electrocatalytic decomposition of abundant seawater into hydrogen utilizing renewable energy has emerged as a green and promising approach.However,natural seawater contains complex components,such as halide ions,which lead to the corrosion of catalysts or the occurrence of competitive side reactions during the electrolysis process[3].展开更多
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 high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for cataly...The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for catalyst innovation.Herein,in situ boron-doped Co_(2)P/CoP(B-Co_(x)P)ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition.Density functional theory(DFT)simulations,comprehensive characterizations,and in-situ analyses reveal that boron doping enhances electron density around Co centers,induces lattice distortions,and significantly elevates catalytic activity and durability.Moreover,boron doping reduces*Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning.In a three-electrode system,B-Co_(x)P achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^(-2),respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts.In an alkaline electrolyzer,it delivers 1.56 A·cm^(-2)at 2.87 V for seawater electrolysis with outstanding stability over 500 h,preserving active site integrity via boron's robust protective role.This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.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
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
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
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
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
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
Fabricating a durable electrocatalyst with performance comparable to noble metals for the alkaline hydrogen evolution reaction(HER)remains a significant challenge.In this work,we introduce a highly efficient and robus...Fabricating a durable electrocatalyst with performance comparable to noble metals for the alkaline hydrogen evolution reaction(HER)remains a significant challenge.In this work,we introduce a highly efficient and robust electrocatalyst by incorporating rhenium(Re)atoms into CoS nanoflakes(Re-CoS)for alkaline HER.The incorporation of Re atoms into the CoS lattice enhances the hybridization of Co 3d and S 2p orbitals,resulting in an optimized electronic structure that accelerates water dissociation on Co sites and optimizes hydrogen adsorptiondesorption on S sites,thereby boosting the HER rate.The optimal Re-CoS catalyst demonstrates a low overpotential of 72 mV at 10 mA cm^(-2)in 1 M KOH,along with excellent long-term stability,maintaining its catalytic activity over 200 h without significant degradation.These results suggest that the incorporation of Re atoms into CoS effectively couples the water dissociation and hydrogen addesorption steps of alkaline HER,offering a promising strategy for the development of noble metal-like electrocatalysts.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
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52273059 and 52473219)the Natural Science Foundation of Tianjin(Grant Nos.22JCYBJC01030 and 23JCYBJC00650)provided by Yantai Tayho Advanced Materials Group Co.,Ltd.
文摘Alkaline water electrolysis(AWE)represents a promising approach for green hydrogen production,yet the development of high-performance separators with gas impermeability,high ion conductivity,and stability under alkaline operating conditions has proven challenging.To address this challenge,we develop a pre-concentration regulated phase separation strategy for scalable fabrication of asymmetric hierarchical porous membranes(AHPMs)for AWE.The resulting AHPMs demonstrate a hierarchical structure composed of an ultrathin dense skin layer and highly interconnected porous support.Benefitting from the structural advantages,the AHPMs exhibit outstanding characteristics,including a high bubble point pressure up to 12.4 bar,extremely low area resistance of 0.03Ωcm^(2) in 30 wt%KOH at 80℃,and excellent hydrophilicity and long-term alkaline stability.When applied in AWE with commercial catalysts,the AHPMs achieved an impressive current density of 1.9 A cm^(-2) at 2.0 V in 30 wt%KOH and the anodic hydrogen contents(AHCs)below 0.5 vol.%at a low current density of 0.1 A cm^(-2),differential pressure of 2 bar,and temperature of 80℃.Moreover,AHPMs demonstrate exceptional stability over 2,400 h of continuous operation and maintain superior performance in a 1 Nm^(3) h^(-1) industrialscale electrolyzer stack.This work advances the development of efficient separators for highperformance AWE systems,contributing to the advancement of hydrogen technologies in sustainable energy applications.
基金funding enabled and organized by CAUL and its Member Institutionsby COMSTEQ-TWAS research grant 2018(18-268 RG/EAS/AS_C)。
文摘Examining carbonate dissolution kinetics at mineral-water interface is crucial to understand numerous environmental and geochemical processes,including global carbon cycling,CO_(2)sequestration in deep geological reservoirs,and trace elements release in terrestrial and aquatic environments.Here we explored the effect of circumneutral to alkaline pH solutions(pH 6-11)on dissolution kinetics of pure dolomite and Ca and Mg release stoichiometry in flow-through reactor experiments at 25±1℃.Results revealed that the dolomite dissolution rates obtained from effluent Ca and Mg concentrations(R_(Ca)and R_(Mg)in mol/cm^(2)/s)were dependent on input solution pH and HCO_(3)^(-)log activity.The pH dependence of dissolution rates showed two distinct trends,i.e.,at circumneutral pH ranging between 6 and 8,the dissolution rate decreased with increasing pH,with minimum rate at pH 8.While in the highly alkaline pH range(pH 9-11),the dolomite dissolution rate increased with an increasing pH.Irrespective of the input pH,the dolomite dissolution rates indicated a reverse relationship with HCO_(3)^(-)log activity,with the lowest dissolution rate(R Ca=3.80×10^(-12)mol/cm^(2)/s)at pH 8 where HCO_(3)^(-)log activity attained the highest value(-3.957).The lower R Ca and R Mg obtained at pH 8 compared to all the other pH could possibly be attributed to an inhibition caused by high HCO_(3)^(-)log activity in solution at this pH.Dolomite dissolution rates were non-stoichiometric at all the experimental pH values,showing higher preferential Ca over Mg release(R_(Ca)>R_(Mg))whereas an opposite trend was observed at pH 8,with R_(Ca)<R_(Mg)at the steady state.Saturation index values calculated using geochemical speciation modelling were positive for Mg-bearing minerals(brucite,dolomite,artinite)at alkaline pH of 10-11,indicating favourable conditions for their precipitation under studied conditions.This study provides insights on the significance of log ion activities of HCO_(3)^(-)and Me-OH^(+)under varying pH for elucidating the dissolution mechanism of dolomite in circumneutral to alkaline aqueous environments.
基金supported by Natural Science Foundation of Shanghai,under the Shanghai Action Plan for Science,Technology and Innovation(22ZR1464800).
文摘Driven by the global energy transition and carbon neutrality targets,alkaline water electrolysis has emerged as a key technology for coupling variable renewable generation with clean hydrogen production,offering considerable potential for absorbing surplus power and enhancing grid flexibility.However,conventional control architectures typically treat the power converter and electrolyzer as independent units,neglecting their dynamic interactions and thereby limiting overall system performance under practical operating conditions.This review critically examines existing control approaches,ranging from classical proportional-integral schemes to model predictive control,fuzzy-logic algorithms,and data-driven methods,evaluating their effectiveness in managing dynamic response,multivariable coupling,and operational constraints as well as their inherent limitations.Attention is then focused on the performance requirements of the hydrogen-production converter,including current ripple suppression,rapid transient response,adaptive thermal regulation,and stable power delivery.An integrated co‑control framework is proposed,aligning converter output with electrolyzer demand across steady-state operation,variable renewable input,and emergency shutdown scenarios to achieve higher efficiency,extended equipment lifetime,and enhanced operational safety.Finally,prospects for advancing unified control methodologies are outlined,with emphasis on constraint-aware predictive control,machine-learning-enhanced modeling,and real‑time co‑optimization for future alkaline electrolyzer systems.
基金financially supported by the National Natural Science Foundation of China(Nos.42272137,42202160)AAPG Foundation Grants-in-Aid and the Strategic Cooperation Technology Projecti of CNPC and CUPB(No.ZLZX2020-01-05)。
文摘The pore structure of shale oil reservoir significantly affects the occurrence and mobility of hydrocarbons.The potential of a new type of alkaline lake shale oil has been demonstrated,but there are few reports on the pore system of alkaline lake shale,which restricts the efficient exploration and development of shale oil.This study investigates the Fengcheng Formation shale in the Mahu sag of the Junggar Basin,employing methods such as low-temperature nitrogecn adsorption(LTNA),mercury intrusion capillary pressure(MICP),and nuclear magnetic resonance(NMR)to quantitatively characterize the multi-scale pore structure and fractal characteristics of shale,while evaluating the applicability of these methods.Based on a comprehensive analysis of material composition,different pore types,and fractal dimensions,the controlling factors for the development of different pore types and their seepage capacity are discussed.The results indicate that inorganic mineral pores are the main development in alkaline lake shale,with the pore morphology being characterized by slit-like and ink-bottle shapes.The multi-scale pore size distribution(PSD)shows that Ⅱ-micropores(10-100 nm)and mesopores(100–1000 nm)are the main contributors to the pore system.The development of Ⅱ-micropores is associated with feldspar and calcareous minerals,the development of Ⅰ-micropores(<10 nm)and mesopores is related to quartz content,while large pores are mainly found in interlayer fissures of clay minerals.The development of Ⅰ-micropores increases the roughness of pore surface and enhances the adsorption capacity of the pores,while the development of Ⅱ-micropores associated with calcareous minerals hinders pore seepage capacity.Mesopores and macropores(>1000 nm)exhibit good flowability.The high content of siliceous minerals plays a positive role in the pore system of alkaline lake shale.The shale with higher fractal dimension Dmin exhibits greater adsorption capacity,which hinders the accumulation of free-state shale oil.Different types of pore space play different roles in the occurrence of shale oil,with free-state shale oil primarily occurring in micro-fractures and inorganic mineral pores,and the pore size is exceeding 10 nm.
基金supported by the National Natural Science Foundation of China(Nos.42077067,42277329)the Projects of Talents Recruitment of GDUPT(No.XJ2005000301)。
文摘Phosphorus(P)leaching in alkaline soils,exacerbated by excessive fertilizer application,represents a significant pathway for P loss.While soil pore structure and texture critically regulate P transport,mechanisms governing P loss in texturally diverse alkaline soils remain unclear.This study investigated P leaching dynamics and transport parameters across four alkaline soil textures(silty clay,clay loam,loam,sandy loam)using a one-dimensional convective-diffusion equation(CDE)based on column experiments.Results indicated that phosphorus leaching kinetics were predominantly governed by diffusion transport,evidenced by low Peclet numbers(P_(e))(ranged from 0.02 to 0.31)across varying textures and initial P concentrations(C_(0)).Comparative analysis of transport parameters revealed significant textural effects on dispersion coefficient(D),retardation factor(R),pore water velocity(V),P_(e),and diffusion coefficient(λ)(F>523.42,p<0.001).Among these,only D,P_(e) andλexhibited substantial differences in response to variations in C_(0)(F>89.47,p<0.001).Saturated hydraulic conductivity(K_(s))(R^(2)=62.9%,p<0.01)and total pore area(A)(R^(2)=12.4%,p<0.01)emerged as primary regulators of P leaching.Enhanced clay content increased total pore area while reducing average pore diameter,concurrently decreasing pore water velocity and saturated infiltration rates.These textural modifications amplified diffusive P transport within soil matrices.The findings provide mechanistic insights into texturedependent P mobility in alkaline environments,informing targeted strategies for agricultural phosphorus management.
基金supported by the National Key R&D Program of China(No.2023YFE0112100)the Science and Technology Planning Project of Fujian Province(No.2023Y4015)the Marine and Fishery Devel-opment Special Fund of Xiamen(No.23YYST064QCB36).
文摘Hexavalent chromium(Cr(Ⅵ)) is an extremely toxic pollutant in aqueous environment.Chemical reduction is the most employed method in decontamination of Cr(Ⅵ).However,the chemical reduction was usually conducted in acidic media,resulting in considerable waste of acid reagents and the following neutralizing agents.In this study,kinetics and mechanisms of Cr(Ⅵ) reduction by sulfite in alkaline conditions(pH:7-10) were investigated.It reveals that Cr(Ⅵ) reduction follows pseudo-zero-order kinetics,where the rate constants increased markedly with an in situ irradiation of Far-UVC(UV_(222)).Decreasing pH levels slightly favored the reduction.Iodide ion displayed a notable accelerating effect,which not only save the energy input but also minimize the reductant usage.Chloride,sulfate,and carbonate ions exhibit little effect on the reduction,whereas nitrate and nitrite ions,dissolved oxygen as well as Cu(Ⅱ) suppressed the reduction significantly,implying that hydrated electrons produced by UV222 played the most important role in the reaction.Compared to the UV254/sulfite/iodide process,UV222/sulfite/iodide demonstrates clear advantages in the reduction kinetics and the sulfite utilization efficiency,underscoring its potential for effective Cr(Ⅵ) remediation in various environmental settings.
基金financially supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(23KJB610003)the Natural Science Foundation of Jiangsu Province(BK20240339)+2 种基金the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(No.2023KJ104)the National Natural Science Foundation of China(No.52202092)the Natural Science Foundation of Shandong Province(No.ZR2022QE076)。
文摘Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve the migration of a highly efficient hydrogen species to Pt sites over Pt/Co@NC,which is obtained through a facile calcination and electrodeposition method.It exhibits an outstanding geometric activity(η_(10)=31 m V),which surpasses the commercial 20 wt%Pt/C(η_(10)=37 mV).Moreover,the mass activity of Pt/Co@NC is 5.6 A mg_(Pt)^(-1) at-50 mV vs.RHE,which is 2.23 times higher than that of 20 wt%Pt/C.Experimental and theoretical results indicate that the work function of the outer carbon layer,which is changed by the introduction of the inner cobalt core,plays a crucial role in reversing the direction of electron migration between the carbon layer and Pt.The negatively charged Pt^(δ-)can spontaneously attract positively charged protons via the electrostatic interaction effect,thereby achieving the directional migration of hydrogen species.This work presents a strategy for designing advanced alkaline HER electrocatalysts by the electrostatic effect.
基金financially supported by the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(No.NY223016)Qinglan Project of Jiangsu Province of China2024 Nanjing Science and Technology Innovation Program(No.NJKCZYZZ2024-06)。
文摘With the in-depth implementation of sustainable development strategies,hydrogen energy as a clean energy source is receiving increasing attention[1,2].Among the various methods of hydrogen production,the electrocatalytic decomposition of abundant seawater into hydrogen utilizing renewable energy has emerged as a green and promising approach.However,natural seawater contains complex components,such as halide ions,which lead to the corrosion of catalysts or the occurrence of competitive side reactions during the electrolysis process[3].
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supported by the National Natural Science Foundation of China(No.U24A20550,52273264)Youth Science Foundation Project ofChina(No.22409056)+1 种基金the Key Project of the Heilongjiang Provincial Natural Science Foundation(No.ZD2024B001)the Excellent Youth Project ofHeilongjiang Provincial Natural Science Foundation of China(No.LH2019B020).
文摘The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for catalyst innovation.Herein,in situ boron-doped Co_(2)P/CoP(B-Co_(x)P)ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition.Density functional theory(DFT)simulations,comprehensive characterizations,and in-situ analyses reveal that boron doping enhances electron density around Co centers,induces lattice distortions,and significantly elevates catalytic activity and durability.Moreover,boron doping reduces*Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning.In a three-electrode system,B-Co_(x)P achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^(-2),respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts.In an alkaline electrolyzer,it delivers 1.56 A·cm^(-2)at 2.87 V for seawater electrolysis with outstanding stability over 500 h,preserving active site integrity via boron's robust protective role.This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.
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.
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 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.
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.
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financially supported by the Institute for Basic Science of Korea(No.IBS-R011-D1)the National Research Foundation of Korea(NRF)(No.NRF-2022R1A2C2093415)+5 种基金the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(No.2022R1A6C101A751)the National Natural Science Foundation of China(Nos.22209186 and 22479149)the Natural Science Foundation of Jiangxi Province(No.310306484080)the Key Research and Development Program of Jiangxi Province(Nos.20223BBG74004 and 20232BBG70003)the Youth Innovation Promotion Association,Chinese Academy of Sciences(No.2023343)the financial support from the National Research Foundation of Korea Grant funded by the Korean government(NRF-2021R1I1A1A01050068)
文摘Fabricating a durable electrocatalyst with performance comparable to noble metals for the alkaline hydrogen evolution reaction(HER)remains a significant challenge.In this work,we introduce a highly efficient and robust electrocatalyst by incorporating rhenium(Re)atoms into CoS nanoflakes(Re-CoS)for alkaline HER.The incorporation of Re atoms into the CoS lattice enhances the hybridization of Co 3d and S 2p orbitals,resulting in an optimized electronic structure that accelerates water dissociation on Co sites and optimizes hydrogen adsorptiondesorption on S sites,thereby boosting the HER rate.The optimal Re-CoS catalyst demonstrates a low overpotential of 72 mV at 10 mA cm^(-2)in 1 M KOH,along with excellent long-term stability,maintaining its catalytic activity over 200 h without significant degradation.These results suggest that the incorporation of Re atoms into CoS effectively couples the water dissociation and hydrogen addesorption steps of alkaline HER,offering a promising strategy for the development of noble metal-like electrocatalysts.
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.
