Photoelectrochemical seawater splitting is promising for renewable hydrogen,yet severe chloride corrosion remains a roadblock.Although amorphous catalysts improve hematite(α-Fe_(2)O_(3))photoanode activity,their defe...Photoelectrochemical seawater splitting is promising for renewable hydrogen,yet severe chloride corrosion remains a roadblock.Although amorphous catalysts improve hematite(α-Fe_(2)O_(3))photoanode activity,their defect-enabled functionality inherently accelerates structural degradation,exacerbating chloride-induced corrosion.Here,a synergistic dual-functional nano-armor is designed by anchoring phosphate(PO_(4)^(3-))to active sites on amorphous NiMoO_(4)(a-NiMoO_(4)@PO_(4)^(3-)),achieving dual activitystability enhancement.Detailed physicochemical characterization and density functional theory(DFT)calculations show that the successful and stable anchoring of phosphate is highly dependent on the amorphous structural properties of a-NiMoO_(4).Its rich disordered coordination environment provides sufficient highly reactive sites,allowing PO_(4)^(3-)to be firmly bound through strong coordination bonds,which is the key for the dual role of PO_(4)^(3-)coordination.As a dynamic Cl-shield,PO_(4)^(3-)coordinates unsaturated Ni sites,forming an anionic layer that resists Cl-via steric-electrostatic blocking.As an electronic modulator,PO_(4)^(3-)triggers metal-to-ligand charge transfer at Ni sites,depleting electron density to optimize the intermediate adsorption of oxygen evolution reaction(OER)and reduce kinetic barriers.Simultaneously,this charge redistribution induces a built-in electric field that accelerates holeselective transport.Benefiting from these dual effects,the Fe_(2)O_(3)/a-NiMoO_(4)@PO_(4)^(3-)achieves 4 mA cm^(-2)at 1.23 V_(RHE) with exceptional stability in seawater.This work leverages the unique coordination flexibility of amorphous structures to construct a phosphate-coordinated bifunctional nano-armor on hematite photoanodes,which simultaneously enables efficient chloride exclusion and electronic structure optimization.The synergistic mechanism,rooted in strong phosphate anchoring on amorphous carriers,establishes a new design paradigm for photoelectrochemical systems that integrate high activity with extreme environmental stability,providing an efficient pathway toward corrosion-resistant seawater splitting.展开更多
Seawater electrolysis has been explored as a viable and sustainable method for green hydrogen production in regions characterized by freshwater scarcity but abundant renewable energy resources.However,the high concent...Seawater electrolysis has been explored as a viable and sustainable method for green hydrogen production in regions characterized by freshwater scarcity but abundant renewable energy resources.However,the high concentration of chlorine ions(Cl^(-))in seawater leads to severe corrosion of metallic electrodes,which significantly challenges the stability of electrode catalysts in seawater electrolysis.Owing to the Cl^(-)corrosion and the competitive oxygen/chlorine evolution reactions,the design of durable and active anode catalysts is key to achieving practical seawater electrolysis.To address this challenge,this review systematically analyzes the chlorine-induced corrosion mechanisms of anode catalysts,evaluates various anticorrosion strategies,and explores future prospects for enhancing anode durability.Three mainstream anticorrosion strategies are summarized and assessed for their effectiveness in mitigating the chlorineinduced damage to anode catalysts:the physical surface coatings,electrostatic repulsion,and Cl^(-)adsorption regulation.In addition,some emerging strategies are further introduced to highlight the future trends of state-of-the-art techniques for seawater electrolysis.This review aims to provide novel insights and practical guidance for developing more stable and efficient anode catalysts for hydrogen production via seawater electrolvsis.展开更多
The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by th...The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.展开更多
Seawater electrolysis is an appealing route toward sustainable hydrogen production,yet its practical deployment is hindered by severe chloride-induced corrosion and parasitic chlorine oxidation.Here,we report noble me...Seawater electrolysis is an appealing route toward sustainable hydrogen production,yet its practical deployment is hindered by severe chloride-induced corrosion and parasitic chlorine oxidation.Here,we report noble metal-doped NiV layered double hydroxides(LDHs)that integrate electronic modulation with a dual chloride confinement mechanism.Ir incorporation simultaneously establishes strong Ir-Cl coordination and dynamically regenerated VO_(4)^(3-)layers,producing an adaptive electrostatic shield that effectively suppresses chloride penetration.As a result,Ir-NiV LDH delivers nearly 100%oxygen evolution reaction selectivity and outstanding stability over2750 h at 500 mA cm^(-2).Meanwhile,Ru doping optimizes the hydrogen evolution pathway,enabling a low overpotential of 195 mV and>2350 h durability.When paired in a twso-electrode electrolyzer,the Ru-NiVLDH‖Ir-NiVLDH system exhibits industrial-level performance and unprecedented robustness in alkaline seawater.This dual chloride confinement concept provides a general framework for catalyst design in corrosive ionic environments,extending beyond seawater splitting toward other electrochemical energy conversion processes.展开更多
Ultra-high molecular weight polyethylene(UHMWPE)is a key material for marine applications owing to its outstanding self-lubrication and corrosion resistance.However,its long-term performance is compromised by plastic ...Ultra-high molecular weight polyethylene(UHMWPE)is a key material for marine applications owing to its outstanding self-lubrication and corrosion resistance.However,its long-term performance is compromised by plastic deformation in seawater.In this study,we performed a comparative analysis of the UHMWPE dynamics under seawater and water conditions to investigate the plastic deformation of UHMWPE induced by seawater.The results show that the plastic deformation of UHMWPE is amplified in seawater relative to the water conditions.Under thin fluid conditions,frictional interfaces exhibit a higher interfacial friction force and interaction energy in seawater than in water.Compared to freely diffused water molecules,hydrated ions occupy larger interchain spaces within polyethylene.Furthermore,the diffusion of hydrated ions weakens the interchain interactions,promoting more severe polyethylene chain rearrangement and accelerating seawater-induced plastic deformation in UHMWPE during friction.Furthermore,the diffused seawater accelerated the disentangling of the polyethylene chains and enhanced the orderly orientation distribution of polyethylene.Compared to free water molecules,the water molecules of hydrated ions exhibit enhanced attraction to free-flowing water molecules,thereby accelerating seawater flow across submerged UHMWPE surfaces.This flow enhancement promotes surface polyethylene chain mobility in seawater.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
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).H...Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).Herein,we report a reversed-active sites strategy,converting Cl^(-)-affinitive metal sites to Cl^(-)-repellent oxygen sites,for OER in alkaline seawater electrolysis.First,ex/in situ experiments confirm the effectiveness of such a strategy using typical perovskites following the adsorbate evolution mechanism(AEM)or lattice oxygen-mediated mechanism(LOM).Furthermore,the origins of the superior activity and durability of as-prepared La_(0.3)SrCo_(0.5)Fe_(0.5)Ox(La_(0.3))can be ascribed to higher participation of lattice oxygen in OER,rapid bulk oxygen diffusion,and excellent OH-adsorption kinetics.Hence,an alkaline seawater electrolytic cell with La_(0.3)as the anode produces 10 mA cm^(-2)at just 1.57 V and maintains near-constant activity over 150 hours.This work introduces novel concepts for the production of superactive and steady electrocatalysts for the electrolysis of seawater.展开更多
To simultaneously enrich,separate,and determine five fluoroquinolone antibiotics(FQs)in marine crude drugs(MCDs),seawater and seafood,we conducted this study using vortex assisted dispersed liquid-liquid microextracti...To simultaneously enrich,separate,and determine five fluoroquinolone antibiotics(FQs)in marine crude drugs(MCDs),seawater and seafood,we conducted this study using vortex assisted dispersed liquid-liquid microextraction(DLLME),followed by capillary electrophoresis(CE)-UV.A single-variable optimization was employed to examine the factors influencing the separation effect of CE and the extraction efficiency of DLLME,including buffer solution,organic solvent,separation voltage,extractant,dispersant,and sample solution pH.Under the optimal conditions,the baseline separation of the five FQs was achieved within 6 min.The analytical performance of the method was assessed using six types of actual samples,including three MCDs of hippocampus,clam,and kelp,seawater,and two seafood of prawn and pomfret,demonstrating good linearity ranging from 0.1-5 or 0.01-5μg/mL.The limits of detection(LODs)and limits of quantification(LOQs)for the five FQs in MCDs were 0.0022-0.0292 and 0.0066-0.0973μg/mL,respectively.The LODs and LOQs in seawater and seafood were 0.0009-0.0262 and 0.0029-0.0874μg/mL,respectively.The matrix effects of this method were evaluated in the hippocampus,seawater,and prawn,and the results show that DLLME could effectively eliminate matrix interference.Satisfactory recovery rates were achieved in all the six tested actual samples.This developed DLLME-CE method was proven simple to operate,accurate and reliable,with high sensitivity,making it suitable for the analysis of multiple antibiotic residues in complex matrices.展开更多
Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent meta...Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent metal hydroxides deposition and boost the hydrogen evolution reaction by adding a chelating agent,EDTA-Na_(4),that chelates with Mg^(2+)/Ca^(2+),thus inhibiting their deposition and gathering them near the cathode surface,resulting in breaking the ordered hydrogen bond networks of interfacial water and reducing the activation energy of water dissociation.Furthermore,hydrolysis of–COO^(-) also promoted water dissociation to produce more active*H and*OH near the electrode surface that in turn serves as a diffusion medium for*OH,accelerating mass transfer and enabling seawater electrolysis to exhibit a stable performance,which operates continuously at 100 mA cm^(-2)@2.20 V and 200 mA cm^(-2)@2.58 V for 400 h in the symmetric electrolyzer and 500 mA cm^(-2)@2.29 V for over 500 h in the asymmetric electrolyzer.This study provides a new perspective to address the issues of stable and scalable direct seawater electrolysis for practical green hydrogen production.展开更多
Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-...Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.展开更多
Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the ...Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.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
Hydrogen is widely regarded as a crucial energy carrier for achieving carbon neutrality and a sustainable future.Direct seawater electrolysis using renewable energy presents a promising approach for large-scale hydrog...Hydrogen is widely regarded as a crucial energy carrier for achieving carbon neutrality and a sustainable future.Direct seawater electrolysis using renewable energy presents a promising approach for large-scale hydrogen production.Reactions of this nature at high current density and Faradaic efficiency are hampered by two challenges.展开更多
Seawater electrolysis offers a promising pathway to generate green hydrogen,which is crucial for the net-zero emission targets.Indirect seawater electrolysis is severely limited by high energy demands and system compl...Seawater electrolysis offers a promising pathway to generate green hydrogen,which is crucial for the net-zero emission targets.Indirect seawater electrolysis is severely limited by high energy demands and system complexity,while the direct seawater electrolysis bypasses pre-treatment,offering a simpler and more cost-effective solution.However,the chlorine evolution reaction and impurities in the seawater lead to severe corrosion and hinder electrolysis’s efficiency.Herein,we review recent advances in the rational design of chlorine-suppressive catalysts and integrated electrolysis systems architectures for chloride-induced corrosion,with simultaneous enhancement of Faradaic efficiency and reduction of electrolysis’s cost.Furthermore,promising directions are proposed for durable and efficient seawater electrolysis systems.This review provides perspectives for seawater electrolysis toward sustainable energy conversion and environmental protection.展开更多
This study proposes and systematically evaluates an optimized integration of warm surface seawater injection with depressurization for the long-term exploitation of marine natural gas hydrates.By employing comprehensi...This study proposes and systematically evaluates an optimized integration of warm surface seawater injection with depressurization for the long-term exploitation of marine natural gas hydrates.By employing comprehensive multiphysics simulations guided by field data from hydrate production tests in the South China Sea,we pinpoint key operational parameters—such as injection rates,depths,and timings—that notably enhance production efficiency.The results indicate that a 3-phase hydrate reservoir transitions from a free-gas-dominated production stage to a hydrate-decomposition-dominated stage.Moderate warm seawater injection supplies additional heat during the hydrate decomposition phase,thereby enhancing stable production;however,excessively high injection rates can impede the depressurization process.Only injection at an appropriate depth simultaneously balances thermal supplementation and the pressure gradient,leading to higher overall productivity.A“depressurization-driven sensible-heat supply window”is introduced,highlighting that timely seawater injection following initial depressurization prolongs reservoir dissociation dynamics.In this study area,commencing seawater injection at 170 d of depressurization proved optimal.This optimized integration leverages clean and renewable thermal energy,providing essential insights into thermal supplementation strategies with significant implications for sustainable,economically feasible,and efficient commercial-scale hydrate production.展开更多
In this study,the occurrence,sources,and ecological risk of microplastics(>60μm)in the surface and bottom seawater were investigated in the Beibu Gulf,the northern South China Sea.The average abundance of micropla...In this study,the occurrence,sources,and ecological risk of microplastics(>60μm)in the surface and bottom seawater were investigated in the Beibu Gulf,the northern South China Sea.The average abundance of microplastics in surface and bottom waters was 1.35±0.93 and 0.79±0.50 items/m~3,respectively.Microplastics in both surface and bottom waters were predominantly in the form of fragments,and mostly in green.The composition of microplastics in surface water was primarily poly(methyl methacrylate)(PMA),whereas in bottom water,polyethylene(PE)dominated.Positive matrix factorization(PMF)modeling revealed that the primary sources of microplastics were pipeline abrasion,fishing activities,plastic waste,landfill disposal,transportation,aquaculture,and construction activities.The pollution load index(PLI)indicated that the overall risk of microplastic pollution in the Beibu Gulf was low.Conversely,the polymer hazard index(PHI)for microplastics was relatively high.These data underscore the importance of timely and effective reduction of human-intensive activities contributing to microplastic pollution and provide valuable information for further research in microplastic ecotoxicology and biogeochemistry.展开更多
Hydrogen production via seawater electrolysis,leveraging sustainable energy sources such as offshore wind or solar energy,has immense application potential.However,the abundance of chloride ions(Cl^(-))in seawater lea...Hydrogen production via seawater electrolysis,leveraging sustainable energy sources such as offshore wind or solar energy,has immense application potential.However,the abundance of chloride ions(Cl^(-))in seawater leads to the generation of chlorine gas and hypochlorite at the anode during electrolysis,pos-ing a severe threat of corrosion of the catalyst and electrolytic equipment.Herein,we synthesize a NiMo-based catalyst adorned with surface-anchored graphene quantum dots(GQDs).This catalyst possesses ex-cellent Cl^(-)exclusion capabilities.The Mo-NiS/Se@GQDs core-shell nanorod catalyst requires only 170 mV of overpotential to attain a current density of 10 mA cm^(-2) and operates stably for 200 h without degra-dation across a broad current density range from 100 to 400 mA cm^(-2).This remarkable electrocatalytic stability arises from the dynamic and efficient repulsion of Cl^(-)at the catalytic interface,as proven by the post-reaction analysis of Cl^(-)distribution within the catalyst.Furthermore,a potentiodynamic polarization test revealed that the Mo-NiS/Se@GQDs catalyst has high corrosion potential(0.66 V)and low corrosion current density(122.93μA cm^(-2)),underscoring its excellent corrosion resistance.This research presents a novel approach to mitigate Cl^(-)corrosion during hydrogen production through seawater electrolysis,laying a solid foundation for advancing sustainable energy conversion technologies.展开更多
A pyrimidine derivative,6-phenyl-2-thiouracil(PT),was synthesized for developing a corrosion inhibitor(CI)applied in the protection of the nickel−aluminum bronze(NAB)in seawater.The anti-corrosion effect of PT was eva...A pyrimidine derivative,6-phenyl-2-thiouracil(PT),was synthesized for developing a corrosion inhibitor(CI)applied in the protection of the nickel−aluminum bronze(NAB)in seawater.The anti-corrosion effect of PT was evaluated by the mass loss experiment,electrochemical tests and surface analysis.The results show that PT exhibits excellent inhibition performance and the maximum inhibition efficiency of PT reaches 99.6%.The interaction mechanism was investigated through X-ray photoelectron spectroscopy(XPS)and molecule dynamics simulation based on the density functional theory(DFT).The S-Cu,Al-N and Cu-N bonds are formed by the chemical interactions,leading to the adsorption of PT on the NAB surface.The diffusion of corrosive species is hindered considerably by the protective PT film with composition of(PT-Cu)_(ads)and(PT-Al)_(ads)on the PT/NAB interface.The degree of suppression is increased with the addition of more PT molecules.展开更多
Defect engineering and interface engineering exhibit remarkable potential in the quest for efficient and stable bifunctional catalysts for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Herein,...Defect engineering and interface engineering exhibit remarkable potential in the quest for efficient and stable bifunctional catalysts for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Herein,we innovatively designed a Ni-MoO_(2)/NiMoO_(4-x) heterojunction electrocatalyst enriched with lattice defects using a novel thermal reduction strategy.For this catalyst,the strain effect induced by the lattice defects optimizes the electronic structure,while the heterogeneous interface significantly accelerates the electron transport efficiency,thereby substantially enhancing catalytic activity and pro-moting reaction kinetics.Using advanced spherical aberration-corrected transmission electron microscopy(AC-TEM)combined with geometric phase analysis(GPA)simulations,we directly visualized and con-firmed the presence of strain effects and heterostructures,which are pivotal factors in improving catalytic performance.In an alkaline seawater environment,the Ni-MoO_(2)/NiMoO_(4-x) catalyst exhibited exceptional performance with the HER overpotential as low as 27 mV and the OER overpotential of 216 mV at a cur-rent density of 10 mA cm^(-2).Furthermore,in a membrane electrode assembly(MEA)electrolyzer,the het-erojunction catalyst can drive a current density of 147 mA cm^(-2) at a voltage of only 1.82 V,and maintain stable operation for over 100 h without degradation.In-depth theoretical simulations and experimen-tal analyses revealed that the enriched Ni defect sites optimized the adsorption energy of hydrogen and oxygen intermediates,thereby boosting the catalytic efficiency for both HER and OER.This study not only pioneers a new approach to optimizing the performance of transition metal oxide catalysts but also pro-vides robust theoretical support and experimental foundations for the practical application of hydrogen production technology through electrolytic water splitting in the future.展开更多
基金supported by the Shandong Provincial Natural Science Foundation(No.ZR2022ME052)the National Natural Science Foundation of China(No.22404153)+4 种基金the TaiShan Scholars of Shandong China(No.tsqn202306113 and tsqn202408081)the Excellent Youth Science Fund Project of Shandong China(No.2025HWYQ-032)the China Postdoctoral Science Foundation(No.2024M753044)the Postdoctoral Fellowship Program of CPSF(No.GZB20240693)the Natural Science Foundation of Qingdao(No.24-4-4-zrjj-9-jch)。
文摘Photoelectrochemical seawater splitting is promising for renewable hydrogen,yet severe chloride corrosion remains a roadblock.Although amorphous catalysts improve hematite(α-Fe_(2)O_(3))photoanode activity,their defect-enabled functionality inherently accelerates structural degradation,exacerbating chloride-induced corrosion.Here,a synergistic dual-functional nano-armor is designed by anchoring phosphate(PO_(4)^(3-))to active sites on amorphous NiMoO_(4)(a-NiMoO_(4)@PO_(4)^(3-)),achieving dual activitystability enhancement.Detailed physicochemical characterization and density functional theory(DFT)calculations show that the successful and stable anchoring of phosphate is highly dependent on the amorphous structural properties of a-NiMoO_(4).Its rich disordered coordination environment provides sufficient highly reactive sites,allowing PO_(4)^(3-)to be firmly bound through strong coordination bonds,which is the key for the dual role of PO_(4)^(3-)coordination.As a dynamic Cl-shield,PO_(4)^(3-)coordinates unsaturated Ni sites,forming an anionic layer that resists Cl-via steric-electrostatic blocking.As an electronic modulator,PO_(4)^(3-)triggers metal-to-ligand charge transfer at Ni sites,depleting electron density to optimize the intermediate adsorption of oxygen evolution reaction(OER)and reduce kinetic barriers.Simultaneously,this charge redistribution induces a built-in electric field that accelerates holeselective transport.Benefiting from these dual effects,the Fe_(2)O_(3)/a-NiMoO_(4)@PO_(4)^(3-)achieves 4 mA cm^(-2)at 1.23 V_(RHE) with exceptional stability in seawater.This work leverages the unique coordination flexibility of amorphous structures to construct a phosphate-coordinated bifunctional nano-armor on hematite photoanodes,which simultaneously enables efficient chloride exclusion and electronic structure optimization.The synergistic mechanism,rooted in strong phosphate anchoring on amorphous carriers,establishes a new design paradigm for photoelectrochemical systems that integrate high activity with extreme environmental stability,providing an efficient pathway toward corrosion-resistant seawater splitting.
基金sponsored by the National Natural Science Foundation of China(52302039,52301043)the Guangdong Basic and Applied Basic Research Foundation(2024A1515240056)+3 种基金the Shenzhen Science and Technology Program(GXWD20231129113217001)the Shenzhen Key Laboratory of New Materials Technology(SYSPG20241211173609003)the Postdoctoral Research Startup Expenses of Shenzhen(NA25501001)Shenzhen Introduce High-level Talents and Scientific Research Start-up Funds(NA11409005)。
文摘Seawater electrolysis has been explored as a viable and sustainable method for green hydrogen production in regions characterized by freshwater scarcity but abundant renewable energy resources.However,the high concentration of chlorine ions(Cl^(-))in seawater leads to severe corrosion of metallic electrodes,which significantly challenges the stability of electrode catalysts in seawater electrolysis.Owing to the Cl^(-)corrosion and the competitive oxygen/chlorine evolution reactions,the design of durable and active anode catalysts is key to achieving practical seawater electrolysis.To address this challenge,this review systematically analyzes the chlorine-induced corrosion mechanisms of anode catalysts,evaluates various anticorrosion strategies,and explores future prospects for enhancing anode durability.Three mainstream anticorrosion strategies are summarized and assessed for their effectiveness in mitigating the chlorineinduced damage to anode catalysts:the physical surface coatings,electrostatic repulsion,and Cl^(-)adsorption regulation.In addition,some emerging strategies are further introduced to highlight the future trends of state-of-the-art techniques for seawater electrolysis.This review aims to provide novel insights and practical guidance for developing more stable and efficient anode catalysts for hydrogen production via seawater electrolvsis.
基金supported by National Natural Science Foundation of China(Grant No.22378066,22108040)Collaboration&Innovation Platform Project of National Independent Innovation Demonstration Zone(Fuzhou,Xiamen&Quanzhou)(Project No:3502ZCQXT2023004).
文摘The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.
基金supported by the National Natural Science Foundation of China(No.22209115,52472226,and U23A20573)the Key Research and Development Program of Shandong Province(No.2022CXGC010305)+2 种基金Guangdong Basic and Applied Basic Research Foundation(No.2025A1515011809,2023B1515120022 and 2022B1515120001)Shenzhen Science and Technology Innovation Program(No.RCBS20231211090522040,KJZD20240903095610014,and KJZD20240903095712017)the High-Level Professional Team in Shenzhen(KQTD20210811090045006)。
文摘Seawater electrolysis is an appealing route toward sustainable hydrogen production,yet its practical deployment is hindered by severe chloride-induced corrosion and parasitic chlorine oxidation.Here,we report noble metal-doped NiV layered double hydroxides(LDHs)that integrate electronic modulation with a dual chloride confinement mechanism.Ir incorporation simultaneously establishes strong Ir-Cl coordination and dynamically regenerated VO_(4)^(3-)layers,producing an adaptive electrostatic shield that effectively suppresses chloride penetration.As a result,Ir-NiV LDH delivers nearly 100%oxygen evolution reaction selectivity and outstanding stability over2750 h at 500 mA cm^(-2).Meanwhile,Ru doping optimizes the hydrogen evolution pathway,enabling a low overpotential of 195 mV and>2350 h durability.When paired in a twso-electrode electrolyzer,the Ru-NiVLDH‖Ir-NiVLDH system exhibits industrial-level performance and unprecedented robustness in alkaline seawater.This dual chloride confinement concept provides a general framework for catalyst design in corrosive ionic environments,extending beyond seawater splitting toward other electrochemical energy conversion processes.
基金financially supported by the National Natural Science Foundation of China(Nos.51909023 and 51775077)the Natural Science Foundation of Liaoning Province(No.2021-MS-140)the Fundamental Research Funds for the Central Universities(No.3132025114)。
文摘Ultra-high molecular weight polyethylene(UHMWPE)is a key material for marine applications owing to its outstanding self-lubrication and corrosion resistance.However,its long-term performance is compromised by plastic deformation in seawater.In this study,we performed a comparative analysis of the UHMWPE dynamics under seawater and water conditions to investigate the plastic deformation of UHMWPE induced by seawater.The results show that the plastic deformation of UHMWPE is amplified in seawater relative to the water conditions.Under thin fluid conditions,frictional interfaces exhibit a higher interfacial friction force and interaction energy in seawater than in water.Compared to freely diffused water molecules,hydrated ions occupy larger interchain spaces within polyethylene.Furthermore,the diffusion of hydrated ions weakens the interchain interactions,promoting more severe polyethylene chain rearrangement and accelerating seawater-induced plastic deformation in UHMWPE during friction.Furthermore,the diffused seawater accelerated the disentangling of the polyethylene chains and enhanced the orderly orientation distribution of polyethylene.Compared to free water molecules,the water molecules of hydrated ions exhibit enhanced attraction to free-flowing water molecules,thereby accelerating seawater flow across submerged UHMWPE surfaces.This flow enhancement promotes surface polyethylene chain mobility in seawater.
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funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金supported by the National Natural Science Foundation of China(No.22278203).
文摘Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).Herein,we report a reversed-active sites strategy,converting Cl^(-)-affinitive metal sites to Cl^(-)-repellent oxygen sites,for OER in alkaline seawater electrolysis.First,ex/in situ experiments confirm the effectiveness of such a strategy using typical perovskites following the adsorbate evolution mechanism(AEM)or lattice oxygen-mediated mechanism(LOM).Furthermore,the origins of the superior activity and durability of as-prepared La_(0.3)SrCo_(0.5)Fe_(0.5)Ox(La_(0.3))can be ascribed to higher participation of lattice oxygen in OER,rapid bulk oxygen diffusion,and excellent OH-adsorption kinetics.Hence,an alkaline seawater electrolytic cell with La_(0.3)as the anode produces 10 mA cm^(-2)at just 1.57 V and maintains near-constant activity over 150 hours.This work introduces novel concepts for the production of superactive and steady electrocatalysts for the electrolysis of seawater.
基金Supported by the National Natural Science Foundation of China(No.22176210)the Major Innovation Fund of Shandong Province(No.2021ZDSYS23)。
文摘To simultaneously enrich,separate,and determine five fluoroquinolone antibiotics(FQs)in marine crude drugs(MCDs),seawater and seafood,we conducted this study using vortex assisted dispersed liquid-liquid microextraction(DLLME),followed by capillary electrophoresis(CE)-UV.A single-variable optimization was employed to examine the factors influencing the separation effect of CE and the extraction efficiency of DLLME,including buffer solution,organic solvent,separation voltage,extractant,dispersant,and sample solution pH.Under the optimal conditions,the baseline separation of the five FQs was achieved within 6 min.The analytical performance of the method was assessed using six types of actual samples,including three MCDs of hippocampus,clam,and kelp,seawater,and two seafood of prawn and pomfret,demonstrating good linearity ranging from 0.1-5 or 0.01-5μg/mL.The limits of detection(LODs)and limits of quantification(LOQs)for the five FQs in MCDs were 0.0022-0.0292 and 0.0066-0.0973μg/mL,respectively.The LODs and LOQs in seawater and seafood were 0.0009-0.0262 and 0.0029-0.0874μg/mL,respectively.The matrix effects of this method were evaluated in the hippocampus,seawater,and prawn,and the results show that DLLME could effectively eliminate matrix interference.Satisfactory recovery rates were achieved in all the six tested actual samples.This developed DLLME-CE method was proven simple to operate,accurate and reliable,with high sensitivity,making it suitable for the analysis of multiple antibiotic residues in complex matrices.
基金the support from the National Key Research and Development Program of China(2023YFB4005000)the Joint Fund of Liaoning Binhai Laboratory(LBLF-2023-04)+3 种基金Dalian Science and Technology Talent Innovation Support Plan(2022RY09)Innovation Research Fund of Dalian Institute of Chemical Physics(DICP I202318)National Natural Science Foundation of China(22478384)the UK EPSRC(EP/W03784X/1)。
文摘Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent metal hydroxides deposition and boost the hydrogen evolution reaction by adding a chelating agent,EDTA-Na_(4),that chelates with Mg^(2+)/Ca^(2+),thus inhibiting their deposition and gathering them near the cathode surface,resulting in breaking the ordered hydrogen bond networks of interfacial water and reducing the activation energy of water dissociation.Furthermore,hydrolysis of–COO^(-) also promoted water dissociation to produce more active*H and*OH near the electrode surface that in turn serves as a diffusion medium for*OH,accelerating mass transfer and enabling seawater electrolysis to exhibit a stable performance,which operates continuously at 100 mA cm^(-2)@2.20 V and 200 mA cm^(-2)@2.58 V for 400 h in the symmetric electrolyzer and 500 mA cm^(-2)@2.29 V for over 500 h in the asymmetric electrolyzer.This study provides a new perspective to address the issues of stable and scalable direct seawater electrolysis for practical green hydrogen production.
基金funding support from Natural Science Foundation of Shanghai(Grant No.23ZR1443900)the National Natural Science Foundation of China(Grant Nos.22178309,22476131 and 22176127)。
文摘Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.
基金support by National Key Research and Development Program of China(2022YFB3803502)National Natural Science Foundation of China(52103076)+5 种基金Science and Technology Commission of Shanghai Municipality(23ZR1400300)special fund of Beijing Key Laboratory of Indoor Air Quality Evaluat ion and Control(NO.BZ0344KF21-02)State Key Laboratory of Electrical Insulation and Power Equipment(EIPE22203)JLF is a member of LSRE-LCM–Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials,supported by national funds through FCT/MCTES(PIDDAC):LSRE-LCM,UIDB/50020/2020(DOI:10.54499/UIDB/50020/2020)UIDP/50020/2020(DOI:10.54499/UIDP/50020/2020)ALiCE,LA/P/0045/2020(DOI:10.54499/LA/P/0045/2020).
文摘Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.
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Hydrogen is widely regarded as a crucial energy carrier for achieving carbon neutrality and a sustainable future.Direct seawater electrolysis using renewable energy presents a promising approach for large-scale hydrogen production.Reactions of this nature at high current density and Faradaic efficiency are hampered by two challenges.
基金supported by the National Natural Science Foundation of China(Nos.22208376,UA22A20429)Shandong Provincial Natural Science Foundation(Nos.ZR2024QB175,ZR2023LFG005)+1 种基金Qingdao New Energy Shandong Laboratory Open Project(QNESL OP 202303)Ministry of Education University-Industry Collaborative Education Program(No.230804132140429).
文摘Seawater electrolysis offers a promising pathway to generate green hydrogen,which is crucial for the net-zero emission targets.Indirect seawater electrolysis is severely limited by high energy demands and system complexity,while the direct seawater electrolysis bypasses pre-treatment,offering a simpler and more cost-effective solution.However,the chlorine evolution reaction and impurities in the seawater lead to severe corrosion and hinder electrolysis’s efficiency.Herein,we review recent advances in the rational design of chlorine-suppressive catalysts and integrated electrolysis systems architectures for chloride-induced corrosion,with simultaneous enhancement of Faradaic efficiency and reduction of electrolysis’s cost.Furthermore,promising directions are proposed for durable and efficient seawater electrolysis systems.This review provides perspectives for seawater electrolysis toward sustainable energy conversion and environmental protection.
基金supported by the National Key R&D Program of China(No.2024YFB4206700)the Joint Geological Funds of the National Natural Science Foundation of China(No.U2244223)+5 种基金the China Scholarship Council Program(No.202404910533)the Guangdong Major Project of Basic and Applied Basic Research(No.2020B0301030003)the China Geological Survey Project(No.DD20211350)the Key Deployment Program of Chinese Academy of Sciences(Nos.YJKYYQ20190043,ZDBS-LY-DQC003,KFZD-SW-422,and ZDRW-ZS-2021-3-1)the Scientific Research and Technology Development Project of China National Petroleum Corporation(No.2022DJ5503)the Supercomputing Laboratory,IGGCAS.
文摘This study proposes and systematically evaluates an optimized integration of warm surface seawater injection with depressurization for the long-term exploitation of marine natural gas hydrates.By employing comprehensive multiphysics simulations guided by field data from hydrate production tests in the South China Sea,we pinpoint key operational parameters—such as injection rates,depths,and timings—that notably enhance production efficiency.The results indicate that a 3-phase hydrate reservoir transitions from a free-gas-dominated production stage to a hydrate-decomposition-dominated stage.Moderate warm seawater injection supplies additional heat during the hydrate decomposition phase,thereby enhancing stable production;however,excessively high injection rates can impede the depressurization process.Only injection at an appropriate depth simultaneously balances thermal supplementation and the pressure gradient,leading to higher overall productivity.A“depressurization-driven sensible-heat supply window”is introduced,highlighting that timely seawater injection following initial depressurization prolongs reservoir dissociation dynamics.In this study area,commencing seawater injection at 170 d of depressurization proved optimal.This optimized integration leverages clean and renewable thermal energy,providing essential insights into thermal supplementation strategies with significant implications for sustainable,economically feasible,and efficient commercial-scale hydrate production.
基金Supported by the National Natural Science Foundation of China(No.U20A20103)the Scientific Research Fund of the Fourth Institute of Oceanography+1 种基金Guangxi Funding Project(No.304024XM20N0006)the Guangxi Talent Science and Technology Project(No.2019AC17008)。
文摘In this study,the occurrence,sources,and ecological risk of microplastics(>60μm)in the surface and bottom seawater were investigated in the Beibu Gulf,the northern South China Sea.The average abundance of microplastics in surface and bottom waters was 1.35±0.93 and 0.79±0.50 items/m~3,respectively.Microplastics in both surface and bottom waters were predominantly in the form of fragments,and mostly in green.The composition of microplastics in surface water was primarily poly(methyl methacrylate)(PMA),whereas in bottom water,polyethylene(PE)dominated.Positive matrix factorization(PMF)modeling revealed that the primary sources of microplastics were pipeline abrasion,fishing activities,plastic waste,landfill disposal,transportation,aquaculture,and construction activities.The pollution load index(PLI)indicated that the overall risk of microplastic pollution in the Beibu Gulf was low.Conversely,the polymer hazard index(PHI)for microplastics was relatively high.These data underscore the importance of timely and effective reduction of human-intensive activities contributing to microplastic pollution and provide valuable information for further research in microplastic ecotoxicology and biogeochemistry.
基金financially supported by the National Natural Science Foundation of China(Nos.22103045 and 52273077)the State Key Laboratory of Bio-Fibers and Eco-Textiles,Qingdao University(Nos.ZDKT202108,RZ2000003334,and G2RC202022).
文摘Hydrogen production via seawater electrolysis,leveraging sustainable energy sources such as offshore wind or solar energy,has immense application potential.However,the abundance of chloride ions(Cl^(-))in seawater leads to the generation of chlorine gas and hypochlorite at the anode during electrolysis,pos-ing a severe threat of corrosion of the catalyst and electrolytic equipment.Herein,we synthesize a NiMo-based catalyst adorned with surface-anchored graphene quantum dots(GQDs).This catalyst possesses ex-cellent Cl^(-)exclusion capabilities.The Mo-NiS/Se@GQDs core-shell nanorod catalyst requires only 170 mV of overpotential to attain a current density of 10 mA cm^(-2) and operates stably for 200 h without degra-dation across a broad current density range from 100 to 400 mA cm^(-2).This remarkable electrocatalytic stability arises from the dynamic and efficient repulsion of Cl^(-)at the catalytic interface,as proven by the post-reaction analysis of Cl^(-)distribution within the catalyst.Furthermore,a potentiodynamic polarization test revealed that the Mo-NiS/Se@GQDs catalyst has high corrosion potential(0.66 V)and low corrosion current density(122.93μA cm^(-2)),underscoring its excellent corrosion resistance.This research presents a novel approach to mitigate Cl^(-)corrosion during hydrogen production through seawater electrolysis,laying a solid foundation for advancing sustainable energy conversion technologies.
基金supported by the National Natural Science Foundation of China(No.52171069).
文摘A pyrimidine derivative,6-phenyl-2-thiouracil(PT),was synthesized for developing a corrosion inhibitor(CI)applied in the protection of the nickel−aluminum bronze(NAB)in seawater.The anti-corrosion effect of PT was evaluated by the mass loss experiment,electrochemical tests and surface analysis.The results show that PT exhibits excellent inhibition performance and the maximum inhibition efficiency of PT reaches 99.6%.The interaction mechanism was investigated through X-ray photoelectron spectroscopy(XPS)and molecule dynamics simulation based on the density functional theory(DFT).The S-Cu,Al-N and Cu-N bonds are formed by the chemical interactions,leading to the adsorption of PT on the NAB surface.The diffusion of corrosive species is hindered considerably by the protective PT film with composition of(PT-Cu)_(ads)and(PT-Al)_(ads)on the PT/NAB interface.The degree of suppression is increased with the addition of more PT molecules.
基金supported by the National Natural Science Foundation of China(Nos.22103045 and 52273077)the State Key Laboratory of Bio-Fibers and Eco-Textiles,Qingdao University(Nos.ZDKT202108,RZ2000003334,and G2RC202022).
文摘Defect engineering and interface engineering exhibit remarkable potential in the quest for efficient and stable bifunctional catalysts for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Herein,we innovatively designed a Ni-MoO_(2)/NiMoO_(4-x) heterojunction electrocatalyst enriched with lattice defects using a novel thermal reduction strategy.For this catalyst,the strain effect induced by the lattice defects optimizes the electronic structure,while the heterogeneous interface significantly accelerates the electron transport efficiency,thereby substantially enhancing catalytic activity and pro-moting reaction kinetics.Using advanced spherical aberration-corrected transmission electron microscopy(AC-TEM)combined with geometric phase analysis(GPA)simulations,we directly visualized and con-firmed the presence of strain effects and heterostructures,which are pivotal factors in improving catalytic performance.In an alkaline seawater environment,the Ni-MoO_(2)/NiMoO_(4-x) catalyst exhibited exceptional performance with the HER overpotential as low as 27 mV and the OER overpotential of 216 mV at a cur-rent density of 10 mA cm^(-2).Furthermore,in a membrane electrode assembly(MEA)electrolyzer,the het-erojunction catalyst can drive a current density of 147 mA cm^(-2) at a voltage of only 1.82 V,and maintain stable operation for over 100 h without degradation.In-depth theoretical simulations and experimen-tal analyses revealed that the enriched Ni defect sites optimized the adsorption energy of hydrogen and oxygen intermediates,thereby boosting the catalytic efficiency for both HER and OER.This study not only pioneers a new approach to optimizing the performance of transition metal oxide catalysts but also pro-vides robust theoretical support and experimental foundations for the practical application of hydrogen production technology through electrolytic water splitting in the future.
