The osteochondral(OC)interface exhibits a mineral gradient,varying in thickness by several hundred micrometers across different species.Disruptions in this interface damage OC tissues,leading to osteoarthritis.The nat...The osteochondral(OC)interface exhibits a mineral gradient,varying in thickness by several hundred micrometers across different species.Disruptions in this interface damage OC tissues,leading to osteoarthritis.The natural architecture and composition of native OC interfaces can be replicated using biomaterial scaffolds via regenerative engineering approaches.A novel one-step bioextrusion process was employed to fabricate a unitary synthetic graft(USG),which mimics the native OC interface’s mineral concentration gradient.This novel USG is composed of an agarose-based cartilage layer and a bone layer,consisting of agarose enriched with 20%(200 g/L)hydroxyapatite.The USG features a gradient interface with mineral concentrations transitioning from 0%to 20%(mass fraction),mimicking the transition between the cartilage and bone.Thermogravimetric analysis revealed that the gradient transition lengths of the graft and native OC tissue harvested from bovine knees were similar((647±21)vs.(633±124)μm).The linear viscoelastic properties of the grafts,which were evaluated using strain sweep and frequency sweep tests with oscillatory shear,indicated a dominant storage modulus over loss modulus similar to that of native OC tissues.The compressive and stress relaxation behaviors of the USGs demonstrated that the graft maintained structural integrity under mechanical stress.Viability assays performed after bioextrusion showed that chondrocytes and human fetal osteoblast cells successfully integrated and survived within their designated regions of the graft.The novel USGs exhibit properties similar to native OC tissue and are promising candidates for regenerating OC defects and restoring knee joint functionality.展开更多
Exploring the influence of the coordination environment of single-atom catalysts(SACs)on the electrochemical CO_(2)reduction reaction is vital for assessing the reaction mechanism and structure-performance relationshi...Exploring the influence of the coordination environment of single-atom catalysts(SACs)on the electrochemical CO_(2)reduction reaction is vital for assessing the reaction mechanism and structure-performance relationship.However,it is challenging to engineer the coordination configuration of isolated active metal atoms precisely.Herein,we strategically manipulate the coordination number of the Co-N_(x) configuration by simply changing the order of adding the metal precursor toward improved CO_(2)electrolysis performance.Compared with the symmetric Co-N_(4)coordination,the asymmetric Co-N_(3)coordination leads to reinforced Co-N interaction and downshifted 3d orbital energy toward the Fermi level of the active Co sites,promoting the activation of CO_(2)molecules and the formation of critical intermediate^(*)COOH.The as-designed Co-N_(3)SAC displays excellent Faradaic efficiency(FE)of 98.4%for CO_(2)-to-CO conversion at a low potential of-0.80 V,together with decent FE over a wide potential range(-0.50 V to-1.10 V)and high durability.This study presents an ideal platform to manipulate the coordination number of atomically dispersed metal catalysts and provides a fundamental understanding of coordination configurationperformance correlation for CO_(2)electroreduction.展开更多
The octahedral tunnel-like three-dimensional(3D)structure of V_(2)O_(3)enables fast metal ion(de)intercalation and high capacity in aqueous zinc-ion batteries(ZIBs),but suffers from phase transition-induced structural...The octahedral tunnel-like three-dimensional(3D)structure of V_(2)O_(3)enables fast metal ion(de)intercalation and high capacity in aqueous zinc-ion batteries(ZIBs),but suffers from phase transition-induced structural degradation and capacity fading.Herein,we demonstrate that the undesirable phase transition of V_(2)O_(3)can be effectively suppressed through a new La^(3+)doping strategy and its implementation as a robust ZIBs cathode.The introduced La^(3+)ions not only can increase cell volume and expand ion channels of V_(2)O_(3)but also offer plentiful Zn^(2+)storage sites and promote the transport of Zn^(2+)ions and electrons.In particular,the doping of La^(3+)maintains the octahedral tunnel structure of V_(2)O_(3)and prevents its phase transition during(dis)charge,which improves the cycle stability of the V_(2)O_(3)cathode in ZIBs.By virtue of the above favorable factors,La-doped V_(2)O_(3)electrode presents an impressive discharge capacity of632.1 m Ah g^(-1)at 0.1 A g^(-1)after 100 cycles with a capacity retention up to 93.1%.Even at 10 A g^(-1),its discharge capacity remains at 342.7 mAh g^(-1)after 1000 cycles with a capacity attenuation of solely0.0069%per cycle.This work establishes rare-earth cation doping as a universal paradigm to reconcile structural stability and multi-electron redox activity in high-capacity battery electrodes.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Microplastics(MPs)are ubiquitous and pose an environmental risk.This review examined MP pollution in terrestrial ecosystems from a myriad of poorly understood sources.Knowledge regarding the occurrence sources,migrati...Microplastics(MPs)are ubiquitous and pose an environmental risk.This review examined MP pollution in terrestrial ecosystems from a myriad of poorly understood sources.Knowledge regarding the occurrence sources,migration behaviors,ecotoxicology,absorption mechanisms,and effects of MPs has also been fully summarized.Microplastics interact with contaminants,such as antibiotics,pesticides,heavy metals,etc.,and may act as vectors for contaminant transfer in terrestrial ecosystems.The transportation and retention of MPs in soil are governed by interactions among their inherent properties,such as size,shape,surface charge,and density.Interestingly,MP migration into soil is lacking research.The MPs and nanoplastics were also found in edible fruits and vegetables.The MP contamination in soil affects ecosystems,causing soil structure changes,fertility reduction,and pollutant leaching into groundwater.The MP concentration lies in the range of 43-2443 and 40-43000 items kg-1in agricultural and urban soils,respectively.This review provides a comprehensive roadmap for future research and a framework for soil MP risk assessment.Future studies on the uptake,accumulation,and translocation of MPs and their associated toxins by plants are essential for evaluating their risks to food security and human health.Research on MPs in terrestrial habitats lacks comprehensive data on their long-term persistence,degradation pathways,and interactions with soil components under varying environmental conditions.Additionally,limited understanding exists regarding MP impacts on soil biodiversity,pollutant mobility,and plant uptake,highlighting the need for innovative detection methods and effective pollution abatement strategies.展开更多
In this study,Palm kernel shell(PKS)is utilized as a raw material to produce activated biochar as adsorbent for dye removal from wastewater,specifically methylene blue(MB)dye,by utilizing a simplified and costeffectiv...In this study,Palm kernel shell(PKS)is utilized as a raw material to produce activated biochar as adsorbent for dye removal from wastewater,specifically methylene blue(MB)dye,by utilizing a simplified and costeffective approach.Production of activated biocharwas carried out using both a furnace and a domesticmicrowave oven without an inert atmosphere.Three samples of palm kernel shell(PKS)based activated biochar labeled as samples A,B and C were carbonized inside the furnace at 800℃ for 1 h and then activated using the microwave-heating technique with varying heating times(0,5,10,and 15 min).The heating was conducted in the absence of an inert gas.Fourier Transform Infrared Spectroscopy(FTIR)highlighted a significant Si-O stretching vibration between 1040.5 to 692.7 cm−1,indicating the presence of key components(Silica and Alumina)in all PKS-based activated biochar samples.For wastewater treatment,activated biochar samples were tested against a 20 mg/LMethylene Blue(MB)solution,and the MB percentage removal was calculated for each run using a standard curve.Central Composite Design(CCD)experiments were conducted for optimization,with activated biochar Sample C exhibiting the highest adsorption capacity at 88.14%MB removal under specific conditions.ANOVA analysis confirmed the significance of the quadratic model,with a p-value of 0.0222 and R^(2)=0.9438.In conclusion,the results demonstrated the efficiency of PKS-based activated biochar as an adsorbent for MB removal in comparison to other commercial adsorbents.展开更多
The transport properties of liquid mixtures confined within porous media can change significantly from those observed for bulk mixtures due to changes in the liquid structuring within the pore space.Here,pulsed field ...The transport properties of liquid mixtures confined within porous media can change significantly from those observed for bulk mixtures due to changes in the liquid structuring within the pore space.Here,pulsed field gradient NMR was used to measure the diffusion coefficient of ethanol in ethanol-water liquid mixtures confined within silicas with pore diameters of 6 nm and 3 nm as a function of composition.For liquids imbibed within the 6 nm pores,the composition dependence of the ethanol diffusion coefficient closely followed that of the bulk liquid mixture and the absolute diffusion coefficients were reduced by a tortuosity factor of 3,with a minor contribution due to liquid-surface interactions.For liquids imbibed within the 3 nm pores,the diffusion coefficient of ethanol decreased as the composition of ethanol within the pore space increased,and for single-component ethanol imbibition the effective tortuosity was 63.Fast field cycling NMR experiments showed that the diffusion behaviour was not controlled by an increase in ethanol adsorption strength.A geometric analysis of the pore space was consistent with a highly confined system in which most molecules interacted with the pore walls.Under such confinement,the liquid structuring within the bulk pore space did not reflect that of the bulk liquid mixtures,and the observed decrease in diffusion coefficient as ethanol composition increased was consistent with an increase in confinement due to the larger size of the ethanol molecule.展开更多
To efficiently remove radioactive nuclides from nuclear industry wastewater and minimize the generation of radioactive secondary waste,this study proposes the concept of a magnetically controlled microchannel adsorber...To efficiently remove radioactive nuclides from nuclear industry wastewater and minimize the generation of radioactive secondary waste,this study proposes the concept of a magnetically controlled microchannel adsorber based on magnetic adsorbents.A novel protocol for achieving high adsorption performance in microchannel adsorbers with periodically distributed particles is developed using the particle-resolved computational fluid dynamics (CFD) method,which addresses the limitations of traditional porous media flow models.To align simulation results more closely with practical scenarios,a typical high-efficiency magnetic adsorbent,magnetic sodium alginate/cobalt-based Prussian blue (M-SA/PB-Co),was synthesized.The M-SA/PB-Co microspheres exhibit a uniform size distribution (300–600 μm),and their Cs^(+) adsorption follows the pseudo-second-order kinetic model with a Langmuir saturated adsorption capacity of 124.84 mg·g^(-1).The performance parameters of M-SA/PB-Co,obtained from characterization and adsorption experiments,were integrated into CFD simulations.CFD results indicate that as the flow velocity increases,the flow field gradually transitions with vortices expanding in scale and streamline bifurcation points shifting rearward.The Cs^(+) concentration decreases progressively along the flow direction,with a more pronounced reduction in the vortex regions downstream of particles.The characteristic velocity and characteristic concentration of specific regions surrounding the particles were extracted based on boundary layer distribution.The amount of concentration reduction of Cs^(+) through particle is positively correlated with the characteristic concentration and negatively correlated with the characteristic velocity.The number of microspheres required in the microchannel adsorber was optimized using the response surface method.Compared with industrial fixed-bed adsorbers,microchannel adsorbers exhibit 8–10 times higher processing capacity,demonstrating significant industrial application potential.展开更多
The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technol...The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.展开更多
Conformational entropy,one of the central concepts of polymer physics,is the key to revealing physical characteristics of polymers.Despite an increased repertoire of conformational-entropy effects in the structural fo...Conformational entropy,one of the central concepts of polymer physics,is the key to revealing physical characteristics of polymers.Despite an increased repertoire of conformational-entropy effects in the structural formation,transition,and properties of polymer systems,the physical origin of conformational entropy remains less understood compared to interaction energy and other types of entropy.This review seeks to provide a conceptual framework unveiling several principles and rules of conformational entropy in governing the structures and properties of polymers,from the perspective of fundamental physics and statistical mechanics.First,we focus on the fundamentals of entropy in thermodynamics,leading to the theoretical basis for the elucidation of conformational entropy.Second,we delineate the physical nature of statistics and dissipation of conformational entropy and its essential dependence on the environmental heat bath.Next,we explore the principles of conformational entropy in driving the ordering transitions of various systems of polymers and their nanocomposites,elucidating the emergent and collective behaviors as well as the interplay between energetic interactions and entropy.Moreover,we demonstrate how the concept of conformational entropy is generalized to the biological systems and other soft matters.Finally,we discuss future directions to signify this framework originated from polymers.展开更多
Space exploration and manufacturing are of critical importance for scientific advancement,technological innovation,national security,and the acquisition of extraterrestrial resources.In view of this,chemical and biolo...Space exploration and manufacturing are of critical importance for scientific advancement,technological innovation,national security,and the acquisition of extraterrestrial resources.In view of this,chemical and biological nano-/micro-/meso-scale manufacturing provide complementary approaches to overcome key space exploration challenges by enabling the in-situ production of essential life-support materials,propellants,and other resources.This review examines the origin and historical evolution of space manufacturing and the latest advances across different environments—from orbital space stations and the lunar surface to Mars and asteroids.It is structured to present the current state of research,outline key manufacturing strategies and technologies,assess the technical and environmental challenges,and discuss emerging trends and future directions.Besides,the potential applications of emerging technologies such as synthetic biology and artificial intelligence in overcoming the limitations of microgravity,limited resources,and extreme conditions are discussed.Ultimately,this integrative review could serve to guide future development,from advancing space science and disruptive manufacturing to enabling interdisciplinary and application-level innovations.展开更多
Dear Editor,This letter presents a new approach to developing interpretable and reliable soft sensors for Industry 5.0 applications.Although sophisticated machine learning methods have made remarkable strides in soft-...Dear Editor,This letter presents a new approach to developing interpretable and reliable soft sensors for Industry 5.0 applications.Although sophisticated machine learning methods have made remarkable strides in soft-sensor predictive accuracy,ensuring interpretability and reliable performance across varying industrial operating conditions remains a challenge[1]–[4].This is precisely what Industry 5.0,proposed by the European Commission in 2021,advocates[5],[6].It integrates various cutting-edge technologies,such as human-machine interaction,digital twins,cybersecurity and artificial intelligence,to facilitate the development of better soft sensors.展开更多
Anode-free lithium-metal batteries(AFLMBs)offer high energy density.However,lithium dendrite growth and interfacial instability remain critical obstacles to their commercialization.Here,lithiophilic nanosized(∼5 nm)L...Anode-free lithium-metal batteries(AFLMBs)offer high energy density.However,lithium dendrite growth and interfacial instability remain critical obstacles to their commercialization.Here,lithiophilic nanosized(∼5 nm)LixSn combined with an inorganic-rich@polymer dual-layer structure was constructed on a Cu current collector,prepared via a galvanostatic process using a dual-lithium salt electrolyte in a Cu||Cu configuration.The polymer outer layer,initiated by LixSn,reinforces the solid electrolyte interphase(SEI),providing mechanical robustness and enabling stable cycling in an ether-based electrolyte.Furthermore,the Sn and LixSn particle sizes can be effectively tuned by adjusting the galvanostatic discharge current.The nanosized LixSn significantly lowers the nucleation overpotential and creates abundant lithiophilic nucleation sites,resulting in uniform,dense Li plating/stripping.The modified Cu collector demonstrates superior performance in ether-based electrolytes,achieving over 92%capacity retention after 100 cycles at a current density of 1.5 mA cm^(−2)and an area capacity of 1.1 mAh cm^(−2).This work provides a simple,eco-friendly,and scalable approach for fabricating high-performance anode-free current collectors for AFLMBs.展开更多
Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon ...Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon neutrality,LIBs are expected to play a pivotal role in reducing CO_(2)emissions by decreasing reliance on fossil fuels and enabling the integration of renewable energy sources.Owing to their technological maturity and exceptional electrochemical performance,the global production of graphite and graphene for LIBs is projected to continue expanding.Over the past decades,numerous researchers have concentrated on reducing the material and energy input whilst optimising the electrochemical performance of graphite and graphene,through novel synthesis methods and various modifications at the laboratory scale.This review provides a comprehensive examination of the manufacturing methods,environmental impact,research progress,and challenges associated with graphite and graphene in LIBs from an industrial perspective,with a particular focus on the carbon footprint of production processes.Additionally,it considers emerging challenges and future development directions of graphite and graphene,offering significant insights for ongoing and future research in the field of green LIBs.展开更多
Single-atom catalysts for alkyne semi-hydrogenation have been extensively investigated due to their high metal utilization and improved olefin selectivity.However,their reactivity is hindered by the sluggish activatio...Single-atom catalysts for alkyne semi-hydrogenation have been extensively investigated due to their high metal utilization and improved olefin selectivity.However,their reactivity is hindered by the sluggish activation of reactants on isolated sites.Herein,a non-precise metal catalyst consisting of Ni-Cu hetero-diatomic pairs was prepared using a sequential deposition method.The diatomic sites catalyst exhibited an unprecedented activity among non-precious catalysts with over 98%conversion and 77 mol_(C2H2) mol_(metal)^(-1) h^(-1) at 180℃,whereas the single-atom catalysts of Cu/C and Ni/C were almost inert under the same conditions.Experimental and theoretical results revealed the crucial diatomic synergy between the Ni-Cu pairs,wherein acetylene was adsorbed on Ni sites and hydrogen was adsorbed on Cu sites,and the diatomic site enabled spontaneous desorption of ethylene.The superior activity of the diatomic catalyst was observed,resulting from the enhanced dominance of d-electrons of Ni near the Fermi level.The research demonstrates an approach to designing non-precise metal catalysts with extraordinary catalytic performance for alkyne hydrogenation.展开更多
This study aimed to produce and characterize mycelium leather(Mylea)derived from oil palm empty fruit bunch(OPEFB).Variations in OPEFB composition(10%,20%,30%,and 40%)were tested using a 10%w/w Ganoderma lucidum inocu...This study aimed to produce and characterize mycelium leather(Mylea)derived from oil palm empty fruit bunch(OPEFB).Variations in OPEFB composition(10%,20%,30%,and 40%)were tested using a 10%w/w Ganoderma lucidum inoculum.The mycelium underwent boiling,plasticization,drying,pressing,waxing,and Tencel fabric reinforcement to form Mylea.The physical,mechanical,and flammability properties of OPEFB-based Mylea were evaluated as a potential animal leather substitute.The highest tensile strength(8.47 MPa)was observed in the 0%OPEFB sample due to reinforcement with the Tencel fabric layer.Meanwhile,the 20%OPEFB sample after drying exhibited a tensile strength of 5.78 MPa and a lower elastic modulus(14.48 MPa),indicating increased flexibility but reduced stiffness.Among the tested compositions,20%OPEFB provided the best balance between growth time and material quality.Flammability tests showed that Mylea with 20%OPEFB had a longer burn time(43.5±7.78 s)compared to 0%OPEFB(21.0±1.41 s).However,the addition of OPEFB did not improve fire resistance,as none of the samples met UL 94 V-0,V-1,or V-2 standards.展开更多
Iron-based single-atom(SA)catalysts offer a promising alternative to noble-metal catalysts for the oxygen reduction reaction(ORR),yet their limited intrinsic activity and durability hinder practical energy device appl...Iron-based single-atom(SA)catalysts offer a promising alternative to noble-metal catalysts for the oxygen reduction reaction(ORR),yet their limited intrinsic activity and durability hinder practical energy device applications.Herein,we introduce a novel TiN/TiC-supported Fe SA catalyst(TiNC/Fe-NC)with a hierarchical heterostructure that synergistically enhances Fe-N_(x) site activity and accessibility.The TiNC/Fe-NC catalyst achieves outstanding ORR performances,with half-wave potentials(E_(1/2))of 0.852 V in acidic media and 0.942 V in alkaline media.Theoretical simulations reveal that strong electronic interaction and efficient charge transfer between TiNC and Fe-N_(x) sites optimize the adsorption energetics of key ORR intermediates,driving the enhanced activity.Remarkably,TiNC effectively scavenges reactive oxygen radicals generated at the Fe centers,ensuring exceptional durability with a minimal 28 mV loss in E_(1/2) after 10,000 cycles at 80℃in acid media.In practical applications,TiNC/Fe-NC delivers peak power densities of 306 mW cm^(-2) in zinc-air battery and 732 mW cm^(-2) in proton exchange membrane fuel cells,with remarkable long-term stability.This work establishes TiNC/Fe-NC as a highperformance,durable catalyst for advanced energy storage and conversion technologies.展开更多
The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-ass...The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.展开更多
Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-con...Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-conjugated polymers.CMPs offer extensive versatility in synthetic approaches,enabling the synthesis of cross-linked and mesoporous structures.Advances in chemical processes,structural design,and synthesis methodologies have been developed,resulting in a diverse range of CMPs with unique configurations and properties,contributing to the fast expansion of the field.CMPs are particularly notable for their ability to enable the competitive utilization ofπ-conjugated structures within mesoporous configurations,making them valuable for investigations across various domains.They have shown considerable promise in addressing fuel and environmental challenges,demonstrated by their exceptional performance in applications such as vapor adsorption,heterogeneous catalysis,light emission,light harvesting,and energy generation.This review examines the chemical engineering principles underlying CMPs,including synthesis approaches,systemic research advancements,multifunctional investigations boundaries,potential applications,and progress in synthesis,dimensionality,and morphology studies.Specifically,it offers a comparative analysis of CMPs and linear polymeric materials,aiding in the development of functional polymers.Furthermore,this review explores the primary fundamental limitations of CMPs in fuel-related domains and discusses alternative strategies,including novel synthesis methods incorporating interactions and morphologies,to address these challenges.Ultimately,this assessment aims to provide a valuable and inspiring resource for professionals in the field of fuel management,guiding future research and development efforts.展开更多
The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behav...The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behavior of dispersed long chains.Using molecular dynamics simulations based on the Kremer-Grest model,we systematically explore the N_(S)-dependence of static conformations,equilibrium dynamics,and nonlinear shear responses in unentangled long-chain/short-chain polymer blends.Our results demonstrate a decoupling between the static and dynamic sensitivity to N_(S):while the static chain size,R_g,follows Flory theory with slight swelling at small N_(S) due to incomplete excluded volume screening,the diffusion coefficient,D,and the relaxation time,τ_(0),exhibit a strong,non-monotonic N_(S)-dependence,transitioning from monomeric friction dominance at small N_(S) to collective segmental rearrangement at large N_(S).Additionally,we observe partial decoupling between the viscous and normal stress responses:while the zero-shear viscosity,η,is strongly N_(S)-dependent,the first and second normal stress coefficients,Ψ_(1) and Ψ_(2),collapse onto universal curves when scaled by the dimensionless shear rate,γτ_(0),suggesting a common mechanism of orientation and stretching.Under shear,long chains compress in the vorticity direction λ_(z)~Wi^(-0.2),which reduces collision frequency and contributes to shear thinning,while the scaling of weaker orientation resistance m_(G)~Wi^(0.35)reflects hydrodynamic screening by the short-chain matrix.These findings highlight the limitations of single-chain models and emphasize the necessity of considering N_(S)-dependent matrix dynamics and flow-induced structural changes in understanding the rheology of unentangled polymer blends.展开更多
基金supported by the School of Engineering and Digital Sciences of Nazarbayev University,Astana,Kazakhstan(to CE)。
文摘The osteochondral(OC)interface exhibits a mineral gradient,varying in thickness by several hundred micrometers across different species.Disruptions in this interface damage OC tissues,leading to osteoarthritis.The natural architecture and composition of native OC interfaces can be replicated using biomaterial scaffolds via regenerative engineering approaches.A novel one-step bioextrusion process was employed to fabricate a unitary synthetic graft(USG),which mimics the native OC interface’s mineral concentration gradient.This novel USG is composed of an agarose-based cartilage layer and a bone layer,consisting of agarose enriched with 20%(200 g/L)hydroxyapatite.The USG features a gradient interface with mineral concentrations transitioning from 0%to 20%(mass fraction),mimicking the transition between the cartilage and bone.Thermogravimetric analysis revealed that the gradient transition lengths of the graft and native OC tissue harvested from bovine knees were similar((647±21)vs.(633±124)μm).The linear viscoelastic properties of the grafts,which were evaluated using strain sweep and frequency sweep tests with oscillatory shear,indicated a dominant storage modulus over loss modulus similar to that of native OC tissues.The compressive and stress relaxation behaviors of the USGs demonstrated that the graft maintained structural integrity under mechanical stress.Viability assays performed after bioextrusion showed that chondrocytes and human fetal osteoblast cells successfully integrated and survived within their designated regions of the graft.The novel USGs exhibit properties similar to native OC tissue and are promising candidates for regenerating OC defects and restoring knee joint functionality.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(No.20240101004JJ)the National Natural Science Foundation of China(No.22409165)+4 种基金the National Foreign Experts Program of the Ministry of Human Resources and Social Security(No.Y20240003)the Shaanxi Province Talent Programfinancially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Nos.XDB0600000,XDB0600100,XDB0600200,XDB0600300,XDB0600400)Liaoning Binhai Laboratory(No.LILBLB-2023-04)Dalian Revitalization Talents Program(No.2022RG01)。
文摘Exploring the influence of the coordination environment of single-atom catalysts(SACs)on the electrochemical CO_(2)reduction reaction is vital for assessing the reaction mechanism and structure-performance relationship.However,it is challenging to engineer the coordination configuration of isolated active metal atoms precisely.Herein,we strategically manipulate the coordination number of the Co-N_(x) configuration by simply changing the order of adding the metal precursor toward improved CO_(2)electrolysis performance.Compared with the symmetric Co-N_(4)coordination,the asymmetric Co-N_(3)coordination leads to reinforced Co-N interaction and downshifted 3d orbital energy toward the Fermi level of the active Co sites,promoting the activation of CO_(2)molecules and the formation of critical intermediate^(*)COOH.The as-designed Co-N_(3)SAC displays excellent Faradaic efficiency(FE)of 98.4%for CO_(2)-to-CO conversion at a low potential of-0.80 V,together with decent FE over a wide potential range(-0.50 V to-1.10 V)and high durability.This study presents an ideal platform to manipulate the coordination number of atomically dispersed metal catalysts and provides a fundamental understanding of coordination configurationperformance correlation for CO_(2)electroreduction.
基金financially supported by the National Natural Science Foundation of China(No.51962027,and 52262039)the Fundamental Research Funds for Inner Mongolia University of Science&Technology(No.2024QNJS071,2023QNJS052 and 2024QNJS064)+2 种基金the Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(No.NJYT24002)the Central Guidance Fund for Local Scientific and Technological Development(2024ZY0012)the Ordos Higher Education Institutions Scientific Research Innovation Project(KYLJ25Z004)。
文摘The octahedral tunnel-like three-dimensional(3D)structure of V_(2)O_(3)enables fast metal ion(de)intercalation and high capacity in aqueous zinc-ion batteries(ZIBs),but suffers from phase transition-induced structural degradation and capacity fading.Herein,we demonstrate that the undesirable phase transition of V_(2)O_(3)can be effectively suppressed through a new La^(3+)doping strategy and its implementation as a robust ZIBs cathode.The introduced La^(3+)ions not only can increase cell volume and expand ion channels of V_(2)O_(3)but also offer plentiful Zn^(2+)storage sites and promote the transport of Zn^(2+)ions and electrons.In particular,the doping of La^(3+)maintains the octahedral tunnel structure of V_(2)O_(3)and prevents its phase transition during(dis)charge,which improves the cycle stability of the V_(2)O_(3)cathode in ZIBs.By virtue of the above favorable factors,La-doped V_(2)O_(3)electrode presents an impressive discharge capacity of632.1 m Ah g^(-1)at 0.1 A g^(-1)after 100 cycles with a capacity retention up to 93.1%.Even at 10 A g^(-1),its discharge capacity remains at 342.7 mAh g^(-1)after 1000 cycles with a capacity attenuation of solely0.0069%per cycle.This work establishes rare-earth cation doping as a universal paradigm to reconcile structural stability and multi-electron redox activity in high-capacity battery electrodes.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
文摘Microplastics(MPs)are ubiquitous and pose an environmental risk.This review examined MP pollution in terrestrial ecosystems from a myriad of poorly understood sources.Knowledge regarding the occurrence sources,migration behaviors,ecotoxicology,absorption mechanisms,and effects of MPs has also been fully summarized.Microplastics interact with contaminants,such as antibiotics,pesticides,heavy metals,etc.,and may act as vectors for contaminant transfer in terrestrial ecosystems.The transportation and retention of MPs in soil are governed by interactions among their inherent properties,such as size,shape,surface charge,and density.Interestingly,MP migration into soil is lacking research.The MPs and nanoplastics were also found in edible fruits and vegetables.The MP contamination in soil affects ecosystems,causing soil structure changes,fertility reduction,and pollutant leaching into groundwater.The MP concentration lies in the range of 43-2443 and 40-43000 items kg-1in agricultural and urban soils,respectively.This review provides a comprehensive roadmap for future research and a framework for soil MP risk assessment.Future studies on the uptake,accumulation,and translocation of MPs and their associated toxins by plants are essential for evaluating their risks to food security and human health.Research on MPs in terrestrial habitats lacks comprehensive data on their long-term persistence,degradation pathways,and interactions with soil components under varying environmental conditions.Additionally,limited understanding exists regarding MP impacts on soil biodiversity,pollutant mobility,and plant uptake,highlighting the need for innovative detection methods and effective pollution abatement strategies.
文摘In this study,Palm kernel shell(PKS)is utilized as a raw material to produce activated biochar as adsorbent for dye removal from wastewater,specifically methylene blue(MB)dye,by utilizing a simplified and costeffective approach.Production of activated biocharwas carried out using both a furnace and a domesticmicrowave oven without an inert atmosphere.Three samples of palm kernel shell(PKS)based activated biochar labeled as samples A,B and C were carbonized inside the furnace at 800℃ for 1 h and then activated using the microwave-heating technique with varying heating times(0,5,10,and 15 min).The heating was conducted in the absence of an inert gas.Fourier Transform Infrared Spectroscopy(FTIR)highlighted a significant Si-O stretching vibration between 1040.5 to 692.7 cm−1,indicating the presence of key components(Silica and Alumina)in all PKS-based activated biochar samples.For wastewater treatment,activated biochar samples were tested against a 20 mg/LMethylene Blue(MB)solution,and the MB percentage removal was calculated for each run using a standard curve.Central Composite Design(CCD)experiments were conducted for optimization,with activated biochar Sample C exhibiting the highest adsorption capacity at 88.14%MB removal under specific conditions.ANOVA analysis confirmed the significance of the quadratic model,with a p-value of 0.0222 and R^(2)=0.9438.In conclusion,the results demonstrated the efficiency of PKS-based activated biochar as an adsorbent for MB removal in comparison to other commercial adsorbents.
文摘The transport properties of liquid mixtures confined within porous media can change significantly from those observed for bulk mixtures due to changes in the liquid structuring within the pore space.Here,pulsed field gradient NMR was used to measure the diffusion coefficient of ethanol in ethanol-water liquid mixtures confined within silicas with pore diameters of 6 nm and 3 nm as a function of composition.For liquids imbibed within the 6 nm pores,the composition dependence of the ethanol diffusion coefficient closely followed that of the bulk liquid mixture and the absolute diffusion coefficients were reduced by a tortuosity factor of 3,with a minor contribution due to liquid-surface interactions.For liquids imbibed within the 3 nm pores,the diffusion coefficient of ethanol decreased as the composition of ethanol within the pore space increased,and for single-component ethanol imbibition the effective tortuosity was 63.Fast field cycling NMR experiments showed that the diffusion behaviour was not controlled by an increase in ethanol adsorption strength.A geometric analysis of the pore space was consistent with a highly confined system in which most molecules interacted with the pore walls.Under such confinement,the liquid structuring within the bulk pore space did not reflect that of the bulk liquid mixtures,and the observed decrease in diffusion coefficient as ethanol composition increased was consistent with an increase in confinement due to the larger size of the ethanol molecule.
基金Dalian distinguished young scholars program(2022RJ17)the Dalian excellent young talents program(2023RY037)provided funding for this study.
文摘To efficiently remove radioactive nuclides from nuclear industry wastewater and minimize the generation of radioactive secondary waste,this study proposes the concept of a magnetically controlled microchannel adsorber based on magnetic adsorbents.A novel protocol for achieving high adsorption performance in microchannel adsorbers with periodically distributed particles is developed using the particle-resolved computational fluid dynamics (CFD) method,which addresses the limitations of traditional porous media flow models.To align simulation results more closely with practical scenarios,a typical high-efficiency magnetic adsorbent,magnetic sodium alginate/cobalt-based Prussian blue (M-SA/PB-Co),was synthesized.The M-SA/PB-Co microspheres exhibit a uniform size distribution (300–600 μm),and their Cs^(+) adsorption follows the pseudo-second-order kinetic model with a Langmuir saturated adsorption capacity of 124.84 mg·g^(-1).The performance parameters of M-SA/PB-Co,obtained from characterization and adsorption experiments,were integrated into CFD simulations.CFD results indicate that as the flow velocity increases,the flow field gradually transitions with vortices expanding in scale and streamline bifurcation points shifting rearward.The Cs^(+) concentration decreases progressively along the flow direction,with a more pronounced reduction in the vortex regions downstream of particles.The characteristic velocity and characteristic concentration of specific regions surrounding the particles were extracted based on boundary layer distribution.The amount of concentration reduction of Cs^(+) through particle is positively correlated with the characteristic concentration and negatively correlated with the characteristic velocity.The number of microspheres required in the microchannel adsorber was optimized using the response surface method.Compared with industrial fixed-bed adsorbers,microchannel adsorbers exhibit 8–10 times higher processing capacity,demonstrating significant industrial application potential.
基金supported by the grants PID2020-113371RA-C22 and TED2021-130845A-C32,funded by MCIN/AEI/10.13039/501100011033.M.Marín-García,R.González-OlmosC.Gómez-Canela are members of the GESPA group(Grup d’Enginyeria i Simulacióde Processos Ambientals)at IQS-URL,which has been acknowledged as a Consolidated Research Group by the Government of Catalonia(No.2021-SGR-00321)+1 种基金In addition,M.Marín-García has been awarded a public grant for the Investigo Programme,aimed at hiring young job seekers to undertake research and innovation projects under the Recovery,Transformation,and Resilience Plan(PRTR),European Union Next Generation,for the year 2022,through the Government of Catalonia and the Spanish Ministry for Work and Social Economy(No.100045ID16)Ana Belén Cuenca for her support and expertise,which helped to confirm the proposed reaction mechanism involved in the UV photolysis of cloperastine.
文摘The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.
基金financially supported by the National Natural Science Foundation of China (Nos. 22533003 and 22025302)financial support from the Ministry of Science and Technology of China (No. 2022YFA1203203)State Key Laboratory of Chemical Engineering (No. SKL-ChE23T01).
文摘Conformational entropy,one of the central concepts of polymer physics,is the key to revealing physical characteristics of polymers.Despite an increased repertoire of conformational-entropy effects in the structural formation,transition,and properties of polymer systems,the physical origin of conformational entropy remains less understood compared to interaction energy and other types of entropy.This review seeks to provide a conceptual framework unveiling several principles and rules of conformational entropy in governing the structures and properties of polymers,from the perspective of fundamental physics and statistical mechanics.First,we focus on the fundamentals of entropy in thermodynamics,leading to the theoretical basis for the elucidation of conformational entropy.Second,we delineate the physical nature of statistics and dissipation of conformational entropy and its essential dependence on the environmental heat bath.Next,we explore the principles of conformational entropy in driving the ordering transitions of various systems of polymers and their nanocomposites,elucidating the emergent and collective behaviors as well as the interplay between energetic interactions and entropy.Moreover,we demonstrate how the concept of conformational entropy is generalized to the biological systems and other soft matters.Finally,we discuss future directions to signify this framework originated from polymers.
基金supported by National Natural Science Foundation of China(22278241)a grant from the Institute Guo Qiang,Tsinghua University(2021GQG1016).
文摘Space exploration and manufacturing are of critical importance for scientific advancement,technological innovation,national security,and the acquisition of extraterrestrial resources.In view of this,chemical and biological nano-/micro-/meso-scale manufacturing provide complementary approaches to overcome key space exploration challenges by enabling the in-situ production of essential life-support materials,propellants,and other resources.This review examines the origin and historical evolution of space manufacturing and the latest advances across different environments—from orbital space stations and the lunar surface to Mars and asteroids.It is structured to present the current state of research,outline key manufacturing strategies and technologies,assess the technical and environmental challenges,and discuss emerging trends and future directions.Besides,the potential applications of emerging technologies such as synthetic biology and artificial intelligence in overcoming the limitations of microgravity,limited resources,and extreme conditions are discussed.Ultimately,this integrative review could serve to guide future development,from advancing space science and disruptive manufacturing to enabling interdisciplinary and application-level innovations.
文摘Dear Editor,This letter presents a new approach to developing interpretable and reliable soft sensors for Industry 5.0 applications.Although sophisticated machine learning methods have made remarkable strides in soft-sensor predictive accuracy,ensuring interpretability and reliable performance across varying industrial operating conditions remains a challenge[1]–[4].This is precisely what Industry 5.0,proposed by the European Commission in 2021,advocates[5],[6].It integrates various cutting-edge technologies,such as human-machine interaction,digital twins,cybersecurity and artificial intelligence,to facilitate the development of better soft sensors.
基金supported by the National Research Foundation of Korea (NRF) grant funded by the Korean Government (MSIT)(No. 2020R1A5A1019131)supported by a Korea Institute of Energy Technology Evaluation and Planning (KETEP)grant funded by the Korean government (MOTIE)(RS-2022-KP002703, Sector coupling energy industry advancement manpower training program)+1 种基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE) of the Republic of Korea (RS-2024-00469587)
文摘Anode-free lithium-metal batteries(AFLMBs)offer high energy density.However,lithium dendrite growth and interfacial instability remain critical obstacles to their commercialization.Here,lithiophilic nanosized(∼5 nm)LixSn combined with an inorganic-rich@polymer dual-layer structure was constructed on a Cu current collector,prepared via a galvanostatic process using a dual-lithium salt electrolyte in a Cu||Cu configuration.The polymer outer layer,initiated by LixSn,reinforces the solid electrolyte interphase(SEI),providing mechanical robustness and enabling stable cycling in an ether-based electrolyte.Furthermore,the Sn and LixSn particle sizes can be effectively tuned by adjusting the galvanostatic discharge current.The nanosized LixSn significantly lowers the nucleation overpotential and creates abundant lithiophilic nucleation sites,resulting in uniform,dense Li plating/stripping.The modified Cu collector demonstrates superior performance in ether-based electrolytes,achieving over 92%capacity retention after 100 cycles at a current density of 1.5 mA cm^(−2)and an area capacity of 1.1 mAh cm^(−2).This work provides a simple,eco-friendly,and scalable approach for fabricating high-performance anode-free current collectors for AFLMBs.
基金supported by European Union's Horizon Europe,UK Research and Innovation(UKRI).
文摘Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon neutrality,LIBs are expected to play a pivotal role in reducing CO_(2)emissions by decreasing reliance on fossil fuels and enabling the integration of renewable energy sources.Owing to their technological maturity and exceptional electrochemical performance,the global production of graphite and graphene for LIBs is projected to continue expanding.Over the past decades,numerous researchers have concentrated on reducing the material and energy input whilst optimising the electrochemical performance of graphite and graphene,through novel synthesis methods and various modifications at the laboratory scale.This review provides a comprehensive examination of the manufacturing methods,environmental impact,research progress,and challenges associated with graphite and graphene in LIBs from an industrial perspective,with a particular focus on the carbon footprint of production processes.Additionally,it considers emerging challenges and future development directions of graphite and graphene,offering significant insights for ongoing and future research in the field of green LIBs.
基金supported by the National Key R&D Program of China(Grant No.2021YFA1501803)the National Natural Science Foundation of China(NSFC,Grant No.21978148&52206156)。
文摘Single-atom catalysts for alkyne semi-hydrogenation have been extensively investigated due to their high metal utilization and improved olefin selectivity.However,their reactivity is hindered by the sluggish activation of reactants on isolated sites.Herein,a non-precise metal catalyst consisting of Ni-Cu hetero-diatomic pairs was prepared using a sequential deposition method.The diatomic sites catalyst exhibited an unprecedented activity among non-precious catalysts with over 98%conversion and 77 mol_(C2H2) mol_(metal)^(-1) h^(-1) at 180℃,whereas the single-atom catalysts of Cu/C and Ni/C were almost inert under the same conditions.Experimental and theoretical results revealed the crucial diatomic synergy between the Ni-Cu pairs,wherein acetylene was adsorbed on Ni sites and hydrogen was adsorbed on Cu sites,and the diatomic site enabled spontaneous desorption of ethylene.The superior activity of the diatomic catalyst was observed,resulting from the enhanced dominance of d-electrons of Ni near the Fermi level.The research demonstrates an approach to designing non-precise metal catalysts with extraordinary catalytic performance for alkyne hydrogenation.
基金supported by the Palm Oil Plantation Fund Management Agency(BPDPKS),Indonesia 2024.
文摘This study aimed to produce and characterize mycelium leather(Mylea)derived from oil palm empty fruit bunch(OPEFB).Variations in OPEFB composition(10%,20%,30%,and 40%)were tested using a 10%w/w Ganoderma lucidum inoculum.The mycelium underwent boiling,plasticization,drying,pressing,waxing,and Tencel fabric reinforcement to form Mylea.The physical,mechanical,and flammability properties of OPEFB-based Mylea were evaluated as a potential animal leather substitute.The highest tensile strength(8.47 MPa)was observed in the 0%OPEFB sample due to reinforcement with the Tencel fabric layer.Meanwhile,the 20%OPEFB sample after drying exhibited a tensile strength of 5.78 MPa and a lower elastic modulus(14.48 MPa),indicating increased flexibility but reduced stiffness.Among the tested compositions,20%OPEFB provided the best balance between growth time and material quality.Flammability tests showed that Mylea with 20%OPEFB had a longer burn time(43.5±7.78 s)compared to 0%OPEFB(21.0±1.41 s).However,the addition of OPEFB did not improve fire resistance,as none of the samples met UL 94 V-0,V-1,or V-2 standards.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSITRS2024-00345635 and RS-2021-NR060090)the Research Grant Council of the Hong Kong SAR(PolyU15302824)。
文摘Iron-based single-atom(SA)catalysts offer a promising alternative to noble-metal catalysts for the oxygen reduction reaction(ORR),yet their limited intrinsic activity and durability hinder practical energy device applications.Herein,we introduce a novel TiN/TiC-supported Fe SA catalyst(TiNC/Fe-NC)with a hierarchical heterostructure that synergistically enhances Fe-N_(x) site activity and accessibility.The TiNC/Fe-NC catalyst achieves outstanding ORR performances,with half-wave potentials(E_(1/2))of 0.852 V in acidic media and 0.942 V in alkaline media.Theoretical simulations reveal that strong electronic interaction and efficient charge transfer between TiNC and Fe-N_(x) sites optimize the adsorption energetics of key ORR intermediates,driving the enhanced activity.Remarkably,TiNC effectively scavenges reactive oxygen radicals generated at the Fe centers,ensuring exceptional durability with a minimal 28 mV loss in E_(1/2) after 10,000 cycles at 80℃in acid media.In practical applications,TiNC/Fe-NC delivers peak power densities of 306 mW cm^(-2) in zinc-air battery and 732 mW cm^(-2) in proton exchange membrane fuel cells,with remarkable long-term stability.This work establishes TiNC/Fe-NC as a highperformance,durable catalyst for advanced energy storage and conversion technologies.
基金financial support of the National Natural Science Foundation of China (21875247,21072221, 21172252)the Project of Talent Cultivation for Carbon Peak and Carbon Neutrality of the University of Chinese of Academy of Science
文摘The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.
基金supported by the King Khalid University,Abha,Saudi Arabiathe Deanship of Scientific Research at King Khalid University for funding this work through Large Groups Project under grant number(R.G.P.2/335/46)the Guangdong Office of Research Projects at the Provincial University(No.2024KCXTD064)。
文摘Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-conjugated polymers.CMPs offer extensive versatility in synthetic approaches,enabling the synthesis of cross-linked and mesoporous structures.Advances in chemical processes,structural design,and synthesis methodologies have been developed,resulting in a diverse range of CMPs with unique configurations and properties,contributing to the fast expansion of the field.CMPs are particularly notable for their ability to enable the competitive utilization ofπ-conjugated structures within mesoporous configurations,making them valuable for investigations across various domains.They have shown considerable promise in addressing fuel and environmental challenges,demonstrated by their exceptional performance in applications such as vapor adsorption,heterogeneous catalysis,light emission,light harvesting,and energy generation.This review examines the chemical engineering principles underlying CMPs,including synthesis approaches,systemic research advancements,multifunctional investigations boundaries,potential applications,and progress in synthesis,dimensionality,and morphology studies.Specifically,it offers a comparative analysis of CMPs and linear polymeric materials,aiding in the development of functional polymers.Furthermore,this review explores the primary fundamental limitations of CMPs in fuel-related domains and discusses alternative strategies,including novel synthesis methods incorporating interactions and morphologies,to address these challenges.Ultimately,this assessment aims to provide a valuable and inspiring resource for professionals in the field of fuel management,guiding future research and development efforts.
基金financially supported by the National Natural Science Foundation of China(Nos.22341304,22303100 and 12205270)the National Key R&D Program of China(Nos.2023YFA1008800 and 2020YFA0713601)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDC0180303)。
文摘The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behavior of dispersed long chains.Using molecular dynamics simulations based on the Kremer-Grest model,we systematically explore the N_(S)-dependence of static conformations,equilibrium dynamics,and nonlinear shear responses in unentangled long-chain/short-chain polymer blends.Our results demonstrate a decoupling between the static and dynamic sensitivity to N_(S):while the static chain size,R_g,follows Flory theory with slight swelling at small N_(S) due to incomplete excluded volume screening,the diffusion coefficient,D,and the relaxation time,τ_(0),exhibit a strong,non-monotonic N_(S)-dependence,transitioning from monomeric friction dominance at small N_(S) to collective segmental rearrangement at large N_(S).Additionally,we observe partial decoupling between the viscous and normal stress responses:while the zero-shear viscosity,η,is strongly N_(S)-dependent,the first and second normal stress coefficients,Ψ_(1) and Ψ_(2),collapse onto universal curves when scaled by the dimensionless shear rate,γτ_(0),suggesting a common mechanism of orientation and stretching.Under shear,long chains compress in the vorticity direction λ_(z)~Wi^(-0.2),which reduces collision frequency and contributes to shear thinning,while the scaling of weaker orientation resistance m_(G)~Wi^(0.35)reflects hydrodynamic screening by the short-chain matrix.These findings highlight the limitations of single-chain models and emphasize the necessity of considering N_(S)-dependent matrix dynamics and flow-induced structural changes in understanding the rheology of unentangled polymer blends.
