The production of valuable chemicals using copper(Cu)catalysts via electrochemical CO or CO_(2)reduction reactions(CORR and CO_(2)RR)has shown great potential in the field of sustainable energy conversion[1].Previous ...The production of valuable chemicals using copper(Cu)catalysts via electrochemical CO or CO_(2)reduction reactions(CORR and CO_(2)RR)has shown great potential in the field of sustainable energy conversion[1].Previous research has primarily focused on analyzing the behavior of reaction intermediates or solely on the dynamics within the solution phase,while the synergistic effects between surface species and the solution,particularly the interfacial water and its non-covalent interactions with the Cu surface,have remained partially understood[2].展开更多
Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance ...Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies.This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems.We outline the principles,capabilities,advantages,and limitations of various in situ techniques.Their applications in in situ studies of fuel cells,water/CO_(2)electrolysis,and lithium batteries are highlighted with representative examples.These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems,including materials,intermediates,products,and surroundings during operation,providing insights critical to rational system design.Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales.Such integration promises precise mechanistic insights and robust structure-performance correlations,ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.展开更多
Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials ...Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.展开更多
Degradation of materials is one of the most critical aging mechanisms affecting the performance of lithium batteries.Among the various approaches to investigate battery aging,phase-field modelling(PFM)has emerged as a...Degradation of materials is one of the most critical aging mechanisms affecting the performance of lithium batteries.Among the various approaches to investigate battery aging,phase-field modelling(PFM)has emerged as a widely used numerical method for simulating the evolution of the phase interface as a function of space and time during material phase transition process.Moreover,PFM coupled with multi-physics analyses is particularly well-suited for investigating the mesoscale microstructural evolution of materials,providing quantitative understandings of aging and failure mechanisms in lithium batteries.In this paper,we comprehensively overview the state-of-art applications of PFM in the research of degradation and failure processes in lithium batteries,particularly focusing on the theoretical framework and development of the PFMs for lithium deposition/dissolution,phase separation,and crack propagation.Furthermore,we summarize the existing challenges and prospect some future developments in PFMs,aiming to offer new insights into the advancement of PFM and ultimately enhance the development of lithium batteries.展开更多
High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address thes...High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address these above issues,solid-state Li–air batteries have been widely developed.However,many commonly-used solid electrolytes generally face huge interface impedance inLi–air cells and also showpoor stability towards ambient air/Li electrodes.Herein,we fabricate a differentiating surface-regulated ceramic-based composite electrolyte(DSCCE)by constructing disparately LiI-containing polymethyl methacrylate(PMMA)coating and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)layer on both sides of Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP).The cathode-friendly LiI/PMMA layer displays excellent stability towards superoxide intermediates and also greatly reduces the decomposition voltage of discharge products in Li–air system.Additionally,the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes.Moreover,Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniformand compact composite framework.As a result,the DSCCE-based Li–air batteries possess high capacity/low voltage polarization(11,836mAh g^(-1)/1.45Vunder 500mAg^(-1)),good rate performance(capacity ratio under 1000mAg^(-1)/250mAg^(-1) is 68.2%)and longterm stable cell operation(~300 cycles at 750 mA g^(-1) with 750 mAh g^(-1))in ambient air.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and ca...Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and carbon-intensive, mainly due to the high activation energy required to break the inert C–H bond, low selectivity, and problematic side reactions, including CO_(2)emissions and coke deposition. Electrochemical conversion of methane(ECM) using intermittent renewable energy offers an attractive solution, due to its modular reactor design and operational flexibility across a broad spectrum of temperatures and pressures. This review emphasizes conversion pathways of methane in various reaction systems, highlighting the significance and advantages of ECM in facilitating a sustainable artificial carbon cycle. This work provides a comprehensive overview of conventional methane activation mechanisms and delineates the complete pathways of methane conversion in electrolysis contexts. Based on surface/interface chemistry, this work systematically analyzes proposed reaction pathways and corresponding strategies to enhance ECM efficiency towards various target products, including syngas, hydrocarbons, oxygenates, and advanced carbon materials. The discussion also encompasses opportunities and challenges for the ECM process, including insights into ECM pathways, rational electrocatalyst design, establishment of benchmarking protocols, electrolyte engineering, enhancement of CH4conversion rates, and minimization of CO_(2)emission.展开更多
Focusing on the mechanism of interfa-cial exciton dissociation in edge-on stacked ZnPc-F_(8)ZnPc aggregate,we employ the fragment particle-hole densities(FPHD)method to con-struct the Hamiltonian of diabatic states an...Focusing on the mechanism of interfa-cial exciton dissociation in edge-on stacked ZnPc-F_(8)ZnPc aggregate,we employ the fragment particle-hole densities(FPHD)method to con-struct the Hamiltonian of diabatic states and use the non-Markovian stochastic Schrödinger equation(NMSSE)to simulate the photo-in-duced dynamics processes.The re-sults show that aggregation effects have a significant impact on the interfacial exciton dissociation process.After photo-excita-tion,the excitons first preferentially delocalize and perform the charge transfer(CT)states in the pure ZnPc or F_(8)ZnPc aggregates within 100 fs.These‘intramolecular’CT states can easi-ly evolve into interfacial CT states by hopping electrons and holes in the intramolecular CT states across the interface.Compared with these exciton dissociation processes,the direct ex-citon dissociation into interfacial CT state is relatively slow due to the small electronic cou-pling and vibrational coherence between the locally excited state and the interfacial CT state.As the temperature rises and the vibronic coherence weakens,the direct dissociation rates are significantly enhanced.This investigation provides valuable insights for the design and opti-mization of high-performance organic photovoltaic devices.展开更多
The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previou...The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previous studies but always required complex synthetic method or harsh reaction conditions.In this work,biomass-derived chitosan was used to prepare nitrogen doped carbon.After the loading of Ru,the Ru/NC(NC:nitrogen-doped carbon)catalyst was employed in the solvent-free hydrogenation of levulinic acid under ambient hydrogen pressure at 50−80℃ to reach full conversion.The calcination temperature was optimized to get Ru/NC-800 catalyst with high intrinsic turnover frequency of 358 h^(−1).The apparent activation energy was studied by kinetic experiments.More significantly,the catalyst was small-scaled tested for 36 h in a fix-bed reactor with 620 g/day productivity of γ-valerolactone.The catalyst can be easily synthesized and have high activity and stability,underscoring the potential of future commercial production of γ-valerolactone from levulinic acid.展开更多
Precise regulation of atomic and electronic structures of two-dimensional tungsten disulfide(WS_(2))is significant for rational design of high-performance and low-cost catalyst for acetylene hydrogenation to ethylene(...Precise regulation of atomic and electronic structures of two-dimensional tungsten disulfide(WS_(2))is significant for rational design of high-performance and low-cost catalyst for acetylene hydrogenation to ethylene(AHE),yet remains a major challenge.Herein,we report that by substituting a W atom of WS_(2) with a series of transition metal atoms,sulfur vacancy-confined Cu in the WS_(2) basal plane(Cu@WS_(2)-Sv)is theoretically screened as a superior non-noble metal-based catalyst with higher activity,selectivity,and stability for the AHE than other candidates.The co-adsorption of C_(2)H_(2) and H_(2) and hydrogenation of C_(2)H_(3)^(*) to C_(2)H_(4)^(*) are revealed as the key steps establishing a volcano-like activity trend among the candidates,which present Cu@WS_(2)-Sv as the optimum catalyst combined with molecular dynamics and reaction kinetics analyses.The kinetically more favorable desorption of C_(2)H_(4) than the over hydrogenation path validates a higher selectivity toward C_(2)H_(4) over C_(2)H_(6).Furthermore,a machine-learning model reveals the significant effect of d-electron number and electronegativity of the metal heteroatoms in modulating the AHE activity.展开更多
The pioneering works have demonstrated that the method of single collisions in crossed molecular beams is an important technique for achieving kinetic cooling of atoms or molecules in specific rotational states.In thi...The pioneering works have demonstrated that the method of single collisions in crossed molecular beams is an important technique for achieving kinetic cooling of atoms or molecules in specific rotational states.In this study,we investigated the elastic and inelastic collisions between Al(^(2)P_(1/2))metal atoms and O_(2)molecules at high collision energies in the range of 6.4-14.8 kcal/mol,utilizing the laser-ablation crossed beams in conjunction with time-sliced ion velocity map imaging technique.We observed kinetic cooling of Al(^(2)P_(1/2))atoms with an upper-limit laboratory-frame root-mean-square velocity of 24±3 m/s,corresponding to a translational temperature of 0.9±0.2 K in the laboratory frame,facilitated by the vibrational excitation of O_(2)(v′=1)in inelastic collisions.The translational cooling of Al atoms in the lab frame enhanced detection probability in the transformation of density-to-flux,as evidenced by the scattering images obtained during the experiments.展开更多
Non-oxidative dehydrogenation of propane(PDH)is an important route for large-scale on purpose propene production.Although cobalt-based catalysts are promising alternatives to currently used platinum-or chromium oxide-...Non-oxidative dehydrogenation of propane(PDH)is an important route for large-scale on purpose propene production.Although cobalt-based catalysts are promising alternatives to currently used platinum-or chromium oxide-based catalysts,their further developments are hindered by the uncertainties related to the kind of the active sites involved in the desired and side reactions.To contribute to closing such a gap,we systematically investigate the role of oxidized CoO_(x) and metallic Co0 species in the PDH reaction over catalysts based in Silicalite-1 with supported CoO_(x) species differing in their redox properties.C_(3)H_(8) pulse experiments with sub-millisecond and second resolution at pulse sizes of about 13 and 2200 nmol,respectively,combined with in-depth catalyst characterization and PDH tests at different propane conversions enabled us to understand how the reaction-induced reduction of CoO_(x) affects product selectivity.Propane readily reacts with CoO_(x) to yield propene,carbon oxides and water.The formed Co0 species show high activity to coking and cracking reactions.However,if the size of such species is below 2 nm,these undesired reactions are significantly hindered due to the coverage of the active sites by carbon-containing species.The remaining uncovered surface Co0 sites selectively dehydrogenate propane to propene.The best-performing catalyst showed higher activity than a commercial-like K-CrOx/Al_(2)O_(3) and operated durable in a series of 10 dehydrogenation/regeneration cycles under industrial relevant conditions.The space time yield of propene formation of 0.97 kg·h^(-1)·kgcat^(-1) was achieved at 550℃,52%equilibrium propane conversion and 95% propene selectivity.展开更多
The structure of water and proton transfer under nanoscale confinement has garnered significant attention due to its crucial role in elucidating various phenomena across multiple scientific disciplines.However,there r...The structure of water and proton transfer under nanoscale confinement has garnered significant attention due to its crucial role in elucidating various phenomena across multiple scientific disciplines.However,there remains a lack of consensus on fundamental properties such as diffusion behavior and the nature of hydrogen bonding in confined environments.In this work,we investigated the influence of confinement on proton transfer in water confined within graphene sheets at various spacings by ab initio molecule dynamic and multiscale analysis with time evolution of structural properties,graph theory and persistent homology.We found that reducing the graphene interlayer distance while maintaining water density close to that of bulk water leads to a decrease in proton transfer frequency.In contrast,reducing the interlayer distance without maintaining bulk-like water density results in an increase in proton transfer frequency.This difference is mainly due to the confinement conditions:when density is unchanged,the hydrogen bond network remains similar with significant layering,while compressive stress that increases density leads to a more planar hydrogen bond network,promoting faster proton transfer.Our findings elucidate the complex relationship between confinement and proton transfer dynamics,with implications for understanding proton transport in confined environments,relevant to energy storage and material design.展开更多
Ethanol steam reforming(ESR)represents a promising route for sustainable hydrogen production,leveraging the high hydrogen content,renewability,and logistical advantages of ethanol.Although Ni-based catalysts are leadi...Ethanol steam reforming(ESR)represents a promising route for sustainable hydrogen production,leveraging the high hydrogen content,renewability,and logistical advantages of ethanol.Although Ni-based catalysts are leading non-noble candidates for ESR,their practical deployment is hindered by compromised H_(2) production efficiency and rapid deactivation.In this work,we combined catalyst synthesis,kinetic analysis,and mechanistic investigation to elucidate the effectsof Ni particle size(3-9 nm)on ESR performance of Ni/CeO_(2) catalysts.These Ni/CeO_(2) catalysts were prepared via a citric acid-assisted coprecipitation method,and systematically characterized using complementary techniques,including high-resolution transmission electron microscopy(HRTEM),in situ X-ray photoelectron spectroscopy(XPS),hydrogen temperature-programmed reduction(H_(2)-TPR),Raman spectroscopy,O_(2)/CO chemisorption,and temperature-programmed surface reaction(TPSR)analyses.Mechanistic study revealed that ethanol dehydrogenation to acetaldehyde is the rate-determining step,defining the intrinsic activity of Ni sites,whereas C-C bond cleavage governs H_(2) selectivity in ESR.At smaller Ni sizes(e.g.,3.1 nm),larger CeO_(2) surface was exposed,which promoted acetaldehyde condensation to acetone,and consequently reduced H_(2) production efficiency.The Ni/CeO_(2) catalyst with~5 nm of Ni particles afforded the highest H_(2) yield(66.3%)and outstanding stability by balancing dehydrogenation activity,H_(2) selectivity,and coking resistance.Conversely,larger Ni particles(>6 nm)facilitated methanation reaction and catalyst deactivation.This work reconciles prior inconsistencies in the Ni size effects on ESR and provides guidance for the design of efficient and durable Ni-based catalysts for H_(2) production.展开更多
Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor...Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.展开更多
Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,c...Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.展开更多
文摘The production of valuable chemicals using copper(Cu)catalysts via electrochemical CO or CO_(2)reduction reactions(CORR and CO_(2)RR)has shown great potential in the field of sustainable energy conversion[1].Previous research has primarily focused on analyzing the behavior of reaction intermediates or solely on the dynamics within the solution phase,while the synergistic effects between surface species and the solution,particularly the interfacial water and its non-covalent interactions with the Cu surface,have remained partially understood[2].
基金supported by the National Key Research and Development Program of China(2023YFA1508004)the National Natural Science Foundation of China(T2293692,22502164,92472203,22222903,52271229,22472074,22272069,22361132532,and 22021001)+6 种基金the Industry-University-Research Joint Innovation Project of Fujian Province(2023H6029)the Beijing National Laboratory for Molecular Sciences(BNLMS202305)the Scientific and Technological Project of Yunnan Precious Metals Laboratory(YPML-20240502063)the Liaoning Binhai Laboratory(Grant No.2024-05)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF 2401)the Postdoctoral Fellowship Program of CPSF under Grant Number GZC20240897the China Postdoctoral Science Foundation(No.2025M770016).
文摘Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies.This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems.We outline the principles,capabilities,advantages,and limitations of various in situ techniques.Their applications in in situ studies of fuel cells,water/CO_(2)electrolysis,and lithium batteries are highlighted with representative examples.These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems,including materials,intermediates,products,and surroundings during operation,providing insights critical to rational system design.Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales.Such integration promises precise mechanistic insights and robust structure-performance correlations,ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.
基金National Key Research and Development Program of China (2022YFB2402200)National Natural Science Foundation of China (22225201,22379028)+2 种基金Fundamental Research Funds for the Central Universities (20720220010)Shanghai Pilot Program for Basic Research–Fudan University 21TQ1400100 (21TQ009)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (23520750400)。
文摘Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.
基金financially supported by the National Key R&D Program of China(2021YFB2401800)。
文摘Degradation of materials is one of the most critical aging mechanisms affecting the performance of lithium batteries.Among the various approaches to investigate battery aging,phase-field modelling(PFM)has emerged as a widely used numerical method for simulating the evolution of the phase interface as a function of space and time during material phase transition process.Moreover,PFM coupled with multi-physics analyses is particularly well-suited for investigating the mesoscale microstructural evolution of materials,providing quantitative understandings of aging and failure mechanisms in lithium batteries.In this paper,we comprehensively overview the state-of-art applications of PFM in the research of degradation and failure processes in lithium batteries,particularly focusing on the theoretical framework and development of the PFMs for lithium deposition/dissolution,phase separation,and crack propagation.Furthermore,we summarize the existing challenges and prospect some future developments in PFMs,aiming to offer new insights into the advancement of PFM and ultimately enhance the development of lithium batteries.
基金supported by the National Natural Science Foundation of China(22379074)Young Science and Technology Talent Program of Inner Mongolia Province(NJYT24001)+4 种基金Natural Sciences and Engineering Research Council of Canada(NSERC)GLABAT Solid-State Battery Inc.,China Automotive Battery Research Institute Co.Ltd,Canada Research Chair Program(CRC)Canada Foundation for Innovation(CFI)Ontario Research Fundsupported by the Chinese Scholarship Council.
文摘High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address these above issues,solid-state Li–air batteries have been widely developed.However,many commonly-used solid electrolytes generally face huge interface impedance inLi–air cells and also showpoor stability towards ambient air/Li electrodes.Herein,we fabricate a differentiating surface-regulated ceramic-based composite electrolyte(DSCCE)by constructing disparately LiI-containing polymethyl methacrylate(PMMA)coating and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)layer on both sides of Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP).The cathode-friendly LiI/PMMA layer displays excellent stability towards superoxide intermediates and also greatly reduces the decomposition voltage of discharge products in Li–air system.Additionally,the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes.Moreover,Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniformand compact composite framework.As a result,the DSCCE-based Li–air batteries possess high capacity/low voltage polarization(11,836mAh g^(-1)/1.45Vunder 500mAg^(-1)),good rate performance(capacity ratio under 1000mAg^(-1)/250mAg^(-1) is 68.2%)and longterm stable cell operation(~300 cycles at 750 mA g^(-1) with 750 mAh g^(-1))in ambient air.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金National Key R&D Program of China (2023YFA1508001 and 2023YFA1508002)National Natural Science Foundation of China (22272120 and U2202251)+1 种基金Hainan Province Science and Technology Special Fund(ZDYF2023SHFZ120)Research Foundation of Marine Science and Technology Collaborative Innovation Center of Hainan University (XTCX2022HYB01)。
文摘Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and carbon-intensive, mainly due to the high activation energy required to break the inert C–H bond, low selectivity, and problematic side reactions, including CO_(2)emissions and coke deposition. Electrochemical conversion of methane(ECM) using intermittent renewable energy offers an attractive solution, due to its modular reactor design and operational flexibility across a broad spectrum of temperatures and pressures. This review emphasizes conversion pathways of methane in various reaction systems, highlighting the significance and advantages of ECM in facilitating a sustainable artificial carbon cycle. This work provides a comprehensive overview of conventional methane activation mechanisms and delineates the complete pathways of methane conversion in electrolysis contexts. Based on surface/interface chemistry, this work systematically analyzes proposed reaction pathways and corresponding strategies to enhance ECM efficiency towards various target products, including syngas, hydrocarbons, oxygenates, and advanced carbon materials. The discussion also encompasses opportunities and challenges for the ECM process, including insights into ECM pathways, rational electrocatalyst design, establishment of benchmarking protocols, electrolyte engineering, enhancement of CH4conversion rates, and minimization of CO_(2)emission.
基金supported by the National Natural Science Foundation of China(Nos.22033006,22173074,22473091, 92372105).
文摘Focusing on the mechanism of interfa-cial exciton dissociation in edge-on stacked ZnPc-F_(8)ZnPc aggregate,we employ the fragment particle-hole densities(FPHD)method to con-struct the Hamiltonian of diabatic states and use the non-Markovian stochastic Schrödinger equation(NMSSE)to simulate the photo-in-duced dynamics processes.The re-sults show that aggregation effects have a significant impact on the interfacial exciton dissociation process.After photo-excita-tion,the excitons first preferentially delocalize and perform the charge transfer(CT)states in the pure ZnPc or F_(8)ZnPc aggregates within 100 fs.These‘intramolecular’CT states can easi-ly evolve into interfacial CT states by hopping electrons and holes in the intramolecular CT states across the interface.Compared with these exciton dissociation processes,the direct ex-citon dissociation into interfacial CT state is relatively slow due to the small electronic cou-pling and vibrational coherence between the locally excited state and the interfacial CT state.As the temperature rises and the vibronic coherence weakens,the direct dissociation rates are significantly enhanced.This investigation provides valuable insights for the design and opti-mization of high-performance organic photovoltaic devices.
基金financially supported by the National Natural Science Foundation of China (No.21905266)the Fundamental Research Funds for the Central Universities (WK3530000013)。
文摘The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previous studies but always required complex synthetic method or harsh reaction conditions.In this work,biomass-derived chitosan was used to prepare nitrogen doped carbon.After the loading of Ru,the Ru/NC(NC:nitrogen-doped carbon)catalyst was employed in the solvent-free hydrogenation of levulinic acid under ambient hydrogen pressure at 50−80℃ to reach full conversion.The calcination temperature was optimized to get Ru/NC-800 catalyst with high intrinsic turnover frequency of 358 h^(−1).The apparent activation energy was studied by kinetic experiments.More significantly,the catalyst was small-scaled tested for 36 h in a fix-bed reactor with 620 g/day productivity of γ-valerolactone.The catalyst can be easily synthesized and have high activity and stability,underscoring the potential of future commercial production of γ-valerolactone from levulinic acid.
文摘Precise regulation of atomic and electronic structures of two-dimensional tungsten disulfide(WS_(2))is significant for rational design of high-performance and low-cost catalyst for acetylene hydrogenation to ethylene(AHE),yet remains a major challenge.Herein,we report that by substituting a W atom of WS_(2) with a series of transition metal atoms,sulfur vacancy-confined Cu in the WS_(2) basal plane(Cu@WS_(2)-Sv)is theoretically screened as a superior non-noble metal-based catalyst with higher activity,selectivity,and stability for the AHE than other candidates.The co-adsorption of C_(2)H_(2) and H_(2) and hydrogenation of C_(2)H_(3)^(*) to C_(2)H_(4)^(*) are revealed as the key steps establishing a volcano-like activity trend among the candidates,which present Cu@WS_(2)-Sv as the optimum catalyst combined with molecular dynamics and reaction kinetics analyses.The kinetically more favorable desorption of C_(2)H_(4) than the over hydrogenation path validates a higher selectivity toward C_(2)H_(4) over C_(2)H_(6).Furthermore,a machine-learning model reveals the significant effect of d-electron number and electronegativity of the metal heteroatoms in modulating the AHE activity.
基金supported by the National Natural Science Foundation of China(Nos.22473029,21327901,and 22073019)the Science and Technology Commission of Shanghai Municipality(No.2024ZDSYS02)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘The pioneering works have demonstrated that the method of single collisions in crossed molecular beams is an important technique for achieving kinetic cooling of atoms or molecules in specific rotational states.In this study,we investigated the elastic and inelastic collisions between Al(^(2)P_(1/2))metal atoms and O_(2)molecules at high collision energies in the range of 6.4-14.8 kcal/mol,utilizing the laser-ablation crossed beams in conjunction with time-sliced ion velocity map imaging technique.We observed kinetic cooling of Al(^(2)P_(1/2))atoms with an upper-limit laboratory-frame root-mean-square velocity of 24±3 m/s,corresponding to a translational temperature of 0.9±0.2 K in the laboratory frame,facilitated by the vibrational excitation of O_(2)(v′=1)in inelastic collisions.The translational cooling of Al atoms in the lab frame enhanced detection probability in the transformation of density-to-flux,as evidenced by the scattering images obtained during the experiments.
文摘Non-oxidative dehydrogenation of propane(PDH)is an important route for large-scale on purpose propene production.Although cobalt-based catalysts are promising alternatives to currently used platinum-or chromium oxide-based catalysts,their further developments are hindered by the uncertainties related to the kind of the active sites involved in the desired and side reactions.To contribute to closing such a gap,we systematically investigate the role of oxidized CoO_(x) and metallic Co0 species in the PDH reaction over catalysts based in Silicalite-1 with supported CoO_(x) species differing in their redox properties.C_(3)H_(8) pulse experiments with sub-millisecond and second resolution at pulse sizes of about 13 and 2200 nmol,respectively,combined with in-depth catalyst characterization and PDH tests at different propane conversions enabled us to understand how the reaction-induced reduction of CoO_(x) affects product selectivity.Propane readily reacts with CoO_(x) to yield propene,carbon oxides and water.The formed Co0 species show high activity to coking and cracking reactions.However,if the size of such species is below 2 nm,these undesired reactions are significantly hindered due to the coverage of the active sites by carbon-containing species.The remaining uncovered surface Co0 sites selectively dehydrogenate propane to propene.The best-performing catalyst showed higher activity than a commercial-like K-CrOx/Al_(2)O_(3) and operated durable in a series of 10 dehydrogenation/regeneration cycles under industrial relevant conditions.The space time yield of propene formation of 0.97 kg·h^(-1)·kgcat^(-1) was achieved at 550℃,52%equilibrium propane conversion and 95% propene selectivity.
基金supported by the Natural Science Foundation of Xiamen,China(3502Z202472001)the National Natural Science Foundation of China(22402163,22021001,21925404,T2293692,and 22361132532).
文摘The structure of water and proton transfer under nanoscale confinement has garnered significant attention due to its crucial role in elucidating various phenomena across multiple scientific disciplines.However,there remains a lack of consensus on fundamental properties such as diffusion behavior and the nature of hydrogen bonding in confined environments.In this work,we investigated the influence of confinement on proton transfer in water confined within graphene sheets at various spacings by ab initio molecule dynamic and multiscale analysis with time evolution of structural properties,graph theory and persistent homology.We found that reducing the graphene interlayer distance while maintaining water density close to that of bulk water leads to a decrease in proton transfer frequency.In contrast,reducing the interlayer distance without maintaining bulk-like water density results in an increase in proton transfer frequency.This difference is mainly due to the confinement conditions:when density is unchanged,the hydrogen bond network remains similar with significant layering,while compressive stress that increases density leads to a more planar hydrogen bond network,promoting faster proton transfer.Our findings elucidate the complex relationship between confinement and proton transfer dynamics,with implications for understanding proton transport in confined environments,relevant to energy storage and material design.
基金supported by the National Key Research and Develop-ment Pr0gram of China(Nos.2021YFA1501104 and 2023YFA1506802)the National Natural Science Foundation of China(No.22032001).
文摘Ethanol steam reforming(ESR)represents a promising route for sustainable hydrogen production,leveraging the high hydrogen content,renewability,and logistical advantages of ethanol.Although Ni-based catalysts are leading non-noble candidates for ESR,their practical deployment is hindered by compromised H_(2) production efficiency and rapid deactivation.In this work,we combined catalyst synthesis,kinetic analysis,and mechanistic investigation to elucidate the effectsof Ni particle size(3-9 nm)on ESR performance of Ni/CeO_(2) catalysts.These Ni/CeO_(2) catalysts were prepared via a citric acid-assisted coprecipitation method,and systematically characterized using complementary techniques,including high-resolution transmission electron microscopy(HRTEM),in situ X-ray photoelectron spectroscopy(XPS),hydrogen temperature-programmed reduction(H_(2)-TPR),Raman spectroscopy,O_(2)/CO chemisorption,and temperature-programmed surface reaction(TPSR)analyses.Mechanistic study revealed that ethanol dehydrogenation to acetaldehyde is the rate-determining step,defining the intrinsic activity of Ni sites,whereas C-C bond cleavage governs H_(2) selectivity in ESR.At smaller Ni sizes(e.g.,3.1 nm),larger CeO_(2) surface was exposed,which promoted acetaldehyde condensation to acetone,and consequently reduced H_(2) production efficiency.The Ni/CeO_(2) catalyst with~5 nm of Ni particles afforded the highest H_(2) yield(66.3%)and outstanding stability by balancing dehydrogenation activity,H_(2) selectivity,and coking resistance.Conversely,larger Ni particles(>6 nm)facilitated methanation reaction and catalyst deactivation.This work reconciles prior inconsistencies in the Ni size effects on ESR and provides guidance for the design of efficient and durable Ni-based catalysts for H_(2) production.
基金supported by the Natural Science Foundation of Guangxi Province(2021GXNSFBA220077,GUIKE AD23026050)National Natural Science Foundation of China(22102035 and 22162006)Innovation Project of Guangxi Graduate Education(XYCBZ2024021).
文摘Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.
基金supported by the Natural Science Foundation of Xiamen,China(3502Z202472001)the National Natural Science Foundation of China(22402163,22021001,21925404,T2293692,and 22361132532)。
文摘Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.
