Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable ...Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.展开更多
We report the results of the experiment on synthesizing ^(287,288)Mc isotopes (Z=115) using the fusionevaporation reaction ^(243)Am(^(48)Ca,4n,3n)^(287,288)Mc at the Spectrometer for Heavy Atoms and Nuclear Structure-...We report the results of the experiment on synthesizing ^(287,288)Mc isotopes (Z=115) using the fusionevaporation reaction ^(243)Am(^(48)Ca,4n,3n)^(287,288)Mc at the Spectrometer for Heavy Atoms and Nuclear Structure-2(SHANS2),a gas-filled recoil separator located at the China Accelerator Facility for Superheavy Elements(CAFE2).In total,20 decay chains are attributed to ^(288)Mc and 1 decay chain is assigned to ^(287)Mc.The measured oa-decay properties of ^(287,288)Mc as well as its descendants are consistent with the known data.No additional decay chains originating from the 2n or 5n reaction channels were detected.The excitation function of the ^(243)Am(^(48)Ca,3n)^(288)Mc reaction was measured at the cross-section level of picobarn,which indicates the promising capability for the study of heavy and superheavy nuclei at the facility.展开更多
Silica nanoparticles-stabilized cobalt and nitrogen-doped carbon materials were synthesized through pyrolysis of metal-organic-framework of ZIF-67 supported by silica nanoparticles.The experimental results reveal that...Silica nanoparticles-stabilized cobalt and nitrogen-doped carbon materials were synthesized through pyrolysis of metal-organic-framework of ZIF-67 supported by silica nanoparticles.The experimental results reveal that the introduction of the silica nanoparticles can stabilize the microstructure of the derived CoN-C materials,which in turn exhibits the promising electrocatalytic activity towards both oxygen reduction and oxygen evolution reactions.The optimized sample exhibits a better oxygen reduction activity than commercial Pt/C catalyst as confirmed by the positive shift of half-wave potential by 20 mV while it has a low overpotential of 273 mV for oxygen evolution reactions with the retained performance over 80%after 25,000 s of continuous operation.It is demonstrated that the introduction of support frame might be an effective way to improve the activity and stability of metal-organic-framework derived electrocatalyst with stabilized microstructure.展开更多
The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeab...The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeable metal-air battery systems.Significant progress has been made in the design of high-performance bifunctional electrocatalysts,the development of novel oxygen electrode architectures,and the in-depth understanding of electrocatalytic mechanisms through combined experimental and computational studies.This work provides a comprehensive review of recent advancements in design strategies for oxygen catalysts,including homogeneous electrodes,asymmetric electrodes,and biomimetic electrodes,are thoroughly discussed and summarized.Then,the advanced catalyst modification strategies for ORR/OER are summarized,focusing on critical factors such as enhancement effect of metal/nonmental and synergistic enhancement effect in multiple catalyst.Subsequently,a representative performance evaluation is presented,based on the reported oxygen electrodes used in rechargeable metal-air battery applications.By focusing on these key areas,the review outlines the current challenges and future prospects for the development of bifunctional oxygen electrocatalysts,aiming to guide the design of high-performance bifunctional electrocatalysts and to elucidate the underlying mechanisms involved.展开更多
The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted ...A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature.Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group ofα,β-disubstituted acrylates derive from H2O in dimethyl sulfoxide(DMSO).Furthermore,a gram-scale experiment and late-stage modification of the products were accomplished,thereby expanding the application potential of this methodology in organic synthesis.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis.Their development has not only promoted the synthesis of drugs,materials,and natu...Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis.Their development has not only promoted the synthesis of drugs,materials,and natural products,but also promoted the development of new synthetic methods,and has also made breakthroughs in mechanism innovation and catalyst design.On this basis,a copper-catalyzed radical reaction between ketones is reported,enabling the synthesis of 2-carbonyl-1,4-diones.The method exhibits excellent applicability to multiple structural types of ketones,including aliphatic ketones with diverse substituents,aromatic ketones,and various simple ketones not limited to acetone,with wide applications,easy implementation,low catalyst toxicity,and low cost,cost-effective,and the product is easy to separate and purify.展开更多
The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.A...The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.展开更多
Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a fo...Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.展开更多
The differences in the competitive reactions of hydrogarnet and quicklime when reacting with titaniumcontaining and silicon-containing minerals during the Bayer digestion process were investigated.Thermodynamic analys...The differences in the competitive reactions of hydrogarnet and quicklime when reacting with titaniumcontaining and silicon-containing minerals during the Bayer digestion process were investigated.Thermodynamic analysis,artificial mineral experiments,and an evaluation of the digestion effect of natural diasporic bauxite were conducted.The results indicate that hydrogarnet shows a preferential reaction with anatase,and this preference becomes more pronounced as the silicon saturation coefficient increases.In contrast,quicklime participates in non-selective reactions with both anatase and desilication products(DSP).The preference of hydrogarnet for anatase significantly enhances the utilization efficiency of CaO in the high-temperature Bayer digestion process.展开更多
To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,w...To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,we report a hollow-structured Ni_(x)Co_(1−x)O/Ni_(3)S_(2)/Co_(9)S_(8)heterostructure synthesized via sequential template-assisted growth,thermal oxidation,and controlled sulfidation process.The abundant bimetallic heterointerfaces not only provide additional active sites but also promote electronic modulation via charge redistribution.Additionally,the porous and hollow architecture enhances active surface area and mass transfer ability,thereby increasing the number of accessible active sites for alkaline OER.As a result,the prepared electrocatalyst achieves low overpotential of 310 mV at 10 mA cm^(−2)and small Tafel slope of 55.94 mV dec^(−1),demonstrating the exceptional electrocatalytic performance for alkaline OER.When integrated as the anode in an AEMWE cell,it delivers outstanding performance with only 1.657 V at 1.0 A cm^(−2)and reaches high current density of 5.0 A cm^(−2)at 1.989 V,surpassing those of commercial RuO_(2).The cell also shows excellent long-term durability over 100 h with minimal degradation.This study highlights the strong potential of rationally engineered oxide/sulfide heterostructures for next-generation alkaline water electrolysis.展开更多
RNA binding proteins(RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process.Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progre...RNA binding proteins(RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process.Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases,making RBPs potential therapeutic targets.However,the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA-protein interactions in mammal tissues.Additionally,RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes(RPCs).Due to these inherent limitations,globally profiling the RNA binding proteome in mammal organs has long been a challenge.Herein,we proposed a novel method,which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation,metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver,called FTYc_UV.In this method,formaldehyde is first used to crosslink the crude RNA-protein complexes(cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation.Furthermore,this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging.After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates,formaldehyde decrosslinking is employed to remove non-specific proteins,leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking.Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75 % of previously reported RBPs.Furthermore,420 candidate RBPs,including 151metabolic enzymes,were also obtained,demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA-protein interactions in biological and clinical research.展开更多
The growing volume of end-of-life lithium-ion batteries(LIBs)represents both an urgent environmental challenge and a critical resource opportunity,especially for cathode materials.Among commercial cathodes,LiFePO4(LFP...The growing volume of end-of-life lithium-ion batteries(LIBs)represents both an urgent environmental challenge and a critical resource opportunity,especially for cathode materials.Among commercial cathodes,LiFePO4(LFP)dominates the market due to its favorable properties;thus,a substantial amount of LFP cathode materials is expected to retire in the near future.The conventional hydrometallurgical method suffers from high costs and serious pollution.Direct regeneration technologies,especially solid-state sintering,provide a more efficient and environmentally benign alternative by repairing cathode structures through high-temperature solid-phase reactions without extra chemical reagents.Traditional solid-state sintering faces challenges in processing spent LFP from diverse sources,struggling to achieve the homogenization of physical–chemical properties and electrochemical performance.To address the limitations above,phase homogenization with a lattice reconstruction strategy has been investigated,which can enable effective lattice reconstruction and microstructural homogenization,demonstrating robust adaptability to spent samples from variable sources.This review systematically summarizes the mechanisms,detailed steps,characterization techniques,and advances in pre-oxidation optimization(including ion-doping and coated carbon layer modification),as well as future research directions for sustainable LFP recycling.Given this,this review is expected to offer theoretical guidance for achieving homogeneous regeneration of LFP cathode.展开更多
Aluminum nanoparticles,owing to their high energy density and excellent reactivity,are widely used to enhance the energy release efficiency of explosives.In this study,reactive molecular dynamics simulations were empl...Aluminum nanoparticles,owing to their high energy density and excellent reactivity,are widely used to enhance the energy release efficiency of explosives.In this study,reactive molecular dynamics simulations were employed to systematically investigate the hotspot evolution and reaction kinetics of aluminum nanoparticles under shock loading.The results show that hotspots predominantly form and evolve along the oxide layer interface,exhibiting a typical"hot shell-cold core"structure.A thicker oxide layer significantly delays the heating and reaction initiation of the aluminum core,with reversible crystal structure transformations observed inside the core.Larger particles facilitate heat accumulation and promote sustained reactions.As the oxide layer thickness increases,the reaction mechanism of aluminum nanoparticles transitions from melting-diffusion and micro-explosion oxidation to an oxidation-diffusion dominated process.A dense nitrogen-containing reaction layer forms on the surface,which suppresses the later-stage reaction.A nonlinear reaction kinetics model based on bond statistics reveals that particles with a thin oxide layer exhibit rapid reaction saturation and are insensitive to shock velocity.Particles with intermediate oxide thickness exhibit a reaction behavior that gradually slows down over time,while those with a thick oxide layer can exhibit accelerated reactions under high-velocity shocks due to enhanced diffusion.Small particles show significantly increased reaction rates at high velocities,whereas large particles tend to slow down due to the thickening of the surface reaction layer.The oxide layer thickness,particle size,and shock velocity exhibit complex competitive and synergistic effects that jointly regulate the initiation,rate,and evolution of aluminum nanoparticle reactions.展开更多
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthes...Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.展开更多
The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton trans...The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton transfer mechanism remains elusive.Herein,we reported a metal-free,room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)as a dual hydrogen bond catalyst to synergistically activate propylamine(PA)and dimethyl carbonate(DMC).This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions.This is enabled by dual hydrogen bonding of TBD with PA and DMC,which facilitates rapid proton transfer and stabilizes tetrahedral intermediates.Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs.Furthermore,it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate.This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.展开更多
Metal halide perovskites(MHPs)with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks...Metal halide perovskites(MHPs)with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks such as inferior stability,severe charge-carrier recombination,and limited active sites.Heterojunctions have recently been widely constructed to improve light absorption,passivate surface for enhanced stability,and promote charge-carrier dynamics of MHPs.However,little attention has been paid to the review of MHPs-based heterojunctions for photocatalytic redox reactions.Here,recent advances of MHPs-based heterojunctions for photocatalytic redox reactions are highlighted.The structure,synthesis,and photophysical properties of MHPs-based heterojunctions are first introduced,including basic principles,categories(such as Schottky junction,type-I,type-II,Z-scheme,and S-scheme junction),and synthesis strategies.MHPs-based heterojunctions for photocatalytic redox reactions are then reviewed in four categories:H2evolution,CO_(2)reduction,pollutant degradation,and organic synthesis.The challenges and prospects in solar-light-driven redox reactions with MHPs-based heterojunctions in the future are finally discussed.展开更多
All-soluble all-iron flow batteries are considered a promising technology for low-cost and large-scale energy storage.In the past few years,efforts have been taken to design various iron chelates to enhance the cyclin...All-soluble all-iron flow batteries are considered a promising technology for low-cost and large-scale energy storage.In the past few years,efforts have been taken to design various iron chelates to enhance the cycling stability of negative electrolytes,while ignoring the kinetic mismatch and the corresponding battery design strategies,which greatly limited the performance of all-soluble all-iron flow batteries.In this regard,combining experimental analysis and numerical simulation,this work analyzed the kinetic performance of iron chelates on the negative side and conducted further investigations on battery asymmetric structure design to balance mass transport and electrochemical reactions within the battery.Results show that the reaction rate constant of the Fe(Ⅱ)(BIS-TRIS)^(2-)/Fe(Ⅲ)(BIS-TRIS)^(-)redox couple is 1:48×10^(-5)cm s^(-1),significantly lower than that of the positive electrolyte(6.0×10^(-5)cm s^(−1)),which limits the performance of the battery.Utilizing an asymmetric electrode design to increase active reaction sites and enhance convection is a critical strategy in achieving balanced mass transport and reaction activity between the positive and negative electrolytes.More notably,the battery with asymmetric geometric characteristics demonstrates a remarkable energy efficiency reaching up to 80.17%at 80 mA cm^(−2),which is 7.95%higher than that of the symmetric structure.This research provides theoretical guidance for the structural design of key components of batteries and reduces the cost of trial and error.展开更多
基金Science and Technology Foundation of Guizhou Province(No.QKHJC-ZK[2024]654)Guizhou Provincial University Key Laboratory of Advanced Functional Electronic Materials(No.QJJ[2023]021).
文摘Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.
基金supported in part by the National Key R&D Program of China (Contract Nos.2023YFA1606500,2024YFE0109800,and 2024YFE0110400)Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB34010000)+5 种基金the Gansu Key Project of Science and Technology (Grant No.23ZDGA014)the Guangdong Major Project of Basic and Applied Basic Research (Grant No.2021B0301030006)the National Natural Science Foundation of China (Grant Nos.12105328,W2412040,12475126,12422507,12035011,12375118,12435008,and W2412043)the Chinese Academy of Sciences Project for Young Scientists in Basic Research(Grant No.YSBR-002)the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Grant Nos.2020409 and 2023439)the Russian Science Foundation (Grant No.25-42-00003)。
文摘We report the results of the experiment on synthesizing ^(287,288)Mc isotopes (Z=115) using the fusionevaporation reaction ^(243)Am(^(48)Ca,4n,3n)^(287,288)Mc at the Spectrometer for Heavy Atoms and Nuclear Structure-2(SHANS2),a gas-filled recoil separator located at the China Accelerator Facility for Superheavy Elements(CAFE2).In total,20 decay chains are attributed to ^(288)Mc and 1 decay chain is assigned to ^(287)Mc.The measured oa-decay properties of ^(287,288)Mc as well as its descendants are consistent with the known data.No additional decay chains originating from the 2n or 5n reaction channels were detected.The excitation function of the ^(243)Am(^(48)Ca,3n)^(288)Mc reaction was measured at the cross-section level of picobarn,which indicates the promising capability for the study of heavy and superheavy nuclei at the facility.
基金Funded by the National Natural Science Foundation of China Guangdong(No.22279096)。
文摘Silica nanoparticles-stabilized cobalt and nitrogen-doped carbon materials were synthesized through pyrolysis of metal-organic-framework of ZIF-67 supported by silica nanoparticles.The experimental results reveal that the introduction of the silica nanoparticles can stabilize the microstructure of the derived CoN-C materials,which in turn exhibits the promising electrocatalytic activity towards both oxygen reduction and oxygen evolution reactions.The optimized sample exhibits a better oxygen reduction activity than commercial Pt/C catalyst as confirmed by the positive shift of half-wave potential by 20 mV while it has a low overpotential of 273 mV for oxygen evolution reactions with the retained performance over 80%after 25,000 s of continuous operation.It is demonstrated that the introduction of support frame might be an effective way to improve the activity and stability of metal-organic-framework derived electrocatalyst with stabilized microstructure.
基金financially supported by the National Natural Science Foundation of China(52302084)the National Key Research and Development Program of China(2022YFE0138900)+1 种基金Fundamental Research Funds for the Central Universities(2232025D-24)the Qin Shen Scholar Program of Jiaxing University。
文摘The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeable metal-air battery systems.Significant progress has been made in the design of high-performance bifunctional electrocatalysts,the development of novel oxygen electrode architectures,and the in-depth understanding of electrocatalytic mechanisms through combined experimental and computational studies.This work provides a comprehensive review of recent advancements in design strategies for oxygen catalysts,including homogeneous electrodes,asymmetric electrodes,and biomimetic electrodes,are thoroughly discussed and summarized.Then,the advanced catalyst modification strategies for ORR/OER are summarized,focusing on critical factors such as enhancement effect of metal/nonmental and synergistic enhancement effect in multiple catalyst.Subsequently,a representative performance evaluation is presented,based on the reported oxygen electrodes used in rechargeable metal-air battery applications.By focusing on these key areas,the review outlines the current challenges and future prospects for the development of bifunctional oxygen electrocatalysts,aiming to guide the design of high-performance bifunctional electrocatalysts and to elucidate the underlying mechanisms involved.
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
文摘A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature.Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group ofα,β-disubstituted acrylates derive from H2O in dimethyl sulfoxide(DMSO).Furthermore,a gram-scale experiment and late-stage modification of the products were accomplished,thereby expanding the application potential of this methodology in organic synthesis.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
基金Project supported by the Basic Research Support Program for Outstanding Young Teachers in Provincial Undergraduate Colleges and Universities in Heilongjiang Province(No.YQJH2024096)the Heilongjiang Province Natural Joint Guidance Cultivation Project(No.PL2024H198)。
文摘Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis.Their development has not only promoted the synthesis of drugs,materials,and natural products,but also promoted the development of new synthetic methods,and has also made breakthroughs in mechanism innovation and catalyst design.On this basis,a copper-catalyzed radical reaction between ketones is reported,enabling the synthesis of 2-carbonyl-1,4-diones.The method exhibits excellent applicability to multiple structural types of ketones,including aliphatic ketones with diverse substituents,aromatic ketones,and various simple ketones not limited to acetone,with wide applications,easy implementation,low catalyst toxicity,and low cost,cost-effective,and the product is easy to separate and purify.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002 and U2202254)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.
基金support from the National Natural Science Foundation of China(Nos.12305373 and 52276220)the Guangzhou Basic Research Program(No.SL2024A04J00234).
文摘Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.
基金the financial support from the Natural Science Foundation of Hunan Province,China(No.2022JJ40616)。
文摘The differences in the competitive reactions of hydrogarnet and quicklime when reacting with titaniumcontaining and silicon-containing minerals during the Bayer digestion process were investigated.Thermodynamic analysis,artificial mineral experiments,and an evaluation of the digestion effect of natural diasporic bauxite were conducted.The results indicate that hydrogarnet shows a preferential reaction with anatase,and this preference becomes more pronounced as the silicon saturation coefficient increases.In contrast,quicklime participates in non-selective reactions with both anatase and desilication products(DSP).The preference of hydrogarnet for anatase significantly enhances the utilization efficiency of CaO in the high-temperature Bayer digestion process.
基金supported by the Korea Institute for Advancement of Technology (KIAT)the Ministry of Trade,Industry&Energy (MOTIE) of the Republic of Korea (No. P0022130)by the Institute of Information&Communications Technology Planning&Evaluation(IITP)-Innovative Human Resource Development for Local Intellectualization program grant funded by the Korea government (MSIT)(IITP-2025-RS-2023-00259678)
文摘To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,we report a hollow-structured Ni_(x)Co_(1−x)O/Ni_(3)S_(2)/Co_(9)S_(8)heterostructure synthesized via sequential template-assisted growth,thermal oxidation,and controlled sulfidation process.The abundant bimetallic heterointerfaces not only provide additional active sites but also promote electronic modulation via charge redistribution.Additionally,the porous and hollow architecture enhances active surface area and mass transfer ability,thereby increasing the number of accessible active sites for alkaline OER.As a result,the prepared electrocatalyst achieves low overpotential of 310 mV at 10 mA cm^(−2)and small Tafel slope of 55.94 mV dec^(−1),demonstrating the exceptional electrocatalytic performance for alkaline OER.When integrated as the anode in an AEMWE cell,it delivers outstanding performance with only 1.657 V at 1.0 A cm^(−2)and reaches high current density of 5.0 A cm^(−2)at 1.989 V,surpassing those of commercial RuO_(2).The cell also shows excellent long-term durability over 100 h with minimal degradation.This study highlights the strong potential of rationally engineered oxide/sulfide heterostructures for next-generation alkaline water electrolysis.
基金financial support from the National Key R&D Program of China (No.2021YFA1302604)Scientific and technological innovation project of China Academy of Chinese Medical Sciences (No.CI2021B017)China Postdoctoral Science Foundation (No.2023T160727)。
文摘RNA binding proteins(RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process.Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases,making RBPs potential therapeutic targets.However,the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA-protein interactions in mammal tissues.Additionally,RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes(RPCs).Due to these inherent limitations,globally profiling the RNA binding proteome in mammal organs has long been a challenge.Herein,we proposed a novel method,which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation,metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver,called FTYc_UV.In this method,formaldehyde is first used to crosslink the crude RNA-protein complexes(cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation.Furthermore,this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging.After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates,formaldehyde decrosslinking is employed to remove non-specific proteins,leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking.Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75 % of previously reported RBPs.Furthermore,420 candidate RBPs,including 151metabolic enzymes,were also obtained,demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA-protein interactions in biological and clinical research.
基金financially supported by National Natural Science Key Foundation of China(52534010)National Natural Science Foundation of China(52374288,52204298)+2 种基金Young Elite Scientists Sponsorship Program by China Association for Science and Technology(2022QNRC001)National Key Research and Development Program of China(2022YFC3900805-4/7)Collaborative Innovation Centre for Clean and Efficient Utilization of Strategic Metal Mineral Resources,Found of State Key Laboratory of Mineral Processing(BGRIMM-KJSKL-2017-13).
文摘The growing volume of end-of-life lithium-ion batteries(LIBs)represents both an urgent environmental challenge and a critical resource opportunity,especially for cathode materials.Among commercial cathodes,LiFePO4(LFP)dominates the market due to its favorable properties;thus,a substantial amount of LFP cathode materials is expected to retire in the near future.The conventional hydrometallurgical method suffers from high costs and serious pollution.Direct regeneration technologies,especially solid-state sintering,provide a more efficient and environmentally benign alternative by repairing cathode structures through high-temperature solid-phase reactions without extra chemical reagents.Traditional solid-state sintering faces challenges in processing spent LFP from diverse sources,struggling to achieve the homogenization of physical–chemical properties and electrochemical performance.To address the limitations above,phase homogenization with a lattice reconstruction strategy has been investigated,which can enable effective lattice reconstruction and microstructural homogenization,demonstrating robust adaptability to spent samples from variable sources.This review systematically summarizes the mechanisms,detailed steps,characterization techniques,and advances in pre-oxidation optimization(including ion-doping and coated carbon layer modification),as well as future research directions for sustainable LFP recycling.Given this,this review is expected to offer theoretical guidance for achieving homogeneous regeneration of LFP cathode.
基金supported by the State Key Program of National Natural Science Foundation of China(No.12272051)the BIT Research and Innovation Promoting Project(No.2023YCXY17).
文摘Aluminum nanoparticles,owing to their high energy density and excellent reactivity,are widely used to enhance the energy release efficiency of explosives.In this study,reactive molecular dynamics simulations were employed to systematically investigate the hotspot evolution and reaction kinetics of aluminum nanoparticles under shock loading.The results show that hotspots predominantly form and evolve along the oxide layer interface,exhibiting a typical"hot shell-cold core"structure.A thicker oxide layer significantly delays the heating and reaction initiation of the aluminum core,with reversible crystal structure transformations observed inside the core.Larger particles facilitate heat accumulation and promote sustained reactions.As the oxide layer thickness increases,the reaction mechanism of aluminum nanoparticles transitions from melting-diffusion and micro-explosion oxidation to an oxidation-diffusion dominated process.A dense nitrogen-containing reaction layer forms on the surface,which suppresses the later-stage reaction.A nonlinear reaction kinetics model based on bond statistics reveals that particles with a thin oxide layer exhibit rapid reaction saturation and are insensitive to shock velocity.Particles with intermediate oxide thickness exhibit a reaction behavior that gradually slows down over time,while those with a thick oxide layer can exhibit accelerated reactions under high-velocity shocks due to enhanced diffusion.Small particles show significantly increased reaction rates at high velocities,whereas large particles tend to slow down due to the thickening of the surface reaction layer.The oxide layer thickness,particle size,and shock velocity exhibit complex competitive and synergistic effects that jointly regulate the initiation,rate,and evolution of aluminum nanoparticle reactions.
基金supported by the National Natural Science Foundation of China (No.52274304)。
文摘Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.
基金financially supported by the National Key R&D Program of China(2023YFC3905400)the Clean Combustion and Low-carbon Utilization of Coal,Strategic Priority Research Program of the Chinese Academy of Sciences,Grant No.XDA 29000000.
文摘The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton transfer mechanism remains elusive.Herein,we reported a metal-free,room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)as a dual hydrogen bond catalyst to synergistically activate propylamine(PA)and dimethyl carbonate(DMC).This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions.This is enabled by dual hydrogen bonding of TBD with PA and DMC,which facilitates rapid proton transfer and stabilizes tetrahedral intermediates.Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs.Furthermore,it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate.This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.
基金financially supported by National Natural Science Foundation of China(No.22302155)the Fundamental Research Funds of the Center Universities(No.D5000240188)the research program of ZJUT(YJY-ZS-20240001)。
文摘Metal halide perovskites(MHPs)with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks such as inferior stability,severe charge-carrier recombination,and limited active sites.Heterojunctions have recently been widely constructed to improve light absorption,passivate surface for enhanced stability,and promote charge-carrier dynamics of MHPs.However,little attention has been paid to the review of MHPs-based heterojunctions for photocatalytic redox reactions.Here,recent advances of MHPs-based heterojunctions for photocatalytic redox reactions are highlighted.The structure,synthesis,and photophysical properties of MHPs-based heterojunctions are first introduced,including basic principles,categories(such as Schottky junction,type-I,type-II,Z-scheme,and S-scheme junction),and synthesis strategies.MHPs-based heterojunctions for photocatalytic redox reactions are then reviewed in four categories:H2evolution,CO_(2)reduction,pollutant degradation,and organic synthesis.The challenges and prospects in solar-light-driven redox reactions with MHPs-based heterojunctions in the future are finally discussed.
基金supported by the National Natural Science Foundation of China(No.52106265)Natural Science Foundation of Tianjin Province,China(No.23JCZDJC01090)+1 种基金Guangdong Major Project of Basic and Applied Basic Research(2023B0303000002)High level of special funds(G03034K001).
文摘All-soluble all-iron flow batteries are considered a promising technology for low-cost and large-scale energy storage.In the past few years,efforts have been taken to design various iron chelates to enhance the cycling stability of negative electrolytes,while ignoring the kinetic mismatch and the corresponding battery design strategies,which greatly limited the performance of all-soluble all-iron flow batteries.In this regard,combining experimental analysis and numerical simulation,this work analyzed the kinetic performance of iron chelates on the negative side and conducted further investigations on battery asymmetric structure design to balance mass transport and electrochemical reactions within the battery.Results show that the reaction rate constant of the Fe(Ⅱ)(BIS-TRIS)^(2-)/Fe(Ⅲ)(BIS-TRIS)^(-)redox couple is 1:48×10^(-5)cm s^(-1),significantly lower than that of the positive electrolyte(6.0×10^(-5)cm s^(−1)),which limits the performance of the battery.Utilizing an asymmetric electrode design to increase active reaction sites and enhance convection is a critical strategy in achieving balanced mass transport and reaction activity between the positive and negative electrolytes.More notably,the battery with asymmetric geometric characteristics demonstrates a remarkable energy efficiency reaching up to 80.17%at 80 mA cm^(−2),which is 7.95%higher than that of the symmetric structure.This research provides theoretical guidance for the structural design of key components of batteries and reduces the cost of trial and error.
