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
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
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
This research proposes an improved Puma optimization algorithm(IPuma)as a novel dynamic recon-figuration tool for a photovoltaic(PV)array linked in total-cross-tied(TCT).The proposed algorithm utilizes the Newton-Raph...This research proposes an improved Puma optimization algorithm(IPuma)as a novel dynamic recon-figuration tool for a photovoltaic(PV)array linked in total-cross-tied(TCT).The proposed algorithm utilizes the Newton-Raphson search rule(NRSR)to boost the exploration process,especially in search spaces with more local regions,and boost the exploitation with adaptive parameters alternating with random parameters in the original Puma.The effectiveness of the introduced IPuma is confirmed through comprehensive evaluations on the CEC’20 benchmark problems.It shows superior performance compared to both established and modern metaheuristic algorithms in terms of effectively navigating the search space and achieving convergence towards near-optimal regions.The findings indicated that the IPuma algorithm demonstrates considerable statistical promise and surpasses the performance of competing algorithms.In addition,the proposed IPuma is utilized to reconfigure a 9×9 PV array that operates under different shade patterns,such as lower triangular(LT),long wide(LW),and short wide(SW).In addition to other programmed approaches,such as the Whale optimization algorithm(WOA),grey wolf optimizer(GWO),Harris Hawks optimization(HHO),particle swarm optimization(PSO),gravitational search algorithm(GSA),biogeography-based optimization(BBO),sine cosine algorithm(SCA),equilibrium optimizer(EO),and original Puma,the indicated method is contrasted to the traditional configurations of TCT and Sudoku.In addition,the metrics of mismatch power loss,maximum efficiency improvement,efficiency improvement ratio,and peak-to-mean ratio are calculated to assess the effectiveness of the indicated approach.The proposed IPuma improved the generated power by 36.72%,28.03%,and 40.97%for SW,LW,and LT,respectively,outperforming the TCT configuration.In addition,it achieved the best maximum efficiency improvement among the algorithms considered,with 26.86%,21.89%,and 29.07%for the examined patterns.The results highlight the superiority and competence of the proposed approach in both convergence rates and stability,as well as applicability to dynamically reconfigure the PV system and enhance its harvested energy.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
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 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
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 rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere f...The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.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
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
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
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 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
Partial least squares (PLS) model maximizes the covariance between process variables and quality variables,making it widely used in quality-related fault detection.However,traditional PLS methods focus primarily on li...Partial least squares (PLS) model maximizes the covariance between process variables and quality variables,making it widely used in quality-related fault detection.However,traditional PLS methods focus primarily on linear processes,leading to poor performance in dynamic nonlinear processes.In this paper,a novel quality-related fault detection method,named DiCAE-PLS,is developed by combining dynamic-inner convolutional autoencoder with PLS.In the proposed DiCAE-PLS method,latent features are first extracted through dynamic-inner convolutional autoencoder (DiCAE) to capture process dynamics and nonlinearity from process variables.Then,a PLS model is established to build the relationship between the extracted latent features and the final product quality.To detect quality-related faults,Hotelling's T^(2) statistic is employed.The developed quality-related fault detection is applied to the widely used industrial benchmark of the Tennessee.展开更多
Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-...Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.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
Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate...Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate reduction(eNO_(3)RR)emerges as an attractive strategy to simultaneously enable nitrate removal and decentralized ammo-nia fabrication,restoring the globally perturbed nitrogen cycle.However,complex deoxygenation-hydrogenationprocesses and sluggish proton-electron transfer kinetics significantly hinder practical application of eNO_(3)RR.In this study,we developed carbon-coated Cu-Ni bimetallic catalysts derived from metal-organic frameworks(MOFs)to facilitate eNO_(3)RR.The unique structural features of catalyst promote enhanced synergy between Cuand Ni,effectively addressing critical challenges in nitrate reduction.Comprehensive structural and electrochem-ical analysis demonstrate that electrochemical nitrate-to-nitrite conversion mainly takes place on active Cu sites,the introduction of Ni could efficiently accelerate the generation of aquatic active hydrogen,promoting the hy-drogenation of oxynitrides during eNO_(3)RR.In addition,Ni introduction could push up the d-band center of thecatalyst,thus enhancing the adsorption and activation of nitrate and the corresponding intermediates.Detailedreaction pathways for nitrate-to-ammonia conversion are illuminated by rotating disk electrode(RDE),in-situFourier-transform infrared spectroscopy,in-situ Raman spectrum and electrochemical impedance spectroscopy(EIS).Benefiting from the synergistic effect of Cu and Ni,optimum catalyst exhibited excellent nitrate reductionperformance.This work provides a new idea for elucidating the underlying eNO_(3)RR reaction mechanisms andcontributes a promising strategy for designing efficient bimetallic electrocatalysts.展开更多
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparti...Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.展开更多
Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using iso...Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source.The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of(S)-rivastigmine.Building on this success,we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal,nickel.展开更多
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.
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.QJ[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 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funded by the Deanship of Scientific Research and Libraries,Princess Nourah bint Abdulrahman University,through the Program of Research Project Funding After Publication,grant No.(RPFAP-82-1445)。
文摘This research proposes an improved Puma optimization algorithm(IPuma)as a novel dynamic recon-figuration tool for a photovoltaic(PV)array linked in total-cross-tied(TCT).The proposed algorithm utilizes the Newton-Raphson search rule(NRSR)to boost the exploration process,especially in search spaces with more local regions,and boost the exploitation with adaptive parameters alternating with random parameters in the original Puma.The effectiveness of the introduced IPuma is confirmed through comprehensive evaluations on the CEC’20 benchmark problems.It shows superior performance compared to both established and modern metaheuristic algorithms in terms of effectively navigating the search space and achieving convergence towards near-optimal regions.The findings indicated that the IPuma algorithm demonstrates considerable statistical promise and surpasses the performance of competing algorithms.In addition,the proposed IPuma is utilized to reconfigure a 9×9 PV array that operates under different shade patterns,such as lower triangular(LT),long wide(LW),and short wide(SW).In addition to other programmed approaches,such as the Whale optimization algorithm(WOA),grey wolf optimizer(GWO),Harris Hawks optimization(HHO),particle swarm optimization(PSO),gravitational search algorithm(GSA),biogeography-based optimization(BBO),sine cosine algorithm(SCA),equilibrium optimizer(EO),and original Puma,the indicated method is contrasted to the traditional configurations of TCT and Sudoku.In addition,the metrics of mismatch power loss,maximum efficiency improvement,efficiency improvement ratio,and peak-to-mean ratio are calculated to assess the effectiveness of the indicated approach.The proposed IPuma improved the generated power by 36.72%,28.03%,and 40.97%for SW,LW,and LT,respectively,outperforming the TCT configuration.In addition,it achieved the best maximum efficiency improvement among the algorithms considered,with 26.86%,21.89%,and 29.07%for the examined patterns.The results highlight the superiority and competence of the proposed approach in both convergence rates and stability,as well as applicability to dynamically reconfigure the PV system and enhance its harvested energy.
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supported by the National Key Research and Development Program of China(2022YFB3805600,2022YFB3805604)the National Natural Science Foundation of China(52201286)+3 种基金the National 111 Project(B20002)the Key R&D Program of Shandong Province,China(2023CXGC010314)the Hubei Provincial Natural Science Foundation of China(2024AFB195)the Fundamental Research Funds for the Central Universities(104972025KFYzxk0014,104972024KFYjlb0008)。
文摘The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.
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 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 in part by the National Natural Science Foundation of China(62573387)the Natural Science Foundation of Zhejiang province,China(LY24F030004)the Fundamental Research Funds of Zhejiang Sci-Tech University(25222139-Y).
文摘Partial least squares (PLS) model maximizes the covariance between process variables and quality variables,making it widely used in quality-related fault detection.However,traditional PLS methods focus primarily on linear processes,leading to poor performance in dynamic nonlinear processes.In this paper,a novel quality-related fault detection method,named DiCAE-PLS,is developed by combining dynamic-inner convolutional autoencoder with PLS.In the proposed DiCAE-PLS method,latent features are first extracted through dynamic-inner convolutional autoencoder (DiCAE) to capture process dynamics and nonlinearity from process variables.Then,a PLS model is established to build the relationship between the extracted latent features and the final product quality.To detect quality-related faults,Hotelling's T^(2) statistic is employed.The developed quality-related fault detection is applied to the widely used industrial benchmark of the Tennessee.
基金financial support of the National Natural Science Foundation of China(No.52472271)the National Key Research and Development Program of China(No.2023YFE0115800)。
文摘Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.
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supported by the Natural Science Foundation of China(No.52101279)the Key Scientific Research Foundation of Education department of Hunan Province(No.24A0003)the Scientific Research Project of Education Department of Hunan Province(No.21B000)and the Fundamental Research Funds for the Central Universities of Central South University.
文摘Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate reduction(eNO_(3)RR)emerges as an attractive strategy to simultaneously enable nitrate removal and decentralized ammo-nia fabrication,restoring the globally perturbed nitrogen cycle.However,complex deoxygenation-hydrogenationprocesses and sluggish proton-electron transfer kinetics significantly hinder practical application of eNO_(3)RR.In this study,we developed carbon-coated Cu-Ni bimetallic catalysts derived from metal-organic frameworks(MOFs)to facilitate eNO_(3)RR.The unique structural features of catalyst promote enhanced synergy between Cuand Ni,effectively addressing critical challenges in nitrate reduction.Comprehensive structural and electrochem-ical analysis demonstrate that electrochemical nitrate-to-nitrite conversion mainly takes place on active Cu sites,the introduction of Ni could efficiently accelerate the generation of aquatic active hydrogen,promoting the hy-drogenation of oxynitrides during eNO_(3)RR.In addition,Ni introduction could push up the d-band center of thecatalyst,thus enhancing the adsorption and activation of nitrate and the corresponding intermediates.Detailedreaction pathways for nitrate-to-ammonia conversion are illuminated by rotating disk electrode(RDE),in-situFourier-transform infrared spectroscopy,in-situ Raman spectrum and electrochemical impedance spectroscopy(EIS).Benefiting from the synergistic effect of Cu and Ni,optimum catalyst exhibited excellent nitrate reductionperformance.This work provides a new idea for elucidating the underlying eNO_(3)RR reaction mechanisms andcontributes a promising strategy for designing efficient bimetallic electrocatalysts.
基金supported by the National Natural Science Foundation of China(No.12205165)Hebei Province Innovation Ability Improvement Plan Project(No.225676111H).
文摘Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
基金supported by the National Natural Science Foundation of China(Nos.22271007,W2431014)Peking University Shenzhen Graduate School+2 种基金State Key Laboratory of Chemical OncogenomicsShenzhen Key Laboratory of Chemical GenomicsShenzhen Bay Laboratory.
文摘Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source.The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of(S)-rivastigmine.Building on this success,we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal,nickel.
