Electrocatalyst activity and stability demonstrate a“seesaw”relationship.Introducing vacancies(Vo)enhances the activity by improving reactant affinity and increasing accessible active sites.However,deficient or exce...Electrocatalyst activity and stability demonstrate a“seesaw”relationship.Introducing vacancies(Vo)enhances the activity by improving reactant affinity and increasing accessible active sites.However,deficient or excessive Vo reduces polysulfide adsorption and lowers catalytic stability.Herein,a novel“heteroatoms synergistic anchoring vacancies”strategy is proposed to address the trade-off between high activity and stability.Phosphorus-doped CoSe_(2)with remained rich selenium vacancies(P-CS-Vo-0.5)was synthesized by producing abundant selenium Vo followed by controlled P atom doping.Atomic-scale microstructure analysis elucidated a dynamic process of surface vacancy generation and the subsequent partial occupation of these vacancies by P atoms.Density functional theory simulations and in situ Raman tests revealed that the Se vacancies provide highly active catalytic sites,accelerating polysulfide conversion,while P incorporation effectively reduces the surface energy of Se vacancies and suppresses their inward migration,enhancing structural robustness.The battery with the optimal P-CS-Vo-0.5 separator delivers an initial discharge capacity of 1306.7 mAh g^(-1)at 0.2C,and maintain 5.04 mAh cm^(-2)at a high sulfur loading(5.7 mg cm^(-2),5.0μL mg^(-1)),achieving 95.1%capacity retention after 80 cycles.This strategy of modifying local atomic environments offers a new route to designing highly active and stable catalysts.展开更多
The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal cent...The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.展开更多
Activated carbons for electrochemical capacitor electrodes are prepared from soyabean using chemical activation with KOH. The pore size is easily controllable by changing the mass ratio between KOH and carbonized prod...Activated carbons for electrochemical capacitor electrodes are prepared from soyabean using chemical activation with KOH. The pore size is easily controllable by changing the mass ratio between KOH and carbonized product. The as-prepared materials possess a large specific surface area, unique structure, well- developed hierarchical porosity and plentiful heteroatoms（mainly O and N）. Thus resulted in its high specific capacitance,good rate capacity and cycling stability. Moreover, attributing to worldwide availability, renewable nature and low-cost, activated carbon prepared from soyabean has a good potential in energy conversion and storage devices.展开更多
Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free he...Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free heteroatoms to obtain the best electrocatalytic performance through three types of dual-doped carbon,including XC-N(first X doping then N doping),NC-X(first N doping then X doping) and NXC(N and X doping)(X=P,S and F).XC-N has more defect than the other two indicated by Raman spectra.X-ray photoelectron spectrom(XPS) measurements indicate that N and X have been dual-doped into the carbon matrix with different doping contents and modes,Electrocatalytic results,including the potential of ORR peak(Ep),the half-wave potential,the diffusion-limiting current density mainly follows the order of XC-N>NC-X> NXC,Furthermore,the synergistic effect of second atom doping are also compared with the single doped carbon(NC,PC,SC and FC).The differences in electronegativity and atomic radius of these metal-free heteroatoms can affect the defect degree,the doping content and mode of hete roatoms on carbon matrix,induce polarization effect and space effect to affect O2 adsorption and product desorption,ultimately to the ORR electrocatalytic performance.展开更多
The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into...The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.展开更多
Accurate regulation of two-dimensional materials has become an effective strategy to develop a wide range of catalytic applications.The introduction of heterogeneous components has a significant impact on the performa...Accurate regulation of two-dimensional materials has become an effective strategy to develop a wide range of catalytic applications.The introduction of heterogeneous components has a significant impact on the performance of materials,which makes it difficult to discover and understand the structure-property relationships at the atomic level.Here,we developed a novel and efficient ensemble learning classifier with synthetic minority oversampling technique(SMOTE) to discover all possible arsenene catalysts with implanted heteroatoms for hydrogen evolution reaction(HER).A total of 850 doped arsenenes were collected as a database and 140 modified arsenene materials with different doping atoms and doping sites were identified as promising candidate catalysts for HER,with a machine learning prediction accuracy of 81%.Based on the results of machine learning,we proposed 13 low-cost and easily synthesized two-dimensional Fe-doped arsenene catalytic materials that are expected to contribute to high-efficient HER.The proposed ensemble method achieved high prediction accuracy,but millions of times faster to predict Gibbs free energies and only required a small amount of data.This study indicates that the presented ensemble learning classifier is capable of screening high-efficient catalysts,and can be further extended to predict other two-dimensional catalysts with delicate regulation.展开更多
Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Hetero...Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Heteroatom modification is one of the most effective strategies for boosting catalytic performance,as it can regulate the physicochemical properties of host catalysts to improve their intrinsic activity.Herein,aiming to provide an overview of the impact of heteroatoms on catalytic activity at the atomic level,we present a review of the key role of heteroatoms in enhancing reaction kinetics based on the reaction pathways of the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline media.In particular,the introduction of heteroatoms can directly and indirectly optimize the interactions between the active sites and intermediates,thus improving the intrinsic activity.To clearly illustrate this influence in detail,we have summarized a series of representative heteroatom-modified electrocatalysts and discussed the important roles of heteroatoms in the OER and HER reaction pathways.Finally,some challenges and perspectives for heteroatom-modified electrodes are discussed.We hope that this review will be helpful for the development of efficient and low-cost electrocatalysts for water electrolysis and other energy conversion applications.展开更多
Two-dimensional covalent organic frameworks(2D COFs)have attracted increasing research attention in photocatalysis-related fields due to their high porosity,large surface area,and tunable band gap.The construction of ...Two-dimensional covalent organic frameworks(2D COFs)have attracted increasing research attention in photocatalysis-related fields due to their high porosity,large surface area,and tunable band gap.The construction of effective and robust 2D COFs for improving photocatalytic activity of 2D COFs is highly desirable.Herein,we propose a strategy for promoting photocatalytic oxidative activity of 2D COFs via doping nitrogen into donor units.Two novel benzothiadiazole-based 2D COFs with kgm topology,namely COF−BD and COF−BP,have been successfully synthesized by reacting tetratopic 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalaldehyde with ditopic benzidine and[2,2'-bipyridine]-5,5'-diamine,respectively.Interestingly,the as-synthesized COF−BP exhibited better performances in photocatalytic oxidative coupling of amines than the corresponding COF−BD.Moreover,the resultant COF−BP exhibited excellent recyclability after being used for ten cycles.Mechanistic investigations revealed that the introduction of electron-withdrawing nitrogen atoms into donor units is favorable for enhancing visible-light absorption,narrowing the band gap,and facilitating the separation and transport of the photogenerated carriers of 2D COFs.This work provides an effective approach for the design of 2D COFs for advanced photocatalytic organic transformations.展开更多
Zinc-ion hybrid supercapacitors(ZIHCs)are compelling candidates for next-generation energy storage owing to their intrinsic safety,low cost,and high power density.However,their practical implementation remains hindere...Zinc-ion hybrid supercapacitors(ZIHCs)are compelling candidates for next-generation energy storage owing to their intrinsic safety,low cost,and high power density.However,their practical implementation remains hindered by the limited energy density of traditional carbon-based cathodes.Here,we rationally design porous carbon nanofibers embedded with atomically dispersed Zn and Fe dual-metal sites(ZnFe/PCNFs),synthesized via electrospinning followed by controlled carbonization.The introduction of Fe modulates the local electronic structure of Zn centers,thereby facilitating enhanced d-orbital hybridization and stronger ion adsorption through the formation of ZnFeN_(6) coordination motifs.Coupled with high surface area and hierarchical porosity,these atomic-level interactions facilitate exceptional ion accessibility and rapid charge-transfer kinetics.As a cathode for ZIHCs,ZnFe/PCNFs deliver a specific capacity of 213 mAh g^(-1),exceptional high-rate capability,and longterm cycling stability over 20000 cycles.This work elucidates mechanisms of dual-metal atomic coordination and provides a robust design strategy for high-performance,durable aqueous energy storage systems.展开更多
Light-weight and exceptional microwave absorption are two vital characteristics for microwave absorbers in practical applications,but still face challenges.Herein,we employ a sacrificial template strategy to fabricate...Light-weight and exceptional microwave absorption are two vital characteristics for microwave absorbers in practical applications,but still face challenges.Herein,we employ a sacrificial template strategy to fabricate heteroatoms-doped carbon nanocages(CNs)via chemical vapor deposition,in which heteroatoms are simultaneously doped into the carbon frameworks by bubbling flowing source liquid.Compared with CNs,doped heteroatoms,accompanied with the inevitably defective arrangements in the lattice,not only decrease the electrical conductivity and balance the impedance characteristics,but also introduce structuralchemical defects and trigger dominant dipolar/defect polarization.As a result,both the minimum reflection loss(R_(L,min))and effective absorption bandwidth(EAB)greatly increase at an ultralow filler loading of 5 wt.%owing to internal hollow void and high specific surface area.The R_(L,min) values reach−53.6,−43.2,and−50.1 dB for N-CNs,S-CNs,and N,S-CNs with the corresponding EAB of 4.9,2.5,and 3.1 GHz,respectively.Furthermore,this work provides an effective strategy for the construction of heteroatoms-doped hollow carbon frameworks in large-scale production and the obtained doped carbon nanocages can be used as light-weight and high-performance microwave absorbers.展开更多
The N-doping strategy is considered an effective method to regulate the electronic structure of carbon materials and improve their electrochemical performance.However,how to reasonably regulate the types of N-doping s...The N-doping strategy is considered an effective method to regulate the electronic structure of carbon materials and improve their electrochemical performance.However,how to reasonably regulate the types of N-doping species remains a major challenge.Herein,we reported a self-supporting carbon nanofiber electrode codoped with N and Se(N/Se-CNF)for flexible zinc ion capacitor(ZIC).It was found that Se atoms can induce the reduction of Pyrrole-N,which is favorable for Zn ions transfer.Furthermore,ex-situ characterizations and theoretical density functional theory(DFT)calculations have shown that additional Se atoms can provide abundant reaction sites and reduce the adsorption energy of Zn ions.Accordingly,the N/Se-CNF electrode demonstrates impressive rate performance.The N/Se-CNF electrode shows impressive rate performance,retaining 60%capacitance at 20 A·g^(-1),with an energy density of 95.3 Wh·kg^(-1) and power density of 160.1 W·kg^(-1),and a commendable stability cycle,the capacitance retention is 88.1%after 18,000 cycles at a discharge rate of 5 A·g^(-1).Moreover,a flexible ZIC with N/Se-CNF electrode exhibits a high energy density of 68.8 Wh·kg^(-1) at 160 W·kg^(-1).This strategy innovatively regulates N-doping species and offers potential flexible electrodes for advanced energy storage devices.展开更多
Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystall...Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demons...Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.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
Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hi...Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hindrance incorporation,coordinated oxygen(O)regulation,and selective fluorination face poor-diversity interfacial chemistry,high cost,or environmental concerns.Here,we propose a heteroatom-substitution strategy to design a WSE composed of lithium bis(fluorosulfonyl)imide(LiFSI)and 1,4-oxathiane(OTA)as a single solvent.Substituting oxygen with sulfur in conventional 1,4-dioxane(1,4-DX)generates OTA with a modulated dipole and charge distribution,weakening Li^(+)-OTA coordination while promoting anion-involved solvation sheath.This unique solvation structure triggers the formation of an inorganic-rich SEI with sulfur-containing species,enabling high Li plating/stripping coulombic efficiency and stable Li‖Li symmetric cells cycling for 1000 h.Benefiting from the superior interfacial chemistry and wettability of the electrolyte to the LiFePO_(4) cathode,full cells exhibit exceptional cycling stability even at low negative-to-positive(N/P)ratios,A pouch cell coupled with3.58 mAh cm^(-2) LiFePO_(4) and 20μm Li(N/P~1.15)maintains 88.77%capacity after 150 cycles.This work shows a fluorine-free solvent design paradigm for advanced WSEs,providing novel insights toward stable LMBs.展开更多
As a potential adsorption material,it is still a challenge for activated carbon fiber(ACF)in efficient adsorption of ethanol due to its nonpolar surface,which is mainly emitted from the grain drying industry.This stud...As a potential adsorption material,it is still a challenge for activated carbon fiber(ACF)in efficient adsorption of ethanol due to its nonpolar surface,which is mainly emitted from the grain drying industry.This study prepared surface polarity-modified ACF using the heteroatom doping method.The modified ACF possessed a richer array of strongly polar oxygen/nitrogen-containing functional groups(primarily phenolic hydroxyl and lactone groups),a larger specific surface are1,and a more developed micropore structure.The adsorption capacities of ethanol for O-ACF and N-ACF were 4.110 mmol/g and 1.698 mmol/g,respectively,which were 11.3 times and 4.7 times those of unmodified ACF.This was a significant improvement over our previous work(0.363 mmol/g).The improvement of adsorption capacity for the N-ACF was mainly due to the higher specific surface are1,greater number of micropores(more adsorption sites)and abundant existence of defects,whereas,for O-ACF,the improvement mainly relied on the abundant presence of oxygen-containing functional groups on the surface.However,water had a negative effect on the adsorption of ethanol for the modified ACF due to competitive adsorption and the disappearance of capillary condensation.It was further revealed that the adsorption process of ethanol and water was quite different.It obeyed the linear driving force(LDF)model for ethanol adsorption,however,the intraparticle diffusion(IPD)model for water adsorption.展开更多
Metallaaromatics are metallacycles that are derived from the formal replacement of a carbon atom in the framework of organic aromatics with a metal fragment. As an important subclass of metallaaromatics, metallaaromat...Metallaaromatics are metallacycles that are derived from the formal replacement of a carbon atom in the framework of organic aromatics with a metal fragment. As an important subclass of metallaaromatics, metallaaromatics that contain main-group heteroatoms have attracted considera- ble attention. In the past ten years, we have developed several new methods to construct metallaaromatics as well as those containing main-group het- eroatoms, such as metallapyridine, metallapyridinium, metallapyridyne, metallafuran, metallabenzothiazole, metallabenzoxazole, metallabenzthiophene, aza-metallapentalene and some novel tricyclic/tetracyclic metallaaromatics. In addition, interesting reactions such as the first hetero-Diels Aider reaction between 1-metalla-1,3-dienes and nitriles, the first intramolecular nucleophilic aromatic substitution （SNAr） reaction of metallabenzene, and the first iodine-mediated electrophilic cyclizations of a metallabenzene complex were demonstrated. In this account, recent and novel approaches for their synthesis and property analyses are summarized. The structural diversity and unique properties of metallaaromatics containing main-group heteroatoms will strongly inspire further investigation of these species and provide a wide range of potential applications.展开更多
1,2-rearrangements of carbenes :CCH_2X(X=CH_2, NH and O) are studied by using ab initio gradient method. Heteroatoms N and O stabilize the carbene and decrease its reactivity, mainly by changing frontier molecular orb...1,2-rearrangements of carbenes :CCH_2X(X=CH_2, NH and O) are studied by using ab initio gradient method. Heteroatoms N and O stabilize the carbene and decrease its reactivity, mainly by changing frontier molecular orbitals, but retain the way of the reaction. The reaction starts from the attack of the migrating hydrogen on the carbene p AO and ends with the entrance of the hydrogen into the carbene σ orbital. Reactivities are in the order of X=CH_2>NH>O. The reaction is exothermic or endothermic according to whether the product is a 4n+2 or 4n π electron molecule.展开更多
Zinc-ion hybrid capacitors (ZIHCs) have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental friendliness.However,their progress has been hampered by low energy...Zinc-ion hybrid capacitors (ZIHCs) have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental friendliness.However,their progress has been hampered by low energy and power density,as well as unsatisfactory long-cycle stability,mainly due to the lack of suitable electrode materials.In this context,we have developed manganese single atoms implanted in nitrogen-doped porous carbon nanosheets (MnSAs/NCNs) using a metal salt template method as cathodes for ZIHCs.The metal salt serves a dual purpose in the synthesis process:It facilitates the uniform dispersion of Mn atoms within the carbon matrix and acts as an activating agent to create the porous structure.When applied in ZIHCs,the MnSAs/NCNs electrode demonstrates exceptional performance,including a high capacity of 203 m Ah g^(-1),an energy density of 138 Wh kg^(-1)at 68 W kg^(-1),and excellent cycle stability with 91%retention over 10,000 cycles.Theoretical calculations indicate that the introduced Mn atoms modulate the local charge distribution of carbon materials,thereby improving the electrochemical property.This work demonstrates the significant potential of carbon materials with metal atoms in zinc-ion hybrid capacitors,not only in enhancing electrochemical performance but also in providing new insights and methods for developing high-performance energy storage devices.展开更多
Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incor...Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe(oxy)hydroxide(Mn-NiFeOOH/LDH)heterojunction.Mn doping regulates heterojunction morphology(reducing nanoparticles and becoming thinner and denser nanosheets),Ni/Fe ratio and valence states(Ni^(2+),Ni^(3+),and Ni^(3+Δ))of Ni ions.The former could effectively increase surface active sites,and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction,en-abling more Ni^(2+)convert to Ni^(3+/3+Δ)that have higher intrinsic OER activity.As a result,the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm^(-2) and 296 mV@500 mA cm^(-2),and the improved OER performance are outdo to those of commercial RuO_(2) catalyst for OER.Moreover,the Mn-NiFeOOH/LDH affords the earliest initial potential(1.392 V vs.RHE),corresponds to a recorded low overpotential(162 mV).Based on the density functional theory(DFT),Mn dopants can alter intermedi-ate adsorption energy and effectively decrease∗OOH’s energy barrier.This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.展开更多
基金supported by the National Key Research and Development Program of China(No.2022YFA1602700 and 2022YFB2502104)the National Natural Science Foundation of China(22375089)the Key Research and Development Program of Jiangsu Provincial Department of Science and Technology of China(BE2022332).
文摘Electrocatalyst activity and stability demonstrate a“seesaw”relationship.Introducing vacancies(Vo)enhances the activity by improving reactant affinity and increasing accessible active sites.However,deficient or excessive Vo reduces polysulfide adsorption and lowers catalytic stability.Herein,a novel“heteroatoms synergistic anchoring vacancies”strategy is proposed to address the trade-off between high activity and stability.Phosphorus-doped CoSe_(2)with remained rich selenium vacancies(P-CS-Vo-0.5)was synthesized by producing abundant selenium Vo followed by controlled P atom doping.Atomic-scale microstructure analysis elucidated a dynamic process of surface vacancy generation and the subsequent partial occupation of these vacancies by P atoms.Density functional theory simulations and in situ Raman tests revealed that the Se vacancies provide highly active catalytic sites,accelerating polysulfide conversion,while P incorporation effectively reduces the surface energy of Se vacancies and suppresses their inward migration,enhancing structural robustness.The battery with the optimal P-CS-Vo-0.5 separator delivers an initial discharge capacity of 1306.7 mAh g^(-1)at 0.2C,and maintain 5.04 mAh cm^(-2)at a high sulfur loading(5.7 mg cm^(-2),5.0μL mg^(-1)),achieving 95.1%capacity retention after 80 cycles.This strategy of modifying local atomic environments offers a new route to designing highly active and stable catalysts.
文摘The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.
文摘Activated carbons for electrochemical capacitor electrodes are prepared from soyabean using chemical activation with KOH. The pore size is easily controllable by changing the mass ratio between KOH and carbonized product. The as-prepared materials possess a large specific surface area, unique structure, well- developed hierarchical porosity and plentiful heteroatoms（mainly O and N）. Thus resulted in its high specific capacitance,good rate capacity and cycling stability. Moreover, attributing to worldwide availability, renewable nature and low-cost, activated carbon prepared from soyabean has a good potential in energy conversion and storage devices.
基金the financial support of this work by the National Natural Science Foundation of China (No.21406139)the Development Project of University of Shanghai for Science and Technology (No.2019KJFZ019)+1 种基金the Scientific Research Innovation Project of Shanghai Education Commission (No.2019-01-07-0007-E00015)the Basic Research Project (No.19JC1410402)。
文摘Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free heteroatoms to obtain the best electrocatalytic performance through three types of dual-doped carbon,including XC-N(first X doping then N doping),NC-X(first N doping then X doping) and NXC(N and X doping)(X=P,S and F).XC-N has more defect than the other two indicated by Raman spectra.X-ray photoelectron spectrom(XPS) measurements indicate that N and X have been dual-doped into the carbon matrix with different doping contents and modes,Electrocatalytic results,including the potential of ORR peak(Ep),the half-wave potential,the diffusion-limiting current density mainly follows the order of XC-N>NC-X> NXC,Furthermore,the synergistic effect of second atom doping are also compared with the single doped carbon(NC,PC,SC and FC).The differences in electronegativity and atomic radius of these metal-free heteroatoms can affect the defect degree,the doping content and mode of hete roatoms on carbon matrix,induce polarization effect and space effect to affect O2 adsorption and product desorption,ultimately to the ORR electrocatalytic performance.
文摘The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.
基金supported by the National Key R&D Program of China(No.2021YFC2100100)the National Natural Science Foundation of China(No.21901157)the Shanghai Science and Technology Project(No.21JC1403400)。
文摘Accurate regulation of two-dimensional materials has become an effective strategy to develop a wide range of catalytic applications.The introduction of heterogeneous components has a significant impact on the performance of materials,which makes it difficult to discover and understand the structure-property relationships at the atomic level.Here,we developed a novel and efficient ensemble learning classifier with synthetic minority oversampling technique(SMOTE) to discover all possible arsenene catalysts with implanted heteroatoms for hydrogen evolution reaction(HER).A total of 850 doped arsenenes were collected as a database and 140 modified arsenene materials with different doping atoms and doping sites were identified as promising candidate catalysts for HER,with a machine learning prediction accuracy of 81%.Based on the results of machine learning,we proposed 13 low-cost and easily synthesized two-dimensional Fe-doped arsenene catalytic materials that are expected to contribute to high-efficient HER.The proposed ensemble method achieved high prediction accuracy,but millions of times faster to predict Gibbs free energies and only required a small amount of data.This study indicates that the presented ensemble learning classifier is capable of screening high-efficient catalysts,and can be further extended to predict other two-dimensional catalysts with delicate regulation.
文摘Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Heteroatom modification is one of the most effective strategies for boosting catalytic performance,as it can regulate the physicochemical properties of host catalysts to improve their intrinsic activity.Herein,aiming to provide an overview of the impact of heteroatoms on catalytic activity at the atomic level,we present a review of the key role of heteroatoms in enhancing reaction kinetics based on the reaction pathways of the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline media.In particular,the introduction of heteroatoms can directly and indirectly optimize the interactions between the active sites and intermediates,thus improving the intrinsic activity.To clearly illustrate this influence in detail,we have summarized a series of representative heteroatom-modified electrocatalysts and discussed the important roles of heteroatoms in the OER and HER reaction pathways.Finally,some challenges and perspectives for heteroatom-modified electrodes are discussed.We hope that this review will be helpful for the development of efficient and low-cost electrocatalysts for water electrolysis and other energy conversion applications.
基金the National Natural Science Foundation of China(52203006,52073046,52373172)the National Key Research and Development Program of China(2022YFB3807100,2022YFB3807102)+1 种基金the Chang Jiang Scholar Program(Y.Z.L.)the Fundamental Research Funds for the Central Universities(2232022D-06).
文摘Two-dimensional covalent organic frameworks(2D COFs)have attracted increasing research attention in photocatalysis-related fields due to their high porosity,large surface area,and tunable band gap.The construction of effective and robust 2D COFs for improving photocatalytic activity of 2D COFs is highly desirable.Herein,we propose a strategy for promoting photocatalytic oxidative activity of 2D COFs via doping nitrogen into donor units.Two novel benzothiadiazole-based 2D COFs with kgm topology,namely COF−BD and COF−BP,have been successfully synthesized by reacting tetratopic 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalaldehyde with ditopic benzidine and[2,2'-bipyridine]-5,5'-diamine,respectively.Interestingly,the as-synthesized COF−BP exhibited better performances in photocatalytic oxidative coupling of amines than the corresponding COF−BD.Moreover,the resultant COF−BP exhibited excellent recyclability after being used for ten cycles.Mechanistic investigations revealed that the introduction of electron-withdrawing nitrogen atoms into donor units is favorable for enhancing visible-light absorption,narrowing the band gap,and facilitating the separation and transport of the photogenerated carriers of 2D COFs.This work provides an effective approach for the design of 2D COFs for advanced photocatalytic organic transformations.
基金supported by the Major Basic Research Projects of Shandong Natural Science Foundation(ZR2024ZD37)the Taishan Scholar Program of Shandong Province,China(No.tsqn202211048)+3 种基金the National Natural Science Foundation of China(No.22179123,22579155)the National Science Fund for Distinguished Young Scholars(52125305)the Science and Technology Key Project of Wuhan(No.2023010302020030)and the Science and Technology Major Project of Xinjiang Autonomous Region(No.2022A03009).
文摘Zinc-ion hybrid supercapacitors(ZIHCs)are compelling candidates for next-generation energy storage owing to their intrinsic safety,low cost,and high power density.However,their practical implementation remains hindered by the limited energy density of traditional carbon-based cathodes.Here,we rationally design porous carbon nanofibers embedded with atomically dispersed Zn and Fe dual-metal sites(ZnFe/PCNFs),synthesized via electrospinning followed by controlled carbonization.The introduction of Fe modulates the local electronic structure of Zn centers,thereby facilitating enhanced d-orbital hybridization and stronger ion adsorption through the formation of ZnFeN_(6) coordination motifs.Coupled with high surface area and hierarchical porosity,these atomic-level interactions facilitate exceptional ion accessibility and rapid charge-transfer kinetics.As a cathode for ZIHCs,ZnFe/PCNFs deliver a specific capacity of 213 mAh g^(-1),exceptional high-rate capability,and longterm cycling stability over 20000 cycles.This work elucidates mechanisms of dual-metal atomic coordination and provides a robust design strategy for high-performance,durable aqueous energy storage systems.
基金supported by the Natural Science Foundation of Shaanxi Province(No.2022JM-260)the Natural Science Foundation of Shandong Province(No.ZR2020ME038)the Fundamental Research Funds of the Central Universities(No.G2022KY05109).
文摘Light-weight and exceptional microwave absorption are two vital characteristics for microwave absorbers in practical applications,but still face challenges.Herein,we employ a sacrificial template strategy to fabricate heteroatoms-doped carbon nanocages(CNs)via chemical vapor deposition,in which heteroatoms are simultaneously doped into the carbon frameworks by bubbling flowing source liquid.Compared with CNs,doped heteroatoms,accompanied with the inevitably defective arrangements in the lattice,not only decrease the electrical conductivity and balance the impedance characteristics,but also introduce structuralchemical defects and trigger dominant dipolar/defect polarization.As a result,both the minimum reflection loss(R_(L,min))and effective absorption bandwidth(EAB)greatly increase at an ultralow filler loading of 5 wt.%owing to internal hollow void and high specific surface area.The R_(L,min) values reach−53.6,−43.2,and−50.1 dB for N-CNs,S-CNs,and N,S-CNs with the corresponding EAB of 4.9,2.5,and 3.1 GHz,respectively.Furthermore,this work provides an effective strategy for the construction of heteroatoms-doped hollow carbon frameworks in large-scale production and the obtained doped carbon nanocages can be used as light-weight and high-performance microwave absorbers.
基金National Natural Science Foundation of China(No.52376060).
文摘The N-doping strategy is considered an effective method to regulate the electronic structure of carbon materials and improve their electrochemical performance.However,how to reasonably regulate the types of N-doping species remains a major challenge.Herein,we reported a self-supporting carbon nanofiber electrode codoped with N and Se(N/Se-CNF)for flexible zinc ion capacitor(ZIC).It was found that Se atoms can induce the reduction of Pyrrole-N,which is favorable for Zn ions transfer.Furthermore,ex-situ characterizations and theoretical density functional theory(DFT)calculations have shown that additional Se atoms can provide abundant reaction sites and reduce the adsorption energy of Zn ions.Accordingly,the N/Se-CNF electrode demonstrates impressive rate performance.The N/Se-CNF electrode shows impressive rate performance,retaining 60%capacitance at 20 A·g^(-1),with an energy density of 95.3 Wh·kg^(-1) and power density of 160.1 W·kg^(-1),and a commendable stability cycle,the capacitance retention is 88.1%after 18,000 cycles at a discharge rate of 5 A·g^(-1).Moreover,a flexible ZIC with N/Se-CNF electrode exhibits a high energy density of 68.8 Wh·kg^(-1) at 160 W·kg^(-1).This strategy innovatively regulates N-doping species and offers potential flexible electrodes for advanced energy storage devices.
基金supported by the National Key R&D Program of China(No.2023YFA1507204)National Natural Science Foundation ofChina(Nos.22475074,22171139,22225109,22302055)+4 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)Key Scientific Research Project Plan of Colleges and Universities of Henan Province(No.24B150004)The Double Thousand Talents Plan of Jiangxi Province(No.jxsq2023102003)Project supported by the Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization(No.2024B121201001)Project supportedby the Major Research plan of the National Natural Science Foundation of China(No.92461310).
文摘Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.
基金financially supported by the Natural Science Foundation of Shandong Province (No.ZR2022QE076)the National Natural Science Foundation of China (No.52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China (No.2023KJ104)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
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the financial support from the National Natural Science Foundation of China,China(Grant Nos.52502258 and 52162030)the Yunnan Fundamental Research Projects,China(Grant Nos.202501AT070298,202401AU070163 and 202401AT070368)+5 种基金the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects,China(Grant No.2023-XMDJ-00617107)the Expert Workstation Support Project of Yunnan Province,China(Grant Nos.202405AF140069 and 202505AF350019)the University Service Key Industry Project of Yunnan Province,China(Grant No.FWCY-ZD2024005)the Shenzhen Science and Technology Program,China(Grant No.KJZD20230923114107014)the Scientific Research Foundation of Kunming University of Science and Technology,China(20220122)the Analysis and Test Foundation of Kunming University of Science and Technology,China(Grant No.2023T20220122)。
文摘Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hindrance incorporation,coordinated oxygen(O)regulation,and selective fluorination face poor-diversity interfacial chemistry,high cost,or environmental concerns.Here,we propose a heteroatom-substitution strategy to design a WSE composed of lithium bis(fluorosulfonyl)imide(LiFSI)and 1,4-oxathiane(OTA)as a single solvent.Substituting oxygen with sulfur in conventional 1,4-dioxane(1,4-DX)generates OTA with a modulated dipole and charge distribution,weakening Li^(+)-OTA coordination while promoting anion-involved solvation sheath.This unique solvation structure triggers the formation of an inorganic-rich SEI with sulfur-containing species,enabling high Li plating/stripping coulombic efficiency and stable Li‖Li symmetric cells cycling for 1000 h.Benefiting from the superior interfacial chemistry and wettability of the electrolyte to the LiFePO_(4) cathode,full cells exhibit exceptional cycling stability even at low negative-to-positive(N/P)ratios,A pouch cell coupled with3.58 mAh cm^(-2) LiFePO_(4) and 20μm Li(N/P~1.15)maintains 88.77%capacity after 150 cycles.This work shows a fluorine-free solvent design paradigm for advanced WSEs,providing novel insights toward stable LMBs.
基金supported by the National Key R&D Program of China(Nos.2022YFB4101500 and 2022YFE0209500)the National Natural Science Foundation of China(Nos.22276191 and 21976177)the Qinghai Province Air Pollution Assessment and Fine Management Support Project,and the University of Chinese Academy of Science.
文摘As a potential adsorption material,it is still a challenge for activated carbon fiber(ACF)in efficient adsorption of ethanol due to its nonpolar surface,which is mainly emitted from the grain drying industry.This study prepared surface polarity-modified ACF using the heteroatom doping method.The modified ACF possessed a richer array of strongly polar oxygen/nitrogen-containing functional groups(primarily phenolic hydroxyl and lactone groups),a larger specific surface are1,and a more developed micropore structure.The adsorption capacities of ethanol for O-ACF and N-ACF were 4.110 mmol/g and 1.698 mmol/g,respectively,which were 11.3 times and 4.7 times those of unmodified ACF.This was a significant improvement over our previous work(0.363 mmol/g).The improvement of adsorption capacity for the N-ACF was mainly due to the higher specific surface are1,greater number of micropores(more adsorption sites)and abundant existence of defects,whereas,for O-ACF,the improvement mainly relied on the abundant presence of oxygen-containing functional groups on the surface.However,water had a negative effect on the adsorption of ethanol for the modified ACF due to competitive adsorption and the disappearance of capillary condensation.It was further revealed that the adsorption process of ethanol and water was quite different.It obeyed the linear driving force(LDF)model for ethanol adsorption,however,the intraparticle diffusion(IPD)model for water adsorption.
基金This work was financially supported by the National Natural Science Foundation of China （21332002 and 21561162001）.
文摘Metallaaromatics are metallacycles that are derived from the formal replacement of a carbon atom in the framework of organic aromatics with a metal fragment. As an important subclass of metallaaromatics, metallaaromatics that contain main-group heteroatoms have attracted considera- ble attention. In the past ten years, we have developed several new methods to construct metallaaromatics as well as those containing main-group het- eroatoms, such as metallapyridine, metallapyridinium, metallapyridyne, metallafuran, metallabenzothiazole, metallabenzoxazole, metallabenzthiophene, aza-metallapentalene and some novel tricyclic/tetracyclic metallaaromatics. In addition, interesting reactions such as the first hetero-Diels Aider reaction between 1-metalla-1,3-dienes and nitriles, the first intramolecular nucleophilic aromatic substitution （SNAr） reaction of metallabenzene, and the first iodine-mediated electrophilic cyclizations of a metallabenzene complex were demonstrated. In this account, recent and novel approaches for their synthesis and property analyses are summarized. The structural diversity and unique properties of metallaaromatics containing main-group heteroatoms will strongly inspire further investigation of these species and provide a wide range of potential applications.
基金This project was supported by the National Natural Science Foundation of China.
文摘1,2-rearrangements of carbenes :CCH_2X(X=CH_2, NH and O) are studied by using ab initio gradient method. Heteroatoms N and O stabilize the carbene and decrease its reactivity, mainly by changing frontier molecular orbitals, but retain the way of the reaction. The reaction starts from the attack of the migrating hydrogen on the carbene p AO and ends with the entrance of the hydrogen into the carbene σ orbital. Reactivities are in the order of X=CH_2>NH>O. The reaction is exothermic or endothermic according to whether the product is a 4n+2 or 4n π electron molecule.
基金National Natural Science Foundation of China (No. 22179123)Taishan Scholar Program of Shandong Province,China (No. tsqn202211048)Fundamental Research Funds for the Central Universities (No.202262010)。
文摘Zinc-ion hybrid capacitors (ZIHCs) have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental friendliness.However,their progress has been hampered by low energy and power density,as well as unsatisfactory long-cycle stability,mainly due to the lack of suitable electrode materials.In this context,we have developed manganese single atoms implanted in nitrogen-doped porous carbon nanosheets (MnSAs/NCNs) using a metal salt template method as cathodes for ZIHCs.The metal salt serves a dual purpose in the synthesis process:It facilitates the uniform dispersion of Mn atoms within the carbon matrix and acts as an activating agent to create the porous structure.When applied in ZIHCs,the MnSAs/NCNs electrode demonstrates exceptional performance,including a high capacity of 203 m Ah g^(-1),an energy density of 138 Wh kg^(-1)at 68 W kg^(-1),and excellent cycle stability with 91%retention over 10,000 cycles.Theoretical calculations indicate that the introduced Mn atoms modulate the local charge distribution of carbon materials,thereby improving the electrochemical property.This work demonstrates the significant potential of carbon materials with metal atoms in zinc-ion hybrid capacitors,not only in enhancing electrochemical performance but also in providing new insights and methods for developing high-performance energy storage devices.
基金funding support by the Changsha Natural Science Foundation(grant no.kq2208023)National Natural Scientific Foundation of China(grant no.12074113).
文摘Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe(oxy)hydroxide(Mn-NiFeOOH/LDH)heterojunction.Mn doping regulates heterojunction morphology(reducing nanoparticles and becoming thinner and denser nanosheets),Ni/Fe ratio and valence states(Ni^(2+),Ni^(3+),and Ni^(3+Δ))of Ni ions.The former could effectively increase surface active sites,and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction,en-abling more Ni^(2+)convert to Ni^(3+/3+Δ)that have higher intrinsic OER activity.As a result,the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm^(-2) and 296 mV@500 mA cm^(-2),and the improved OER performance are outdo to those of commercial RuO_(2) catalyst for OER.Moreover,the Mn-NiFeOOH/LDH affords the earliest initial potential(1.392 V vs.RHE),corresponds to a recorded low overpotential(162 mV).Based on the density functional theory(DFT),Mn dopants can alter intermedi-ate adsorption energy and effectively decrease∗OOH’s energy barrier.This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.
