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
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
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
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
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
Organic-rich mudstones and shales,which hold significant potential for shale oil resources,characterize the first member of the Upper Cretaceous Qingshankou Formation(K_(2)qn~1)in the Sanzhao sag of the Songliao Basin...Organic-rich mudstones and shales,which hold significant potential for shale oil resources,characterize the first member of the Upper Cretaceous Qingshankou Formation(K_(2)qn~1)in the Sanzhao sag of the Songliao Basin,NE China.Focusing on 30 core samples obtained from the first shale oil parameter well,named SYY3 in the study area,we systematically analyzed the composition and stratigraphic distribution of the K_(2)qn~1 heteroatomic compounds using electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry(ESI FT-ICR MS),to assess their geological relevance to shale oil.The findings indicate that in the negative ion mode,the heteroatomic compounds predominantly consist of N_(1),N_(1)O_(1)-N_(1)O_(8),O_(1)-O_(8),O_(1)S_(1)-O_(6)S_(1);contrastingly,in the positive ion mode,they are primarily composed of N_(1)-N_(2),N_(1)O_(1)-N_(1)O_(4),N_(2)O_(1),O_(1)-O_(4),O_(1)S_(1)-O_(2)S_(1).Heteroatomic compound distributions vary significantly with depth in the negative ion mode,with minor variations in the positive ion mode.These distributions are categorized into three types based on the negative ion ratio((N_(1)+N_(1)O_(x))/O_(x)):TypeⅠ(>1.5),TypeⅡ(0.8-1.5),and TypeⅢ(<0.8);typesⅠandⅡgenerally exhibit a broader range of carbon numbers compared to TypeⅢ.The distribution of double bond equivalent(DBE)values across various sample types exhibits minimal variance,whereas that of carbon numbers shows substantial differences.Variations in heteroatomic compound compositions among the samples might have resulted from vertical sedimentary heterogeneity and differing biotic contributions.TypeⅢsamples show a decrease in total organic carbon(TOC)and free oil content(S_(1))compared to typesⅠandⅡ,but an increased oil saturation index(OSI),indicating a lower content of free oil but a higher proportion of movable oil.The reduced content of N-containing compounds implies lower paleolake productivity during deposition,leading to a reduction in TOC and S_(1).A lower TOC can enhance oil movability due to reduced oil adsorption,and the decreased presence of polar nitrogenous macromolecules with fewer highC-number heteroatomic compounds further promote shale oil movability.Additionally,the negative ion ratios of N1/N1O1and O2/O1 exhibit positive and negative correlations with the values of TOC,S_(1),and extractable organic matter(EOM),respectively,indicating that the salinity and redox conditions of the depositional water body are the primary controlling factors for both organic matter enrichment and shale oil accumulation.展开更多
Nickel-rich(Ni≥90%)layered oxides materials have emerged as a promising candidate for nextgeneration high-energy-density lithium-ion batteries(LIBs).However,their widespread application is hindered by structural fati...Nickel-rich(Ni≥90%)layered oxides materials have emerged as a promising candidate for nextgeneration high-energy-density lithium-ion batteries(LIBs).However,their widespread application is hindered by structural fatigue and lattice oxygen loss.In this work,an epitaxial surface rock-salt nanolayer is successfully developed on the LiNi_(0.9)Co_(0.1)O_(2)sub-surface via heteroatom anchoring utilizing high-valence element molybdenum modification.This in-situ formed conformal buffer phase with a thickness of 1.2 nm effectively suppresses the continuous interphase side-reactions,and thus maintains the excellent structure integrity at high voltage.Furthermore,theoretical calculations indicate that the lattice oxygen reversibility in the anion framework of the optimized sample is obviously enhanced due to the higher content of O 2p states near the Fermi level than that of the pristine one.Meanwhile,the stronger Mo-O bond further reduces cell volume alteration,which improves the bulk structure stability of modified materials.Besides,the detailed charge compensation mechanism suggests that the average oxidation state of Ni is reduced,which induces more active Li+participating in the redox reactions,boosting the cell energy density.As a result,the uniquely designed cathode materials exhibit an extraordinary discharge capacity of 245.4 mAh g^(-1)at 0.1 C,remarkable rate performance of 169.3 mAh g^(-1)at 10 C at 4.5 V,and a high capacity retention of 70.5% after 1000 cycles in full cells at a high cut-off voltage of 4.4 V.This strategy provides an valuable insight into constructing distinctive heterostructure on highperformance Ni-rich layered cathodes for LIBs.展开更多
The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally...The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.展开更多
Heavy oil,constituting a significant portion of global oil reserves,presents unique challenges in extraction and processing due to its high viscosity,largely influenced by asphaltenes and their heteroatom content.This...Heavy oil,constituting a significant portion of global oil reserves,presents unique challenges in extraction and processing due to its high viscosity,largely influenced by asphaltenes and their heteroatom content.This study employs molecular dynamics(MD)simulations to investigate the selfaggregation and adsorption mechanisms of heteroatom/non-heteroatom asphaltenes,comparing linear and island structural configurations.Key findings reveal that linear heteroatom asphaltenes form dense,multi-layered aggregates,while island heteroatom asphaltenes exhibit stronger aggregation energy.On solid surfaces,linear asphaltenes display multi-layered adsorption,whereas island asphaltenes adopt a dispersed structure with higher adsorption energy,making them more resistant to removal.Compared to non-heteroatom asphaltenes,heteroatom asphaltenes significantly enhance the aggregation energy of the asphaltene itself and the interaction energy with light oil components,reducing the diffusion capacity of oil droplets and increasing viscosity.Although the viscosity of island heteroatom asphaltene oil drops is the largest,the role of heteroatom in linear asphaltene is more obvious,and linear heteroatom asphaltene and non-heteroatom show great differences in properties.Additionally,heteroatom-containing oil droplets exhibit stronger interactions with solid surfaces,driven by the influence of heteroatom asphaltenes on lighter oil components.These insights provide a deeper understanding of heavy oil viscosity mechanisms,offering a foundation for developing targeted viscosity-reduction strategies and optimizing heavy oil recovery and processing techniques.展开更多
Heterocyclic compounds play an important role in organic hole transport materials(HTMs)for perovskite solar cells(PSCs).Herein,a series of linear D-π-D HTMs(O-CBz,S-CBz,SO_(2)-CBz)with different dibenzoheterocycles c...Heterocyclic compounds play an important role in organic hole transport materials(HTMs)for perovskite solar cells(PSCs).Herein,a series of linear D-π-D HTMs(O-CBz,S-CBz,SO_(2)-CBz)with different dibenzoheterocycles core(dibenzofuran,dibenzothiophene,dibenzothiophene sulfone)were designed and synthesized,and their applications in PSCs were investigated.The intrinsic properties(CV,UV-vis,hole mobility and conductivity)were systematically investigated,demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs.Benefiting from the excellent hole mobility and conductivity,good film forming ability,and outstanding charge extraction and transport capability of S-CBz,FAPbI_(3)-based PSCs using S-CBz as HTM achieved a PCE of 25.0%,which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions(23.9%).Furthermore,due to the interaction between S and Pb^(2+),SCBz-based PSC devices exhibited improved stability.This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.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 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(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.
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jointly funded by the National Natural Science Foundation of China(Grant Nos.42072178 and U2244207)the funding project of Northeast Geological S&T Innovation Center of China Geological Survey(Grant No.QCJJ2022-37)Geological Survey Project of China Geological Survey(Grant Nos.DD20190114,DD20230022,and DD20240045)。
文摘Organic-rich mudstones and shales,which hold significant potential for shale oil resources,characterize the first member of the Upper Cretaceous Qingshankou Formation(K_(2)qn~1)in the Sanzhao sag of the Songliao Basin,NE China.Focusing on 30 core samples obtained from the first shale oil parameter well,named SYY3 in the study area,we systematically analyzed the composition and stratigraphic distribution of the K_(2)qn~1 heteroatomic compounds using electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry(ESI FT-ICR MS),to assess their geological relevance to shale oil.The findings indicate that in the negative ion mode,the heteroatomic compounds predominantly consist of N_(1),N_(1)O_(1)-N_(1)O_(8),O_(1)-O_(8),O_(1)S_(1)-O_(6)S_(1);contrastingly,in the positive ion mode,they are primarily composed of N_(1)-N_(2),N_(1)O_(1)-N_(1)O_(4),N_(2)O_(1),O_(1)-O_(4),O_(1)S_(1)-O_(2)S_(1).Heteroatomic compound distributions vary significantly with depth in the negative ion mode,with minor variations in the positive ion mode.These distributions are categorized into three types based on the negative ion ratio((N_(1)+N_(1)O_(x))/O_(x)):TypeⅠ(>1.5),TypeⅡ(0.8-1.5),and TypeⅢ(<0.8);typesⅠandⅡgenerally exhibit a broader range of carbon numbers compared to TypeⅢ.The distribution of double bond equivalent(DBE)values across various sample types exhibits minimal variance,whereas that of carbon numbers shows substantial differences.Variations in heteroatomic compound compositions among the samples might have resulted from vertical sedimentary heterogeneity and differing biotic contributions.TypeⅢsamples show a decrease in total organic carbon(TOC)and free oil content(S_(1))compared to typesⅠandⅡ,but an increased oil saturation index(OSI),indicating a lower content of free oil but a higher proportion of movable oil.The reduced content of N-containing compounds implies lower paleolake productivity during deposition,leading to a reduction in TOC and S_(1).A lower TOC can enhance oil movability due to reduced oil adsorption,and the decreased presence of polar nitrogenous macromolecules with fewer highC-number heteroatomic compounds further promote shale oil movability.Additionally,the negative ion ratios of N1/N1O1and O2/O1 exhibit positive and negative correlations with the values of TOC,S_(1),and extractable organic matter(EOM),respectively,indicating that the salinity and redox conditions of the depositional water body are the primary controlling factors for both organic matter enrichment and shale oil accumulation.
基金financially supported by the National Natural Science Foundation of China(No.52202228,52402298)funded by the Science Research Project of Hebei Education Department(No.BJK2022011)+3 种基金the Central Funds Guiding the Local Science and Technology Development of Hebei Province(No.236Z4404G)the Beijing Tianjin Hebei Basic Research Cooperation Special Project(No.E2024202273)the Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)supported by the U.S.Department of Energy’s Office of Science,Office of Basic Energy Science,Materials Sciences and Engineering Division。
文摘Nickel-rich(Ni≥90%)layered oxides materials have emerged as a promising candidate for nextgeneration high-energy-density lithium-ion batteries(LIBs).However,their widespread application is hindered by structural fatigue and lattice oxygen loss.In this work,an epitaxial surface rock-salt nanolayer is successfully developed on the LiNi_(0.9)Co_(0.1)O_(2)sub-surface via heteroatom anchoring utilizing high-valence element molybdenum modification.This in-situ formed conformal buffer phase with a thickness of 1.2 nm effectively suppresses the continuous interphase side-reactions,and thus maintains the excellent structure integrity at high voltage.Furthermore,theoretical calculations indicate that the lattice oxygen reversibility in the anion framework of the optimized sample is obviously enhanced due to the higher content of O 2p states near the Fermi level than that of the pristine one.Meanwhile,the stronger Mo-O bond further reduces cell volume alteration,which improves the bulk structure stability of modified materials.Besides,the detailed charge compensation mechanism suggests that the average oxidation state of Ni is reduced,which induces more active Li+participating in the redox reactions,boosting the cell energy density.As a result,the uniquely designed cathode materials exhibit an extraordinary discharge capacity of 245.4 mAh g^(-1)at 0.1 C,remarkable rate performance of 169.3 mAh g^(-1)at 10 C at 4.5 V,and a high capacity retention of 70.5% after 1000 cycles in full cells at a high cut-off voltage of 4.4 V.This strategy provides an valuable insight into constructing distinctive heterostructure on highperformance Ni-rich layered cathodes for LIBs.
文摘The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.
基金supported financially by the National Natural Science Foundation of China(No.52204069,No.22306171)the Natural Science Foundation of Zhejiang Province(No.LQ24B070005)the Jinhua Natural Science Foundation of China(2023-4-024)。
文摘Heavy oil,constituting a significant portion of global oil reserves,presents unique challenges in extraction and processing due to its high viscosity,largely influenced by asphaltenes and their heteroatom content.This study employs molecular dynamics(MD)simulations to investigate the selfaggregation and adsorption mechanisms of heteroatom/non-heteroatom asphaltenes,comparing linear and island structural configurations.Key findings reveal that linear heteroatom asphaltenes form dense,multi-layered aggregates,while island heteroatom asphaltenes exhibit stronger aggregation energy.On solid surfaces,linear asphaltenes display multi-layered adsorption,whereas island asphaltenes adopt a dispersed structure with higher adsorption energy,making them more resistant to removal.Compared to non-heteroatom asphaltenes,heteroatom asphaltenes significantly enhance the aggregation energy of the asphaltene itself and the interaction energy with light oil components,reducing the diffusion capacity of oil droplets and increasing viscosity.Although the viscosity of island heteroatom asphaltene oil drops is the largest,the role of heteroatom in linear asphaltene is more obvious,and linear heteroatom asphaltene and non-heteroatom show great differences in properties.Additionally,heteroatom-containing oil droplets exhibit stronger interactions with solid surfaces,driven by the influence of heteroatom asphaltenes on lighter oil components.These insights provide a deeper understanding of heavy oil viscosity mechanisms,offering a foundation for developing targeted viscosity-reduction strategies and optimizing heavy oil recovery and processing techniques.
基金supported by the financial support from the National Natural Science Foundation of China(Nos.22279046,22179053)Natural Science Excellent Youth Foundation of Jiangsu Province(No.BK20220112)Special Foundation for Carbon Peak Carbon Neutralization Technology Innovation Program of Jiangsu Province(No.BE2022026-2).
文摘Heterocyclic compounds play an important role in organic hole transport materials(HTMs)for perovskite solar cells(PSCs).Herein,a series of linear D-π-D HTMs(O-CBz,S-CBz,SO_(2)-CBz)with different dibenzoheterocycles core(dibenzofuran,dibenzothiophene,dibenzothiophene sulfone)were designed and synthesized,and their applications in PSCs were investigated.The intrinsic properties(CV,UV-vis,hole mobility and conductivity)were systematically investigated,demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs.Benefiting from the excellent hole mobility and conductivity,good film forming ability,and outstanding charge extraction and transport capability of S-CBz,FAPbI_(3)-based PSCs using S-CBz as HTM achieved a PCE of 25.0%,which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions(23.9%).Furthermore,due to the interaction between S and Pb^(2+),SCBz-based PSC devices exhibited improved stability.This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
