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
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
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
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
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
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
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
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
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
Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru...Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-Co O/CP with doping strategy and heterostructure was synthesized for overall water splitting.The Ru/V-Co O exhibits excellent activity for HER and OER with low overpotentials of 49, 147 m V at a current density of 10 m A/cm^(2) in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 m A/cm^(2)current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial Ru O_(2)||Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts,providing new ideas for the design and development of efficient and stable electrocatalysts.展开更多
Designing exceptional-performance and long-lasting oxygen reduction reaction(ORR)catalysts is a critical challenge for the development of rechargeable Zn-air batteries(ZABs).In this study,we introduce a metal-free ORR...Designing exceptional-performance and long-lasting oxygen reduction reaction(ORR)catalysts is a critical challenge for the development of rechargeable Zn-air batteries(ZABs).In this study,we introduce a metal-free ORR catalyst composed of F-N co-doped hollow carbon(FNC),specifically engineered to address the limitations of conventional catalysts.The FNC catalysts were synthesized using a template-assisted pyrolysis method,resulting in a hollow,porous architecture with a high specific surface area and numerous active sites.Concurrently,F doping optimized the electronic configuration of pyridinic nitrogen.The introduction of C-F bonds reduced the reaction energy barrier,and the resulting N-C-F configuration enhanced the stability of the nitrogen center.The catalyst exhibits outstanding ORR activity in alkaline media,exhibiting a half-wave potential(E_(1/2))of 0.87 V,surpassing that of commercial Pt/C(E_(1/2)=0.85 V).When applied to both aqueous and flexible ZAB configurations,the FNC catalyst achieved peak power densities of 172 and 85 mW cm^(-2),respectively,along with exceptional cycling stabilities exceeding 5300 and 302 h,respectively.This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs,particularly for use in flexible and wearable microelectronic 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
The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a ...The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.展开更多
The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalyst...The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalysts by Fe^(3+)etching during the hydrothermal and chemical deposition process.The as-prepared CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4 catalyst exhibits a lowoverpotential of 225 mV at 10 mA·cm^(-2)with a Tafel slope of 30.47 mV·dec^(-1).An overall water splitting electrolyzer(CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4‖Pt/C)is constructed,delivering a voltage of 1.48 V at a current density of10 mA·cm^(-2)with excellent durability.The dynamic phase evolution during the OER process is revealed by in situ Raman and XPS measurement,which represents that the introduced V and Fe ions facilitate the formation of active CoOOH as well as modify the electronic structure of the catalyst.Density functional theory(DFT)calculations further evidence that V and Fe introduction optimize the adsorption energies of oxygen intermediates*OH and*O,respectively,thereby enabling a synergistic optimization of the multi-step OER process and advancing electrocatalytic performance.展开更多
The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(EC...The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(ECR)frequently encounter high energy barriers and competitive hydrogen evolution reactions(HERs),which are urgent problems that need to be addressed.In this study,a catalyst(P100-Fe-N/C)with homogeneous P-tuned FeN_(2)binuclear sites(N_(2)PFe-FePN_(2))was successfully synthesised,demonstrating satisfactory performance in the ECR to CO.P100-Fe-N/C attains a peak FECOof 98.01%and a normalized TOF of 664.7 h-1at-0.7 VRHE,surpassing the performance of the Fe binuclear catalyst without P and singleatoms catalysts.In the MEA cell,a FECOexceeding 90%can still be achieved.Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system's energy.The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level,which facilitates the interaction of the catalyst with CO_(2),allowing more electrons to be injected into the CO_(2)molecule at the Fe binuclear sites and inhibiting the HER.The P-tuned FeN_(2)binuclear sites effectively lower the^(*)CO desorption barrier.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.
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.
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 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.
基金supported by National Natural Science Foundation of China (No. 22006120)the Fundamental Research Funds for the Central Universities (No. SWU-XDJH202314)+1 种基金the Program for Innovation Team Building at Institutions of Higher Education in Chongqing (No. CXTDX201601011)Chongqing Municipal Natural Science Foundation (No. cstc2018jcyj AX0625)。
文摘Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-Co O/CP with doping strategy and heterostructure was synthesized for overall water splitting.The Ru/V-Co O exhibits excellent activity for HER and OER with low overpotentials of 49, 147 m V at a current density of 10 m A/cm^(2) in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 m A/cm^(2)current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial Ru O_(2)||Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts,providing new ideas for the design and development of efficient and stable electrocatalysts.
文摘Designing exceptional-performance and long-lasting oxygen reduction reaction(ORR)catalysts is a critical challenge for the development of rechargeable Zn-air batteries(ZABs).In this study,we introduce a metal-free ORR catalyst composed of F-N co-doped hollow carbon(FNC),specifically engineered to address the limitations of conventional catalysts.The FNC catalysts were synthesized using a template-assisted pyrolysis method,resulting in a hollow,porous architecture with a high specific surface area and numerous active sites.Concurrently,F doping optimized the electronic configuration of pyridinic nitrogen.The introduction of C-F bonds reduced the reaction energy barrier,and the resulting N-C-F configuration enhanced the stability of the nitrogen center.The catalyst exhibits outstanding ORR activity in alkaline media,exhibiting a half-wave potential(E_(1/2))of 0.87 V,surpassing that of commercial Pt/C(E_(1/2)=0.85 V).When applied to both aqueous and flexible ZAB configurations,the FNC catalyst achieved peak power densities of 172 and 85 mW cm^(-2),respectively,along with exceptional cycling stabilities exceeding 5300 and 302 h,respectively.This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs,particularly for use in flexible and wearable microelectronic 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Natural Science Foundation of Xinjiang Uygur Autonomous Region,Grant/Award Number:2023D01C11National Natural Science Foundation of China,Grant/Award Numbers:22369019,U2003216+2 种基金Special Projects on Regional Collaborative Innovation-SCO Science and Technology Partnership Program,International Science and Technology Cooperation Program,Grant/Award Number:2022E01020Tianshan Talent Training Program,Grant/Award Number:2023TSYCLJ0019National Key Research and Development Program of China,Grant/Award Numbers:2022YFB4101600,2022YFB4101601。
文摘The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.
基金financially supported by Yunnan Major Scientific and Technological Projects(No.202202AG050017-02)Yunnan Fundamental Research Projects(No.202101BE070001-017)the National Natural Science Foundation of China(Nos.52101258 and 52272202)
文摘The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalysts by Fe^(3+)etching during the hydrothermal and chemical deposition process.The as-prepared CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4 catalyst exhibits a lowoverpotential of 225 mV at 10 mA·cm^(-2)with a Tafel slope of 30.47 mV·dec^(-1).An overall water splitting electrolyzer(CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4‖Pt/C)is constructed,delivering a voltage of 1.48 V at a current density of10 mA·cm^(-2)with excellent durability.The dynamic phase evolution during the OER process is revealed by in situ Raman and XPS measurement,which represents that the introduced V and Fe ions facilitate the formation of active CoOOH as well as modify the electronic structure of the catalyst.Density functional theory(DFT)calculations further evidence that V and Fe introduction optimize the adsorption energies of oxygen intermediates*OH and*O,respectively,thereby enabling a synergistic optimization of the multi-step OER process and advancing electrocatalytic performance.
基金financially supported by the National Natural Science Foundation of China-Yunnan Joint Fund(U2002213)Science and Technology Talent and Platform Program of Yunnan Provincial Science and Technology Department(202305AM070001)+1 种基金the Xingdian Talent Program of Yunnan Provincethe Double-First Class University Plan(C176220100042).
文摘The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(ECR)frequently encounter high energy barriers and competitive hydrogen evolution reactions(HERs),which are urgent problems that need to be addressed.In this study,a catalyst(P100-Fe-N/C)with homogeneous P-tuned FeN_(2)binuclear sites(N_(2)PFe-FePN_(2))was successfully synthesised,demonstrating satisfactory performance in the ECR to CO.P100-Fe-N/C attains a peak FECOof 98.01%and a normalized TOF of 664.7 h-1at-0.7 VRHE,surpassing the performance of the Fe binuclear catalyst without P and singleatoms catalysts.In the MEA cell,a FECOexceeding 90%can still be achieved.Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system's energy.The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level,which facilitates the interaction of the catalyst with CO_(2),allowing more electrons to be injected into the CO_(2)molecule at the Fe binuclear sites and inhibiting the HER.The P-tuned FeN_(2)binuclear sites effectively lower the^(*)CO desorption barrier.
