Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible s...Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.展开更多
Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modificat...Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.展开更多
High temperature piezoelectric energy harvester(HTPEH)is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors.However,simultaneously excellent performances,inclu...High temperature piezoelectric energy harvester(HTPEH)is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors.However,simultaneously excellent performances,including high figure of merit(FOM),insulation resistivity(ρ)and depolarization temperature(Td)are indispensable but hard to achieve in lead-free piezoceramics,especially operating at 250°C has not been reported before.Herein,well-balanced performances are achieved in BiFeO3–BaTiO3 ceramics via innovative defect engineering with respect to delicate manganese doping.Due to the synergistic effect of enhancing electrostrictive coefficient by polarization configuration optimization,regulating iron ion oxidation state by high valence manganese ion and stabilizing domain orientation by defect dipole,comprehensive excellent electrical performances(Td=340°C,ρ250°C>10^(7)Ωcm and FOM_(250°C)=4905×10^(–15)m^(2)N^(−1))are realized at the solid solubility limit of manganese ions.The HT-PEHs assembled using the rationally designed piezoceramic can allow for fast charging of commercial electrolytic capacitor at 250°C with high energy conversion efficiency(η=11.43%).These characteristics demonstrate that defect engineering tailored BF-BT can satisfy high-end HT-PEHs requirements,paving a new way in developing selfpowered wireless sensors working in HT environments.展开更多
Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,th...Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.展开更多
Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the e...Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the electronic structure of active sites.This optimization influences the adsorption energy of intermediates,thereby mitigating reaction energy barriers,altering paths,enhancing selectivity,and ultimately improving the catalytic efficiency of electrocatalysts.To elucidate the impact of defects on the electrocatalytic process,we comprehensively outline the roles of various point defects,their synthetic methodologies,and characterization techniques.Importantly,we consolidate insights into the relationship between point defects and catalytic activity for hydrogen/oxygen evolution and CO_(2)/O_(2)/N_(2) reduction reactions by integrating mechanisms from diverse reactions.This underscores the pivotal role of point defects in enhancing catalytic performance.At last,the principal challenges and prospects associated with point defects in current electrocatalysts are proposed,emphasizing their role in advancing the efficiency of electrochemical energy storage and conversion materials.展开更多
In this work,a CoOOH/ZnCdS-Vs sensor with high photoelectrochemical(PEC)performance was successfully developed through a heterojunction design and defect engineering.An S-type heterojunction was formed by the composit...In this work,a CoOOH/ZnCdS-Vs sensor with high photoelectrochemical(PEC)performance was successfully developed through a heterojunction design and defect engineering.An S-type heterojunction was formed by the composite of the cocatalyst CoOOH and ZnCdS and the introduction of sulfur vacancies by annealing,which regulated the strength of Zn-S and Cd-S bonds and promoted a charge transfer.The two synergistically endowed CoOOH/ZnCdS-Vs with the highest photocurrent density of 11.17 mA/cm^(2)at 1.23 V versus the reversible hydrogen electrode(vs.RHE).Subsequently,it was used to fabricate a PEC sensor for the continuous detection of Cu^(2+)and D-penicillamine(D-PA).Due to the transfer of photogenerated electron-hole pairs,Cu^(2+)was reduced to Cu^(+)and Cu^(0)and formed a new CoOOH/ZnCdS/Cu_(2)S heterojunction,resulting in a decrease in photocurrent density.But the introduction of D-PA restored the photocurrent density because its mercapto and amino groups formed a more stable five-membered ring chelate with Cu^(+).The fabricated PEC sensor exhibited an excellent selectivity,and there was no significant attenuation in photocurrent after 15 days of storage at room temperature.The limits of detection for Cu^(2+)and D-PA were 0.12 nM and 1.26μM,respectively.展开更多
Hydrogen peroxide(H_(2)O_(2))photosynthesis represents an advanced on-site production method with significant potential for on-demand supply.However,various challenges hinder the efficiency of H_(2)O_(2) yield,includi...Hydrogen peroxide(H_(2)O_(2))photosynthesis represents an advanced on-site production method with significant potential for on-demand supply.However,various challenges hinder the efficiency of H_(2)O_(2) yield,including weak oxygen adsorption capacity,reliance on sacrificial agents,low charge separation and transfer efficiency.In this regard,doping design and defect engineering have emerged as robust and effective strategies for catalyst modification,particularly through their synergistic effects.Additionally,advanced in situ characterization techniques for investigating reaction mechanisms are gaining momentum.Herein,this review provides a comprehensive analysis of the fundamentals and challenges associated with photocatalytic H_(2)O_(2) production,and highlights the advantages of doping and defect engineering.Subsequently,it outlines preparation methods and applications of these strategies.More importantly,it emphasizes the advanced characterization techniques utilized to validate doping and defects,as well as to investigate underlying mechanisms.Finally,the potential prospects and challenges of this reaction are anticipated.This review aims to offer valuable insights for researchers from both experimental and theoretical perspectives.展开更多
Solution-processed Cu(In,Ga)Se_(2)(CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency(PCE) loss because of the poor film properties and easy formation of defects.Herein, we pro...Solution-processed Cu(In,Ga)Se_(2)(CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency(PCE) loss because of the poor film properties and easy formation of defects.Herein, we propose Ag&Se co-selenization strategy to enhance the crystallization and passivate harmful defects of the CIGS films. The formation of Ag-Se phase during the selenization process enables the formation of large grains and suppresses the deep level defects. It is found that Ag doping can enlarge the depletion region width, lower the Urbach energy and prolong the carrier lifetime. As a result, a champion solution-processed CIGS solar cell presents a high efficiency of 16.48% with the highly improved opencircuit voltage(VOC) of 662 m V and fill factor(FF) of 75.8%. This work provides an efficient strategy to prepare high quality solution-processed CIGS films for high-performance CIGS solar cells.展开更多
The linker defect engineering for MOFs is a viable strategy that usually can effectively augment conductivity to further promote charge carrier separation,which is the most excellent conductivity of preserved metal cl...The linker defect engineering for MOFs is a viable strategy that usually can effectively augment conductivity to further promote charge carrier separation,which is the most excellent conductivity of preserved metal clusters.However,the partially missing photosensitive linker often leads to the diminished light utilization efficiency.As we know,in the linker defect engineering,addressing the lack of photosensitivity while maintaining outstanding conductivity is still in its infancy.In this essay,the linkerdefective NH_(2)-MIL-125 was obtained by adding the glacial acetic acid regulator,subsequently,the excellent light-responsive Pt/CQDs with up-conversion effect was in-situ encapsulated into the enlarged pore space of linker-defective NH_(2)-MIL-125.It is excited that the fabricated dual-functional composite ideally integrates photosensitivity and conductivity for photocatalytic hydrogen evolution and NO elimination.The optimal Pt/CQDs@NM-125-4 exhibited very superior photocatalytic hydrogen evolution(28.75mmol/g),it was 11.63 times as that of the initial NH_(2)-MIL-125(2.47 mmol/g)and 1.4 times as that of the defective NM-125-4(20.46 mmol/g).In addition,the excellent photocatalytic NO removal efficiency was 52.12%for Pt/CQDs@NM-125-4,whereas the original NH_(2)-MIL-125 only reached 30%and the defective NM-125-4 achieved 44.96%.The corresponding optical and electrical characterization based on UV-vis,up-conversion photoluminescence(UCPL),and electrochemical impedance spectroscopy(EIS)etc.demonstrated the defect engineering accelerates the charge carriers transfer via enhancing conductivity,and the in-situ confined up-conversion Pt/CQDs promote the visible light response.Our work presents a feasible avenue to integrate photosensitivity and conductivity via in-situ fabricating excellent lightresponsive Pt/CQDs within linker-defective NH_(2)-MIL-125 for further significantly boosting photocatalytic performance.展开更多
Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conduct...Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.展开更多
Defect sites on oxide semiconductors play a crucial role in promoting photocatalytiperformance and mod-ulating the bandgap structure of photocatalysts.However,the role of interfacial coordinatively unsatu-rated defect...Defect sites on oxide semiconductors play a crucial role in promoting photocatalytiperformance and mod-ulating the bandgap structure of photocatalysts.However,the role of interfacial coordinatively unsatu-rated defect sites between metal and oxide in photocatalysis is still under debate.So,we designed an experiment to probe the role of interfacial coordinatively unsaturated defect sites.In this work,a se-ries of Ti/TiO_(2) photocatalysts with varying concentrations of interfacial Ti^(3+)sites were prepared through an epitaxial growth method under hydrothermal conditions.Through experimental and computational investigations,the roles of interfacial defect sites were discussed in detail.On the one hand,the inter-facial coordinatively unsaturated Ti^(3+)sites could act as visible-light-responsive sites in photocatalytic reactions due to the overlap and hybridization of multiple electronic orbitals.On the other hand,the Ti/TiO_(2) interface exhibited a certain degree of metallic character near the Fermi level because of the par-tial delocalization and redistribution of electrons,facilitating the charge migration and separation across the metal-oxide interface.Consequently,the obtained Ti/TiO_(2) catalysts showed notably enhanced charge transfer efficiency and visible light photocatalytic activity compared to their pristine counterparts.This work may provide a new perspective to interfacial defect engineering in classic metal/oxide heterojunc-tion photocatalysts and figure a more precise direction to synthesize higher effective photocatalysts for environmental governance.展开更多
Electrochemical nitrogen reduction reaction(e-NRR)under ambient conditions is an emerging strategy to tackle the hydrogen-and energy-intensive operations for traditional Haber-Bosch process in industrial ammonia(NH_(3...Electrochemical nitrogen reduction reaction(e-NRR)under ambient conditions is an emerging strategy to tackle the hydrogen-and energy-intensive operations for traditional Haber-Bosch process in industrial ammonia(NH_(3))synthesis.However,the e-NRR performance is currently impeded by the inherent inertness of N_(2) molecules,the extremely slow kinetics and the overwhelming competition from the hydrogen evolution reaction(HER),all of which cause unsatisfied yield and ammonia selectivity(Faradaic efficiency,FE).Defect and interface engineering are capable of achieving novel physical and chemical properties as well as superior synergistic effects for various electrocatalysts.In this review,we first provide a general introduction to the NRR mechanism.We then focus on the recent progress in defect and interface engineering and summarize how defect and interface can be rationally designed and functioned in NRR catalysts.Particularly,the origin of superior NRR catalytic activity by applying these approaches was discussed from both theoretical and experimental perspectives.Finally,the remaining challenges and future perspectives in this emerging area are highlighted.It is expected that this review will shed some light on designing NRR electrocatalysts with excellent activity,selectivity and stability.展开更多
Owing to adjustable microstructure and stable physiochemical properties,carbon-based materials are regarded as promising materials as anodes for potassium-ion batteries(PlBs).Building amorphous structure and introduci...Owing to adjustable microstructure and stable physiochemical properties,carbon-based materials are regarded as promising materials as anodes for potassium-ion batteries(PlBs).Building amorphous structure and introducing defects are favorable methods to generate active sites and improve the electrochemical performances of carbon-based materials.In this work,we develop a facile carbonization method to prepare sulfur-doped amorphous carbon microspheres with hierarchical structure and modulated defects concentration(S-CM-700) for potassium storage.Benefiting from the special microstructure,S-CM-700 exhibits the optimal performance and obtains high reversible capacity of 199.6 mAh·g^(-1) at 100 mA·g^(-1),excellent rate property and prominent durability(0.0055%capacity decay per cycle during 1800 cycles).Kinetics analysis and electrochemical characterization are carried out to reveal that the potassium storage could be boosted by regulating the defect level,layer spacing and the content of sulfur-doping.The work provides a general synthesis approach to prepare sustainable carbon anodes for advanced PlBs.展开更多
The diamond-like compound Cu_(3)PSe_(4)with low lattice thermal conductivity is deemed to be a promising thermoelectric material,which can directly convert waste heat into electricity or vice versa with no moving part...The diamond-like compound Cu_(3)PSe_(4)with low lattice thermal conductivity is deemed to be a promising thermoelectric material,which can directly convert waste heat into electricity or vice versa with no moving parts and greenhouse emissions.However,its performance is limited by its low electrical conductivity.In this study,we report an effective method to enhance thermoelectric performance of Cu_(3)PSe_(4)by defect engineering.It is found that the carrier concentrations of Cu_(3-x)PSe_(4)(x=0,0.03,0.06,0.09,0.12)compounds are increased by two orders of magnitude as x>0.03,from 1×10^(17)to 1×10^(19)cm^(-3).Combined with the intrinsically low lattice thermal conductivities and enhanced electrical transport performance,a maximum zT value of 0.62 is obtained at 727 K for x=0.12 sample,revealing that Cu defect regulation can be an effective method for enhancing thermoelectric performance of Cu_(3)PSe_(4).展开更多
Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIB...Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.展开更多
BiTe is a potentially attractive candidate for thermoelectric applications because it is the structural analogue of the state-of-the-art thermoelectric material,bismuth telluride(Bi_(2)Te_(3)). However, BiTe has attra...BiTe is a potentially attractive candidate for thermoelectric applications because it is the structural analogue of the state-of-the-art thermoelectric material,bismuth telluride(Bi_(2)Te_(3)). However, BiTe has attracted little attention due to its small band gap and high electron concentration. In this study, remarkable increase in thermoelectric performance in the n-type Bi_(1-x)Sb_(x)Te compounds through tuning the carrier concentration with chemical doping is shown. The Seebeck coefficient of Bi_(1-x)Sb_(x)Te increases remarkably while the electronic thermal conductivity decreases gradually as Sb content is increased, leading to enhanced thermoelectric figure of merit(ZT). Moreover, the simultaneous optimization of the electrical and thermal transport properties leads the peak temperature of the figure of merit to shift toward lower temperature with Sb content increasing in Bi_(1-x)Sb_(x)Te, thus making Bi_(1-x)Sb_(x)Te a potential alternative to bismuth telluride for near-room-temperature thermoelectric applications. In addition, the presence of multiple low-frequency optical phonons and their coupling with the long-wavelength heat carrying acoustic phonons in all the Bi_(1-x)Sb_(x)Te investigated are revealed based on the combined Debye-Einstein model. The present results provide the underlying mechanism connecting thermoelectric performance and lattice dynamics in Bi_(1-x)Sb_(x)Te compounds.展开更多
MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Here...MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Herein,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was constructed.The synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled process.The MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy barrier.Additionally,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical reactions.The abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change sequentially.As a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is achieved.The density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in MFCHHS.We believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.展开更多
With the quick development of sustainable energy sources, aqueous zinc-ion batteries(AZIBs) have become a highly potential energy storage technology. It is a crucial step to construct desired electrode materials for i...With the quick development of sustainable energy sources, aqueous zinc-ion batteries(AZIBs) have become a highly potential energy storage technology. It is a crucial step to construct desired electrode materials for improving the total performance of AZIBs. In recent years, considerable efforts have focused on the modification of vanadium-based cathode materials. In this review, we summarized defect engineering strategies of vanadium-based cathodes, including oxygen defects, cation vacancies and heterogeneous doping. Then, we discussed the effect of various defects on the electrochemical performance of electrode materials. Finally, we proposed the future challenges and development directions of V-based cathode materials.展开更多
The thermoelectric transport properties of Zr0.43Hf0.57 NiSn half-Heusler compounds were investigated for samples sintered with different spark plasma sintering(SPS)periods:8,32 and 72 min.By means of scanning transmi...The thermoelectric transport properties of Zr0.43Hf0.57 NiSn half-Heusler compounds were investigated for samples sintered with different spark plasma sintering(SPS)periods:8,32 and 72 min.By means of scanning transmission electron microscopy with a highangular annular dark-field detector(STEM-HAADF),it was found that sintering time affected the defect concentration,namely the amount of Ni interstitial atoms,and created locally ordered inclusions of full-Heusler phase.The structural information,phase composition and electrical transport properties could be consistently explained by the assumption that Ni interstitials give rise to an impurity band situated about 100 meV below the bottom of the conduction band via a self-doping behavior.The impurity band was found to merge with the conduction band for the sample with intermediate SPS time.The effect was ascribed to the gradual dissolution of full-Heusler phase inclusions and production of interstitial Ni defects,which eventually vanished for the sample with the longest sintering time.It was demonstrated that the modification of the density of states near the edge of the conduction band and enhanced overall charge carrier concentration provided by defect engineering led to overall 26%increase in the thermoelectric figure of merit(ZT)with respect to the other samples.展开更多
Electrocatalytic carbon dioxide(CO_(2))reduction is an important way to achieve carbon neutrality by converting CO_(2)in-to high-value-added chemicals using electric energy.Carbon-based materials are widely used in va...Electrocatalytic carbon dioxide(CO_(2))reduction is an important way to achieve carbon neutrality by converting CO_(2)in-to high-value-added chemicals using electric energy.Carbon-based materials are widely used in various electrochemical reactions,including electrocatalytic CO_(2)reduction,due to their low cost and high activity.In recent years,defect engineering has attracted wide attention by constructing asymmetric defect centers in the materials,which can optimize the physicochemical properties of the mater-ial and improve its electrocatalytic activity.This review summarizes the types,methods of formation and defect characterization tech-niques of defective carbon-based materials.The advantages of defect engineering and the advantages and disadvantages of various defect formation methods and characterization techniques are also evaluated.Finally,the challenges of using defective carbon-based materials in electrocatalytic CO_(2)reduction are investigated and opportunities for their use are discussed.It is believed that this re-view will provide suggestions and guidance for developing defective carbon-based materials for CO_(2)reduction.展开更多
基金financially supported by the supported by Shandong Provincial Natural Science Foundation(ZR2024MB108)Taishan Young Scholar Program(tsqn202312312)Excellent Young Scholars of the Shandong Provincial Natural Science Foundation(Overseas)(2023HWYQ-112)。
文摘Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.
基金supported by The National Key R&D Program of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04)。
文摘Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.
基金supported by the National Natural Science Foundation of China(Grant Nos.52272103 and 52072010)Beijing Natural Science Foundation(Grant Nos.2242029 and JL23004).
文摘High temperature piezoelectric energy harvester(HTPEH)is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors.However,simultaneously excellent performances,including high figure of merit(FOM),insulation resistivity(ρ)and depolarization temperature(Td)are indispensable but hard to achieve in lead-free piezoceramics,especially operating at 250°C has not been reported before.Herein,well-balanced performances are achieved in BiFeO3–BaTiO3 ceramics via innovative defect engineering with respect to delicate manganese doping.Due to the synergistic effect of enhancing electrostrictive coefficient by polarization configuration optimization,regulating iron ion oxidation state by high valence manganese ion and stabilizing domain orientation by defect dipole,comprehensive excellent electrical performances(Td=340°C,ρ250°C>10^(7)Ωcm and FOM_(250°C)=4905×10^(–15)m^(2)N^(−1))are realized at the solid solubility limit of manganese ions.The HT-PEHs assembled using the rationally designed piezoceramic can allow for fast charging of commercial electrolytic capacitor at 250°C with high energy conversion efficiency(η=11.43%).These characteristics demonstrate that defect engineering tailored BF-BT can satisfy high-end HT-PEHs requirements,paving a new way in developing selfpowered wireless sensors working in HT environments.
基金support of the National Natural Science Foundation of China(Grant No.22225801,22178217 and 22308216)supported by the Fundamental Research Funds for the Central Universities,conducted at Tongji University.
文摘Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.
基金supported by the National Natural Science Foundation of China(U21A20281)the Special Fund for Young Teachers from Zhengzhou University(JC23557030,JC23257011)+1 种基金the Key Research Projects of Higher Education Institutions of Henan Province(24A530009)the Project of Zhongyuan Critical Metals Laboratory(GJJSGFYQ202336).
文摘Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the electronic structure of active sites.This optimization influences the adsorption energy of intermediates,thereby mitigating reaction energy barriers,altering paths,enhancing selectivity,and ultimately improving the catalytic efficiency of electrocatalysts.To elucidate the impact of defects on the electrocatalytic process,we comprehensively outline the roles of various point defects,their synthetic methodologies,and characterization techniques.Importantly,we consolidate insights into the relationship between point defects and catalytic activity for hydrogen/oxygen evolution and CO_(2)/O_(2)/N_(2) reduction reactions by integrating mechanisms from diverse reactions.This underscores the pivotal role of point defects in enhancing catalytic performance.At last,the principal challenges and prospects associated with point defects in current electrocatalysts are proposed,emphasizing their role in advancing the efficiency of electrochemical energy storage and conversion materials.
基金financially supported by Guangdong Basic and Applied Basic Research Foundation(2023A1515011228,2021A1515011513,2019A1515012169)Special Project in Key Fields of Colleges and Universities in Guangdong Province(Science and Technology Services for Rural Revitalization)(2021ZDZX4002)National Natural Science Foundation of China(81573678)。
文摘In this work,a CoOOH/ZnCdS-Vs sensor with high photoelectrochemical(PEC)performance was successfully developed through a heterojunction design and defect engineering.An S-type heterojunction was formed by the composite of the cocatalyst CoOOH and ZnCdS and the introduction of sulfur vacancies by annealing,which regulated the strength of Zn-S and Cd-S bonds and promoted a charge transfer.The two synergistically endowed CoOOH/ZnCdS-Vs with the highest photocurrent density of 11.17 mA/cm^(2)at 1.23 V versus the reversible hydrogen electrode(vs.RHE).Subsequently,it was used to fabricate a PEC sensor for the continuous detection of Cu^(2+)and D-penicillamine(D-PA).Due to the transfer of photogenerated electron-hole pairs,Cu^(2+)was reduced to Cu^(+)and Cu^(0)and formed a new CoOOH/ZnCdS/Cu_(2)S heterojunction,resulting in a decrease in photocurrent density.But the introduction of D-PA restored the photocurrent density because its mercapto and amino groups formed a more stable five-membered ring chelate with Cu^(+).The fabricated PEC sensor exhibited an excellent selectivity,and there was no significant attenuation in photocurrent after 15 days of storage at room temperature.The limits of detection for Cu^(2+)and D-PA were 0.12 nM and 1.26μM,respectively.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20231342,BK20210867)National Natural Science Foundation of China(22008163)+1 种基金Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(SKLPEE–KF202309)Natural Science Research Project of Higher Education Institutions in Jiangsu Province(21KJB150038).
文摘Hydrogen peroxide(H_(2)O_(2))photosynthesis represents an advanced on-site production method with significant potential for on-demand supply.However,various challenges hinder the efficiency of H_(2)O_(2) yield,including weak oxygen adsorption capacity,reliance on sacrificial agents,low charge separation and transfer efficiency.In this regard,doping design and defect engineering have emerged as robust and effective strategies for catalyst modification,particularly through their synergistic effects.Additionally,advanced in situ characterization techniques for investigating reaction mechanisms are gaining momentum.Herein,this review provides a comprehensive analysis of the fundamentals and challenges associated with photocatalytic H_(2)O_(2) production,and highlights the advantages of doping and defect engineering.Subsequently,it outlines preparation methods and applications of these strategies.More importantly,it emphasizes the advanced characterization techniques utilized to validate doping and defects,as well as to investigate underlying mechanisms.Finally,the potential prospects and challenges of this reaction are anticipated.This review aims to offer valuable insights for researchers from both experimental and theoretical perspectives.
基金National Natural Science Foundation of China (62104061, 62074052, 61974173 and 52072327)。
文摘Solution-processed Cu(In,Ga)Se_(2)(CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency(PCE) loss because of the poor film properties and easy formation of defects.Herein, we propose Ag&Se co-selenization strategy to enhance the crystallization and passivate harmful defects of the CIGS films. The formation of Ag-Se phase during the selenization process enables the formation of large grains and suppresses the deep level defects. It is found that Ag doping can enlarge the depletion region width, lower the Urbach energy and prolong the carrier lifetime. As a result, a champion solution-processed CIGS solar cell presents a high efficiency of 16.48% with the highly improved opencircuit voltage(VOC) of 662 m V and fill factor(FF) of 75.8%. This work provides an efficient strategy to prepare high quality solution-processed CIGS films for high-performance CIGS solar cells.
基金supported by the National Natural Science Foundation of China(Nos.22001026,22171233,22201193)Sichuan Science and Technology Program(No.2023NSFSC0109)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Hundred Talent Program of Sichuan University(No.YJ2021158)。
文摘The linker defect engineering for MOFs is a viable strategy that usually can effectively augment conductivity to further promote charge carrier separation,which is the most excellent conductivity of preserved metal clusters.However,the partially missing photosensitive linker often leads to the diminished light utilization efficiency.As we know,in the linker defect engineering,addressing the lack of photosensitivity while maintaining outstanding conductivity is still in its infancy.In this essay,the linkerdefective NH_(2)-MIL-125 was obtained by adding the glacial acetic acid regulator,subsequently,the excellent light-responsive Pt/CQDs with up-conversion effect was in-situ encapsulated into the enlarged pore space of linker-defective NH_(2)-MIL-125.It is excited that the fabricated dual-functional composite ideally integrates photosensitivity and conductivity for photocatalytic hydrogen evolution and NO elimination.The optimal Pt/CQDs@NM-125-4 exhibited very superior photocatalytic hydrogen evolution(28.75mmol/g),it was 11.63 times as that of the initial NH_(2)-MIL-125(2.47 mmol/g)and 1.4 times as that of the defective NM-125-4(20.46 mmol/g).In addition,the excellent photocatalytic NO removal efficiency was 52.12%for Pt/CQDs@NM-125-4,whereas the original NH_(2)-MIL-125 only reached 30%and the defective NM-125-4 achieved 44.96%.The corresponding optical and electrical characterization based on UV-vis,up-conversion photoluminescence(UCPL),and electrochemical impedance spectroscopy(EIS)etc.demonstrated the defect engineering accelerates the charge carriers transfer via enhancing conductivity,and the in-situ confined up-conversion Pt/CQDs promote the visible light response.Our work presents a feasible avenue to integrate photosensitivity and conductivity via in-situ fabricating excellent lightresponsive Pt/CQDs within linker-defective NH_(2)-MIL-125 for further significantly boosting photocatalytic performance.
基金the National Natural Science Foundation of China(52062012)Key Science&Technology Project of Hainan Province(ZDYF2020028)+2 种基金Key-Area Research and Development Program of Guangdong Province(2019B1102109003)the Innovation Team of Universities of Guangdong Province(2020KCXTD011)Guangdong Province Key Discipline Construction Project(2021ZDJS102).
文摘Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.
基金financialy supported by the National Key Research and Development Plan of China (No.2016YFC0209305)the Science and Technology Plans of Tianjin (No.18PTZWHZ00180)+1 种基金the Major National Science and Technology Projects (No.2017ZX07106001)the Tianjin Development Program for Innovation and Entrepreneurship。
文摘Defect sites on oxide semiconductors play a crucial role in promoting photocatalytiperformance and mod-ulating the bandgap structure of photocatalysts.However,the role of interfacial coordinatively unsatu-rated defect sites between metal and oxide in photocatalysis is still under debate.So,we designed an experiment to probe the role of interfacial coordinatively unsaturated defect sites.In this work,a se-ries of Ti/TiO_(2) photocatalysts with varying concentrations of interfacial Ti^(3+)sites were prepared through an epitaxial growth method under hydrothermal conditions.Through experimental and computational investigations,the roles of interfacial defect sites were discussed in detail.On the one hand,the inter-facial coordinatively unsaturated Ti^(3+)sites could act as visible-light-responsive sites in photocatalytic reactions due to the overlap and hybridization of multiple electronic orbitals.On the other hand,the Ti/TiO_(2) interface exhibited a certain degree of metallic character near the Fermi level because of the par-tial delocalization and redistribution of electrons,facilitating the charge migration and separation across the metal-oxide interface.Consequently,the obtained Ti/TiO_(2) catalysts showed notably enhanced charge transfer efficiency and visible light photocatalytic activity compared to their pristine counterparts.This work may provide a new perspective to interfacial defect engineering in classic metal/oxide heterojunc-tion photocatalysts and figure a more precise direction to synthesize higher effective photocatalysts for environmental governance.
基金supported by the National Natural Science Foundation of China(grant no.21904071 and 22071115)。
文摘Electrochemical nitrogen reduction reaction(e-NRR)under ambient conditions is an emerging strategy to tackle the hydrogen-and energy-intensive operations for traditional Haber-Bosch process in industrial ammonia(NH_(3))synthesis.However,the e-NRR performance is currently impeded by the inherent inertness of N_(2) molecules,the extremely slow kinetics and the overwhelming competition from the hydrogen evolution reaction(HER),all of which cause unsatisfied yield and ammonia selectivity(Faradaic efficiency,FE).Defect and interface engineering are capable of achieving novel physical and chemical properties as well as superior synergistic effects for various electrocatalysts.In this review,we first provide a general introduction to the NRR mechanism.We then focus on the recent progress in defect and interface engineering and summarize how defect and interface can be rationally designed and functioned in NRR catalysts.Particularly,the origin of superior NRR catalytic activity by applying these approaches was discussed from both theoretical and experimental perspectives.Finally,the remaining challenges and future perspectives in this emerging area are highlighted.It is expected that this review will shed some light on designing NRR electrocatalysts with excellent activity,selectivity and stability.
基金financially supported by the National Natural Science Foundation of China (No.51904216)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (No.WUT:2022-KF-4)the National Innovation Training Program for College Students (No. 312040000254)。
文摘Owing to adjustable microstructure and stable physiochemical properties,carbon-based materials are regarded as promising materials as anodes for potassium-ion batteries(PlBs).Building amorphous structure and introducing defects are favorable methods to generate active sites and improve the electrochemical performances of carbon-based materials.In this work,we develop a facile carbonization method to prepare sulfur-doped amorphous carbon microspheres with hierarchical structure and modulated defects concentration(S-CM-700) for potassium storage.Benefiting from the special microstructure,S-CM-700 exhibits the optimal performance and obtains high reversible capacity of 199.6 mAh·g^(-1) at 100 mA·g^(-1),excellent rate property and prominent durability(0.0055%capacity decay per cycle during 1800 cycles).Kinetics analysis and electrochemical characterization are carried out to reveal that the potassium storage could be boosted by regulating the defect level,layer spacing and the content of sulfur-doping.The work provides a general synthesis approach to prepare sustainable carbon anodes for advanced PlBs.
基金the Graduate Scientific Research and Innovation Foundation of Chongqing,China(No.CYB 19064)the Project for Fundamental and Frontier Research in Chongqing(No.CSTC2017JCYJAX0388)+2 种基金Shenzhen Science and Technology Innovation Committee(No.JCYJ20170818155752559)the National Natural Science Foundation of China(Nos.51772035,11674040 and 51472036)the Fundamental Research Funds for the Central Universities(No.106112017CDJQJ308821)。
文摘The diamond-like compound Cu_(3)PSe_(4)with low lattice thermal conductivity is deemed to be a promising thermoelectric material,which can directly convert waste heat into electricity or vice versa with no moving parts and greenhouse emissions.However,its performance is limited by its low electrical conductivity.In this study,we report an effective method to enhance thermoelectric performance of Cu_(3)PSe_(4)by defect engineering.It is found that the carrier concentrations of Cu_(3-x)PSe_(4)(x=0,0.03,0.06,0.09,0.12)compounds are increased by two orders of magnitude as x>0.03,from 1×10^(17)to 1×10^(19)cm^(-3).Combined with the intrinsically low lattice thermal conductivities and enhanced electrical transport performance,a maximum zT value of 0.62 is obtained at 727 K for x=0.12 sample,revealing that Cu defect regulation can be an effective method for enhancing thermoelectric performance of Cu_(3)PSe_(4).
基金financially supported by the National key Research & Development Program of China (2022YFE0115900, 2021YFA1501500)the National Natural Science Foundation of China (Nos. 22225902, U22A20436, 22209185)+3 种基金the CAS-Commonwealth Scientific and Industrial Research Organization (CSIRO) Joint Research Projects (121835KYSB20200039)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (Grant. YLUDNL Fund 2021011)Fujian Province Central Government Guides to Science and Technology Development Special Project (No. 2022L3024)Natural Science Foundation of Fujian Province, China (No. 2021J02020)。
文摘Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.
基金financially supported by the National Key R&D Program of China(Nos.2018YFB0703602 and 2017YFA0303500)the National Natural Science Foundation of China(Nos.21622107 and U1832142)+2 种基金the Youth Innovation Promotion Association CAS(No.2016392)the Fundamental Research Funds for the Central University(No.WK2340000094)the Key Research Program of Frontier Sciences(No.QYZDY-SSW-SLH011)。
文摘BiTe is a potentially attractive candidate for thermoelectric applications because it is the structural analogue of the state-of-the-art thermoelectric material,bismuth telluride(Bi_(2)Te_(3)). However, BiTe has attracted little attention due to its small band gap and high electron concentration. In this study, remarkable increase in thermoelectric performance in the n-type Bi_(1-x)Sb_(x)Te compounds through tuning the carrier concentration with chemical doping is shown. The Seebeck coefficient of Bi_(1-x)Sb_(x)Te increases remarkably while the electronic thermal conductivity decreases gradually as Sb content is increased, leading to enhanced thermoelectric figure of merit(ZT). Moreover, the simultaneous optimization of the electrical and thermal transport properties leads the peak temperature of the figure of merit to shift toward lower temperature with Sb content increasing in Bi_(1-x)Sb_(x)Te, thus making Bi_(1-x)Sb_(x)Te a potential alternative to bismuth telluride for near-room-temperature thermoelectric applications. In addition, the presence of multiple low-frequency optical phonons and their coupling with the long-wavelength heat carrying acoustic phonons in all the Bi_(1-x)Sb_(x)Te investigated are revealed based on the combined Debye-Einstein model. The present results provide the underlying mechanism connecting thermoelectric performance and lattice dynamics in Bi_(1-x)Sb_(x)Te compounds.
基金the National Natural Science Foundation of China(NSFC)(22105059,22279112)the Talent Introduction Program of Hebei Agricultural University(YJ201810)+5 种基金the Youth Topnotch Talent Foundation of Hebei Provincial Universities(BJK2022023)the Natural Science Foundation of Hebei Province(B2022203018)the Fok Ying-Tong Education Foundation of China(171064)the Natural Science Foundation of Shandong Province,China(ZR2021QE192)the China Postdoctoral Science Foundation(2018M630747)the 333 Talent Program of Hebei Province(C20221018)for their support。
文摘MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Herein,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was constructed.The synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled process.The MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy barrier.Additionally,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical reactions.The abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change sequentially.As a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is achieved.The density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in MFCHHS.We believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.
基金supported by National Natural Science Foundation of China (No. 52172218)。
文摘With the quick development of sustainable energy sources, aqueous zinc-ion batteries(AZIBs) have become a highly potential energy storage technology. It is a crucial step to construct desired electrode materials for improving the total performance of AZIBs. In recent years, considerable efforts have focused on the modification of vanadium-based cathode materials. In this review, we summarized defect engineering strategies of vanadium-based cathodes, including oxygen defects, cation vacancies and heterogeneous doping. Then, we discussed the effect of various defects on the electrochemical performance of electrode materials. Finally, we proposed the future challenges and development directions of V-based cathode materials.
基金financially supported by German Research Foundation Priority Programme 1386(No.WE 2803/2-2)the European Union under Marie Sklodowska-Curie Program(W.J.X.)。
文摘The thermoelectric transport properties of Zr0.43Hf0.57 NiSn half-Heusler compounds were investigated for samples sintered with different spark plasma sintering(SPS)periods:8,32 and 72 min.By means of scanning transmission electron microscopy with a highangular annular dark-field detector(STEM-HAADF),it was found that sintering time affected the defect concentration,namely the amount of Ni interstitial atoms,and created locally ordered inclusions of full-Heusler phase.The structural information,phase composition and electrical transport properties could be consistently explained by the assumption that Ni interstitials give rise to an impurity band situated about 100 meV below the bottom of the conduction band via a self-doping behavior.The impurity band was found to merge with the conduction band for the sample with intermediate SPS time.The effect was ascribed to the gradual dissolution of full-Heusler phase inclusions and production of interstitial Ni defects,which eventually vanished for the sample with the longest sintering time.It was demonstrated that the modification of the density of states near the edge of the conduction band and enhanced overall charge carrier concentration provided by defect engineering led to overall 26%increase in the thermoelectric figure of merit(ZT)with respect to the other samples.
文摘Electrocatalytic carbon dioxide(CO_(2))reduction is an important way to achieve carbon neutrality by converting CO_(2)in-to high-value-added chemicals using electric energy.Carbon-based materials are widely used in various electrochemical reactions,including electrocatalytic CO_(2)reduction,due to their low cost and high activity.In recent years,defect engineering has attracted wide attention by constructing asymmetric defect centers in the materials,which can optimize the physicochemical properties of the mater-ial and improve its electrocatalytic activity.This review summarizes the types,methods of formation and defect characterization tech-niques of defective carbon-based materials.The advantages of defect engineering and the advantages and disadvantages of various defect formation methods and characterization techniques are also evaluated.Finally,the challenges of using defective carbon-based materials in electrocatalytic CO_(2)reduction are investigated and opportunities for their use are discussed.It is believed that this re-view will provide suggestions and guidance for developing defective carbon-based materials for CO_(2)reduction.
