Intrinsic pentagon defect engineering in multiple spatial-scale carbon frameworks for efficient triiodide reduction

Intrinsic topological defect engineering has been proven as a promising strategy to elevate the electrocatalytic activity of carbon materials.However,the controllable construction of high-density and specific topological defects in carbon frameworks to reveal the relationship between reactivity and defect structure remains a challenging task.Herein,the intrinsic pentagon carbon sites that can favor electron overflow and enhance their binding affinity towards the intermediates of catalytic reaction are firstly presented by the work function and the p-band center calculations.To experimentally verify this,the cage-opening reaction of fullerene is proposed and utilized for synthesizing carbon quantum dots with specific pentagon configuration(CQDs-P),subsequently utilizing CQDs-P to modulate the micro-scale defect density of three-dimensional reduced graphene oxide(rGO)viaπ-πinteractions.The multiple spatial-scale rGO-conjugated CQDs-P structure simultaneously possesses abundant pentagon and edge defects as catalytic active sites and long-range-orderedπelectron delocalization system as conductive network.The defects-rich CQDs-P/rGO-4 all-carbon-based catalyst exhibits superb catalytic activity for triiodide reduction reaction with a high photoelectric conversion efficiency of 8.40%,superior to the Pt reference(7.97%).Theoretical calculations suggest that pentagon defects in the carbon frameworks can promote charge transfer and modulate the adsorption/dissociation behavior of the reaction intermediates,thus enhancing the electrocatalytic activity of the catalyst.This work confirms the role of intrinsic pentagon defects in catalytic reactions and provides a new insight into the synthesis of defects-rich carbon catalysts.

Defect Engineering of Carbons for Energy Conversion and Storage Applications

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.

Defect engineering of ternary Cu-In-Se quantum dots for boosting photoelectrochemical hydrogen generation

Heavy-metal-free ternary Cu–In–Se quantum dots(CISe QDs)are promising for solar fuel production because of their low toxicity,tunable band gap,and high light absorption coefficient.Although defects significantly affect the photophysical properties of QDs,the influence on photoelectrochemical hydrogen production is not well understood.Herein,we present the defect engineering of CISe QDs for efficient solar-energy conversion.Lewis acid–base reactions between metal halide–oleylamine complexes and oleylammonium selenocarbamate are modulated to achieve CISe QDs with the controlled amount of Cu vacancies without changing their morphology.Among them,CISe QDs with In/Cu=1.55 show the most outstanding photoelectrochemical hydrogen generation with excellent photocurrent density of up to 10.7 mA cm-2(at 0.6 VRHE),attributed to the suitable electronic band structures and enhanced carrier concentrations/lifetimes of the QDs.The proposed method,which can effectively control the defects in heavy-metal-free ternary QDs,offers a deeper understanding of the effects of the defects and provides a practical approach to enhance photoelectrochemical hydrogen generation.

Anion Defects Engineering of Ternary Nb-Based Chalcogenide Anodes Toward High-Performance Sodium-Based Dual-Ion Batteries

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.

Synergy mechanism of defect engineering in MoS_(2)/FeS_(2)/C heterostructure for high-performance sodium-ion battery

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.

Decade Milestone Advancement of Defect-Engineered g-C_(3)N_(4) for Solar Catalytic Applications

Over the past decade, graphitic carbon nitride(g-C_(3)N_(4)) has emerged as a universal photocatalyst toward various sustainable carbo-neutral technologies. Despite solar applications discrepancy, g-C_(3)N_(4) is still confronted with a general fatal issue of insufficient supply of thermodynamically active photocarriers due to its inferior solar harvesting ability and sluggish charge transfer dynamics. Fortunately, this could be significantly alleviated by the “all-in-one” defect engineering strategy, which enables a simultaneous amelioration of both textural uniqueness and intrinsic electronic band structures. To this end, we have summarized an unprecedently comprehensive discussion on defect controls including the vacancy/non-metallic dopant creation with optimized electronic band structure and electronic density, metallic doping with ultraactive coordinated environment(M–N_(x), M–C_(2)N_(2), M–O bonding), functional group grafting with optimized band structure, and promoted crystallinity with extended conjugation π system with weakened interlayered van der Waals interaction. Among them, the defect states induced by various defect types such as N vacancy, P/S/halogen dopants, and cyano group in boosting solar harvesting and accelerating photocarrier transfer have also been emphasized. More importantly, the shallow defect traps identified by femtosecond transient absorption spectra(fs-TAS) have also been highlighted. It is believed that this review would pave the way for future readers with a unique insight into a more precise defective g-C_(3)N_(4) “customization”, motivating more profound thinking and flourishing research outputs on g-C_(3)N_(4)-based photocatalysis.

Improvement strategy on thermophysical properties of A_(2)B_(2)O_(7)-type rare earth zirconates for thermal barrier coatings applications:A review

The A_(2)B_(2)O_(7)-type rare earth zirconate compounds have been considered as promising candidates for thermal barrier coating(TBC) materials because of their low sintering rate,improved phase stability,and reduced thermal conductivity in contrast with the currently used yttria-partially stabilized zirconia (YSZ) in high operating temperature environments.This review summarizes the recent progress on rare earth zirconates for TBCs that insulate high-temperature gas from hot-section components in gas turbines.Based on the first principles,molecular dynamics,and new data-driven calculation approaches,doping and high-entropy strategies have now been adopted in advanced TBC materials design.In this paper,the solid-state heat transfer mechanism of TBCs is explained from two aspects,including heat conduction over the full operating temperature range and thermal radiation at medium and high temperature.This paper also provides new insights into design considerations of adaptive TBC materials,and the challenges and potential breakthroughs are further highlighted for extreme environmental applications.Strategies for improving thermophysical performance are proposed in two approaches:defect engineering and material compositing.

Anion storing,oxygen vacancy incorporated perovskite oxide composites for high-performance aqueous dual ion hybrid supercapacitors

Dual ion storage hybrid supercapacitors(HsCs)are considered as a promising device to overcome the limited energy density of existing supercapacitors while preserving high power and long cyclability.However,the development of high-capacity anion-storing materials,which can be paired with fast charg-ing capacitive electrodes,lags behind cation-storing counterparts.Herein,we demonstrate the surface faradaic OH-storage mechanism of anion storing perovskite oxide composites and their application in high-performance dual ion HsCs.The oxygen vacancy and nanoparticle size of the reduced LaMnO_(3)(r-LaMnO_(3))were controlled,while r-LaMnO_(3) was chemically coupled with ozonated carbon nanotubes(oCNTs)for the improved anion storing capacity and cycle performance.As taken by in-situ and ex-situ spectroscopic and computational analyses,OH-ions are inserted into the oxygen vacancies coordi-nating with octahedral Mn with the increase in the oxidation state of Mn during the charging process or vice versa.Configuring OH-storing r-LaMnO_(3)/oCNT composite with Na*storing MXene,the as-fabricated aqueous dual ion HSCs achieved the cycle performance of 73.3%over 10,000 cycles,delivering the max-imum energy and power densities of 47.5 w h kg^(-1) and 8 kw kg^(-1),respectively,far exceeding those of previously reported aqueous anion and dual ion storage cells.This research establishes a foundation for the unique anion storage mechanism of the defect engineered perovskite oxides and the advancement of dual ion hybrid energy storage devices with high energy and power densities.

Defect and interface engineering for electrochemical nitrogen reduction reaction under ambient conditions

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.

Modulating of MoSe_(2)functional plane via doping-defect engineering strategy for the development of conductive and electrocatalytic mediators in Li-S batteries

The lithium polysulfide shuttle and sluggish sulfur reaction kinetics still pose significant challenges to lithium-sulfur(Li-S)batteries.The functional plane of Fe-MoSe_(2)@r GO nanohybrid with abundant defects has been designed and applied in Li-S batteries to develop the functional separator and multi-layer sulfur cathode.The cell with a functional separator exhibits a retention capacity of 462 m Ah g^(-1)after the 1000th at 0.5 C and 516 m Ah g^(-1)after the 600th at 0.3 C.Even at low electrolyte conditions(7.0μL_(mgsulfur)^(-1)and 15μL_(mgsulfur)^(-1))under high sulfur loadings(3.46 mg cm^(-2)and 3.73 mg cm^(-2)),the cell still presents high reversible discharge capacities 679 and 762 m Ah g^(-1)after 70 cycles,respectively.Further,at sulfur loadings up to 8.26 and 5.2 mg cm^(-2),the cells assembled with the bi-layers sulfur cathode and the tri-layers sulfur cathode give reversible capacities of 3.3 m Ah cm^(-2)after the 100th cycle and 3.0 m Ah cm^(-2)after the 120th cycle,respectively.This research not only demonstrates that the FeMoSe_(2)@r GO functional plane is successfully designed and applied in Li-S batteries with superior electrochemical performances but also paves the novel way for developing a unique multi-layer cathode technique to enhance and advance the electrochemical behavior of Li-S cells at a high-sulfur-loading cathode under lean electrolyte/sulfur(E/S)ratio.

Abnormal enhancement to the quality factors of carbon nanotube via defects engineering

Low quality(Q) factor is often the limiting factor for high performance carbon nanotube(CNT) resonators. The most commonly used approach to enhance the Q factor of CNTs is to reduce/eliminate the intrinsic defects.Herein, we show surprisingly that hole defects of suitable size and position are able to enhance the Q factor of CNT, which strongly contradicts to the common notion that the presence of defects promote intrinsic dissipation via defects dissipation. By analyzing the strain distribution, we find that such abnormal enhancement in Q factor of defected CNT originates from a coupling competition mechanism between the atomic mismatch around defected atoms and the thermoelastic damping. Although the presence of holes will introduce an additional defect dissipation source, suitable holes are capable of reducing the energy dissipation arisen from the thermoelastic damping, through changing the spatial strain field of defected CNT. This coupling competition mechanism provides a new route for designing high performance CNT resonators via defects engineering.

Review:Phonon Engineering in Thermoelectric Materials

One of the abundantly available energies that could be found in industrial power plants, running vehicles, nuclear power stations, etc. is known as thermal energy. A physical phenomenon known as thermoelectricity converts thermal energy into electrical energy and vice versa, providing a green route for power generation and a potential solution to the world energy crisis. The thermoelectric conversion efficiency is generally characterized by the temperature-dependent dimensionless figure of merit(zT), which is generally promoted by increasing the power factor and reducing the thermal conductivity. The present work reviews heat transmission in thermoelectric materials, particularly phonon engineering to reduce the lattice thermal conductivity. The two leading strategies of point defects engineering and nanostructuring for reducing thermal conductivity have been summarized. The optimized reported zTs of various thermoelectric materials in terms of reduced thermal conductivity have been presented.

Quasi‑Solid Electrolyte Interphase Boosting Charge and Mass Transfer for Dendrite‑Free Zinc Battery

The practical applications of zinc metal batteries are plagued by the dendritic propagation of its metal anodes due to the limited transfer rate of charge and mass at the electrode/electrolyte interphase.To enhance the reversibility of Zn metal,a quasi-solid interphase composed by defective metal-organic framework(MOF)nanoparticles(D-UiO-66)and two kinds of zinc salts electrolytes is fabricated on the Zn surface served as a zinc ions reservoir.Particularly,anions in the aqueous electrolytes could be spontaneously anchored onto the Lewis acidic sites in defective MOF channels.With the synergistic effect between the MOF channels and the anchored anions,Zn^(2+)transport is prompted significantly.Simultaneously,such quasi-solid interphase boost charge and mass transfer of Zn^(2+),leading to a high zinc transference number,good ionic conductivity,and high Zn^(2+)concentration near the anode,which mitigates Zn dendrite growth obviously.Encouragingly,unprecedented average coulombic efficiency of 99.8%is achieved in the Zn||Cu cell with the proposed quasi-solid interphase.The cycling performance of D-UiO-66@Zn||MnO_(2)(~92.9%capacity retention after 2000 cycles)and D-UiO-66@Zn||NH_(4)V_(4)O_(10)(~84.0%capacity retention after 800 cycles)prove the feasibility of the quasi-solid interphase.

Defect-engineered two-dimensional transition metal dichalcogenides towards electrocatalytic hydrogen evolution reaction

Recently,two-dimensional transition metal dichalcogenides(TMDs)demonstrated their great potential as cost-effective catalysts in hydrogen evolution reaction.Herein,we systematically summarize the existing defect engineering strategies,including intrinsic defects(atomic vacancy and active edges)and extrinsic defects(metal doping,nonmetal doping,and hybrid doping),which have been utilized to obtain advanced TMD-based electrocatalysts.Based on theoretical simulations and experimental results,the electronic structure,intermediate adsorption/desorption energies and possible catalytic mechanisms are thoroughly discussed.Particular emphasis is given to the intrinsic relationship between various types of defects and electrocatalytic properties.Furthermore,current opportunities and challenges for mechanical investigations and applications of defective TMD-based catalysts are presented.The aim herein is to reveal the respective properties of various defective TMD catalysts and provide valuable insights for fabricating high-efficiency TMD-based electrocatalysts.

Recent update on electrochemical CO_(2)reduction catalyzed by metal sulfide materials

Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides have attracted attention as promising nature-inspired materials due to multiple adsorption sites which are enhanced by the covalent character of sulfur.This article summarizes the current status regarding the utilization and development of metal sulfide materials as CO_(2)RR electrocatalysts.First,the research background and basic principles of electrochemical CO_(2)RR are introduced.Next,an overview of the main obstacles to developing efficient CO_(2)RR electrocatalysts is presented.The section is followed by a summary of the empirical evidence supporting the application of metal sulfides as CO_(2)RR electrocatalysts beside nature-inspired motivation.The summary of synthesis methods of various metal sulfides is also presented.Furthermore,the paper also highlights the recent works on metal sulfide as efficient CO_(2)RR including the undertaking strategy on the activity enhancement,and finally,discusses the challenges and prospect of metal sulfides-based CO_(2)RR electrocatalysts.Despite recent efforts,metal sulfides remain relatively unexplored as materials for CO_(2)RR electrocatalytic applications.Therefore,this review aims to stimulate novel ideas and research for improved catalyst designs and functionality.

Engineering tantalum nitride for efficient photoelectrochemical water splitting

Photoelectrochemical(PEC)water splitting is a promising energy conversion strategy for directly converting solar energy into green hydrogen fuel.Constructing an efficient PEC device,finding an efficient photoanode material with a suitable band gap and favorable band-edge positions is essential.Tantalum nitride(Ta_(3)N_(5))meets these fundamental requirements,and its theoretical maximum solar-to-hydrogen(STH)conversion efficiency can reach 15.9%.Consequently,it has been widely applied as a photoanode material for the PEC oxygen evolution reaction(OER).However,severe bulk and interface charge recombination,along with sluggish water oxygen kinetics,seriously limits its STH conversion efficiency for PEC water splitting.Herein,this feature article briefly reviews recent advances by our research group in improving the STH conversion efficiency of the Ta_(3)N_(5)photoanode using various strategies,including defect engineering,construction of a gradient band structure,interface engineering,and surface modification of self-healing OER cocatalyst.Up to now,the obtained half-cell STH efficiency has exceeded 4%,providing a solid foundation for the development of tandem PEC devices for unbiased solar-driven overall water splitting toward practical application.

Defect engineering of W^(6+)-doped NiO for high-performance black smart windows

In this report,W^(6+)doping as a defect engineering strategy has been proposed to improve the electrochromic properties of NiO film.Further research was conducted to explore the electrochromic properties and the modified mechanism of W-doped NiO film.Compared to the pure NiO,W-doped NiO film exhibits improved electrochromic properties with significant optical modulation(61.56%at 550 nm),fast switching speed(4.42 s/1.40 s for coloring/bleaching),high coloration efficiency(45.41 cm^(2)·C-1)and outstanding cycling stability(no significant attenuation after 2000 cycles)in Li-based electrolytes.Density functional theory(DFT)calculations combined with the experimental results indicate that the improved electrochromic properties were due to enhanced the electronic conductivity and ion conductivity after the introduction of W^(6+).The charge capacity of W-doped NiO has also been improved,and it can function with WO_(3) to achieve a high performance black electrochromic smart window(ECSW)by balancing charge.This work could advance the fundamental understanding of defect engineering as an effective strategy to boost the electrochromic properties of NiO anodic material,manifesting a significant development as a candidate counter electrode in high-performance black smart windows.

Controllable defect engineering based on cobalt metal-organic framework for boosting oxygen evolution reaction

Defect engineering on metal-organic frameworks(MOFs)provides high flexibility to rationally design advanced oxygen evolution reaction(OER)catalysts with low overpotential and high stability.However,fundamental understanding the effect of defect concentration on catalytic OER activity is still quite ambiguous.Herein,the Co-MOF-Dx catalysts with regulated oxygen defects concentration are deliberately constructed via coupling one-pot solvothermal synthesis with NaBH_(4)chemical reduction process.Experimental findings propose that the oxygen defect concentration within Co-MOF-Dx gradually increases with raising the NaBH_(4)content,which could provide a flexible platform to tailor the electronic structure around active Co site and optimize adsorption/desorption capacity of oxygen intermediates.When the introduction content of NaBH_(4)is up to 5 mg,the resulting abundant unsaturated coordination defects could endow the Co-MOF-D5 catalyst with optimized electronic structure and more exposed active sites for improving charge transfer and adsorption/desorption capacity.It is found that the optimized Co-MOF-D5 can drive the current density of 10 mA cm^(-2)only at a low overpotential of 300 mV with the small Tafel slope of 53.1 mV dec^(-1)in alkaline medium.This work sheds light on the way for the development of high-performance MOF catalysts via modulating defect concentration.

Better engineering layered vanadium oxides for aqueous zinc‐ion batteries: Going beyond widening the interlayer spacing

Aqueous zinc‐ion batteries(ZIBs)are regarded as among the most promising candidates for large‐scale grid energy storage,owing to their high safety,low costs,and environmental friendliness.Over the past decade,vanadium oxides,which are exemplified by V2O5,have been widely developed as a class of cathode materials for ZIBs,where the relatively high theoretical capacity and structural stability are among the main considerations.However,there are considerable challenges in the construction of vanadium‐based ZIBs with high capacity,long lifespan,and excellent rate performance.Simple widenings of the interlayer spacing in the layered vanadium oxides by pre‐intercalations appear to have reached their limitations in improving the energy density and other key performance parameters of ZIBs,although various metal ions(Na+,Ca2+,and Al3+)and even organic cations/groups have been explored.Herein,we discuss the advances made more recently,and also the challenges faced by the high‐performance vanadium oxides(V2O5‐based)cathodes,where there are several strategies to improve their electrochemical performance ranging from the new structural designs down to sub‐nano‐scopic/molecular/atomic levels,including cation pre‐intercalation,structural water optimization,and defect engineering,to macroscopic structural modifications.The key principles for an optimal structural design of the V2O5‐based cathode materials for high energy density and fast‐charging aqueous ZIBs are examined,aiming at paving the way for developing energy storage designed for those large scales,high safety,and low‐cost systems.