Coregulation of Li/Li+ Spatial Distribution by Electric Field Gradient with Homogenized Li-Ion Flux for Dendrite-Free Li Metal Anodes.

Lithium (Li) metal batteries are highly sought after for their exceptional energy density. However, their practical implementation is impeded by the formation of dendrites and significant volume fluctuations in Li, which stem from the uneven distribution of Li-ions and uncontrolled deposition of Li on the current collector. Here, an amino-functionalized reduced graphene oxide covered with polyacrylonitrile (PrGN) film with an electric field gradient structure is prepared to deal with such difficulties. This novel current collector serves to stabilize Li-metal anodes by regulating Li-ion flux through vertically aligned channels formed by porous polyacrylonitrile (PAN). Moreover, the amino-functionalized reduced graphene oxide (rGN) acts as a three-dimensional (3D) host, reducing nucleation overpotential and accommodating volume expansion during cycling. The combination of the insulating PAN and conducting rGN creates an electric field gradient that promotes a bottom-up mode of Li electrodeposition and safeguards the anode from interfacial parasitic reactions. Consequently, the electrodes exhibit exceptional cycle life with stable voltage profiles and minimal hysteresis under high current densities and large areal capacities.

Pseudopyrolysis of Metal-Organic Frameworks: A Synchronous Nucleation Mechanism to Synthesize Ultrafine Metal Compound Nanoparticles.

Metal-Organic frameworks (MOFs) are increasingly being investigated for the synthesis of carbon-supported metal-based ultrafine nanoparticles (UNPs). However, the collapse of the carbon framework and aggregation of metal particles in the pyrolysis process have severely hindered their stability and applications. Here, we report the synchronous nucleation pseudopyrolysis of MOFs to confine Fe/FeOx UNPs in intact porous carbon nanorods (IPCNs), revealed by in situ transmission electron microscopy experiments and ex situ structure analysis. The pseudopyrolysis mechanism enables strong physical and chemical confinement effects between UNPs and carbon by moderate thermal kinetics and abundant oxygen defects. Further, this strong confinement is greatly beneficial for subsequent chemical transformations to obtain different Fe-based UNPs and excellent electrochemical performance. As a proof of concept, the as-prepared FeSe UNPs in IPCNs show superior lithium storage performance with an ultrahigh and stable capacity of 815.1 mAh g-1 at 0.1 A g -1 and 379.7 mAh g-1 at 5 A g-1 for 1000 cycles.

Red Phosphorus Anchored on Nitrogen-Doped Carbon Bubble-Carbon Nanotube Network for Highly Stable and Fast-Charging Lithium-Ion Batteries.

A nitrogen-doped carbon bubble-carbon nanotube@red phosphorus (N-CBCNT@rP) network composite is fabricated, featuring an rP film embedded in a highly N-doped CBCNT network with hierarchical pores of different sizes and interior void spaces. Highly N-doped CBCNT with an optimized structure is utilized to achieve an ultrahigh rP content of 53 wt% in the N-CBCNT@rP composite by the NP bond, which shows a record rP content for rP-carbon composites by the vaporization-condensation process. When tested as an anode for lithium-ion batteries, the N-CBCNT@rP composite exhibits an ultrahigh initial Coulombic efficiency of 87.5%, high specific capacity, outstanding rate performance, and superior cycling stability at a high current density (capacity decay of 0.011% per cycle over 1500 cycles at 5 A g-1 ), which is the lowest capacity fading rate of those previously reported for rP-based electrodes. The superior lithium-ion storage performance of the N-CBCNT@rP composite electrode is primarily attributed to its structure. The 3D hierarchical conducting network of the N-CBCNT@rP composite with abundant N-P bonds endows the entire electrode with maximized conductivity for superior ion and electron transfer kinetics. Moreover, N-CBCNT networks with hierarchical pores of different sizes can fix the location of rP, prevent agglomeration, and avoid volume expansion of rP.

Boosting Charge Transfer Via Heterostructure Engineering of Ti2 CTx /Na2 Ti3 O7 Nanobelts Array for Superior Sodium Storage Performance.

The poor conductivity, inert charge transmission efficiency, and irreversible Na+ trapping of Na2 Ti3 O7 result in retardant electrons/ions transportation and deficient sodium-ion storage efficiency, leading to sluggish reaction kinetics. To address these issues, an urchin-like Ti2 CTx /Na2 Ti3 O7 (Ti2 C/NTO) heterostructure sphere consisting of Ti2 C/NTO heterostructure nanobelts array is developed via a facile one-step in situ hydrothermal strategy. The Ti2 C/NTO heterostructure can obviously decrease Na+ diffusion barriers and increase electronic conductivity to improve reaction kinetics due to the built-in electric field effect and high-quantity interface region. In addition, the urchin-like vertically aligned nanobelts can reduce the diffusion distance of electrons and ions, provide favored electrolyte infiltration, adapt large volume expansion, and mitigate the aggregation to maintain structural stability during cycles, further enhancing the reaction kinetics. Furthermore, the Ti2 C/NTO heterostructure can effectively suppress many unwanted side reactions between reactive surface sites of NTO and electrolyte as well as irreversible trapping of Na+ . As a result, systematic electrochemical investigations demonstrate that the Ti2 C/NTO heterostructure as an anode material for record sodium-ion storage delivers the highest reversible capacity, the best cycling stability with 0.0065% decay rate for 4500 cycles at 2.0 A g-1 , and excellent rate capability of 172.1 mAh g-1 at 10.0 A g-1 .

Enhancing the Electrochemical Performance of Sodium-Ion Batteries by Building Optimized NiS2 /NiSe2 Heterostructures.

NiS1.23 Se0.77 nanosheets closely attached to the internal surface of hollow mesoporous carbon sphere (HMCS) to form a NiS1.23 Se0.77 nanosheets embedded in HMCS (NSSNs@HMCS) composite as the anode of sodium ion batteries (SIBs) is reported by a facile synthesis route. The anode exhibits a superior reversible capacity (520 mAh g-1 at 0.1 A g-1 ), impressive coulombic efficiency (CE) of up to 95.3%, a high rate capacity (353 mAh g-1 at 5.0 A g-1 ), excellent capacity retention at high current density (95.6%), and high initial coulombic efficiency (ICE) (95.1%). Firstly, the highest ICE for NiS2 /NiSe2 -based anode can be ascribed to ultrathin layered structure of NiS1.23 Se0.77 nanosheet and highly efficient electron transfer between the active material and HMCS. Secondly, the optimized NiS2 /NiSe2 heterostructure at the nanoscale of the inside HMCS is formed after the first discharge/charge cycles, which can provide rich heterojunction interfaces/boundaries of sulfide/selenides to offer faster Na+ pathways, decrease the Na+ diffusion barriers, increase electronic conductivity, and limit the dissolution of polysulfides or polyselenides in the electrolyte. Finally, the hollow structure of the HMCS accommodates the volume expansion, prevents the pulverization and aggregation issues of composite materials, which can also promote outstanding electrochemical performance.

Stabilizing Lithium-Sulfur Batteries through Control of Sulfur Aggregation and Polysulfide Dissolution.

Lithium-sulfur (Li-S) batteries are investigated intensively as a promising large-scale energy storage system owing to their high theoretical energy density. However, the application of Li-S batteries is prevented by a series of primary problems, including low electronic conductivity, volumetric fluctuation, poor loading of sulfur, and shuttle effect caused by soluble lithium polysulfides. Here, a novel composite structure of sulfur nanoparticles attached to porous-carbon nanotube (p-CNT) encapsulated by hollow MnO2 nanoflakes film to form p-CNT@Void@MnO2 /S composite structures is reported. Benefiting from p-CNTs and sponge-like MnO2 nanoflake film, p-CNT@Void@MnO2 /S provides highly efficient pathways for the fast electron/ion transfer, fixes sulfur and Li2 S aggregation efficiently, and prevents polysulfide dissolution during cycling. Besides, the additional void inside p-CNT@Void@MnO2 /S composite structure provides sufficient free space for the expansion of encapsulated sulfur nanoparticles. The special material composition and structural design of p-CNT@Void@MnO2 /S composite structure with a high sulfur content endow the composite high capacity, high Coulombic efficiency, and an excellent cycling stability. The capacity of p-CNT@Void@MnO2 /S electrode is ≈599.1 mA h g-1 for the fourth cycle and ≈526.1 mA h g-1 after 100 cycles, corresponding to a capacity retention of ≈87.8% at a high current density of 1.0 C.

Design and Functionalization of the NIR-Responsive Photothermal Semiconductor Nanomaterials for Cancer Theranostics.

Despite the development of medical technology, cancer still remains a great threat to the survival of people all over the world. Photothermal therapy (PTT) is a minimally invasive method for selective photothermal ablation of cancer cells without damages to normal cells. Recently, copper chalcogenide semiconductors have emerged as a promising photothermal agent attributed to strong absorbance in the near-infrared (NIR) region and high photothermal conversion efficiency. An earlier study witnessed a rapid increase in their development for cancer therapy, including CuS, Cu2-xSe and CuTe nanocrystals. However, a barrier is that the minimum laser power intensity for effective PTT is still significantly higher than the conservative limit for human skin exposure. Improving the photothermal conversion efficiency and reducing the laser power density has become a direction for the development of PTT. Furthermore, in an effort to improve the therapeutic efficacy, many multimode therapeutic nanostuctures have been formulated by integrating the photothermal agents with antitumor drugs, photosensitizers, or radiosensitizers, resulting in a synergistic effect. Various functional materials also have been absorbed, attached, encapsulated, or coated on the photothermal nanostructures, including fluorescence, computed tomography, magnetic resonance imaging, realizing cancer diagnosis, tumor location, site-specific therapy, and evaluation of therapeutic responses via incorporation of diagnosis and treatment. In this Account, we present an overview of the NIR-responsive photothermal semiconductor nanomaterials for cancer theranostics with a focus on their design and functionalization based on our own work. Our group has developed a series of chalcogenides with greatly improved NIR photoabsorption as photothermal agents, allowing laser exposure within regulatory limits. We also investigated the photothermal bioapplications of hypotoxic oxides including WO3-x, MoO3-x, and RuO2, expanding their applications into a new field of photothermal materials. Furthermore, considering a much more enhanced therapeutic effect of multifunctional nanoagents, our group elaborately designed many nanocomposites, such as core-shell nanoparticles of Fe3O4@Cu2-xS and Cu9S5@mSiO2, based on the integration of photothermal agents with contrast agents or other anticancer medicines, achieving cancer theranostic and synergistic treatment. Ternary compound nanocrystals were also prepared with synthetic simplicity for multimodal imaging-guided therapy for cancer. This Account summarizes our past work, including the design and concept, synthesis, and characterization for in vitro and in vivo applications. Then, we analyzed the tendencies of the NIR-responsive photothermal semiconductor nanomaterials for clinical applications, highlighting their prospects and challenges. We believe that the photothermal technology from the NIR-responsive photothermal semiconductor nanomaterials would promote cancer theranostics to result in giant strides forward in the future.

Morphology Control and Growth Mechanism Study of Quantum-Sized ZnS Nanocrystals from Single-Source Precursors.

The growing demand of metal sulfides using in various applications has in turn greatly stimulated basic research to develop novel nanomaterials with controlled size, shape, phase and desired properties. Specifically, ultrathin ZnS nanowires with diameter of less than 2 nm have attracted significant interest because of their considerable promise in sensors, phosphor host materials, photodetectors, and other devices. A novel method for the synthesis of controlled morphology, phase and size of ZnS nanocrystals has been developed. Especially, ultrathin ZnS nanowires with 1.5 nm in diameter were synthesized from single-source precursor zinc dicarbazoledithiocarbamate using oleylamine as capping ligand and solvent. Strong quantum confinement effects related to the unique nature of these ultrathin ZnS nanowires were observed. More importantly, we have presented the evidence for the assembly of ultra-small ZnS nanoparticles in 1-D polymer-like structures achieved by oriented attachment mechanism for synthesis of ultrathin ZnS nanowires.

Surface Coating Constraint Induced Anisotropic Swelling of Silicon in Si-Void@SiO x Nanowire Anode for Lithium-Ion Batteries.

Here a simple and an environmentally friendly approach is developed for the fabrication of Si-void@SiOx nanowires of a high-capacity Li-ion anode material. The outer surface of the robust SiOx backbone and the inside void structure in Si-void@SiOx nanowires appropriately suppress the volume expansion and lead to anisotropic swelling morphologies of Si nanowires during lithiation/delithiation, which is first demonstrated by the in situ lithiation process. Remarkably, the Si-void@SiOx nanowire electrode exhibits excellent overall lithium-storage performance, including high specific capacity, high rate property, and excellent cycling stability. A reversible capacity of 1981 mAh g-1 is obtained in the fourth cycle, and the capacity is maintained at 2197 mAh g-1 after 200 cycles at a current density of 0.5 C. The outstanding overall properties of the Si-void@SiOx nanowire composite make it a promising anode material of lithium-ion batteries for the power-intensive energy storage applications.

Molten Au/Ge alloy migration in Ge nanowires.

Herein, we report time-resolved in situ transmission electron microscopy observation of Au particle melting at a Ge nanowire tip, subsequent forming of Au/Ge alloy liquid, and its migrating within the Ge nanowire. The migration direction and position of the Au/Ge liquid can be controlled by the applied voltage and the migration speed shows a linear deceleration in the nanowire. In a migration model proposed, the relevant dynamic mechanisms (electromigration, thermodiffusion, and viscous force, etc.) are discussed in detail. This work associated with the liquid mass transport in the solid nanowires should provide new insights into the crystal growth, interface engineering, and fabrication of the heterogeneous nanostructure-based devices.

High detectivity solar-blind high-temperature deep-ultraviolet photodetector based on multi-layered (l00) facet-oriented ß-Ga2O3 nanobelts.

Fabrication of a high-temperature deep-ultraviolet photodetector working in the solar-blind spectrum range (190-280 nm) is a challenge due to the degradation in the dark current and photoresponse properties. Herein, ß-Ga2O3 multi-layered nanobelts with (l00) facet-oriented were synthesized, and were demonstrated for the first time to possess excellent mechanical, electrical properties and stability at a high temperature inside a TEM studies. As-fabricated DUV solar-blind photodetectors using (l00) facet-oriented ß-Ga2O3 multi-layered nanobelts demonstrated enhanced photodetective performances, that is, high sensitivity, high signal-to-noise ratio, high spectral selectivity, high speed, and high stability, importantly, at a temperature as high as 433 K, which are comparable to other reported semiconducting nanomaterial photodetectors. In particular, the characteristics of the photoresponsivity of the ß-Ga2O3 nanobelt devices include a high photoexcited current (>21 nA), an ultralow dark current (below the detection limit of 10(-14) A), a fast time response (<0.3 s), a high R(λ) (≈851 A/W), and a high EQE (~4.2 × 10(3)). The present fabricated facet-oriented ß-Ga2O3 multi-layered nanobelt based devices will find practical applications in photodetectors or optical switches for high-temperature environment.

Crosslinking and fluorination reinforced PTFE nanofibrous membrane with excellent amphiphobic performance for low-scaling membrane distillations.

Membrane distillation (MD) has emerged as a promising technology for desalination and concentration of hypersaline brine. However, the efficient preparation of a structurally stable and salinity-resistant membrane remains a significant challenge. In this study, an amphiphobic polytetrafluoroethylene nanofibrous membrane (PTFE NFM) with exceptional resistance to scaling has been developed, using an energy-efficient method. This innovative approach avoids the high-temperature sintering treatment, only involving electrospinning with PTFE/PVA emulsion and subsequent low-temperature crosslinking and fluorination. The impact of the PVA and PTFE contents, as well as the crosslinking and subsequent fluorination on the morphology and MD performance of the NFM, were systematically investigated. The optimized PTFE NFM displayed robust amphiphobicity, boasting a water contact angle of 155.2º and an oil contact angle of 132.7º. Moreover, the PTFE NFM exhibited stable steam flux of 52.1 L·m-2·h-1 and 26.7 L·m-2·h-1 when fed with 3.5 wt % and 25.0 wt % NaCl solutions, respectively, and an excellent salt rejection performance (99.99 %, ΔT = 60 °C) in a continuous operation for 24 h, showing exceptional anti-scaling performance. It also exhibited stable anti-wetting and anti-fouling properties against surfactants (sodium dodecyl sulfate) and hydrophobic contaminants (diesel oil). These results underscore the significant potential of the PTFE nanofibrous membrane for practical applications in desalination, especially in hypersaline or polluted aqueous environments.

A narrow-bandgap RuI3 nanoplatform to synergize radiotherapy, photothermal therapy, and thermoelectric dynamic therapy for tumor eradication.

Therapeutic resistance is an essential challenge for nanotherapeutics. Herein, a narrow bandgap RuI3 nanoplatform has been constructed firstly to synergize radiotherapy (RT), photothermal therapy (PTT), and thermoelectric dynamic therapy (TEDT) for tumor eradication. Specifically, the photothermal performance of RuI3 can ablate tumor cells while inducing TEDT. Noteworthy, the thermoelectric effect is found firstly in RuI3, which can spontaneously generate an electric field under the temperature gradient, prompting carrier separation and triggering massive ROS generation, thus aggravating oxidative stress level and effectively inhibiting HSP-90 expression. Moreover, RuI3 greatly enhances X-ray deposition owing to its high X-ray attenuation capacity, resulting in a pronounced computed tomography imaging contrast and DNA damage. In addition, RuI3 possesses both catalase-like and glutathione peroxidase-like properties, which alleviate tumor hypoxia and reduce antioxidant resistance, further exacerbating 1O2 production during RT and TEDT. This integrated therapy platform combining PTT, TEDT, and RT significantly inhibits tumor growth. STATEMENT OF SIGNIFICANCE: RuI3 nanoparticles were synthesized for the first time. RuI3 exhibited the highest photothermal properties among iodides, and the photothermal conversion efficiency was 53.38 %. RuI3 was found to have a thermoelectric effect, and the power factor could be comparable to that of most conventional thermoelectric materials. RuI3 possessed both catalase-like and glutathione peroxidase-like properties, which contributed to enhancing the effect of radiotherapy.

Sub-10 nm Fe3O4@Cu(2-x)S core-shell nanoparticles for dual-modal imaging and photothermal therapy.

Photothermal nanomaterials have recently attracted significant research interest due to their potential applications in biological imaging and therapeutics. However, the development of small-sized photothermal nanomaterials with high thermal stability remains a formidable challenge. Here, we report the rational design and synthesis of ultrasmall (<10 nm) Fe3O4@Cu2-xS core-shell nanoparticles, which offer both high photothermal stability and superparamagnetic properties. Specifically, these core-shell nanoparticles have proven effective as probes for T2-weighted magnetic resonance imaging and infrared thermal imaging because of their strong absorption at the near-infrared region centered around 960 nm. Importantly, the photothermal effect of the nanoparticles can be precisely controlled by varying the Cu content in the core-shell structure. Furthermore, we demonstrate in vitro and in vivo photothermal ablation of cancer cells using these multifunctional nanoparticles. The results should provide improved understanding of synergistic effect resulting from the integration of magnetism with photothermal phenomenon, important for developing multimode nanoparticle probes for biomedical applications.

High-detectivity nanowire photodetectors governed by bulk photocurrent dynamics with thermally stable carbide contacts.

Photodetectors fabricated from one-dimensional semiconductors are always dominated by the surface states due to their large surface-to-volume ratio. Therefore, the basic 5S requirements (high sensitivity, high signal-to-noise ratio, high spectral selectivity, high speed, and high stability) for practical photodetectors are difficult to satisfy. We report on high-temperature and high-detectivity solar-blind deep-ultraviolet (DUV) photodetectors based on ß-Ga2O3 nanowires, in which the photoresponse behavior is dominated by the bulk instead of the surface states. Ohmic contact to the ß-Ga2O3 nanowires was achieved by using a thermally stable tungsten carbide electrode. As a result, the DUV responsivity at 250 nm shows the highest values--4492 A W(-1) at room temperature (RT) and 3000 A W(-1) at 553 K (280 °C)--among the DUV photodetectors. The detectivity is as high as 1.26×10(16) cm Hz(1/2) W(-1) at RT, and still remains 4.1×10(14) cm Hz(1/2) W(-1) at as high a temperature as 553 K. The photocurrent dynamics from the ß-Ga2O3 nanowire is discussed in terms of the bulk dominated photoresponse behavior. Other wide bandgap DUV detectors based on nanostructures could also be developed for high-temperature applications based on this work.

Bi nanoparticles confined in N,S co-doped carbon nanoribbons with excellent rate performance for sodium-ion batteries.

Bismuth (Bi) has emerged as a promising candidate for sodium-ion battery anodes because of its unique layered crystal structure, superior volumetric capacity, and high theoretical gravimetric capacity. However, the large volume expansion and severe aggregation of Bi during the alloying/dealloying reactions are extremely detrimental to cycling stability, which seriously hinders its practical application. To overcome these issues, we propose an effective synthesis of composite materials, encapsulating Bi nanoparticles in N,S co-doped carbon nanoribbons and composites with carbon nanotubes (N,S-C@Bi/CNT), using Bi2S3 nanobelts as templates. The uniform distribution of Bi nanoparticles and the structure of carbon nanoribbons can reduce the diffusion path of ions/electrons, efficiently buffer the large volume change and prevent Bi from aggregating during cycles. As expected, the N,S-C@Bi/CNT electrode shows superior sodium storage performance in half cells, including a high specific capacity (345.3 mA h g-1 at 1.0 A g-1), long cycling stability (1000 cycles), and superior rate capability (336.0 mA h g-1 at 10.0 A g-1).

Constructing a Micrometer-Sized Structure through an Initial Electrochemical Process for Ultrahigh-Performance Li+ Storage.

Orthorhombic niobium pentoxide (T-Nb2O5) is a promising anode to fulfill the requirements for high-rate Li-ion batteries (LIBs). However, its low electric conductivity and indistinct electrochemical mechanism hinder further applications. Herein, we develop a novel method to obtain a micrometer-sized layer structure of S-doped Nb2O5 on an S-doped graphene (SG) surface (the composite is denoted S-Nb2O5/SG) after the initial cycle, which we call "in situ electrochemically induced aggregation". In situ and ex situ characterizations and theoretical calculations were carried out to reveal the aggregation process and Li+ storage process. The unique merits of the composite with a micrometer-sized layer structure increased the reaction degree, structural stability, and electrochemical kinetics. As a result, the electrode exhibited a large capacity (∼598 mAh g-1 at 0.1 A g-1), outstanding cycling stability (∼313 mAh g-1 at 5 A g-1 and remains at ∼313 mAh g-1 after 1000 cycles), and a high Coulombic efficiency and has a high fast-charging performance and excellent cycling stability.

Tailoring the Void Space Using Nanoreactors on Carbon Fibers to Confine SnS2 Nanosheets for Ultrastable Lithium/Sodium-Ion Batteries.

Herein, a rational design of SnS2 nanosheets confined into bubble-like carbon nanoreactors anchored on N,S doped carbon nanofibers (SnS2 @C/CNF) is proposed to prepare the self-standing electrodes, which provides tunable void space on carbon fibers for the first time by introducing hollow carbon nanoreactors. The SnS2 @C/CNF provides the stable support with greatly enhanced ion and electron transport, alleviates aggregation and volume expansion of SnS2 nanosheets, and promotes the formation of abundant exposed edges and active sites. The volume balance between SnS2 nanosheets and hollow carbon nanoreactors is reached to accommodate the expansion of SnS2 during cycles by controlling the thickness of SnO2 shells, which achieves the best space utilization. The doping of N,S elements enhances the wettability of the carbon nanofiber matrix to electrolyte and Li ions and further improves the electrical conductivity of the whole electrode. Thus, the SnS2 @C/CNF benefits greatly in structural stability and pseudocapacitive capacity for improved lithium/sodium storage performance. As a result of these improvements, the self-standing SnS2 @C/CNF film electrodes exhibit the highly stable capacity of 964.8 and 767.6 mAh g-1 at 0.2 A g-1 , and excellent capacity retention of 87.4% and 82.4% after 1000 cycles at high current density for lithium-ion batteries and sodium-ion batteries, respectively.

Construction of Ultrathin Layered MXene-TiN Heterostructure Enabling Favorable Catalytic Ability for High-Areal-Capacity Lithium-Sulfur Batteries.

Catalysis has been regarded as an effective strategy to mitigate sluggish reaction kinetics and serious shuttle effect of Li-S batteries. Herein, a spherical structure consists of ultrathin layered Ti3C2Tx-TiN heterostructures (MX-TiN) through in-situ nitridation method is reported. Through controllable nitridation, highly conductive TiN layer grew on the surface and close coupled with interior MXene to form unique 2D heterostructures. The ultrathin heterostructure with only several nanometers in thickness enables outstanding ability to shorten electrons diffusion distance during electrochemical reactions and enlarge active surface with abundant adsorptive and catalytic sites. Moreover, the (001) surface of TiN is dominated by metallic Ti-3d states, which ensures fast transmitting electrons from high conductive MX-TiN matrix and thus guarantees efficient catalytic performance. Calculations and experiments demonstrate that polysulfides are strongly immobilized on MX-TiN, meanwhile the bidirectional reaction kinetics are catalytically enhanced by reducing the conversion barrier between liquid LiPSs and solid Li2S2/Li2S. As a result, the S/MX-TiN cathode achieves excellent long-term cyclability with extremely low-capacity fading rate of 0.022% over 1000 cycles and remarkable areal capacity of 8.27 mAh cm-2 at high sulfur loading and lean electrolytes.

Modulating the Electronic Structure of FeCo Nanoparticles in N-Doped Mesoporous Carbon for Efficient Oxygen Reduction Reaction.

The development of highly efficient and stable oxygen reduction electrocatalysts and revealing their underlying catalytic mechanism are crucial in expanding the applications of metal-air batteries. Herein, an excellent FeCo alloy nanoparticles (NPs)-decorated N-doped mesoporous carbon electrocatalyst (FeCo/NC) for oxygen reduction reaction, prepared through the pyrolysis of a dual metal containing metal-organic framework composite scaffold is reported. Benefiting from the highly exposed bimetal active sites and the carefully designed structure, the Fe0.25 Co0.75 /NC-800 catalyst exhibits a promising electrocatalytic activity and a superior durability, better than those of the state-of-the-art catalysts. Suggested by both the X-ray absorption fine structures and the density functional theoretical calculation, the outstanding catalytic performance is originated from the synergistic effects of the bimetallic loading in NC catalysts, where the electronic modulation of the Co active sites from the nearby Fe species leads to an optimized binding strength for reaction intermediates. This work demonstrates a class of highly active nonprecious metals electrocatalysts and provides valuable insights into investigating the structure-performance relationship of transition metal-based alloy catalysts.