Charge Dynamics Engineering Sparks Hetero-Interfacial Polarization for an Ultra-Efficient Microwave Absorber with Mechanical Robustness.

Microwave absorbers with high efficiency and mechanical robustness are urgently desired to cope with more complex and harsh application scenarios. However, manipulating the trade-off between microwave absorption performance and mechanical properties is seldom realized in microwave absorbers. Here, a chemistry-tailored charge dynamic engineering strategy is proposed for sparking hetero-interfacial polarization and thus coordinating microwave attenuation ability with the interfacial bonding, endowing polymer-based composites with microwave absorption efficiency and mechanical toughness. The absorber designed by this new conceptual approach exhibits remarkable Ku-band microwave absorption efficiency (-55.3 dB at a thickness of 1.5 mm) and satisfactory effective absorption bandwidth (5.0 GHz) as well as desirable interfacial shear strength (97.5 MPa). The calculated differential charge density depicts the uneven distribution of space charge and the intense hetero-interfacial polarization, clarifying the structure-performance relationship from a theoretical perspective. This work breaks through traditional single performance-oriented design methods and ushers a new direction for next-generation microwave absorbers.

Defective ZnIn2S4 Nanosheets for Visible-Light and Sacrificial-Agent-Free H2O2 Photosynthesis via O2/H2O Redox.

H2O2 photosynthesis has attracted great interest in harvesting and converting solar energy to chemical energy. Nevertheless, the high-efficiency process of H2O2 photosynthesis is driven by the low H2O2 productivity due to the recombination of photogenerated electron-hole pairs, especially in the absence of a sacrificial agent. In this work, we demonstrate that ultrathin ZnIn2S4 nanosheets with S vacancies (Sv-ZIS) can serve as highly efficient catalysts for H2O2 photosynthesis via O2/H2O redox. Mechanism studies confirm that Sv in ZIS can extend the lifetimes of photogenerated carriers and suppress their recombination, which triggers the O2 reduction and H2O oxidation to H2O2 through radical initiation. Theoretical calculations suggest that the formation of Sv can strongly change the coordination structure of ZIS, modulating the adsorption abilities to intermediates and avoiding the overoxidation of H2O to O2 during O2/H2O redox, synergistically promoting 2e- O2 reduction and 2e- H2O oxidation for ultrahigh H2O2 productivity. The optimal catalyst displays a H2O2 productivity of 1706.4 µmol g-1 h-1 under visible-light irradiation without a sacrificial agent, which is ∼29 times higher than that of pristine ZIS (59.4 µmol g-1 h-1) and even much higher than those of reported photocatalysts. Impressively, the apparent quantum efficiency is up to 9.9% at 420 nm, and the solar-to-chemical conversion efficiency reaches ∼0.81%, significantly higher than the value for natural synthetic plants (∼0.10%). This work provides a facile strategy to separate the photogenerated electron-hole pairs of ZIS for H2O2 photosynthesis, which may promote fundamental research on solar energy harvest and conversion.

Manipulating Molecular Structure to Trigger Ultrafast and Long-Life Potassium Storage of Fe0.4 Ni0.6 S Solid Solution.

Currently, the main obstacle to the widespread utilization of metal chalcogenides (MSx ) as anode for potassium-ion batteries (PIBs) is their poor rate capability and inferior cycling stability as a result of the undesirable electrical conductivity and severe pulverization of the nanostructure during large K-ions intercalation-extraction processes. Herein, an ultrafast and long-life potassium storage of metal chalcogenide is rationally demonstrated by employing Fe0.4 Ni0.6 S solid-solution (FNS/C) through molecular structure engineering. Benefiting from improved electroactivity and intense interactions within the unique solid solution phase, the electrical conductivity and structure durability of Fe0.4 Ni0.6 S are vastly improved. As anticipated, the FNS/C electrode delivers superior rate properties (538.7 and 210.5 mAh g-1 at 0.1 and 10 A g-1 , respectively) and long-term cycle stability (180.8 mAh g-1 at 5 A g-1 after 2000 cycles with a capacity decay of 0.011% per cycle). Moreover, the potassium storage mechanisms of Fe0.4 Ni0.6 S solid solution are comprehensively revealed by several in situ characterizations and theoretical calculations. This innovative molecular structure engineering strategy opens avenues to achieve high-quality metal chalcogenides for future advanced PIBs.

Medium/High-Entropy Amalgamated Core/Shell Nanoplate Achieves Efficient Formic Acid Catalysis for Direct Formic Acid Fuel Cell.

High-entropy alloys (HEAs) have been attracting extensive research interests in designing advanced nanomaterials, while their precise control is still in the infancy stage. Herein, we have reported a well-defined PtBiPbNiCo hexagonal nanoplates (HEA HPs) as high-performance electrocatalysts. Structure analysis decodes that the HEA HP is constructed with PtBiPb medium-entropy core and PtBiNiCo high-entropy shell. Significantly, the HEA HPs can reach the specific and mass activities of 27.2 mA cm-2 and 7.1 A mgPt -1 for formic acid oxidation reaction (FAOR), being the record catalyst ever achieved in Pt-based catalysts, and can realize the membrane electrode assembly (MEA) power density (321.2 mW cm-2 ) in fuel cell. Further experimental and theoretical analyses collectively evidence that the hexagonal intermetallic core/atomic layer shell structure and multi-element synergy greatly promote the direct dehydrogenation pathway of formic acid molecule and suppress the formation of CO*.

Integrating Multi-Heterointerfaces in a 1D@2D@1D Hierarchical Structure via Autocatalytic Pyrolysis for Ultra-Efficient Microwave Absorption Performance.

Developing microwave absorption (MA) materials with ultrahigh efficiency and facile preparation method remains a challenge. Herein, a superior 1D@2D@1D hierarchical structure integrated with multi-heterointerfaces via self-assembly and an autocatalytic pyrolysis is designed to fully unlock the microwave attenuation potential of materials, realizing ultra-efficient MA performance. By precisely regulating the morphology of the metal organic framework precursor toward improved impedance matching and intelligently integrating multi-heterointerfaces to boosted dielectric polarization, the specific return loss value of composites can be effectively tuned and optimized to -1002 dB at a very thin thickness of 1.8 mm. These encouraging achievements shed fresh insights into the precise design of ultra-efficient MA materials.

Enhancing Li-Ion Affinity of Molybdenum Dioxide/Carbon Fabric to Achieve High Pseudocapacitance.

High-energy electrodes at high mass loadings (usually >8.0 mg cm-2 ) are desired for aqueous pseudocapacitors. Yet, how to overcome the thickness-dependent resistance increase of ion/electron transport in pseudocapacitive materials is still challenging. Herein, a high-performance electrode (denoted as AMC) adapted to high mass loading is achieved by promoting the Li-ion affinity of 3D MoO2 /carbon fabric. The experimental results and corresponding computational results reveal that the oxygen-activated surface of AMC, combined with the wettability and conductivity superiority of 3D graphite network, significantly facilitates the Li-ion adsorption and diffusion at the electrode/electrolyte interface, even at large thicknesses. Consequently, even at a high mass loading up to 8.1 mg cm-2 , the AMC electrode also displays an impressive specific capacity (567.5 C g-1 at 2.5 A g-1 ), substantially superior to most advanced pseudocapacitive electrodes. The strategy of boosting energy characteristic by enhancing the affinity of charge carriers is applicable to other pseudocapacitive electrodes.

The Efficient K Ion Storage of M2 P2 O7 /C (M=Fe, Co, Ni) Anode Derived from Organic-Inorganic Phosphate Precursors.

Metal phosphates have been widely explored in lithium ion batteries and sodium ion batteries owing to high theoretical capacities, mild toxicity and low cost. However, their potassium ion battery applications are less reported due to the limited conductivity and the slow diffusion kinetics. Considering these drawbacks, novel structured M2 P2 O7 /C (M=Fe, Co, Ni) nanoflake composites are prepared through an organic-phosphors precursor-assisted solvothermal method and a subsequent high temperature annealing process. The designed Co2 P2 O7 /C composite exhibits the highest rate capacity with 502 mAh g-1 at 0.1 A g-1 and good cyclability for 900 cycles at 1 A g-1 and 2 A g-1 when compared with Ni and Fe based composites. The superior electrochemical performance can be attributed to their unique nanoparticle-assembled nanoflake structure, which can afford enough active sites for K+ intercalation. In addition, the robust pyrophosphate crystal structure and the in situ formed carbon composition also have positive effects on enhancing the long-term cycling performance and the electrode's conductivity. Finally, this organic-phosphors precursor induced simple approach can be applied for easy fabrication of other pyrophosphate/carbon hybrids as advanced electrodes.

Two-Dimensional Germanium Sulfide Nanosheets as an Ultra-Stable and High Capacity Anode for Lithium Ion Batteries.

Lithium ion batteries (LIBs) at present still suffer from low rate capability and poor cycle life during fast ion insertion/extraction processes. Searching for high-capacity and stable anode materials is still an ongoing challenge. Herein, a facile strategy for the synthesis of ultrathin GeS2 nanosheets with the thickness of 1.1 nm is reported. When used as anodes for LIBs, the two-dimensional (2D) structure can effectively increase the electrode/electrolyte interface area, facilitate the ion transport, and buffer the volume expansion. Benefiting from these merits, the as-synthesized GeS2 nanosheets deliver high specific capacity (1335 mAh g-1 at 0.15 A g-1 ), extraordinary rate performance (337 mAh g-1 at 15 A g-1 ) and stable cycling performance (974 mAh g-1 after 200 cycles at 0.5 A g-1 ). Importantly, our fabricated Li-ion full cells manifest an impressive specific capacity of 577 mAh g-1 after 50 cycles at 0.1 A g-1 and a high energy density of 361 Wh kg-1 at a power density of 346 W kg-1 . Furthermore, the electrochemical reaction mechanism is investigated by the means of ex-situ high-resolution transmission electron microscopy. These results suggest that GeS2 can use to be an alternative anode material and encourage more efforts to develop other high-performance LIBs anodes.

Optimization of the Hydrogen-Adsorption Free Energy of Ru-Based Catalysts towards High-Efficiency Hydrogen Evolution Reaction at all pH.

The utilization of noble-metal catalysts for the hydrogen evolution reaction (HER) provides an efficient strategy for hydrogen acquisition. However, exploring catalysts with suitable hydrogen binding strength for the HER process is always of great importance, but extremely challenging. In this work, sulfur and phosphor as electron-withdrawing elements were incorporated into carbon nanotube (CNT)-supported Ru catalysts, which were prepared through a facile solution reduction reaction and post thermo treatment. Owing to the suitable electronegativity provided by P and synergistic effects of the carbon nanotubes, the RuP2 /CNT achieved a high catalytic performance as a HER electrocatalyst. This may result from the modulation effect of the electronic properties and the depressed adsorption free energy of RuP2 . Electrochemical tests present that the RuP2 /CNT composite exhibit a small overpotential of 58 mV at 10 mA cm-2 in acidic electrolyte. In a neutral or alkaline environment, the overpotential is 82 and 40 mV, respectively. The RuP2 /CNT electrode also possesses stable durability for long-time cycling, suggesting its remarkable property as promising all-pH HER catalyst.

Three-Dimensional Graphene/Ag Aerogel for Durable and Stable Li Metal Anodes in Carbonate-Based Electrolytes.

The use of Li metal as the anode for Li-based batteries has attracted considerable attention due to its ultrahigh energy density. However, the formation of Li dendrites, uneven deposition, and huge volume changes hinder its reliable implementation. These issues become much more severe in commercial carbonate-based electrolytes than in ether-based electrolytes. Herein, a rationally designed three-dimensional graphene/Ag aerogel (3D G-Ag aerogel) is proposed for Li metal anodes with long cycle life in carbonate-based electrolytes. The modified lithiophilic nature of G-Ag aerogel, realized through decoration with Ag NPs, effectively decreases the energy barrier for Li nucleation, regulating uniform Li deposition behavior. Moreover, the highly flexible, conductive 3D porous architecture with hierarchical mesopores and macropores can readily accommodate deposited Li and ensures the integrity of the conductive network during cycling. Consequently, high coulombic efficiency (over 93.5 %) and a significantly long cycle life (1589 h) over 200 cycles, with a relatively high cycling capacity of 2.0 mAh cm-2 , can easily be achieved, even in a carbonate-based electrolyte. Considering the intrinsic high voltage windows of carbonate-based electrolytes, matching the G-Ag aerogel Li metal anode with a high-voltage cathode can be envisaged for the fabrication of high-energy-density Li secondary batteries.

Phosphorus-Doping-Induced Surface Vacancies of 3D Na2 Ti3 O7 Nanowire Arrays Enabling High-Rate and Long-Life Sodium Storage.

Sodium-ion batteries have attracted interest as an alternative to lithium-ion batteries because of the abundance and cost effectiveness of sodium. However, suitable anode materials with high-rate and stable cycling performance are still needed to promote their practical application. Herein, three-dimensional Na2 Ti3 O7 nanowire arrays with enriched surface vacancies endowed by phosphorus doping are reported. As anodes for sodium-ion batteries, they deliver a high specific capacity of 290 mA h g-1 at 0.2 C, good rate capability (50 mA h g-1 at 20 C), and stable cycling capability (98 % capacity retention over 3100 cycles at 20 C). The superior electrochemical performance is attributed to the synergistic effects of the nanowire arrays and phosphorus doping. The rational structure can provide convenient channels to facilitate ion/electron transport and improve the capacitive contributions. Moreover, the phosphorus-doping-induced surface vacancies not only provide more active sites but also improve the intrinsic electrical conductivity of Na2 Ti3 O7 , which will enable electrode materials with excellent sodium storage performance. This work may provide an effective strategy for the synthesis of other anode materials with fast electrochemical reaction kinetics and good sodium storage performance.

Nanostructured Li3 V2 (PO4 )3 Cathodes.

To further increase the energy and power densities of lithium-ion batteries (LIBs), monoclinic Li3 V2 (PO4 )3 attracts much attention. However, the intrinsic low electrical conductivity (2.4 × 10-7 S cm-1 ) and sluggish kinetics become major drawbacks that keep Li3 V2 (PO4 )3 away from meeting its full potential in high rate performance. Recently, significant breakthroughs in electrochemical performance (e.g., rate capability and cycling stability) have been achieved by utilizing advanced nanotechnologies. The nanostructured Li3 V2 (PO4 )3 hybrid cathodes not only improve the electrical conductivity, but also provide high electrode/electrolyte contact interfaces, favorable electron and Li+ transport properties, and good accommodation of strain upon Li+ insertion/extraction. In this Review, light is shed on recent developments in the application of 0D (nanoparticles), 1D (nanowires and nanobelts), 2D (nanoplates and nanosheets), and 3D (nanospheres) Li3 V2 (PO4 )3 for high-performance LIBs, especially highlighting their synthetic strategies and promising electrochemical properties. Finally, the future prospects of nanostructured Li3 V2 (PO4 )3 cathodes are discussed.

Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined.

Three-dimensional nitrogen and sulfur co-doped holey-reduced graphene oxide frameworks anchored with MoO2 nanodots for advanced rechargeable lithium-ion batteries.

In this manuscript, we synthesize a porous three-dimensional anode material consisting of molybdenum dioxide nanodots anchored on nitrogen (N)/sulfur (S) co-doped reduced graphene oxide (GO) (3D MoO2/NP-NSG) through hydrothermal, lyophilization and thermal treatment. First, the NP-NSG is formed via hydrothermal treatment using graphene oxide, hydrogen peroxide (H2O2), and thiourea as the co-dopant for N and S, followed by calcination of the N/S co-doped GO in the presence of ammonium molybdate tetrahydrate to obtain the 3D MoO2/NP-NSG product. This novel material exhibits a series of out-bound electrochemical performances, such as superior conductivity, high specific capacity, and excellent stability. As an anode for lithium-ion batteries (LIBs), the MoO2/NP-NSG electrode has a high initial specific capacity (1376 mAh g-1), good cycling performance (1250 mAh g-1 after 100 cycles at a current density of 0.2 A g-1), and outstanding Coulombic efficiency (99% after 450 cycles at a current density of 1 A g-1). Remarkably, the MoO2/NP-NSG battery exhibits exceedingly good rate capacities of 1021, 965, 891, 760, 649, 500 and 425 mAh g-1 at different current densities of 200, 500, 1000, 2000, 3000, 4000 and 5000 mA g-1, respectively. The superb electrochemical performance is owed to the high porosity of the 3D architecture, the synergistic effect contribution from N and S co-doped in the reduced graphene oxide (rGO), and the uniform distribution of MoO2 nanodots on the rGO surface.

S-Doped TiSe2 Nanoplates/Fe3 O4 Nanoparticles Heterostructure.

2D Sulfur-doped TiSe2 /Fe3 O4 (named as S-TiSe2 /Fe3 O4 ) heterostructures are synthesized successfully based on a facile oil phase process. The Fe3 O4 nanoparticles, with an average size of 8 nm, grow uniformly on the surface of S-doped TiSe2 (named as S-TiSe2 ) nanoplates (300 nm in diameter and 15 nm in thickness). These heterostructures combine the advantages of both S-TiSe2 with good electrical conductivity and Fe3 O4 with high theoretical Li storage capacity. As demonstrated potential applications for energy storage, the S-TiSe2 /Fe3 O4 heterostructures possess high reversible capacities (707.4 mAh g-1 at 0.1 A g-1 during the 100th cycle), excellent cycling stability (432.3 mAh g-1 after 200 cycles at 5 A g-1 ), and good rate capability (e.g., 301.7 mAh g-1 at 20 A g-1 ) in lithium-ion batteries. As for sodium-ion batteries, the S-TiSe2 /Fe3 O4 heterostructures also maintain reversible capacities of 402.3 mAh g-1 at 0.1 A g-1 after 100 cycles, and a high rate capacity of 203.3 mAh g-1 at 4 A g-1 .

Co9 S8 /MoS2 Yolk-Shell Spheres for Advanced Li/Na Storage.

Uniform sized Co9 S8 /MoS2 yolk-shell spheres with an average diameter of about 500 nm have been synthesized by a facile route. When evaluated as anodes for lithium-ion and sodium-ion batteries, these Co9 S8 /MoS2 yolk-shell spheres show high specific capacities, excellent rate capabilities, and good cycling stability.

Facile preparation of carbon wrapped copper telluride nanowires as high performance anodes for sodium and lithium ion batteries.

Uniform carbon wrapped copper telluride nanowires were successfully prepared by using an in situ conversion reaction. The length of these nanowires is up to several micrometers and the width is around 30-40 nm. The unique one dimensional structure and the presence of conformal carbon coating of copper telluride greatly accommodate the large volumetric changes during cycling, significantly increase the electrical conductivity and reduce charge transfer resistance. The copper telluride nanowires show promising performance in a lithium ion battery with a discharge capacity of 130.2 mA h g-1 at a high current density of 6.0 A g-1 (26.74 C) and a stable cycling performance of 673.3 mA h g-1 during the 60th cycle at 100 mA g-1. When evaluated as anode material for a sodium ion battery, the copper telluride nanowires deliver a reversible capacity of 68.1 mA h g-1 at 1.0 A g-1 (∼4.46 C) and have a high capacity retention of 177.5 mA h g-1 during the 500th cycle at 100 mA g-1.

Preparation of a γ-Fe2 O3 /Ag nanowire coaxial nanocable for high-performance lithium-ion batteries.

In this study, we report the design and synthesis of a silver nanowire-γ-Fe2 O3 coaxial nanocable architecture (Ag NWs@γ-Fe2 O3 nanocable) through mild oxidation of [Fe(CO)5 ] on the surface of silver nanowires followed by a calcination process. After optimization of the structural design, the Ag NWs@γ-Fe2 O3 nanocable could deliver superior lithium storage performance in terms of high reversible capacity, good rate performance, and excellent stability, such as a high reversible capacity of about 890 mA h g(-1) after 60 cycles at a current rate of 0.1 C (1.0 C=1005 mA g(-1) ). The reversible capacity remains as high as about 550 mA h g(-1) even at a high current rate of 2.0 C. This dramatic performance is mainly attributed to the smart coaxial design, which can not only alleviate the large volume change and prevent the aggregation of γ-Fe2 O3 nanoparticles, but also enables good conductivity and thus enhances fast charge transfer. The unique structural features of the Ag NWs@γ-Fe2 O3 nanocable represent a promising anode material in lithium-ion battery applications.

Metal-injection and interface density engineering induced nickel diselenide with rapid kinetics for high-energy sodium storage.

The key to the innovation of sodium-ion batteries (SIBs) is to find efficient sodium-storage electrode. Here, metal Mo doping of NiSe2 is proposed by modified electrospinning strategy followed by in situ conversion process. The Mo-NiSe2 anchoring on hollow carbon nanofibers (HCNFs) would make full use of the multi-channel HCNFs in the inner layer and the active sites of Mo-NiSe2 in the outer layer, which plays an important role in buffering the volume stress of Na+ (de)insertion and reducing the adsorption energy barrier of Na+. Innovatively, it is proposed to jointly regulate the SIBs performance of NiSe2 by both metal atom doping and interface effects, thereby adjusting the sodium ion adsorption barrier of NiSe2. The Mo-NiSe2@HCNFs exhibits remarkable performance in SIBs, demonstrating a high specific capacity of 396 mAh/g after 100 cycles at 1 A/g. Moreover, it maintains outstanding cycling stability, retaining 77.6 % of its capacity (211 mAh/g) even after 1000 cycles at 10 A/g. This comprehensive electrochemical performances are due to the structural stability and outstanding electronic conductance of the Mo-NiSe2@HCNFs, as evidenced by the diffusion analysis and ex situ charge-discharge process characterization. Furthermore, coupled with the Na3V2(PO4)2O2F cathodes, the full cell also achieves a high energy density of 123 Wh kg-1. The theoretical calculation of the hypervalent Mo doing further proves the benefit of its Na+ adsorption and denser conduction band distribution. This study provides a reference for the construction of transition metal selenide via doping and interface engineering in sodium storage.

Structural regulation enabled stable hollow molybdenum diselenide nanosheet anode for ultrahigh energy density sodium ion pouch cell.

For the continued use of sodium-ion batteries (SIBs), which require matching anode materials, it is crucial to create high energy density energy storage devices. Here, hollow nanoboxes shaped carbon supported sulfur-doped MoSe2 nanosheets (S-MoSe2@NC) are fabricated by in situ growth and heterodoping strategy. This ensures that the MoSe2 nanosheets are tightly anchored to the nanoboxes carbon, and the structure can effectively buffer the volume stress caused by sodium ion (de)intercalation, as well as providing abundant ion/electron migration transportations. As anode for SIBs, the S-MoSe2@NC shows a higher rate capability and excellent cycling stability (431.1 mAh/g after 1100 cycles at 10 A/g). This excellent cycle life and high rate ability are due to the structural stability and outstanding electronic conductance with reduced band gap of the S-MoSe2@NC, as evidenced by the diffusion analysis and theoretical calculation. In order to promote the application of SIBs, the S-MoSe2@NC and NaNi1/3Fe1/3Mn1/3O2 were assembled into a pouch cell, and the test found that besides the excellent cycle rate performance, the ultrahigh energy density of 256 Wh kg-1 and flexible characteristics can be achieved. This study has proven that building a structure with a rock-steady foundation and quick ion migration may efficiently control sodium storage and pave the way for novel applications of high-performance transition metal dichalcogenides in sodium storage.