High Energy Storage Performance in BiFeO3-Based Lead-Free High-Entropy Ferroelectrics.

Dielectric capacitors are widely used in advanced electrical and electronic systems due to the rapid charge/discharge rates and high power density. High comprehensive energy storage properties are the ultimate ambition in the field of application achievements. Here, the high-entropy strategy is proposed to design and fabricate single-phase homogeneous (Bi0.5Ba0.1Sr0.1Ca0.2Na0.1)(Fe0.5Ti0.3Zr0.1Nb0.1)O3 ceramic, the hierarchical heterostructure including rhombohedral-tetragonal multiphase nanoclusters and locally disordered oxygen octahedral tilt can lead to the increased dielectric relaxation, diffused phase transition, diverse local polarization configurations, grain refinement, ultrasmall polar nanoregions, large random field, delayed polarization saturation and improved breakdown field. Accordingly, a giant Wrec ≈13.3 J cm-3 and a high η ≈78% at 66.4 kV mm-1 can be simultaneously achieved in the lead-free high-entropy BiFeO3-based ceramic, showing an obvious advantage in overall energy-storage properties over BiFeO3-based lead-free ceramics. Moreover, an ultrafast discharge rate (t0.9 = 18 ns) can be achieved at room temperature, concomitant with favorable temperature stability in the range of 20-160 °C, due to the enhanced diffuse phase transition and fast polarization response. This work provides a feasible pathway to design and generate dielectric materials exhibiting high comprehensive energy-storage performance.

A 3D hierarchical TiO2/CaIn2S4/C3N4arrays photoanode with dual-heterojunction for enhanced photoelectrochemical performance.

A novel 3D hierarchical TiO2/CaIn2S4/C3N4arrays with dual heterojunctions photoanode is constructed by stepwise deposition of CaIn2S4nanosheets and ultrathin C3N4onto the well-aligned TiO2nanorods arrays. Integrating the merit of the superior ability of CaIn2S4and C3N4to harvest visible light, dual type-Ⅱ heterojunction band structure and one-dimensional ordered nanostructures, the TiO2/CaIn2S4/C3N4photoanode exhibits simultaneous significant improvements in visible-light harvesting, charge separation and electron transfer capability. At 1.23 V (versus reversible hydrogen electrode) under AM 1.5 G irradiation, the TiO2/CaIn2S475/C3N4photoanode exhibits a photocurrent density of 4.5 mA cm-2, which is 5.2 and 51.1-fold higher than that of TiO2/CaIn2S475 and pristine TiO2photoanode, respectively. Moreover, the applied bias photo-to-current efficiency (ABPE) of the TiO2/CaIn2S475/C3N4photoanode reaches 3.5% at 0.36 V (versus reversible hydrogen electrode). These results are helpful for fabricating more efficient heterostructure photoelectrodes.

Hierarchical Heterostructure Engineering of Layered Double Hydroxides on Nickel Sulfides Heteronanowire Arrays as Efficient Cathode for Alkaline Aqueous Zinc Batteries.

Aqueous alkaline rechargeable nickel-zinc (Ni-Zn) batteries possess great potential for large-scale energy storage systems because of their high output voltage, cheap cost, and intrinsic safety. However, the practical applicability of Ni-Zn batteries has been limited by traditional Ni-based cathodes with low capacity and poor cycle stability. Rational design of electrode structure and composition is highly desired but still significantly challenging. Herein, uniform self-supported hierarchical heterostructure composites interacting NiCo-layered double hydroxide with 1D nickel sulfides heteronanowire rooted on Ni foam (NF\Ni3 S2 /NiS@NiCo-LDH) are successfully developed by a hydrothermal sulfurization-electrodeposition process. The self-supported 3D hierarchical heterostructured composites nanoarray provides abundant reactive sites, rapid ion diffusion channels, and fast electron transfer routes, as well as strong structural stability. More significantly, the strong interfacial charge transfer between Ni3 S2 /NiS heteronanowire and NiCo-LDH effectively modifies the electronic structure of the composites and thereby improving the reaction kinetics. Consequently, the NF\Ni3 S2 /NiS@NiCo-LDH electrode presents a superior capacity of 434.5 mAh g-1 (1.73 mAh cm-2 ) at 3 mA cm-2 . In addition, the fabricated NF\Ni3 S2 /NiS@NiCo-LDH//Zn battery can offer a maximal energy density and power density as large as 556.3 Wh kg-1 and 26.3 kW kg-1 , respectively, as well as an exceptional cycling performance.

The Multicomponent Synergistic Effect of Sandwich Structure Hierarchical Nanofibers for Enhanced Sodium Storage.

Constructing hierarchical micro/nanostructures as anodes for sodium ion batteries is an important approach for exploiting efficient energy storage devices. Herein, sandwich structure hierarchical nanofibers composed of hollow carbon fibers as the substrate, and MoS2 as the interlayer with Co and/or ZnS nanoparticles anchoring in carbon skeletons as the outer shell (carbon nanofiber/MoS2 /Co-ZnS⊂NC) are prepared via a multistep reaction strategy. Profiting from the unique hierarchical structure, abundant migration channels of Na+ , and multicomponent synergistic effects, the rapid diffusion kinetics are ensured and the utilization of active materials is maximized. The coaxial structure can evenly disperse volumetric strain, making structural stability guaranteed. Hierarchical nanofibers deliver a high reversible capacity of 352.3 mAh g-1 at 5.0 A g-1 over 3000 cycles. A discharge capacity of 182.5 mAh g-1 is retained even after 10 000 cycles at 10.0 A g-1 as well as a high rate capacity of 202.0 mAh g-1 up to 30 A g-1 . The optimal atomic ratio of Co element is further verified by the kinetic analysis. The full-cells assembled with Na3 V2 (PO4 )3 cathode provide a high capacity of 179.2 mAh g-1 at 1.0 A g-1 for 500 cycles. Combining in situ and ex situ characterizations and theoretical calculations, possible sodium storage mechanisms and the origin of superior electrochemical properties are revealed.

In2S3 nanoflakes grounded in Bi2WO6 nanoplates: A novel hierarchical heterojunction catalyst anchored on W mesh for efficient elimination of toluene.

Toxic toluene can be completely oxidized in CO2 and H2O with novel three-dimensional (3D) In2S3@Bi2WO6 hierarchical crystals under visible light. Dense and uniform In2S3 nanoflakes are rooted in Bi2WO6 nanoplates which intercross with each other and are anchored on a pliable tungsten mesh. This leads to the construction of a stable and porous interface for adsorbing and decomposing target gaseous toluene. The firm contact between In2S3 and Bi2WO6 initiates the formation of a built-in electric field that helps in channeling the photogenerated electrons in Bi2WO6 CB to quench the holes in2S3 VB. This results in highly capable electrons and holes, as well as notable increase in the yields of •O2- and •OH. 99.7% of toluene is removed and 93.4% is converted to CO2 when it is degraded in simulated air. This validates its remarkable efficacy in detoxifying toluene.

Tunable Surface Selenization on MoO2 -Based Carbon Substrate for Notably Enhanced Sodium-Ion Storage Properties.

Transition metal chalcogenides with high theoretical capacity are promising conversion-type anode materials for sodium ion batteries (SIBs), but often suffer from unsatisfied cycling stability (hundreds of cycles) caused by structural collapse and agglomerate. Herein, a rational strategy of tunable surface selenization on highly crystalline MoO2 -based carbon substrate is designed, where the sheet-like MoSe2 can be coated on the surface of bundle-like N-doped carbon/granular MoO2 substrate, realizing partial transformation from MoO2 to MoSe2 , and creating b-NC/g-MoO2 @s-MoSe2 -10 with robust hierarchical MoO2 @MoSe2 heterostructures and strong chemical couplings (MoC and MoN). Such well-designed architecture can provide signally improved reaction kinetics and reinforced structural integrity for fast and stable sodium-ion storage, as confirmed by the ex situ results and kinetic analyses as well as the density functional theory calculations. As expected, the b-NC/g-MoO2 @s-MoSe2 -10 delivers splendid rate capability and ultralong cycling stability (254.2 mAh g-1 reversible capacity at 5.0 A g-1 after 6000 cycles with ≈89.0% capacity retention). Therefore, the tunable surface strategy can provide new insights for designing and constructing heterostructures of transition metal chalcogenides toward high-performance SIBs.

Construction of Hierarchical Hollow Co9 S8 /ZnIn2 S4 Tubular Heterostructures for Highly Efficient Solar Energy Conversion and Environmental Remediation.

Visible-light-responsive hierarchical Co9 S8 /ZnIn2 S4 tubular heterostructures are fabricated by growing 2D ZnIn2 S4 nanosheets on 1D hollow Co9 S8 nanotubes. This design combines two photoresponsive sulfide semiconductors in a stable heterojunction with a hierarchical hollow tubular structure, improving visible-light absorption, yielding a large surface area, exposing sufficient catalytically active sites, and promoting the separation and migration of photogenerated charges. The hierarchical nanotubes exhibit excellent photocatalytic H2 evolution and CrVI reduction efficiency. Under visible-light illumination, the optimized Co9 S8 /ZnIn2 S4 heterostructure provides a remarkable H2 generation rate of 9039 µmol h-1 g-1 without the use of any co-catalysts and CrVI is completely reduced in 45 min. The Co9 S8 /ZnIn2 S4 heterostructure is stable after multiple photocatalytic cycles.

Long-Lifespan Fibrous Aqueous Ni//Bi Battery Enabled by Bi2O3-Bi2S3 Hierarchical Heterostructures.

Bismuth oxide (Bi2O3) materials are considered as great promising anodes for aqueous batteries on account of the high capacity as well as wide potential plateau. Nevertheless, the low conductivity and severe volumetric change of Bi2O3 in the course of cycling are the main limiting factors for their application in energy-storage systems. Herein, we propose and design unique hierarchical heterostructures constructed by Bi2O3 and Bi2S3 nanosheets (NSs) manufactured immediately on the surface of carbon nanotube fibers (CNTFs). The Bi2O3-Bi2S3 (BO-BS) exhibits enhanced conductivity and increased stability in comparison with pure Bi2O3 and Bi2S3. The BO-BS NSs/CNTF electrode indicates exceptional rate capability and cycling stability, while creating a high reversible capacity of 0.68 mAh cm-2 at 4 mA cm-2, as anticipated. Additionally, the quasi-solid-state fibrous aqueous Ni//Bi battery that was built with the BO-BS NSs/CNTF anode delivers an exceptional cycling stability of 52.7% capacity retention after 4000 cycles at 80 mA cm-2, an ultrahigh capacity of 0.35 mAh cm-2 at 4 mA cm-2, and a high energy density of 340.1 mWh cm-3 at 880 mW cm-3. This work demonstrates the potential of constructing hierarchical heterostructures of bismuth-based materials for high-performance aqueous Ni//Bi batteries and other energy-storage devices.

Gradient Hierarchical Hollow Heterostructures of Ti3C2Tx@rGO@MoS2 for Efficient Microwave Absorption.

Heterostructure engineering has emerged as a promising approach for creating high-performance microwave absorption materials in various applications such as advanced communications, portable devices, and military fields. However, achieving strong electromagnetic wave attenuation, good impedance matching, and low density in a single heterostructure remains a significant challenge. Herein, a unique structural design strategy that employs a hollow structure coupled with gradient hierarchical heterostructures to achieve high-performance microwave absorption is proposed. MoS2 nanosheets are uniformly grown onto the double-layered Ti3C2Tx MXene@rGO hollow microspheres through self-assembly and sacrificial template techniques. Notably, the gradient hierarchical heterostructures, comprising a MoS2 impedance matching layer, a reduced graphene oxide (rGO) lossy layer, and a Ti3C2Tx MXene reflective layer, have demonstrated significant improvements in impedance matching and attenuation capabilities. Additionally, the incorporation of a hollow structure can further improve microwave absorption while reducing the overall composite density. The distinctive gradient hollow heterostructures enable Ti3C2Tx@rGO@MoS2 hollow microspheres with exceptional microwave absorption properties. The reflection loss value reaches as strong as -54.2 dB at a thin thickness of 1.8 mm, and the effective absorption bandwidth covers the whole Ku-band, up to 6.04 GHz. This work provides an exquisite perspective on heterostructure engineering design for developing next-generation microwave absorbers.

Hierarchical Ti3C2Tx@ZnO Hollow Spheres with Excellent Microwave Absorption Inspired by the Visual Phenomenon of Eyeless Urchins.

Ingenious microstructure design and rational composition selection are effective approaches to realize high-performance microwave absorbers, and the advancement of biomimetic manufacturing provides a new strategy. In nature, urchins are the animals without eyes but can "see", because their special structure composed of regular spines and spherical photosensitive bodies "amplifies" the light-receiving ability. Herein, inspired by the above phenomenon, the biomimetic urchin-like Ti3C2Tx@ZnO hollow microspheres are rationally designed and fabricated, in which ZnO nanoarrays (length: ~ 2.3 µm, diameter: ~ 100 nm) as the urchin spines are evenly grafted onto the surface of the Ti3C2Tx hollow spheres (diameter: ~ 4.2 µm) as the urchin spherical photosensitive bodies. The construction of gradient impedance and hierarchical heterostructures enhance the attenuation of incident electromagnetic waves. And the EMW loss behavior is further revealed by limited integral simulation calculations, which fully highlights the advantages of the urchin-like architecture. As a result, the Ti3C2Tx@ZnO hollow spheres deliver a strong reflection loss of - 57.4 dB and broad effective absorption bandwidth of 6.56 GHz, superior to similar absorbents. This work provides a new biomimetic strategy for the design and manufacturing of advanced microwave absorbers.

Simultaneous Piezoelectrocatalytic Hydrogen-Evolution and Degradation of Water Pollutants by Quartz Microrods@Few-Layered MoS2 Hierarchical Heterostructures.

Intense light attenuation in water/wastewater results in photocatalysts exhibiting a low quantum efficiency. This study develops a novel piezoelectrocatalysis system, which involves quartz microrods (MRs) abundantly decorated with active-edge-site MoS2 nanosheets to form a quartz microrods@few-layered MoS2 hierarchical heterostructure (QMSH). Through theoretical calculations, it is found that the quartz MRs serve as a parallel-plate capacitor, which is self-powered to provide an internal electric field to the few-layered MoS2 nanosheets surrounding the quartz MR surfaces, and the piezoelectric potential (piezopotential) effectively facilitates redox reactions with the free carriers in MoS2 . The self-powered quartz MRs in the QMSH present an internal bias to the MoS2 nanosheets, thus yielding a piezoelectrocatalysis system. An efficient piezoelectrocatalytic hydrogen evolution reaction and decomposition of wastewater without light irradiation can be achieved simultaneously. The second-order rate constant of the QMSH is ≈0.631 L mg-1 min-1 , which is 650-fold that of quartz MRs, indicating that the piezoelectric heterostructural catalysts display exceptionally high efficiency on piezoelectrocatalytic redox reactions rather than in the piezocatalytic process. The H2 -production rate of QMSH catalysts approaches ≈6456 µmo1 g-1 h-1 and peaks at ≈16.8 mmol g-1 in 8 h. The piezoelectrocatalytic process may be a promising method for treating industrial wastewater and producing clean energy.

Visible-light-driven, hierarchically heterostructured, and flexible silver/bismuth oxyiodide/titania nanofibrous membranes for highly efficient water disinfection.

Constructing a flexible inorganic membrane photocatalyst for efficient visible-light-driven water disinfection is highly desired but remains a great challenge. Herein, we fabricated a flexible and heterostructured silver/bismuth oxyiodide/titania (Ag/BiOI/TiO2) nanofibrous membrane by combining the electrospinning technique with simple successive ionic layer adsorption and reaction (SILAR) and photodeposition process. In this ternary nanocomposite, ultrathin BiOI nanoplates were firmly anchored onto TiO2 nanofibers, while Ag nanoparticles were uniformly decorated on the surface of both BiOI and TiO2. Benefiting from the large surface area, improved visible-light absorption, and the effective interfacial charge transfer induced by multi-heterojunctions, the resultant Ag/BiOI/TiO2 membrane exhibited superior photocatalytic disinfection activity (7.5 log inactivation of E. coli within 1 h) under visible light illumination. Moreover, the plasmonic Z-scheme charge transfer mode was also proposed for Ag/BiOI/TiO2 system according to the band structure and reactive species analysis. More significantly, the Ag/BiOI/TiO2 membrane-based photoreactor could be facilely constructed for high-efficiency disinfection of high volume contaminated water, and the membrane still maintained good structural integrity and mechanical flexibility after utilization. This work may open up new avenues for designing and constructing flexible high-performance photocatalytic membranes for environmental applications.

Three dimensional hierarchical heterostructures of g-C3N4 nanosheets/TiO2 nanofibers: Controllable growth via gas-solid reaction and enhanced photocatalytic activity under visible light.

Graphitic C3N4 nanosheets were uniformly grown on electrospun TiO2 nanofibers with three-dimensional nanofibrous networks via a facial gas-solid reaction. The mass loading of g-C3N4 nanosheets could be easily controlled by adjusting the mass ratios of gaseous precursors (urea) to TiO2 NFs. The three-dimensional hierarchical heterostructures of g-C3N4 nanosheets/TiO2 nanofibers could be obtained with excellent distribution and high specific surface area of 121.5m2g-1, when the mass loading of g-C3N4 was 59.8wt.%. Under visible light irradiation, the degradation rate constant (rhodamine B) and the H2 evolution rate of the heterostructures were about 4.6 and 1.6 times of pure g-C3N4, while 23 and 167.8 times of TiO2 nanofibers, respectively. Their enhanced performance could be attributed to the effective charge separation and electron transfer process. Our work provides an attractive strategy to construct various three-dimensional hierarchical heterostructures of g-C3N4 nanosheets for environmental and energy applications.

In situ controlled rapid growth of novel high activity TiB2/(TiB2-TiN) hierarchical/heterostructured nanocomposites.

In this work, a reaction coupling self-propagating high-temperature synthesis (RC-SHS) method was developed for the in situ controlled synthesis of novel, high activity TiB2/(TiB2-TiN) hierarchical/heterostructured nanocomposites using TiO2, Mg, B2O3, KBH4 and NH4NO3 as raw materials. The as-synthesized samples were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray energy dispersive spectroscopy (EDX), transition electron microscopy (TEM), high-resolution TEM (HRTEM) and selected-area electron diffraction (SAED). The obtained TiB2/TiN hierarchical/heterostructured nanocomposites demonstrated an average particle size of 100-500 nm, and every particle surface was covered by many multibranched, tapered nanorods with diameters in the range of 10-40 nm and lengths of 50-200 nm. In addition, the tapered nanorod presents a rough surface with abundant exposed atoms. The internal and external components of the nanorods were TiB2 and TiN, respectively. Additionally, a thermogravimetric and differential scanning calorimetry analyzer (TG-DSC) comparison analysis indicated that the as-synthesized samples presented better chemical activity than that of commercial TiB2 powders. Finally, the possible chemical reactions as well as the proposed growth mechanism of the TiB2/(TiB2-TiN) hierarchical/heterostructured nanocomposites were further discussed.

One-dimensional hierarchical heterostructures of In2S3 nanosheets on electrospun TiO2 nanofibers with enhanced visible photocatalytic activity.

In2S3 nanosheets were assembled on electrospun TiO2 nanofibers template by a hydrothermal technique. For the obtained one-dimensional In2S3/TiO2 hierarchical heterostructures (1D In2S3/TiO2 H-HSs), the density and size of the secondary In2S3 nanosheets could be controlled by adjusting the reactant concentrations for the preparation of In2S3 in the hydrothermal process. The 1D In2S3/TiO2 H-HSs exhibited higher visible-light photocatalytic activity for the degradation of Methyl orange (MO) and the reduction of Cr(VI), as compared with the pure TiOv nanofibers and pure In2S3 nanosheets. The enhanced visible light photocatalytic activity might be attributed to the extended absorption in the visible light region from the narrow band-gap In2S3, the effective photogenerated electron-hole separation by the photosynergistic effects of the In2S3/TiO2 H-HSs and quick electron-transfer in the 1D TiO2 nanofibers. Meanwhile, the 1D In2S3/TiO2 H-HSs could be recycled easily by sedimentation due to their nanofibrous nonwoven web structure. Moreover, the mechanisms of photodegradation of MO and photoreduction of Cr(VI) were proposed through systematical investigations. This work provided new insights into utilizing 1D In2S3/TiO2 H-HSs as high efficiency visible-light-driven photocatalysts for environmental remediation and energy conversion.