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An efficient approach for fabrication of non-noble metal-based electrocatalyst is desirable for designing the energy storage and conversion devices in real-world usages due to low cost and excellent catalytic properties. The preparation of hollow carbon capsules (HCC) containing cobalt (Co)-based electrocatalyst is reported by a simple synthesis process without using templates for the first time. Initially, cobalt phenylphosphonate (Co-MOF) nanorods are fabricated through a simple hydrothermal approach. The as-formed Co-MOF is covered with a thin coating of polydopamine (DP-Co-MOF) through chemical polymerization of dopamine in Tris-HCl (pH 8.5). The DP-Co-MOF is used as self-degraded template for the formation of HCC under pyrolysis. The formation mechanism and hydrogen evolution reaction (HER) activity of HCC are investigated. The hollow structure derived under N 2  exhibits a low overpotential (295 mV at 100 mA cm -2 ) with excellent stability (90.98%) for 150 h, which is further verified by density functional theory (DFT) calculations. Finally, the designed anion exchange membrane (AEM) water electrolyzer based on C─Co─N as cathode delivers a current density of 500 mA cm -2  (at 2.19 V) and 1000 mAcm -2 (at 2.33 V) in 1.0 m KOH at 60 °C. The fabricated new Co-based electrocatalyst is highly beneficial for the fabrication of cost-effective and high-performance AEMWEs., (© 2025 Wiley‐VCH GmbH.) more...

Avoiding the stacking of active sites in catalyst structural design is a promising route for realizing active oxygen evolution reaction (OER). Herein, using a CoFe Prussian blue analoge cube with hollow structure (C-CoFe PBA) as a derived support, a highly effective Ni 2 P-FeP 4 -Co 2 P catalyst with a larger specific surface area is reported. Benefiting from the abundant active sites and fast charge transfer capability of the phosphide nanosheets, the Ni 2 P-FeP 4 -Co 2 P catalyst in 1 m KOH requires only overpotentials of 248 and 277 mV to reach current density of 10 and 50 mA cm -2 and outperforms the commercial catalyst RuO 2 and most reported non-noble metal OER catalysts. In addition, the two-electrode system consisting of Ni 2 P-FeP 4 -Co 2 P and Pt/C is able to achieve a current density of 10 and 50 mA cm -2 at 1.529 and 1.65 V. This work provides more ideas and directions for synthesizing transition metal catalysts for efficient OER performance., (© 2024 Wiley‐VCH GmbH.) more...

Effective intratumoral drug penetration is pivotal for successful cancer treatment. However, due to the disrupted capillary networks and poor perfusion in solid tumors, there exist challenges to realize autonomous directional drug penetration and controlled drug release within the tumor. Considering the specificity of glucose within tumor tissue, we draw inspiration from nature and engineer asymmetrical hollow structures exhibiting chemotaxis towards high glucose levels. By incorporating multiple shells into these structures, we enhance the local chemical concentration gradients, thereby improving cellular uptake and precise targeting. The advantages of anisotropic hollow multishell structure (a-HoMS) can be reflected from the diffusion coefficient and directivity, which increase by 73.4 % and 273 % respectively compared to conventional isotropic hollow spheres, achieving the most linear movement while ensuring the speed of movement. Furthermore, the multi-level porosity and temporal-spatial order of a-HoMS enable sequential drug delivery that inhibits angiogenesis with inducing cell apoptosis. After the eradication of localized tumor cells, the a-HoMS can automatically migrate to the alive tumor cells under the glucose gradient, inducing another cycle of drug delivery and chemotaxis, resulting in excellent antitumor efficacy. These anisotropic HoMS demonstrate intelligence, adaptability, and precision in tumor therapy, providing valuable insights for programmable treatment within tissues., (© 2024 Wiley-VCH GmbH.) more...

Metal-enzyme integrated catalysts (MEICs) that combine metal and enzyme offer great potential for sustainable chemoenzymatic cascade catalysis. However, rational design and construction of optimal microenvironments and accessible active sites for metal and enzyme in individual nanostructures are necessary but still challenging. Herein, Pd nanoparticles (NPs) and Candida antarctica lipase B (CALB) are co-immobilized into the pores and surfaces of covalent organic frameworks (COFs) with tunable functional groups, affording Pd/COF-X/CALB (X = ONa, OH, OMe) MEICs. This strategy can regulate the microenvironment around Pd NPs and CALB, and their interactions with substrates. As a result, the activity of the COF-based MEICs in catalyzing dynamic kinetic resolution of primary amines is enhanced and followed COF-OMe > COF-OH > COF-ONa. The experimental and simulation results demonstrated that functional groups of COFs modulated the conformation of CALB, the electronic states of Pd NPs, and the affinity of the integrated catalysts to the substrate, which contributed to the improvement of the catalytic activity of MEICs. Further, the MEICs are prepared using COF with hollow structure as support material, which increased accessible active sites and mass transfer efficiency, thus improving catalytic performance. This work provides a blueprint for rational design and preparation of highly active MEICs., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.) more...

Core@shell catalyst composited of dual aluminosilicate zeolite can effectively regulate the distribution of acid sites to control hydrocarbon conversion process for the stable formation of target product. However, the diffusion restriction reduces the accessibility of inner active sites and affects synergy between core and shell. Herein, hollow ZSM-5 zeolite nanoreactor with inverse aluminum distribution and double shells are prepared and employed for methanol aromatization. It is demonstrated that the intershell cavity alleviated the steric hindrance from zeolites channel and provided more paths and pore entrance for guest molecule. Correspondingly, olefin intermediates generated from methanol over the external shell are easier to adsorb at internal acid sites for further reactions. Importantly, the diffusion of generated aromatic macromolecules to the external surface is also promoted, which slows down the formation of internal coke, and ensures the use of internal acid sites for aromatization. The aromatics selectivity of the nanoreactor remained at 8% after 154 h, while that of solid core@shell catalyst decreased to 2% after 75 h. This finding promises broader insight to improve internal active site utilization of core@shell catalyst at the diffusion level and can be great aid in the flexible design of multifunctional nanoreactors to enhance the relay efficiency., (© 2024 Wiley‐VCH GmbH.) more...

Photocatalytic hydrogen production based on noble metal-free systems is a promising technology for the conversion of solar energy into green hydrogen, it is pivotal and challenging to tailor-make photocatalysts for achieving high photocatalytic efficiency. Herein, we reported a hollow double-shell dyad through uniformly coating covalent organic frameworks (COFs) on the surface of hollow Co 9 S 8 . The double shell architecture enhances the scattering and refraction efficiency of incident light, shortens the transmission distance of the photogenerated charge carriers, and exposes more active sites for photocatalytic conversion. The hydrogen evolution rate is as high as 23.15 mmol g -1  h -1 , which is significantly enhanced when compared with that of their physical mixture (0.30 mmol g -1  h -1 ) and Pt-based counterpart (11.84 mmol g -1  h -1 ). This work provides a rational approach to the construction of noble-metal-free photocatalytic systems based on COFs to enhance hydrogen evolution performance., (© 2024 Wiley‐VCH GmbH.) more...

With the rapid development of high-power electronic instruments and communication technology, efficient electromagnetic shielding materials with strong absorption of electromagnetic waves and low reflection characteristics have become the focus of the world's attention. This study designs and synthesizes N-doped carbon-coated hollow Fe 3 O 4 nanospheres (Fe 3 O 4 @NC) by spraying Ag nanowires (AgNWs) on textiles as conductive networks. Because of the high permeability and hollow structure Fe 3 O 4 @NC, electromagnetic wave goes through a unique process of "absorption, reflection, and reabsorption" when it passes through the surface of the composite textile. In X-band (≈8.2-12.4 GHz), the average electromagnetic interference shielding effectiveness (EMI SE) reaches 50.1 dB, while the reflectance shielding efficiency (SE R ) is only 2.6 dB, and the average reflectance power coefficient (R) is as low as 0.45. The composite fabric has excellent properties and provides an effective strategy for electromagnetic interference shielding based on absorption., (© 2023 Wiley‐VCH GmbH.) more...

High entropy metal oxides (HEO) are superior to many reactions involving multi-step elementary reactions. However, controlled synthesis of hollow-structured HEO catalysts, which offers large surface area and fast mass transfer kinetics, remains challenging and unexplored due to the complicated metal precursors. Herein, a metal organic framework-templated synthesis of hollow-structured and polyhedron-shaped HEO catalysts assembled with ultra-small nanoparticles, with up to ten metal elements, can be achieved, by taking advantage of the ion-exchange method. ZnFeNiCuCoRu-O HEO catalyst displays excellent activity and ultra-stability for oxygen evolution reaction in full pH range, with an overpotential of 170 mV at a current density of 10 mA cm -2 , a Tafel slope of 56 mV dec -1 , and a decay of activity by 7% in 30 h in alkaline medium, as well as a 12% and 8% decay in acidic and neutral medium, respectively. DFT calculation indicates that the energy barrier of the potential determining step on Ru-Fe bridge site is significantly lower than any other Ru-related bridge sites for the unique hollow structured HEO structures. This work highlights the importance of ion-exchange method in preparing highly stable and active hollow-structured HEOs catalysts toward highly efficient energy conversion and storage devices., (© 2023 Wiley-VCH GmbH.) more...

More and more attention has been paid to lithium-sulfur (Li─S) batteries due to their high energy density and low cost. However, the intractable "shuttle effect" and the low conductivity of S and its reaction product, Li 2 S, compromise battery performance. To address the inherent challenges, a hollow composite catalyst as a separator coating material is designed, in which CoFe alloy is embedded in a carbon skeleton (CoFeNC@NC). In the hybrid structure, the carbon layer can endow the batteries with high electrical conductivity, while the CoFe alloy can effectively bidirectionally catalyze the conversion between lithium polysulfides (LiPSs) and Li 2 S, accelerating the reaction kinetics and reducing the dissolution of LiPSs. Furthermore, the distinctive hollow structure with a cracked surface can facilitate the exposure of a more accessible catalytically active site and enhance Li + diffusion. Benefiting from the synergistic effects, Li─S batteries with a CoFeNC@NC catalyst achieve a high sulfur utilization (1250.8 mAh g -1 at 0.2 C), superior rate performance (756 mAh g -1 at 2 C), and excellent cycling stability (an ultralow capacity fading of 0.054% per cycle at 1 C for 1000 cycles). Even at a sulfur loading of 5.3 mg cm -2 , a high area capacity of 4.05 mAh cm -2 can still be achieved after 100 cycles, demonstrating its potential practicality., (© 2023 Wiley-VCH GmbH.) more...

Controlled assembly of nanoparticles into well-defined assembled architectures through precise manipulation of spatial arrangement and interactions allows the development of advanced mesoscale materials with tailored structures, hierarchical functionalities, and enhanced properties. Despite remarkable advancements, the controlled assembly of highly anisotropic 2Dnanosheets is significantly challenging, primarily due to the limited availability of selective edge-to-edge connectivity compared to the abundant large faces. Innovative strategies are needed to unlock the full potential of 2D-nanomaterialsin self-assembled structures with distinct and desirable properties. This research unveils the discovery of controlled self-assembly of 2D-silica nanosheets (2D-SiNSs) into hollow micron-sized soccer ball-like shells (SA-SiMS). The assembly is driven by the physical flexibility of the 2D-SiNSs and the differential electricdouble-layer charge gradient creating electrostatic bias on the edge and face regions. The resulting SA-SiMS structures exhibit high mechanical stability, even at high-temperatures, and exhibit excellent performance as catalyst support in the dry reforming of methane. The SA-SiMS structures facilitate improved mass transport, leading to enhanced reaction rates, while the thin silica shell prevents sintering of small catalyst nanocrystals, thereby preventing coke formation. This discovery sheds light on the controllable self-assembly of 2D nanomaterials and provides insights into the design and synthesis of advanced mesoscale materials with tailored properties., (© 2023 Wiley-VCH GmbH.) more...

High-efficiency electromagnetic (EM) wave (EMW)-absorbing materials have attracted extensive scientific and technical interest. Although identifying the dominant EM loss mechanism in dielectric-loss materials is indispensable, it is challenging due to a complex synergism between dipole/interfacial polarization and conduction loss. Modulation of defects and microstructures can be a possible approach to determine the dominant EM loss mechanism and realize high-efficiency absorption. Herein, 2D reduced graphene oxide (rGO) flakes are integrated into a 3D hollow bowl-like structure, which increases defect sites (i.e., oxygen vacancy and lattice defect) and reduces the stacked thickness of rGO. Despite their lower stacked thicknesses, the hollow rGO bowls with more defects exhibit lower conductivities but higher permittivities. Accompanied by the transformation from 2D flakes to 3D hollow bowls, the dominant EM loss mechanism of rGO transforms from conduction loss to defect-induced polarization. Furthermore, the defect engineering and structural design endow rGO with well-matched impedance and strong EMW-absorbing capacity. A minimum reflection loss of -41.6 dB (1.3 mm) and an effective absorption bandwidth of 4.8 GHz (1.5 mm) is achieved at a filler loading of 5 wt%. This study will provide meaningful insights into the development of materials with superior EMW-absorbing performances via defect engineering and structural design., (© 2023 Wiley-VCH GmbH.) more...

Precise manipulation of the coordination environment of single-atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two-step strategy to fabricate a series of hollow carbon-based SACs featuring asymmetric Zn-N 2 O 2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn-N 2 O 2 -S). Systematic analyses demonstrate that the synergetic effects between the N 2 O 2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O 2 reduction to H 2 O 2 . Remarkably, the Zn-N 2 O 2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H 2 O 2 generation. Consequently, the Zn-N 2 O 2 -S SAC exhibits impressive electrochemical H 2 O 2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm -2 in the flow cell, it shows a high H 2 O 2 production rate of 6.924 mol g cat -1  h -1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h., (© 2023 Wiley-VCH GmbH.) more...

Mimicking the structures and functions of cells to create artificial organelles has spurred the development of efficient strategies for production of hollow nanoreactors with biomimetic catalytic functions. However, such structure are challenging to fabricate and are thus rarely reported. We report the design of hollow nanoreactors with hollow multishelled structure (HoMS) and spatially loaded metal nanoparticles. Starting from a molecular-level design strategy, well-defined hollow multishelled structure phenolic resins (HoMS-PR) and carbon (HoMS-C) submicron particles were accurately constructed. HoMS-C serves as an excellent, versatile platform, owing to its tunable properties with tailored functional sites for achieving precise spatial location of metal nanoparticles, internally encapsulated (Pd@HoMS-C) or externally supported (Pd/HoMS-C). Impressively, the combination of the delicate nanoarchitecture and spatially loaded metal nanoparticles endow the pair of nanoreactors with size-shape-selective molecular recognition properties in catalytic semihydrogenation, including high activity and selectivity of Pd@HoMS-C for small aliphatic substrates and Pd/HoMS-C for large aromatic substrates. Theoretical calculations provide insight into the pair of nanoreactors with distinct behaviors due to the differences in energy barrier of substrate adsorption. This work provides guidance on the rational design and accurate construction of hollow nanoreactors with precisely located active sites and a finely modulated microenvironment by mimicking the functions of cells., (© 2023 Wiley-VCH GmbH.) more...

Creating more pleated and collapsed structures for carbon-based electrode materials is an important measure to enhance the performance of supercapacitors. Herein, a polymer formed by the aldimine reaction of terephthalaldehyde and aminopropyltriethoxysilane was utilized as the carbon source, and tetraethoxysilane was added as a silica additive to achieve the wrinkled structure on hollow carbon spheres. The silica had a significant modulating effect on the structure of the obtained wrinkled hollow carbon sphere (WHCS), which displayed a visible pleated structure, hollow structure, high specific surface area, and pore volume. As an electrode material for supercapacitors, WHCS exhibits excellent performance with a capacitance of 312 F ⋅ g -1 and remarkable cycle life stability, demonstrating its great potential for use in supercapacitors., (© 2023 Wiley-VCH Verlag GmbH.) more...

Lithium-sulfur (Li-S) batteries are considered as promising candidates for next-generation energy storage systems in view of the high theoretical energy density and low cost of sulfur resources. The suppression of polysulfide diffusion and promotion of redox kinetics are the main challenges for Li-S batteries. Herein, we design and prepare a novel type of ZnCo-based bimetallic metal-organic framework nanoboxes (ZnCo-MOF NBs) to serve as a functional sulfur host for Li-S batteries. The hollow architecture of ZnCo-MOF NBs can ensure fast charge transfer, improved sulfur utilization, and effective confinement of lithium polysulfides (LiPSs). The atomically dispersed Co-O 4 sites in ZnCo-MOF NBs can firmly capture LiPSs and electrocatalytically accelerate their conversion kinetics. Benefiting from the multiple structural advantages, the ZnCo-MOF/S cathode shows high reversible capacity, impressive rate capability, and prolonged cycling performance for 300 cycles., (© 2023 Wiley-VCH GmbH.) more...

The electrosynthesis of recyclable ammonia (NH 3 ) from nitrate under ambient conditions is of great importance but still full of challenges for practical application. Herein, an efficient catalyst design strategy is developed that can engineer the surface microenvironment of a PdCu hollow (PdCu-H) catalyst to confine the intermediates and thus promote selective NH 3 electrosynthesis from nitrate. The hollow nanoparticles are synthesized by in situ reduction and nucleation of PdCu nanocrystals along a self-assembled micelle of a well-designed surfactant. The PdCu-H catalyst shows a structure-dependent selectivity toward the NH 3 product during the nitrate reduction reaction (NO 3 - RR) electrocatalysis, enabling a high NH 3 Faradaic efficiency of 87.3% and a remarkable NH 3 yield rate of 0.551 mmol h -1 mg -1 at -0.30 V (vs reversible hydrogen electrode). Moreover, this PdCu-H catalyst delivers high electrochemical performance in the rechargeable zinc-NO 3 - battery. These results provide a promising design strategy to tune catalytic selectivity for efficient electrosynthesis of renewable NH 3 and feedstocks., (© 2023 Wiley-VCH GmbH.) more...

Exploring cost-efficient/durability bifunctional electrocatalysts are of upmost importance for the practical application of metal-air batteries. However, preparing bifunctional electrocatalysts with the above three advantages remains conceptually challenging. This work reports the preparation of N-doped carbon confined NiCo alloy hollow spheres (NiCo@N-C HS) as bifunctional oxygen electrocatalyst for Zn-air battery with a higher energy density (788.7 mWh g Zn -1 ) and outstanding cycling stability (over 200 h), which are more durable than the commercialized Pt/C+RuO 2 -based device. Electrochemical results and theoretical calculation demonstrate that the synergy in the NiCo@N-C accelerates the electronic transmission for improving activation of O 2 * and OH* intermediates and optimizing reacted free energy pathways, while the hollow structures exposure more active sites for improving the reaction kinetics and enhancing the activity of ORR/OER reaction. This work provides crucial understanding for constructing low-cost transition metal-based catalyst to overcome the efficiency and durability barriers of metal-air batteries for widespread applications., (© 2023 Wiley-VCH GmbH.) more...

Integrating the hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) is an energy-saving approach for electrolytic H 2 production. Here, hollow NiCoP nanoprisms are derived from Prussian blue analogues by a combined self-template coordination reaction and gas-phase phosphorization strategy. Benefiting from the strong electron interaction, unique hollow nanostructure, and enhanced mass/charge transfer, NiCoP nanoprisms display outstanding alkaline HER and UOR performance. Specifically, low potentials of -0.052, -0.115, and -0.159 V for HER and ultralow potentials of 1.30, 1.36, and 1.42 V for UOR at current densities of 10, 50, and 100 mA cm -2 are obtained. Moreover, in a urea-assisted water electrolysis system, NiCoP nanoprisms only require cell voltages of 1.36, 1.49, and 1.57 V to offer current densities of 10, 50, and 100 mA cm -2 , about 170, 180, and 200 mV less than the traditional water electrolysis. Theoretical calculations indicate the Co substitution in Ni 2 P promotes the adsorption and dissociation of water molecules, optimizes the desorption energy of active hydrogen atoms, and enhances the adsorption of urea molecules, thus accelerating the kinetics of HER and UOR. This work facilitates the application of hollow bimetallic phosphides in electrochemical preparation of clean energy and provides a successful paradigm for urea-rich wastewater electrolysis., (© 2022 Wiley-VCH GmbH.) more...

Nickel sulfides with high theoretical capacitance have aroused tremendous attention for next-generation supercapacitors. Unfortunately, the structural durability of nickel sulfides is insufficient to support the long-term working situation. Herein, Ni 3 S 4-x hollow microspheres with sulfur vacancies (Ni 3 S 4-x HMs) are constructed by a liquid-phase anion exchange process using the Ni-MOF as the precursor. Both experimental investigation and theoretical analysis suggest that the deliberately introduced sulfur vacancies effectively improve the anionic adsorptive ability of nickel sulfides in the KOH electrolyte, significantly enhancing the reversible capacitance and structural durability (1884 F g -1 at 2 A g -1 , capacity retention of 97.9% after 10 000 cycles). In addition, an asymmetrical solid-state supercapacitor consisting of Ni 3 S 4-x HMs cathode and activated carbon anode shows infusive energy/power density (33.05 Wh kg -1 /1.68 kW kg -1 ) and remains 82.4% over 10 000 repeated charging/discharging processes in the KOH-PVA gel electrolyte. The strategies can be developed to enlighten the structural design of various metal sulfides materials adopted in electrochemical energy storage devices including alkali ion batteries, supercapacitors, and electrocatalysts., (© 2021 Wiley-VCH GmbH.) more...

The development of high-efficiency, robust, and available electrode materials for oxygen evolution reaction (OER) and lithium-ion batteries (LIBs) is critical for clean and sustainable energy system but remains challenging. Herein, a unique yolk-shell structure of Fe 2 O 3 nanotube@hollow Co 9 S 8 nanocage@C is rationally prepared. In a prearranged sequence, the fabrication of Fe 2 O 3 nanotubes is followed by coating of zeolitic imidazolate framework (ZIF-67) layer, chemical etching of ZIF-67 by thioacetamide, and eventual annealing treatment. Benefiting from the hollow structures of Fe 2 O 3 nanotubes and Co 9 S 8 nanocages, the conductivity of carbon coating and the synergy effects between different components, the titled sample possesses abundant accessible active sites, favorable electron transfer rate, and exceptional reaction kinetics in the electrocatalysis. As a result, excellent electrocatalytic activity for alkaline OER is achieved, which delivers a low overpotential of 205 mV at the current density of 10 mA cm -2 along with the Tafel slope of 55 mV dec -1 . Moreover, this material exhibits excellent high-rate capability and excellent cycle life when employed as anode material of LIBs. This work provides a novel approach for the design and the construction of multifunctional electrode materials for energy conversion and storage., (© 2021 The Authors. Small published by Wiley-VCH GmbH.) more...

Sulfur hosts with rationally designed chemistry to confine and convert lithium polysulfides are of prime importance for high-performance lithium-sulfur batteries. A molten salt electrochemical modulation of iron-carbon-nitrogen is herein demonstrated as formation of hollow nitrogen-doped carbon with grafted Fe 3 C nanoparticles (Fe 3 C@C@Fe 3 C), which is rationalized as an excellent sulfur host for lithium-sulfur batteries. Fe 3 C over nitrogen-doped carbon contributes to enhanced adsorption and catalytic conversion of lithium polysulfides. The sulfur-loaded Fe 3 C@C@Fe 3 C electrodes hence show a high capacity, good cyclic stability, and enhanced rate performance. This work highlights the unique chemistry of metal carbides on facilitating adsorption-conversion process of lithium polysulfides, and also extends the scope of molten salt electrolysis to elaboration of energy materials., (© 2021 Wiley-VCH GmbH.) more...

Hollow metal oxide microspheres (HMMs) have drawn enormous attention in different research fields. Reliable and scalable synthetic protocols applicable for a large variety of metal oxides are in emergent demand. Here we demonstrated that polymer hydrogel, such as the resorcinol formaldehyde (RF) one, existed as an efficient synthetic platform to build HMMs. Specifically, the RF gel forms stacked RF microspheres enlaced with its aqueous phase, where the following evaporation of the highly dispersed water leads to a gel-assisted precipitation (GAP) of the dissolved metal precursor onto the embedded polymeric solids suited for the creation of HMMs. By taking advantage of the structural features of hydrogel, this synthesis design avoids the delicate control on the usually necessitated coating process and provides a simple and effective synthetic process versatile for functional HMMs, particularly Nb 2 O 5 as a high-performance electrode material in Li-ion intercalation pseudocapacitor., (© 2021 Wiley-VCH GmbH.) more...

Oxygen defects and hollow structures positively impact pseudocapacitive properties of diffusion/surface-controlled processes, a component of critical importance when building high-performance supercapacitors. Hence, we fabricated hollow nickel/cobalt molybdate rods with O-defects (D-H-NiMoO 4 @CoMoO 4 ) through a soft-template and partial reduction method, enhancing D-H-NiMoO 4 @CoMoO 4 's electrochemical performance, yielding a specific capacitance of 1329 F g -1 , and demonstrating excellent durability with 95.8 % capacity retention after 3000 cycles. D-H-NiMoO 4 @CoMoO 4 was used as the positive electrode to construct an asymmetric supercapacitor, displaying an energy density of up to 34.13 Wh kg -1 and demonstrating good predisposition towards practical applications. This work presents an effective approach to fabricate and use hollow nickel/cobalt molybdate rods with O-defects as pseudocapacitor material for high-performance capacitive energy storage devices., (© 2021 Wiley-VCH GmbH.) more...

Hollow organic molecular cocrystals comprised of 9-methylanthracene-1,2,4,5-tetracyanobenzene (9MA-TCNB) and naphthalene-1,2,4,5-tetracyanobenzene (NAPH-TCNB) were fabricated using a surfactant-mediated co-reprecipitation method. The crystals exhibit a narrow size distribution that can be easily tuned by varying the concentration of surfactant and incubation temperature. The rectangular crystals possess symmetrical twinned cavities with an estimated storage volume on the order of 10 -10  L. An aqueous dye solution can be incorporated into the cavities during crystal growth and stored inside for up to several hours, confirming the sealed nature of the hollow chambers. Our results demonstrate that it is possible to harness non-classical crystal growth to fabricate organic molecular crystals with novel topologies., (© 2020 Wiley-VCH GmbH.) more...

Sodium-ion batteries (SIBs) are receiving considerable attention as economic candidates for large-scale energy storage applications. Na 3 V 2 (PO ript>4 ) 2 O 2 F (NVPF) is intensively regarded as one of the most promising cathode materials for SIBs, due to its high energy density, fast ionic conduction, and robust Na + -super-ionic conductor (NASICON) framework. However, poor rate capability ascribed to the intrinsically low electronic conductivity severely hinders their practical applications. Here, high-rate and highly reversible Na + storage in NVPF is realized by optimizing nanostructure and rational porosity construction. Hierarchical porous NVPF hollow nanospheres are designed to modify the issues of inconvenient electrolyte transportation and unfavorable charge transfer behavior faced by solid-structured electrode materials. The individual unique nanosphere is assembled from numerous nanoparticles, which shortens the length of Na + transport in solid state and thus facilites the Na + migration. Hollow nanostructure hierarchically porous configuration enables adequate electrolyte penetration, continuous electrolyte supplementation, and facile electrolyte transportation, leading to barrier-free Na + /e - diffusion and high-rate cycling. In addition, the large electrolyte accessible surface area boosts the charge transfer in the whole electrode. Therefore, the present NVPF demonstrates unprecedented rate capability (85.4 mAh g -1 at 50 C) and long-term cyclability (62.2% capacity retention after 2000 cycles at 20 C)., (© 2020 Wiley-VCH GmbH.) more...

Copper(II) oxide featuring a narrow bandgap and low toxicity has been frequently applied in the visible-light-driven photocatalytic hydrogen evolution, but it suffers from large intrinsic overpotential and low water adsorption capacity. Herein, we report a self-templated strategy for the preparation of carbon-doped CuO hollow spheres (C-CuO HSs) through thermal transformation of a hierarchical MOF. The hierarchical Cu-MOFs not only act as a template to form interior voids during the thermal transformation, but also serve as precursors to dope C atoms into the CuO lattice. The as-synthesized C-CuO HSs exhibits remarkable photocatalytic performance with a H 2 evolution rate of 67.3 mmol/g/h and the apparent quantum efficiency of 25.3 % at 520 nm in the present of eosin-Y photosensitizer. The high performance of C-CuO HSs is attributed to the hierarchical porous structure and modulated electronic structure of CuO by C-doping with well exposed reactive sites, high water adsorption capability, and low water reduction reaction barrier. The results presented in this work might shed light on the design of high-performance photocatalysts for various energy-related applications., (© 2020 Wiley-VCH GmbH.) more...

It is of great importance to develop highly efficient and stable Pt-free catalysts for electrochemical hydrogen generation from water electrolysis. Here, monodisperse 7.5 nm copper-doped ruthenium hollow nanoparticles (NPs) with abundant defects and amorphous/crystalline hetero-phases were prepared and employed as efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Specifically, these NPs only require a low overpotential of 25 mV to achieve a current density of 10 mA cm -2 in 1.0 M KOH and show acceptable stability after 2000 potential cycles, which represents one of the best Ru-based electrocatalysts for hydrogen evolution. Mechanism analysis indicates that Cu incorporation can modify the electronic structure of Ru shell, thereby optimizing the energy barrier for water adsorption and dissociation processes or H adsorption/desorption. Cu doping paired with the defect-rich and highly open hollow structure of the NPs greatly enhances hydrogen evolution activity., (© 2020 Wiley-VCH GmbH.) more...

The development of efficient and stable electrocatalysts for the oxygen reduction reaction (ORR) is critical for the large-scale production of fuel cells. Platinum (Pt) nanoparticle catalysts show excellent performance for ORR, though the high cost of Pt is a limiting factor that directly impacts fuel cell production costs. Alloying Pt with other transition metals is an effective strategy to reduce Pt utilization whilst maintaining good ORR performance. In this work, novel hollow PtFe alloy catalysts were successfully synthesized by high-temperature pyrolysis of SiO 2 -coated Pt-Fe 3 O 4 nanoparticle dimers supported on carbon at 900 °C, followed by SiO 2 shell removal and partial dealloying of the PtFe nanoparticles formed using HF. The obtained hollow PtFe nanoparticle catalysts (denoted herein as PtFe-900) showed a 2.3-fold enhancement in ORR mass activity compared to PtFe nanoparticles synthesized without SiO 2 protection, and a remarkable 7.8-fold enhancement relative to a commercial Pt/C catalyst. Further, after 10 000 potential cycles, the ORR mass activity of PtFe-900 remained very high (90.9 % of the initial mass activity). The outstanding ORR performance of PtFe-900 can be attributed to the modification of Pt lattice and electronic structure by alloying with Fe at high temperature under the protection of the SiO 2 coating. This work guides the development of improved, highly dispersed Pt-based alloy nanoparticle catalysts for ORR and fuel cell applications., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

The efficient chemical conversion of carbon dioxide (CO 2 ) into value-added fine chemicals is an intriguing but challenging route in sustainable chemistry. Herein, a hollow-structured bimetallic zeolitic imidazole framework composed of Zn and Co as metal centers (H-ZnCo-ZIF) has been successfully prepared via a post-synthetic strategy based on controllable chemical-etching of the preformed solid ZnCo-ZIF in tannic acid. The creation of hollow cavities inside each monocrystalline ZIFs could be achieved without destroying the intrinsic frameworks, as characterized by field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffraction technologies. The as-synthesized H-ZnCo-ZIF exhibited remarkable catalytic activity in the cycloaddition of CO 2 with epoxides to the corresponding cyclic carbonates, outperforming the solid ZnCo-ZIF analogue due to the improved mass transfer originating from the hollow structure. More importantly, due to stabilization of metal centers in the ZIF framework by the tannic acid shell, H-ZnCo-ZIF exhibited good recyclability, and no activity loss could be observed in six runs. The present study provides a simple and effective strategy to enhance the catalytic performance of ZIFs by creating a hollow structure via chemical etching., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

Research on sodium-ion batteries (SIBs) has recently been revitalized due to the unique features of much lower costs and comparable energy/power density to lithium-ion batteries (LIBs), which holds great potential for grid-level energy storage systems. Transition metal dichalcogenides (TMDCs) are considered as promising anode candidates for SIBs with high theoretical capacity, while their intrinsic low electrical conductivity and large volume expansion upon Na + intercalation raise the challenging issues of poor cycle stability and inferior rate performance. Herein, the designed formation of hybrid nanoboxes composed of carbon-protected CoSe 2 nanoparticles anchored on nitrogen-doped carbon hollow skeletons (denoted as CoSe 2 @C∩NC) via a template-assisted refluxing process followed by conventional selenization treatment is reported, which exhibits tremendously enhanced electrochemical performance when applied as the anode for SIBs. Specifically, it can deliver a high reversible specific capacity of 324 mAh g -1 at current density of 0.1 A g -1 after 200 cycles and exhibit outstanding high rate cycling stability at the rate of 5 A g -1 over 2000 cycles. This work provides a rational strategy for the design of advanced hybrid nanostructures as anode candidates for SIBs, which could push forward the development of high energy and low cost energy storage devices., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

Lithium-oxygen (Li-O 2 ) batteries are attracting more attention owing to their superior theoretical energy density compared to conventional Li-ion battery systems. With regards to the catalytically electrochemical reaction on a cathode, the electrocatalyst plays a key role in determining the performance of Li-O 2 batteries. Herein, a new 3D hollow α-MnO 2 framework (3D α-MnO 2 ) with porous wall assembled by hierarchical α-MnO 2 nanowires is prepared by a template-induced hydrothermal reaction and subsequent annealing treatment. Such a distinctive structure provides some essential properties for Li-O 2 batteries including the intrinsic high catalytic activity of α-MnO 2 , more catalytic active sites of hierarchical α-MnO 2 nanowires on 3D framework, continuous hollow network and rich porosity for the storage of discharge product aggregations, and oxygen diffusion. As a consequence, 3D α-MnO 2 achieves a high specific capacity of 8583 mA h g -1 at a current density of 100 mA g -1 , a superior rate capacity of 6311 mA h g -1 at 300 mA g -1 , and a very good cycling stability of 170 cycles at a current density of 200 mA g -1 with a fixed capacity of 1000 mA h g -1 . Importantly, the presented design strategy of 3D hollow framework in this work could be extended to other catalytic cathode design for Li-O 2 batteries., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

Rational design of metal compounds in terms of the structure/morphology and chemical composition is essential to achieve desirable electrochemical performances for fast energy storage because of the synergistic effect between different elements and the structure effect. Here, an approach is presented to facilely fabricate mixed-metal compounds including hydroxides, phosphides, sulfides, oxides, and selenides with well-defined hollow nanocage structure using metal-organic framework nanocrystals as sacrificial precursors. Among the as-synthesized samples, the porous nanocage structure, synergistic effect of mixed metals, and unique phosphide composition endow nickel cobalt bimetallic phosphide (NiCo-P) nanocages with outstanding performance as a battery-type Faradaic electrode material for fast energy storage, with ultrahigh specific capacity of 894 C g -1 at 1 A g -1 and excellent rate capability, surpassing most of the reported metal compounds. Control experiments and theoretical calculations based on density functional theory reveal that the synergistic effect between Ni and Co in NiCo-P can greatly increase the OH - adsorption energy, while the hollow porous structure facilitates the fast mass/electron transport. The presented work not only provides a promising electrode material for fast energy storage, but also opens a new route toward structural and compositional design of electrode materials for energy storage and conversion., Competing Interests: The authors declare no conflict of interest. more...

Highly efficient earth-abundant electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of great importance for renewable energy conversion systems. Herein, hollow porous heterometallic phosphide nanocubes are developed as a highly active and robust catalyst for electrochemical water splitting via one-step phosphidation of a NiCoFe Prussian blue analogue. Through modulation of the composition of metals in the precursors, the optimal NiCoFeP exhibiting increased electrical conductivity and abundant electrochemically active sites, leading to high electrocatalytic activities and outstanding kinetics for both HER and OER, is successfully obtained. NiCoFeP shows low overpotentials of 273 mV for OER and 131 mV for HER at a current density of 10 mA cm -2 and quite low Tafel slopes of 35 mV dec -1 for OER and 56 mV dec -1 for HER., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

The hollow noble metal nanostructures have attracted wide attention in catalysis/electrocatalysis. Here a two-step procedure for constructing hollow Rh nanospheres (Rh H-NSs) with clean surface is described. By selectively removing the surfactant and Au core of Au-core@Rh-shell nanostructures (Au@Rh NSs), the surface-cleaned Rh H-NSs are obtained, which contain abundant porous channels and large specific surface area. The as-prepared Rh H-NSs exhibit enhanced inherent activity for the methanol oxidation reaction (MOR) compared to state-of-the-art Pt nanoparticles in alkaline media. Further electrochemical experiments show that Rh H-NSs also have high activity for the electrooxidation of formaldehyde and formate (intermediate species in the course of the MOR) in alkaline media. Unfortunately, Rh H-NSs have low electrocatalytic activity for the ethanol and 1-propanol oxidation reactions in alkaline media. All electrochemical results indicate that the order of electrocatalytic activity of Rh H-NSs for alcohol oxidation reaction is methanol (C 1 ) > ethanol (C 2 ) > 1-propanol (C 3 ). This work highlights the synthesis route of Rh hollow nanostructures, and indicates the promising application of Rh nanostructures in alkaline direct methanol fuel cells., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

A biomass-templated pathway is developed for scalable synthesis of NiCo 2 O 4 @carbon aerogel electrodes for supercapacitors, where NiCo 2ubscript> O 4 hollow nanoparticles with an average outer diameter of 30-40 nm are conjoined by graphitic carbon forming a 3D aerogel structure. This kind of NiCo 2 O 4 aerogel structure shows large specific surface area (167.8 m 2 g -1 ), high specific capacitance (903.2 F g -1 at a current density of 1 A g -1 ), outstanding rate performance (96.2% capacity retention from 1 to 10 A g -1 ), and excellent cycling stability (nearly without capacitance loss after 3000 cycles at 10 A g -1 ). The unique structure of the 3D hollow aerogel synergistically contributes to the high performance. For instance, the 3D interconnected porous structure of the aerogel is beneficial for electrolyte ion diffusion and for shortening the electron transport pathways, and thus can improve the rate performance. The conductive carbon joint greatly enhances the specific capacity, and the hollow structure prohibits the volume changes during the charge-discharge process to significantly improve the cycling stability. This work represents a giant step toward the preparation of high-performance commercial supercapacitors. more...

Appropriate adjuvant aiding in generating robust anticancer immunity is crucial for cancer immunotherapy. Herein, hollow ZnO (HZnO) nanospheres are synthesized by a facile method using carbon nanospheres as the template. The HZnO nanospheres significantly promote the cellular uptake of a model antigen, and cytokine secretion by antigen-presenting cells in vitro. HZnO loaded with ovalbumin and polyinosinic-polycytidylic acid (poly(I:C)) inhibits cancer growth and metastasis to inguinal lymph node in a cancer cell challenge model. Moreover, HZnO loaded with autologous cancer antigens inhibits cancer cell growth in a cancer cell re-challenge model. HZnO nanospheres significantly improve the CD4 + and/or CD8 + T cell population in splenocytes of mice in both cancer cell challenge model and re-challenge model. The HZnO nanospheres can be used for cancer immunotherapy as adjuvant., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

Skin cancers caused by UV irradiation have been a major public health problem. One simple and effective way to avoid the above detrimental effects is the use of UV-protective sunscreens. However, there has been considerable concern with the issue of the production of reactive oxygen species (ROS) through the photodegradation of commercial UV filters. Herein, for the first time, it is reported that the integration of ZnO nanoparticles and CeO x nanoparticles into hollow microspheres (ZnO/CeO x HMS) could provide broad-spectrum UV protection and scavenge generated ROS under UV irradiation. Benefiting from the cooperative effect of the hollow structure and the antioxidative activity of CeO x , ROS generated under UV irradiation could be confined to a limited space and effectively conversion into nontoxic molecules is catalyzed as a consequence of increased collision frequency. Therefore, both primary, direct UV-induced damage and secondary ROS toxicity could be greatly reduced., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

Mesoporous hollow carbon nanospheres (MHCS) have been extensively studied owning to their unique structural features and diverse potential applications. A surfactant-free self-assembly approach between resorcinol/formaldehyde and silicon alkoxide has emerged as an important strategy to prepare MHCS. Extending such a strategy to other substituted phenols to produce heterogeneous-atom-doped MHCS remains a challenge due to the very different polymerization kinetics of various resins. Herein, we report an ethylenediamine-assisted strategy to control the cooperative self-assembly between a 3-aminophenol/formaldehyde resin and silica templates. Nitrogen-doped mesoporous invaginated carbon nanospheres (N-MICS) with an N content of 6.18 at %, high specific surface areas (up to 1118 m 2  g -1 ), large pore volumes (2.47 cm 3  g -1 ), and tunable mesopores (3.7-11.1 nm) have been prepared. When used as electrical double-layer supercapacitors, N-MICS show a high capacitance of 261 F g -1 , an outstanding cycling stability (≈94 % capacitance retention after 10 000 cycles), and a good rate performance., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...

Monodisperse poly(methacrylic acid/ethyleneglycoldimethacrylate) (MAA/EGDMA) hollow microcapsules, which exhibit pH-responsive behavior, are prepared by diffusion of cationic surfactants and hydrophobic interaction. During the association of the negatively charged hydrogel microspheres and an oppositely charged surfactant (cetyltrimethylammonium bromide, CTA(+)B), the hydrophobic polymer-surfactant complexes that form are separated from the internal water; consequently, a hollow structure can be formed. Confocal laser scanning microscopy, UV spectro-scopy and zeta potential are employed to study the formation of the hollow structure during the diffusion of the cationic surfactant. The controlled release behavior of methylene blue as a model drug from the as-prepared poly(MAA/EGDMA) microcapsules with a hollow structure is investigated under different pH conditions. The hollow structure can be retained, even during repetitive pH changes., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) more...