Hierarchical Hybrid Nanostructures Research Articles

Heterojunction nanoarchitectonics of WOx/Au-g-C3N4 with efficient photogenerated carrier separation and transfer toward improved NO and benzene conversion

Topics on effectively improving the photochemical CO2/benzene/NO oxidation conversion performances of g-C3N4 based materials via charge transfer and separation enhancement are still considered challenging, despite the growing popularity of applying these materials in a variety of energy conversion related applications. Based on the idea of nanoarchitectonics, a post-nanotechnology concept, WOx/Au-g-C3N4 heterostructures are synthesized using two-step thermal polymerization and solvothermal treatment methods in this paper. Small Au nanoparticles are incorporated in superior thin g-C3N4 via mechano-chemical pre-reaction and two-step thermal polymerization (treated at 500 and 700 °C). Enhanced photocurrent density is observed after incorporation of Au, which is also in good agreement with the photocatalytic activity (H2 generation and CO2 reduction) data. Layered WOx with abundant oxygen vacancies are further incorporated into Au-modified g-C3N4 nanosheets to form heterojunctions possessing excellent photocatalytic CO2 photo-reduction performances with CO and CH4 generation rate of 5.64 and 2.58 μmolg−1h−1, respectively, under full solar spectrum. The heterojunctions constructed via in-situ formation show direct Z-scheme charge transfer pathway with improved charge separation and transport efficiencies. These highly stable and recyclable hierarchical g-C3N4 hybrid nanostructures (WOx/Au-g-C3N4 heterojunctions) show outstanding conversion rate (88.1%) and selectivity (99.3%) for benzene to phenol conversion under full solar spectrum condition, as well as excellent NO removal rate (61%).

CoSe-catalyzed growth of graphene sheath to construct CNF@graphene-CoSe cable/sheath heterostructure for high-performance Lithium–Sulfur batteries

Advanced hierarchical hybrid nanostructures of polar, conductive and catalytic chemical traps/carbon with rationally tailored components, structures, and chemistries are important in determining the performance of lithium-sulfur (Li–S) batteries. Herein we propose a facile strategy to prepare 3D-structured CNF@graphene-CoSe (CNF@GL-CoSe) cable/sheath heterostructure with the in-situ formed CoSe as a catalyst for graphene-like carbon growth and Se as a catalyst promoter. The architecture integrates high electrical conductivity, effective ion transport, notable polysulfide entrapment, and polysulfide redox kinetics, availing lithium/sulfur conversion when applied as an interlayer in a Li–S battery. As expected, the battery delivered a low decay of 0.053% per cycle over 700 cycles at 1 C. The capacity even remained 649.4 and 524.5 mA h g−1 at 4 and 6 C, respectively. Furthermore, an areal capacity of about 3 mA h cm−2 at 0.1 C after long-term tests can still maintain with sulfur loading of 4.5 mg cm−2.

In situ self-boosting catalytic synthesizing free-standing N, S rich transition metal sulfide/hierarchical CNF-CNT architectures enable high-performance lithium-sulfur batteries

Advanced hierarchical carbon-based hybrid (CH) nanostructures, typical carbon nanotubes/carbon nanofibers hybrid (CNT-CNF), with rationally tailored components, structures, and chemistries, have been widely dedicated to potential energy storage and conversion applications. Here we report a facile methodology for the synthesis of precise hierarchical heteroatom-doped carbon hybrid/transition metal sulfide (CNF-CNT/TMS) nanostructure assemblies with novel in-situ formed TMSs as the catalysts for secondary CNTs growth via a self-boosting catalytic pyrolysis. The key to in situ growth of CNT arrays is obtaining small high active TMS nanocatalysts and sufficient supply of carbon sources originated from polystyrene. Such special structure provides abundant active sites, beneficial for the application of N, S codoped CNF-CNT/TMS hybrid film in the electrochemistry without introducing extra dopants. As a proof-of-concept application, the representative CNF-CNT/Co9S8 hybrid was exploited as a conductive and catalytic membrane reactor in a lithium–sulfur (Li-S) battery. This unique architecture can achieve a maximized synergistic effect of electron/ion transport, polysulfide entrapment and catalytic conversion, which enables significant enhancement in electrochemical performance of Li-S batteries. As anticipated, the Li-S battery exhibits ultrastable long-life (over 1000 cycles, with an ultralow decay of 0.034% per cycle) and high-rate performance (6 C). Moreover, at high loading of sulfur of 3.7 mg cm−2, stable cycling performance with high capacity retention can still be achieved after long-term tests. This work also presents a facile and effective strategy in the development of complex hierarchical carbon nanostructure, which may be a competitive candidate in other energy storage and conversion system.

Urchin-like hybrid nanostructures of CuOx/Fe2O3 from Cu-mediated pyrolysis of Fe-MOFs for catalytic reduction of organic pollutants.

MOFs have been widely used as templates to design and construct catalysis materials, such as LDH, metal oxides, and carbon. Herein, we developed a Cu-mediated pyrolysis protocol for the synthesis of urchin-like CuOx/Fe2O3 hybrid nanostructures using Fe-MOFs as the precursor. The hierarchical hybrids were composed of an inner CuOx-dispersed Fe2O3 octahedral matrix covered with radially grown Fe2O3 nanorods. This novel hierarchical hybrid nanostructure was generated likely due to the difference in the inward contraction rates between the Cu and Fe species during pyrolysis. Given the structural and compositional benefits, the urchin-like CuOx/Fe2O3 hybrids exhibited outstanding catalytic activity for the chemical reduction of 4-nitrophenol (4-NP) and dyes. Besides, CuOx/Fe2O3 was found to be highly catalytic in the reduction of 4-NP even after 30 consecutive runs, manifesting outstanding durability for continuous operation.

Hierarchical hybrid nanostructure of 1T-tungsten disulfide quantum dots/multihollow capillary bundle-type mesoporous carbon for ultrafast and ultrastable lithium storage

Transition metal dichalcogenides such as tungsten disulfide (WS2), a typical 2D layered structure, have attracted increasing attention as promissing anode materials for ultrafast Li-ion batteries (LIBs), because of their high theoretical specific capacity and excellent Li-ion diffusion kinetics. Furthermore, the ionic/electrical properties of WS2, which can improve ultrafast cycling performance, can be effectively enhanced by its unique metallic phase (1T-WS2). Despite these significant advantages, the application of WS2 anodes is limited by critical issues such as large volume expansion and poor ultrafast cycling performance, because the control and synthesis of nano-sized 1T-WS2 crystals is difficult.Therefore, to improve the ultrafast and ultrastable Li storage of LIBs, herein, a novel architecture comprising 1T-WS2 quantum dots (QDs) embedded in mesoporous carbon nanofibers (PCNFs) with multihollow capillary bundle-type mesopores is proposed. This novel hierarchical hybrid nanostructure exhibits a high specific capacity (716.5 mAh g−1 after 100 cycles at 100 mA g−1) and an outstanding rate capability, because of increased Li-ion storage sites and fast Li-ion diffusion and significant ultrafast cycling capacity (528.1 mAh g−1) and long-term cycling stability (87.8% after 1000 cycles) under ultrafast cycling conditions (2000 mA g−1). The increase in the Li storage sites is attributed to the high specific capacity due to the well-dispersed 1T-WS2 QDs in the PCNFs; the increased Li-ion transfer rate is attributed to the high rate capability due to the multihollow capillary bundle-type mesopores; the long-term cycling stability is attributed to the WS2 QDs embedded within the PCNFs, which effectively prevent volume expansion.

3D hierarchical porous hybrid nanostructure of carbon nanotubes and N-doped activated carbon

In this work, carbon nanotubes (CNTs)/nitrogen-doped activated carbon (AC) hybrids were designed and fabricated using a facile and one-step synthesis. The synthesis of CNTs is based on the recently discovered phenomenon of thermally-induced polyfurfuryl alcohol (PFA) conversion. Hybrid materials are fabricated through the in-situ free growth of closed carbon nanotubes on low-cost activated carbon substrates which were obtained from green algae or amino acids. Herein, three types of carbon nanotubes were observed to freely grow on an activated carbon background from Chlorella vulgaris or l-lysine, types such as multiwalled carbon and bamboo-like nanotubes, whose structure depends on the background used and conditions of the synthesis. Structure type is identified by analyzing transmission electron microscopy images. HRTEM images reveal the tubes’ outer diameter to be in the range of 20–120 nm. Because the carbon surface for the growth of carbon tubes contains nitrogen, the final hybrid materials also possess pyridinic-N and quaternary-N groups, as indicated by X-ray photoelectron spectra.

Fabrication of NiMn2O4 nanosheets on reduced graphene oxide for non-enzymatic detection of glucose

ABSTRACT A distinctive hierarchical hybrid nanostructure which consists of the ultrathin and vertical NiMn2O4 nanosheets grown on reduced graphene oxide (NiMn2O4 NSs@rGO) is synthesised as a non-enzyme glucose sensor by a simple co-precipitation and hydrothermal procedure. The structures and morphologies of the NiMn2O4 NSs@rGO nanocomposites are investigated through X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry and amperometry measurement are applied to analyse the glucose sensing characteristics of NiMn2O4 NSs@rGO. The obtained NiMn2O4 NSs@rGO sensor exhibits two wide linear ranges of 0.001 mM-1 mM and 1 mM-3.5 mM with high sensitivity of 2615.2μAmM−1 cm−2 and 294.8μAmM−1 cm−2, which is much better than other Ni-based and Mn-based glucose sensors. In addition, the NiMn2O4 NSs@rGO nanocomposites have excellent anti-interference and stability. Moreover, the constructed sensor is viable in the analysis of real serum samples, which makes it become a medically dependable non-enzymatic glucose sensor with great possibility.

Yolk-shelled Sn@C@MnO hierarchical hybrid nanospheres for high performance lithium-ion batteries

Metallic tin exhibits great potential as an alternative to commercial graphite anode materials. However, its tremendous volume change during cycles leads to significant capacity fading, which hampers its practical application. In this work, Sn nanoparticles are confined to a carbon nanocage to form Sn@C@MnO yolk-shell hierarchical hybrid nanospheres as anode nanomaterials for Li-ion battery. In the novel nanostructures, the yolk-shell nanostructures can well buffer the volume contraction/expansion of Sn nanocores during cycles; the carbon shell can provide high conductivity and inhibit Sn and MnO nanocrystals from stacking; MnO nanocrystals on the C shell can not only offer sufficient active sites for Li-ion adsorption, but also validly consolidate the structural stability of the shell in the yolk-shell nanostructure. Benefiting from the unique nanostructures, Sn@C@MnO yolk-shell hierarchical hybrid nanospheres exhibit superior electrochemical lithium storage performances (822mAhg−1 after 250 cycles at 0.1Ag-1) and long-term cyclic stability (603mAhg−1 after 500 cycles at 0.5Ag-1). This work offers valuable insight into the synthetic strategy of Sn-based anode materials with novel hierarchical hybrid nanostructures.

Construction of T-Nb2O5 nanoparticles on/in N-doped carbon hollow tubes for Li-ion hybrid supercapacitors

In recent years, hybrid supercapacitors (HSCs) with good characteristics of both lithium batteries (LIBs) and supercapacitors (SCs) have become a hot research topic to meet the growing market demand for electric and hybrid electric vehicles. The key for high-performance HSCs is the reaction kinetics imbalance between the slow faradaic intercalation anode and fast non-faradaic physical adsorption/desorption cathode. Herein, we simultaneously grow ultrafine Nb2O5 nanoparticles on the inner walls and outer surface of hollow heteroatomic (N) carbon tube, giving a unique hierarchical hybrid nanostructure materials named T-Nb2O5@NC. The LIB test show its excellent high-rate capability and long-term cyclic stability. At current density of 0.25C (1.0–3.0 V, vs Li/Li+), the reversible specific capacity of this material is up to 194 mAh g−1. Importantly, the HSC device, assembled by T-Nb2O5@NC as anode and commercial activated carbon as cathode with an organic electrolyte, exhibits good electrochemical performance, including high energy density (49.7 Wh kg−1) and power density (8750 W kg−1), obviously superior to traditional HSC electrode materials. The results prove that T-Nb2O5@NC can be used as a promising HSC anode material.

Graphene-based hierarchical sandwich-type hybrid nanostructures for optical limiters

Graphene-based multi-layer ordered nanostructures have drawn considerable research interest and revealed great potential for various applications. Here, we constructed silver nanoparticle (NP)/graphene-oxide (GO) hierarchical sandwich-type hybrid nanostructures with the use of a highly efficient and convenient chemical self-assembly method, which might be further extended to fabricate other hierarchical graphene-metal NPs hybrid nanostructures. We characterized the morphology, structure, surface chemical states, and linear optical properties of the materials. A hierarchical sandwich-type hybrid nanostructure was obtained through interactions between silver NPs and amino groups on the GO surface. Owing to the protective effect of the multilayer GO, metallic silver was preserved in the sandwich-type nanostructures. Features in the UV/Vis spectrum of the sandwich-type nanostructure were considerably red-shifted and broadened compared with those of silver NPs on a single sheet of GO. We attribute these changes to enhanced coupling of the collective electron excitation within the silver NPs to the graphene oxide. We investigated the nonlinear optical and optical limiting (OL) properties by a nanosecond open-aperture Z-scan technique at 532 nm. These results showed that the hierarchical sandwich-type hybrid nanostructure underwent an intensity-dependent transformation from saturable absorption to reverse saturable absorption. The OL effect of the hierarchical sandwich-type hybrid nanostructure was greater than that of monolayer graphene oxide with silver NPs at the same linear transmittance. We attribute this enhanced OL performance to the unique sandwich structure, which increased interfacial interactions between graphene oxide and the silver NPs and facilitated charge transfer between the two components. The excellent OL performance of hierarchical sandwich-type hybrid nanostructures arises from a combination of photoinduced electron and/or energy transfer, nonlinear absorption, and nonlinear scattering mechanisms. Together, our results indicate that hierarchical sandwich-type hybrid nanostructures might have extensive applications in optoelectronic fields.

Electrochemical hydrogen evolution and CO2 reduction over hierarchical MoSxSe2-x hybrid nanostructures

Abstract Hydrogen production and CO2 energy conversion have increasingly attracted attention and developing electrochemical energy catalysts has widely been performed to achieve clean energy and energy-recycle goals. Herein, hierarchical MoSxSe2-x hybrid nanostructures were synthesized by the hydrothermal method, and the fundamental physiochemical properties were fully characterized by X-ray diffraction crystallography, scanning electron microscopy, high-resolution transmission electron microscopy, elemental mapping, Raman, and X-ray photoelectron spectroscopy. Electrochemical hydrogen evolution reaction was tested in an acidic electrolyte to show a catalytic activity order of MoS2

Hierarchical Hybrid Nanostructures Constructed by Fullerene and Molecular Tweezer.

For the construction of well-defined hierarchical superstructures of pristine [60]fullerene (C60) arrays, pyrene-based molecular tweezers (PT) were used as host molecules for catching and arranging C60 guest molecules. The formation of host-guest complexes was systematically studied in solution as well as in the solid state. Two-dimensional proton nuclear magnetic resonance spectroscopic studies revealed that PT-host and C60-guest complexes were closely related to the molecular self-assembly of PT. Ultraviolet and fluorescence spectroscopic titrations indicated the formation of stable 1:1 and 2:1 (PT/C60) complexes. From the nonlinear curve-fitting analysis, equilibrium constants for the 1:1 (log K1) and 2:1 (log K2) complexes were estimated to be 4.96 and 5.01, respectively. X-ray diffraction results combined with transmission electron microscopy observations clearly exhibited the construction of well-defined layered superstructures of the PT-host and C60-guest complexes. From electron mobility measurements, it was demonstrated that the well-defined hierarchical hybrid nanostructure incorporating a C60 array exhibited a high electron mobility of 1.7 × 10-2 cm2 V-1 s-1. This study can provide a guideline for the hierarchical hybrid nanostructures of host-guest complex and its applications.

Construction of ultrafine ZnSe nanoparticles on/in amorphous carbon hollow nanospheres with high-power-density sodium storage

Sodium-ion batteries (SIBs) are considered as a promising candidate to lithium-ion batteries (LIBs) owing to the inexpensive and abundant sodium reserves. However, the application of anode materials for SIBs still confront rapid capacity fading and undesirable rate capability. Here we simultaneously grow ultrafine ZnSe nanoparticles on the inner walls and the outer surface of hollow carbon nanospheres (ZnSe@HCNs), giving a unique hierarchical hybrid nanostructure that can sustain a capacity of 361.9 mAh g−1 at 1 A g−1 over 1000 cycles and 266.5 mAh g−1 at 20 A g−1. Our investigations indicate that the sodium storage mechanism of ZnSe@HCNs electrodes is a mixture of alloying and conversion reactions, where ZnSe converts to Na2Se and NaZn13 through a series of intermediate compounds. Also, a full cell is constructed from our designed ZnSe@HCNs anode and Na3V2(PO4)3 cathode. It delivers a reversible discharge capacity of about 313.1 mAh g−1 after 100 cycles at 0.5 A g−1 with high Columbic efficiency over 98.2%. The outstanding sodium storage of as-prepared ZnSe@HCNs is attributed to the confinement of ZnSe structural changes both inside/outside of hollow nanospheres during the sodiation/desodiation processes. Our work offers a promising design to enable high-power-density electrodes for the various battery systems.

Programmed Hierarchical Hybrid Nanostructures from Fullerene-Dendrons and Pyrene-Dendrons.

The construction of fullerene (C60 ) hierarchical nanostructures with the help of amphiphilic molecules remains a challenging task in nanoscience and nanotechnology. Utilizing the host-guest complex concept, sub-10 nm layered superstructures are constructed from a monofunctionalized C60 dendron (C60 D, guest) and tweezer-like pyrene dendron (PD, host). Since C60 D and PD are asymmetric shape amphiphiles having liquid crystal (LC) dendrons, both C60 D and PD construct head-to-head bilayer superstructures by themselves. From fluorescence titration experiments, it is realized that the host-guest complex shows 1:1 stoichiometric binding with a binding constant (Ksv = 2.45 × 105 m-1 ). Based on the morphological observations and scattering analyses, it is found that buckle-like asymmetric building blocks (C60 D·PD) are self-assembled by the host-guest complex and construct multilayer hybrid nanostructures. The hierarchical hybrid nanostructures consist of the self-assembled C60 D·PD bilayer with a 2D C60 ·P nanoarray sandwiched between LC dendrons. This advanced strategy is expected to be a practicable and rational guideline for the fabrication of programmed hierarchical hybrid nanostructures.

Dopamine-Assisted Synthesis of MoS2 Nanosheets on Carbon Nanotube for Improved Lithium and Sodium Storage Properties

Hybrid materials with delicate composition and morphology usually promote advanced functions. We report a simple synthesis approach to coaxially grow MoS2 nanosheets on carbon nanotubes (CNTs), which were precoated with polydopamine (PDA), with the ability to readily control phase and morphology. It is found that the thin PDA layer on CNTs surface with abundant catechol base and chinone base can effectively attract both Mo4+ and S2– for subsequently in situ forming MoS2 shell and sheet-like morphology, and therefore, it is essential for the successful deposition of MoS2. The as-prepared MoS2 nanosheets/CNTs (MoS2@CNT) composite with a unique hierarchical hybrid nanostructure with large active surface and enhanced structural robustness has greatly promoted the charge-transfer process and enhanced the electrochemical properties when used as the electrode materials for lithium-ion batteries and sodium-ion batteries. As the anode materials for LIBs, the MoS2@CNTs electrode exhibited extremely stable cycling p...

Rational Design of Hierarchical Nanotubes through Encapsulating CoSe2 Nanoparticles into MoSe2/C Composite Shells with Enhanced Lithium and Sodium Storage Performance.

Transition-metal diselenides have been extensively studied as desirable anode candidates for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of their high theoretical capacities. However, it is of great challenge to achieve satisfactory cycling performance, especially for larger sodium ion storage, originated from electrode deterioration upon large volume change. Herein, we reported the construction of hierarchical tubular hybrid nanostructures through encapsulating CoSe2 nanoparticles into MoSe2/C composite shells via a simple two-step strategy including a hydrothermal method followed by vapor-phase selenization process. The unique tubular structure enables the highly reversible Li/Na storage with high specific capacity, enhanced cycling stability, and superior rate performance. It is indicated that the contribution of partial pseudocapacitive behavior greatly improves the rate capability for SIBs, where a high capacity retention of 81.5% can be obtained when the current densities range from 0.1 to 3 A g-1 (460 mA h g-1 at 0.1 A g-1 vs 379 mA h g-1 at 3 A g-1). This work provides an effective design rationale on transition-metal diselenide-based tubular nanostructures as superior hosts for both Li and Na ions, which could push forward the development of practical applications of transition-metal diselenide-based anodes in LIBs and SIBs.

3D hierarchical defect-rich NiMo3S4 nanosheet arrays grown on carbon textiles for high-performance sodium-ion batteries and hydrogen evolution reaction

A hierarchical hybrid nanostructure composed of NiMo3S4 nanosheet arrays with abundant exposed edges on flexible carbon textiles (denoted as NiMo3S4/CTs) has been designed and synthesized for sodium ion batteries (SIBs) and electrocatalytic hydrogen evolution reaction (HER). The novel NiMo3S4 nanostructure, formed by incorporating Ni2+ into Mo-S lattice, shows plenty of substantial defects and active sites, which are favorable for the improvement of the overall electrochemical performances for both SIBs and HER. When evaluated as the anode of SIBs, the NiMo3S4/CT electrode delivers a high specific capacity of ~ 480 mA h g−1 at a current density of 0.12 A g−1 and a high Coulombic efficiency of 100%. Moreover, the NiMo3S4/CT electrode shows an excellent long-term cycling performance with a high reversible capacity of ~ 302 mA h g−1 after 1000 cycles at 0.48 A g−1, showing a high capacity retention of 73.9%. Furthermore, as a HER catalyst, the NiMo3S4/CT hybrid nanostructure exhibits a low onset over-potential of 0.124 V, a small Tafel slope of 46.2 mV dec−1 as well as an excellent long-term stability, which are among the best values of current noble-metal-free electrocatalysts. These results may open up a new route to introduce more active defect sites to enhance the electrochemical performance of metal sulfides by incorporation of metal elements.

Metal\u2013Organic Framework-Assisted Synthesis of Compact Fe2O3 Nanotubes in Co3O4 Host with Enhanced Lithium Storage Properties

Transition metal oxides are promising candidates for the high-capacity anode material in lithium-ion batteries. The electrochemical performance of transition metal oxides can be improved by constructing suitable composite architectures. Herein, we demonstrate a metal–organic framework (MOF)-assisted strategy for the synthesis of a hierarchical hybrid nanostructure composed of Fe2O3 nanotubes assembled in Co3O4 host. Starting from MOF composite precursors (Fe-based MOF encapsulated in a Co-based host matrix), a complex structure of Co3O4 host and engulfed Fe2O3 nanotubes was prepared by a simple annealing treatment in air. By virtue of their structural and compositional features, these hierarchical composite particles reveal enhanced lithium storage properties when employed as anodes for lithium-ion batteries.

Rational design of SnO2@C@MnO2 hierarchical hollow hybrid nanospheres for a Li-ion battery anode with enhanced performances

SnO2@C@MnO2 hierarchical hollow hybrid nanospheres have been obtained by coating the MnO2 nanosheet-based hierarchical shell on SnO2@C hollow nanospheres via a redox method. The hierarchical hollow hybrid nanospheres are composed of the SnO2 internal layer with hollow nanostructures, the carbon interlayer and the MnO2 hierarchical nanostructured external layer built from two dimensional nanosheets. SnO2@C@MnO2 nanomaterials exhibit a large initial discharge capacity (1378 mAhg−1), extraordinary cyclic stability (644.5 mAhg−1 after 200 cycles) and rate capability as Li-ion battery anodes. The excellent properties may benefit from the rational design of hierarchical hollow hybrid nanostructures and the synergistic effects between the three layers of SnO2, carbon and MnO2.

General Synthesis and Lithium Storage Properties of Metal Oxides/MnO2 Hierarchical Hollow Hybrid Spheres

AbstractMetal oxides/MnO2 hierarchical hollow hybrid nanostructures have attracted significant attention because of their wide potential applications. However, the exploration of a general synthetic approach for fabricating hierarchical hollow hybrid nanostructures is still a great challenge. Herein, a “penetration‐carbonization and reduction‐coating–annealing” route is presented for the generalized synthesis of metal oxides/MnO2 hierarchical hollow hybrid spheres, including NiO/MnO2, Co3O4/MnO2, and CuO/MnO2. Because of the unique hierarchical hollow hybrid nanostructures, NiO/MnO2 nanomaterials possess a desirable capacity (1520 mA h g−1) and outstanding cyclic stability (909 mA h g−1 at the 200th cycle) as Li‐ion battery anode materials. The work reported herein can not only pave the way for the generalized synthetic strategy of metal oxides/MnO2 hierarchical hollow hybrid nanostructures, but also provide a promising application of NiO/MnO2 nanomaterials for Li‐ion battery anode.